Structurally Modelling the 2-His-1-Carboxylate Facial Triad with a Bulky N,N,O Phenolate Ligand

We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, Im^Ph2NNO ^{t Bu} ( L ), designed to model the 2-His-1-carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4-di-tert-butyl-subtituted phenolate. Reacting K-L with MCl₂ (M = Fe, Zn) affords the isostructural, tetrahedral non-heme complexes [Fe(L)(Cl)] ( 1 ) and [Zn(L)(Cl)] ( 2 ) in high yield. The tridentate N,N,O ligand coordination observed in their X-ray crystal structures remains intact and well-defined in MeCN and CH₂Cl₂ solution. Reacting 2 with NaSPh affords a tetrahedral zinc thiolate complex, [Zn(L)(SPh)] ( 4 ), that is relevant to isopenicillin N synthase (IPNS) biomimicry. Cyclic voltammetry studies demonstrate the ligand's redox non-innocence, where phenolate oxidation is the first electrochemical response observed in K-L , 2 and 4 . However, the first electrochemical oxidation in 1 is iron-centred, the assignment of which is supported by DFT calculations. Overall, Im^Ph2NNO ^{t Bu} provides access to well-defined mononuclear, monoligated, N,N,O-bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved.     

Target-induced mimic enzyme deactivation based on mixed-node metal-organic frameworks for colorimetric assay of hydrogen sulfide

Accurate detection of hydrogen sulfide (H₂S) is of great significance for environmental monitoring and protection. We propose a colorimetric method for the detection of H₂S by the use of mixed-node Cu-Fe metal organic frameworks (Cu-Fe MOFs) as highly efficient mimic enzymes for target-induced deactivation. The Cu-Fe MOFs were synthesized by a simple solvothermal method and could catalyze the H₂O₂ mediated oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to oxTMB with a blue color. The presence of dissolved H₂S would deactivate the mimic enzymes, and then the blue color disappeared. The mechanism of the sensor was discussed by steady-state kinetic analysis. The designed assay was highly sensitive for H₂S detection with a linear range of 0−80 μmol/L and a detection limit of 1.6 μmol/L. Moreover, some potential substances in the water samples had no interference. This method with the advantages of low cost, high sensitivity, selectivity, and visual readout with the naked eye was successfully applied to the determination of H₂S in industrial wastewater samples.     

牛血清白蛋白模板法制备的金属复合纳米材料在生物检测中的应用

随着纳米科技的快速发展,纳米材料得到广泛应用,其功能也得到全面的研究。由于蛋白质外壳和金属内核,以牛血清白蛋白为模板制备的金属复合纳米材料拥有很好的稳定性、高荧光特性、优良的催化活性、环保的制备过程和潜在的多功能特性。本文综述了近年来牛血清白蛋白-金属复合纳米材料的相关研究,包括已开发的种类、制备方法、性能、生物检测及临床相关应用。     

血管紧张素转换酶与抑制肽结合模式的分子动力学研究

应用分子模拟方法研究了血管紧张素转换酶(Angiotensin-converting enzyme,ACE)C端结构域(C-domain)与两种抑制肽(RIGLF/AHEPVK)的结合机制,预测了两个体系的结合模式,提出在C-domain-RIGLF中His353,Asp377,Asp453,Phe457,His513,Tyr523和Phe527为RIGLF主要结合残基,而在C-domainAHEPVK中Gln281,His353,Ser355,Glu384,Lys511,His513和Tyr523等残基起关键作用.应用结合自由能计算比较了两个体系的结合能力,结果表明,RIGLF和AHEPVK均与C-domain活性位点残基存在较强作用,且AHEPVK对C-domain的结合能力较强,与实验结果一致.     

聚脲多孔材料的简单制备及在酶固定和手性拆分中的应用

以甲苯二异氰酸酯(TDI)为单体,在水与丙酮混合溶剂中通过沉淀聚合一步法制备了富含胺基的聚脲多孔材料(PPU),通过扫描电镜和压汞法对其表面形貌和孔结构进行了表征.PPU经戊二醛(GA)活化后用于荧光假单胞菌脂肪酶(PFL)的固定,考察了GA活化过程中GA浓度对酶固定量及固定酶活性的影响.结果表明,PPU是一种粒子尺寸分布在30~50μm范围的形状不规则的多孔粒子,孔径在2 nm~100μm之间呈连续分布.在pH=8.0的缓冲溶液中用0.17 mol/L的GA对PPU进行改性,将改性后的PPU用于PFL的固定,当酶溶液浓度为2.56 mg/m L时,得到酶的最大固定量为95.2 mg/g,固定酶的活性为375 U/mg,相对活性为76%.将此固定酶作为催化剂,用于1-苯乙醇外消旋化合物的手性拆分,并与游离酶催化的结果相比较.结果表明,固定酶的反应活性和立体选择性都明显优于游离酶.通过沉淀聚合制备的聚脲多孔材料在酶固定及手性分子拆分方面具有应用前景.     

Carrageenan for encapsulation and immobilization of flavor,fragrance, probiotics,and enzymes: A review

Carrageenans are sulfated polysaccharides obtained from sea weed. There are six types of carrageenans. They have been explored as gelling agents, control release vehicles, and encapsulating agents. It has been established that carrageenans, in the form of gels, beads and films, can efficiently encapsulate flavors, fragrances, probiotics, and enzymes. Flavors and fragrances are encapsulated to reduce their volatility. Probiotic encapsulation results in enhanced stability. Immobilization of enzymes in carrageenans improves their biocatalytic performance and stability. This review has summarized how carrageenans have been extensively investigated as potential encapsulating agents for the above-mentioned attributes.     

Potassium Acyltrifluoroborate (KAT) Ligations are Orthogonal to Thiol‐Michael and SPAAC Reactions: Covalent Dual Immobilization of Proteins onto Synthetic PEG Hydrogels

The covalent immobilization of peptides, proteins, and other biomolecules to hydrogels provides a biologically mimicking environment for cell and tissue growth. Bioorthogonal chemical reactions can serve as a tool for this, but the paucity of such reactions and mutual incompatibilities limits the number of distinct molecules that can be introduced. We now report that the potassium acyltrifluoroborate (KAT ) amide‐forming ligation is orthogonal to both thiol‐Michael and strain promoted azide alkyne cycloadditions (SPAAC ) and the requisite functional groups – KAT s and hydroxylamines – are stable and compatible to hydrogel formation, protein modification, and post‐assembly immobilization of biomolecules onto hydrogels. In combination these ligations enables stepwise covalent protein immobilization of multiple BSA ‐derivatives onto the hydrogel scaffold regardless of the order of addition.     

Evaluation of a Gelatin-Modified Poly(ε-Caprolactone) Film as a Scaffold for Lung Disease

Lung transplantation is a necessary step for the patients with the end stage of chronic obstructive pulmonary disease. The use of artificial lungs is a promising alternative to natural lung transplantation which is complicated and is restricted by low organ donations. For successful lung engineering, it is important to choose the correct combination of specific biological cells and a synthetic carrier polymer. The focus of this study was to investigate the interactions of human lung epithelial cell line NCl-H292 that is involved in lung tissue development with the biodegradable poly(ε-caprolactone) before and after its chemical modification to evaluate potential for use in artificial lung formation. Also, the effect of polymer chemical modification on its mechanical and surface properties has been investigated. The poly(ε-caprolactone) surface was modified using aminolysis followed by immobilization of gelatin. The unmodified and modified polymer surfaces were characterized for roughness, tensile strength, and NCl-H292 metabolic cell activity. The results showed for the first time the possibility for NCI-H292 cells to adhere on this polymeric material. The resazurin assay showed that the metabolic activity at 24?h postseeding of 80% in the presence of the unmodified and greater than 100% in the presence of the modified polymer was observed. The roughness of the poly(ε-caprolactone) increased from 4 to 26?nm and the film strength increased from 0.01 to 0.045 kN when the material was chemically modified. The results obtained to date show potential for using modified poly(ε-caprolactone) as a scaffold for lung tissue engineering.     

Phytosynthesis of Silver Nanoparticles Using Walnut (Juglans regia) Bark with Characterization of the Antibacterial Activity against Streptococcus mutans

A green method using Juglans regia bark extract was used to synthesize silver nanoparticles at room temperature with monitoring by absorption spectroscopy. The size and shape of the synthesized nanoparticles were characterized by infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, high-resolution transmission electron microscopy, and small-angle X-ray scattering. The average particle size was from 10 to 30?nm. Gas chromatography–mass spectrometry (GC–MS) was used for the separation, identification, and quantification of components of the plant extracts. A possible mechanism for the synthesis of nanoparticles was elucidated based on the GC–MS results. The synthesized silver nanoparticles showed effective inhibition against Streptococcus mutans, which is the main causative agent for dental caries. The nanoparticles also showed promising antibiofilm activity by inhibiting the glucosyltransferase enzyme.