The exploitation of the metallacarboranes’ potential in various fields of research and practical ap-plications requires the availability of convenient and versatile methods for their functionalization with various functional moieties and/or linkers of different types and lengths. Herein we report a study on cobalt bis(1,2-dicarbollide) functionalization at 8,8’-boron atoms with different het-ero-bifunctional moieties containing protected hydroxyl function allowing further modification after deprotection. Moreover, an approach to the synthesis of three and four functionalized metallacarboranes, at boron and carbon atoms simultaneously, via additional functionalization at carbon to obtain derivatives carrying three or four rationally oriented and distinct reactive surfaces, is described

A four-step synthesis of bifunctional, noncovalent organocatalysts based on the chiral (1R,2R)-cyclohexane-1,2-diamine scaffold containing a 1,2-benzenediamine H-bond donor was developed. Nucleophilic aromatic substitution of the 2-fluoronitrobenzene derivative with the commercial (1R,2R)-cyclohexane-1,2-diamine was followed by selective alkylation of the primary amino group, reduction of the aromatic nitro group and final derivatization of the primary aromatic amino group, i.e. acylation, sulfonation, reductive alkylation and arylation, leading to the four subtypes of organocatalysts. All new compounds were fully characterized. The prepared organocatalysts (32 examples) were tested in the Michael addition of acetylacetone to trans-β-nitrostyrene, yielding the addition product with incomplete conversions (up to 93%) and enantioselectivities of up to 41% ee.

Herein we present the biocatalysed preparation of mono-N-carbamate-protected precursor of antitumoral Nutlin-3a, through enantioselective alkoxycarbonylation of meso-1,2-disubstituted-1,2-diaminoethane, using enzyme lipases and dialkyl carbonates as acylating agents. A series of supported or free lipase enzymes were screened in combination with commercially available diallyl-, diethyl and dimethyl- carbonate. The reactions were conducted at different temperatures, reaction times and with variable co-solvent systems to evaluate the effect on the enzyme catalytic activity. The best results in terms of conversion, enantiomeric excess and yield were obtained when lipase from Candida antarctica B (CAL-B) was used with diallyl carbonate (DAC) conducting the reaction solventless at 75 °C.

Since its initial development in the 1970’s by Phil Burke and his collaborators, the R-matrix theory and associated computer codes have become the de facto approach for the calculation of accurate data for general electron-atom/ion/molecule collision and photoionization processes. The use of a non-orthonormal set of orbitals based on B-splines, now called the B-spline R-matrix (BSR) approach, was pioneered by Zatsarinny. It has considerably extended the flexibility of the approach and improved particularly the treatment of complex many-electron atomic and ionic targets, for which accurate data are needed in many modelling applications for processes involving low-temperature plasmas. Both the original R-matrix approach and the BSR method have been extended to the interaction of short, intense electromagnetic (EM) radiation with atoms and molecules. Here we provide an overview of the theoretical tools that were required to facilitate the extension of the theory to the time domain. As an example of a practical application, we show results for two-photon ionization of argon by intense short-pulse extreme ultraviolet radiation

Arylmagnesium and -calcium reagents are easily accessible, however, ether degradation processes limit the storability especially of the calcium-based heavy Grignard reagents. Ortho-bound substituents with phosphanyl donor sites usually block available coordination sites and stabilize such complexes. The reaction of bromo-2,6-bis(diphenylphosphanylmethyl)benzene (1a) with magnesium in tetrahydrofuran yields [Mg{C₆H₃-2,6-(CH₂PPh₂)₂}₂] (2) after recrystallization from 1,2-dimethoxyethane. However, the similarly performed reduction of bromo- (1a) and iodo-2,6-bis(diphenylphosphanylmethyl)benzene (1b) with calcium leads to ether cleavage and subsequent degradation products. α-Deprotonation of THF yields 1,3-bis(diphenylphosphanylmethyl)benzene. Furthermore, the insoluble THF adducts of dimeric calcium diphenylphosphinate halides, [(thf)₃Ca(X)(µ-O₂PPh₂)]₂ [X = Br (3a), I (3b)], precipitate verifying ether decomposition and cleavage of P-C bonds. Ether adducts of calcium halides [such as [(dme)₂(thf)CaBr₂] (4)] form supporting the initial Grignard reaction and a subsequent Schlenk-type dismutation reaction.

The reaction between cadmium nitrate tetrahydrate and N,N'-bis(pyridin-3-ylmethyl)oxalamide (L) in 1:3 molar ratio in water/acetonitrile (1:6 v/v) mixture afforded single crystals of compound 1 suitable for X-ray diffraction analysis. Compound 1 consists of the coordination polymer (CP) [[Cd(L)2(H2O)2](NO3)2·4H2O]∞, in which CdII ions are bridged by the neutral L antiperiplanar N-ligands in a wavy ribbon fashion developing along the c-axis. Two trans-disposed water molecules complete the pseudo-octahedral coordination geometry of the metal ion. The crystal packing of 1 revealed the interplay between π-π stacking interactions and an intricate hydrogen-bonded network involving oxalamides, nitrates and water molecules. The donor properties of L and the intermolecular interactions in compound 1 are interpreted based on hybrid-DFT calculations.

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.

Catechol dioxygenases in microorganisms cleave catechol into cis-cis-muconic acid or 2-hydroxymuconic semialdehyde via the ortho- or meta-pathway, respectively. The aim of the study was to purify, characterize and predict template-based three-dimensional structure of catechol 1,2-dioxygenase (C12O) from indigenous Pseudomonas chlororaphis strain UFB2 (PcUFB2). Preliminary studies showed that PcUFB2 could degrade 40 ppm of 2,4-dichlorophenol (2,4-DCP). The crude cell extract showed 10.34 U/mL of C12O activity with a specific activity of 2.23 U/mg of protein. A 35 kDa protein was purified to 1.5-fold with total yield of 13.02 % by applying anion exchange and gel filtration chromatography. The enzyme was optimally active at pH 7.5 and temperature 30 °C. The Lineweaver-Burk plot showed the v_max and K_m values of 16.67 µM/min and 35.76 µM, respectively. ES-MS spectra of tryptic digested SDS-PAGE band and bioinformatics studies revealed that C12O share 81% homology to homogentisate 1,2-dioxygenase reported in other Pseudomonas chlororaphis strains. Characterization and optimization of C12O activity can assist in understanding the 2,4-DCP metabolic pathway in PcUFB2 and its possible application in bioremediation strategies.

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2’-bis(aminomethyl)-1,1’-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = 5-C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium with retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to 67% ee.

The compound, C27H23N3 (1), crystallizes in the triclinic system of the P-1 space group. The unit cell comprises a dimer of 1, in which the monomers are linked by two complementary hydrogen bonds between N1 and H1-C1 of another molecule. The dimers form chains along the a-axis through intermolecular interactions between the N2 acceptor atoms and C17 donors from molecules in the nearest neighbouring dimer. These interactions form extended sheets of the dimers of 1, along the ab plane. The quinolinylmeth-2-yl groups of 1 lie in almost orthogonal planes and their N1/2(q) donor atoms being away from the apical amino N3 atom.

The ethylene-regulated hypocotyl elongation of Arabidopsis thaliana's involves many transcription factors. The specific role of MYC transcription factors in ethylene signal transduction is not completely understood. The results here revealed that two MYCs, MYC2 and MYC3, act as negative regulators in ethylene-suppressed hypocotyl elongation. Etiolated seedlings of the lost-of-function mutant of MYC2 or MYC3 were longer than wild type seedlings. Single- or double-null mutants of MYC2 and MYC3 displayed an enhanced response to ACC(1-aminocyclopropane-1-carboxylate), the ethylene precursor, compared to wild type seedlings. MYC2 and MYC3 directly bind to the promoter zone of ERF1, suppressing its expression. Additionally, EIN3, a key component in ethylene signaling, interacts with MYC2 or MYC3 and suppresses their binding to ERF1’s promoter. MYC2 and MYC3 play crucial roles in the ethylene-regulated expression of functional genes. The results revealed these transcription factors’ novel role and functional mechanism in ethylene signal transduction.

2,7-bis(pyridin-4-ylethynyl)-9H-carbazole (1) was synthesized by reacting 4-ethynylpyridine hydrochloride with 2,7-dibromo-9H-carbazole. The full characterization of compound 1 is presented, and the crystal structure of its monohydrate co-crystal was determined by single-crystal XRD analysis.

In this work, the properties of a composition based on synthetic rubber ethylene-propylene ter-polymer and polymers with functional groups of the mixture are studied. Low efficiency of some compositions based on ethylene and propylene copolymer limits their use in the production of tires and rubber products. Therefore, we conducted a study to improve the disadvantages of SREPT-60 using butyl rubber + choro polyisoprene + butadiene-nitrile + butadiene styrene rubber and adding a plasticizer to the composition = α, methacrylate-(bis-diethylene glycol phthalate) -(btegf-9) The data obtained showed that a number of its indicators of rubber based on them were improved. Tear resistance, resistance to repeated stretching increased, adhesion of the composition to metal, chemical resistance increased, the degree of swelling in benzene and gasoline-benzene mixture decreased. Compositions based on the mixture SREPT-60 using butyl rubber + choro polyisoprene + butadiene-nitrile + butadiene styrene rubber and adding a plasticizer to the composition = α, methacrylate-(bis-diethylene glycol phthalate) -(btegf-9) +Dioctyl phthalate: (70:20:10) have high resistance to swelling in an aggressive environment (Benzene, gasoline, alcohol, acid, oil, etc.) mixture.

Climacteric fruits undergo a characteristic ripening process regulated by ethylene, a key plant hormone. Extending the shelf life of these fruits while preserving their postharvest quality poses a significant challenge for the food industry. This review provides a comprehensive overview of physiological and molecular strategies to delay ethylene-mediated ripening in climacteric fruits and their impact on shelf life, postharvest quality, sensory attributes, and volatile compounds. Additionally, it examines the role of ethylene in fruit ripening analysing various ethylene managing strategies including ethylene inhibitors, ethylene adsorbents and ethylene scavengers by catalytic oxidation The review concludes with future research directions including integrated strategies, environmental considerations and commercial applications for improving postharvest handling and fruit quality.

Two ferrocene derivatives, namely, 1,2-(tetramethylene)-ferrocene and 1,2,1’,2’-bis(tetramethylene)-ferrocene, were synthesized in a four-step reaction sequence starting from ferrocene. Friedel-Craft acylation of ferrocene with succinic anhydride gave mono- or bis(3-carboxypropinoyl)ferrocene depending on the stoichiometry of succinic anhydride. The reduction of the keto groups to methylene, followed by ring-closing using trifluoroacetic anhydride gave 1,2-(α-ketotetramethylene)-ferrocene or 1,2,1’,2’-bis(α-ketotetramethylene)ferrocene. The diastereomeric mixture of the latter diketones was separated by column chromatography, characterized by single-crystal X-ray analysis, and assigned their stereochemistry. Reduction of the keto groups to methylene under Clemmensen conditions gave homoannular mono- or bis(tetramethylene) ferrocene derivatives. The molecular structure of 1,2-(tetramethylene)-ferrocene revealed that the ipso carbon atoms of the cyclopentadienyl group are 0.023(3) Å farther away from Fe(II) compared to the remaining three carbon atoms. Both complexes exhibit lower half-wave oxidation potentials than ferrocene, possibly due to the electron-releasing effects of the tetramethylene bridges.

The increasing emergence of multidrug resistant (MDR) pathogens, due to antibiotics misuse, translates in obstinate infections, with high morbidity and high-cost hospitalizations. To oppose these MDR superbugs, new antimicrobial options are necessary. Although both quaternary ammonium (QASs) and phosphonium salts (QPSs) possess antimicrobial effects, QPSs have been studied at lesser extent. Recently, we have successfully reported on the bacteriostatic and cytotoxic effects of a triphenyl phosphonium salt against MDR isolates of Enterococcus and Staphylococcus genus. Here, aiming at finding new antibacterial devices possibly bactericidal towards a broader spectrum of clinically relevant bacteria, responsible for severe human infections, we synthesized a water-soluble, sterically hindered quaternary phosphonium salt (BPPB). It encompasses two triphenyl phosphonium groups linked by a C12 alkyl chain, thus embodying the characteristics of molecules known as bola-amphiphiles. BPPB was characterized by ATR-FTIR, NMR and UV spectroscopy, FIA-MS (ESI), elemental analysis and potentiometric titrations. Optical and DLS analyses evidenced BPPB tendency to self-forming spherical vesicles in solution (45 nm by DLS), having a positive zeta potential (+18 mV). The antibacterial effects of BPPB were for the first time assessed against fifty clinical isolates of both Gram-positive and Gram-negative species. Excellent antibacterial effects were observed on all strains tested, involving all the most worrying species included in ESKAPE bacteria. The lowest MICs were 0.250 µg/mL, while the highest ones (32 µg/mL) were observed on MDR Gram-negative metallo-β-lactamase-producing bacteria and/or species resistant also to colistin, carbapenems, cefiderocol, so that intractable with current available antibiotics. Moreover, when administered to HepG2 human hepatic and Cos-7 monkey kidney cell lines, BPPB showed selectivity indices > 10 for all Gram-positive isolated and for clinically relevant Gram-negative superbugs such as those of E. coli species, thus being very promising to be clinically developed.

Ethylene is a plant hormone controlling physiological and developmental processes such fruit maturation, hairy root formation and leaf abscission. Its effect on regeneration systems, such as organogenesis and somatic embryogenesis (SE), has been studied and progresses in molecular biology techniques have contributed to unveil mechanisms behind its effects. This compound affects regeneration differently, depending on the species, genotype and explant. In some species, ethylene seems to revert recalcitrance in genotypes with low regeneration capacity. However, its effect is not addictive, since in genotypes with high regeneration capacity this ability decreases in the presence of ethylene precursors, suggesting that regeneration is modulated by ethylene. Several lines of evidence have shown that the role of ethylene on regeneration is markedly connected to biotic and abiotic stresses as well as to hormonal-crosstalk, in particular with key regeneration hormones and growth regulators of the auxin and cytokinin families. Transcriptional factors of the ethylene response factor (ERF) family are regulated by ethylene and strongly connected to SE induction. Thus, an evident connection between ethylene, stress responses and regeneration capacity is markedly established. In this review the effect of ethylene and the way it interacts with other players during organogenesis and somatic embryogenesis is discussed.

The reactivity of 3,5-di-(pyridin-4-yl)-1,2,4-thiadiazole (L1) with 1,4-diiodotetrafluorobenzene (1,4-DITFB) was explored and the halogen-bonded 1:1 co-crystal (1) was successfully isolated and structurally characterized.

In this study, we report a detailed experimental and theoretical investigation of three glycols, namely ethane-1,2-diol, 2-methoxyethan-1-ol and 1,2-dimethoxy ethane. For the first time, the X-Ray spectra of the latter two liquids was measured at room temperature, and they were compared with the newly measured spectrum of ethane-1,2-diol. The experimental diffraction patterns were interpreted very satisfactorily with molecular dynamics calculations, and suggest that in liquid ethane-1,2-diol most molecules are found in gauche conformation, with intramolecular hydrogen bond between the two hydroxyl groups. Intramolecular H-bonds are established in the mono-alkylated diol, but the interaction is weaker. The EDXD study also evidences strong intermolecular hydrogen-bond interactions, with short O···O correlations in both systems, while longer methyl-methyl interactions are found in 1,2-dimethoxy ethane. X-Ray studies are complemented by micro Raman investigations at room temperature and at 80°C, that confirm the conformational analysis predicted by X-Ray experiments and simulations.

Auxin and ethylene pathways cooperatively regulate a variety of developmental processes in plants. Growth responses to ethylene are largely dependent on auxin, the key regulator of plant morphogenesis. Auxin, in turn, is capable of inducing ethylene biosynthesis and signaling making the interaction of these hormones reciprocal. Recent studies discovered a bunch of molecular events underlying auxin-ethylene crosstalk. In this review, we summarize the results of fine-scale and large-scale experiments on interaction of auxin and ethylene pathways in Arabidopsis. We integrate the knowledge on the molecular crosstalk events, their tissue specificity and associated phenotypic responses to decipher the crosstalk mechanisms at a systems level. We also discuss the prospects of applying systems biology approaches to study the mechanisms of crosstalk between plant hormones.

Modern organic synthesis is majorly focused on developing environmentally benign synthetic protocols by employing green chemistry principles. Accordingly, in our recent research work, we herein report the use of modified supramolecular host cyclodextrin as an effective solid based green catalyst for accessing structurally diverse and medicinally relevant pyrimidone architectures. The catalyst and the synthesized compounds 4 (a-r) were characterized using FT-IR, NMR and GC-Mass spectroscopy. Major highlights of the reported work include: atom economical process, extremely milder reaction conditions, operational simplicity, high isolated yields, and excellent catalyst turnover number. The molecular docking studies suggest that the compound 4n has the hydrogen bonding, hydrophobic and π-pair interactions with the active site of active sites of CXT M 15 receptor.

In order to investigate the coordination chemistry of O-alkyl N-aryl thiocarbamate ligands, BiI3 has been reacted with two equivalents of MeOC(=S)N(H)Ph in MeCN solution to afford the dinuclear title compound complexes [{I2Bi(μ2-I)2BiI2}{1-MeOC(=S)N(H)Ph}4] 1. Compound 1 has been characterized by IR, UV and NMR spectroscopy, the dinuclear framework has be ascertained by a single-crystal X-ray diffraction study performed at 100 K.

Photophysical properties of a series of bis(arylydene)cycloalkanone dyes with various donor substituentns are studied by quantum chemistry. Their capacity for luminescence and nonradiative relaxation through trans-cis isomerization is related to their structure, in particular, to the donor capacity of the substituents and the degree of conjugation due to the central cycloalkanone moiety. It is shown that cyclohexanone central moiety introduces distortions and disrupts the conjugation, thus leading to a nonmonotonic change in their properties. The increasing donor capacity of the substituents causes increase in the HOMO energy (raise of the oxidation potential) and decrease in the HOMO-LUMO gap, which results in the red shift of the absorption spectra. The ability of the excited dye to relax through fluorescence or through trans-cis isomerization is governed by the height of the barrier between the Franck–Condon and S1-S0 conical intersection regions on the potential energy surface of the lowest π-π* excited state. This barrier also correlates with the donor capacity of the substituents and the degree of conjugation between the central and donor moieties. The calculated fluorescence and trans-cis isomerization rates are in good agreement with the observed fluorescence quantum yields.

2-(5,6-diphenyl-1,2,4-triazin-3-yl)pyridinium dichloroiodate (I) (1) was synthesized by reacting 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine with ICl in dichloromethane solution. The structural characterization of 1 by SC-XRD analysis was accompanied by elemental analysis, FT-IR, and FT-Raman spectroscopy measurements.

Oligonucleotide conjugates with boron clusters have found applications in different fields of molecular biology, biotechnology, and biomedicine as potential agents for boron neutron capture therapy, siRNA components, and antisense agents. Particularly, closo-dodecaborate anion represents a high-boron containing residue with remarkable chemical stability and low toxicity, suitable for the engineering of different constructs for biomedicine and molecular biology. In the present work, we synthesized novel oligonucleotide conjugates of closo-dodecaborate attached to the 5'-, 3'-, or both terminal positions of DNA, RNA, 2'-O-Me RNA, and 2'-F-Py RNA oligomers. For their synthesis, we employed click reaction with the azido derivative of closo-dodecaborate. The key physicochemical characteristics of the conjugates have been investigated using high-performance liquid chromatography, gel electrophoresis, UV thermal melting, and circular dichroism spectroscopy. Incorporation of closo-dodecaborate residues at the 3'-end of all oligomers stabilized their complementary complexes, while analogous 5'-modification decreased duplex stability. Two boron clusters attached to the opposite ends of the oligomer only slightly influence the stability of complementary complexes of RNA oligonucleotide and its 2'-O-methyl and 2'-fluoro analogs. On the contrary, the same modification of DNA oligonucleotides significantly destabilized DNA/DNA duplex but gave a strong stabilization of the duplex with RNA target. According to CD spectroscopy results, two terminal closo-dodecaborate residues cause a prominent structural rearrangement of complementary complexes with a substantial shift from B-form to the A-form of the double helix. The revealed changes of key characteristics of oligonucleotides caused by incorporation of terminal boron clusters, such as the increase of hydrophobicity, change of duplex stability, and prominent structural changes for DNA conjugates, should be taken into account for the development of antisense oligonucleotides, siRNAs, or aptamers bearing boron clusters. These features may also be used for engineering of developing NA constructs with pre-defined properties.

This article has been studied the synthesis of a new derivative of the known alkaloid cytisine contained in the seeds of plants of Cytisus laburnum L. and Thermopsis lanceolata R.Br., both of the Lugiminosae family. The new compound has been obtained from two biologically active compounds such as isoxazole and cytisine. It has been demonstrated that the reaction led to the single-stage method under very mild conditions to obtain some 4-[(3,5-dimethyl-1,2-oxazole-4-yl)sulfonyl]amides. This class of compounds is promising to obtain the new biologically active compounds. This article has examined in detail a structure with using the 1H and 13C NMR and two-dimensional NMR spectroscopy of COSY (1H-1H), HMQC (1H-13C) and NMVS (1H-13C). As a result, the homo- and heteronuclear spin-spin couplings should be established. The X-ray diffraction analysis has determined the spatial structure of a new derivative based on cytisine alkaloid. Thus, its hemorheological activity has been studied.

Insulin resistance is a condition characterized by a reduced biological response to insulin. It is one of the most common metabolic diseases of modern civilization. Numerous naturally occurring substances have shown to have a positive effect in restoring the proper sensitivity to insulin. Mature 3T3-L1 adipocytes with artificially induced insulin resistance by palmitic acid (16:0) were used for the study. Cinnamic acid and 1,2-dicinnamoyl-sn-glycero-3-phosphocholin (1,2-diCA-PC) were tested at three concentrations: 25 μM, 50 μM, and 125 μM. The number of mitochondria and the expression of genes encoded by mtDNA were elucidated in control and experimental cells. In experimental cells treated with 1,2-diCA-PC, we displayed increased insulin-stimulated glucose uptake in a dose-dependent manner, accompanied by an increase in mtDNA copy number. Moreover, in experimental cells treated with 1,2-diCA-PC at the concentration of 125 μM, we observed a significant increase in the expression level of all analyzed genes encoded by mtDNA compared to control cells. Our study showed a relationship between improved cellular sensitivity to insulin by 1,2-diCA-PC and an increase in the number of mitochondria and expression levels of genes encoded by mtDNA. Summarizing, the results suggest a therapeutic potential of cinnamic acid derivative 1,2-diCA-PC in enhancing the insulin sensitivity of adipocytes.

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.

The objective of this study is to design and synthesize substituted η6-chromium tricarbonyl metal complexes carrying o-carborane units as potential boron neutron capture therapy (BNCT) agents. In this study, 1,2-Diphenyl-o-carborane units were used as starting materials to generate biologically active species. We investigated how the structural changes of 1,2-diphenyl-o-carborane substituted with chromium(0) tricarbonyl affect the biological properties; [(CO)3Cr]Ph2C2 (2) and [(CO)3Cr]2Ph2C2 (3) species were produced in moderate yields. The molecular structures of compounds 1–3 were identified and established by infrared (IR), 1H, 11B, and 13C nuclear magnetic resonance (NMR), and X-ray crystallography analyses. Crystal structures of o-carboranyl chromium complexes 1 [a = 10.859(1) Å, b = 24.953(3) Å, c = 13.938(2) Å, β = 111.854(2)º], 2 [a = 10.621(3) Å, b = 17.056(5) Å, c = 12.174(4) Å, β = 106.622(5)º], and 3 [a = 17.540(2) Å, b = 18.060(2) Å, c = 19.484(4) Å, α = 105.746(2)º, β = 110.226(2)º, γ = 91.256(2)º] were obtained. In vitro study using B16 and CT26 cancer cells containing the triphenyl-o-carboranyl chromium (0) complexes Ph3C2BCr2 and Ph3C2BCr3, which we have previously reported, the compounds 2 and 3 accumulated at higher levels than compounds Ph3C2BCr2 and Ph3C2BCr3. However, the phenylated o-carboranyl chromium(0) complexes have been found to be more cytotoxic than p-boronophenylalanine (BPA).

Imidazo[1,2-a]pyridines have been studied regarding drug development. The objective of this work was to evaluate the antileukemic capacity of imidazo[1,2-a]pyridine derivatives by screening its ability as a pro-oxidant. Imidazo[1,2-a]pyridine derivatives were synthesized and oral bioavailability and toxicity were analyzed in silico. Redox screening was performed on human Kasumi, KG-1, K562 and Jurkat leukemia cells. The imidazo[1,2-a]pyridine derivative and the most responsive leukemic cell were selected for cytotoxicity, cell proliferation, cell senescence and oxidative stress assays. The predictive toxicity analysis showed a possible effect on the reproductive system, but without mutagenic, carcinogenic or irritability effects. MRK-107 against K562 cells was the compound that showed the best redox profile. MRK-107 did not induce cell death in K562 and monocyte cells. However, this compound was able to decrease cell proliferation and increase cell senescence after 48 and 72 hours. Furthermore, MRK-107 induced oxidative stress in K562 cells after 72h, increasing lipid peroxidation and decreasing reduced glutathione (GSH) contents. This study demonstrated that MRK-107-induced senescence with the involvement of oxidative stress as a possible mechanism of action, addressing this compound as a potential antitumor drug against chronic myeloid leukemia.

A series of N-acyl derivatives of anabasine and cytisine were prepared to discover novel natural product-based medicinal agents. All synthesized compounds were tested for antimicrobial, antifungal, antiviral and analgesic activity. The most pronounced antibacterial activity was shown by the compounds with isoxazole fragments, while adamantane derivatives showed the greatest antiviral effect. It was found that the majority of anabasine derivatives showed significant analgesic activity reducing the pain response of animals to the irritating effect of acetic acid. The presence of a high level of antimicrobial and antiviral activity in newly synthesized compounds makes it possible to consider them promising for further study of their pharmacological properties.

Understanding speech in noise is particularly difficult for individuals occupationally exposed to noise due to a to a mix between noise-induced auditory lesions and energetic masking of speech signal. For years, the monitoring of conventional audiometric thresholds has been the usual way to check and preserve the auditory function. But the highlighting of supra-threshold deficits, notably speech in noise understanding difficulties, has pointed out the need for new monitoring tools. The present study aims to identify the most important variables that predict speech in noise under-standing in order to suggest a new way of regular monitoring. Physiological (distortion products of otoacoustic emissions, electrocochleography) and behavioral (amplitude and frequency modula-tion detection thresholds, conventional and extended high frequency audiometric thresholds) variables were collected in a population of individuals presenting a relative homogeneous occu-pational noise exposure. Those variables were used as predictors in a statistical model (random forest) to predict scores of three different speech in noise tests and a self-report of speech in noise ability. The extended high frequency threshold appears to be the best predictor and therefore an interesting candidate for a new way of monitoring noise exposed professionals.

Optimization of post polymerization processing of polyolefin elastomers (POE) is of considerable industrial interest. To this aim, experimental determination and theoretical interpretation of the thermodynamics and mass transport properties of POE-solvent mixtures is relevant. Sorption behaviour of n-hexane vapour in a commercial propylene-ethylene elastomer (V8880 VistamaxxTM from ExxonMobil) is addressed here, determining experimentally the sorption isotherms at temperatures ranging from 115 to 140 °C and pressure values of n-hexane vapour up to 1 atm. Sorption isotherms have been interpreted with the Non-Random-Hydrogen-Bonding Equation of State model retrieving, from data fitting, the value of the binary interaction parameter for the n-hexane/V8880 system. Both the case of temperature-independent and of temperature-dependent binary interaction parameter have been considered. Sorption kinetics was also investigated at different pressures and has been interpreted using a Fick’s model determining values of the mutual diffusivity as a function of temperature and of n-hexane/V8880 mixture composition. From these values, n-hexane intra-diffusion coefficient has been calculated interpreting its dependence on mixture concentration and temperature by a semi-empiric model based on free volume arguments.

Phase change refers to the process of maturation and transition from the juvenile to the adult stage. In response to this shift, certain species like chestnut lose the ability to form adventitious roots, thereby hindering the successful micropropagation of adult plants. While auxin is the main hormone involved in adventitious root formation, other hormones, such as ethylene, are also thought to play a role in its induction and development. In this study, experiments were carried out to determine the effects of ethylene on the induction and growth of adventitious roots. The analysis was performed in two types of chestnut microshoots derived from the same tree, a juvenile-like line with high rooting ability derived from basal shoots (P2BS) and a line derived from crown branches (P2CR) with low rooting responses. By means of the application of compounds to modify ethylene content or inhibit its signalling, the potential involvement of this hormone in the in-duction of adventitious roots was analyzed. Our results show that ethylene can modify the rooting competence of mature shoots, while the response in juvenile material was barely affected. To further characterize the molecular reasons underlying this maturation-derived shift in behaviour, specific gene expression analyses were developed. Findings suggest that several mechanisms, including ethylene signalling, auxin transport and epigenetic modifications, relate to the modu-lation of the rooting ability of mature chestnut microshoots and their recalcitrant behaviour.

After a long limbo, RNA has gained its credibility as a druggable target, fully earning its de-served role in the next-generation area of pharmaceutical R&D. We have recently probed the Trans-Activation Response element (TAR), a RNA stem–bulge–loop domain of the HIV-1 genome with bis-3-chloropiperidines (B-CePs), and revealed the compounds unique behavior in stabiliz-ing TAR structure, thus impairing in vitro the chaperone activity of the HIV-1 nucleocapsid (NC) protein. Seeking to elucidate the determinants of B-CePs inhibition, we have further characterized here their effects on the target TAR and its NC recognition, while developing quantitative analyti-cal approaches for the study of multicomponent RNA-based interactions.

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a‒c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2); m-, R = Me (3c-Zr2) were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

As part of valorisation of agricultural waste into bioactive compounds, a series of structurally novel oleanolic acid ((3β-hydroxyolean-12-en-28-oic acid, OA-1)-phtalimidines (isoindolinones) conjugates 18a-v bearing 1,2,3-triazole moieties were designed and synthesized by treating a previously azide 4 prepared from OA-1 isolated from olive pomace (Olea europaea L.) with a wide range of propargylated phtalimidines using the Cu(I)-catalyzed click chemistry approach. OA-1 and its newly prepared analogues 18a-v were screened in vitro for their antibacterial activity against two Gram-positive bacteria, Staphylococcus aureus and Listeria monocytogenes; and two Gram-negative bacteria, Salmonella thyphimurium and Pseudomonas aeruginosa. Attractive results were obtained notably against L. monocytogenes. Compounds 18d, 18g and 18h exhibited the highest antibacterial activity when compared with OA-1 and other compounds in the series against tested pathogenic bacterial strains. Molecular docking study was performed to explore the binding mode of the most active derivatives against the target protein from L. monocytogenes. Results showed the importance of both hydrogen bonding and hydrophobic interactions with the target protein and are in favor to the experimental data.

To explore a new set of anticancer agents, a novel series of pyrazolo[4,3-e]pyrido[1,2-a]pyrimidine derivatives 7a-l have been designed and synthesized via cyclocondensation reactions of pyrazolo-enaminone 5 with a series of arylidene malononitriles; compound 5 was obtained from 5-amino-4-cyanopyrazole (3). The structures of the target compounds 7a-l were investigated by spectral techniques and elemental analysis (IR, UV-Vis, 1H NMR, 13C NMR and ESI-MS). All compounds were evaluated for their in vitro cytotoxicity employing a panel of different human tumor cell lines, A375, HT29, MCF7, A2780, FaDu as well as non-malignant NIH 3T3 and HEK293 cells. It has been found that the conjugate 7e was the most active towards many cell lines with EC50 values ranging between 9.1 and 13.5 µM, respectively. Moreover, in silico docking studies of 7e with six anticancer drug targets, i.e. DHFR, VEGFR2, HER-2/neu, hCA-IX, CDK6 and LOX also was performed, in order to gain some insights into their putative mode of binding interaction and to estimate the free binding energy of this bioactive molecule.

Nanoporous films of Eu-doped organosilicate glass (OSG) have been synthesized using sol-gel technology and spin-coating, employing evaporation-induced self-assembly (EISA), on silicon wafers. The Eu doping is achieved by dissolution of Eu(NO3)3·6H2O in the precursor solution. The deposited films are characterized by using Fourier transform infrared (FTIR) spectroscopy, ellipsometric porosimetry (EP), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy. It is observed that Eu doping makes the films more hydrophilic and reduces the pore size and open porosity. The reduction Eu3+ → Eu2+ occurs in the pores of OSG films, which is confirmed by depth profiling XPS. However, Eu3+ still presents on the film’s top surface. Presence of Eu3+ and Eu2+ gives characteristic luminescence emission in the range of 600‒630 nm (Eu3+) and 290‒400 nm (Eu2+). The Eu2+/Eu3+ concentrations ratio depends on CH3 groups concentration in the films. Moreover, concentration of Eu2+ ions in the pores can be reduced by exposure in inductively coupled (ICP) oxygen plasma. The observed shift of the luminescence spectra towards the UV region, in comparison to previously reported Eu-doped organosilicate films, can be attributed to the energy transfer occurring between the host material and Eu2+ ions.

The electrical, mechanical and thermal conductivity of ethylene butene copolymer (EBC) composites with carbon fibers were studied. EBC/carbon-fiber composites can be utilized as an electro-mechanical material which is capable of changing it electric resistance with mechanical strain. Carbon fibers were introduced to EBC with different concentrations (5-25 wt%). The results showed that the addition of carbon fibers to EBC could increase the electric resistance up to 10 times. Increasing the load to 2.9 MPa could increase the electric resistance change by 4500% compared 25% fiber sample with pure EBC. It is also noted that the electric resistance of the EBC/CF composites underwent a dramatic increase with raising the strain, for example, the resistance change was around 13 times more at 15% strain in comparison to 5% of strain; The thermal conductivity tests showed that the addition of carbon fibers could increase the thermal conductivity by 40%, from 0.19 to 0.27 (Wm-1K-1). It was also observed that the addition of carbon fibers to EBC could increase the thermal conductivity.

Among phosphorylated derivatives, phosphinates occupy a prominent place due to their ability to be bioisosteres of phosphates and carboxylates. These properties imply the necessity to develop efficient methodologies leading to phosphinate scaffolds. For the past years our team have explored the nucleophilic potential of silylated phosphonite towards various electrophiles. In this paper, we propose to extend our study over other electrophiles. We describe here the implementation of a cascade reaction between (trimethylsilyl)imidates and hypophosphorous acid mediated by a Lewis acid allowing the synthesis of aminomethylenebisphosphinate derivatives.

The photoelectrochemical (PEC) conversion of organic small molecules offers a dual benefit of synthesizing value-added chemicals and concurrently producing hydrogen (H2). Ethylene glycol, with its dual hydroxyl groups, stands out as a versatile organic substrate capable of yielding various C1 and C2 chemicals. In this study, we demonstrate that pH modulation markedly enhances the photocurrent of BiVO4 photoanodes, thus facilitating the efficient oxidation of ethylene glycol while simultaneously generating H2. Our findings reveal that in a pH=1 ethylene glycol solution, the photocurrent density at 1.23 V vs. RHE can attain an impressive 7.1 mA cm−2, significantly surpassing the outputs in neutral and highly alkaline environments. The increase in photocurrent is attributed to the augmented adsorption of ethylene glycol on BiVO4 under acidic conditions, which in turn elevates the activity of the oxidation reaction, culminating in the maximal production of formic acid. This investigation sheds light on the pivotal role of electrolyte pH in the PEC oxidation process and underscores the potential of the PEC strategy for biomass valorization into value-added products alongside H2 fuel generation.

Ethylene, a gaseous phytohormone, is emerging as a central player in the intricate web of plant developmental processes from germination to senescence under optimal and stressed conditions. It is present in different plant parts, encompassing the stems, leaves, flowers, roots, seeds, and fruits. This review aims to provide a comprehensive overview of ethylene's fascinating roles in shaping various plant growth and adaptation aspects. It intricately examines the multifaceted impact of ethylene on pivotal aspects of plant development, including but not limited to cell division and elongation, senescence, abscission, fruit and flower development, root hair formation, chloroplast maturation, and photosynthesis. This comprehensive assessment encompasses the intricate pathways of ethylene biosynthesis and signaling, providing a snapshot of the regulatory mechanisms governing ethylene production. Understanding ethylene's multifaceted functions has significant implications for agriculture, biotechnology, and our fundamental comprehension of plant biology. This review underscores the need for continued investigation into ethylene's intricate mechanisms and its potential to revolutionize plant development and crop management.

Ethylene is an ideal CO2 product in an electrocatalytic CO2 reduction reaction (CO2RR), which has high economic value. In this paper, Al–doped octahedral Cu2O (Al–Cu2O) catalyst was synthesized by a simple wet chemical method. The selectivity of CO2RR products was improved by doping Al onto the surface of octahedral Cu2O by regulating the Al content. The Al–Cu2O was used as an efficient electrocatalyst for CO2RR with selective ethylene production. The Al–Cu2O exhibited a high Faradic efficiency (FEC2H4) of 44.9% at -1.23 V (vs. RHE) in CO2 saturated 0.1 M KHCO3 electrolyte. Charge transferring from Al atom to Cu atom take place after Al doping in Cu2O, thereby optimizing the electronic structure, which facilitates CO2RR to ethylene production. The DFT calculation showed that the Al–Cu2O catalyst can effectively reduce the adsorption energy of the *CHCOH intermediate and promote the mass transfer of charges, thus improving the FEC2H4. After Al doping into Cu2O, the center of d orbitals shift positively, which makes the d–band closer to the Fermi level. Furthermore, the density of electronic states increases, which was conducted to the interaction between Cu atoms and intermediates, thus accelerating the electrochemical CO2 reduction process. This work proved that the metal doping strategy can effectively improve the catalytic properties of Cu2O, thus providing a useful way for CO2 cycling and green production of C2H4.

The organic extract of the Caribbean sponge Smenospongia aurea has been shown to contain an array of novel chlorinated secondary metabolites derived from a mixed PKS-NRPS biogenetic route, such as the smenamides. Here we report the presence of a biogenetically different compound, smenopyrone (1), a polypropionate containing two -pyrone rings. The structure of smenopyrone, including its relative and absolute stereochemistry, was determined by spectroscopic analysis (NMR, MS, ECD) supported by comparison with model compounds from the literature. Pyrone polypropionates are unprecedented in marine sponges, but are commonly found in marine mollusks, where their biosynthesis by symbiotic bacteria has been hypothesized and at least in one case demonstrated. As pyrones have recently been recognized as bacterial signaling molecules, we speculate that smenopyrone could mediate inter-kingdom chemical communication between S. aurea and its symbiotic bacteria.

As one of the most promising ablative fillers, multi-walled carbon nanotubes (MWCNTs) have been used to improve the ablative resistance of Ethylene-Propylene-Diene Monomer (EPDM) insulators by facilitating the carbothermal reduction reaction of silica. However, the contribution of MWCNTs to char layer structure of the insulators was unclear. In this work, the effects of MWCNTs on char layer structure and ablative resistance were investigated in different EPDM-based insulators with and without silica. The results showed that adding only 3 phr MWCNTs can reduce the linear ablation rate of EPDM-based insulators without silica by 31.7%, while 6 phr MWCNTs are required to obtain similar results in EPDM-based insulators with silica. Both the char layer morphology of the two insulators gradually evolved into dense porous structure as MWCNTs content increasing, but their formation mechanisms are different. The XRD and Raman spectrum showed that different physicochemical reactions occurred around MWCNTs under different charring components. The proposed ablation mechanism was further verified by designing alternating multilayer distribution of MWCNTs and silica. This work can guide the construction of desirable char layer structure for increasing ablative resistance of EPDM-based insulators.

The flavonoid silymarin (SMN) has been widely used in preclinical and clinical studies to treat various types of cancer, either alone or in combination with chemotherapy agents. Herein, we investigated the therapeutic efficacy of SMN and its combination with capecitabine (CAP) and irinotecan (IRI) in a mouse model of colon cancer. A modified diet supplemented with SMN (2500 ppm) with mono- and combined therapy of CAP and IRI were used following 1, 2 dimethylhydrazine (DMH)-induced colon cancer. The lipid profile, liver function tests, and cytokine levels were measured. Additionally, the lipid peroxidation and inflammation indices as well as the antioxidant activities were examined. Eventually, western blotting analysis for colonic BAX and Bcl-2 levels and histopathological examination of colon sections were carried out. SMN alone and in combination with the chemotherapeutic agents could attenuate the DMH-induced hyperlipidemia and elevated liver function enzyme levels. SMN supplementation with chemotherapy agents could also improve antioxidant activity and reverse the elevated levels of lipid peroxidation and inflammatory markers. Furthermore, significant upregulation of BAX and downregulation of Bcl-2 were observed. Besides, carcinogen-induced polyp multiplicity, dysplastic, and inflammatory changes were ameliorated considerably by treatment regimens. Our results showed that the potential anticancer properties of SMN could enhance the therapeutic effects of chemotherapy agents and reduce hepatotoxicity.

An efficient approach to the previously unknown furo[2',3':2,3]pyrrolo[2,1-a]isoquinoline deriv-atives from readily available 1-R-1-ethynyl-2-vinylisoquinolines is described. The reaction fea-tures a simple procedure, occurs in hexaflouroisopropanol and does not require elevated tem-peratures. It has been found that the addition of glacial acetic acid significantly increases the yields of the target spirolactone products. Using trifluoroethanol instead of hexaflouroisopro-panol results into formation of pyrido[2,1-a]isoquinolines.

Photocatalytic decomposition of ethylene was performed under UV-Led irradiation at the presence of nanocrystalline TiO2 (anatase, 15 nm) supported on the porous nickel foam. Process was carried out in the high temperature chamber with regulated temperature from ambient to 125°C under flow of reacted gas (ethylene in a synthetic air, 50 ppm) with simultaneous FTIR measurements of sample surface. Ethylene was decomposed with higher efficiency in elevated temperatures with maximum of 28% at 100-125°C. The nickel foam used as support for TiO2 allowed to enhance the ethylene decomposition at the temperature of 50°C. However, at 50°C the stability of ethylene decomposition was not retained within the following reaction run, but it was at 100°C. Performed photocatalytic measurements at the presence of some radicals scavengers indicated that higher efficiency of ethylene decomposition was obtained due to the improved separation of charge carriers and increased formation of superoxide anionic radicals, which were formed at the interface of thermally activated nickel foam and TiO2.

Although cofactor regeneration is an established system in biocatalysis, work remains in developing new and alternative cofactor regeneration systems with greater efficiency, ease of use, and higher atom economy. In addition, cofactor regeneration system only works if the cofactor regeneration reaction operates at similar kinetics compared to the biotransformation reaction. This meant that only specific cofactor regeneration system is capable of coupling with particular biotransformation reaction. This then leaves open the field for the development of a plethora of alternative cofactor regeneration systems each capable of coupling with different biotransformation reaction of different kinetics. This short write-up examines the possibility of tapping on the NADH regenerated from a two-step ethylene glycol utilization pathway. Current knowledge suggests that this angle has not been explored; thereby, opening up possibilities for future experimental investigations into the feasibility of coupling ethylene glycol utilization pathway with biotransformation reaction as a coupled cofactor regeneration system.

Climacteric fruits are characterized by a dramatic increase in autocatalytic ethylene production, which is accompanied by a spike in respiration, at the onset of ripening. The change in the mode of ethylene production from autoinhibitory to auto-stimulatory is known as the system 1 (S1) to system 2 (S2) transition. Existing physiological models explain the basic and overarching genetic, hormonal, and transcriptional regulatory mechanisms governing the S1 to S2 transition of climacteric fruit. However, the links between ethylene and respiration, the two main factors that characterize the respiratory climacteric, have been largely understudied at the molecular level. Results of recent studies indicate that the AOX respiratory pathway may play an important role in mediating cross talk between ethylene response, carbon metabolism, ATP production, and ROS signaling during climacteric ripening. New genomic, metabolic, and epigenetic information sheds light on the interconnectedness of ripening-associated metabolic pathways, necessitating expanding the current, ethylene-centric physiological models. Understanding points at which ripening responses can be manipulated may reveal key, speciesand cultivar-specific targets for regulation of ripening enabling superior strategies for reducing postharvest wastage.

One-dimensional shape memory polymer fibers (SMPFs) have obvious advantages in mechanical properties, dispersion properties and weavability. In this work, a method for fabricating semi-crystallization ethylene-vinyl acetate copolymer (EVA) fiber with two-way shape memory effect by melt spinning and ultraviolet (UV) curing was developed. Here, the effect of crosslink density on its performance was systematically analyzed by gel fraction measurement, tensile tests, DSC and TMA analysis. The results showed that the crosslink density and shape memory properties of EVA fiber could be facilely adjusted by controlling UV curing time. The resulting EVA fiber with cylindrical structure had a diameter of 247.13 ± 10.07 μm, and its mechanical strength and elongation at break were 64.46 MPa and 114.33%, respectively. The critical impact of the crosslink density and applied constant stress on the two-way shape memory effect were analyzed. Moreover, the single EVA fiber could lift more than 143 times its own weight and achieve 9% reversible actuation strain. The reversible actuation capability was significantly enhanced by a simple winding design of the single EVA fiber, which provided great potential applications in smart textiles, flexible actuators and artificial muscles.

The binding of actinide ions (Am(III) and U(VI)) in aqueous solutions by hybrid silica-hyperbranched poly(ethylene imine) nanoparticles (NP) and xerogels (XG) has been studied by means of batch experiments at different pH values (4, 7 and 9) under ambient atmospheric conditions. Both materials present relatively high removal efficiency at pH 4 and pH 7 (> 70%) for Am(III) and U(VI). The lower removal efficiency for the nanoparticles is basically associated with the compact structure of the nanoparticles and the lower permeability and access to active amine groups compared to xerogels, and the negative charge of the radionuclide species formed under alkaline conditions (e.g. UO2(CO3)34- and Am(CO3)2-). Generally, the adsorption process is relatively slow due to the very low radionuclide concentrations used in the study and is basically governed by the actinide diffusion from the aqueous phase to the solid surface. On the other hand, the adsorption is favored with increasing temperature assuming that the reaction is endothermic and entropy-driven, which is associated with increasing randomness at the solid-liquid interphase upon actinide adsorption. To the best of our knowledge, this is the first study on hybrid silica-hyperbranched poly(ethylene imine) nanoparticle and xerogel materials used as adsorbents for americium and uranium at ultra-trace levels. Compared to other adsorbent materials used for binding americium and uranium ions, both materials show far higher binding efficiency. Xerogels could remove both actinides even from seawater by almost 90%, whereas nanoparticles could remove uranium by 80% and americium by 70%. The above, along with their simple derivatization to increase the selectivity towards a specific radionuclide and their easy processing to be included in separation technologies, could make these materials attractive candidates for the treatment of radionuclide/actinide contaminated water.

The alkylation of 1,1,2-trimethyl-1H-benzo[e]indole with 2-chloroacetamide, followed by work-up of the reaction mixture with a base and the subsequent treatment of a crude product with acetic acid gives 10a,11,11-trimethyl-10a,11-dihydro-8H-benzo[e]imidazo[1,2-a]indol-9(10H)-one. The structure assignments were based on data from ¹H, ¹³C and ¹⁵N NMR spectroscopy. The optical properties of the obtained compound were studied by UV-vis and fluorescence spectroscopy.

Two different silica conformations (Xerogels and Nanoparticles) both formed by the mediation of dendritic poly (ethylene imine) were tested at low pHs on the problematic uranyl cation sorption. The effect of crucial factors i.e., temperature, electrostatic forces, adsorbent composition, accessibility of the pollutant to the dendritic cavities and MW of the organic matrix was investigated to conclude the optimum formulation for water purification under these conditions. This was attained with the aid of UV-Visible and FTIR spectroscopy, dynamic light scattering (DLS), ζ-potential; Brunauer–Emmett–Teller (BET) porosimetry, Thermo Gravimetric Analysis (TG) and Scanning Electron Microscopy (SEM) Results highlighted that both adsorbents have extraordinary sorp-tion capacity. Xerogels are cost-effective since they approximate the performance of na-noparticles with much lesser organic content. Furthermore, they are more practicable materials since they may penetrate the pores of a metal or ceramic solid substrate in the form of a precursor, gel-forming solution.

A thermal-oxidative aging test at 120°C was condutcted on Ethylene Propylene Diene Monomer (EPDM) vulcanizates of the semi-efficient vulcanization system. The effect of thermal-oxidative aging on EPDM vulcanizates was systematically studied by curing kinetics, aging coefficient, cross-linking density, macroscopic physical properties, contact angle, Fourier Transform Infrared Spectrometer (FTIR), Thermogravimetric analysis (TGA) and thermal decomposition kinetics. The results show that the content of hydroxyl and carbonyl groups as well as the carbonyl index increased with increasing aging time, indicating that EPDM vulcanizates are gradually oxidized and degraded. As a result, the EPDM vulcanized rubber chains were cross-linked, and its conformational transformation was limited and its flexibility was weakened. The thermogravimetric analysis demonstrates the thermal degradation of EPDM vulcanizates had competitive reactions of cross-linking and degradation, and the thermal decomposition curve can be divided into three stages, meanwhile the thermal stability of EPDM vulcanizates gradually decreases with the increase of aging time. The introduction of antioxidant in the system can promote the cross-linking speed and reduce the cross-linking density of EPDM vulcanizates, while inhibiting the surface thermal and oxygen aging reaction. This is attributed to the fact that the antioxidant can reduce the thermal degradation reaction level, but it is not conducive to the formation of a perfect crosslinking network structure and reduce the activation energy of thermal degradation of the main chain.

The article describes the use of microwave irradiation in the synthesis of bis(cyclo carbonate) compounds (BCC) in bulk (without solvent) from carbon dioxide capture using an epoxidized compound - a commercial epoxy resin, and compares this process to the conventional method. CO2 cycloaddition to epoxides is an ecological and efficient method for the formation of bis(cyclic carbonates). Moreover, the introduction of gas into the reaction mixture was carried out at atmospheric pressure with a controlled flow rate, which is advantageous from an economic point of view. Progressive structural changes and the presence of characteristic chemical groups were monitored using attenuated total reflectance infrared spectroscopy with Fourier transform. The obtained crude products were purified to obtain three fractions, which were subjected to detailed structural analysis using FT-IR and 13CNMR. The formation of the main product with two cyclic carbonates was confirmed. The presence of monomers, dimers and trimers in individual fractions as well as their thermal stability were determined, and the molecular masses in individual fractions were determined using gel permeation chromatography (GPC).

A Pt(II) complex featuring chelating tridentate bis-aryloxide tetrahydropyrimidinium based N-heterocyclic carbene (NHC) was synthesized and characterized by using different techniques. The electrochemical properties of the complex were investigated by cyclic voltammetry as well as differential pulse voltammetry, which revealed two reversible one-electron oxidation processes. The chemical generation and isolation of one-electron-oxidized species were performed oxidizing the initial complex by means of AgBF4. The combined UV-Vis/NIR- and EPR-spectroscopy studies supported by density functional theory (DFT) calculations suggest the formation of Pt(II)-phenoxyl radical complex. The latter open-shell derivative was structurally characterized by means of X-ray diffraction analysis. Finally, the neutral platinum complex was tested as a mediator in the process of electrocatalytic oxidation of 2-(methylamino)ethanol (MEA).

We hereby describe an efficient method for the preparation of a series of new 1-substituted 1,2,3-triazole-based acetaminophen derivatives through a clean, good-yielding, simple, and expeditious procedure based on the O-propargylation reaction of the acetaminophen (APAP) obtained from expired commercial tablets and the CuBr(PPh3)3-catalyzed Huisgen reaction be-tween O-propargylated APAP and diverse organoazides prepared from commercially available anilines as available starting reagents. An interesting nitric oxide-releasing 1,2,3-triazole hybrid of APAP was also obtained easily using the developed method. The structures of the designed hybrid compounds, which are expected to be pharmacologically active, were fully characterized by FT-IR, 1H- and 13C-NMR and are reported for the first time. According to the in-silico studies performed in this work and literature analysis, these hybrids are interesting models in search of new pharmacological nontoxic agents endowed with anti-inflammatory and anticancer properties.

Three-dimensional matrices are a new strategy used to tackle type I diabetes; a chronic metabolic disease characterized by the destruction of beta pancreatic cells. Type I collagen is an abundant extracellular matrix (ECM), component that has been used to support cell growth. However, pure collagen possesses some difficulties including low stiffness and strength, and high susceptibility to cell-mediated contraction. Therefore, we developed a collagen hydrogel with a poly(ethylene glycol) diacrylate (PEGDA) interpenetrating network (IPN), functionalized with vascular endothelial growth factor (VEGF) to mimic the pancreatic environment for the sustenance of beta-pancreatic cells. We analyzed the physicochemical characteristic of the hydrogels and found that they were successfully synthesized. The mechanical behavior of the hydrogels improved with the addition of VEGF, and the swelling degree and the degradation were stable over time. In addition, it was found that 5 ng/mL VEGF-functionalized collagen/PEGDA IPN hydrogels sustained and enhanced viability, proliferation, respiratory capacity and functionality of beta pancreatic cells. Hence, this is a potential candidate for future preclinical evaluation, which may be favorable for diabetes treatment.

Four models of Ce(III) complexes with four ligands based on a 1,2,3-triazole derivatives were studied at four DFT levels. The effect of different ligands on the atomic charge value on the cerium ion was analyzed. Several relationships were clearly established between this atomic charge and that of the surrounding atoms, as well as with several geometric parameters of the ligand and with the molecular properties of the Ce(III) complex. The experimental IR and Raman spectra of the newly obtained Ce(III) complex with the (pyrrolidin-1-yl)-2H-1,2,3-triazole-4-carboxylate ligand were interpreted based on their comparison to the theoretical scaled ones using the scaling equations determined by two procedures and four DFT levels. Therefore, the structure predicted for the synthesized Ce(III) complex was clearly characterized and confirmed. The potential antioxidant action of Ce(III) complex was elucidated and compared with other Ln(III) complexes in order to find out the differences in their biological activity profiles.

1,2-Dihydroisoquinolines are important compounds due to their biological and medicinal activities, and numerous approaches to their synthesis have been reported. In this study, a palladium-catalyzed cascade cyclization-coupling of trisubstituted allenamides containing a bromoaryl moiety with arylboronic acids is described. The reaction proceeds via intramolecular cyclization, followed by transmetallation with the arylboronic acid of the resulting allylpalladium intermediate. A variety of substituted 1,2-dihydroisoquinolines were concisely obtained using this methodology because the allenamides, as reaction substrates, were prepared from readily available propargylamines in one step.

Type 2 diabetes mellitus (T2DM) is a chronic metabolic disorder characterized by elevated blood glucose levels. Despite the availability of pharmacological treatments, dietary plans, and exercise regimens, T2DM remains a significant global cause of mortality. Consequently, there is a growing interest in exploring lifestyle interventions, such as Intermittent Fasting (IF). This study aims to identify underlying patterns and principles for effectively improving T2DM risk parameters through IF. By analyzing data from multiple randomized clinical trials investigating various IF interventions in humans, a machine learning algorithm was employed to develop a personalized recommendation system. This system advises pre-diabetic and diabetic individuals on the most suitable IF interventions to improve T2DM risk parameters. With a success rate of 95%, this recommendation system offers highly tailored guidance, optimizing intermittent fasting's benefits for diverse population subgroups. The results of this study allow us to conclude that weight is the crucial feature for females, while age is the determining factor for males to reduce glucose levels in blood. By revealing patterns in diabetes risk parameters among individuals, this study not only provides practical guidance but also sheds light on the underlying mechanisms of T2DM, contributing to a deeper understanding of this complex metabolic disorder.

The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows to form constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is endorsed by pi-staking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)‐silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6–, BF4–, SbF6–, ClO4–, NTf2–, OTf2–. These compounds were characterized in the solid-state by single crystal XRD and reflectance spectra, and in solution by 1H NMR, mass spectrometry, electroanalysis and UV-visible absorption spectroscopy. The X-ray diffraction (XRD) structure of complexes {[Ag(3)][PF6]}∞ (4) and {[Ag(3)][SbF6]∞ (6), where 3 is 3,3'-[(1,1'-biphenyl)-2,2'-diyl]-6,6'-bis[phenyl]-1,2,4,5-tetrazine, revealed the formation of 1D polymeric chains, characterized by an evolution to a large opening of the original tweezer and a coordination of silver(I) via two chelating nitrogen atom and some C=C pi-interactions. Electrochemical and UV spectroscopic properties of the original tweezer and of the corresponding silver complex are reported and compared. 1H NMR titrations with AgNTf2 allowed to determine the stoichiometry, and apparent stability of two solution species, namely [Ag(3)]+ and [Ag(3)2]2+, that formed in CDCl3/CD3OD 2:1 v/v mixtures.

A series of novel chiral nonmetallocene pincer-type rare earth metal dialkyl complexes bearing the chiral monoanionic tridentate C2-symmetric 1,3-bis(oxazolinymethylidene)isoindoline (BOXMI) ligand (BOXMI)Ln(CH2SiMe3)2 1-3 (1, Ln = Sc, yield = 57%; 2, Ln = Lu, yield = 55%; 3, Ln = Y, yield = 62%) have been prepared in moderate yields via the acid-base reaction between the BOXMI ligand and rare earth metal tri(trimethylsilylmethyl) complexes. The X-ray diffractions show that both of the complexes 1 and 2 contain one Boxmi ligand and two trimethylsilylmethyl ligands, adopting a distorted-trigonal-bipyramidal configuration. In the presence of cocatalyst such as borate and AlR3, these complexes 1-3 exhibit high activities up to 6.8 × 104 (g of polymer)/(molLn h) and high cis-1,4-selectivities up to 97%) in the polymerization of isoprene in toluene, yielding the cis-1,4-polyisoprenes with high molecular weights (Mn up to 710000 g/mol) and bimodal molecular weight distributions (Mw/Mn = 2.0-4.5).

This paper presents results from numerical and experimental investigation on Charpy tests in order to point out failure mechanisms and to evaluate new polymeric blends PP+PA6+EPDM. Charpy tests were done for initial velocity of the impactor of 0.96 m/s and its mass of 3.219 kg and these data were also introduced in the finite element model. The proposed model take into account the system of four balls, including support and the ring of fixing the three balls and it has a finer discretization of the impact area to highlight the mechanisms of failure and their development in time. The constitutive models for four materials (polypropylene with 1% Kritilen, two blends PP+PA6+EPDM and a blend PA6+EPDM) were derived from tensile tests. Running simulations for each constitutive model of material makes possible to differentiate the destruction mechanisms according to the material introduced in the simulation, including the initiation and the development of the crack(s), based on equivalent plastic strain at break (EPS) for each material. The validation of the model and the simulation results was done qualitatively, analysing the shape of broken surfaces and comparing them to SEM images and quantitatively by comparing the impact duration, energy absorbed by the sample, the value of maximum force during impact. The duration of the destruction of the specimen is longer than the actual one, explainable by the fact that the material model does not take into account the influence of the material deformation speed in Charpy test, the model being designed with the help of tests done at 0.016 m/s (1000 mm/min) (maximum strain rate for the tensile tests). Experimental results are encouraging for recommending the blends 20% PP+42% PA6+28% EPDM and 60% PA6+ 40%EPDM as materials for impact protection at low velocity (1m/s). Simulation results are closer to the experimental ones for the more brittle tested materials (with less content of PA6 and EPDM) and more distanced for the more ductile materials (with higher content of PA6 and EPDM).

Postharvest 1-MCP treatment can inhibit lignification of fruit and vegetables. It has been suggested that the mode of action of 1-MCP is through inhibiting ethylene production, but the effect of 1-MCP and ethylene on lignification of common bean remain unknown. This work compared the effect of 0.5 μL L-1 1-MCP and 100 μL L-1 ethylene on lignification of common bean during storage. Postharvest 1-MCP significantly inhibited the increase of lignified cell group, sclerenchyma became thicker, vascular bundles thickened and lignified cells grew during storage, while ethylene is the opposite. 1-MCP inhibited the increase in respiration rate, sucrose phosphate synthase (SPS), sucrose synthase (SuSy), phenylalanine ammonialyase (PAL), cinnamyl-alcohol dehydrogenase (CAD), and peroxidase (POD) activities, whereas ethylene hastened all. Ethylene treatment can be stimulated and 1-MCP inhibited the decline of reducing sugar and cellulose content. Expression of genes, including PvACO1, PvAOG1, PvSuSy, PvPAL3, and Pv4CL1, PvCOMT1 together with lignin content were significantly increased in common bean during storage. 1-MCP treatment markedly inhibited expression of PvACO1, PvSuSy2, PvPAL3, Pv4CL1 and PvCOMT1 genes, while strengthened expression of PvETR1 and PvAOG1, while ethylene was opposite. This work provides evidence that ethylene plays a key role in regulating the lignin biosynthesis of common bean, and also provides strategies for the maintenance of fruit quality during storage.

Bis-benzimidazole derivative (BBM) molecule, consisting of two 2-(2’-Hydroxyphenyl) benzim-idazole (HBI) halves, has been synthesized and successfully utilized as a ratiometric fluorescence sensor for the sensitive detection of Cu2+ based on enol-keto excited state intramolecular proton transfer (ESIPT). In this study, we strategically implement femtosecond stimulated Raman spec-troscopy and several time-resolved electronic spectroscopies, aided by quantum chemical calcula-tions to investigate the detailed primary photodynamics of BBM molecule. The results demonstrate that the ESIPT from BBM-enol* to BBM-keto* was observed in only one of HBI halves with a time constant of 300 fs, after that, the rotation of the dihedral angle between two HBI halves generate a planarized BBM-keto* isomer in 3 ps, leading to dynamics red shift of BBM-keto* emission.

Two isotropic pitches were prepared by air blowing and nitrogen distillation method using ethylene tar (ET) as a raw material. And correspondent carbon fibers were obtained through conventional melt spinning, stabilization and carbonization. The structures and properties of resultant pitches and fibers were characterized and their differences were discussed in this work. The results showed that introduction of the oxygen by air blowing method could quickly increase the yield and softening point of pitch. Moreover, the air blown pitch (ABP) composed of linear methylene chains of aromatic molecules while the nitrogen distilled pitch (NDP) mainly contained polycondensed aromatic rings, which was due to the oxygen containing functional groups existed in ABP could impede order stack of pitch molecules and form methylene bridge structure, instead of aromatic condensed structure like NDP. Meanwhile, the spinnability of ABP was not decreased even containing 2.31 wt% oxygen. In contrast, ABP had narrower molecular weight distribution, which contributed to better stabilization properties and higher tensile strength of carbon fiber. The tensile strength of carbon fibers from ABP was reached to 860 MPa with fiber diameter of about 10 μm, which was higher than that of NDP-derived carbon fibers of 640 MPa.

In the present work, effect of basic components on the energy pathway of ethylene oligomerization by landmark Chevron-Phillips catalyst has been explored in detail using density functional theory (DFT). Studied factors were chosen considering the main components of Chevron-Phillips catalyst, i.e. ligand, cocatalyst and halocarbon compounds, comprising i) the type of alkyl substituents in pyrrole ligand as methyl, iso-propyl, tert-butyl, and phenyl, as well as the simple hydrogen, and the electronwithdrawing fluoro and trifluoromethyl; ii) the number of Cl atoms in Al-compound (as AlMe2Cl, AlMeCl2 and AlCl3) which indicates halocarbon amount and iii) cocatalyst type as alkylboron, alkylaluminium, or alkylgallium. Besides main ingredients, solvent effect, from toluene or methylcyclohexane, on oligomerization pathway was explored as well. In this regard, the full catalytic cycles for the main product (1-hexene) formation as well as side reactions, i.e. 1-butene release and chromacyclononane formation, were calculated on the basis of the metallacycle based mechanism. Based on results, a modification on the Chevron-Phillips catalyst system, to reach higher 1-hexene selectivity and activity, is suggested.

A series of alpha,omega-bis(o-methoxyphenyl)arenes were prepared through Suzuki-Miyaura coupling reactions of dibromoarenes with o-methoxyphenyl boronic acid. P2O5-CH3SO3H-mediated direct polycondensation of alpha,omega-bis(o-methoxyphenyl)arenes with trans-1,4-cyclohexanedicarboxylic acid proceeded regioselectively to afford 1,4-cyclohexanediyl-containing aromatic polyketones. The resulting aromatic polyketones have high Tg and excellent solubility in typical organic solvents. In addition, the polyketone films fabricated by solution casting method are more colorless and transparent than those without cyclohexanediyl units.

In this article, a method for the moisture mapping of the soil surface of agrophytocenosis was proposed using neural network based on synchronized radar and multispectral optoelectronic data of Sentinel-1,2. To verify the developed method, data from two experimental plots were used. These plots were located two on irrigated soybean crops. The first of them was located on the right bank (1st plot) and the second one on the left bank (2nd plot) of the down part of Volga River. Two experimental soil moisture geo-datasets were done by measurements and geo-referencing points using gravimetric method (1st plot) and with proximal sensing method (2nd plot) using Soil Moisture Sensor ML3-KIT (THETAKIT, Delta). The soil moisture retrieval algorithm was based on the use of a neural network to predict reflection coefficient of an electromagnetic wave from the soil surface, followed by inversion into soil moisture using a dielectric model that takes into account the soil texture. The input parameter of the neural network was the ratio of the microwave radar vegetation index (calculated on the basis of Sentinel-1 data) to the index (calculated on the basis of data of multispectral optoelectronic channels 8 and 11 of Sentinel-2). Such way calculated index reveals showed a significantly greater dependence on soil moisture than on vegetation height that was been used in previous studies. The retrieved values of soil moisture were compared with the soil moisture measured in-situ. The proposed method with a determination coefficient of 0.44-0.65 and a standard deviation of 2.4%-4.2% for the 1st plot as well as with and of the same metrics for the 2nd allows predicting the soil moisture of both a test plots covered by soybean plants, relative to soil moisture measured in-situ. The conducted research created the scientific basis for a new technology for remote sensing the moisture content of the soil surface of agrophytocenosis as an element of the precision farming system and agroecology.

Pool boiling heat transfer is recognized as one of the most effective heat transfer methods and has extensive applications in industry. The application of non-azeotropic binary mixtures can not only meet the environmental requirements of modern industrial development, but also improve the coefficient of performance (COP) of many systems. Therefore, studying the boiling heat transfer characteristics of non-azeotropic mixtures is important on improving their potential industrial application. This article selected ethylene glycol/deionized water (EG/DW) at varies concentration as the research working fluids, and conducted experimental research on the pool boiling performance. At the same time, the thermophysical parameters of the mixtures were studied and analyzed. The results showed that the concentration of EG in the mixture had a significant impact on the thermal properties and temperature glide of the mixture, where both affected the heat transfer deterioration. Based on experimental data, six widely used heat transfer coefficient prediction correlations were used for calculation, and two of them were modified. The deviation between the modified correlations and the experimental results remained within 20%.

An understanding of the mechanism underlying fruit ripening is critical for fruit quality improvement. Although post-harvest ethylene application is known to enhance the onset of fruit ripening, exact mechanisms remain unclear. To characterize the fruit ripening process and mechanism, we investigated the effects of exposing kiwifruit cultivars ‘Hayward’ and ‘Gamrok’ to exogenous ethylene treatment post-harvest using comprehensive proteomic analyses. Comparative two-dimensional gel electrophoresis showed that most of the proteins aggregated in ethylene-treated samples compared to the control (non-treated). We observed that among all ethylene treatments, 95 proteins from ‘Hayward’ and 106 from ‘Gamrok’ were differentially expressed. Interestingly, among the elicited protein successfully identified by matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometry, 50% from “Hayward’ and 60% from ‘Gamrok’ are associated with fruit ripening. Furthermore, 18% and 10% of proteins, respectively, are associated with defense response, whereas other major proteins are related to protein biosynthesis and photosynthesis/Calvin cycle. Interactions between identified proteins were demonstrated by bioinformatic analysis, providing insights into biological pathways and molecular functions in post-harvest kiwifruit ripening elicited by ethylene application. The present proteomic study in accordance with physiological analysis provides a quantitative evaluation of fruit ripening in response to exogenous ethylene in post-harvest kiwifruit.

The reaction mechanisms of C-S borylation of aryl sulfides catalyzed by the 1,4-benzoquinone (BQ), were investigated by employing M06-2X-D3/ma-def2SVP method and basis set. In this study, the SMD model was taken to simulate the solvent effect of 1,4-dioxane. Also, TD-DFT calculations of BQ and methyl(p-tolyl)sulfane were performed in SMD solvent model. The computational results indicated that BQ and methyl(p-tolyl)sulfane, serving as a photo-catalyst, would be excited under blue LED of 450 nm, aligning well with experimental observations. Additionally, the role of 3O2 was investigated, revealing that it could be activated to 1O2 from the released energy of 1[BQ+methyl(p-tolyl)sulfane]* or 3[BQ+ methyl(p-tolyl)sulfane]*→BQ+ methyl(p-tolyl)sulfane process. Then 1O2, bis(pinacolato)diboron, and methyl(p-tolyl)sulfane would through a series of reactions to yield the final product P. The Gibbs free energy surface show that path a2-2 is optimal and this path has less steps and lower energy barrier. The electron spin density isosurface graphs were employed to analyze structures and elucidate the single electron distribution. These computational results offer valuable insights into the studied interactions and related processes and shed light on the mechanisms governing C–S borylation from aryl sulfides and b2pin2 catalyzed by BQ and methyl(p-tolyl)sulfane.

Dendrite growth and parasitic reactions with liquid electrolyte are the two key factors that restrict the practical application of the lithium metal anode. Herein, a bis(benzene sulfonyl)imide based single-ion polymer artificial layer for lithium metal anode is successfully constructed, which is prepared via blending the as-prepared copolymer of lithiated 4, 4’-dicarboxyl bis(benzene sulfonyl)imide and 4,4’-diaminodiphenyl ether on the surface of lithium foil. This single-ion polymer artificial layer enables compact structure with unique continuous aggregated Li+ clusters, thus reducing the direct contact between lithium metal and electrolyte, and ensuring Li+ transport fast and homogeneous simultaneously. Based on which, the coulombic efficiency of the Li|Cu half-cell is effectively improved, and the cycle stability of the Li|Li symmetric cell can be prolonged from 160 h to 240 h. Surficial morphology and elemental valence analysis confirm that the bis(benzene sulfonyl)imide based single-ion polymer artificial layer effectively facilitates the Li+ uniform deposition and suppresses parasitic reactions between lithium metal anode and liquid electrolyte in the LFP|Li full-cell. This strategy provides a new perspective to achieve steady lithium metal anode, which can be a promising candidate in practical application.

Substituted bis(iminophosphoranyl)methanes are CH acidic compounds that can form complexes with formally dianionic central carbon centres. The reaction of H₂C(Ph₂P=NDip)₂ (≡ H₂L), Dip = 2,6-diisopropylphenyl, with one equivalent of di-n-butylmagnesium afforded the methanide complex [HLMgnBu] 1. Treatment of complex 1 with phenylsilane in aromatic solvents at elevated temperatures afforded the methanediide complex [(LMg)₂] 2 presumably via the MgH intermediate [(HLMgH)_n] (n = 1 or 2). The reaction of 1 with LiAlH₄ in diethyl ether yielded the AlH complex [HLAlH₂] 3. Alternatively, this complex was also obtained from the reaction of H₂L with AlH₃∙NMe₃. The molecular structures of [HLMgnBu] 1, [(LMg)₂] 2, and [HLAlH₂] 3 are reported. Complex 3 shows no sign of H₂ elimination to a methanediide species at elevated temperatures in contrast to the facile elimination of the putative reaction intermediate [(HLMgH)_n] (n = 1 or 2) to form [(LMg)₂] 2. The chemical properties of complex 2 were investigated and this complex appears to be stable against coordination with strong donor molecules.

Synthesis and antitumour activity of a palladium compound, [Bis (quinoline) palladium (II) chloride] (coded as NH1) alone and in combination along with its proposed mechanism of action has been described in the present study. Antitumour activity has been performed in seven different cancer cell lines using colorimetric 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. The investigated palladium compound demonstrated superiority over clinical standard cisplatin against drug resistant ovarian cancer cell lines. NH1 also demonstrates 4.4 times greater activity than cisplatin against breast cancer model. Binary sequenced combination study showed that NH1 in combination with curcumin is mostly additive to antagonistic. However, combination of NH1 with 6-shogaol demonstrated synergism depending on dose and sequence. Proteomic study revealed that changes in expression of 14 proteins were significantly associated with anticancer mechanism of NH1. In vivo anticancer activity of NH1 at a dose of 0.75 mg/kg was also evaluated using Erlich Ascites Carcinoma (EAC) cell lines in Swiss-albino mice model. Preliminary toxicity study in Swiss-albino mice proved that NH1 is comparatively less toxic at both of the administered doses, either 2.5 mg/kg or 5 mg/kg. However, cisplatin demonstrated significant toxicity at both of the administered doses. Biochemical investigations also supported that NH1 demonstrated lesser toxicity profile towards liver or kidney compared to clinical standard cisplatin.

γ-Aminobutyric acid (GABA) plays an important role in plant development and postharvest properties of fruits. However, studies on regulation of kiwifruit ripening by GABA are scarce. Here, we evaluted physicochemical characters and the expression profile of genes related to ripening in hardy kiwifruit treated with exogenous GABA compared to control during postharvest storage period. The results showed that (1) exogenous GABA treatment not only improved the fruit quality but also inhibited respiration rate and ethylene production, as well as reduced the enzyme activities of ACC oxidase (ACO) and ACC synthase (ACS), via down-regulating the expression of AaACO1 and AaACO3, AaACS1 and AaACS2 during kiwifruit storage period; (2) on the one hand, overexpression of AaGAD1 or AaGAD4 gene which is involved in GABA biosynthesis inhibited ethylene production by reducing the enzyme activities of ACO and ACS, whereas silencing of AaGAD1 or AaGAD4 gene led to the reverse effect. On the other hand, overexpression of AaGAD1 or AaGAD4 decreased the expression levels of AaACO1 and AaACO3, AaACS1 and AaACS2, whereas silencing of AaGAD1 or AaGAD4 gene increased the expression levels of these four genes. Above all, our findings demonstrate that exogenous GABA treatment could improve the storage quality and extend the shelf life of kiwifruit, Additionally, the content of GABA was participated in the regulation of ethylene biosynthesis at the molecular level.

With the aim to develop novel scaffolds for sustained release of drugs, we initially developed an easy approach for the synthesis of α,ω-homobifunctional mercaptoacyl poly(alkyl oxide)s. This was based on the esterification of the terminal hydroxyl groups of poly(alkyl oxide)s with suitably S-4-methoxytrityl (Mmt) protected mercapto acids, followed by removal of the acid labile S-Mmt group. This method allowed the efficient synthesis of the title compounds in high yield and purity, which were further used in the development a thioether cross-linked liposome scaffold, by thia-Michael reaction of the terminal thiol groups with preformed nano-sized liposomes bearing maleimide groups on their surface. The reaction process was followed by 1H-NMR, using a Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion NMR experiment (1H-NMR CPMG), which allowed real-time monitoring and optimization of the reaction process. The thioether cross-linked liposomal scaffold that was synthesized was proven to preserve the nanosized characteristics of the initial liposomes and allowed sustained release of calcein (which was used as a chromophore), providing evidence for the efficient synthesis of a novel drug release scaffold consisted of nanoliposome building blocks.

Co/TiO2 catalysts with different cobalt loadings (3.8, 7.5 and 15 wt%) were prepared by impreg-nation method of Co(NO3)2 .6H2O over titania. Samples containing Co(NO3)2 .6H2O and TiO2 in stoichiometric proportions in order to obtain CoTiO3 and Co2 TiO4 phases were also synthesized. The effect of the calcination treatment at two different temperatures, 550 and 1150 °C was investigated. Characterizations by several techniques, such as XRD UV-vis-NIR, DRS, Raman and XPS were carried out. XRD showed the coexistence of three phases: CoTiO3; Co2TiO4 and Co3O4 after calci-nation at 550°C, while the calcination at high temperature (1150°C) leads to single-phase systems (CoTiO3 or Co2TiO4). Diffuse reflection and XPS spectroscopy showed that divalent cobalt occupies octahedral sites in the ilmenite phase and both tetrahedral and octahedral sites in the spinel phase. The catalytic performances of the prepared catalysts, calcined at the two different temperatures, were evaluated in the oxidative dehydrogenation reaction (ODH) of ethane to ethylene. The con-version values were almost comparable for all the samples, calcined at 550 °C, and comparable the ethylene selectivity were recorded, slightly higher only in the case of CoTiO3. The calcination at 1150°C did not modify the overall activity (ethane conversion values around 20%), however, the production of COx becomes more significant. The study examined the influence of the reaction mixture composition, specifically the presence of water, and reveals a slight increase in the yield of ethylene accompanied by a decrease in the overall catalyst activity. This behavior is likely attributed to an increase in the surface concentration of hydroxyl species (OH), resulting in heightened surface acidity.

Naphtho[1,8-de][1,2]oxazin-4-ol and its acyl or benzyl derivatives ring open to various 2,8-dihydroxy-1-naphthonitriles, that undergo methylation, reduction, demethylation and debenzylation reactions, to afford the target compound (E)-2-hydroxy-8-methoxy-1-naphthaldehyde. The best overall yield of the latter was 28.7%. This compound was converted to its corresponding (E)-2-hydroxy-8-methoxy-1-naphthaldehyde ox-ime, which was oxidatively o-cyclized with phenyliodine(III) diacetate (PIDA) to 9-methoxynaphtho[1,2-d]isoxazole 2-oxide. The latter in deuterated DMSO, at room temperature, rearranged to its isomer to 2-hydroxy-8-methoxy(naphthalen-1-yl)nitrile oxide. The isomeriza-tion was detected by a time-course plot 1H NMR spectroscopy and further identified from its13C NMR and HRMS spectra. The nitrile oxide was stable in (non)deuterated DMSO for at least 18 hours. A 3,4-bis(2-hydroxy-8-methoxynaphthalen-1-yl)-1,2,5-oxadiazole 2-oxide as a dimeriza-tion product or an isocyanate as a rearrangement isomer were both ruled out, the former by the absence of the relevant molecular ion in its HRMS spectrum while the latter by 1,3-dipolar cy-cloaddition reactions with various dipolarophiles that gave substituted isoxazoles, thus con-firming the nitrile oxide structure.

: Introduction: Discovering compounds with antibacterial activity is crucial in the current fight against antibiotic-resistance. Material and Methods: We generate two QSAR model to design six new heteroaryl drug candidates; we assessed the antibacterial properties of the compounds against nine ATCC strains, the majority being part of the ESKAPE group, that include Enterococcus faecalis, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and also Salmonella enterica and Escherichia coli. We performed a synergic assay in which we combined PB4, a compound that we have previously tested in published studies, with GC-VI-70, one of the new compounds with the best cytotoxicity/MIC profile. We tested sub-MIC concentrations of PB4 with five antibiotics (linezolid, gentamycin, ampicillin, erythromycin, rifampin and imipenem) to examine the synergic effect on the ATCC strains. To evaluate compounds’ cytotoxicity, we performed a 24-hour and 48-hour 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay on Colorectal Adenocarcinoma (CaCo-2) cells. The antibiotics were tested, alone and in combination with PB4. Results: PB4 lowered the MIC measured for GC-VI-70 and for the various antibiotics employed in clinical use, and all the compounds presented in this study have cytotoxic activity against cells. Conclusions: These compounds show promising use in combination with antibiotics to improve their effectiveness at low concentrations, to prevent unwanted cytotoxic effects.

Poly(2-methoxyethyl acrylate) (PMEA) and poly(ethylene oxide) (PEO) have protein-antifouling properties and blood compatibility. ABA triblock copolymers (PMEAn-PEO11340-PMEAn (MEOMn)) were prepared using single-electron transfer-living radical polymerization (SET-LRP) using a bi-functional PEO macroinitiator. Two types of MEOMn composed of PMEA blocks with a degree of polymerization (DP = n) of 85 and 777 were prepared using the same PEO macroinitiator. MEOMn formed flower micelles with a hydrophobic PMEA (A) core and hydrophilic PEO (B) loop shells in diluted water with a similar appearance to petals. The hydrodynamic radii of MEOM85 and MEOM777 were 151 and 108 nm, respectively. The PMEA block with a large DP formed a tightly packed core. The aggregation number (Nagg) of the PMEA block in a single flower micelle for MEOM85 and MEOM777 was 156 and 164, respectively, which were estimated using a light scat-tering technique. The critical micelle concentrations (CMCs) for MEOM85 and MEOM777 were 0.01 and 0.002 g/L, respectively, as determined by the light scattering intensity and fluorescence probe techniques. The size, Nagg, and CMC for MEOM85 and MEOM777 were almost the same inde-pendent of hydrophobic DP of the PMEA block.

The effect of CO2 pre-treatments on tomato quality prior to cold storage was investigated using physiochemical and transcriptome changes. Three hours CO2 treated fruits were firmer than untreated fruits and had a good appearance even after being transferred from 4°C storage to 20°C for 8 d. CO2 pretreatment with cold storage showed a synergistic effect on delayed ripening through reduced respiration; these tomatoes exhibited a lower lycopene content than untreated fruit under cold storage. Tomatoes treated with 30% CO2 had fewer pits than untreated fruits subjected to chilling temperatures, even after being transferred to 20°C for 8 d. Functional enrichment analyses from transcriptome and metabolome commonly showed that CO2-responsive genes or metabolites were involved in the sucrose and starch and biosynthesis of secondary metabolisms. The most frequently detected domain, ethylene-responsive factor domain and reduced glycolysis provide insights into the mechanism that CO2 regulates tomato quality.

Literature reported the insulin is an important for the humans and it is secreted in the pancreas and controls, regulates the glucose level. It also controls the mechanism and growth. On decreasing the amount of insulin can caused diabetes, several cancers and other disease. Therefore, there is a need to find promising candidates can binds with insulin and stabilize them. Organic compounds containing hetero atoms have lots of biological potency in different area, therefore, researchers are designing new biological potent compounds. Further, insilico studies attracted the researchers in last one decade mainly to get the drug in less time with a clear strategy. In the present work, authors have designed two types of conjugates, xanthenes with trizole as well benzisoxazole and study their interaction with the insulin using computational methods. The library of compounds was screened through molecules docking in terms of binding energy between the designed compound and the active site of the receptor. Further, their ADME properties are investigated. CMPD19 showed best binding affinity with the insulin and may be considered as oral drug based on the bioactive scores.

High purity TiO2 and CuO powders were synthesized by the Pechini method, an inexpensive and easy-to-implement procedure to synthetize metal oxides. The variables of synthesis were the ethylene glycol:citric acid molar ratio and the pH. High reproducibility of the anatase and tenorite phase was obtained for all synthesis routes. The degree of purity of the powders was confirmed by XRD, FTIR, UV-vis absorption and XPS spectra. SEM and TEM images revealed the powders are composed by micrometer grains that can have a spherical shape (only in the TiO2) or formed by a non-compacted nanocrystalline conglomerate. FTIR spectra only vibrational modes associated to the TiO2 or CuO with a nanoparticle behavior. UV-vis absorption spectra revealed the values of maximum absorbance percentage of both systems are reached in the ultraviolet region, with percentages above 83 % throughout the entire visible light spectrum for the CuO system, a relevant result for solar cell applications. Finally, XPS experiments allow the observation of the valence bands and the calculation of the energy bands of all oxides.

Polyethylene terephthalate (PET) pollution poses significant environmental consequences, and thus new degradation methods must be explored to mitigate this problem. We previously demonstrated that a consortium of three Pseudomonas and two Bacillus species can synergistically degrade PET in culture. The consortium more readily consumes Bis(2-Hydroxyethyl) terephthalate (BHET), a byproduct made in PET depolymerization, compared to PET, and can fully convert BHET into metabolically usable monomers terephthalic acid (TPA) and ethylene glycol (EG). Because of its crystalline structure, the main limitation of the biodegradation of post-consumer PET is the initial transesterification from PET to BHET, depicting the need for the transesterification step in the degradation process. Additionally, there have been numerous studies done on the depolymerization reaction of PET to BHET, yet few have tested the biocompatibility of that product with a bacterial consortium. In this report, a two-step process was implemented for sustainable PET biodegradation, where PET is first depolymerized to form BHET using an Orange Peel Ash (OPA) catalyzed glycolysis reaction, followed by complete degradation of the BHET glycolysis product by the bacterial consortium. Results show that OPA-catalyzed glycolysis reactions can fully depolymerize PET, with an average BHET yield of 92% (w/w) and that the reaction product is biocompatible with the bacterial consortium. After inoculation with the consortium, 19% degradation of the glycolysis product was observed in 2 weeks, for a total degradation percentage of 17% when taking both steps into account. Furthermore, the 10-week total BHET degradation rate was 35%, demonstrating that the glycolysis products are biocompatible with the consortium for longer periods of time, for a total two-step degradation rate of 33% over 10 weeks. While we predict complete degradation is achievable using this method, further experimentation with the consortium can allow for a circular recycling process, where TPA can be recovered from culture media and reused to create new materials.

Background and Objectives: Treatment of visceral artery pseudoaneurysms (VAP) is always indicated regardless of their diameters, as their risk of rupture is significantly higher than that of visceral artery aneurysms. The invasiveness of surgery and its associated complications have led to a shift in favour of radiological interventions as the initial treatment of choice. However, there are still some unanswered questions on endovascular treatment of VAP regarding the optimal endovascular technique and the efficacy and safety outcomes. The purpose of this multicenter study was to retrospectively evaluate the effectiveness and safety of endovascular treatment of visceral pseudoaneurysms using Ethylene-Vinyl Alcohol (EVOH) Copolymer-Based Non-Adhesive Liquid Embolic Agents (NALEAs). Materials and Methods: Consecutive patients who underwent endovascular embolization with EVOH-based NALEAs for visceral artery pseudoaneurysms between January 2018 and June 2023 were retrospectively evaluated. Results: 38 embolizations were performed. Technical success was achieved in all patients. The clinical success rate was high (92.1% overall), with no significant differences between ruptured and unruptured VAPs (p=0.679). 7 patients (18.4%) experienced procedure-related complications, related to a case of non-target embolization, four splenic abscesses due to end-organ infarction and two femoral pseudoaneurysms. The rates of procedure-related complications, end-organ infarction, and vascular access-site complications did not significantly differ between ruptured and unruptured VAPs (p>0.05). Conclusions: Both ruptured and unruptured visceral pseudoaneurysms can be effectively and safely treated with NALEA-based endovascular embolization. We suggest considering the use of NALEAs, particularly in specific clinical cases that highlight their advantages, including patients with coagulopathy, fragile vessels, and embolization targets that are located at a considerable distance from the microcatheter tip and are otherwise difficult to reach.

Ethylene is an essential plant hormone critical in various physiological processes. These processes include seed germination, leaf senescence, fruit ripening, and the plant's response to environmental stressors. Ethylene biosynthesis is tightly regulated by two key enzymes, namely 1-aminocyclopropane-1-carboxylate synthase (ACS) and 1-aminocyclopropane-1-carboxylate oxidase (ACO). Initially, the prevailing hypothesis suggested that ACS is the limiting factor in the ethylene biosynthesis pathway. Nevertheless, accumulating evidence from various studies has demonstrated that ACO, under specific circumstances, acts as the rate-limiting enzyme in ethylene production. Under normal developmental processes, ACS and ACO collaborate to maintain balanced ethylene production, ensuring proper plant growth and physiology. However, under abiotic stress conditions, such as drought, salinity, extreme temperatures, or pathogen attack, the regulation of ethylene biosynthesis becomes critical for plants’ survival. This review highlights the structural characteristics, examines the transcriptional, post-transcriptional, and post-translational regulation of ACS and ACO, and their role under abiotic stress conditions. Reviews on the role of ethylene signaling in abiotic stress adaptation are available. However, a review that delineates the role of ACS and ACO in abiotic stress acclimation is not available.

Addition of the bulky redox-active diphosphine 1,8-bis(diphenylphosphino)naphthalene (dppn) to [Fe2(CO)6(-edt)] (1) (edt = 1,2-ethanedithiolate) affords [Fe2(CO)4(2-dppn)(-edt)] (3) as the major product, together with small amounts of a P-C bond cleavage product [Fe2(CO)5{1-PPh2(1-C10H7)}(-edt)] (2). The redox properties of 3 have been examined by cyclic voltammetry and it has been tested as a proton-reduction catalyst. It undergoes a reversible reduction at E1/2 = –2.18 V and exhibits two overlapping reversible oxidations at E1/2 = –0.08 V and E1/2 = 0.04 V. DFT calculations show that while the HOMO is metal-centred (Fe-Fe -bonding), the LUMO is primarily ligand-based but also contains an antibonding Fe-Fe contribution, highlighting the redox-active nature of the diphosphine. It is readily protonated upon addition of strong acids to afford two isomeric hydride complexes and catalyzes the electrochemical reduction of protons at Ep = –2.00 V in the presence of CF3CO2H. The catalytic current indicates that it is one of the most efficient diiron electrocatalysts for the reduction of protons, albeit operating at quite negative potential.

Cariogenic oral biofilms cause a considerable amount of recurrent dental caries around composite restorations every year, resulting in unprosperous oral health status and expensive restorative treatment for many patients. Quaternary ammonium monomers that can be copolymerized with the current dental resin systems have been increasingly explored for modulation of dental plaque biofilm growth over dental composite surfaces. Here, we investigated the effect of bis(2-methacryloyloxyethyl) dimethylammonium bromide (QADM), against human overlying mature oral biofilms grown intra-orally in human participants for 7 and 14 days, for the first time. Seventeen volunteers wore palatal devices containing composite specimens containing 10% by mass of QADM or a control composite without QADM. After 7 and 14 days, the adherent biofilms were collected for determination of bacterial counts via colony-forming unit (CFU) counts. The biofilm viability, chronological changes, and percentage coverage were also determined by live/dead staining. QADM composites caused a significant inhibition of S. mutans biofilm formation for up to seven days. No difference in the CFU values were found for the 14-day period. Our findings suggest that (1) QADM composite was successful in inhibiting 1-3 day biofilms in the oral environment in vivo; (2) QADM significantly reduced the portion of S.mutans group in a time course where patients at high risk of caries would develop initial enamel carious lesions; and (3) stronger antibiofilm activity is required for the control of mature long-term cariogenic biofilms. These results provide a perspective on the value of integrating bioactive restorative materials with traditional caries management approaches into clinical practice. Contact-killing strategies via dental materials aiming to prevent or at least reduce high numbers of cariogenic bacteria seem to be a promising approach in patients at high risk of recurrence of dental caries around composites.

In the present study, the potential of ethylene as ethephon (an ethylene source) was investigated individually or with a combination of the split dosage of nitrogen (N) and sulfur (S) soil treatments for the removal of damaging effects of salt stress (100 mM NaCl) in mustard (Brassica juncea L.). Plants were grown with 50 mg N plus 50 mg S kg−1 soil at sowing time and an equivalent dosage at 20 days after sowing ([N50 + S50]0d + [N50 + S50]20d). Ethephon at 200 μL L‒1 was applied to combined split dosage of N and S with or without NaCl. Plants subjected to NaCl showed a deceased in growth and photosynthetic characteristics as well as N and S assimilation, though, proline metabolism and antioxidants increased. The application of ethephon to plants grown with split N and S dosages significantly enhanced the photosynthetic efficiency by increasing the assimilation of N and S, improving the content of proline and induction of the antioxidant system with or without NaCl. The regulation of ethylene and/or split form N and S application may be the potential tools for overcoming salt stress effects in this species and in related Brassicaceae.

New [1,2]dithiolo[3,4-b]pyridine-5-carboxamides were synthesized through the reaction of dithiomalondianilide (N,N'-diphenyldithiomalondiamide) with 3-aryl-2-cyanoacrylamides or by a three-component reaction involving aromatic aldehydes, cyanoacetamide and dithiomalon- dianilide in the presence of morpholine. The structure of 6-amino-4-(2,4-dichlorophenyl)- 7-phenyl-3-(phenylimino)-4,7-dihydro-3H-[1,2]dithiolo[3,4-b]pyridine-5-carboxamide was con-firmed using X-ray crystallography. To understand the reaction mechanism in detail, density functional theory (DFT) calculations were performed with a Grimme B97-3c composite computa-tional scheme. The results revealed that the rate limiting step is a cyclization process leading to the closure of 1,4-dihydropyridine ring with an activation barrier of 28.8 kcal/mol. Some of dithiolo[3,4-b]pyridines exhibited moderate herbicide safening effects against 2,4-D . Additional-ly, ADMET parameters were calculated and molecular docking studies were performed to identify potential protein targets.

2-(Morpholin-4-yl)-4,5-bis(2’’,2’’,2’’-trinitroethoxy)-1,3,5-triazine having QSAR-predicted anti-tumor activity was tested for the cytotoxicity using MTT and LDH cell viability tests. The experiments were conducted using human fibroblasts, peripheral blood mononuclear cells and breast cancer cells and allowed to identify effective cytotoxic concentration ant therapeutic range of this compound. The data obtained suggest the feasibility of the further studies of the test compound as a potential anti-cancer agent.

Ethylene Oxide (EtO) is a colorless, flammable gas at room temperature, produced by the catalytic oxidation of ethylene. EtO is widely used by medical sterilization facilities to clean medical supplies and equipment. Recent epidemiological studies showed that EtO is a more potent carcinogen than previously documented, leading the Environmental Protection Agency (EPA) to update, in December 2016, the inhalation unit risk estimate for EtO. This resulted in the identification of EtO as a potential health concern in several areas across the US, including the state of Utah. The geography surrounding Salt Lake Valley creates a bowl; ideal for collecting air pollution emissions. The region often experiences inversion episodes which inhibit vertical mixing and cause an accumulation of air pollutants, leading to unhealthy pollution levels. Using the EPA's dispersion modeling software, AERMOD, this study estimated EtO concentrations through facility stack and fugitive emissions modeling results. These values were compared with those of canister-based concentrations from ambient air samples taken near a medical device sterilization facility in the Salt Lake Valley. Stainless steel, whole-air passivated canisters were used to collect 24-hour ambient concentration samples of EtO. Eight locations surrounding a Salt Lake Valley medical device sterilization facility and four background sites were chosen to measure the ambient concentrations. Accounting for potential atmospheric impacts on EtO, measurements were sampled in winter 2022 (January-March) and summer 2022 (July-September). The modeled EtO concentrations were adjusted to account for background values associated with the winter or summer data. Then the two methodologies were compared using a Wilcoxon Sign-ranked, paired test. The statistical analysis resulted in six of the eight sample locations surrounding the sterilization facility being significantly different when comparing canister-based measurements of ambient EtO to modeled estimates. Canister-based measurements taken at sites one, three, and four were statistically greater than the modeled estimates, while sites two, five, and seven were statistically less than the modeled estimates. Also, the summer background value calculated was almost 2.5 times greater than the winter. The results do not suggest whether one method is more or less conservative than the other. In conclusion, the five of the closest sites and site seven were statistically different when comparing measured and modeled ambient concentrations of EtO. The comparison results do not clearly indicate if a correction factor could be derived for future human exposure to cancer risk assessment modeling. However, it is reasonable that the closer to the sterilization facility, the more total EtO exposure will be realized.

We report on the successful preparation of wet dressings hydrogels based on Chitosan-Poly(N-Vinyl-Pyrrolidone)-Poly(ethylene glycol)-Poly(acrylic acid) and Poly(ethylene oxide) by e-beam cross-linking in weakly acidic media, to be used for rapid healing and pain release of infected skin wounds. The structure and compositions of hydrogels investigated according to sol-gel and swelling studies, network parameters, as well as FTIR and XPS analyses showed the efficient interaction of the hydrogel components upon irradiation, maintaining the bonding environment while the cross-linking degree increasing with the irradiation dose and the formation of a structure with the mesh size in the range 11-67 nm. Hydrogels with gel fraction above 85% and the best-swelling properties in different pH solutions were obtained for hydrogels produced with 15 kGy. The hydrogels are stable in the simulated physiological condition of an infected wound and show appropriate moisture retention capability and the water vapor transmission rate up to 272.67 g m-2 day-1, to ensure fast healing. The hydrogels proved to have a significant loading capacity of ibuprofen (IBU), being able to incorporate a therapeutic dose for the treatment of severe pains. Simultaneously, IBU was released up to 25% in the first 2h, having a release maximum after 8h.

Excessive CO₂ emissions and alternative energy fuels are two major difficult issues. The utilization of CO₂ into fine chemicals is an optimal route. Diethyl carbonate (DEC) is an extremely versatile chemical intermediate. DEC is used in gasoline, pharmaceutical, chemical and other fields. DEC synthesis from CO₂ and ethanol is a typical green synthetic route. Ni-Cu@Na₃PW₁₂O₄₀ catalysts were synthesized by two novel methods of supported and mixed. The catalyst prepared by mixed method showed nice catalytic performance. It was confirmed that water removal was the key to improving conversion efficiency. In the presence of dehydrating agent of ethylene, ethanol conversion increased from ca. 3% to ca. 40%. Propylene oxide (PO) was participated in the reaction and ethanol conversion continued to reach to ca.90% while DEC selectivity dropped by half. Under optimal conditions, our Ni-Cu@Na₃PW₁₂O₄₀ catalyst effectively solved the two major issues above.

As a special class of “green” elastomers, thermoplastic vulcanizates (TPVs) have been widely used in industries due to the combination of the excellent resilience of conventional elastomers and the easy recyclability of thermoplastics. Here, the morphology evolution of TPVs based on polyamide 6/ethylene-propylene-diene rubber (PA6/EPDM) blends was investigated by varying the content of the curing agent, phenolic resin (PF). With the incorporation of 6 wt% PF, the gel content of the EPDM phase reaches a high value of 49.6wt% and a typical sea-island structure is formed with EPDM domain in a micro-nano size. The dynamic rheology behaviors of TPVs showed that with the curing degree of EPDM phase increasing, a denser network of EPDM particles is formed in PA6 matrix. Also, a lower crystal degree and crystal peak temperature are observed, indicating that the presence of a growth restriction of PA6 crystal plate induced by a thinner plastic layer between the adjacent EPDM particles. However, the crystal form of PA6 is not changed with the increasing curing degree of the EPDM phase. This study provides an effective strategy to realize a new kind of TPVs, which can be easily introduced into industrial applications.

Redox-flow batteries are rechargeable batteries that store energy in two liquid electrolytes, separated by a membrane. During charging and discharging, the electrolytes flow through the membrane and undergo chemical reactions that generate or consume electrical energy. These batteries are known for their scalability and long cycle life and are versatile energy storage technologies developed to enhance efficiency and lower costs. Deep Eutectic Solvents (DES) are eco-friendly alternatives to traditional electrolytes, and their properties have been studied to improve the performance of redox-flow batteries. We investigated choline chloride/ethylene glycol (ChlCl/Eg) mixtures with LiPF6 salt at four concentrations through experimental and MD simulations. The thermophysical and transport properties of the mixture, including density, diffusion coefficient, viscosity, and ionic conductivity, were calculated across a temperature range of 298.15–398.5 K. Our findings indicate that an increase in salt concentration leads to a decrease in diffusion coefficients and ionic conductivity, while increasing the viscosity of the deep eutectic solvent. This research provides valuable insights into the behavior of DES mixtures and can aid in the design and optimization of DES-based processes for use in redox-flow batteries.