Studies on thermokinetic and reactive mechanism of graphdiyne-based NC composite via multi isoconversional methods and model reconstruction

Cellulose - In this work, graphdiyne (GDY) is used for the first time as the catalyst for the pyrolysis process of nitrocellulose (NC). By DSC and TG-IR-MS results, the compatibility and the...     

The CGC enantiomer separation of 2-arylcarboxylic acid esters by using β-cyclodextrin derivatives as chiral stationary phases

Chiral 2-arylcarboxylic acid esters are important intermediates in preparation of enantioenriched 2-arylpropionic acids type Non-steroidal anti-inflammatory drugs (NSAIDs). Enantiomer separation of 2-arylcarboxylic acid esters is crucial for evaluation of the asymmetric synthesis efficiency and the enantiomer excess of chiral 2-arylcarboxylic acid derivatives. The capillary gas chromatography (CGC) enantiomer separation of 17 pairs of 2-arylcarboxylic acid esters enantiomers was conducted by using seven different β-cyclodextrin derivatives (CDs) as chiral stationary phases. It was found that for the 7 pairs of 2-phenylpropionates enantiomers, CDs with both alkyl and acyl substituents especially 2,6-di-O-pentyl-3-O-butyryl-β-cyclodextrin exhibited better enantiomer separation abilities than the other CDs examined. For the 7 pairs of 2-(4-substituted phenyl)propionates enantiomers, 2,3,6-tri-O-methyl-β-cyclodextrin possessed better enantiomer separation abilities than the other CDs. Among the 3 pairs of 2-phenylbutyrates enantiomers examined, only methyl 2-phenylbutyrate enantiomers could be separated by three CDs among the 7 CDs tested, while enantiomers of ethyl 2-phenylbutyrate and isopropyl 2-phenylbutyrate couldn't be separated by any of the 7 CDs tested. Besides the structures of CDs, the structures of 2-arylcarboxylic acid esters including different ester moieties, substituents of phenyl, and different carboxylic acids moieties in 2-arylcarboxylic acid esters also affected the enantiomer separation results greatly. The CGC enantiomer separation results of 2-arylcarboxylic acid esters on different CDs are useful for solving the enantiomer separation problem of 2-arylcarboxylic acid esters.     

Palladium‐Catalyzed Asymmetric Allylic Alkylations with Toluene Derivatives as Pronucleophiles

The first two highly enantioselective palladium‐catalyzed allylic alkylations with benzylic nucleophiles, activated with Cr(CO)₃, have been developed. These methods enable the enantioselective synthesis of α‐2‐propenyl benzyl motifs, which are important scaffolds in natural products and pharmaceuticals. A variety of cyclic and acyclic allylic carbonates are competent electrophilic partners furnishing the products in excellent enantioselectivity (up to 99 % ee and 92 % yield). This approach was employed to prepare a nonsteroidal anti‐inflammatory drug analogue.     

吡咯并[3,4-c]吡唑衍生的Aurora激酶抑制剂在电喷雾质谱中的裂解规律研究

吡咯并[3,4-c]吡唑衍生的Aurora激酶抑制剂是具有良好开发前景的新型抗肿瘤药物之一. 采用电喷雾-四级杆飞行时间串联质谱技术, 对4种吡咯并[3,4-c]吡唑衍生的Aurora激酶抑制剂在电喷雾质谱中的裂解途径及其碎片离子结构进行研究. 实验结果表明: 吡咯并[3,4-c]吡唑衍生物拥有4个可能的质子化模式, 不同的质子化作用会产生不同的碎片离子, 且吡咯并[3,4-c]吡唑衍生物N(5)-CO键断裂所产生的碎片离子相对丰度较高, 可以作为药物代谢动力学及酶学水平研究中质谱的特征性碎片离子. 需要指出的是, 化合物3, 4能够分别丢失一分子水形成碎片离子[M+H-H₂O]⁺, 根据高分辨质谱和理论计算结果我们推测该过程是由质子化作用发生在酰胺氧原子上引发的, 而CID条件下N(5)-CO键的进一步断裂可产生相对丰度较高的碎片离子.     

Non-isothermal crystallization kinetics of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–CaO–SiO<Subscript>2</Subscript> glass containing nucleation agent P<Subscript>2</Subscript>O<Subscript>5</Subscript>/TiO<Subscript>2</Subscript>

Fe₂O₃–CaO–SiO₂ glass ceramics containing nucleation agent P₂O₅/TiO₂ were prepared by sol-gel method. The samples were characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The activation energy and kinetic parameters for crystallization of the samples were calculated by the Johnson-Mehi-Avrami (JMA) model and Augis-Bennett method according to the results of DSC. The results showed that the crystallization mechanism of Fe₂O₃–CaO–SiO₂ glass, whose non-isothermal kinetic parameter n = 2.3, was consistent with surface crystallization of the JMA model. The kinetics model function of Fe₂O₃–CaO–SiO₂ glass, f(α) = 2.3(1–α)[–ln(1–α)]^0.57, was also obtained. The addition of nucleation agent P₂O₅/TiO₂ could reduce the activation energy, which made the crystal growth modes change from onedimensional to three-dimensional.     

Study on Purification and Characterization of Polyphenol Oxidase from Acetes chinensis

Acetes chinensis (belonging to the Decapoda Sergestidae genus) is widely distributed in East Asian waters and is extremely widespread and present in the shallow coastal areas of China. Polyphenol oxidase (PPO), which was extracted from Acetes chinensis, was purified in a four-step procedure involving phosphate-buffered saline treatment, ammonium sulphate precipitation, DEAE-Cellulose chromatography, and Phenyl-Sepharose HP chromatography, and then, its biochemical characterization was measured. The specific activity of the purified enzyme was increased to 643.4 U/mg, which is a 30.35 times increase in purification, and the recovery rate was 17.9%. L-dopa was used as the substrate, the enzymatic reactions catalyzed by PPO conformed to the Michaelis equation, the maximum reaction velocity was 769.23 U/mL, and the Michaelis constant K_m was 0.846 mmol/L. The optimal pH of PPO from Acetes chinensis was 7.5, and the optimal temperature was 35 °C. The metal ions experiment showed that Mn²⁺ and K⁺ could enhance the activity of PPO; that Ba²⁺ and Ca²⁺ could inhibit the activity of PPO; and that Cu²⁺ had a double effect on PPO, increasing the PPO activity at low concentrations and inhibiting the PPO activity at high concentrations. The inhibitor experiment showed that the inhibitory effects of EDTA and kojic acid were weak and that ascorbic acid and sodium pyrophosphate had good inhibitory effects. The purification and characterization of Acetes chinensis serve as guidelines for the prediction of enzyme behavior, leading to effective prevention of enzymatic browning during processing.     

Polysaccharide conjugate vaccine:A kind of vaccine with great development potential

Diseases caused by microbial bacteria such as Haemophilus influenzae type b(Hib),Streptococcus pneumoniae and Neisseria meningitidis are still very serious disease,which has brought a lot of burden to many countries.Development of vaccine has brought hope for the prevention of such diseases.Polysaccharide conjugate vaccines have been shown to have very good effects in preventing such diseases.The polysaccharide co njugate vaccine adds the positive characteristics of protein antigens to the polysaccharide antigen,thereby improving the immunogenicity of the polysaccharide antigen,solving the problem that the polysaccharide vaccine cannot be effectively applicated in toddler or children,which greatly promoting the development of this vaccine.This review introduces the progress of polysaccharide conjugate vaccines.We introduce the typical polysaccharide conjugate vaccines currently on the market firstly,and then elucidate the protein carriers,the coupling chemistry methods and quality control that required in the preparation of polysaccharide conjugate vaccines.We can see that polysaccharide conjugate vaccine is a kind of vaccine with great development potential,which can be a sharp edge for us to prevent diseases.     

Nickel‐Catalyzed Allylic Alkylation with Diarylmethane Pronucleophiles: Reaction Development and Mechanistic Insights

Palladium‐catalyzed allylic substitution reactions are among the most efficient methods to construct C?C bonds between sp³‐hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a “soft”‐nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with “hard” nucleophiles, which attack the metal before C?C bond formation. Introduced herein is a rare nickel‐based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft‐nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising.     

Transmission resonance for a Dirac particle in a one-dimensional Hulthén potential

We have solved exactly the two-component Dirac equation in the presence of a spatially one-dimensional Hulthén potential, and presented the Dirac spinors of scattering states in terms of hypergeometric functions. We have derived the reflection and transmission coefficients using the matching condition on the wavefunctions, and investigated the condition for the existence of transmission resonance. Furthermore, we have demonstrated how the transmission resonance depends on the shape of the potential.