有机硅氨基酸衍生物的研究

本文利用含氢有机硅化合物与含双键的氨基酸酯的加成反应,合成了5种新的有机硅氨基酸衍生物。介绍了一种合成N-烷基取代氨基酸酯的新方法。对新化合物进行了元素和光谱分析鉴定。     

催化动力学光度法测定痕量钒（Ⅴ）的研究

本文研究了在酸性介质中痕量钒（Ⅴ）催化氯酸钾氧化变色酸及抗坏血酸体系的反应和动力学条件，建立了催化动力学光度法测定痕量钒（Ⅴ）的新方法。该方法的检出限为０．０８ｎｇ／ｍＬ Ｖ（Ⅴ），线性范围为０～０．３μｇ／２５ｍＬ Ｖ（Ⅴ）。将该方法用于水样及人发中痕量钒（Ⅴ）测定，结果令人满意。     

高效液相色谱/串联质谱法快速鉴定Z/E盐酸头孢吡肟异构体

采用高效液相色谱/串联质谱技术建立了快速鉴定Z型盐酸头孢吡肟原料药中E型异构体杂质的新方法。以乙腈-醋酸盐缓冲溶液(4∶96)为流动相经C18柱分离,通过高分辨电喷雾串联质谱在线检测,获得了相关的色谱和质谱信息。在所建立条件下,Z型盐酸头孢吡肟及其E型异构体杂质获得了有效分离,保留时间分别为5.22 m in和14.60 m in,同时它们的二级质谱及裂解方式呈现明显差异。本法能在无对照品情况下,快速、准确地分离鉴定盐酸头孢吡肟原料药中的Z/E异构体。     

Hydrosilylation Catalyzed with Rh(PPh3)3Cl/Ionic-Liquid–Functionalized SiO2

Ionic liquid–modified silica has been prepared by a “one-pot” reaction of activated silica, 3-chloropropyltriethoxysilane, and alkylimidazole or pyridine. It was found that the catalytic activity and β-adduct selectivity of the supported catalyst Rh(PPh₃)₃Cl/ionic-liquid–modified-SiO₂ for the hydrosilylation reaction of alkenes with triethoxysilane was significantly improved. Furthermore, the catalyst system could be recovered easily.     

Formation of reversible shell cross-linked micelles from the biodegradable amphiphilic diblock copolymer poly(L-cysteine)-block-poly(L-lactide)

A novel biodegradable diblock copolymer, poly(L-cysteine)-b-poly(L-lactide) (PLC-b-PLLA), was synthesized by ring-opening polymerization (ROP) of N-carboxyanhydride of beta-benzyloxycarbonyl-L-cysteine (ZLC-NCA) with amino-terminated poly(L-lactide) (NH 2-PLLA) as a macroinitiator in a convenient way. The diblock copolymer and its precursor were characterized by (1)H NMR, Fourier transform infrared (FT-IR), gel permeation chromatography (GPC), and X-ray photoelectron spectroscopy (XPS) measurements. The length of each block polymer could be tailored by molecular design and the ratios of feeding monomers. The cell adhesion and cell spread on the PZLC-b-PLLA and PLC-b-PLLA films were enhanced compared to those on pure PLA film. PLC-b-PLLA can self-assemble to form micelles in aqueous media. A pyrene probe is used to demonstrate the micelle formation of PLC-b-PLLA in aqueous solution. Due to the ease of disulfide exchange with thiols, the obtained micelles are reversible shell cross-linked (SCL) micelles. The morphology and size of the micelles are studied by dynamic light scattering (DLS) and environmental scanning electron microscopy (ESEM).     

SBA-15负载Pd催化剂的制备及其在Heck反应中的应用研究

利用水热反应制备了表面离子液体功能化的SBA-15介孔材料,在丙酮溶液中与氯化钯反应,然后使用水合肼在乙醇中还原.测试了这种催化剂在Mizoroki-Heck反应中的催化活性.与直接负载在SBA-15上的钯催化剂相比,这种表面修饰的介孔SBA-15负载催化剂表现出更高的催化活性、可回收性和反应稳定性.氮气吸脱附实验和小角XRD衍射实验表明,在合成中,材料的介孔性能并没有被破坏.透视电镜也表征了该材料的表面形貌.最后,Mizoroki-Heck反应表明该催化剂具有很高的催化活性,且循环五次后,其催化活性降低并不明显.     

4-苯基-1,3-硒唑衍生物的合成及其对蛋白酪氨酸磷酸酯酶-1B抑制活性

蛋白酪氨酸磷酸酯酶-1B(PTP1B)是抗糖尿病治疗的重要靶点,因此创制活性优良的PTP1B抑制剂具有重要意义。 本文设计并合成了11个含1,3-硒唑和1,2,4-三唑活性组块新型结构目标分子(ZLXZ1-ZLXZ11),并利用傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(NMR)和高分辨质谱(HRMS)等对其进行了结构表征。 首先选择ZLXZ1和ZLXZ11在MOE 2015.10程序上,与PTP1B进行分子对接模拟,结果表明,在ZLXZ1分子中硒唑环上的硒原子与PTP1B中副催化位点Tyr46、Ala217、Lys120和Asp 48分别形成了π-H作用和氢键作用。 在ZLXZ11分子中硒唑上的硒原子与PTP1B中Asp181、Arg221和Asp48形成了氢键作用。 在分子对接模拟的基础上,测试了11个目标分子的抑制活性,结果表明,所有目标分子的抑制率均在87.02%以上,其中3个目标分子PTP1B抑制活性高于阳性参照物齐墩果酸,抑制活性优良,有望成为潜在的PTP1B抑制剂。     

In situ vaccination and gene-mediated PD-L1 blockade for enhanced tumor immunotherapy

Despite of the promising achievements of immune checkpoints blockade therapy (ICB) in the clinic, which was often limited by low objective responses and severe side effects. Herein, we explored a synergistic strategy to combine in situ vaccination and gene-mediated anti-PD therapy, which was generated by unmethylated cytosine-phosphate-guanine (CpG) and pshPD-L1 gene co-delivery. PEI worked as the delivery carrier to co-deliver the CpG and pshPD-L1 genes, the formed PDC (PEI/DNA/CpG) nanoparticles were further shielded by aldehyde modified polyethylene glycol (OHC-PEG-CHO) via pH responsive Schiff base reaction for OHC-PEG-CHO-PEI/DNA/CpG nanoparticles (P(PDC) NPs) preparation. All steps could be finished within 30 min. Such simple nanoparticles achieved the synergistic antitumor efficacy in B16F10 tumor-bearing mice, and the amplified T cell responses, together with enhanced NK cells infiltration were observed after the combined treatments. In addition, the pH responsive delivery system reduced the side effects triggered by anti-PD therapy. The facile and effective combination strategy we presented here might provide a novel treatment for tumor inhibition.     

BSA‐IrO2: Catalase‐like Nanoparticles with High Photothermal Conversion Efficiency and a High X‐ray Absorption Coefficient for Anti‐inflammation and Antitumor Theranostics

Intrinsically integrating precise diagnosis, effective therapy, and self‐anti‐inflammatory action into a single nanoparticle is attractive for tumor treatment and future clinical application, but still remains a great challenge. In this study, bovine serum albumin–iridium oxide nanoparticles (BSA‐IrO₂ NPs) with extraordinary photothermal conversion efficiency, good photocatalytic activity, and a high X‐ray absorption coefficient were prepared through one‐step biomineralization. The nanoparticles allow tumor phototherapy and simultaneous photoacoustic/thermal imaging and computed tomography. More importantly, BSA‐IrO₂ NPs can also act as a catalase to protect normal cells against H₂O₂‐induced reactive oxygen pressure and inflammation while significantly enhancing photoacoustic imaging through microbubble‐based inertial cavitation. These remarkable features may open up the exploration iridium‐based nanomaterials in theranostics.     

A High Sensitivity Electrochemical Sensor Based on Fe3+‐Ion Molecularly Imprinted Film for the Detection of T‐2 Toxin

The excellent detection sensitivity in various matrices of T‐2 toxin (T‐2), which has cytotoxic and immunosuppressive effects in DNA and RNA synthesis, is a highly desirable characteristic. A sensitive molecularly imprinted electrochemical sensor was constructed for the selective detection of T‐2. In this study, iron ions (Fe³⁺) were introduced to increase the chelation of the metal ions and templates for preparing molecularly imprinted polymers (MIPs). With the increased chelation of the metal ions and templates, the selectivity and sensitivity of the MIPs were effectively improved. The imprinted sensor was successfully employed to detect T‐2 in cereals and human serum samples.