Towards carbon neutrality: Sustainable recycling and upcycling strategies and mechanisms for polyethylene terephthalate via biotic/abiotic pathways.

Polyethylene terephthalate (PET), one of the most ubiquitous engineering plastics, presents both environmental challenges and opportunities for carbon neutrality and a circular economy. This review comprehensively addressed the latest developments in biotic and abiotic approaches for PET recycling/upcycling. Biotically, microbial depolymerization of PET, along with the biosynthesis of reclaimed monomers [terephthalic acid (TPA), ethylene glycol (EG)] to value-added products, presents an alternative for managing PET waste and enables CO2 reduction. Abiotically, thermal treatments (i.e., hydrolysis, glycolysis, methanolysis, etc.) and photo/electrocatalysis, enabled by catalysis advances, can depolymerize or convert PET/PET monomers in a more flexible, simple, fast, and controllable manner. Tandem abiotic/biotic catalysis offers great potential for PET upcycling to generate commodity chemicals and alternative materials, ideally at lower energy inputs, greenhouse gas emissions, and costs, compared to virgin polymer fabrication. Remarkably, over 25 types of upgraded PET products (e.g., adipic acid, muconic acid, catechol, vanillin, and glycolic acid, etc.) have been identified, underscoring the potential of PET upcycling in diverse applications. Efforts can be made to develop chemo-catalytic depolymerization of PET, improve microbial depolymerization of PET (e.g., hydrolysis efficiency, enzymatic activity, thermal and pH level stability, etc.), as well as identify new microorganisms or hydrolases capable of degrading PET through computational and machine learning algorithms. Consequently, this review provides a roadmap for advancing PET recycling and upcycling technologies, which hold the potential to shape the future of PET waste management and contribute to the preservation of our ecosystems.

Liquid crystal monomers (LCMs) in indoor residential dust from Beijing, China: occurrence and human exposure.

Liquid crystal monomers (LCMs) are widely used in electronic devices and emerging as an environmental pollutant, while their occurrence in indoor environments is still less studied. In this study, 32 out of 37 target LCMs were detected in indoor residential dust samples (n = 112) from Beijing, China. Concentrations of Σ32LCMs ranged from 17.8 to 197 ng/g, with a median value of 54.7 ng/g. Fluorinated biphenyls and analogs (FBAs) and cyanobiphenyls and analogs (CBAs), with median concentrations of 22.8 and 15.9 ng/g, respectively, were the main kinds of LCMs. Although 32 LCMs can be detected, four monomers with the highest contamination levels contributed to almost 70% of the total LCMs. Spearman correlation analysis found significant correlations among some monomers, which indicated that they might share similar sources in the residential environment. Estimated daily intakes (EDIs) of LCMs via indoor dust for Beijing residents were calculated, and the results showed that dust ingestion and dermal contact were both main intake pathways to LCMs, and younger people may face higher exposure to LCMs. A comparison to the results of China's total diet study showed that EDIs of LCMs via food consumption might be higher than that via dust intake, while health risks caused by exposure of LCMs for the general population, both through food and dust, were insignificant at present.

Construction of Supramolecular Polymers and Covalent Polymers via the Same Monomers.

Nature owns the ability to construct structurally different polymers from the same monomers. While polymers can be classified as covalent polymers (CPs) and supramolecular polymers (SPs), it is still difficult to synthesize CPs and SPs using same monomers like nature do. Herein, M1 with two diazo salts on both the ends was designed. Additionally, hydroquinone was chosen to be M2 for the existence of two hydroxyl groups. When mixing at room temperature, M1 and M2 self-assembled to SPs via N…H hydrogen bonds. In another way, upon the exposure to ultraviolet irradiation when blending M1 with M2, CPs were fabricated in the presence of covalent bonds. The excellent thermal stability of CPs was determined by TGA and DSC, while the great corrosion resistance of covalent polymers was detected by acid or alkali immersion. In this way, constructing two kinds of polymers using the same monomers was successfully achieved. This shows tremendous potential in fields of polymer science, supramolecular chemistry, which would boom the development of polymers.

Revealing the variances in color formation and bioactivities of seven catechin monomers throughout the enzymatic reaction by colorimetric and mass spectrometry.

The capacity differences of seven catechin monomers to produce colors after treating with catechin-free extract were investigated. After 240-min reaction, only (-)-epicatechin (EC) and (+)-catechin (C) presented obvious luminous red color with L* values of 63.32-71.73, a* values of 37.13-46.44, and b* values of 65.64-69.99. Meanwhile, the decrease rate of EC and C was 43.52 %-50.35 %, which were significantly lower than those of other catechin monomers (85.91 %-100 %). The oxidized products of catechin monomers were analyzed by ultra-high performance liquid chromatography-quadrupole-time of flight-mass spectrometry coupled with diode array detector, wherein dehydro-dimers and -trimers (oxidative coupling products of catechins' A-B ring) were found to be the major chromogenic compounds of EC and C. Additionally, the antioxidant capacity of catechin monomers only decreased after 30-min reaction, while along with further enzymatic reaction, catechin monomers presented comparable oxyradical scavenging ability (e.g., the DPPH inhibitory rates of catechin monomers were in the range of 24.42 %-50.77 %) to vitamin C (positive control, DPPH inhibitory rate was 27.66 %). Meanwhile, the inhibitory effects of most catechin monomers on α-glucosidase were enhanced in different degrees. These results provided basis for the development of enzymatically-oxidized catechin monomers as functional food color additives.

Characterization of Microstructure, Optical Properties, and Mechanical Behavior of a Temporary 3D Printing Resin: Impact of Post-Curing Time.

The present study aimed to characterize the microstructure of a temporary 3D printing polymer-based composite material (Resilab Temp), evaluating its optical properties and mechanical behavior according to different post-curing times. For the analysis of the surface microstructure and establishment of the best printing pattern, samples in bar format following ISO 4049 (25 × 10 × 3 mm) were designed in CAD software (Rhinoceros 6.0), printed on a W3D printer (Wilcos), and light-cured in Anycubic Photon for different lengths of time (no post-curing, 16 min, 32 min, and 60 min). For the structural characterization, analyses were carried out using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The mechanical behavior of this polymer-based composite material was determined based on flexural strength tests and Knoop microhardness. Color and translucency analysis were performed using a spectrophotometer (VITA Easy Shade Advanced 4.0), which was then evaluated in CIELab, using gray, black, and white backgrounds. All analyses were performed immediately after making the samples and repeated after thermal aging over two thousand cycles (5-55 °C). The results obtained were statistically analyzed with a significance level of 5%. FT-IR analysis showed about a 46% degree of conversion on the surface and 37% in the center of the resin sample. The flexural strength was higher for the groups polymerized for 32 min and 1 h, while the Knoop microhardness did not show a statistical difference between the groups. Color and translucency analysis also did not show statistical differences between groups. According to all of the analyses carried out in this study, for the evaluated material, a post-polymerization time of 1 h should be suggested to improve the mechanical performance of 3D-printed devices.

Aquatic photolysis of high-risk fluorinated liquid crystal monomers: Kinetics, toxicity evaluation, and mechanisms.

Despite the frequent detection of fluorinated liquid-crystal monomers (FLCMs) in the environment, the level of understanding of their fate, toxicity, and transformation remains insufficient. Herein, we investigated the degradation kinetics and mechanism of an FLCM (4-cyano-3-fluorophenyl 4-ethylbenzoate, CEB-F) under ultraviolet (UV) photolysis in aquatic environment. Our findings demonstrated that the UV photolysis of CEB-F followed first-order kinetics. Photodegradation products were identified using liquid chromatography with mass spectrometry, and detailed reaction pathways were proposed. It is postulated that through the attack of reactive oxygen species, hydroxylation, and CO/C-F bond cleavage, CEB-F gradually degraded into small molecular compounds, releasing fluorine ions. Acute immobilization tests with Daphnia magna (D. magna) revealed significant acute toxicity of CEB-F, with LC50 values ranging from 1.023 to 0.0536 µM over 24 to 96 h, emphasizing the potential high risk of FLCMs in aquatic ecosystems if inadvertently discharged. Interestingly, we found that the toxicity of CEB-F photolysis reaction solutions was effectively reduced. Through catalase and acetylcholinesterase activities analysis along with molecular docking simulation, we proposed differences in the underlying toxicity mechanisms of CEB-F and its photolysis products to D. magna. These findings highlight the potential harmful effects of FLCMs on aquatic ecosystems and enrich our understanding of the photolysis behavior of FLCMs.

Acid-Catalyzed Activation and Condensation of the =C5H Bond of Furfural on Aldehydes, an Entry Point to Biobased Monomers.

Furfural is an industrially relevant biobased chemical platform. Unlike classical furan, or C-alkylated furans, which have been previously described in the current literature, the =C5H bond of furfural is unreactive. As a result, on a large scale, C=C and C=O bond hydrogenation/hydrogenolysis is mainly performed, with furfuryl alcohol and methyl tetrahydrofuran being the two main downstream chemicals. Here, we show that the derivatization of the -CHO group of furfural restores the reactivity of its =C5H bond, thus permitting its double condensation on various alkyl aldehydes. Overcoming the recalcitrance of the =C5H bond of furfural has opened an access to a biobased monomer, whose potential have been investigated in the fabrication of renewably-sourced poly(silylether). By means of a combined theoretical-experimental study, a reactivity scale for furfural and its protected derivatives against carbonylated compounds has been established using an electrophilicity descriptor, a means to predict the molecular diversity and complexity this pathway may support, and also to de-risk any project related to this topic. Finally, by using performance criteria for industrial operations in the field of fuels and commodities, we discussed the industrial potential of this work in terms of cost, E-factor, reactor productivity and catalyst consumption.

Review of the application of bimetallic catalysts coupled with internal hydrogen donor for catalytic hydrogenolysis of lignin to produce phenolic fine chemicals.

Lignocellulosic biomass contains lignin, an aromatic and oxygenated substance and a potential method for lignin utilization is achieved through catalytic conversion into useful phenolic and aromatic monomers. The application of monometallic catalysts for lignin hydrogenolysis reaction remains one of the major reasons for the underutilization of lignin to produce valuable chemicals. Monometallic catalysts have many limitations such as limited catalytic sites for interacting with different lignin linkages, poor catalytic activity, low lignin conversion, and low product selectivity. It is due to lack of synergy with other metallic catalysts that can enhance the catalytic activity, stability, selectivity, and overall catalytic performance. To overcome these limitations, works on the application of bimetallic catalysts that can offer higher activity, selectivity, and stability have been initiated. In this review, cutting-edge insights into the catalytic hydrogenolysis of lignin, focusing on the production of phenolic and aromatic monomers using bimetallic catalysts within an internal hydrogen donor solvent are discussed. The contribution of this work lies in a critical discussion of recent reported findings, in-depth analyses of reaction mechanisms, optimal conditions, and emerging trends in lignin catalytic hydrogenolysis. The specific effects of catalytic active components on the reaction outcomes are also explored. Additionally, this review extends beyond current knowledge, offering forward-looking suggestions for utilizing lignin as a raw material in the production of valuable products across various industrial processes. This work not only consolidates existing knowledge but also introduces novel perspectives, paving the way for future advancements in lignin utilization and catalytic processes.

Enzymatic synthesis of furan-based copolymers: Material characterization and potential for biomedical applications.

BACKGROUND: Today's growing demand for advanced and sustainable polyester materials is driven by an increasing awareness of the environmental impact of traditional materials, emphasizing the need for eco-friendly alternatives. Sustainability has become central in materials development, including the biomedical area, where biobased and environmentally friendly solutions are a rapidly growing field. OBJECTIVES: This research aims to comprehensively evaluate a new enzymatically catalyzed furan-based copolymer, poly(decamethylene furanoate)-co-(dilinoleic furanoate) (PDF-DLF), with a 70-30 wt% hard-to-soft segment ratio. Then, its performance across medical applications is explored, with a particular focus on its potential as a nanofibrous scaffolding material. MATERIAL AND METHODS: PDF-DLF was synthesized from biobased monomers using Candida antarctica lipase B (CAL-B) as the biocatalyst. Material characterization included dynamic mechan­ical thermal analysis (DMTA) to assess the mechanical behavior and thermal properties. Enzymatic degradation studies determined biodegradability, while cytotoxicity tests established in vitro biocompatibility. The copolymer was electrospun into nanofibers, with scanning electron microscopy (SEM) employed to analyze their morphology. RESULTS: PDF-DLF displays mechanical and thermal properties indicating high storage modulus and 2 main temperature transitions. Enzymatic degradation studies and cytotoxicity assessments confirm biodegradability and in vitro biocompatibility. Electrospinning successfully transformed the copolymer into nanofibers with diameters ranging from 500 nm to 700 nm. CONCLUSIONS: This study significantly advances our understanding of sustainable polyesters with versatile processing capabilities. The successful electrospinning highlights its potential as a biodegradable scaffold for medical engineering, supported by biocompatibility and sufficient mechanical properties. It opens new opportunities for sustainable materials in critical biomedical industries, including tissue engineering.

Selective production of phenolic monomer via catalytic depolymerization of lignin over cobalt-nickel-zirconium dioxide catalyst.

The utilization of lignin, an abundant and renewable bio-aromatic source, is of significant importance. In this study, lignin oxidation was examined at different temperatures with zirconium oxide (ZrO2)-supported nickel (Ni), cobalt (Co) and bimetallic Ni-Co metal catalysts under different solvents and oxygen pressure. Non-catalytic oxidation reaction produced maximum bio-oil (35.3 wt%), while catalytic oxidation significantly increased the bio-oil yield. The bimetallic catalyst Ni-Co/ZrO2 produced the highest bio-oil yield (67.4 wt%) compared to the monometallic catalyst Ni/ZrO2 (59.3 wt%) and Co/ZrO2 (54.0 wt%). The selectively higher percentage of vanillin, 2-methoxy phenol, acetovanillone, acetosyringone and vanillic acid compounds are found in the catalytic bio-oil. Moreover, it has been observed that the bimetallic Co-Ni/ZrO2 produced a higher amount of vanillin (43.7% and 13.30 wt%) compound. These results demonstrate that the bimetallic Ni-Co/ZrO2 catalyst promotes the selective cleavage of the ether ß-O-4 bond in lignin, leading to a higher yield of phenolic monomer compounds.

Recent advances of novel targeted drug delivery systems based on natural medicine monomers against hepatocellular carcinoma.

Hepatocellular carcinoma (HCC), the most prevalent type of liver cancer, is often diagnosed at an advanced stage. Surgical interventions are often ineffective, leading HCC patients to rely on systemic chemotherapy. Unfortunately, commonly used chemotherapeutic drugs have limited efficacy and can adversely affect vital organs, causing significant physical and psychological distress for patients. Natural medicine monomers (NMMs) have shown promising efficacy and safety profiles in HCC treatment, garnering attention from researchers. In recent years, the development of novel targeted drug delivery systems (TDDS) combining NMMs with nanocarriers has emerged. These TDDS aim to concentrate drugs effectively in HCC cells by manipulating the characteristics of nanomedicines, leveraging receptor and ligand interactions, and utilizing endogenous stimulatory responses to promote specific nanomedicines distribution. This comprehensive review presents recent research on TDDS for HCC treatment using NMMs from three perspectives: passive TDDS, active TDDS, and stimuli-responsive drug delivery systems (SDDS). It consolidates the current state of research on TDDS for HCC treatment with NMMs and highlights the potential of these innovative approaches in improving treatment outcomes. Moreover, the review also identifies research gaps in the related fields to provide references for future targeted therapy research in HCC.

Water temperature for fabrication of autopolymerizing polymethyl methacrylate (PMMA) interim fixed restoration affects cytotoxicity and residual methyl methacrylate (MMA).

Background/purpose: Clinically, dentists are suggested to immerse autopolymerizing interim fixed restorations in hot water during fabrication. However, this suggestion, without including the best temperature, mostly comes from clinical experience instead of scientific evidence. This in vitro study evaluated the effect of water temperature on the cytotoxicity of interim partial fixed dental prostheses (FDPs) and examined its correlation with residual MMA. Materials and methods: Tempron was chosen as the autopolymerizing polymethyl methacrylate material. Tempron was mixed and then soaked in water at different temperatures, except control group (Controlair) was not being soaking in water. The specimens were incubated with conditioned medium. The concentration of residual MMA was determined by liquid chromatography-tandem mass spectrometry (LC-MS-MS). The cell viability of human gingival fibroblasts (HGFs) was evaluated by MTT assay. Results: The 60 °C and 80 °C groups exhibited significantly higher cell viabilities than those of the other groups (P < 0.05) at 48 and 72 h. The concentration of residual MMA was highly correlated with this outcome: the higher the concentration of residual MMA detected in the eluates, the poorer the cell viability was; the longer the incubation time was, the stronger the correlation was between the concentration of residual MMA and the cell viability. Conclusion: Autopolymerizing PMMA interim FDPs that are polymerized in water up to at least 60 °C could reduce cell toxicity. Higher water temperature could certainly decrease the amount of residual MMA, which is closely correlated with the outcome of cell viability.

Toxicity Assessment of Environmental Liquid Crystal Monomers: A Bacteriological Investigation on Escherichia coli and Staphylococcus epidermidis.

The widespread existence of liquid crystal monomers (LCMs) in various environmental matrices has been demonstrated, yet studies on the toxicological effects of LCMs are considerably scarce and are urgently needed to be conducted to assess the adverse impacts on ecology and human health. Here, we conducted a bacteriological study on two representative human commensal bacteria, Escherichia coli (E. coli) and Staphylococcus epidermidis (S. epidermidis), to investigate the effect of LCMs at human-relevant dosage and maximum environmental concentration on growth, metabolome, enzymatic activity, and mRNA expression. Microbial growth results exhibited that the highest inhibition ratio of LCMs on S. epidermidis reached 33.6% in our set concentration range, while the corresponding data on E. coli was only 14.3%. Additionally, LCMs showed more dose-dependent toxicity to S. epidermidis rather than E. coli. A novel in vivo solid-phase microextraction (SPME) fiber was applied to capture the in vivo metabolites of microorganisms. In vivo metabolomic analyses revealed that dysregulated fatty acid metabolism-related products of both bacteria accounted for >50% of the total number of differential substances, and the results also showed the species-specific and concentration-dependent metabolic dysregulation in LCM-exposed bacteria. The determination of enzymatic activity and mRNA relative expression levels related to oxidative stress confirmed our speculation that the adverse effects were related to the oxidative metabolism of fatty acids. This study complements the gaps in toxicity data for LCMs against bacteria and provides a new and important insight regarding metabolic dysregulation induced by environmental LCMs in human commensal bacteria.

Diversity in the HLA-I Recognition of HLA-F Monoclonal Antibodies: HLA-F or HLA-Ib Monospecific, HLA-E or HLA-G Bispecific Antibodies with or without HLA-Ia Reactivity.

Previous investigators have used various anti-HLA-F monoclonal antibodies (mAbs) to demonstrate that the tissue distribution of HLA-F is highly restricted. Notably, these mAbs differed in their immunodiagnostic capabilities. Specifically, mAbs Fpep1.1 and FG1 detected HLA-F intracellularly in B cells but not on the cell surface, whereas mAb 3D11 detected HLA-F on the cell surface. The presence of HLA-F on T cells was recognized by mAb FG1 but not by mAb Fpep1.1. mAb 3D11 detected HLA-F on the cell surface of activated B cells and on peripheral blood lymphocytes, but not on the normal cells. Importantly, mAb 3D11 revealed that HLA-F exists as a heavy chain (HC) monomer, rather than as an HC associated with B2m. Although these mAbs are believed to be specific to HLA-F, their monospecificity has not been formally established, which is critical for immunodiagnostic and therapeutic purposes. Previously, we investigated the diversity of HLA class I reactivities of anti-HLA-E mAbs using HLA-I coated multiplex bead assays on a Luminex platform. We reported that more than 80% of the HLA-E mAbs were cross-reactive with other HLA-I molecules, with exceptionally few truly HLA-E-monospecific mAbs. In the present investigation, we generated IgG mAbs against HCs of HLA-F in Balb/C mice and examined the cross-reactivity of anti-HLA-F mAbs with other HLA-I alleles using a multiplex bead assay on the Luminex platform. Beads coated with an array of HLA homo- and heterodimers of different HLA-Ia (HLA-A, HLA-B, and HLA-C) and Ib (HLA-E, HLA-F, and HLA-G) alleles were used to examine the binding of the anti-HLA-F mAbs. Only two mAbs were HLA-F monospecific, and five were HLA-Ib restricted. Several anti-HLA-F mAbs cross-reacted with HLA-E (n = 4), HLA-G (n = 3), HLA-Ia alleles (n = 9), HLA-G and HLA-Ia (n = 2), and HLA-Ib and HLA-Ia (n = 6). This monospecificity and polyreactivity were corroborated by the presence of HLA-F monospecific and HLA-I-shared sequences. This study emphasizes the need to monitor the mono-specificity of HLA-F for reliable immunodiagnostics and passive immunotherapy.

Novel Conversions of a Multifunctional, Bio-sourced Lactone Carboxylic Acid.

The plant-derived compounds furfuryl alcohol and itaconic anhydride are known to undergo a Diels-Alder reaction at room temperature and in bulk to efficiently give an alkene-containing lactone carboxylic acid. Reported here is the conversion of this substance to a variety of derivatives via hydrogenation, epoxidation, or halolactonization reactions. Most notable is the formation of a set of three related acrylate or methacrylate esters (see graphical abstract) produced by direct acylative ring opening of ether bonds using Sc(OTf)3 and (meth)acrylic anhydride. These esters are viewed as promising candidates for use as biorenewable monomers in reversible addition-fragmentation chain transfer (RAFT) polymerization reactions.

A new concept of biocatalytic synthesis of acrylic monomers for obtaining water-soluble acrylic heteropolymers.

Rhodococcus strains were designed as model biocatalysts (BCs) for the production of acrylic acid and mixtures of acrylic monomers consisting of acrylamide, acrylic acid, and N-alkylacrylamide (N-isopropylacrylamide). To obtain BC strains, we used, among other approaches, adaptive laboratory evolution (ALE), based on the use of the metabolic pathway of amide utilization. Whole genome sequencing of the strains obtained after ALE, as well as subsequent targeted gene disruption, identified candidate genes for three new amidases that are promising for the development of BCs for the production of acrylic acid from acrylamide. New BCs had two types of amidase activities, acrylamide-hydrolyzing and acrylamide-transferring, and by varying the ratio of these activities in BCs, it is possible to influence the ratio of monomers in the resulting mixtures. Based on these strains, a prototype of a new technological concept for the biocatalytic synthesis of acrylic monomers was developed for the production of water-soluble acrylic heteropolymers containing valuable N-alkylacrylamide units. In addition to the possibility of obtaining mixtures of different compositions, the advantages of the concept are a single starting reagent (acrylamide), more unification of processes (all processes are based on the same type of biocatalyst), and potentially greater safety for personnel and the environment compared to existing chemical technologies.

Recent Advances in Quaternary Ammonium Monomers for Dental Applications.

Resin-based dental materials have been one of the ideal choices among various materials in the treatment of dental caries. However, resin-based dental materials still have some drawbacks, such as the lack of inherent antibacterial activity. Extensive research has been conducted on the use of novel quaternary ammonium monomers (QAMs) to impart antibacterial activity to dental materials. This review provides a comprehensive overview of the recent advances in quaternary ammonium monomers (QAMs) for dental applications. The current progress and limitations of QAMs are discussed based on the evolution of their structures. The functional diversification and enhancement of QAMs are presented. QAMs have the potential to provide long-term antibacterial activity in dental resin composites, thereby prolonging their service life. However, there is a need to balance antibacterial performance with other material properties and the potential impact on the oral microbiome and general health. Finally, the necessity for further scientific progress in the development of novel quaternary ammonium monomers and the optimization of dental resin formulations is emphasized.

The Triumph of the Spin Chemistry of Fullerene C60 in the Light of Its Free Radical Copolymerization with Vinyl Monomers.

The spin theory of fullerenes is taken as a basis concept to virtually exhibit a peculiar role of C60 fullerene in the free radical polymerization of vinyl monomers. Virtual reaction solutions are filled with the initial ingredients (monomers, free radicals, and C60 fullerene) as well as with the final products of a set of elementary reactions, which occurred in the course of the polymerization. The above objects, converted to the rank of digital twins, are considered simultaneously under the same conditions and at the same level of the theory. In terms of the polymerization passports of the reaction solutions, a complete virtual picture of the processes considered is presented.

The substitution sites of hydroxyl and galloyl groups determine the inhibitory activity of human pancreatic α-amylase in twelve tea polyphenol monomers.

Tea polyphenols have been reported as potential α-amylase inhibitors. However, the quantitative structure-activity relationship (QSAR) between tea polyphenols and human pancreas α-amylase (HPA) is not well understood. Herein, the inhibitory effect of twelve tea polyphenol monomers on HPA was investigated in terms of inhibitory activity, as well as QSAR analysis and interaction mechanism. The results revealed that the HPA inhibitory activity of theaflavins (TFs), especially theaflavin-3'-gallate (TF-3'-G, IC50: 0.313 mg/mL), was much stronger than that of catechins (IC50: 18.387-458.932 mg/mL). The QSAR analysis demonstrated that the determinant for the inhibitory activity of HPA was not the number of hydroxyl and galloyl groups in tea polyphenol monomers, while the substitution sites of these groups potentially might play a more important role in modulating the inhibitory activity. The inhibition kinetics and molecular docking revealed that TF-3'-G as a mixed-type inhibitor had the lowest inhibition constant and bound to the active sites of HPA with the lowest binding energy (-7.74 kcal/mol). These findings could provide valuable insights into the structures-activity relationships between tea polyphenols and the HPA inhibitors.

Molecular understanding on ultraviolet photolytic degradation of cyano liquid crystal monomers.

Cyano liquid crystal monomers (LCMs) are proposed as emerging chemical pollutants with persistent, bioaccumulative, and toxic properties. Herein, five cyano LCMs, including 4-cyano-4'-ethylbiphenyl (2CB), 4-Butyl-4'-cyanobiphenyl (4CB), 4-cyano-4'-ethoxybiphenyl (2OCB), 4-(trans-4-Ethylcyclohexyl)benzonitrile (2CHB) and 4-(trans-4-Vinylcyclohexyl)benzonitrile (2eCHB), were selected to investigate the reaction kinetics and excited state characteristic variations with their molecular structures by ultraviolet (UV) photolysis. Theoretical calculations reveal that the benzene ring, ethoxy and double bond can deeply alter the electron distribution of cyano LCMs. This will affect the exciton separation ability, excitation properties and active sites to electrophilic attack, causing the distinction in photolysis efficiency. Due to the effective charge separation during local excitation (LE) process and the property of being most susceptible to electrophilic attack by 1O2 and O2•-, 2eCHB with double bond exhibits the largest degradation rate. Conversely, the weakest exciton separation of 2OCB with ethoxy during charge transfer (CT) process limits its subsequent sensitized photolysis process. The molecular orbital and fragment contributions to holes and electrons further deepen the understanding of the excited states charge transfer. This study confirmed that the intrinsic molecular structure, chemical nature and existing sites directly defined the excitation and decomposition activity in the UV photolysis of cyano LCMs.