Syntheses and Structural Characterization of Dimethyltin Complexs of N-(3-Methoxysalicylidene)-α-amino Acid

Three new dimethyltin complexes of N-（3-methoxysalicylidene）-α-amino acid,（CH3）2Sn（3-CH3O-2-OC6H3CH=NCHRCOO）（R = H,1;CH3,2;（CH3）2CH,3）,have been synthe-sized by treating dimethyltin dichloride with the potassium salt of the ligand and characterized by elemental analysis,IR and 1H NMR spectra.The crystal structure of [（CH3）2Sn（3-CH3O-2-OC6H3CH=NCH2COO）（CH3OH）]2 H2O（1a）,formed from methanol solution of 1,has been deter-mined.The crystal belongs to the monoclinic system,space group C/2c with a = 20.636（3）,b = 7.8854（9）,c = 20.668（2） ,β= 113.265（2）°,V = 3089.7（6） 3,Z = 4,Dc = 1.707 g/cm3,= 1.675 mm-1,F（000） = 1592,R = 0.0301 and wR = 0.0841.In complex 1a,the tin atom is six-coordinate and possesses a distorted [SnC2NO3] octahedral geometry with the two methyl groups occupying the trans positions.The weak Sn O interactions and intermolecular hydrogen bonds connected the molecules into an infinite chain.

Synthesis and Characterization of the Tetrazole Analogues of α-Amino Acids

The tetrazole analogues have been synthesized from fluorenylmethoxycarbonyl （Fmoc）- protected amino acids by three steps. The structures of the analogues were characterized by HPLC-MS, ^1H NMR and ^13C NMR.

Calix[4]arene Polyaza Derivatives: Novel Effective Neutral Receptors for Cations and α-Amino Acids

Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry.

Synthesis of novel fullereneα-amino acid conjugates

Aspartic acid and glutamic acid with protected α-amino and α-carboxyl groups had been used to react with the activated hydroxyl group of N-substituted 3,4-fullero pyrrolidine. The products were deprotected, affording two monofuUerene α-amino acids, monofullerene aspartic acid （mFas） and monofullerene glutamic acid （mFgu）. Then a bifullerene glutamic acid conjugate （bFguC） was synthesized by reaction of mFgu containing protected amino group with N-substituted 3,4-fullero pyrrolidine.

Syntheses and Crystal Structures of Two Diethyltin Complexes of N-Salicylidene-α-amino Acid

Two novel diethyltin（IV） complexes of N-salicylidenevaline （H2L1） and N-Sali- cylidenetryptophan （H2L^2）, Et2SrtL^1 1 and Et2SnL^2 2, were synthesized and characterized by elemental analysis, IR, ^1H NMR and X-ray single-crystal diffraction analysis. Complex 1 belongs to the trigonal system, space group R-3 with a = b = 19.2730（5）, c = 23.6890（13）A^°, V= 7620.4（5） A^°^3, Z = 6, Dc= 1.553 g/cm^3,μ= 1.518 mm^-1, F（000） = 3600, R = 0.0238 and wR = 0.0636. Complex 2 is of monoelinie system, space group P21/c with a = 13.7550（8）, b = 11.5425（7）, c = 12.7876（7）A^°, β= 93.585（1）°, V = 2026.3（2） A^°^3, Z = 4, Dc= 1.548 g/cm^3,μ = 1.286 mm^-1, F（000） = 976, R = 0.0298 and wR = 0.0722. Complex 1 is a cyclic trimer with a macrocyclic 12-membered ring structure formed by the bidentate bridging coordination of carboxylate group to tin atoms. The tin atom is six-coordinated in a distorted octahedral geometry. In complex 2, the distorted trigonal bipyramidal Et2SnL2 units are linked into polymeric chains by the weak Sn…O interaction involving Sn and the earbonyl O of an adjacent ligand, and the chains are further connected by intermolecular N-H…O hydrogen bonds to form a two-dimensional supramolecular structure.

Thermodynamic solvation of a series of homologous α-amino acids in non-aqueous mixture of ethylene-glycol and N,N-dimethyl formamide

Standard free energies (ΔG0t(i) ) and entropies (ΔS0t(i)) of transfer of some homologous α-amino acids viz. glycine (gly), dl-alanine (ala), dl-α-amino butyric acid (aba) and dl-nor-valine (nor-val) from protic ethylene glycol (EG) to dipolar aprotic N,N-dimethyl formamide (DMF) have been evaluated from solubility measure-ments at five equidistant temperatures i.e from 15 to 350C. The observed ΔG0t(i) and TΔS0t(i) Vs composition profiles are complicated because of the various interaction effects. The chemical effects of the transfer Gibbs energies (ΔG0t.ch(i)) and entropies of transfer (ΔS0t.ch(i)) have been obtained after elimination of cavity effect, estimated by the scaled particle theory and dipole-dipole interaction effects, estimated by the use of Keesom-orientation expression. The chemical contributions of transfer energetics of homologous α-amino acids are guided by the composite effects of increased dispersion interaction, basicity and decreased acidity, hydrogen bonding effects and solvophobic solvation of ethylene glycol and N, N-dimethyl formamide mixed solvent as compared to that of reference solvent (ethylene glycol).

Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O′)-Coordinated α-Amino Acids

Four dinuclear amino acid cadmium（II） complexes [Cd2（tren）2（dl-alaninato）]（ClO4）3·H2O（I）, [Cd2（tren）2· （l-alaninato）]（ClO4）3·H2O（II）, [Cd2（tren）2（dl-phenylalaninato）]（ClO4）3（III） and [Cd2（tren）2（l-phenylalaninato）]· （ClO4）3（IV）, constructed from mixed ligands of tris（2-aminoethyl）amine（tren） and racemic or natural amino ac ids（amino acids=dl or l-alanine, and dl or l-phenylalanine）, have been synthesized and characterized by X-ray crys tallography. The structural analysis of complexes I and III reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual （N,O,O′）-bridged mode, resulting in asymmetric chromo phores of CdN4O and CdN5O in complex I, CdN4O2 and CdN5O in complex III, respectively. The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined. The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield. Moreover, the dias tereoselectivity of the reaction favors the formation of the syn-isomers.

A NOVEL METHOD FOR SYNTHESIZING α,α-DISUBSTITUTED α-AMINO ACID——DIALKYLATION OF 2-OXAZOLIN-5-ONE

4,4-Dialkyl-2-oxazolin-5-ones are prepared by one step reaction of 2-oxazolin-5-one with the magnesium methyl carbonate(MMC)and alkyIhalides.It is a novel and convenient method for synthesis of α, Υ-disubstitutcd α-amino acid by hydrolysis of 4,4-dialkyl-2-oxazolin-5-ones.

SOLID-LIQUID PHASE TRANSFER CATALYTIC SYN THESIS Ⅸ: THE SYNTHESIS OF α-AMINO ACIDS VIA ALICYLATION OF ALDIMINE UNDER MICROWAVE IRRADIATION,

The rapid alkylation of methyl N-benzylidene glycinate with halides under microwave irradiation using solid-liquid phase transfer condition without solvent has been achieved wilhin only one minute. After hydrolysis of alkylated products the corresponding α-amino acids were obtained in overall yield 43.6～62.5%.

ASYMMETRIC SYNTHESIS Ⅻ:HIGHLY ENANTIOSELECTIVE SYNTHESIS OF α-AMINO ACIDS BY ALKYLATION OF THE KETIMINE FROM 2-HYDROXY-PINAN-3-ONE AND MENTHYL GLYCIN-ATE A DOUBLE ASYMMETRIC INDUCTION SYSTEM

A series of α-amino acids are obtained in 72-96% optical yields by alkylation of the ketimine derived from(+)-2-hydroxy-pinan-3-one and(-)-menthyl glycinate fol- lowed by hydrolysis of the alkylated intermediates with mineral acid.The double asymmetric induction are explained by the transition model of lithium enolate.

Volumetric,Viscometric and Refractive Index Behaviors of α-Amino Acids in Aqueous Caffeine Solution at Varying Temperatures

Measurements of density(ρ), viscosity(η), and refractive index(n), were carried out on α-amino acids, DL-alanine (Ala), D-phenylalanine (Phe), and DL-threonine (Thr) (0.01-0.05 mol·L-1), in 0.05 mol·L-1 aqueous caffeine solution at 298.15, 303.15, 308.15, and 313.15 K. These measurements have been carried out to evaluate some important parameters, viz., apparent molar volume (фυ), partial molar volume (фυ0v), transfer volume (фυ0v(tr)), viscosity A and B coefficients of Jones-Dole equation, free energies of activation per mole of solvent (Δμ0#1) and solute (Δμ0#2), enthalpies (ΔH) and entropies (ΔS) of activation of viscous flow, variation of B with temperature (αB/αT)P, and molar refractive index (RD). These parameters have been interpreted in terms of solute-solute and solute-solvent interactions and structure making/breaking ability of solutes in the given solution.

Cognitive dysfunction in schizophrenia patients caused by downregulation of γ-aminobutyric acid receptor subunits

BACKGROUND The expression pattern of gamma aminobutyric acid(GABA)receptor subunits are commonly altered in patients with schizophrenia,which may lead to nerve excitation/inhibition problems,affecting cognition,emotion,and behavior.AIM To explore GABA receptor expression and its relationship with schizophrenia and to provide insights into more effective treatments.METHODS This case-control study enrolled 126 patients with schizophrenia treated at our hospital and 126 healthy volunteers who underwent physical examinations at our hospital during the same period.The expression levels of the GABA receptor subunits were detected using 1H-magnetic resonance spectroscopy.The recognized cognitive battery tool,the MATRICS Consensus Cognitive Battery,was used to evaluate the scores for various dimensions of cognitive function.The correlation between GABA receptor subunit downregulation and schizophrenia was also analyzed.RESULTS Significant differences in GABA receptor subunit levels were found between the case and control groups(P<0.05).A significant difference was also found between the case and control groups in terms of cognitive function measures,including attention/alertness and learning ability(P<0.05).Specifically,as the expression levels of GABRA1(α1 subunit gene),GABRB2(β2 subunit gene),GABRD(δsubunit),and GABRE(εsubunit)decreased,the severity of the patients’condition increased gradually,indicating a positive correlation between the downregulation of these 4 receptor subunits and schizophrenia(P<0.05).However,the expression levels of GABRA5(α5 subunit gene)and GABRA6(α6 subunit gene)showed no significant correlation with schizophrenia(P>0.05).CONCLUSION Downregulation of the GABA receptor subunits is positively correlated with schizophrenia.In other words,when GABA receptor subunits are downregulated in patients,cognitive impairment becomes more severe.

P-aminobenzoic acid promotes retinal regeneration through activation of Ascl1a in zebrafish

The retina of zebrafish can regenerate completely after injury.M ultiple studies have demonstrated that metabolic alte rations occur during retinal damage;however to date no study has identified a link between metabolites and retinal regeneration of zebrafish.Here,we performed an unbiased metabolome sequencing in the N-methyl-D-aspartic acid-damaged retinas of zebrafish to demonstrate the metabolomic mechanism of retinal regeneration.Among the differentially-ex pressed metabolites,we found a significant decrease in p-aminobenzoic acid in the N-methyl-D-aspartic acid-damaged retinas of zebrafish.Then,we investigated the role of p-aminobenzoic acid in retinal regeneration in adult zebrafish.Impo rtantly,p-aminobenzoic acid activated Achaetescute complex-like 1a expression,thereby promoting Müller glia reprogramming and division,as well as Müller glia-derived progenitor cell proliferation.Finally,we eliminated folic acid and inflammation as downstream effectors of PABA and demonstrated that PABA had little effect on Müller glia distribution.Taken together,these findings show that PABA contributes to retinal regeneration through activation of Achaetescute complex-like 1a expression in the N-methyl-Daspartic acid-damaged retinas of zebrafish.

A comparison study on structure-function relationship of polysaccharides obtained from sea buckthorn berries using different methods:antioxidant and bile acid-binding capacity

In this study,the structural characters,antioxidant activities and bile acid-binding ability of sea buckthorn polysaccharides(HRPs)obtained by the commonly used hot water(HRP-W),pressurized hot water(HRP-H),ultrasonic(HRP-U),acid(HRP-C)and alkali(HRP-A)assisted extraction methods were investigated.The results demonstrated that extraction methods had significant effects on extraction yield,monosaccharide composition,molecular weight,particle size,triple-helical structure,and surface morphology of HRPs except for the major linkage bands.Thermogravimetric analysis showed that HRP-U with filamentous reticular microstructure exhibited better thermal stability.The HRP-A with the lowest molecular weight and highest arabinose content possessed the best antioxidant activities.Moreover,the rheological analysis indicated that HRPs with higher galacturonic acid content and molecular weight showed higher viscosity and stronger crosslinking network(HRP-C,HRP-W and HRP-U),which exhibited stronger bile acid binding capacity.The present findings provide scientific evidence in the preparation technology of sea buckthorn polysaccharides with good antioxidant and bile acid binding capacity which are related to the structure affected by the extraction methods.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Abiotic stress treatment reveals expansin like A gene OfEXLA1 improving salt and drought tolerance of Osmanthus fragrans by responding to abscisic acid

Sweet osmanthus(Osmanthus fragrans) is a having general approval aromatic tree in China that is widely applied to landscaping and gardening. However, the evergreen tree adaptability is limited by many environmental stresses. Currently, limited information is available regarding the genetic analysis and functional identification of expansin genes in response to abiotic stress in sweet osmanthus. In this study, a total of 29 expansin genes were identified and divided into four groups by genome-wide analysis from the sweet osmanthus genome. Transcriptome and quantitative Real-time PCR analysis showed that the cell wall-localized protein expansin-like A(OfEXLA1) gene was significantly induced by salt and drought treatment. Histochemical GUS staining of transgenic Arabidopsis lines in which GUS activity was driven with the OfEXLA1 promoter, GUS activity was significantly induced by salt, drought, and exogenous abscisic acid(ABA). In yeast, we found OfEXLA1overexpression significantly improved the population of cells compared with wild-type strains after NaCl and polyethylene glycol(PEG)treatment. Additionally, OfEXLA1 overexpression not only promoted plant growth, but also improved the salt and drought tolerance in Arabidopsis. To gain insight into the role of ABA signaling in the regulation of OfEXLA1 improving abiotic tolerance in sweet osmanthus, four differentially expressed ABA Insensitive 5(ABI5)-like genes(OfABL4, OfABL5, OfABL7, and OfABL8) were identified from transcriptome, and dualluciferase(dual-LUC) and yeast one hybrid(Y1H) assay showed that OfABL4 and OfABL5 might bind to OfEXLA1 promoter to accumulate the OfEXLA1 expression by responding to ABA signaling to improve abiotic tolerance in sweet osmanthus. These results provide the information for understanding the molecular functions of expansin-like A gene and molecular breeding of sweet osmanthus in future.

Bile acids,gut microbiota,and therapeutic insights in hepatocellular carcinoma

Hepatocellular carcinoma(HCC)is a prevalent and aggressive liver malignancy.The interplay between bile acids(BAs)and the gut microbiota has emerged as a critical factor in HCC development and progression.Under normal conditions,BA metabolism is tightly regulated through a bidirectional interplay between gut microorganisms and BAs.The gut microbiota plays a critical role in BA metabolism,and BAs are endogenous signaling molecules that help maintain liver and intestinal homeostasis.Of note,dysbiotic changes in the gut microbiota during pathogenesis and cancer development can disrupt BA homeostasis,thereby leading to liver inflammation and fibrosis,and ultimately contributing to HCC development.Therefore,understanding the intricate interplay between BAs and the gut microbiota is crucial for elucidating the mechanisms underlying hepatocarcinogenesis.In this review,we comprehensively explore the roles and functions of BA metabolism,with a focus on the interactions between BAs and gut microorganisms in HCC.Additionally,therapeutic strategies targeting BA metabolism and the gut microbiota are discussed,including the use of BA agonists/antagonists,probiotic/prebiotic and dietary interventions,fecal microbiota transplantation,and engineered bacteria.In summary,understanding the complex BA-microbiota crosstalk can provide valuable insights into HCC development and facilitate the development of innovative therapeutic approaches for liver malignancy.

Coordination and Photoisomerization of Azobenzene-Amino Acid Schiff Base Copper(II) Complexes to Lysozyme

In this study, we exhibited an amino acid (arginine and threonine) derivative Schiff base copper(II) complexes incorporating an azobenzene moiety as a photoresponsive site and conjugated it to egg white lysozyme, a well-known protein, to change ligand conformation under binding to lysozyme. Among several spectroscopic investigations, ESR clearly showed that the nitrogen atom of the amino acid residue of lysozyme was bound to the paramagnetic copper(II) ion of the complex, and UV light irradiation confirmed photoisomerization of the azobenzene moiety of the ligand to cis-form. The binding mode was considered by means of spectroscopic as well as computational methods, whereas complete crystallographic verification was still a preliminary stage.