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1.
Curr Issues Mol Biol ; 46(7): 6961-6985, 2024 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-39057057

RESUMO

Human leukocyte antigens (HLAs) are polymorphic glycoproteins expressed on the cell surface of nucleated cells and consist of two classes, HLA class I and HLA class II. In contrast, in mice, these molecules, known as H-2, are expressed on both nucleated cells and erythrocytes. HLA-I molecules (Face-1) are heterodimers consisting of a polypeptide heavy chain (HC) and a light chain, B2-microglobulin (B2m). The heterodimers bind to antigenic peptides and present them to the T-cell receptors of CD8+ cytotoxic T lymphocytes. The HCs can also independently emerge on the cell surface as B2m-free HC monomers without peptides (Face-2). Early investigators suggested that the occurrence of B2m-free HCs on the cell surface resulted from the dissociation of B2m from Face-1. However, others documented the independent emergence of B2m-free HCs (Face-2) from the endoplasmic reticulum (ER) to the cell surface. The clustering of such HC molecules on either the cell surface or on exosomes resulted in the dimerization of B2m-free HCs to form homodimers (if the same allele, designated as Face-3) or heterodimers (if different alleles, designated as Face-4). Face-2 occurs at low levels on the cell surface of several normal cells but is upregulated on immune cells upon activation by proinflammatory cytokines and other agents such as anti-CD3 antibodies, phytohemagglutinin, and phorbol myristate acetate. Their density on the cell surface remains high as long as the cells remain activated. After activation-induced upregulation, Face-2 molecules undergo homo- and heterodimerization (Face-3 and Face-4). Observations made on the structural patterns of HCs and their dimerization in sharks, fishes, and tetrapod species suggest that the formation of B2m-free HC monomers and dimers is a recapitalization of a phylogenetically conserved event, befitting the term Proto-HLA for the B2m-free HCs. Spontaneous arthritis occurs in HLA-B27+ mice lacking B2m (HLA-B27+ B2m-/-) but not in HLA-B27+ B2m+/+ mice. Anti-HC-specific monoclonal antibodies (mAbs) delay disease development. Some HLA-I polyreactive mAbs (MEM series) used for immunostaining confirm the existence of B2m-free variants in several cancer cells. The conformational alterations that occur in the B2m-free HCs enable them to interact with several inhibitory and activating receptors of cellular components of the innate (natural killer (NK) cells) and adaptive (T and B cells) immune systems. The NK cells express killer immunoglobulin-like receptors (KIRs), whereas leukocytes (T and B lymphocytes, monocytes/macrophages, and dendritic cells) express leukocyte immunoglobulin-like receptors (LILRs). The KIRs and LILRs include activating and inhibitory members within their respective groups. This review focuses on the interaction of KIRs and LILRs with B2m-free HC monomers and dimers in patients with spondylarthritis. Several investigations reveal that the conformational alterations occurring in the alpha-1 and alpha-2 domains of B2m-free HCs may facilitate immunomodulation by their interaction with KIR and LILR receptors. This opens new avenues to immunotherapy of autoimmune diseases and even human cancers that express B2m-free HCs.

2.
Chemistry ; 30(32): e202400394, 2024 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-38584129

RESUMO

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.

3.
Crit Rev Food Sci Nutr ; : 1-21, 2024 Jun 22.
Artigo em Inglês | MEDLINE | ID: mdl-38907585

RESUMO

Molecularly imprinted polymers (MIPs) as artificial synthetic receptors are in high demand for food analysis due to their inherent molecular recognition abilities. It is common practice to employ functional monomers with basic or acidic groups that can interact with analyte molecules via hydrogen bonds, covalent bonds, and other interactions (π-π, dipole-ion, hydrophobic, and Van der Waals). Therefore, selecting the appropriate functional monomer and cross-linker is crucial for determining how precisely they interact with the template and developing the polymeric network's three-dimensional structure. This study summarizes the advancements made in MIP's functional monomers and cross-linkers for food analysis from 2018 to 2023. The subsequent computational design of MIP has been thoroughly explained. The discussion has concluded with a look at the difficulties and prospects for MIP in food analysis.


Benefits of MIP in food analysis have been discussed.Different functional monomers of MIPs have been discussed.Different cross-linkers of MIPs have been discussed.Theoretical interactions between functional monomers and templates for MIP design have been discussed.

4.
Environ Sci Technol ; 58(28): 12400-12408, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38967412

RESUMO

Liquid crystal monomers (LCMs) are biphenyl- or cyclohexane-based organic chemicals used in electronic digital displays, and several of them possess bioaccumulative and toxic properties. Little is known about their occurrence in indoor dust from the United States. We analyzed 60 LCMs in 104 residential indoor dust samples collected from 16 states across the United States. Forty-seven of 60 LCMs were detected in dust samples at a median ∑LCM concentration of 402 ng/g (range: not detected to 4300 ng/g). Trans-4-propylcyclohexyl trans,trans-4'-propylbicyclohexyl-4-carboxylate (MPVBC) and (trans,trans)-4-fluorophenyl 4'-pentyl-[1,1'-bi(cyclohexane)]-4-carboxylate (FPeBC) were frequently detected in dust samples. We investigated potential sources of LCMs in dust by determining concentrations and profiles of these chemicals in smartphone screens, desktop and laptop computer monitors, and displays of other electronic devices and found that profiles in smartphones matched closely with those found in dust. The calculated median daily intake of ∑LCM through dust ingestion was 1.19 ng/kg bw/d for children, whereas that through dermal absorption was 0.18 ng/kg bw/d for adults in the United States.


Assuntos
Poluição do Ar em Ambientes Fechados , Poeira , Cristais Líquidos , Poeira/análise , Poluição do Ar em Ambientes Fechados/análise , Estados Unidos , Monitoramento Ambiental , Humanos
5.
Environ Sci Technol ; 58(36): 15949-15959, 2024 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-39143808

RESUMO

Fluorinated liquid-crystal monomers (FLCMs) are a potential emerging class of persistent, bioaccumulative, and toxic compounds. Humans inevitably ingest FLCMs via food and the environment. However, there are limited studies on internal exposure biomonitoring of FLCMs. Herein, we evaluated the estimated daily intakes (EDIs) of FLCMs in the general population based on serum residue levels. For the first time, 38 FLCMs were detected in 314 serum samples from the general population in Beijing, with a median value of 132.48 ng/g of lipid weight (lw). BDPrB is a predominant FLCM in serum. The median EDI of ∑38FLCMs in the general residents was 37.96 pg/kg bw/day. The residual levels of most FLCMs were higher in urban than in suburban areas (p < 0.05). The concentrations of EFPEB, EDPrB, EDFPBB, and PDTFMTFT in serum showed positive associations with blood glucose (GLU) (r = 0.126-0.275, p < 0.05). Logistic regression analysis showed that FLCMs were significantly positively correlated with dyslipidemia, with an odds ratio of 2.19; BDPrB was significantly positively correlated with hyperglycemia (OR: 2.48). Overall, the present study suggests the occurrence of FLCMs in the nonoccupational population, and the exposure of certain FLCMs may cause abnormal blood glucose and lipid levels.


Assuntos
Cristais Líquidos , Soro , Feminino , Humanos , Masculino , Cristais Líquidos/análise , Soro/química
6.
Environ Sci Technol ; 58(36): 16131-16141, 2024 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-39190601

RESUMO

Liquid crystal monomers (LCMs) are emerging organic pollutants due to their potential persistence, toxicity, and bioaccumulation. This study first characterized the levels and compositions of 19 LCMs in organisms in the Pearl River Estuary (PRE), estimated their bioaccumulation and trophic transfer potential, and identified priority contaminants. LCMs were generally accumulated in organisms from sediment, and the LCM concentrations in all organisms ranged from 32.35 to 1367 ng/g lipid weight. The main LCMs in organisms were biphenyls and analogues (BAs) (76.6%), followed by cyanobiphenyls and analogues (CBAs) (15.1%), and the least were fluorinated biphenyls and analogues (FBAs) (11.2%). The most abundant LCM monomers of BAs, FBAs, and CBAs in LCMs in organisms were 1-(4-propylcyclohexyl)-4-vinylcyclohexane (15.1%), 1-ethoxy-2,3-difluoro-4-(4-(4-propylcyclohexyl) cyclohexyl) benzene (EDPBB, 10.1%), and 4'-propoxy-4-biphenylcarbonitrile (5.1%), respectively. The niche studies indicated that the PRE food web was composed of terrestrial-based diet and marine food chains. Most LCMs exhibited biodilution in the terrestrial-based diet and marine food chains, except for EDPBB and 4,4'-bis(4-propylcyclohexyl) biphenyl (BPCHB). The hydrophobicity, position of fluorine substitution of LCMs, and biological habits may be important factors affecting the bioaccumulation and trophic transfer of LCMs. BPCHB, 1-(prop-1-enyl)-4-(4-propylcyclohexyl) cyclohexane, and EDPBB were characterized as priority contaminants. This study first reports the trophic transfer processes and mechanisms of LCMs and the biomonitoring in PRE.


Assuntos
Monitoramento Ambiental , Estuários , Rios , Poluentes Químicos da Água , Rios/química , Cadeia Alimentar , Cristais Líquidos , Animais
7.
Environ Sci Technol ; 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38321847

RESUMO

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.

8.
Clin Chem Lab Med ; 62(3): 464-471, 2024 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-37747270

RESUMO

OBJECTIVES: Diagnosis of light chain amyloidosis (AL) requires demonstration of amyloid deposits in a tissue biopsy followed by appropriate typing. Previous studies demonstrated increased dimerization of monoclonal serum free light chains (FLCs) as a pathological feature of AL. To further examine the pathogenicity of FLC, we aimed at testing amino acid sequence homology between circulating and deposited light chains (LCs). METHODS: Matched tissue biopsy and serum of 10 AL patients were subjected to tissue proteomic amyloid typing and nephelometric FLC assay, respectively. Serum FLC monomers (M) and dimers (D) were analyzed by Western blotting (WB) and mass spectrometry (MS). RESULTS: WB of serum FLCs showed predominance of either κ or λ type, in agreement with the nephelometric assay data. Abnormal FLC M-D patterns typical of AL amyloidosis were demonstrated in 8 AL-λ patients and in one of two AL-κ patients: increased levels of monoclonal FLC dimers, high D/M ratio values of involved FLCs, and high ratios of involved to uninvolved dimeric FLCs. MS of serum FLC dimers showed predominant constant domain sequences, in concordance with the tissue proteomic amyloid typing. Most importantly, variable domain sequence homology between circulating and deposited LC species was demonstrated, mainly in AL-λ cases. CONCLUSIONS: This is the first study to demonstrate homology between circulating FLCs and tissue-deposited LCs in AL-λ amyloidosis. The applied methodology can facilitate studying the pathogenicity of circulating FLC dimers in AL amyloidosis. The study also highlights the potential of FLC monomer and dimer analysis as a non-invasive screening tool for this disease.


Assuntos
Amiloidose , Amiloidose de Cadeia Leve de Imunoglobulina , Humanos , Projetos Piloto , Homologia de Sequência de Aminoácidos , Proteômica , Amiloidose de Cadeia Leve de Imunoglobulina/diagnóstico , Cadeias Leves de Imunoglobulina , Amiloidose/diagnóstico , Proteínas Amiloidogênicas , Cadeias lambda de Imunoglobulina
9.
Macromol Rapid Commun ; : e2400402, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-39235433

RESUMO

Modified polyvinylidene chloride (PVDC) resin was prepared using octafluoropentyl methacrylate and trimethylolpropane trimethacrylate as modifying monomers through seeded emulsion polymerization. The successful incorporation of octafluoropentyl methacrylate into the PVDC resin was confirmed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses. Scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and XPS were utilized to investigate the element distribution in the modified monomer emulsion and the mechanism of monomer modification. The results demonstrated that the fluorine monomer was reacted in the resin, and mainly concentrated on the surface of the resin. The addition of octafluoropentyl methacrylate and trimethylolpropane trimethacrylate improved the water resistance of the resin. Compared to unmodified PVDC resin, the contact angle of the modified PVDC resin increased from 89.46° to 109.51°, and the water resistance at room temperature increased from 120 to 500 h. Furthermore, the modified resin exhibited excellent mechanical properties, thermal stability, and storage stability.

10.
Macromol Rapid Commun ; 45(15): e2400147, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38875713

RESUMO

Hydrophilicity is one important drawback of bio-based aerogels. To overcome this issue, a novel approach for the preparation of mesoporous, water repellent aerogels is introduced, which combines synthesis of cross-linked bio-based copolymers from methacrylate copolymerizations, followed by solvent exchange and supercritical drying steps. The influence of monomers with different nonpolar ester groups (methyl, vanillin, tetrahydrofurfuryl) on textural properties and water contact angles of the dry products is assessed. Final aerogels show generally high overall porosities (≈96%), low densities (0.07-0.11 g cm-3) as well as fine, mainly mesoporous networks, and specific surface areas in the range of 120-240 m2 g-1. Hereby, choice of the methacrylate ester groups results in differences of the resulting pore-size distributions. Water repellency tests show stable static water contact angles in the hydrophobic range (≈100°) achieved for the substrate containing the vanillin ester group. On the contrary the other substrates absorb water quickly, which indicates a decisive role of the ester group. The presented approach opens up a new pathway to bio-based aerogels with intrinsic hydrophobicity. It is suggested that the properties are tailored by the choice of the monomer structure, hence enabling further adaption and optimization of the products.


Assuntos
Géis , Interações Hidrofóbicas e Hidrofílicas , Polimerização , Polímeros , Géis/química , Géis/síntese química , Polímeros/química , Polímeros/síntese química , Porosidade , Água/química , Compostos de Vinila/química , Estrutura Molecular , Benzaldeídos/química
11.
Pharmacology ; : 1-13, 2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39250889

RESUMO

BACKGROUND: Cardiovascular diseases are now the second leading cause of death among cancer patients. Heart injury in patients with terminal cancer can lead to significant deterioration of left ventricular morphology and function. This specific heart condition is known as cancer-induced cardiac cachexia (CICC) and is characterized by cardiac dysfunction and wasting. However, an effective pharmacological treatment for CICC remains elusive. SUMMARY: The development and progression of CICC are closely related to pathophysiological processes, such as protein degradation, oxidative responses, and inflammation. Traditional Chinese medicine (TCM) monomers offer unique advantages in reversing heart injury, which is the end-stage manifestation of CICC except the regular treatment. This review outlines significant findings related to the impact of eleven TCM monomers, namely Astragaloside IV, Ginsenosides Rb1, Notoginsenoside R1, Salidroside, Tanshinone II A, Astragalus polysaccharides, Salvianolate, Salvianolic acids A and B, and Ginkgolide A and B, on improving heart injury. These TCM monomers are potential therapeutic agents for CICC, each with specific mechanisms that could potentially reverse the pathological processes associated with CICC. Advanced drug delivery strategies, such as nano-delivery systems and exosome-delivery systems, are discussed as targeted administration options for the therapy of CICC. KEY MESSAGE: This review summarizes the pathological mechanisms of CICC and explores the pharmacological treatment of TCM monomers that promote anti-inflammation, antioxidation, and pro-survival. It also considers pharmaceutical strategies for administering TCM monomers, highlighting their potential as therapies for CICC.

12.
Proc Natl Acad Sci U S A ; 118(23)2021 06 08.
Artigo em Inglês | MEDLINE | ID: mdl-34074793

RESUMO

Liquid crystal displays (LCDs) have profoundly shaped the lifestyle of humans. However, despite extensive use, their impacts on indoor air quality are unknown. Here, we perform flow cell experiments on three different LCDs, including a new computer monitor, a used laptop, and a new television, to investigate whether their screens can emit air constituents. We found that more than 30 volatile organic compounds (VOCs) were emitted from LCD screens, with a total screen area-normalized emission rate of up to (8.25 ± 0.90) × 109 molecules ⋅ s-1 ⋅ cm-2 In addition to VOCs, 10 liquid crystal monomers (LCMs), a commercial chemical widely used in LCDs, were also observed to be released from those LCD screens. The structural identification of VOCs is based on a "building block" hypothesis (i.e., the screen-emitted VOCs originate from the "building block chemicals" used in the manufacturing of liquid crystals), which are the key components of LCD screens. The identification of LCMs is based upon the detailed information of 362 currently produced LCMs. The emission rates of VOCs and LCMs increased by up to a factor of 9, with an increase of indoor air humidity from 23 to 58% due to water-organic interactions likely facilitating the diffusion rates of organics. These findings indicate that LCD screens are a potentially important source for indoor VOCs that has not been considered previously.


Assuntos
Poluentes Atmosféricos/química , Cristais Líquidos/química , Compostos Orgânicos Voláteis/química , Poluição do Ar em Ambientes Fechados
13.
Phytother Res ; 38(7): 3564-3582, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38715375

RESUMO

Type 2 diabetes mellitus (T2DM), a metabolic disease with persistent hyperglycemia primarily caused by insulin resistance (IR), has become one of the most serious health challenges of the 21st century, with considerable economic and societal implications worldwide. Considering the inevitable side effects of conventional antidiabetic drugs, natural ingredients exhibit promising therapeutic efficacy and can serve as safer and more cost-effective alternatives for the management of T2DM. Saponins are a structurally diverse class of amphiphilic compounds widely distributed in many popular herbal medicinal plants, some animals, and marine organisms. There are many saponin monomers, such as ginsenoside compound K, ginsenoside Rb1, ginsenoside Rg1, astragaloside IV, glycyrrhizin, and diosgenin, showing great efficacy in the treatment of T2DM and its complications in vivo and in vitro. However, although the mechanisms of action of saponin monomers at the animal and cell levels have been gradually elucidated, there is a lack of clinical data, which hinders the development of saponin-based antidiabetic drugs. Herein, the main factors/pathways associated with T2DM and the comprehensive underlying mechanisms and potential applications of these saponin monomers in the management of T2DM and its complications are reviewed and discussed, aiming to provide fundamental data for future high-quality clinical studies and trials.


Assuntos
Diabetes Mellitus Tipo 2 , Hipoglicemiantes , Saponinas , Diabetes Mellitus Tipo 2/tratamento farmacológico , Saponinas/farmacologia , Saponinas/química , Humanos , Hipoglicemiantes/farmacologia , Hipoglicemiantes/uso terapêutico , Animais , Plantas Medicinais/química , Resistência à Insulina
14.
Phytochem Anal ; 2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38830775

RESUMO

INTRODUCTION: Traditional Chinese medicine (TCM) has been used for thousands of years in China, characterizing with novel pharmacological mechanisms, low toxicity, and limited side effects. However, the application of TCM active ingredients is often hindered by their physical and chemical properties, including poor solubility, low bioavailability, short half-life, toxic side effects within therapeutic doses, and instability in biological environments. Consequently, an increasing number of researchers are directing their attention towards the discovery of nano-delivery systems for TCM to overcome these clinical challenges. OBJECTIVES: This review aims to provide the latest knowledge and results concerning the studies on the nano-delivery systems for the active ingredients from TCM. MATERIALS AND METHODS: Recent literature relating to nano-delivery systems for the active ingredients from TCM is summarized to provide a fundamental understanding of how such systems can enhance the application of phytochemicals. RESULTS: The nano-delivery systems of six types of TCM monomers are summarized and categorized based on the skeletal structure of the natural compounds. These categories include terpenoids, flavonoids, alkaloids, quinones, polyphenols, and polysaccharides. The paper analyzes the characteristics, types, materials used, and the efficacy achieved by TCM-nano systems. Additionally, the advantages and disadvantages of nano-drug delivery systems for TCM are summarized in this paper. CONCLUSION: Nano-delivery systems represent a promising approach to overcoming clinical obstacles stemming from the physical and chemical properties of TCM active ingredients, thereby enhancing their clinical efficacy.

15.
Int J Mol Sci ; 25(2)2024 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-38279316

RESUMO

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.


Assuntos
Fulerenos , Polimerização , Radicais Livres , Cloreto de Polivinila
16.
Molecules ; 29(10)2024 May 16.
Artigo em Inglês | MEDLINE | ID: mdl-38792201

RESUMO

High-performance electrochromic (EC) and electrofluorochromic (EFC) materials have garnered considerable interest due to their diverse applications in smart windows, optoelectronics, optical displays, military camouflage, etc. While many different EC and EFC polymers have been reported, their preparation often requires multiple steps, and their polymer molecular weights are subjected to batch variation. In this work, we prepared two triphenylamine (TPA)-based and two tetraphenylethylene (TPE)-based derivatives functionalized with terminal styryl groups via direct Suzuki coupling with (4-vinylphenyl)boronic acid and vinylboronic acid pinacol ester. The two novel TPE derivatives exhibited green-yellow aggregation-induced emission (AIE). The EC and EFC properties of pre- and post-thermally treated derivatives spin-coated onto ITO-glass substrates were studied. While all four derivatives showed modest absorption changes with applied voltages up to +2.4 V, retaining a high degree of optical transparency, they exhibited obvious EFC properties with the quenching of blue to yellow fluorescence with IOFF/ON contrast ratios of up to 7.0. The findings therefore demonstrate an elegant approach to preparing optically transparent, heat-induced, cross-linkable styryl-functionalized EFC systems.

17.
Molecules ; 29(17)2024 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-39275084

RESUMO

BACKGROUND: In recent years, the advancement of computational chemistry has offered new insights into the rational design of molecularly imprinted polymers (MIPs). From this aspect, our study tried to give quantitative parameters for evaluating imprinting efficiency and exploring the formation mechanism of MIPs by combining simulation and experiments. METHODS: The pre-polymerization system of sulfadimethoxine (SDM) was investigated using a combination of quantum chemical (QC) calculations and molecular dynamics (MD) simulations. MIPs were prepared on the surface of silica gel by a surface-initiated supplemental activator and reducing agent atom transfer radical polymerization (SI-SARA ATRP). RESULTS: The results of the QC calculations showed that carboxylic monomers exhibited higher bonding energies with template molecules than carboxylic ester monomers. MD simulations confirmed the hydrogen bonding sites predicted by QC calculations. Furthermore, it was observed that only two molecules of monomers could bind up to one molecule of SDM, even when the functional monomer ratio was up to 10. Two quantitative parameters, namely, the effective binding number (EBN) and the maximum hydrogen bond number (HBNMax), were defined. Higher values of EBN and HBNMax indicated a higher effective binding efficiency. Hydrogen bond occupancies and RDF analysis were performed to analyze the hydrogen bond formation between the template and the monomer from different perspectives. Furthermore, under the influence of the EBN and collision probability of the template and the monomers, the experimental results show that the optimal molar ratio of template to monomer is 1:3. CONCLUSIONS: The method of monomer screening presented in this study can be extended to future investigations of pre-polymerization systems involving different templates and monomers.

18.
Polim Med ; 54(1): 59-69, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38533623

RESUMO

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.


Assuntos
Materiais Biocompatíveis , Proteínas Fúngicas , Furanos , Lipase , Furanos/química , Lipase/química , Materiais Biocompatíveis/química , Polímeros/química , Teste de Materiais , Nanofibras/química
19.
Beilstein J Org Chem ; 20: 1955-1966, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39161709

RESUMO

This article provides a comprehensive overview of the synthesis and chemistry of 1,2-difluoroethylene (HFO-1132). The major routes for the preparation of the E- and Z-isomer of HFO-1132 are reviewed, along with the chemistry in radical, nucleophilic, and electrophilic reactions.

20.
Small ; 19(44): e2303497, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37376810

RESUMO

Homochiral supramolecular assembly (HSA) based on achiral molecules has provided important clues to understand the origin of biological homochirality from the aspect of symmetry breaking. However, planar achiral molecules still face the challenge of forming HSA due to the lack of driving force for twisted stacking, which is a prerequisite for homochirality. Here, with the benefit of the formation of 2D intercalated layered double hydroxide (LDH, host-guest nanomaterials) in vortex motion, planar achiral guest molecules can form the chiral units with spatially asymmetrical structure in the confinement space of LDH. Once the LDH is removed, these chiral units are in a thermodynamic non-equilibrium state, which can be amplified to HSA by self-replicating. Especially, the homochiral bias can be predicted in advance by controlling the vortex direction. Therefore, this study breaks the bottleneck of complicated molecular design and provides a new technology to achieve HSA made of planar achiral molecules with definite handedness.

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