The influence of chemical structure on the antimicrobial activities of thiosemicarbazone-chitosan

We have previously reported the preparation of acetyl and benzoyl phenyl-thiosemicarbazone derivatives of chitosan and their antimicrobial activities. The purpose of this study was to further assess the relationship between chemical structure and antimicrobial activity of chloracetyl phenyl-thiosemicarbazone-chitosan. Ten new chloracetyl phenyl-thiosemicarbazone-chitosans were prepared, and their structures were characterized using FT-IR and elemental analysis. The synthesized compounds were tested against four species of bacteria and four crop-threatening pathogenic fungi. Different molecular weights and concentrations were evaluated. The antifungal activities of the synthesized compounds were related to the positive polarity of the N₄ atom and the distribution of the electron atmosphere in the C=S group. All chitosan compounds had inhibitory effects when tested with bacteria. The minimum MIC and MBC with Escherichia coli were 7.03 and 56.25 μg mL^?1, respectively.     

Polymeric biocomposites of poly (butylene adipate-co-terephthalate) reinforced with natural Munguba fibers

In this work, polymeric biocomposites of poly (butylene adipate-co-terephthalate), PBAT, were reinforced with Munguba fibers (Pseudobombax munguba). This tree is found in great abundance in the marshy areas of the Amazon forest. The motivation for using this fiber in polymer composites comes from the fact that although research for this fiber has not been reported in the scientific literature, it is commonly used by the local population because its bark is strong and flexible. Most important is that the extraction of Munguba fibers does not damage the supplier tree because as it is extracted from the bark, its regeneration starts as it is removed. The fibers were chemically treated by mercerization/acetylation and evaluated by Fourier transform infrared spectroscopy, thermogravimetric analysis and tensile tests. The Munguba fiber presented mechanical properties similar to those of other natural fibers traditionally used in composites, and the chemical treatment provided improvements of its thermal stability and stiffness. The biocomposites showed a better elastic modulus in relation to the pure PBAT. The addition of fibers caused changes in the T _g, T _m and T _c of PBAT as observed by differential scanning calorimetry analysis. The Russel, Halpin-Tsai and Maxwell models were employed to provide the theoretical elastic modulus of the biocomposites.     

Molecular dynamics simulation study of xyloglucan adsorption on cellulose surfaces: effects of surface hydrophobicity and side-chain variation

The effect of surface hydrophobicity and side-chain variation on xyloglucan adsorption onto cellulose microfibrils (CMF) is investigated via molecular dynamics simulations. A molecular model of CMF with (100), (010), (1–10), (110) and (200) crystal faces was built. We considered xylogluco-oligosaccharides (XGO) with three repeating units, namely (XXXG)_3, (XXLG)₃, and (XXFG)₃ (where each (1,4)-β-d-glucosyl residue in the backbone is given a one-letter code according to its substituents: G = β-d-Glc; X = α-d-Xyl-(1,6)-β-d-Glc; L = β-d-Gal-(1,2)-α-d-Xyl-(1,6)-β-d-Glc; F = α-l-Fuc-(1,2)-β-d-Gal-(1,2)-α-d-Xyl-(1,6)-β-d-Glc). Our work shows that (XXXG)₃ binds more favorably to the CMF (100) and (200) hydrophobic surfaces than to the (110), (010) and (1–10) hydrophilic surfaces. The origin of this behavior is attributed to the topography of hydrophobic CMF surface, which stabilizes (XXXG)₃ in flat conformation. In contrast, on the rough hydrophilic CMF surface (XXXG)₃ adopts a less favorable random-coil conformation to facilitate more hydrogen bonds with the surface. Extending the xyloglucan side chains from (XXXG)₃ to (XXLG)₃ hinders their stacking on the CMF hydrophobic surface. For (XXFG)₃, the interaction with the hydrophobic surface is as strong as (XXXG)₃. All three XGOs have similar binding to the hydrophilic surface. Steered molecular dynamics simulation was performed on an adhesive model where (XXXG)₃ was sandwiched between two CMF hydrophobic surfaces. Our analysis suggests that this sandwich structure might help provide mechanical strength for plant cell walls. Our study relates to a recently revised model of primary cell walls in which extensibility is largely determined by xyloglucan located in limited regions of tight contact between CMFs.     

Novel hydrothermal carbonization of cellulose catalyzed by montmorillonite to produce kerogen-like hydrochar

The conversion of cellulose to petroleum-like fuel is a very challenging yet attractive route to developing biomass-to-fuel technology. Many attempts have been made in liquefaction, pyrolysis and gasification of cellulose to produce fuels or intermediate chemicals. Previous studies indicate that these processes are tough. Hence, the present work is concerned with the development of new technologies for the conversion of cellulose into materials which are analogies to the precursor of petroleum. Montmorillonite-catalyzed hydrothermal carbonization of microcrystalline cellulose for the production of kerogen-like hydrochar under mild conditions was investigated. It was revealed that the hydrothermal carbonization of microcrystalline cellulose alone resulted in hydrochar with type III kerogen-like structure, whereas in the presence of montmorillonite, the hydrothermal carbonization of microcrystalline cellulose yielded a hydrochar-mineral complex, of which the isolated organic fraction was oil-prone type II kerogen-like structure. Results suggested that further improved montmorillonite-aided biomass conversion to more oil-prone kerogen-like solid products could be an alternative efficient route to obtain biofuel and chemicals.     

圆二色法研究铜离子存在下葛根素对牛血清白蛋白二级结构的影响

采用圆二色光谱法(CD)研究了Cu2+存在下葛根素(PUE)对牛血清白蛋白(BSA)二级结构的影响。结果表明,在pH 7.4的条件下,BSA的各种二级结构分别为56.3%α-螺旋,26.1%β-折叠,17.6%转角和无规则卷曲。葛根素和Cu2+-葛根素都能诱导BSA二级结构发生改变。葛根素使BSA的α-螺旋含量增加,β-折叠含量减少,这表明葛根素与BSA的相互作用,可使蛋白质分子的疏水作用增强,导致BSA的肽链结构收缩。Cu2+-葛根素使BSA的α-螺旋含量大幅度降低,β-折叠含量略有增加,这表明Cu2+-葛根素与BSA的相互作用以配位作用为主,使得BSA的肽链结构伸展,蛋白质的构象发生变化。     

侧链为端羧基聚乙二醇的梳形聚氨酯的合成与表征

以L-赖氨酸、乙二胺和端羧基聚乙二醇(PEG)为原料合成一种带聚乙二醇侧链的二元胺扩链剂(Lys-NH-PEG),然后以4,4'-二苯基甲烷二异氰酸酯(MDI)和Lys-NH-PEG为硬段,聚碳酸酯二醇(PCD)为软段,制备一种含端羧基聚乙二醇侧链的梳形聚氨酯.对所合成聚氨酯材料进行傅立叶变换红外光谱(FTIR)、氢核磁共振谱(1H-NMR)、凝胶渗透色谱(GPC)测试,测试结果表明得到了目标聚合物.该聚合物能在水中形成胶体,并能化学接枝白蛋白,表明所合成的聚氨酯的PEG侧链端羧基具有反应活性.这种具有可反应性的聚氨酯为进一步接枝生物分子以提高生物相容性提供了广阔的空间.     

Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone

A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported.     

Enhancement of Solar Hydrogen Evolution from Water by Surface Modification with CdS and TiO2 on Porous CuInS2 Photocathodes Prepared by an Electrodeposition–Sulfurization Method

Porous films of p‐type CuInS₂, prepared by sulfurization of electrodeposited metals, are surface‐modified with thin layers of CdS and TiO₂. This specific porous electrode evolved H₂ from photoelectrochemical water reduction under simulated sunlight. Modification with thin n‐type CdS and TiO₂ layers significantly increased the cathodic photocurrent and onset potential through the formation of a p–n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H₂ production under the present reaction conditions.     

A Molecular Copper Catalyst for Electrochemical Water Reduction with a Large Hydrogen‐Generation Rate Constant in Aqueous Solution

The copper complex [(bztpen)Cu](BF₄)₂ (bztpen=N‐benzyl‐N,N′,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine) displays high catalytic activity for electrochemical proton reduction in acidic aqueous solutions, with a calculated hydrogen‐generation rate constant (k_obs) of over 10000 s^?1. A turnover frequency (TOF) of 7000 h^?1 cm^?2 and a Faradaic efficiency of 96 % were obtained from a controlled potential electrolysis (CPE) experiment with [(bztpen)Cu]²⁺ in pH 2.5 buffer solution at ?0.90 V versus the standard hydrogen electrode (SHE) over two hours using a glassy carbon electrode. A mechanism involving two proton‐coupled reduction steps was proposed for the dihydrogen generation reaction catalyzed by [(bztpen)Cu]²⁺.     

Ultrasound/microwave‐assisted extraction and comparative analysis of bioactive/toxic indole alkaloids in different medicinal parts of Gelsemium elegans Benth by ultra‐high performance liquid chromatography with MS/MS

Indole alkaloids are the main bioactive/toxic components in Gelsemium elegans Benth. To determine the distribution and contents of indole alkaloids in its different medicinal parts, a novel and rapid method using ultra‐high performance LC (UPLC) with MS/MS has been established and validated with an optimized ultrasound/microwave‐assisted extraction method. Four constituents, namely, humantenidine, humantenmine, gelsemine, and koumine, were simultaneously determined in 6 min. Chromatographic separation was achieved on an ultra‐high performance LC BEH C₁₈ column with a gradient mobile phase consisting of methanol and water (containing 0.1% formic acid both in methanol and water) at a flow rate of 0.3 mL/min. The detection was performed on a triple quadrupole electrospray MS/MS by positive ion multiple‐reaction monitoring mode. All the analytes showed good linearity (r ≥ 0.9934) within a concentration range from 0.1–25 μg/mL with a LOQ of 25–50 ng/mL. The overall intra‐ and intervariations of four components were <4.7% with an accuracy of 97.3–101.3%. The analysis results showed that there were remarkable differences in the distribution and contents of four chemical markers in the roots, stems, and leaves of G. elegans Benth. The findings can provide necessary and meaningful information for the rational utilization of its resources.