基于氮掺杂活性炭催化氧化合成氮甲基氧化吗啉的研究

以三聚氰胺为氮源,商用活性炭为研究对象,通过“浸渍吸附+高温热处理”的方式制得系列氮掺杂活性炭,并用于催化氧化合成氮甲基氧化吗啉（NMMO）。采用N₂吸附/脱附、Raman、XPS等对氮掺杂活性炭的孔结构和表面性质进行了表征。结果表明：随着三聚氰胺负载量的增大,氮掺杂活性炭的表面碱性含氮官能团含量增大,进而体现出更好的催化氧化合成NMMO活性。最佳催化剂（ACO850-20N）在催化剂加量为0.02 wt%,反应温度70 ℃和反应时间4 h的工艺条件下,氮甲基吗啉的转化率和NMMO收率可达99.76%和94.31%。      

油井用相变微胶囊的制备与性能

针对深水固井作业过程中水泥水化放热较大,易致使环空地层天然气水合物分解的技术难题,本文以石蜡为芯材,碳酸钡为壁材,制备了一种油井用相变微胶囊。首先,利用FT-IR、DSC、TGA与SEM对相变微胶囊的化学组成、热性能与微观形貌进行了表征。结果表明：相变微胶囊的封装效率为67.40%,具有较高的封装效率和良好的潜热储存能力。其次,对粒径分布与润湿性能进行了测试。结果表明：微胶囊颗粒平均粒径为4.946 μm,小于水泥颗粒粒径17.201 μm,可较好的镶嵌在水泥石中,并充填于水泥水化产物之间,减小对水泥石力学性能的负面影响;微胶囊与水的静态接触角为46.8°,具有良好的亲水性能,可应用于水基的水泥浆环境中。最后,将微胶囊应用于水泥浆体系,研究了水泥浆的水化温升和水化热。结果表明：与空白水泥浆相比,加入12%相变微胶囊水泥浆的最高水化温升与水化热（48 h）分别下降了14.56%和43.23%。      

新型喹喔啉-三苯胺衍生物的合成及其对Fe3+的识别性能

以4,4-二溴苯偶酰为原料,经过两步反应得到一种新的喹喔啉-三苯胺衍生物4',4''-（6-溴喹喔啉-2,3-二基）双（N,N-二苯基-[1,1'-联苯] -4-胺）（TP1）。通过¹H NMR、¹³C NMR和HR-MS对其结构进行了表征,并利用紫外-可见吸收光谱和荧光光谱研究了衍生物对Fe³⁺的识别性能。光谱测试结果表明：衍生物溶液与Fe³⁺作用后,296nm处的吸光度出现明显变化,说明TP1能选择性识别Fe³⁺;当Fe³⁺浓度为4～200μmol/L时,TP1吸光度与Fe³⁺浓度呈现良好的线性回归关系(R²=0.9977)。      

Sin-QuEChERS净化-超高效液相色谱-串联质谱法测定鱼肉中8种喹诺酮类药物残留量北大核心CSCD

将粉碎后的鱼肉样品2.00 g置于50 mL离心管中,加入100μg·L^(-1)内标溶液200μL和水5 mL,涡旋1 min后,用含5%(体积分数)乙酸的乙腈溶液10 mL超声提取10 min,加盐包(6 g无水硫酸镁、1.5 g氯化钠)使水相和乙腈相进行分层.涡旋、离心后,使用Sin-QuEChERS快速滤过柱直接插入离心管内,待提取液透过净化层上升至净化柱内时,移取5 mL提取液置于15 mL离心管内,加入体积比1∶1的乙腈-正己烷混合液5 mL,混匀静置,取上层正己烷层涡旋,离心,于40℃氮气吹至近干,用0.2%(体积分数)甲酸溶液定容至1 mL,过滤后上机UHPLC-MS/MS,在多反应监测模式下测定8种喹诺酮类药物的残留量.结果显示:该净化方法溶剂消耗降低至10 mL,前处理时间缩短至20~25 min.环丙沙星、培氟沙星、诺氟沙星、二氟沙星和达氟沙星标准曲线的线性范围均为1.00~500.0μg·L^(-1),检出限(3S/N)均为1.0μg·kg^(-1);氧氟沙星、恩诺沙星和沙拉沙星标准曲线的线性范围为0.50~500.0μg·L^(-1),检出限(3S/N)均为0.5μg·kg^(-1).用此法平行测定同一样品7次,测定值的相对标准偏差为1.3%~6.3%.按标准加入法进行回收试验,回收率为92.0%~108%.此法用于抽检兰州4家超市的3种鱼类,8种喹诺酮类药物均未检出,说明兰州市的鱼类食品中的药物残留问题相对安全.同时,与国家农业部1077号公告-1-2008中方法进行比对,测定结果基本一致.     

Enantioselective Synthesis of Chiral Carboxylic Acids from Alkynes and Formic Acid by Nickel-Catalyzed Cascade Reactions: Facile Synthesis of Profens

We report a stereoselective conversion of terminal alkynes to α-chiral carboxylic acids using a nickel-catalyzed domino hydrocarboxylation-transfer hydrogenation reaction. A simple nickel/BenzP* catalyst displayed high activity in both steps of regioselective hydrocarboxylation of alkynes and subsequent asymmetric transfer hydrogenation. The reaction was successfully applied in enantioselective preparation of three nonsteroidal anti-inflammatory profens (>90 % ees) and the chiral fragment of AZD2716.     

高效液相色谱-串联质谱法同时检测血液中3种季铵盐类肌松剂

维库溴铵、罗库溴铵和泮库溴铵是一类广泛使用的非去极化肌松剂,使用过程中引起过敏反应甚至死亡的情况时有发生,快速检测血液中该类肌松剂的浓度,可为临床早期诊断提供有价值的信息.该类肌松剂为强极性的季铵盐类化合物,在反相色谱柱上难以保留,主要采用离子对色谱法进行分离.采用离子对色谱法时,加入的离子对试剂有离子抑制作用,可降低...     

Surface Functionalization of PEO Nanofibers Using a TiO2 Suspension as Sheath Fluid in a Modified Coaxial Electrospinning Process

Convenient and integration fabrication process is a key issue for the application of functional nanofibers. A surface functionalization method was developed based on coaxial electrospinning to produce ultraviolet(UV) protection nanofibers. The titanium dioxide(TiO₂) nanoparticles suspension was delivered through the shell channel of the coaxial spinneret, by which the aggregation of TiO₂ nanoparticles was overcome and the distribution uniformity on the surface of polyethylene oxide(PEO) nanofiber was obtained. With the content of TiO₂ increasing from 0 to 3%(mass fraction), the average diameter of nanofibers increased from (380±30) nm to (480±100) nm. The surface functionalization can be realized during the electrospinning process to gain PEO/TiO₂ composite nanofibers directly. The uniform distribution of TiO₂ nanoparticles on the surface of nanofibers enhanced the UV absorption and resistance performance. The maximum UV protection factor(UPF) value of composite nanofibers reaches 2751. This work presented a novel surface-functionalized way for the preparation of composite nanofiber, which has great application potential in the field of micro/nano system integration fabrication.     

Intelligent stimuli-responsive nano immunomodulators for cancer immunotherapy

Cancer immunotherapy is a revolutionary treatment method in oncology, which uses a human''s own immune system against cancer. Many immunomodulators that trigger an immune response have been developed and applied in cancer immunotherapy. However, there is the risk of causing an excessive immune response upon directly injecting common immunomodulators into the human body to trigger an immune response. Therefore, the development of intelligent stimuli-responsive immunomodulators to elicit controlled immune responses in cancer immunotherapy is of great significance. Nanotechnology offers the possibility of designing smart nanomedicine to amplify the antitumor response in a safe and effective manner. Progress relating to intelligent stimuli-responsive nano immunomodulators for cancer immunotherapy is highlighted as a new creative direction in the field. Considering the clinical demand for cancer immunotherapy, we put forward some suggestions for constructing new intelligent stimuli-responsive nano immunomodulators, which will advance the development of cancer immunotherapy.

Progress relating to intelligent stimuli-responsive nano immunomodulators for cancer immunotherapy is highlighted. Suggestions for constructing new strategies have been put forward, which will advance the clinical development of cancer immunotherapy.     

Streamlined construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation in solution and on DNA

A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.

A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed.