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20 pages, 8046 KiB  
Article
Gelatin-Based Scaffolds with Carrageenan and Chitosan for Soft Tissue Regeneration
by Chiara Pasini, Federica Re, Federica Trenta, Domenico Russo and Luciana Sartore
Gels 2024, 10(7), 426; https://doi.org/10.3390/gels10070426 - 28 Jun 2024
Viewed by 329
Abstract
Motivated by the enormous potential of hydrogels in regenerative medicine, new biocompatible gelatin-based hybrid hydrogels were developed through a green process using poly(ethylene glycol) diglycidyl ether as a cross-linking agent, adding carrageenan and chitosan polysaccharides to the network to better mimic the hybrid [...] Read more.
Motivated by the enormous potential of hydrogels in regenerative medicine, new biocompatible gelatin-based hybrid hydrogels were developed through a green process using poly(ethylene glycol) diglycidyl ether as a cross-linking agent, adding carrageenan and chitosan polysaccharides to the network to better mimic the hybrid composition of native extracellular matrix. Overall, the hydrogels show suitable structural stability, high porosity and pore interconnectivity, good swellability, and finally, biocompatibility. Their mechanical behavior, investigated by tensile and compression tests, appears to be characterized by nonlinear elasticity with high compliance values, fast stress-relaxation, and good strain reversibility with no sign of mechanical failure for compressive loading–unloading cycles at relatively high deformation levels of 50%. Degradation tests confirm the hydrogel bioresorbability by gradual hydrolysis, during which the structural integrity of both materials is maintained, while their mechanical behavior becomes more and more compliant. Human Umbilical Cord-derived Mesenchymal Stem Cells (hUC-MSCs) were used to test the hydrogels as potential carriers for cell delivery in tissue engineering. hUC-MSCs cultured inside the hydrogels show a homogenous distribution and maintain their growth and viability for at least 21 days of culture, with an increasing proliferation trend. Hence, this study contributes to a further understanding of the potential use of hybrid hydrogels and hUC-MSCs for a wide range of biomedical applications, particularly in soft tissue engineering. Full article
(This article belongs to the Special Issue Design and Development of Gelatin-Based Materials)
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13 pages, 4557 KiB  
Article
Molecular Dynamics Simulation of Cumulative Microscopic Damage in a Thermosetting Polymer under Cyclic Loading
by Naoki Yamada, Mayu Morita, Maruri Takamura, Takahiro Murashima, Yutaka Oya and Jun Koyanagi
Polymers 2024, 16(13), 1813; https://doi.org/10.3390/polym16131813 - 26 Jun 2024
Viewed by 1183
Abstract
To develop durable composite materials, it is crucial to elucidate the correlation between nanoscale damage in thermosetting resins and the degradation of their mechanical properties. This study aims to investigate this correlation by performing cyclic loading tests on the cross-linked structure of diglycidyl [...] Read more.
To develop durable composite materials, it is crucial to elucidate the correlation between nanoscale damage in thermosetting resins and the degradation of their mechanical properties. This study aims to investigate this correlation by performing cyclic loading tests on the cross-linked structure of diglycidyl ether bisphenol A (DGEBA) and 4,4′-diaminodiphenyl sulfone (44-DDS) using all-atom molecular dynamics (MD) simulations. To accurately represent the nanoscale damage in MD simulations, a bond dissociation algorithm based on interatomic distance criteria is applied, and three characteristics are used to quantify the microscopic damage: stress–strain curves, entropy generation, and the formation of voids. As a result, the number of covalent bond dissociations increases with both the cyclic loading and its amplitude, resulting in higher entropy generation and void formation, causing the material to exhibit inelastic behavior. Furthermore, our findings indicate the occurrence of a microscopic degradation process in the cross-linked polymer: Initially, covalent bonds align with the direction of the applied load. Subsequently, tensioned covalent bonds sequentially break, resulting in significant void formation. Consequently, the stress–strain curves exhibit nonlinear and inelastic behavior. Although our MD simulations employ straightforward criteria for covalent bond dissociation, they unveil a distinct correlation between the number of bond dissociations and microscale damage. Enhancing the algorithm holds promise for yielding more precise predictions of material degradation processes. Full article
(This article belongs to the Section Polymer Composites and Nanocomposites)
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17 pages, 2807 KiB  
Article
Enhancing Oil–Water Separation Efficiency with WO3/MXene Composite Membrane
by Abdelfattah Amari, Haitham Osman, Mohamed Boujelbene, Maha Khalid Abdulameer, Miklas Scholz and Saad Sh. Sammen
Water 2024, 16(13), 1767; https://doi.org/10.3390/w16131767 - 21 Jun 2024
Viewed by 527
Abstract
In this study, a novel method for the high-performance treatment of oily wastewater was introduced using a tungsten (VI) oxide (WO3)/MXene composite membrane based on poly (arylene ether sulfone) (PAES). Composite membranes were fabricated with superhydrophilic (SH) and superoleophobic (SO) characteristics, [...] Read more.
In this study, a novel method for the high-performance treatment of oily wastewater was introduced using a tungsten (VI) oxide (WO3)/MXene composite membrane based on poly (arylene ether sulfone) (PAES). Composite membranes were fabricated with superhydrophilic (SH) and superoleophobic (SO) characteristics, which allow for the high-performance treatment of oily wastewater. The fabricated composite membrane can also photodegrade organic types of pollutants with just a short period of UV, enabling self-cleaning and anti-fouling properties. Moreover, the comprehensive characterization of the composite membrane through FTIR, SEM, and XRD analyses yielded valuable insights. The FTIR analysis revealed the characteristic peaks of WO3, MXene, PAES, and the synthesized composite membrane, providing essential information on the chemical composition and properties of the materials. The XRD results demonstrated the crystal structures of WO3, MXene, PAES, and the synthesized composite membrane, further enhancing our understanding of the composite membrane. Additionally, the SEM images illustrated the surface and cross-section of the fabricated membranes, highlighting the differences in pore size and porosity between the PAES membrane and the WO3–MXene composite membrane, which directly impact permeate flux. The study showed that the composite membrane had a remarkable recovery time of only 0.25 h, and the efficiency of the separation process and water flux recovered to 99.98% and 6.4 L/m2.h, respectively. The joint influence of WO3 and MXene on composite membranes degraded contaminants into non-polluting substances after sunlight irradiation. This process effectively solves the treatment performance and decrease in permeate flux caused by contamination. The technology is membrane-based filtration, which is a simple and advanced method for treating polluted water. This innovative work offers promising solutions to address water pollution challenges and holds potential for practical applications from a self-cleaning and anti-fouling point of view. Full article
(This article belongs to the Special Issue Wastewater Treatment by Membrane)
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15 pages, 8596 KiB  
Article
Influence of Surfactant Types on the Anti-Corrosion Performance of Phosphate Chemical Conversion Coated Mg-8wt.%Li Alloy
by Liji Cui, Baojie Wang, Jiyu Hou, Daokui Xu and Jie Sun
Coatings 2024, 14(5), 641; https://doi.org/10.3390/coatings14050641 - 18 May 2024
Viewed by 800
Abstract
In this work, the morphology, anti-corrosion performance and degradation mechanisms of two phosphate chemical conversion coatings containing the AEO (fatty alcohol polyoxyethylene ether) and AES (fatty alcohol polyoxyethylene ether sodium sulfate) on an as-cast Mg-8wt.%Li alloy were explored and compared. Although two coating [...] Read more.
In this work, the morphology, anti-corrosion performance and degradation mechanisms of two phosphate chemical conversion coatings containing the AEO (fatty alcohol polyoxyethylene ether) and AES (fatty alcohol polyoxyethylene ether sodium sulfate) on an as-cast Mg-8wt.%Li alloy were explored and compared. Although two coating layers had a petal-shaped structure and were composed of leaf-shaped particles, the coating layer of the AES-coated sample was relatively dense due to the smaller size of the formed petal-shaped structure. Based on the electrochemical data and hydrogen evolution measurements, the corrosion protectability of the coating layer on the AES-coated sample was better than that on the AEO-coated sample. The determined corrosion current densities (icorr) of the AES-coated and AEO-coated samples in the 3.5 wt.% NaCl solution were, respectively, 7.8 mA·cm−2 and 11.7 mA·cm−2, whereas the icorr value of the coated sample without a surfactant was 36.2 mA·cm−2. Full article
(This article belongs to the Special Issue Environmental Corrosion of Metals and Its Prevention)
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18 pages, 2427 KiB  
Article
Anatomical and Metabolome Features of Haloxylon aphyllum and Haloxylon persicum Elucidate the Resilience against Gall-Forming Insects
by Nina V. Terletskaya, Aigerim Mamirova, Kazhybek Ashimuly, Yekaterina P. Vibe and Yana A. Krekova
Int. J. Mol. Sci. 2024, 25(9), 4738; https://doi.org/10.3390/ijms25094738 - 26 Apr 2024
Viewed by 694
Abstract
Globally, gall-forming insects significantly contribute to the degradation of desert ecosystems. Recent studies have demonstrated that Haloxylon persicum suffers less damage from gall-formers compared to Haloxylon aphyllum. However, the mechanisms driving the long-term metabolic responses of these species to gall-forming biotic stress [...] Read more.
Globally, gall-forming insects significantly contribute to the degradation of desert ecosystems. Recent studies have demonstrated that Haloxylon persicum suffers less damage from gall-formers compared to Haloxylon aphyllum. However, the mechanisms driving the long-term metabolic responses of these species to gall-forming biotic stress in their natural environment remain unclear. The current study comparatively analyzes the anatomical features and metabolomic changes in H. aphyllum and H. persicum damaged by gall-forming insects. This research aimed to uncover potential metabolic tolerance mechanisms through GC-MS analysis. The study findings indicate that gall-forming insects cause a reduction in nearly all the anatomical structures of Haloxylon shoots, with the effects being less severe in H. persicum than in H. aphyllum. Thus, the metabolic pathways responsible for the biosynthesis of biologically active substances that enhance resistance to gall inducers were different, specifically in H. aphyllum—the biosynthesis of fatty acids (+their derivatives) and γ-tocopherol (vitamin E) and H. persicum—the biosynthesis of fatty acids (+their derivatives), dialkyl ethers, carbohydrates (+their derivatives), aromatic acid derivatives, phytosterols, γ-tocopherol (vitamin E), phenols, and terpenoids. The results suggest that the modulation of metabolic pathways under biotic stress plays a crucial role in the enhanced survival and growth of H. persicum. Full article
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23 pages, 9874 KiB  
Article
Exploring Sustainable Coating Solutions for Applications in Highly Corrosive Environments
by Ana Suárez-Vega, Gemma Berriozabal, Aiala Urbegain, Daniela Minudri, Anthony Somers, Maria Forsyth, Raúl Caracena and Nevena Marinova
Coatings 2024, 14(5), 521; https://doi.org/10.3390/coatings14050521 - 24 Apr 2024
Viewed by 878
Abstract
To protect carbon steel from degradation via corrosion, it is usually coated using a multilayer system of paints composed of petroleum-based polymers. The chemical industry is currently moving towards more sustainable chemistry, in which one of the main objectives is to reduce fossil [...] Read more.
To protect carbon steel from degradation via corrosion, it is usually coated using a multilayer system of paints composed of petroleum-based polymers. The chemical industry is currently moving towards more sustainable chemistry, in which one of the main objectives is to reduce fossil fuel use and the derived raw materials. However, the replacement of petroleum-based raw materials with those that are bio-based is not straightforward since the properties of these new materials are often inferior to the traditional ones. One of the most used resins in primer paints is Diglycidyl ether bisphenol A (DGEBA). This is an epoxy resin synthesized from bisphenol A (BPA), a toxic and carcinogenic petroleum-based compound. This study investigates the substitution of the primer coating in a three-layer coating system with two different types of primer coating formulations, one which is partially bio-based and another that is BPA-free. The corrosion protection effectiveness of these sustainable coatings is assessed not only at the laboratory scale but also in real offshore conditions. Moreover, the adhesion of the different coating systems is evaluated before and after each ageing test. The results reveal that these novel coatings exhibit comparable performance to conventional paints while providing a more sustainable corrosion protection alternative. Full article
(This article belongs to the Special Issue Advanced Anticorrosion Coatings and Coating Testing)
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14 pages, 1631 KiB  
Article
Evaluation of Dynamic Changes of Volatile Organic Components for Fishmeal during Storage by HS-SPME-GC-MS with PLS-DA
by Jie Geng, Qing Cao, Shanchen Jiang, Jixuan Huangfu, Weixia Wang and Zhiyou Niu
Foods 2024, 13(9), 1290; https://doi.org/10.3390/foods13091290 - 23 Apr 2024
Viewed by 672
Abstract
Headspace solid-phase microextraction, combined with gas chromatography–mass spectrometry and partial least squares discriminant analysis, was adopted to study the rule of change in volatile organic compounds (VOCs) for domestic and imported fishmeal during storage with different freshness grades. The results showed that 318 [...] Read more.
Headspace solid-phase microextraction, combined with gas chromatography–mass spectrometry and partial least squares discriminant analysis, was adopted to study the rule of change in volatile organic compounds (VOCs) for domestic and imported fishmeal during storage with different freshness grades. The results showed that 318 kinds of VOCs were detected in domestic fishmeal, while 194 VOCs were detected in imported fishmeal. The total relative content of VOCs increased with storage time, among which acids and nitrogen-containing compounds increased significantly, esters and ketones increased slightly, and phenolic and ether compounds were detected only in domestic fishmeal. Regarding the volatile base nitrogen, acid value, pH value, and mold counts as freshness indexes, the freshness indexes were significantly correlated with nine kinds of VOCs (p < 0.05) through the correlation analysis. Among them, volatile base nitrogen had a significant correlation with VOCs containing nitrogen, acid value with VOCs containing carboxyl group and hydrocarbons, pH value with acids which could be used to adjust pH value, and mold counts with part of acids adjusting pH value and VOCs containing nitrogen. Due to the fact that the value of all freshness indexes increased with freshness degradation during storage, based on volatile base nitrogen and acid value, the fishmeal was divided into three freshness grades, superior freshness, corrupting, and completely corrupted. By using partial least squares discriminant analysis, this study revealed the differences in flavor of the domestic and imported fishmeal during storage with different freshness grades, and it identified four common characteristic VOCs, namely ethoxyquinoline, 6,7,8,9-tetrahydro-3H-benzo[e]indole-1,2-dione, hexadecanoic acid, and heptadecane, produced by the fishmeal samples during storage, as well as the characteristic VOCs of fishmeal at each freshness grade. Full article
(This article belongs to the Section Food Analytical Methods)
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15 pages, 2110 KiB  
Article
Water-Insoluble, Thermostable, Crosslinked Gelatin Matrix for Soft Tissue Implant Development
by Viktória Varga, László Smeller, Róbert Várdai, Bence Kocsis, Ibolya Zsoldos, Sara Cruciani, Renzo Pala and István Hornyák
Int. J. Mol. Sci. 2024, 25(8), 4336; https://doi.org/10.3390/ijms25084336 - 14 Apr 2024
Viewed by 1227
Abstract
In this present study, the material science background of crosslinked gelatin (GEL) was investigated. The aim was to assess the optimal reaction parameters for the production of a water-insoluble crosslinked gelatin matrix suitable for heat sterilization. Matrices were subjected to enzymatic degradation assessments, [...] Read more.
In this present study, the material science background of crosslinked gelatin (GEL) was investigated. The aim was to assess the optimal reaction parameters for the production of a water-insoluble crosslinked gelatin matrix suitable for heat sterilization. Matrices were subjected to enzymatic degradation assessments, and their ability to withstand heat sterilization was evaluated. The impact of different crosslinkers on matrix properties was analyzed. It was found that matrices crosslinked with butanediol diglycidyl ether (BDDE) and poly(ethylene glycol) diglycidyl ether (PEGDE) were resistant to enzymatic degradation and heat sterilization. Additionally, at 1 v/v % crosslinker concentration, the crosslinked weight was lower than the starting weight, suggesting simultaneous degradation and crosslinking. The crosslinked weight and swelling ratio were optimal in the case of the matrices that were crosslinked with 3% and 5% v/v BDDE and PEGDE. FTIR analysis confirmed crosslinking, and the reduction of free primary amino groups indicated effective crosslinking even at a 1% v/v crosslinker concentration. Moreover, stress–strain and compression characteristics of the 5% v/v BDDE crosslinked matrix were comparable to native gelatin. Based on material science measurements, the crosslinked matrices may be promising candidates for scaffold development, including properties such as resistance to enzymatic degradation and heat sterilization. Full article
(This article belongs to the Special Issue Application of Biomolecular Materials in Tissue Engineering)
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16 pages, 6797 KiB  
Article
Structure and Properties of Exopolysaccharide Produced by Gluconobacter frateurii and Its Potential Applications
by Yingying Ning, Huiying Cao, Shouqi Zhao, Dongni Gao and Dan Zhao
Polymers 2024, 16(7), 1004; https://doi.org/10.3390/polym16071004 - 7 Apr 2024
Viewed by 752
Abstract
An exopolysaccharide (EPS)-producing bacterium was isolated from apricot fermentation broth and identified as Gluconobacter frateurii HDC-08 (accession number: OK036475.1). HDC-08 EPS is a linear homopolysaccharide mainly composed of glucose linked by α-(1,6) glucoside bonds. It contains C, H, N and S elements, with [...] Read more.
An exopolysaccharide (EPS)-producing bacterium was isolated from apricot fermentation broth and identified as Gluconobacter frateurii HDC-08 (accession number: OK036475.1). HDC-08 EPS is a linear homopolysaccharide mainly composed of glucose linked by α-(1,6) glucoside bonds. It contains C, H, N and S elements, with a molecular weight of 4.774 × 106 Da. Microscopically, it has a smooth, glossy and compact sheet structure. It is an amorphous noncrystalline substance with irregular coils. Moreover, the EPS showed surface hydrophobicity and high thermal stability with a degradation temperature of 250.76 °C. In addition, it had strong antioxidant properties against DPPH radicals, ABPS radicals, hydroxyl radicals and H2O2. The EPS exhibited high metal-chelating activity and strong emulsifying ability for soybean oil, petroleum ether and diesel oil. The milk solidification test indicated that the EPS had good potential in fermented dairy products. In general, all the results demonstrate that HDC-08 EPS has promise for commercial applications as a food additive and antioxidant. Full article
(This article belongs to the Special Issue Advances in Natural Polysaccharides: Function and Application)
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19 pages, 6328 KiB  
Review
Poly(silyl ether)s as Degradable and Sustainable Materials: Synthesis and Applications
by Vladimir Zotov, Srikanth Vijjamarri, Seyed-Danial Mousavi and Guodong Du
Molecules 2024, 29(7), 1498; https://doi.org/10.3390/molecules29071498 - 27 Mar 2024
Viewed by 990
Abstract
Polymer research is currently focused on sustainable and degradable polymers which are cheap, easy to synthesize, and environmentally friendly. Silicon-based polymers are thermally stable and can be utilized in various applications, such as columns and coatings. Poly(silyl ether)s (PSEs) are an interesting class [...] Read more.
Polymer research is currently focused on sustainable and degradable polymers which are cheap, easy to synthesize, and environmentally friendly. Silicon-based polymers are thermally stable and can be utilized in various applications, such as columns and coatings. Poly(silyl ether)s (PSEs) are an interesting class of silicon-based polymers that are easily hydrolyzed in either acidic or basic conditions due to the presence of the silyl ether Si-O-C bond. Synthetically, these polymers can be formed in several different ways, and the most effective and environmentally friendly synthesis is dehydrogenative cross coupling, where the byproduct is H2 gas. These polymers have a lot of promise in the polymeric materials field due to their sustainability, thermal stability, hydrolytic degradability, and ease of synthesis, with nontoxic byproducts. In this review, we will summarize the synthetic approaches for the PSEs in the recent literature, followed by the properties and applications of these materials. A conclusion and perspective will be provided at the end. Full article
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13 pages, 5312 KiB  
Article
The Thermo-Mechanical Properties of Carbon-Fiber-Reinforced Polymer Composites Exposed to a Low Earth Orbit Environment
by Kiho Nishihara, Kei-ichi Okuyama, Rafael Rodriguez and Isai Fajardo
Aerospace 2024, 11(3), 201; https://doi.org/10.3390/aerospace11030201 - 2 Mar 2024
Viewed by 1429
Abstract
In this study, we focus on 3D-printed PEEK/CFRTP (Carbon-Fiber-Reinforced Thermoplastic) and PEEK (Polyether Ether Ketone) materials as new space materials. In space, there are intense ultraviolet (UV) rays that are weakened by the atmosphere on Earth, so it is essential to understand the [...] Read more.
In this study, we focus on 3D-printed PEEK/CFRTP (Carbon-Fiber-Reinforced Thermoplastic) and PEEK (Polyether Ether Ketone) materials as new space materials. In space, there are intense ultraviolet (UV) rays that are weakened by the atmosphere on Earth, so it is essential to understand the degradation of materials due to UV rays in advance. Therefore, we developed a materials science experiment called the Material Mission, which will be carried out on board Ten-Koh 2. This mission measures the coefficient of thermal expansion (CTE) of the CFRTP samples and the PEEK samples in LEO without recovery. So, we developed a thermal expansion observation system to be installed on the Ten-Koh 2 satellite. In addition, UV irradiation tests simulating the UV environment in LEO were conducted as ground tests. From the results of the ground tests, it was possible to determine in advance the degree of degradation of each material in the UV environment, even up to 100 ESD. By utilizing these results in mission operations, more meaningful measurement results can be obtained, and this mission development can contribute greatly to developing new space materials in the future. Full article
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21 pages, 5699 KiB  
Article
High-Performance PEEK/MWCNT Nanocomposites: Combining Enhanced Electrical Conductivity and Nanotube Dispersion
by Sofia Silva, José M. Barbosa, João D. Sousa, Maria C. Paiva and Paulo F. Teixeira
Polymers 2024, 16(5), 583; https://doi.org/10.3390/polym16050583 - 21 Feb 2024
Viewed by 1142
Abstract
High-performance engineering thermoplastics offer lightweight and excellent mechanical performance in a wide temperature range. Their composites with carbon nanotubes are expected to enhance mechanical performance, while providing thermal and electrical conductivity. These are interesting attributes that may endow additional functionalities to the nanocomposites. [...] Read more.
High-performance engineering thermoplastics offer lightweight and excellent mechanical performance in a wide temperature range. Their composites with carbon nanotubes are expected to enhance mechanical performance, while providing thermal and electrical conductivity. These are interesting attributes that may endow additional functionalities to the nanocomposites. The present work investigates the optimal conditions to prepare polyether ether ketone (PEEK)/multi-walled carbon nanotube (MWCNT) nanocomposites, minimizing the MWCNT agglomerate size while maximizing the nanocomposite electrical conductivity. The aim is to achieve PEEK/MWCNT nanocomposites that are suitable for melt-spinning of electrically conductive multifilament’s. Nanocomposites were prepared with compositions ranging from 0.5 to 7 wt.% MWCNT, showing an electrical percolation threshold between 1 and 2 wt.% MWCNT (107–102 S/cm) and a rheological percolation in the same range (1 to 2 wt.% MWCNT), confirming the formation of an MWCNT network in the nanocomposite. Considering the large drop in electrical conductivity typically observed during melt-spinning and the drawing of filaments, the composition PEEK/5 wt.% MWCNT was selected for further investigation. The effect of the melt extrusion parameters, namely screw speed, temperature, and throughput, was studied by evaluating the morphology of MWCNT agglomerates, the nanocomposite rheology, and electrical properties. It was observed that the combination of the higher values of screw speed and temperature profile leads to the smaller number of MWCNT agglomerates with smaller size, albeit at a slightly lower electrical conductivity. Generally, all processing conditions tested yielded nanocomposites with electrical conductivity in the range of 0.50–0.85 S/cm. The nanocomposite processed at higher temperature and screw speed presented the lowest value of elastic modulus, perhaps owing to higher matrix degradation and lower connectivity between the agglomerates. From all the process parameters studied, the screw speed was identified to have the higher impact on nanocomposite properties. Full article
(This article belongs to the Special Issue Carbon-Integrated Polymer Composites and Foams II)
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17 pages, 4728 KiB  
Article
Stability and Reactivity of Guaiacylglycerol-β-Guaiacyl Ether, a Compound Modeling β-O-4 Linkage in Lignin
by Zeinab Rabiei, Andrew Simons, Magdalena Folkmanova, Tereza Vesela, Ondrej Uhlik, Evguenii Kozliak and Alena Kubátová
Separations 2024, 11(2), 59; https://doi.org/10.3390/separations11020059 - 14 Feb 2024
Viewed by 1380
Abstract
Lignin, a complex and abundant biopolymer, is a major constituent of plant cell walls. Due to its chemical and structural complexity, lignin degradation is a challenging task for both natural and engineered systems. Therefore, investigation of lignin degradation using so called “model compounds” [...] Read more.
Lignin, a complex and abundant biopolymer, is a major constituent of plant cell walls. Due to its chemical and structural complexity, lignin degradation is a challenging task for both natural and engineered systems. Therefore, investigation of lignin degradation using so called “model compounds” has been the focus of many research efforts in recent years. This study addresses the utility of guaiacylglycerol-β-guaiacyl ether (Gβ2) as a model compound for evaluating the β-O-4 bond cleavage under diverse thermal and aqueous medium conditions. Experimental conditions included varied pH (3–10), microbial biodegradation, subcritical water environment (150–250 °C), and mild pyrolysis (150–250 °C). A high-performance liquid chromatography with high-resolution mass spectrometry was employed for accurate detection and quantification of both Gβ2 and its degradation/modification products in an aqueous environment. Pyrolysis experiments were performed using gas chromatography-mass spectrometry analysis with a pyrolyzer. The results showed that Gβ2 remained stable under exposure to moderate pH and several bacterial strains, which were successfully used previously for biodegradation of other recalcitrant pollutants. We report, for the first time, differing Gβ2 breakdown pathways for subcritical water treatment vs. pyrolysis under an inert atmosphere. The scientific novelty lies in the presentation of differences in the degradation pathways of Gβ2 during subcritical water treatment compared to pyrolysis in an inert atmosphere, with water playing a key role. The observed differences are ascribed to the suppression of homolytic reactions by water as a solvent. Full article
(This article belongs to the Topic Advances in Chemistry and Chemical Engineering)
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15 pages, 2658 KiB  
Article
Cell Staining Microgels Derived from a Natural Phenolic Dye: Hematoxylin Has Intriguing Biomedical Potential
by Mehtap Sahiner, Aydin K. Sunol and Nurettin Sahiner
Pharmaceutics 2024, 16(1), 147; https://doi.org/10.3390/pharmaceutics16010147 - 22 Jan 2024
Viewed by 915
Abstract
Hematoxylin (HT) as a natural phenolic dye compound is generally used together with eosin (E) dye as H&E in the histological staining of tissues. Here, we report for the first time the polymeric particle preparation from HT as poly(Hematoxylin) ((p(HT)) microgels via microemulsion [...] Read more.
Hematoxylin (HT) as a natural phenolic dye compound is generally used together with eosin (E) dye as H&E in the histological staining of tissues. Here, we report for the first time the polymeric particle preparation from HT as poly(Hematoxylin) ((p(HT)) microgels via microemulsion method in a one-step using a benign crosslinker, glycerol diglycidyl ether (GDE). P(HT) microgels are about 10 µm and spherical in shape with a zeta potential value of −34.6 ± 2.8 mV and an isoelectric point (IEP) of pH 1.79. Interestingly, fluorescence properties of HT molecules were retained upon microgel formation, e.g., the fluorescence emission intensity of p(HT) at 343 nm was about 2.8 times less than that of the HT molecule at λex: 300 nm. P(HT) microgels are hydrolytically degradable and can be controlled by using an amount of crosslinker, GDE, e.g., about 40%, 20%, and 10% of p(HT) microgels was degraded in 15 days in aqueous environments for the microgels prepared at 100, 200, and 300% mole ratios of GDE to HT, respectively. Interestingly, HT molecules at 1000 mg/mL showed 22.7 + 0.4% cell viability whereas the p(HT) microgels exhibited a cell viability of 94.3 + 7.2% against fibroblast cells. Furthermore, even at 2000 mg/mL concentrations of HT and p(HT), the inhibition% of α-glucosidase enzyme were measured as 93.2 ± 0.3 and 81.3 ± 6.3%, respectively at a 0.03 unit/mL enzyme concentration, establishing some potential application of p(HT) microgels for neurogenerative diseases. Moreover, p(HT) microgels showed two times higher MBC values than HT molecules, e.g., 5.0 versus 2.5 mg/mL MIC values against Gram-negative E. coli and Gram-positive S. aureus, respectively. Full article
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16 pages, 2357 KiB  
Article
Dissipation, Residue and Human Dietary Risk Assessment of Pyraclostrobin and Cyazofamid in Grapes Using an HPLC-UV Detector
by Peiying Zhao, Rong Liu and Longfei Yuan
Foods 2024, 13(2), 314; https://doi.org/10.3390/foods13020314 - 18 Jan 2024
Viewed by 916
Abstract
Pyraclostrobin is a new broad-spectrum methoxyacrylic acid fungicide. Cyazofamid is a new selective foliar spray acaricide. Here, we studied the degradation rate and final residues of pyraclostrobin and cyazofamid in grape and evaluated their dietary risk to consumers. The average recoveries of pyraclostrobin [...] Read more.
Pyraclostrobin is a new broad-spectrum methoxyacrylic acid fungicide. Cyazofamid is a new selective foliar spray acaricide. Here, we studied the degradation rate and final residues of pyraclostrobin and cyazofamid in grape and evaluated their dietary risk to consumers. The average recoveries of pyraclostrobin ether ester, cyazofamid and cyazofamid metabolite (CCIM) in grapes were 84–94%, 92–98% and 99–104%, respectively. The relative standard deviations (RSDs) were 6.0–20.3%, 2.4–10.5% and 1.3–4.0%, respectively, and the LOQs were all 0.05 mg/kg. The digestion dynamics of the experimental sites were in accordance with the first-order kinetic equation. The degradation half-lives of pyraclostrobin ether ester and cyazofamid were 17.8 d–28.9 d and 4.3 d–7.8 d, respectively. The final residues of pyraclostrobin ether ester, cyazofamid and CCIM in grapes were <0.05–1.88 mg/kg, <0.05–0.31 mg/kg and <0.05–0.47 mg/kg, respectively. Using probability models, the total chronic risk values for pyraclostrobin and cyazofamid were calculated to be 0.112–189.617% and 0.021–1.714%, respectively. The results of the contribution analysis indicate that pyraclostrobin poses a much greater risk to Chinese consumers than cyazofamid, especially to children and adolescents, who have a significantly greater risk than adults. This suggests that more consideration should be given to the cumulative risk of compounds for vulnerable groups in the future. Full article
(This article belongs to the Special Issue Risk Assessment and Dietary Exposure of Hazardous Substances in Foods)
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