This article presents, for the first time, the kinetics and the general conversion features of a 3-initiator system (A/B/N), based on proposed mechanism of Mokbel et al, for both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using copper complex as the initiator. Higher FRP and CP conversion can be achieved by co-initiators concentration [B] and [N], via the dual function of (i) regeneration [A], and (ii) generation of extra radicals S' and S. The FRP and CP conversion is proportional to, respectively, the nonlinear and linear power of bI[A][B], where b and I are the absorption coefficient and the light intensity, respectively. System in air has lower conversion than in laminate due to the oxygen inhibition effects. For thick samples (with thickness z), there is an optimal concentration [A*] which is inverse proportional (bzI), in contrast with very thin sample, in which the conversion is an increasing function of [A] and [B]. The unique feature of dark polymerization in CP conversion enables the polymerization to continue in living mode, in contrasts with that of the radical-mediated pathway in most conventional FRP. The measured results of Mokbel et al are well analyzed and matching the predicted features of our modeling.

Surface initiated atom transfer radical polymerization (SI-ATRP) is one of the most versatile technique to modify the surface properties of material. Recent developed metal free SI-ATRP makes such technique more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N- dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. SBA-15 based polymeric composite with adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous. This procedure provides a low cost, ready availability, and facile modification way to synthesize the polymeric composites without the contamination of metal.

. This article presents, for the first time, the kinetics and the general conversion features of a 3-component system (A/B/N), based on proposed mechanism of Mau et al, for both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using various new copper complex (G2) as the initiator. Higher FRP and CP conversion can be achieved by co-additive of [B] and N, via the dual function of (i) regeneration [A], and (ii) generation of extra radicals. The FRP and CP conversion efficacy (CE) are proportional to the nonlinear power of bI[A][B], where b and I are the effective absorption coefficient and the light intensity, respectively. In the interpenetrated polymer network (IPN) capable of initiating both FRP and CP in a blend of TMPTA and EPOX, (as the monomer for FRP and CP, respectively), the synergic effects due to CP include:: (i) CP can increase viscosity limiting the diffusional oxygen replenishment, such that oxygen inhibition effects are reduced; (ii) the cationic monomer also acts as a diluting agent for the IPN network , and (iii) the exothermic property of the CP. Many new findings are explored via our analytical formuals include: (i) the CE of FRP is about twice of the CE of CP, due to the extra radicals involved in FRP; (ii) the catalytic cycle enhancing the efficacy is mainly due to the regenaration of the initiator, and (iii) the nonlinear dependence of light intensity of the CE (in both FRP and CP). For the first time, the catalytic cycle, synergic effects, and the oxygen inhibition are theoretically confirmed to support the experimental hypothesis. The measured results of Mau et al are well analyzed and matching the predicted features of our modeling. .

The synergetic features of a three-component photoinitiating systems (A/B/C) based on the measured data and proposed mechanism of Liu et al (Polymers, 2020, 12(6), 1394) are analyzed. The co-initiators/additives B and C have dual functions of : (i) regeneration of photoinitiator A and (ii) generation of extra radicals. The synergic effects lead to higher conversion of free radical polymerization (FRP) and cationic polymerization (CP). The key factors and rate constants influencing the conversion efficacy are explored by analytic formulas. Enhancing strategies for various photopolymerization systems are summarized including one component (or monomer) and one-wavelength, two-component and one, two and three-wavelength, and three-component, one-wavelength system. The synergetic effects for higher monomer conversion can be achieved by co-initiators for extra radicals and multiple wavelengths for reduced oxygen-inhibition. Co-initiator B, however, might also reduces the CP radical produced by initiator C. The conversion rate of FRP is proportional to the square root of the light intensity (I), absorption (b) and the initiator initial concentratios (A0, B0, C0), whereas CP is proportional to the linear power of a parameter defined as P=bIA0C0, a stronger dependence than FRP. The CP conversion is governed by a steady-state value proportional to P, and a rate fucntion defining the depletion rate of [A][C], or the increasing rate of the conversion profile. The measured results of Liu et al (Polymers, 2020, 12(6), 1394) are well analyzed and matching the predicted features of our modeling. The specific systems analyzed are: benzophenone derivatives (A) ethyl 4-(dimethylamino)benzoate (B), and (4-tert-butylphenyl)iodonium hexafluorophosphate (C) under a UV (365 nm) LED irradiation; and monomers of trimethylolpropane triacrylate (TMPTA, for FRP) and (3,4- epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate (EPOX, for CP).

The synergistic features of a three-component, photoinitiating system (A/B/C) based on the measured data and proposed mechanism of Liu et al. are analyzed. The co-initiators/additives B and C have dual-functions of : (i) regeneration of photoinitiator A, and (ii) generation of extra radicals for enhanced conversion efficacy (CE). The synergistic effects led to higher CE for both free radical polymerization (FRP) and cationic polymerization (CP). The CE of FRP has 3 terms due to the direct (tyep-I) coupling of the triplet state of A with the monomer (M) and the coupling of the two radicals, R and R', with M. The CE of CP has a transient state proportional to the effective absorption constant (b), the light intensity (I) and initiator concentration (A0), but a steady state is independent of the light intensity (I). For the CE of FRP, the contribution from radical R had two cases: (i) linear dependence on T=bIA0, or (ii) nonlinear square root dependence T0.5. The synergistic effects led to higher conversion of FRP and CP, consistent with the measured results. The theoretically predicted new features include: (i) co-initiator [C] which always enhances both FRP and CP conversions, and (ii) co-initiator [B] which leads to more efficient FRP, but it also reduces CP.

The commercial oxygen-free copper sheets were cold-rolled with reduction rates ranging from 20% to 87% reduction rate and annealed at 400, 500 and 600 °C. The microstructure and texture evolution during cold-rolling and annealing processes were studied using optical microscopy (OM), the scanning electron microscopy (SEM) and the electron back-scattered diffraction (EBSD). The results show that the deformation textures of {123} (S) , {112} (Copper) and {110} (Brass) were continuously enhanced with the increase of cold-rolling reduction. The orientations along the α-oriented fiber converged towards Brass and the orientation density of β fiber obviously increased when the rolling reduction exceeded 60%. The recrystallization texture was significantly affected by the cold-rolling reduction. After 60% cold-rolling reduction, Copper and S textures components gradually decreased and {011} recrystallization texture component formed with the increase of annealing temperature. After 87% cold-rolling reduction, a strong Cube texture formed and other textures were inhibited with the increase of annealing temperature. The strong Brass and S deformation texture was conducive to the formation of a strong Cube annealing texture. The density of annealing twin boundary decreased with the increase of annealing temperature, and more annealing twin boundaries formed in the oxygen-free copper sheets with the increase of cold rolling reduction.

This article presents, for the first time, the kinetics and the general conversion features of a 3-component system, BT(BC)/iodonium/Amine, based on proposed mechanism of Liu et al, for both free radical polymerization (FRP) of acrylates and the free radical promoted cationic polymerization (CP) of epoxides using the new multi-functional initiator of benzophenone–triphenylamine (BT). The additives, iodonium and EDB, have the dual function of (i) regeneration BT and (ii) produce of extra radicals for improved FRP and CP. Analytic formulas are developed to explore the new features including: (i) the conversion efficacy (CE) of FRP is an increasing function of the light intensity, the effective absorption coefficient, and the concentration sum of each of the components, BT, Iod, amine, for transient state. However, CE at steady-state is independent to the light intensity; (ii) the trifunctional hybrid structures of BT3 leads to larger light absorption than other types of BT; it also provides more active sites for the H-abstraction in the presence of EDB, leading to high CE; (iii) the efficacy of FRP is an increasing function of the amine (EDB) concentration, in contrast to that of CP having an opposite dependence; (iv) the consumption rate of BT3 in the BT3/ Iod/EDB system is slower than that of the BT3/Iod system due to photoredox catalytic cycle, and the larger initiator regeneration (RGE)
in the three-component system. A comprehensive model is also proposed that the CE (for both FRP and CP) is governed by (N_jK_jbI), whereas more complex formulas are developed; where Kj is an effective rate constant proportional to the electron transfer quantum yield, and the combined effects of other coupling rate constants; b is an effective absorption coefficient given by the light absorption and excited state quantum yield.

Abstract: Calcium-based catalysts are of a high interest for glycerol polymerization due to their high catalytic activity and large availability. However, their poor stability under reaction conditions is an issue. In the present study, we investigated the stability and catalytic activity of Ca-hydroxyapatites (HAps) as one of the most abundant Ca-source in nature. A stochiometric, a Ca-deficient and a Ca-rich HAps have been synthetized and tested as catalysts in the glycerol polymerization reaction. Deficient and stochiometric HAps exhibited a remarkable 100% selectivity to triglycerol at 15 % of glycerol conversion at 245 °C after 8 h of reaction in the presence 0.5 mol.% of catalyst. Moreover, under the same reaction conditions, Ca-rich HAp showed a high selectivity (88 %) to di- and triglycerol at a glycerol conversion of 27 %. Most importantly, these catalysts were unexpectedly stable towards leaching under the reaction conditions based on the ICP-OES results. However, based on the catalytic tests and characterization analysis performed by XRD, XPS, IR, TGA-DSC and ICP-OES, we found that HAps can be deactivated by the presence of the reaction products themselves, i.e., water and polymers.

This study explores the stability of electrodeposited copper catalysts utilized in electrochemical CO2 reduction (ECR) across various amine media. The focus is on understanding the influence of different amine types, corrosion ramifications, and the efficacy of pulse ECR methodologies. Employing a suite of electrochemical techniques including potentiodynamic polarization, linear resistance polarization, cyclic voltammetry, and chronopotentiometry, the investigation reveals useful insights. The findings show that among the tested amines, CO2-rich monoethanolamine (MEA) exhibits the highest corrosion rate. However, in most cases the rates remain within tolerable limits for ECR operations. Primary amines, notably monoethanolamine (MEA), show enhanced compatibility with ECR processes, attributable to their resistance against carbonate salt precipitation and sustained stability in potential over extended durations. Conversely, tertiary amines such as methyldiethanolamine (MDEA) present challenges due to the formation of carbonate salts during ECR, impeding their effective utilization. The study highlights the effectiveness of pulse ECR strategies in stabilizing ECR. A noticeable shift in cathodic potential and reduced deposit formation on the catalyst surface through periodic oxidation underscores the efficacy of such strategies. These findings offer insights for optimizing ECR in amine media, thereby providing promising pathways for advancements in CO2 emission reduction technologies.

A novel type of phosphazene containing additive that act both as catalyst and as flame retardant for benzoxazine binders is presented in this study. The synthesis of a derivative of hexachlorocyclotriphosphazene (HCP) and meta-toluidine was carried out in the medium of the latter, which made it possible to achieve complete substitution of chlorine atoms in the initial HCP. Thermal and flammability characteristics of modified compositions are revealed. The modifier catalyzes the process of curing and shifts the beginning of reaction from 222.0 C for pure benzoxazine to 205.9 C for composition with 10 phr of modifier. The additive decreases the glass transition temperature of compositions. Achievement of the highest category of flame resistance (V-0 in accordance with UL-94) is ensured both by increasing the content of phenyl residues in the composition and by the synergistic effect of phosphorus and nitrogen. Brief research of the curing kinetics disclosed the complex nature of the reaction. An accurate two-step model is obtained using extended Prout-Tompkins equation for both steps.

The bipartite entanglement is comprehensively investigated in the mononuclear molecular complex (Et3NH)[Ni(hfac)2L], where HL denotes 2-(2-hydroxy-3-methoxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl and hfacH stands for hexafluoroacetylacetone. From the magnetic point of view, the molecular compound (Et3NH)[Ni(hfac)2L] consists of an exchange-coupled spin-1 Ni2+ magnetic ion and a spin-12 nitronyl-nitroxide radical substituted nitrophenol. The nickel-radical molecular complex affords an experimental realization of a mixed spin-(12, 1) Heisenberg dimer with a strong antiferromagnetic exchange coupling J/kB= 505 K and two distinct g-factors gRad=2.005 and gNi=2.275. By adopting this set of magnetic parameters we demonstrate that the Zeeman splitting of a quantum ferrimagnetic ground-state doublet due to a weak magnetic field may substantially reinforce the strength of bipartite entanglement at low temperatures. The molecular compound (Et3NH)[Ni(hfac)2L] maintains sufficiently strong thermal entanglement even at room temperature, vanishing only above 546 K. Specifically, the thermal entanglement in the nickel-radical molecular complex retains approximately 40% of the maximum value corresponding to perfectly entangled Bell states at room temperature, which implies that this magnetic compound provides suitable platform of a molecular qubit with potential implications for room-temperature quantum computation and quantum information processing.

The prediction of tertiary RNA structures is significant to the field of medicine (e.g. mRNA vaccines, genome editing), and the exploration of viral transcripts. Though many RNA folding software exist, few studies have condensed their locus of attention solely to viral pseudoknotted RNA. These regulatory pseudoknots play a role in genome replication, gene expression, and protein synthesis. This study explores five RNA folding engines that compute either the minimum free energy (MFE) or the maximum expected accuracy (MEA). These folding engines were tested against 26 experimentally derived short pseudoknotted sequences (20-150nt) using metrics that are commonly applied to software prediction accuracy (e.g. F1 scoring, PPV). This paper reports higher accuracy RNA prediction engines (pKiss) when compared to previous iterations of the software, and when compared to older folding engines. They show that MEA folding software does not always outperform MFE folding software in prediction accuracy when assessed with metrics such as percent error, sensitivity, PPV, and F1 scoring when applied to viral pseudoknotted RNA. Moreover, the results suggest that thermodynamic model parameters will not ensure accuracy if auxiliary parameters such as Mg2+ binding, dangling end options, and H-type penalties are not applied. The observations reported in this paper highlight the quality between different ab initio prediction methods while enforcing the idea that a better understanding of intracellular thermodynamics is necessary for a more efficacious screening of RNAs.

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron-sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from DFT calculations. The distal cubane FeS-cluster has a three cysteine and one histidine coordination [Fe₄S₄](His)(Cys)₃ first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and the all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe₄S₄](Cys)₄ case. The fast and efficient electron transfer from the distal iron-sulfur cluster is realized by a fine-tuned protein environment which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering.

During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF) unit by a -conjugated bridge (1). Interestingly, this system behaves as a semiconductor with high conductivity and small energy gap under high pressure. With the aim of developing a new material with improved conducting properties, we have designed and synthesized the radical dyad 2 which was functionalized with an ethylenedithio (EDT) group in order to improve the intermolecular interactions of the TTF subunits. The physical properties of the new radical dyad 2 were studied in detail in solution to further analyze its electronic structure as well as its potential use as radical conductor in the solid state.

Iterated games, in which the same economic interaction is repeatedly played between the same agents, are an important framework for understanding the effectiveness of strategic choices over time. To date very little work has applied information theory to the information sets used by agents in order to decide what action to take next in such strategic situations. This article looks at the mutual information between previous game states and an agent's next action by introducing two new classes of games: ’invertible games’ and ‘cyclical games'. By explicitly expanding out the mutual information between past states and the next action we show under what circumstances these expressions can be simplified. These information measures are then applied to the Traveler's Dilemma game and the Prisoner's Dilemma game, the Prisoner's Dilemma being invertible, to illustrate their use. In the Prisoner's Dilemma a novel connection is made between the computational principles of logic gates and both the structure of games and the agents' decision strategies. This approach is applied to the cyclical game Matching Pennies to analyse the foundations of a behavioural ambiguity between two well studied strategies: ‘Tit-for-Tat' and ’Win-Stay, Lose-Switch'.

There is an urgent demand worldwide for the development of highly selective adsorbents and sensors of heavy metal ions and other organic pollutants. Within these environmental and public health frameworks, we are combining the salient features of clays and chelatant polymers to design selective metal ion adsorbents. Towards this end, the ion imprinting approach has been used to develop a novel nanohybrid material for the selective separation of Cu2+ ions in aqueous solution. The Cu2+-imprinted polymer/ montmorillonite nanocomposite (IIP/Mt) and non-imprinted polymer/montmorillonite nanocomposite (NIP/Mt) were prepared by radical photopolymerization process in the visible light. Ion imprinting was indeed important as the recognition of copper ions by IIP/Mt was significantly superior to that of NIP/Mt that is the nanocomposite synthesized in the same way but in the absence of Cu2+ ions. The adsorption process as batch study was investigated under the experimental condition affecting same parameters such as contact time, concentration of ions metals and pH. The adsorption capacity of Cu2+ ions is maximized at pH 5. Removal of Cu2+ ion achieved equilibrium within 15 minutes; the results obtained were found to be fitted by the pseudo-second order kinetics model. The equilibrium process was well described by the Langmuir isothermal model and the maximum adsorption capacity was found to be 23.6 mg/g.

Keywords: olfactory rehabilitation; chronic pain; fMRI;

Composite fiber materials are superior materials due to their high strength and light weight. Composites reflect the properties of their constituents, which is proportional to the volume fraction of each phase. There are different fiber reinforcement types and each affects it’s flexural, tensile and compression strength. When selecting a composite for a specific application, the forces excreted on the composite must be known in order to determine the reinforcement type. Unidirectional fiber reinforcement will allow very strong load resistance but only in one direction where as a random orientated fiber reinforcement can resist less load but can maintain this quota in all directions. These materials are said to be anisotropic. Certain composite fibers, taking into consideration there weights, are physically stronger than conventional metals. This research deals with the analysis of three composite materials with different reinforcement types, volume fraction and phase content. It was found that material A (glass epoxy) was the strongest in the longitudinal direction with a flexural strength of 534 MPa in the longitudinal and 420 MPa in the transverse direction. The flexural stresses of material B (glass silicone) and material C (glass polyester) where both found in the 120 to 135 MPa range. Differences were due to their differences in matrix composition and reinforcement type.

Chitosan decorated copper nanoparticles (CS/CuNPs) catalysts were synthesized via reduction methods utilizing green protocol. The CS/CuNPs hybrid catalysts were tested for the synthesis of quinoline derivatives utilizing one-pot multicomponent reaction (MCR) under ultrasonic irradiation. The best catalyst (CS/CuNPs) that provided good conversion reaction yield and high turnover frequency (TOF) was characterized using Fourier transform infrared (FTIR), Thermogravimetric analyses (TGA), X-ray diffraction (XRD), , scanning electron microscopy (SEM), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. Generalization of the scope of the proposed catalytic process was studied using different aldehydes. Excellent products yield and high TOF in even shorter reaction time (~5 min) was attained. Recyclability performance of the catalyst over five times re-use without detectable loss in product yield was recorded. The current method is green process utilizing environmentally benign catalyst and considered to be promising sustainable protocol for the synthesis of fine chemicals.

In the paper it is demonstrated that a valid path to a contradiction in complex number theory exists. In the path use is made of Euler’s identity and simple trigonometry. Each step can be easily verified.

We generalize the point information gain (PIG) and derived quantities, i.e., point information gain entropy (PIE) and point information gain entropy density (PIED), for the case of the Rényi entropy and simulate the behavior of PIG for typical distributions. We also use these methods for the analysis of multidimensional datasets. We demonstrate the main properties of PIE/PIED spectra for the real data on the example of several images, and discuss further possible utilizations in other fields of data processing.

There are many medicinal plants that have various medicinal properties in their different parts. The medicinal plants are major backbone of pharmaceutical industries. In this article we compare the antioxidants properties from various plants parts (root, stem, leaf, flower and bark) of the most important medicinal plant, Justicia adhatoda L. Various plant parts showed the good amount of antioxidant properties. These results enhance the medicinal properties of this plant due to the presence of good amount of antioxidants; among all the plant parts leaves and flowers showed maximum natural antioxidants, hence the study could be saying that this plant has good efficacy of antioxidants.

Frontal Polymerization (FP) is recognized as a polymer synthesis method capable of generating a highly localized and self-propagating exothermic front, considered a more rapid and energy-efficient manufacturing scheme for polymer-based fiber-reinforced composite materials. This study conducts a numerical investigation based on the Finite Element Method into the initiation and propagation of frontal polymerization of acrylamide. Utilizing Differential Scanning Calorimetry (DSC) experiments, the study phenomenologically tests the curing kinetics reactions of acrylamide (AM) in deep eutectic solvent (DES)-based polymerizable systems, thereby establishing a curing kinetics model for the autocatalytic reaction of polyacrylamide. By coupling the heat conduction diffusion equation of the frontal polymerization reaction, the Finite Element Method is employed to solve the reaction-diffusion model, aiming to explore the evolution of temperature and degree of curing during the manufacturing process. The results demonstrate the reliability and accuracy of the nth-order autocatalytic model in the study of curing kinetics for DES-based synthesis, indicating that the front propagation speed of the AM-based FP reaction is influenced by the activation temperature, duration of activation temperature, and initial temperature of the solution. Experimental validation of the polyacrylamide manufacturing through frontal polymerization corroborates the accuracy and reliability of the model predictions, providing a reference for the numerical model study and temperature control in the synthesis of acrylamide composite hydrogels via FP.

A visible-light photoredox functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones through a Friedel-Crafts reaction with indoles using an inexpensive organophotoredox catalyst is described. The reaction uses a dual catalytic system formed by a photocatalyst simple and cheap, 9,10-phenanthrenedione, and a Lewis acid, Zn(OTf)₂. 5W white LEDs are used as visible-light source and oxygen from air as a terminal oxidant, obtaining the corresponding products with good yields. The reaction can be extended to other electron-rich arenes.

This study reports a computational investigation on the antioxidant activity of five plant food benzoic acid derivatives, namely gallic acid (GA), para-hydroxybenzoic acid (PHBA), protocatechuic acid (PCA), syringic acid (SA), and vanillic acid (VA). Based on computed thermodynamics parameters, a detailed comparative debate is developed concerning their free radical scavenging activity in the gas phase and polar solutions (in water and methanol solvents). This discussion goes on to elucidate both the most preferred mechanism and the order of antioxidant activity for these molecules in each environment. Paradoxically, calculations using the harmonic oscillator model of aromaticity (HOMA) suggest that H abstraction radicals gain in stability as the central benzene ring loses in structural aromaticity. Finally, spin densities and fukui function f⁰ seem to be good indicators of the local reactivity of these compounds towards free radicals.

Suzuki cross-coupling reaction has developed one of the furthermost effectual approaches for the synthesis of biaryls or substituted aromatic moieties from aryl halides and arylboronic acids with a palladium-catalyst in the past two era’s. Herein, Pd-free layered double hydroxide containing nickel catalysts were prepared by co-precipitation method under ultrasonic irradiation and N2 atmosphere with different molar ratios of Ni: Mg: Al and coded as (1NiLDHs-Dr), (1.5NiLDHs-Dr) and (2NiLDHs-Dr). A series of reduced catalysts under 5%H2/N2 at different temperatures were coded as 1NiLDHs-R200, 1.5NiLDHs-R200 and 2NiLDHs-R200. As-synthesized 2NiLDHs-Dr was the superlative catalyst when coupling different aryl halides with different boronic acids derivatives. Deep investigation of all catalysts was done using different techniques such as inductively coupled plasma optical emission spectroscopy (ICP-OES), x-ray photoelectron spectroscopy (XPS), powder x-ray diffraction (XRD), thermogravimetric analyses (TGA), Fourier transfer infrared (FTIR), scanning electron microscope (SEM) connected with energy dispersive x-ray (EDX) and N2-physisorption at -196 ℃. The results attained verified that ɑ-Ni(OH)2 was fashioned for 2NiLDHs-Dr catalyst and the enclosure of nickel ions in the cationic sheet of layered structure were responsible for the fascinating catalytic efficacy rather than the basic nature of material. The Ni-containing LDHs catalysts encourage forthcoming studies in Pd-free catalyzed C-C coupling reactions.

The symmetry properties of an ornament contain information about its civilisation and its interactions with other cultural sources. Two-dimensional periodic ornaments can be strictly classified into a limited set of 17 mathematical symmetry groups, also known as wallpaper groups. The collection of ornaments thus classified for a civilisation is characteristic of the cultural group and serves as a fingerprint to identify that group. If the distribution of wallpaper groups is available for several societies, mathematical methods can be applied to determine similarities and differences between the art practices of these communities. This method allows a systematic approach to the general ornamental practices within a culture and their interactions in the form of similarity of fingerprints. We test the feasibility of the method on examples of medieval Armenians, Byzantium, Seljuks first in Persia and then in Anatolia and among Arabs in the Middle East. For this purpose we present the distribution of the planar ornaments and calculate the Euclidean distances in pairs. We tested to what extend geographical and religious factors could account for the observed similarity of ornamental groups between cultures. The results suggest an intensive interaction between the Seljuk Turks and Arab craftsmen who produced the ornaments. Therefore the cultural interactions are religiously motivated.

CuAl8Fe5Ni4Zn4Sn1 (OF 2238) is a new lead-free copper alloy for plain bearing applications that was first officially presented in a scientific journal in 2020. Soon after its invention, the use of the alloy for connecting rod bushings in heavy duty internal combustion engines was promoted and validated with customers. The aim of this article is to describe the material properties of the new alloy in more detail than previously and explain how the advantageous properties of CuAl8Fe5Ni4Zn4Sn1 are generated. At the beginning of the article, the general development trends in the field of copper alloys for sliding applications are presented. This is followed by a presentation of the latest research results about CuAl8Fe5Ni4Zn4Sn, before concluding with a brief summary and future outlook, emphasizing on the fact that recent trends in copper-based sliding applications show great additional potential for further material developments.

Background and Objectives: Knee osteoarthritis (KOA) is a degenerative disease that is targeting continuously people of different ages, but especially the elderly population, the number of which tends to increase continuously at the global level. Apart from age, excess weight can influence the evolution of the disease, with obesity being associated with a weak inflammation stage, and an imbalance between pro-inflammatory and anti-inflammatory cytokines. The present work aimed to identify specific biomarkers alike ACRP-30, IL-10, TNF-α, and IL-6 in synovial fluid and correlate them with patients’ clinical data. Materials and Methods: 24 subjects with KOA and over 50 years of age are involved in the present study. All patients performed a supine X-ray at the target knee. Ultrasound was performed using an ESAOTE MyLab Omega (ESAOTE Spa, Italy) ultrasound device and a 6-19 MHz linear array transducer. Results: The obtained results highlighted a significant correlation between age and adiponectin level (p=0.0451, r=-0.412). Also, the IL-10 values are lower in cases where the intensity of the pain is more pronounced (p=0.0405, r=-0.421). In addition, analyzing the data by gender, it was observed that in the case of males, stiffness is more related to age (p=0.0079, r=0.7993), compared to women (p=0.0203, r=0.6223). In the case of women, the progression of the disease tends to increase more intensively total WOMAC score’s values (p=0.00031, r=0.8342), compared with men (p=0.0289, r=7013). Regarding interleukins and BMI, significant correlations were observed only in the case of men. Conclusions: A significant correlation between age and adiponectin, and adiponectin and IL-6, suggests that advanced age may contribute to adiponectin reduction. Comparing men with women, it was observed that men's age is more related to rigidity, and IL-6 and IL-10 are directly correlated to BMI and women seem to be more sensitive to pain and stiffness.

The activity and cyclability of Cu-MOF-74 as catalyst was studied for the ligand-free C-O cross-coupling reaction of 4-nitrobenzaldehyde (NB) with phenol (Ph) to form 4-formyldiphenyl ether (FDE). Cu-MOF-74 is characterized by unsaturated copper sites in a highly porous metal-organic framework. The influence of solvent, reaction temperature, NB/Ph ratio, catalyst concentration and basic agent (type and concentration) were evaluated. High conversions were achieved at 120°C, 5 mol% of catalyst, NB/Ph ratio of 1:2, DMF as solvent and 1 equivalent of K2CO3 base. The activity of Cu-MOF-74 material was higher than other ligand-free copper catalytic systems tested in this study. This catalyst was easily separated and reused in five successive runs, achieving a remarkable performance without significant porous framework degradation. The leaching of copper species in the reaction medium was negligible. The O-arylation between NB and Ph took place only in the presence of Cu-MOF-74 material, being negligible without the solid catalyst.

As companies increasingly undergo digital transformation, the role of talent management pro-cesses becomes pivotal in enhancing overall organizational performance. The research addresses the significance of talent management in corporate digital transformation, examining whether variations in the digitalization of these processes can be attributed to company size. A qualitative approach was employed, utilizing a questionnaire, collecting responses from 202 organizations across diverse sectors. Findings reveal disparities in digitalization throughout the talent man-agement process, with pronounced presence in the attracting, selecting, and rewarding phases, but diminishing in deployment and development, further declining in planning. A positive cor-relation between company size and adoption of specific digital platforms was observed. Larger enterprises exhibit greater utilization of digital platforms in talent deployment and development. Moreover, corporate communication tools are consistently utilized in the rewarding phase, irre-spective of company size. These findings offer practical insights for organizations to optimize their digitalization strategies based on their scale, thereby contributing to more effective and tailored digitalization endeavors. The uniqueness of this research lies in its exploration of the in-fluence of company size on the digitalization of talent management processes and its potential to explain variations across different stages of these processes.

In this work, we synthesized chitosan grafted-poly acrylic acid (CS-g-PA) through surface-initiated atom transfer radical polymerization (SI-ATRP). We also studied the adsorption process of copper and lead ions onto CS-g-PA surface. Adsorption equilibrium studies indicated pH 4.0 as the best pH for the adsorption process, while the maximum adsorption capacity for Pb2+ ions was 98 mg*g-1 and for Cu2+ was 164 mg*g-1, higher adsorption capacities than chitosan alone (CS), where Pb2+ was only 14.8 mg*g-1and Cu2+ was 140 mg*g-1, respectively. Furthermore, the adsorption studies indicated that Langmuir model describes all the experimental data. All these results suggest that the new CS-g-PA polymers had potential as adsorbent for hazardous and toxic metal ions produced by different industries.

The review scrutinizes the currently performed research on the new methods for enhancing bituminous binder performance through radiation and radical grafting of polymer modifers of bitumen. It investigates innovative methods, including using waste polymers as modifiers, and applying radiation for polymer grafting, to overcome challenges like high costs, low aging resistance and storage stability issues, of which separation of phases polymer/bitumen is the most significant obstacle. These advanced modification techniques promise sustainability through the decrease of the carbon footprint of transportation systems by improving the properties and durability of binders. Additionally, the review discusses the parameters and mechanistic aspects from a scientific perspective, shedding light on the underlying processes that contribute to the improved performance of modified bituminous binders.

Selective hydrogenation of nitrobenzene was carried out under solvent-free conditions using supported AuPd nanoparticles catalyst, prepared by modified impregnation method (MIm), as efficient catalyst. >99% yield of aniline (AN) was obtained after 15 hours at 90 °C, 3 bar H2 that can be used without any further purification or separation, therefore reducing cost and energy input. Supported AuPd nanoparticles catalyst, prepared by MIm, was found to be active and stable even after 4 recycle experiments whereas the same catalyst prepared by SIm deactivated during the recycle experiments. The most effective catalyst was tested for the chemoselective hydrogenation of 4-chloronitrobenzene (CNB) to 4-chloroaniline (CAN). The activation energy of CNB to CAN was found to be 25 kJ mol-1, while that of CNB to AN was found to be 31 kJ mol-1. Based on this, the yield of CAN was maximized (92%) by lowering the reaction temperature to 25 °C.

Here we report highly efficient, indium tin oxide (ITO)-free polymer solar cells (PSCs) with an ultrathin copper (Cu) film(~10 nm) coated with a thin layer of poly[(9,9-bis(3‘-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) as transparent electrode. Despite of its lower far-field transmittance of the electrode, the obtained ITO-free device based on the ultrathin Cu film can delivery higher absorption efficiency than that of the device based on ITO substrate in the long wavelength region, which can be attributed to the formation of metal resonant microcavity between the opaque back metal mirror (MoO3/Al electrode) and the transparent Cu film with high reflectance. As a result, polymer solar cells based on poly[[2,6'-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene][3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7-Th) and [6,6]-phenyl C71-butyric acid methyl ester (PC71BM) blend show a high power conversion efficiency (PCE) of 8.21 %, comparable to that of the control device based on ITO electrode (with a PCE of 9.60% ). The results demonstrate that thermally evaporated Cu thin film electrode can be promising candidate to replace ITO for highly efficient PSCs, thus may open up the possibility for massive production of PSCs with low cost.

Microwave technology has a potential application in the extraction of zinc from sulphide ores, knowledge of the dielectric properties of these ores plays a major role in the microwave design and simulation for any process. The dielectric properties of zinc sulfide concentrate for two different apparent densities—1.54 and 1.63 g/cm³—have been measured by using the resonance cavity perturbation technique at 915 and 2450 MHz during the roasting process for the temperature ranging from room temperature to 850 °C. The variations of dielectric constant, the dielectric loss factor, the dielectric loss tangent and the penetration depth with the temperature, frequency and apparent density have been investigated numerically. The results indicate that the dielectric constant increases as the temperature increases and temperature has a pivotal effect on the dielectric constant, while the dielectric loss factor has a complicated change and all of the temperature, frequency and apparent density have a significant impact to dielectric loss factor. Zinc sulfide concentrate is high loss material from 450 to 800 °C on the basis of theoretical analyses of dielectric loss tangent and penetration depth, its ability of absorbing microwave energy would be enhanced by increasing the apparent density as well. The experimental results also have proved that zinc sulfide concentrate is easy to be heated by microwave energy from 450 to 800 °C. In addition, the experimental date of dielectric constant and loss factor can be fitted perfectly by Boltzmann model and Gauss model, respectively.

A new sustainable heterogenous catalyst for copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC) was investigated. The preparation of the sustainable catalyst was carried out through the complexation reaction between the polysaccharide cellulose acetate backbone (CA) and copper(II) ions. The resulting complex [Cu(II)-CA] was fully characterized by using different spectroscopic methods such as FTIR, SEM, EDX, UV-Vis, and ICP analyses. The Cu(II)-CA complex exhibits a high activity in the CuAAC reaction for substituted alkynes and organic azides, leading to a selective synthesis of the corresponding 1,4-isomer 1,2,3-triazoles in water as solvent and working at room temperature. It is worth noting that this catalyst has several advantages from the sustainable chemistry point of view including no use of additives, biopolymer support, reactions carried out in water at room temperature, and easy recovery of the catalyst. These characteristics make it a potential candidate not only for the CuAAC reaction but also for other catalytic organic reactions.

A comprehensive kinetic model of the Fischer-Tropsch synthesis (FTS) is developed in a fixed bed reactor under operating conditions (temperature, 230–235°C, pressure, 20–25 bar, gas hourly space velocity, 4000–5000 cm³(STP)/h/g_catalyst ,H₂/CO feed molar ratio, 2.1) over a Co based catalyst. Reaction rate equations based on Eley-Rideal (ER) type model for initiation step and Langmuir-Hinshelwood-Hougen-Watson (LHHW) type model for propagation and termination steps of the FTS reactions have been considered and the readsorption of olefins were taken into account. The model that was reported in the literature was modified in order to explain many significant deviations from the ASF distribution. Optimum parameters have been obtained by Genetic Algorithms (GA). The calculated activation energies to produce n-paraffins and 1-olefins were in the range of 82.24 to 90.68 kJ/mol and 100.66 to 105.24 kJ/mol, respectively. The hydrocarbon distribution in FTS reactions was satisfactorily predicted particularly for paraffins.

Primary biliary cholangitis (PBC) is a cholestatic liver disease characterized by immune-mediated injury to small bile ducts. Although PBC is an autoimmune disease, the results of traditional immunosuppressive therapy are disappointing. Nearly 40% of PBC patients do not respond to the first-line drug UDCA. Without appropriate intervention, PBC patients would eventually progress to liver cirrhosis and even death. There is an urgent need to develop new therapies. The gut-liver axis emphasizes the interconnection between the gut and the liver, and there is increasing evidence that gut microbiota and bile acids play an important role in cholestatic diseases. Dysbiosis of gut microbiota, imbalance of bile acids, and immune-mediated bile duct injury constitute the triad of pathophysiology in PBC. Understanding the gut microbiota-bile acid network and corresponding immune functions in PBC provides a new perspective for its treatment strategies. Therefore, we summarize the latest advancements in research of gut microbiota and bile acids in PBC and, for the first time, explore the potential of immune factors related to them as novel immunotherapy targets. This article discusses potential therapeutic approaches focusing on regulating gut microbiota, maintaining bile acid homeostasis, their interactions, and related immune factors.

The purpose of this study was to elucidate patterns and mechanisms driving seasonal and inter-annual variations of carbon and nitrogen stable isotopes in the zooplankton crustacean commu-nity of Lake Maggiore (Italy), during the period 2009-2020. Different zooplankton taxa and groups revealed different ranges of d13C signatures, giving an insight into food sources and niche partition. In particular, cyclopoids had a restricted range with most negative d13C‰ values and increase in d13C fractionation with the establishment of water thermal vertical stratification, high-lighting the importance of vertical distribution as key factor for taxa coexistence in a vertically heterogenous environment. d13C of the zooplankton community and of Daphnia were positively related to water temperature (R2=0.58 p <0.0001 and R2=0.68 p <0.0001, respectively) and d13C Daphnia signature to chlorophyll-a (R2=0.32, p < 0.0001). Decomposition of time series data for zooplankton carbon and nitrogen signatures and environmental parameters identified increasing trends in water temperature, chlorophyll-a and water conductivity and decrease in nitrate, that matched changes in carbon isotopic signature trend in some zooplankton taxa (Bosmina, Daphnia and diaptomids). Overall, the observed patterns in zooplankton isotopic signatures were interpreted as integrations of climate warming effects in Lake Maggiore, affecting both food sources availability and environmental conditions.

A dioxomolybdenum catalyst [(MoO2Cl2-O-MoO2Cl2)(L)] (1) (with L (1S,2S)-N,N´-bis(2-pyridinecarboxamide)-1,2-cyclohexane) was prepared and used as catalyst for the desulfurization of a multicomponent model fuel containing the most refractory sulfur compounds in real fuels. This complex showed to have a high efficiency to oxidize the aromatic benzothiophene derivative compounds present in fuels, mainly using a biphasic 1:1 model fuel/MeOH system. This process conciliates catalytic oxidative and extractive desulfurization, occurring the oxidation of the sulfur compounds in the polar organic solvent. The oxidative catalytic performance of (1) showed to be influenced by the presence of water in the system. Using 50% aq. H2O2 it was possible to reuse the catalyst and the extraction solvent MeOH during ten consecutive cycles without loss of desulfurization efficiency.

Self-assembly is a spontaneous process through which macroscopic structures are formed from basic microscopic constituents (e.g. molecules or colloids). By contrast, the formation of large biological molecules inside the cell (such as proteins or nucleic acids) is a process more akin to self-organization than to self-assembly, as it requires a constant supply of external energy. Recent studies have tried to merge self-assembly with self-organization by analyzing the assembly of self-propelled (or active) colloid-like particles whose motion is driven by a permanent source of energy. Here we present evidence that points to the fact that self-propulsion considerably enhances the assembly of polymers: self-propelled molecules are found to assemble into polymer-like structures, the average length of which increases towards a maximum as the self-propulsion force increases. Beyond this maximum, the average polymer length decreases due to the competition between bonding energy and disruptive forces that result from collisions. The assembly of active molecules might have promoted the formation of large pre-biotic polymers that could be the precursors of the informational polymers we observe nowadays.

Surface processes such as coatings, corrosion, photocatalysis, and tribology are greatly diversified by acid-base interaction at the surface overlayer. This study focuses on the action of metallic copper surface as an electron donor/acceptor related to inactivation of viruses; it was found that regarding Cu2O or Cu materials electrostatic interaction plays a major role in virus inactivation. We applied TPPE method to clarify the mechanism of electron transfer (ET) occurring at light irradiated copper surfaces. The TPPE characteristics was strongly influenced by the environments, which correspond to the temperature and environment dependence of the total count of emitted electrons in the incident light wavelength scan (PE total count, NT), the photothreshold, and further the activation energy (E) analyzed from Arrhenius plot of NT values obtained in the temperature-increase and subsequent temperature-decrease processes. In this study we reexamined the dependence of the TPPE data from two types of Cu metal surfaces: Sample A, which was mechanically abraded in alcohols, water, and air, and Sample C, which was only ultrasonically cleaned in these liquids. The NT for both Samples slowly increased with increasing temperature, reached a maximum (NTmax) at 250C (maximum temperature, Tmax), and after that decreased. For Sample A the NTmax value decreased in the order H2O > CH3OH > C2H5OH > (CH3)2CHOH > C3H7OH, although the last alcohol gave Tmax = 100C, while with Sample C the NTmax value decreased in the order: C3H7OH > (CH3)2CHOH > C2H5OH > CH3OH > H2O. Interestingly, both orders of the liquids were completely opposite: this means that Cu surface can possess two-way character. The NT intensity was found to be strongly associated with the change of the hydroxyl group (Cu-OH) to the oxide oxygen (O2) in the O1s spectra in the XPS measurement. The difference between the above orders was explained by the acid-base interaction mode of the Cu-OH group with the adsorbed molecule on the surfaces. The H2O adsorbed on Sample A produces the electric dipole Cu-OH+---:OH2 (--- hydrogen bond), while the C3H7OH and (CH3)2CHOH adsorbed on Sample C produce ROH+---:O(H)-Cu (R = alkyl groups). Gutmann’s acceptor number (AN) representing the basicity of the liquid molecules was found to be related to the TPPE characteristics: (CH3)2CHOH (33.5), C2H5OH (37.1), CH3OH (41.3), H2O (54.8) (the AN of C3H7OH could not be confirmed). With Sample A the values of NTmaxa and EaUp1 both increased with increasing AN (Up1 means the 1st temperature-increase process). On the other hand, with Sample C the values of NTmaxc and EcUp1 both decreased with increasing AN. These findings suggest that Sample A acts as an acid, while Sample C functions as a base. However, in the case of both types of Samples A and C the NTmax values were found to increase with increasing EUp1. It was explained that the EUp1 values depending on the liquids originate from the difference in the energy level of the hydroxyl group radical at the surface denoted. This is able to attract electrons in the neighborhood of the Fermi level of the base metal by tunnelling. After that due to Auger emission electrons are released, leading to the ET in the overlayer. These electrons are considered to have a strong ability of reducibility.

In this study, a new type of temperature sensor device was developed. The circular electrode of the thermal sensitive sensor was modified with TMT and O₂ plasma to enhance the conductivity by forming a thin SnOxCy layer on the electrode surface. The Nano-Au particles were subjected to O₂ plasma pretreatment to form peroxide groups on the surface. The thermally sensitive sensor was made by mixing the above-treated Nano-Au particles with N-isopropylacrylamide (NIPAAm) to form solution and then UV-induced grafting polymerization of the NIPAAm-containing solution onto the electrode substrate. The composite hydrogels on the electrode introduce thermo-sensitive polymeric surface films for temperature sensing. Using ambient environment resistance test to measure the resistance, the LCST (lower critical solution temperature) of Nano-Au (MUA) mixed with NIPAAm hydrogel was found to be 32 °C. At ambient temperatures higher than LCST, the electrode resistance decreases linearly.

The effects of rare earth Ce on the microstructure and properties of cast pure copper were investigated through thermodynamic calculations, XRD analysis, mechanical testing, metallographic microscopy, and scanning electron microscopy (SEM). The experimental results demonstrate that the reaction between rare earth Ce and oxygen as well as sulfur in copper exhibits a significantly negative Gibbs free energy value, indicating a strong thermodynamic driving force for deoxidation and desulfurization reactions. Ce is capable of removing trace amounts of O and S from copper. Moreover, the maximum solid solubility of Ce in Cu falls within the range of 0.009% to 0.01%. Furthermore, Ce can refine columnar grains while enlarging equiaxed grains in as-cast copper.Upon addition of rare earth Ce, the tensile strength increased by 8.45%, elongation increased by 12.1%, and microhardness rose from 73.5HV to 81.2HV-an increase of 10.5%. Overall, rare earth Ce has been found to enhance both the microstructure and mechanical properties of cast pure copper.

Abstract: As a low-input crop, Miscanthus offers numerous advantages that, in addition to agricultural applications, permits its exploitation for energy, fuel, and material production. Depending on the Miscanthus genotype, season, and harvest time as well as plant component (leaf versus stem), correlations between structure and properties of the corresponding isolated lignins differ. Here, a comparative study is presented between lignins isolated from M. x giganteus, M. sinensis, M. robustus and M. nagara using a catalyst-free organosolv pulping process. The lignins from different plant constituents are also compared regarding their similarities and differences regarding monolignol ratio and important linkages. Results showed that the plant genotype has the weakest influence on monolignol content and interunit linkages. In contrast, structural differences are more significant among lignins of different harvest time and/or season. Analyses were performed using fast and simple methods such as nuclear magnetic resonance (NMR) spectroscopy. Data was assigned to four different linkages (A: b-O-4 linkage, B: phenylcoumaran, C: resinol, D: b-unsaturated ester). In conclusion, A content is particularly high in leaf-derived lignins at just under 70 % and significantly lower in stem and mixture lignins at around 60 % and almost 65 %. The second most common linkage pattern is D in all isolated lignins, the proportion of which is also strongly dependent on the crop portion. Both stem and mixture lignins, have a relatively high share of approximately 20 % or more (maximum is M. sinensis Sin2 with over 30 %). In the leaf-derived lignins, the proportions are significantly lower on average. Stem samples should be chosen if the highest possible lignin content is desired, specifically from the M. x giganteus genotype, which revealed lignin contents up to 27 %. Due to the better frost resistance and higher stem stability, M. nagara offers some advantages compared to M. x giganteus. Miscanthus crops are shown to be very attractive lignocellulose feedstock (LCF) for second generation biorefineries and lignin generation in Europe.

In recent decades, the requirements for implantable medical devices increased, but the risks of implant rejection still exist. These issues are primarily associated with poor osseointegration, leading to biofilm formation on the implant surface. This study focuses on addressing these issues by developing a biomaterial for implant coatings. 45S5 Bioglass has been widely used in tissue engineering due to its ability to form a hydroxyapatite layer, ensuring a strong bond between the hard tissue and the bioglass. In this context, 45S5 bioglasses, modified by the incorporation of different amounts of copper oxide, from 0 to 8 mol%, were synthesized by the melt-quenching technique. The incorporation of Cu ions does not show a significant change in the glass structure. Since the bioglass exhibited the capacity of being polarized, and therefore promoting the osseointegration effectiveness, the electrical properties of the prepared samples were studied using the impedance spectroscopy method, in the frequency range of 102-106 Hz and temperature range of 200-400 K. The effects of CuO on charge transport mobility were investigated. Additionally, the bioactivity of the modified bioglasses was evaluated through immersion tests in simulated body fluid. The results revealed the initiation of a Ca-P-rich layer formation on the surface within 24 h, indicating the potential of the bioglasses to enhance the bone regeneration process.

Tailings generated by mining account for the largest proportion of global waste from industrial activities. Copper is relatively uncommon world-wide, with low concentrations in sediments and waters, yet is very elevated around mining sites. On the Keweenaw Peninsula of Michigan, USA, jutting out into Lake Superior, 140 mines extracted native copper from the Portage Lake Volcanic Series, part of an intercontinental rift system. Between 1901-1932, two mills at Gay (Mohawk, Wolverine) sluiced 22.7 million metric tonnes (MMT) of copper-rich tailings (stamp sands) into Grand (Big) Traverse Bay. Here we examine: 1) 3D coastal elevation and reef bathymetry, 2) particle dispersal, 3) copper concentrations and leaching, plus 4) shoreline toxicity. About 10 MMT of tailings created a migrating coastal beach that stretches 7 km from the Gay pile to the Traverse River Seawall. Another 10 MMT are moving underwater on the coastal shelf, threatening Buffalo Reef, an important lake trout and whitefish breeding ground. Aerial photos, ALS (plane) LiDAR, and relatively inexpensive UAS (drone) surveys characterize shoreline structure and aid initial remediation. Because sands (natural beach quartz, stamp sand basalt) are silicates of similar density, particle dispersal is similar and challenging. However, stamp sand beaches contrast greatly with natural sand beaches in both physical profile and chemistry. Dispersing particles retain copper, and release toxic concentrations. Leaching is elevated by exposure to high DOC and low pH waters. Field experiments, shoreline seining, and benthic sampling confirm serious impacts on aquatic biota, supporting tailings removal.

OBJECTIVES: To assess the predictive value of serum trypsin and Trypsinogen Activation Peptide (TAP) for the severity of AP by means of a single center cohort study as well as a systematic review of the current literature. METHODS: The literature search was conducted using Medline (PubMed), EMBASE and the Cochrane Central Register. A total of 142 patients with acute pancreatitis (AP) were included in the cohort study and parameters of the revised Atlanta criteria of 2012 and the APACHE II were assessed. RESULTS: The review showed promising results for the predictive value of serum trypsinogen-2, but conflicting results for serum TAP and trypsin. In the cohort study, patients were observed for 4 days after diagnosis of AP: 9 patients had severe AP, 35 patients had moderate AP and 81 patients had mild AP. The ratio of the geometric mean of severe vs mild AP for trypsin was 0.72 (95% CI: 0.51-1.00), p=0.053 and for TAP 0.74 (95% CI: 0.54-1.01), p=0.055 respectively. CONCLUSION: The cohort study showed an inverse correlation of serum levels of TAP and trypsin with severity of AP. Serum TAP and trypsin have an inferior predictive value of severity of AP compared to the clinical APACHE II score.

Polymer hydrogels are 3D networks consisting of hydrophilic crosslinked macromolecular chains, able to swell and retain water. Since their invention in the 1960s, they have become an outstanding pillar in the design, development, and application of engineered polymer systems suitable for biomedical and pharmaceutical applications (such as drug or cell delivery, regeneration of hard and soft tissues, wound healing, and bleeding prevention, among others). Despite several well-established synthetic routes of polymer hydrogels based on batch polymerization techniques, about fifteen years ago academia started to look for alternative methods involving simpler reaction paths, shorter reaction times, and lower energy consumption. In this context, frontal polymerization (FP) undoubtedly has become an alternative and efficient reaction model that allows for converting monomers into polymers via a localized and propagating reaction, by exploiting the formation and propagation of a “hot” polymerization front, able to self-sustain and propagate throughout the monomeric mixture. Therefore, the present work aims to summarize the main research outcomes, achieved during the last years, concerning the design, preparation, and application of FP-derived polymeric hydrogels, demonstrating the feasibility of this technique for the obtainment of functional 3D networks, and providing the reader with some perspectives for the forthcoming years.

The objective of this study was to develop an ultrasonic-assisted procedure for the extraction of total phenolics from Citrus aurantium L. blossoms (CAB) and evaluate the free radical scavenging activity, anti-HMG-CoA reductase activity of total phenolics. In this work, a Box-Behnken design based on the single-factor experiments was used to explore the optimum extraction process. Under the optimum conditions (extraction solvent 70.31% ethanol, extraction temperature 61.94 °C, extraction time 51.73 min and liquid-to-solid ratio 35.63 mL/g), the extraction yield of total phenolics was 95.84 mg gallic acid equivalents (GAE)/g dry matter (DM), which was highly consistent with the theoretical value (96.12 mg GAE/g DM). The total phenolic extract showed excellent free radical scavenging properties against DPPH·, ABTS+·, ·OH and ·O2-, with the IC50 values of 197.007, 83.878, 218.643 and 158.885 μg/mL, respectively, and the extracts also showed good inhibition of HMG-CoA reductase activity, with the IC50 value of 117.165 μg/mL. Total phenolics from CAB could be a potential source of natural free radical scavenger and HMG-CoA reductase inhibitor.

Abstract: High step-up voltage gain nonisolated DC-DC converter have attracted much attention in photovoltaic, fuel cells and other renewable energy system applications. In this paper, by combining input current ripple-free boost cell with coupled-inductor voltage-doubler cell, an input current ripple-free high voltage gain nonisolated converter is proposed. In addition, passive lossless clamp circuit is adopted to recycle the leakage inductor energy and to reduce the voltage spike across the power switch. By utilizing voltage-doubler cell consisting of diode and capacitor, the voltage stress of switch is further reduced and the resonance between the leakage inductor and the stray capacitor of the output diode is eliminated. A low switch-on-resistance low-voltage-rated MOSFET can therefore be employed to reduce the conduction loss and cost. The reverse recovery loss of output diode is reduced, and the efficiency of converter can be improved. Furthermore, the proposed converter can achieve nearly zero input current-ripple and make the design of electromagnetic interference (EMI) filter easy. Steady state analysis and operation mode of the converter is performed. Finally, experimental results are presented to verify the analysis results of the proposed converter.

The objective of this study was to investigate the concentration and spatial distribution patterns of six potentially toxic heavy metal elements (Mn, Zn, Cr, Pb, Cu and Ni) in bus station dusts in the Xifeng district of Gansu province, NW China. The contents were analyzed for Mn, Zn, Cr, Pb, Cu and Ni by using S8 TIGER Brochures wavelength dispersive X-ray fluorescence spectrometry. Geoaccumulation index (Igeo ), enrichment factor (EF), pollution index (PI) and integrated pollution index(IPI) were calculated to evaluate the heavy metal contamination level of bus station dusts. The results indicate that, in comparison with the background values of local soil, bus station dusts in Xifeng have elevated metal concentrations as a whole. The concentrations of heavy metals investigated in this paper are compared with the reported data of other cities. The results show that the arithmetic means of Mn, Zn, Cr, Pb, Cu and Ni are 440.8, 137.9, 60.0, 42.8, 33.5 and 19.8mg kg−1 respectively. The mean values of Igeo reveal the order of Ni<Mn<Cr<Cu<Zn<Pb. The high Igeo and EF for Cu, Zn and Pb in bus station dusts indicate that there is a considerable Cu, Zn and Pb pollution, which mainly originate from traffic and industry activities. The Igeo and EF of Ni, Mn and Cr are low and the assessment results indicate an absence of distinct Ni, Mn and Cr pollution in bus station dusts. The assessment results of PI also support Cu, Zn and Pb in bus station dusts presented middle pollution, and IPI indicates heavy metals of bus station dusts polluted seriously.

Copper-nitride (Cu3N) semiconductor material is attracting much attention as a potential, next-generation thin-film solar-light absorber in solar cells. In this communication, polycrystalline Cu3N thin films were prepared using reactive-RF-magnetron-sputtering deposition, at room temperature, onto glass and silicon substrates. The very-broadband optical properties of the Cu3N thin film layers were studied by UV-MIR (0.2-40 μm) ellipsometry and optical transmission, to be able to achieve the goal of a low-cost absorber material to replace the conventional silicon. The reactive-RF-sputtered Cu3N films were also investigated by focused ion beam scanning electron microscopy, and both FTIR and Raman spectroscopies.

The valorization of the large amount of crude glycerol formed from biodiesel industry, is of primordial necessity. One possible direction with high interest to the biorefiniery sector is the production of fuel additives as solketal, though the acetalization of glycerol with acetone. This is a chemical process that conciliates high sustainability and economic interest, since solketal contributes to the fullfilment of a Circular Economy Model through its use in biodiesel blends. The key to guarantee high efficiency and high sustainability for solketal production is the use of a recovery and recyclable heterogeneous catalyst. Some examples are already reported in the literature (first example in 2012), and this review intends to conciliate the information spreaded in this topic and established the most important reacional parameters and the main catalytic characteristics strategies to achieve high solketal production in short reaction time.

Apple replant disease (ARD) is a complex issue caused by various fungal, oomycetes pathogens and parasites which can differ in their abundance between sites within a geographic region. Knowledge of the specific etiology of ARD at a particular site is required in order to develop commercially viable soil management strategies to combat specific/individual components of the disease. In this study we analyzed the soil from six ARD sites for the presence of fungal, bacterial and oomycetes communities and plant parasitic nematodes. Five fungal, and 17 bacterial classes were differentially represented in the microbiomes from different locations. Mortierellomycetes was the most abundant fungal taxa represented followed by Sordariomycetes. Mortierella exigua a fungal endophyte was the most abundant fungal amplicon sequence variant (ASV) in the core microbiome. Proteobacteria was the most prevalent phylum identified in orchard soils. Several potential phytopathogenic fungi involved in ARD and endophytes including Fusarium oxysporum, F. solani, Nectria ramulariae, Ilyonectria robusta and Nectriaceae were identfied in the orchard soil. Pythium attrantheridium (Globisporangium attrantheridium), P. monospermum and P. ultimum (Globisporangium ultimum) were the most abundant oomycete taxa identified in these soil samples. Six different groups of plant-parasitic nematodes were found across the six orchards soil. Root-lesion nematodes, Pratylenchus spp., which are commonly associated with ARD, were identified in all orchards soil at population densities ranging from 12 to 33/100 cm3 soil. This research contributes valuable understanding of the ARD complex as the apple industry needs alternative approaches to combat the disease.

Background: Clinical trails have revealed that patients with depression generally accompanied with learning and memory impairment, which critically impact on individual’s health and development. Danggui-Shaoyao-San (DSS), a famous Chinese complex prescription, significantly overcame depression and relieved cognitive disorder based on previous research and publication. However, its effectsand potential mechanism against chronic restraint stress (CRS) remained unknown. Methods: CRS animal model was established and mice were divided to six groups while they were oral administrated with Danggui-Shaoyao-San at doses of 1.25, 2.5 and 5 g/kg for 14 days. Emotional and cognitive performances were detected by behavior tests, meanwhile neural plasticity and its molecular mechanism were examined by Dil staining, western blot and immunofluorescence. Results: DSS treatment dose-dependently improved locomotion ability in open filed test, overcame depression behavior in forced swimming test and elevated plus maze test, enhanced learning and memory ability in Morris water maze test. CRS decreased number of total spines and mushroom spines, while DSS treatment dose-dependently restored these by Dil staining. Expression of BDNF and GluR1 were significantly down-regulated in CRS group, which were significantly normalized by DSS. Conclusions: DSS treatment dose-dependently reversed CRS-induced cognitive impairments by inducing structural remodeling of neurons.

The constant increase in current density in electrical wires leads to increasingly significant heat losses due to Joule effect. Therefore, reducing the electrical resistivity of copper wires becomes necessary. To achieve this goal, the development of a composite material incorporating a more conductive reinforcement, the graphene, is a promising way. The design of a copper/graphene composite using a powder metallurgy-based method is presented. This synthesis method allows for interface control through the growth of CuO(Cu) nanoparticles tightly bonded to the reinforcement. It also involves the dispersion of graphene through ultrasonic treatment and its alignment within the matrix using a uniaxial pressing densification method. The increase in the hardness (+12 HV) demonstrates the effective dispersion and separation of graphene layers. The impact on the electrical properties of dendritic copper (ρe = 2.30 µΩ.cm) remains limited, with a decrease in electrical resistance of approximately 1.4%. However, for copper with higher electrical resistivity, flake copper (at 2.71 µΩ.cm) and brass at (7.66 µΩ.cm), reductions of 2.7% and 10% have been achieved, respectively. With the improvement of graphene quality, there is more room to improve the electrical properties. This work paves the way for the development of composites with improved electrical resistivity.

This paper addresses the input coupling problem for the shape memory alloy (SMA) actuated parallel platform with completely unknown nonlinear dynamics. The problem means that in a parallel platform with multiple SMA actuators acting together, the displacement of one of the actuators will simultaneously affect the remaining actuators to change. Due to the coupling problem and nonlinear characteristics of the SMA actuators, it is not easy to control the platform to achieve bi-directional swing with completely unknown nonlinear dynamics. Therefore, a model-free adaptive sliding mode control method is proposed to improve the control accuracy of the complex motion of the platform, avoiding the complex modeling process of the SMA actuated parallel platform. Based on the model-free adaptive control (MFAC) theory, a multiple input and multiple output (MIMO) dynamic linearized mathematical model of the parallel platform is established using the online input and output data of the system. Then, a sliding mode controller is designed based on the dynamic model. A rigorous theoretical analysis proves that the proposed model-free adaptive sliding mode controller is able to stably control the SMA actuated parallel platform, and its tracking error is uniformly ultimately bounded (UUB). Finally, experiments are conducted on the established SMA actuated parallel platform. The results show that the proposed model-free controller is feasible and effective, and can control the system well to achieve the complex motion of bi-directional swing.

β-Ga2O3 is a well-known semiconductor material for power devices and other applications. Recently, β-Ga2O3 has also been reported as a scintillator material with a light yield of approximately 8400 ph./MeV, scintillation decay time of &lt;1 μs, and density of 6.44 g/cm3. In this study, 2-inch diameter β-Ga2O3 single crystals were prepared by oxide crystal growth using the cold crucible (OCCC) method under various oxygen partial pressures. In the OCCC method, as in the cold crucible method, a high frequency is applied directly to the oxide materials, which are heated and melted, and the melt is held by the outermost solid material itself that is cooled by water using a copper hearth. In the OCCC method, crystal growth is performed while rotating the seed crystal, as in the Czochralski method, to increase the crystal diameter. The optical properties and radiation responses of the crystals grown under various oxygen partial pressures were evaluated.

This paper describes the first results of an Image Recognition Based Location (IRBL) for mobile application focusing on the procedure to generate a Database of range images (RGB-D). In an indoor environment, to estimate the camera position and orientation, a prior spatial knowledge of the surrounding is needed. In order to achieve this objective a complete 3D survey of two different environment (Bangbae metro station of Seoul and E.T.R.I. building in Daejeon – Republic of Korea) was performed using LiDAR (Light Detection And Ranging) instrument and the obtained scans were processed in order to obtain a spatial model of the environments. From this, two databases of reference images were generated using a specific software realized by the Geomatics group of Politecnico di Torino (ScanToRGBDImage). This tool allow to generate synthetically different RGB-D images) centered in the each scan position in the environment. Later, the external parameters (X, Y, Z, ω, φ, κ) and the range information extracted from the DB images retrieved, are used as reference information for pose estimation of a set of acquired mobile pictures in the IRBL procedure. In this paper the survey operations, the approach for generating the RGB-D images and the IRB strategy are reported. Finally the analysis of the results and the validation test are described.

Ensuring access to water, sanitation, and hygiene (WASH) facilities, coupled with behavior change education in schools, is fundamental for fostering a conducive learning environment and promoting principles of inclusion, dignity, and equality. This study focuses on 12 primary schools in Anápolis, Brazil, encompassing 4,394 students and 248 teachers. WASH assessments were conducted through a questionnaire, observation of water and sanitation facilities and structures, and microbiological analysis. Over the period 2018 to 2020, the proportion of schools with safely managed drinking water surged from 42% to 92%. However, sanitation conditions in the schools were categorized as a basic level, with hygiene services rated as limited in 92% of the schools due to the absence of soap. While this study reveals that Anápolis schools generally align with WASH guidelines for basic/advanced drinking water services, there is a crucial need for enhancements in both hardware and software facilities to address sanitation and hygiene challenges.

Some peptide-based drugs including oxytocin, vasopressin, ziconotide, pramlintide, nesiritide, and octreotide, contain one intramolecular disulfide bonds. A novel and reusable monodispersed silica nanosphere-supported Pt(IV) complex (SiO2@TPEA@Pt(IV)) was synthesized via a four-step procedure and used for formation of intramolecular disulfide bonds in peptides. TEM and chemical mapping results for the Pt(II) intermediates and for SiO2@TPEA@Pt(IV) show that the silica nanospheres possess a monodisperse spherical structure and contain uniformly distributed Si, O, C, N, Cl, and Pt. The valence state of Pt on the silica nanospheres was characterized by XPS. The Pt(IV) loaded on SiO2@TPEA@Pt(IV) was 0.15 mmol/g, as determined by UV-vis spectrometry. Formation of intramolecular disulfides in six dithiol-containing peptides of variable lengths by use of SiO2@TPEA@Pt(IV) was investigated and the relative oxidation yields were determined by HPLC. In addition, peptide 1 (Ac-CPFC-NH2) was utilized to study the reusability of SiO2@TPEA@Pt(IV). No significant decrease in the relative oxidation yield was observed after ten reaction cycles. Moreover, the structure of SiO2@TPEA@Pt(IV) after being used ten cycles was determined to be similar to its initial one, demonstrating the cycling stability of the complex.

Underwater Sensor Networks (UWSNs) can enable a broad range of applications such as resource monitoring, disaster prevention, and navigation-assisted. It is especially relevant for sensor nodes location in UWSNs. Global Positioning System (GPS) is not suitable for using in UWSNs because of the underwater propagation problems. Hence some localization algorithms based on the precise time synchronization between sensor nodes have been proposed which are not feasible for UWSNs. In this paper, we propose a localization algorithm called Two-Phase Time Synchronization-Free Localization Algorithm (TP-TSFLA). TP-TSFLA contains two phases, namely, range-based estimation phase and range-free evaluation phase. In the first phase, we address a time synchronization-free localization scheme base on the Particle Swarm Optimization (PSO) algorithm to decrease the localization error. In the second phase, we propose a Circle-based Range-Free Localization Algorithm (CRFLA) to locate the unlocalized sensor nodes which cannot obtain the location information through the first phase. In the second phase, sensor nodes which are localized in the first phase act as the new anchor nodes to help realize localization. Hence in this algorithm, we use a small number of mobile beacons to help achieve location without any other anchor nodes. Besides, to improve the precision of the range-free method, an extension of CRFLA by designing a coordinate adjustment scheme is updated. The simulation results show that TP-TSFLA can achieve a relative high localization ratio without time synchronization.

The one-dimensional MoS₂/carbon nanofibers (1D MoS₂/CNFs) are synthesized by electrospinning using exfoliated MoS₂ nanosheets and polyacrylonitrile as raw materials. The exfoliated MoS₂ nanosheets with size of about 150 nm are encapsulated in carbon nanofibers, and the free-standing MoS₂/CNFs can be easily cut into flexible tablet and directly used as binder-free anode for lithium storage. The resultant 1D MoS₂/CNFs exhibit a very high reversible capacity of 700 mAh g^-1 at 100 mA g^-1 after 50 cycles, high rate capacity (450 mAh g^-1 at 1000 mA g^-1 after 200 cycles) and good cycle stability.

This article presents, for the first time, comprehensive model based on the proposed mechanism of Rahal et al [17], Bonardi {20], Tar et al [20], and Mau et al [24], for 3-component systems of G1/Iod/EDB, G1/Iod/amine (in gold chloride), and Iod/Benzoic/Borate (for reduced oxygen inhibition) for the hybri free radical (FRP) and cationic (CP) photopolymerization of interpenetrated polymer network (IPN) systems. Analytic formulas are developed to explore the new features including: (i) conversion efficacy(CE) of FRP is an increasing function of the light intensity (I), the effective absorption coefficient (b), for transient state, whereas, CE at steady-state is independent to the light intensity; (ii) initiator regeneration (RGE)
provides a catalytic cycle for improved CE for FRP and CP; (iii) in the IPN system, the synergic effects due to the co-exist of FRP and CP include: (i) CP can increase the medium viscosity limiting the diffusional oxygen replenishment, such that OIH is reduced; (ii) the cationic monomer also acts as a diluting agent for the radical polymer network, and (iii) the exothermic property of the CP polymerization. We have proposed ascaling law for the transient and steady-state dependence of CE on the key parameter P=bIC₀, given by a an m-order power law of P^m, with m = 0.5 to 1.5, depending on various conditions. The CE also has an optimal value for maximum CE. The presented comprehensive model (with minimum mathematics) focusing on the enhancement mechanisms/pathways, provides analytic formulas which can be used to analyze reported data, and, more importantly, serves as guidance for exploring new functional materials or new kinetic schemes for improved conversion or procedures for both industrial and medical applications such as additive manufacturing (AM), 3D and 4D bioprinting. Finally, we have proposed new directions/experiments based on our theoretical predictions.

In addition to their importance in statistical thermodynamics, probabilistic entropy measurements are crucial for understanding and analyzing complex systems, with diverse applications in time series and one-dimensional profiles. However, extending these methods to two- and three-dimensional data still requires further development. In this study, we present a new method to classify spatiotemporal processes based on entropy measurements. To test and validate the method, we selected four classes of similar processes related to the evolution of random patterns: dynamic colored noises ((i)~white and (ii)~red); (iii)~weak turbulence from reaction-diffusion; (iv)~hydrodynamic fully developed turbulence, and (v)~plasma turbulence from MHD. Considering seven possible ways to measure entropy from a matrix, we present the method as a parameter space composed of the two best separating measures of the five selected classes. The results highlight better combined performance of Shannon Permutation Entropy ($S^p_H$) and a new approach based on Tsallis Spectral Permutation Entropy ($S^s_q$). Notably, our observations reveal the segregation of reaction terms in this $S^p_H \times S^s_q$ space, a result that identifies specific sectors for each class of dynamic process, and can be used to train machine learning models for automatic classification of complex spatiotemporal patterns.

The field of controlled polymerization is growing and evolving at unprecedented rates, facilitating polymer scientists to engineer the structure and property of polymer materials for a variety of applications. However, the lack of degradability, particularly in vinyl polymers, is a general concern for not only environmental sustainability but also biomedical applications. In recent years, there has been a significant effort to develop reversible polymerization approaches in those well-established controlled polymerization systems. Reversible polymerization typically involves two steps including (i) forward polymerization which converts small monomers into macromolecules, and (ii) depolymerization capable of regenerating original monomers. Furthermore, recycled monomers can be repolymerized into new polymers. In this perspective, we highlight recent developments of reversible polymerization in those controlled polymerization systems and offer insight into the promise and utility of reversible polymerization systems. More importantly, the current challenges and future directions to solve those problems are discussed. We hope this perspective can serve as an “initiator” to promote continuing innovations in this fairly new area.

The conventional well placement was done manually by using a numerical reservoir simulator, and it required a lengthy trial-and-error process. It required great experience and expertise to manipulate the variables and uncertainties that lie on the reservoir to determine the best placement of the well. In addition, the traditional gradient-based methods such as Line-search and Trust-region were not viable in terms of maximum results obtained. Gradient-based methods were too dependent on the surface gradient of the solution and may only converge to local optima instead of global optima. Complex reservoirs have rough surfaces with high uncertainties, which hinders the traditional gradient-based method from converging to global optima. Thus, genetic algorithms were utilized to automate the manual trial-and-error process and to overcome the limitations of the traditional gradient-based method. The objectives of this study were to analyse the effect of different initial well placement distributions, the number of random solution sizes, and the crossover rate on cumulative oil production. A synthetic reservoir model built using CMG Builder was used as the testing platform for the optimization problems. Well-placement parameterization and optimization set-up were carried out using the CMG CMOST optimization tool. The integration of CMG IMEX and CMOST optimized cumulative oil production based on the objectives of the study. The results obtained showed that the higher number of random solutions used resulted in higher cumulative oil production, with more generations needed to reach the optimum solution. It can be concluded that the larger number of random solutions used increased the probability of reaching the optimum solution, but will take more generations.

Human Activity Recognition (HAR) technology enables continuous behavior monitoring, particularly valuable in healthcare. This study investigates the viability of using an ear-worn motion sensor for classifying daily activities, including lying, sitting/standing, walking, ascending stairs, descending stairs, and running. Fifty healthy participants (between 20 and 47 years old) engaged in these activities while under monitoring. Various machine learning algorithms, ranging from interpretable shallow models to state-of-the-art deep learning approaches designed for HAR, were employed for classification. Results demonstrate the ear sensor's efficacy, with deep learning models achieving 98% accuracy rate of classification. The obtained classification models are agnostic regarding which ear the sensor is worn and robust against moderate variations in sensor orientation (e.g., due to differences in auricle anatomy), meaning no initial calibration of the sensor orientation is required. The study underscores the ear's efficacy as a suitable site for monitoring human daily activity and suggests its potential for combining HAR with in-ear vital signs monitoring. This approach offers a practical method for comprehensive health monitoring by integrating sensors in a single anatomical location. This integration facilitates individualized health assessments, with potential applications in tele-monitoring, personalized health insights, and optimizing athletic training regimes.

The Dph1•Dph2 heterodimer from yeast is a radical SAM (RS) enzyme that generates the 3-amino-3-carboxy-propyl (ACP) precursor for diphthamide, a clinically relevant modification on eukaryotic elongation factor 2 (eEF2). ACP formation requires SAM cleavage and atypical Cys-bound Fe-S clusters in each Dph1 and Dph2 subunit. Intriguingly, the first Cys residue in each motif locates next to another, ill-defined cysteine that we show in-here is conserved across eukaryotes. As judged from structural modeling, the orientation of these tandem cysteine motifs (TCM) suggests a candidate Fe-S cluster ligand role. Hence, we generated by site-directed DPH1 and DPH2 mutagenesis, Dph1•Dph2 variants with cysteines from each TCM replaced individually or in combination by serines. Assays diagnostic for diphthamide formation in vivo reveal that while single substitutions in the TCM of Dph2 cause mild defects, double mutations almost entirely inactivate the RS enzyme. Based on enhanced Dph1 and Dph2 subunit instability in response to cycloheximide chases, the variants with Cys substitutions in their cofactor motifs are particularly prone to protein degradation. In sum, we identify a fourth functionally cooperative Cys residue within the Fe-S motif of Dph2 and show that the Cys-based cofactor binding motifs in Dph1 and Dph2 are critical for the structural integrity of the dimeric RS enzyme in vivo.

Furthermore, the nasal congestion typical of rhinitis can contribute to upper airway obstruction and sleep-disordered breathing. A vicious circle is created between asthma and sleep-disordered breathing: uncontrolled asthma and sleep-disordered breathing can worsen each other. In children with genetic obesity, despite alterations in the immune system, fewer allergies are found compared to the general population. The causes of this reduced allergenicity are unclear but probably involve genetic, immunological, and environmental factors. Further studies are needed to understand the mechanisms. The study emphasizes the importance of jointly evaluating and managing allergies, obesity, and sleep-disordered breathing in children, considering their close interconnection.

Abstract: An efficient and environmentally Pumice as a new catalyst for designing of 3,4- dihydropyrimidin-2(1H) ones / thiones via one-pot multi component condensation of aromatic aldehydes, urea/ thiourea and ethyl acetoacetate or acetyl acetone in excellent yields (96-99 %). The advantages using of this new catalyst is very cheap, available, non-toxic, stable under thermal conditions, easy work-up, improved yields, the product of reaction is very pure without using chromatographic methods and solvent free conditions.

This work shows the physicochemical and mineralogical characterization of diatomites form the Hidalgo and Jalisco States, Mexico. In the case of the mineral from Hidalgo State, this has the following chemical composition; 70.0 % wt. SiO₂, 11.63 wt. % Al₂O₃, 1.95 wt. % FeO, 1.79 wt. % MgO, 2.41 wt. % K₂O, 0.85 wt. % CaO and 6.10 wt. % Na₂O. On the other hand, the mineral from Jalisco has the following chemical composition; 93.58 wt. % SiO₂, 3.03 wt. % Al₂O₃, 1.81 wt. % FeO, 0.40 wt. % MgO, 0.92 wt. % K₂O, 0.11 wt. % CaO and 0.24 wt. % Na₂O. For recovery of metals, both minerals got arsenic, silver, lead and nickel recoveries upper to 95 % and lower to 10 % for chromium. According to efficiency of interchange, the mineral from Hidalgo is slightly higher in the case of arsenic, lead and silver; while for nickel and particularly chromium (VI) the efficiency is higher for the mineral from Jalisco.

Furfuryl alcohol (FA) is a biobased monomer derived from lignocellulosic biomass. The present work describes its polymerization in presence of protic polar solvents, i.e. water or isopropyl alcohol (IPA), using maleic anhydride (MA) as acidic initiator. The polymerization was followed from the liquid to the rubbery state by combining DSC and DMA data. In the liquid state, IPA disrupts the expected reactions during all the FA polymerization due to a stabilization of the furfuryl carbenium center. This causes the initiation of the polymerization at higher temperature, which is also reflected by higher activation energy. In water system, the MA opening allows to start the reaction at lower temperature. A higher pre-exponential factor value is obtained in that case. The DMA study of final branching reaction occurring in the rubbery state has highlighted continuous increase of elastic modulus until 290 °C. This increasing tendency of modulus was exploited to obtain activation energy dependences (Eα) of FA polymerization in the rubbery state.

Based on the dynamic strength variation mechanism of concrete under complex loading conditions, two approaches were devised: numerical testing and CT scanning, guided by the principle of minimizing energy dissipation. A methodology for calculating concrete's failure area and measuring its strength was developed. The analysis delves into the mechanisms behind failure patterns and variations in concrete specimen strength, focusing on crack initiation, development, and the resultant failure surface formed by crack propagation, along with the stress distribution in concrete specimens subjected to diverse loading conditions. Through evaluating the strength and computed failure area of concrete specimens, it is evident that the loading method influences both the strength and failure area of concrete specimens. In general, a larger failure area correlates with a higher measured strength.

Drosophila melanogaster serves as a important research model both for genetic investigations and for the study of metal toxicity, facilitating the elucidation of physiological mechanisms comparable to those of human organisms. In our research, we evaluated the toxicity effect resulting from exposure to various concentrations of lead and copper on the prolificity rates throughout the life cycle (egg-adult) of four genotypes of Drosophila melanogaster: wild-type (control), white, brown, and white-vestigial. During our study, the prolificity rates were examined across three repetitions under the impact of exposure to concentrations of 0.50, 1.00, 2.00, and 4.00 mM of copper (CuSO₄) and lead (Pb(C₂H₃O₂₎₂). Prolificity rates throughout the life cycle exhibited variations as a direct consequence of genetic factors, the concentration of exposure, and the specific type of metal, either copper or lead. The mutant white-vestigial genotype revealed an IC₅₀ concentration for prolificity inhibition at lower doses of 2.00 mM for copper and 4.00 mM for lead, in contrast to the control genotype (wild-type), which exhibited an inhibition concentration rate >IC₅₀ of 4.00 mM only in the case of copper. Our results concluded that the (i) dose influences the prolificity rate in a directly proportional manner, (ii) comparative analyses between copper and lead revealed that copper displayed toxicity across all genotypes within the concentration range of 0.50 mM to 2.00 mM. In contrast, lead exhibited toxicity within the concentration range of 1.00 mM to 4.00 mM, highlighting a (iii) more acute toxicity characteristic in the case of copper. Thus, the results of this research reflect the importance of using Drosophila melanogaster as a genetic model in the comparative study of the interaction between genetic factors and the toxicity of metals, offering significant insights into monitoring their impact and defining the maximum permissible doses on organisms.

The dopamine and uric acid are primary products of purine metabolism and they coexist in serum and the extracellular fluid of the central nervous system. Some diseases of the human body are due to abnormal levels of uric acid and dopamine. Thus, the clinical diagnosis of some diseases needs a sensitive and simultaneous analysis of uric acid and dopamine. In this study, a novel conductive composite film containing multi-walled carbon nanotubes (MWTs) with cooper phthalocyanine attached to acrylate polymer (MWCNTs-CuMAPC-PnBA) was fabricated and dropped on a glassy carbon electrode and used for the simultaneous determination of Uric Acid (UA) and dopamine (DA). The modified glassy carbon electrode showed satisfactory electrocatalytic activity toward dopamine and uric acid. Low detection limits were achieved at 0.174 µM of DA and 6.87 µM of UA and the linear detection ranges of DA and UA are 5-200 µM and 20-250 µM respectively. The proposed sensing system based on the modified GCE offers promising results for rapid, cost-effective and selective simultaneous detection of uric acid and dopamine. Also, the complex modified electrode showed satisfactory results to detecting simultaneously UA and DA in real human samples (human Urine) via the standard addition method.

Fibrodysplasia Ossificans Progressiva (FOP) is an enigmatic, ultra-rare genetic disorder characterized by progressive heterotopic ossification, wherein soft connective tissues undergo pathological transformation into bone structures. This incapacitating process severely limits patient mobility and poses formidable challenges for therapeutic intervention. Predominantly caused by missense mutations in the ACVR1 gene, the disorder has hitherto defied comprehensive mechanistic understanding and effective treatment paradigms. This write-up offers a comprehensive overview of the contemporary understanding of FOP's complex pathobiology, underscored by advances in molecular genetics and proteomic studies. We shed light on targeted therapy, spanning genetic therapeutics, enzymatic and transcriptional modulation, stem cell therapies, and innovative immunotherapies. We also focused on the intricate complexities surrounding clinical trial design for ultra-rare disorders like FOP, addressing fundamental statistical limitations, ethical conundrums, and methodological advancements essential for the success of interventional studies. We advocate for the adoption of a multi-disciplinary approach that converges bench-to-bedside research, clinical expertise, and ethical considerations to tackle the challenges of ultra-rare diseases like FOP and comparable ultra-rare diseases. Overall, this article serves a dual role: as a definitive scientific resource for ongoing and future FOP research and as a call to action for innovative solutions to address methodological and ethical challenges that impede progress in the broader field of medical research for ultra-rare conditions.

Radical reactions are powerful in the synthesis of diverse molecular scaffolds bearing functional groups. In pervious review articles, we have presented 1,2-difunctionalizations, remote 1,3-, 1,4-, 1,5-, 1,6- and 1,7-difunctionalizations, and addition followed by cyclization reactions. Presents in this paper are radical cyclization followed by the second functionalization reactions. The second functionalization could be realized by atom transfer reactions, radical or transition metal-assisted coupling reactions, and reactions with neutral molecules, cationic and anionic species.

Solid particle cationic polyacrylamide (CPAM) is one of the most commonly used organic polymer flocculants in oilfield wastewater treatment, but there are some problems, such as slow dissolution rate, and easy to form a "fish-eye" in the process of diluting into aqueous solution. However, the current liquid CPAM products also have some problems, such as low effective content, poor storage stability, degradation in a short time and high preparation cost. In this paper, a secondary processing technology of solid particle CPAM was studied, and a CPAM suspension was successfully prepared. This suspension has an effective content of 50.00%, No separation in 7 days of storage at room temperature, no separation in 30 min of centrifugation at a speed of 2000 r/min, and diluted to a 0.40 % weak gel solution in just 16.00 min. For 1000 NTU of diatomite simulated wastewater, the optimal turbidity removal rate of the suspension was 99.50%, which was higher than the optimal turbidity removal rate of 98.40% for the inorganic flocculant polymeric aluminum chloride (PAC). For oil and gas field oily wastewater, the optimal turbidity removal rate of CPAM suspension was 35.60%, which was higher than the optimal turbidity removal rate of 28.40% for solid particle CPAM.

Polyglycerols (PGs) are biocompatible and highly functional polyols with a wide range of applications, such as emulsifiers, stabilizers, antimicrobial agents, in many industries including cosmetics, food, plastic and biomedical. The demand increase for biobased PGs encourages researchers to develop new catalytic systems for glycerol polymerization. This review focuses on alkaline homogeneous and heterogeneous catalysts. The performances of the alkaline catalysts are compared in terms of conversion and selectivity, and their respective advantages and disadvantages are commented. While homogeneous catalysts exhibit a high catalytic activity, they cannot be recycled and reused, whereas solid catalysts can be partially recycled. The key issue for heterogenous catalytic systems, which is unsolved so far, is linked to their instability due to partial dissolution in the reaction medium. Further, this paper also reviews the proposed mechanisms of glycerol polymerization over alkaline-based catalysts and discuss the various operating conditions with an impact on the performances. More particularly, temperature and amount of catalyst proved to have a significant influence on glycerol conversion and on its polymerization extent.

Millions of people worldwide are affected by diabetes, a chronic disease that continuously grows due to abnormal glucose concentration levels present in the blood. Monitoring blood glucose concentrations is therefore an essential diabetes indicator to aid in the management of the disease. Enzymatic electrochemical glucose sensors presently account for the bulk of glucose sensors in the market. However, their disadvantages are that they are expensive and are dependent on environmental conditions, hence affecting their performance and sensitivity. To meet the increasing demand, non-enzymatic glucose sensors based on chemically modified electrodes for the direct electrocatalytic oxidation of glucose are a good alternative to the costly enzymatic-based sensors currently on the market, and the research thereof continues to grow. Nanotechnology-based biosensors have been explored for their electronic and mechanical properties, resulting in enhanced biological signalling through the direct oxidation of glucose. Copper oxide and copper sulfide exhibit attractive attributes for sensor application, due to their non-toxic nature, abundance, and their unique properties. Thus, in this review, copper oxide and copper sulfide-based materials, are evaluated based on their chemical structure, morphology, and fast electron mobility as suitable electrode materials for non-enzymatic glucose sensors. The review highlights the present challenges of non-enzymatic glucose sensors that have limited their deployment into the market.

This communication explores the transition from Cognitive Behavioural Therapy (CBT) to a more holistic model, named Complex Therapy, developed by Tullio Scrimali for explaining and treating mental disorders. The Author delves into the limitations of traditional CBT and introduces an innovative framework that integrates multiple therapeutic modalities. While CBT is based on the study and modification of behaviour and cognition, Complex Therapy includes, in its focus, the theory of human relationships, the attachment theory, neuroscience, applied neuroscience, complex systems theory and ecology.Complex Therapy addresses the multifaceted nature of mental health issues by combining evidence-based techniques with personalized care strategies. The goal is to enhance patient outcomes through a tailored, comprehensive treatment plan that adapts to the evolving needs of individuals facing mental health challenges.Two innovative and original items which Scrimali has developed, which are a device for Applied Neuroscience MindLAB Set and a new botanical drug, NegEnt, are presented and discussed.The topic also describes, an original and integrated protocol, named Negative Entropy, the author has developed for treating a challenging disorder, such as schizophrenia, he renamed Entropy of Mind.

A hybrid material, consisting of commercially available nitrocellulose (NC) membrane non-covalently modified with amino-polyethylene glycol functionalized reduced graphene oxide (NH2-PEG-rGO) nanoparticles, was successfully synthesized for oligonucleotide extraction. Fourier Transform Infrared Spectroscopy (FTIR) confirmed the modification of the NC membrane, revealing characteristic peaks of both compounds NC and NH2-PEG-rGO. Scanning Electron Microscopy (SEM) exhibited morphological changes in the NC/NH2-PEG-rGO hybrid membrane, marked by the introduction of NH2-PEG-rGO particles, resulting in a distinctly smothered surface compared to the porous surface of the NC control membrane. Wettability assays revealed hydrophobic behavior for the NC/NH2-PEG-rGO hybrid membrane, with a water contact angle exceeding 90°, contrasting with the hydrophilic behavior characterized by a 16.7° contact angle in the NC membrane. The performance of the NC/NH2-PEG-rGO hybrid membrane was evaluated for the extraction of ssDNA with fewer than 50 nucleotides from solutions containing various ionic species (MnCl2, MgCl2, and MnCl2/MgCl2). The NC/NH2-PEG-rGO hybrid membrane exhibited optimal performance when incubated in MgCl2, presenting the highest fluorescence emission at 525 relative fluorescence units (r.f.u.). This corresponds to the extraction of approximately 610 pg (≈13%) of the total oligo-DNA, underscoring the efficacy of the pristine material, which extracts 286 pg (≈6%) of oligo-DNA in complex solutions.

Dental agenesis is one of the most common developmental anomaly in humans and it is frequently as-sociated with several other oral abnormalities. The present case describes nonfamilial agenesis of per-manent teeth in a twenty-one-year-old boy, with no apparent systemic abnormalities. The treatment in-cluded a personalized and interdisciplinary approach by the means of endodontics, orthodontics, im-plants supported restorations and prosthetic treatments. The treatment plan was thoroughly elaborated using photographic analysis, study models, orthopantomogram, CBCT and cephalograms. Virtual smile design, diagnostic waxing, and mock-up previsualized the treatment objectives. The edentulous spaces were reconstructed by inserting dental implants, and monolithic Zirconia implant supported restorations. The final results showed a highly aesthetic and functional rehabilitation. Periodic checkups have shown that the stability of the result is well maintained and that the implant supported restorations are an op-timal solution for patients with multiple anodontia.

Different therapeutic strategies have been investigated to target and eliminate HIV-1-infected cells by using armed antibodies specific to viral proteins, with varying degrees of success. Herein, we propose a new strategy by combining photodynamic therapy (PDT) with HIV Env-targeted immunotherapy, and refer to it as HIV photoimmunotherapy (PIT). A human anti-gp41 antibody (7B2) was conjugated to two photosensitizers with different charges through different linking strategies; “Click” conjugation by using an azide-bearing porphyrin attached via a disulfide bridge linker with a drug-to-antibody ratio (DAR) of exactly 4, and “Lysine” conjugation by using phthalocyanine IRDye 700DX dye with average DARs of 2.1, 3.0 and 4.4. These photo-immunoconjugates (PICs) were compared via biochemical and immunological characterizations regarding the dosimetry, solubility, and cell targeting. Photo-induced cytotoxicity of the PICs were compared using assays for apoptosis, reactive oxygen species (ROS), photo-cytotoxicity, and confocal microscopy. Targeted phototoxicity seems to be primarily dependent on the binding of PS-antibody to the HIV antigen on the cell membrane, whilst being independent of the PS type. This is the first report of the application of PIT for HIV immunotherapy by killing HIV Env-expressing cells.

Radical reactions in water or aqueous media are important for organic synthesis, realizing high yielding processes under non-toxic and environmentally friendly conditions. This overview includes (i) a general introduction to organic chemistry in water and aqueous media, (ii) synthetic approaches in-, on- and with-water as well as in heterogeneous phase, (iii) reaction of carbon-centered radicals with water (or deuterium oxide) activated through coordination with various Lewis acids, (iv) photocatalysis in water and aqueous media, and (v) synthetic applications bioinspired from naturally occurring processes. A wide range of chemical processes and synthetic strategies under different experimental conditions have been reviewed that lead to important functional group translocation and transformation reactions, leading to the preparation of complex molecules. These results reveal how water as a solvent/medium/reagent in radical chemistry has matured over the last two decades and how further discoveries are foreseen to come in the near future.

Human papillomavirus (HPV) uses the cellular trafficking machinery to reach the cell nucleus and initiate a successful infection. The HPV capsid consists of two proteins: L1 (the major capsid protein) and L2 (minor capsid protein), and L2 is known to be responsible for trafficking the viral genome to the nucleus. From previous studies, we know that many cellular proteins interact with L2 and are involved in the trafficking process at different stages of the infectious entry process. To further investigate how HPV-16 achieves successful viral entry, we have performed a mass spectrometry analysis to identify novel interacting proteins that associate with incoming HPV-16 virions. We show that HPV-16 pseudovirions interact with a group of cellular cargo proteins (COPI), and here we confirm that this is mediated by the direct binding of L2, but not L1, to the COPB1 subunit. We also show that the ability of L2 to interact with COPB1 is conserved in both low- and high-risk HPV types. Furthermore, we also show that the interaction is essential for successful infection entry of multiple HPV types, thereby identifying a novel constituent of the infectious entry pathway of the HPV.

Binary mixtures of surfactants build a binary mixed micelle in which the ratio of surfactants usually differs from the initial ratio of surfactants in their binary mixture. The thermodynamic stabilization of the binary mixed micellar pseudophase about the hypothetical ideal state (intermolecular interactions between the different particles and the conformational states of the particles are identical to those of monocomponent states) is described by the molar excess Gibbs free energy (gE). The dependence of gE on the molar fraction of surfactant i (xi) from the binary mixed micelle can be described by a symmetric function (symmetry is described to the line parallel to the y-axis and passes through xi = 0.5) or by an asymmetric function. Theoretical analysis (canonical partition function, conformational analysis) examines how the presence of different polar functional groups, some of which are sterically shielded from the steroid skeleton of bile salt (surfactant), affect the symmetry of the function gE of the binary mixed micelle of the cholic acid anion (bile salt) and classical cationic surfactant (hydrophobic tail and polar head). Suppose the steroid skeleton of the bile salt contains non-sterically shielded polar groups (or the temperature is relatively high). In that case, gE is a symmetric function. At the same time, if the steroid skeleton also contains sterically shielded polar groups, then the gE function is asymmetric.

After 40 years of the discovery of metallocene catalysts, there are still several aspects that remain unresolved, especially when the “conventional” alkylaluminum activators are not used. Herein, we systematically investigate the synthesis of PE via three different zirconocene catalysts, with different alkyl substituents, activated via different organoboron compounds. The polymerization behavior, as well as the properties of the materials, are evaluated. The results demonstrate that the highest catalytic activity is shown by Bis(cyclopentadienyl)dimethylzirconium activated by trityl tetra(pentafluorophenyl)borate. Also finding that toluene is the optimum solvent for these systems and at these reaction conditions. Moreover, to validate our experimental results, a comprehensive mathematical model is developed on the basis of thermodynamic and kinetic principles. The concentration of ethylene transferred to the solvent phase (toluene) in a liquid-vapor equilibrium (LVE) system is estimated based on the Duhem’s theorem. Arrhenius expressions for the kinetic rate constants of a proposed kinetic mechanism are estimated by a kinetic model, in which the rate of polymerization is fitted by a least-square optimization procedure and the molecular weight averages by the method of moments. The simulations of the coordination polymerization suggest the presence of two types of active sites, principally at low temperatures, and the reactivation of the deactivated sites via a boron-based activator. However, the effect of the temperature on the reactivation step is no clear; a deeper understanding via designed experiments is required.

Microporous organic polymers (MOPs) are promising materials for gas sorption because of the intrinsic and permanent porosity, designable framework and low density. The introduction of nitrogen-rich building block in MOPs will greatly enhance the gas sorption capacity. Here, we report the synthesis of MOPs from the 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine unit and aromatic azides linkers via click polymerization reaction. FTIR and solid state 13C CP-MAS NMR confirm the formation of the polymers. CMOP-1 and CMOP-2 exhibit microporous networks with BET surface area of 431 and 406 m2 g-1 and narrow pore size distribution under 1.2 nm. Gas sorption isotherms including CO2 and H2 were measured. CMOP-1 stores superior CO2 level of 8.2 wt% (1.88 mmol g-1) at 273 K/1.0 bar and H2 uptake up to 0.6 wt% at 77 K/1.0 bar, while CMOP-2 with smaller surface area shows lower CO2 adsorption capacity of 7.3 wt% (1.66 mmol g-1) and H2 uptake (0.5 wt%). In addition, I2 vapor adsorption was tested at 353 K. CMOP-1 shows higher gravimetric load of 160 wt%. Despite of the moderate surface area, the CMOPs display excellent sorption ability for CO2 and I2 due to the nitrogen-rich content in the polymers.

Direct-to-blister copper flash smelting slag contains up to 14% of copper and 2-4% of lead. Considering this fact, this material is subjected to the high-temperature reduction process. After this, converting process is performed on the Cu-Pb-Fe alloy being the product of decopperization process in electric furnace. An alternative to the presently used processing of flash smelting slag would be its hydrometallurgical treatment and selective recovery of Pb and Cu. This paper presents the results of laboratory tests on flash smelting slag leaching with citric acid solutions. The experiments performed allowed to determine the process parameters at which the Pb concentration in the post-leaching sediment reached the value of 0.41-0.6% while the Pb content in flash smelting slag was 3.05%. Analogous values for copper were 11.5-11.8% (after leaching) and 12.44% (before). Material after leaching in citric acid solutions can be processed, in the second step, using sulfuric acid solutions, and it could lead to the recovery of almost all copper contained in it.

Aiming at the limitations of single-functionality, limited applicability, and complex designs prevalent in current metasurfaces, we propose a terahertz multifunctional and multiband tunable metasurface utilizing a VO2-metal hybrid structure. This metasurface structure comprises a top VO2-metal resonance layer, a middle polyimide dielectric layer, and a gold film reflective layer at the bottom. This metasurface exhibits multifunctionality, operating independently of polarization and incident angle. The varying conductivity states of the VO2 layers, enable the metasurface to achieve various terahertz functionalities, including single-band absorption, broadband THz absorption, and multiband perfect polarization conversion for linear (LP) and circularly polarized (CP) incident waves. Finally, we believe that the functional adaptability of the proposed metasurface expands the repertoire of options available for future terahertz device designs.

Azobenzene photoswitches are fundamental components in contemporary approaches aimed at light-driven control of intelligent materials. Significant endeavors are directed towards enhancing the light-triggered reactivity of azobenzenes for such applications and obtaining water-soluble molecules able to act as crosslinkers in a hydrogel. Here, we report the rational design and the synthesis of azobenzene/alginate photoresponsive hydrogels endowed with fast reversible sol-gel transition. We started with the synthesis of three cationic azobenzenes (AZO A, B, and C) and then incorporated them in sodium alginate (SA) to obtain photoresponsive supramolecular hydrogels (SMHGs). The photoresponsive properties of the azobenzenes were investigated by UV-Vis and ¹H NMR spectroscopy. Upon irradiation with 365 nm UV light, the azobenzenes demonstrated efficient trans-to-cis isomerization, with complete isomerization occurring within seconds. The return to the trans form took several hours, with AZO C exhibiting the fastest return, possibly due to higher trans isomer stability. In the photoresponsive SMHGs, the minimum gelation concentration (MGC) of azobenzenes was determined for different compositions, indicating that small amounts of azobenzenes could induce gel formation, particularly in 5 wt% SA. Upon exposure to 365 nm UV light, the SMHGs exhibited reversible gel-sol transitions, underscoring their photoresponsive nature. This research offers valuable insights into the synthesis and photoresponsive properties of cationic, water-soluble azobenzenes, as well as their potential application in the development of photoresponsive hydrogels.

Redox mediators comprising I–, Co3+, and Ti3C2Tx MXene were applied to dye-sensitized solar cells (DSCs). In the as-prepared DSCs (I-DSCs), wherein hole conduction occurred via the redox reaction of I−/I3− ions, the power conversion efficiency (PCE) was not altered by the addition of Ti3C2Tx MXene. The I-DSCs were exposed to light to produce Co2+/Co3+-based cells (Co-DSCs), wherein the holes were transferred via the redox reaction of Co2+/Co3+ ions. A PCE of 9.01% was achieved in a Co-DSC with Ti3C2Tx MXene (Ti3C2Tx-Co-DSC), which indicated an improvement from the PCE of a bare Co-DSC without Ti3C2Tx MXene (7.27%). It was also found that the presence of Ti3C2Tx MXene in the redox mediator increased the hole collection, dye regeneration, and electron injection efficiencies of the Ti3C2Tx-Co-DSC, leading to an improvement in both the short-circuit current and the PCE when compared with those of the bare Co-DSC without MXene.

Optimal conditions for maximum efficacy of photoinitiated polymerization are theoretically presented. Analytic formulas are shown for the crosslink time, crosslink depth and efficacy function. The roles of photoinitiator (PI) concentration, diffusion depth and light intensity on the polymerization spatial and temporal profiles, for both uniform and non-uniform cases, are presented. For optimal efficacy, a strategy via controlled PI concentration is proposed, where re-supply of PI in high light intensity may achieve a combined-efficacy similar to low light intensity, but has a much faster procedure. A new criterion of efficacy based on the polymerization (crosslink) [strength] and [depth] is introduced. Experimental data are analyzed for the role of PI concentration and light intensity on the gelation time and efficacy.

Copper (Cu) is an essential micronutrient for the correct development of eukaryotic organisms. This metal plays a key role in many cellular and physiological activities, including enzymatic activity, oxygen transport, and cell signaling. Although the redox activity of Cu is crucial for enzymatic reactions, this property also makes it potentially toxic when found at high levels. Due to this dual action of Cu, highly regulated mechanisms are necessary to prevent both the deficiency and the accumulation of this metal since its dyshomeostasis may favor the development of multiple diseases, such as Menkes’ and Wilson’s diseases, neurodegenerative diseases, diabetes mellitus, and cancer. As the relationship between Cu and cancer has been the most studied, we analyze how this metal can affect three fundamental processes for tumor progression: cell proliferation, angiogenesis, and metastasis. Gynecological diseases are characterized by high prevalence, morbidity, and mortality, depending on the case, and mainly include benign and malignant tumors. The cellular processes that promote their progression are affected by Cu, and the mechanisms that occur may be similar. We analyze the crosstalk between Cu deregulation and gynecological diseases, focusing on therapeutic strategies derived from this metal.

This paper investigates the impact of debt financing on dividend payments when they face the agency costs of free cash flow. Focusing on a sample of 120 firms listed on the Saudi Stock Exchange during the period 2011-2021. The study found a negative association between agency cost of free cash flow and dividend payment. More importantly, our research highlights the significant role of long-term debt in making more prudent use of free cash flow. The obligation to meet interest and principal payments acts as an incentive for them to steer clear of unprofitable expenses and risky investments. Concurrently, long-term debt imposes restrictive clauses in debt contracts, such as minimum dividend distribution requirements, which further encourage higher dividend payments. Since interest and debt repayments are fixed obligations, using free cash flow for dividend disbursement is considered a more profitable and beneficial approach for shareholders in the context of Saudi Arabia.

Three kinds of hydrophobic groups grafted starches of maleic anhydride grafted starch (MAH-g-starch), lactic acid grafted starch (LA-g-starch), and methyl acrylate grafted starch (MA-g-starch) were prepared by in-situ solid phase polymerization. The results of Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) were confirmed successful grafting. The grafting ratios of MAH-g-starch, LA-g-starch and MA-g-starch were 6.50%, 12.45%, and 0.57%, respectively. Influenced by the grafting ratio, LA-g-starch had the best hydrophobic properties and the largest molecular weight, and those for MA-g-starch was the worst. The surfaces of grafted starches were covered with graft polymer, with obvious surface roughness and bond degree of MAH-g-starch and LA-g-starch. The crystalline structure of grafted starches showed some damage, with LA-g-starch exhibiting the greatest decrease in crystallinity, and less of a change for MA-g-starch. Overall, the grafting reaction improved thermoplasticity, with LA-g-starch the most improved, followed by MAH-g-starch, and then MA-g-starch.