Crystal Structures of Two Potential Tumor Imaging Agents and Therapeutic Agents Copper（Ⅱ） Ternary Complexes with Salicylidene-tyrosinato Schiff Base and Nitrogen-donor Chelating Lewis Base

The crystal structures of two potential tumor imaging agents and therapeutic agents -copper(Ⅱ) complexes with salicylidene-tyrosinato Schiff base and nitrogen-donor chelating Lewis base, [Cu(sal-tyr)(bipy)] 1 and [Cu(sal-tyr)(phen)]2CH3OH 2 are presented. Our work is helpful to get deep understanding of novel 64Cu tumor imaging agents and therapeutic agents.     

辣素微胶囊的原位聚合法制备与热降解动力学

在乳液体系中,以尿醛为壁材,以原位聚合法制备了辣素同系物———N-香草基壬酰胺微胶囊。红外光谱证实了尿醛的形成,X-射线衍射显示了同样作为半晶高分子囊壁,尿醛包裹囊心前后出现的结构晶型差异。根据吸附等温曲线假设微胶囊为紧密堆积形式,对于尿醛单体颗粒和尿醛微胶囊的TGA,采用Achar-B rind ley-Sharp-W endworth方法,对两者进行热重数据的处理,以作图法求得了动力学参数,确定了热降解动力学模式函数,回归系数良好。TGA求解的活化能数据证明由于晶型差异,导致单体与微胶囊热稳定性不同,从而与XRD结论一致。     

Preparation and characterization of poly(isobutyl methacrylate) microbeads with grafted amidoxime groups

Poly(isobutyl methacrylate) (PiBMA) microspheres with a 800- to 1500-μm diameter range synthesized by suspension polymerization technique were used as the trunk polymer in the preparation of a highly efficient new adsorbent. Glycidyl methacrylate (GMA) was grafted onto the trunk polymer by pre-irradiation grafting technique. Grafting conditions were optimized, and GMA grafted PiBMA beads were modified with iminodiacetonitrile (IDAN) in ethanol at 80 °C. The nitrile groups were then amidoximated by using 6% (m/v) hydroxylamine hydrochloride in methanol solution. The IDAN modification and the conversion of the nitrile groups to amidoxime were followed by FT-IR spectroscopy. The surface morphology and thermal behavior of the PiBMA and its modificated forms were also characterized by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques further confirming modification and amidoximation.     

手性镧系位移试剂核磁共振法测定芳氧丙酸酯类除草剂对映体纯度

以Eu(hfc)3和Pr(hfc)3为手性镧系位移试剂(CLSR),比较了两种CLSR对2,4-滴丙酸甲酯的1HNMR和13C NMR谱手性分离效果,结果表明:Pr(hfc)3比Eu(hfc)3对手性中心相连的甲基具有更好的手性分离效果。首次应用Pr(hfc)3测定了盖草能、稳杀得和喹禾灵3种手性芳氧丙酸酯类除草剂的1HNMR和13CNMR谱,其1HNMR谱分离度R约为1,盖草能和喹禾灵的13C NMR谱分离度R大于1.5,说明1H NMR和13CNMR谱手性分离效果适用于对映体纯度测定。与手性色谱法相比,CLSR-NMR法测定对映体纯度具有操作简便、分析速度快的显著优势。     

芥子气模拟剂2-氯乙基乙基硫醚的光催化降解

利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚（2-CEES）在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S；少量小分子的羧酸、醚和砜；微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C－S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活.     

联吡啶铁/H2O2体系在可见光下降解芥子气模拟剂2-CEES

采用联吡啶铁/H2O2体系在可见光照射条件下(λ>450nm)降解芥子气模拟剂2-氯乙基乙基硫醚(2-CEES).考察了不同反应条件下的降解效果,通过EPR分析确定了反应过程中产生的高活性物种,利用GC-MS和NMR等方法分析了反应的产物,跟踪了反应过程中TOC的变化,并根据结果对2-CEES光催化降解的反应机理进行了探讨.     

预富集装置在QCM传感器检测芥子气中的运用

在化学战剂的诸种检测方法中, 质量型微传感器以其响应快速、使用简便等优点成为一种理想的检测手段. 但是这种传感器的使用往往受到检出限的限制, 对于低浓度的毒剂不能及时报警. 预富集技术的运用可以提高微传感器的检测限. 本文研制了一种预富集装置并对其进行了初步测试. 芥子气通过此预富集装置之后在QCM(石英晶体微天平)传感器上的检出限可以达到0.1 mg/m3.     

Photoassisted reaction of chemical warfare agent VX droplets under UV light irradiation

A photoassisted reaction of O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX) droplets in air was carried out. The experimental results indicated that VX droplets could be easily and chemically transformed into other compounds under irradiation of a germicidal lamp over sufficient time. Quantum chemical calculation results demonstrated that UV light less than 278 nm wavelength could possibly initiate photoreaction of VX and that both P-S and P=O bonds in the VX molecule were lengthened. The identification of reaction products by gas and liquid chromatography mass spectroscopy and NMR revealed that the VX molecule in air under UV light irradiation could undergo isomerization of S-esters to O-esters, cleavage of P-S, S-C, and C-N bonds, and ozonation of tertiary amines.     

声表面波技术检测糜烂性毒剂芥子气的研究

声表面波技术是这些年来得到迅猛发展的一门前沿学科,是传感器技术中引人注目的新兴分支。由于声表面波化学传感器具有体积小、成本低、灵敏度高、易于集成化、智能化、实现远距离检测等多种优点,因而在军用、民用领域显示了良好的应用前景[1-3]。芥子气是糜烂性化学毒剂中最为     

一种高亲核怀长链咪唑肟的合成与反应

报道了一种新的高亲核长链咪唑肟N-十四烷基咪唑-2-甲醛肟的设计与合成， 并比较了它及其他长链咪唑肟与有机磷酸酯二苯基、对硝基苯基磷酸酯（PNPDPP） 、对硫磷及V_x的反应活性。结果表明，该肟对PNPDPP、对硫磷等磷酸酯反应活性 很高，超过目前已报道的反应活性最强的肟基试剂5～10倍，可用于毒性高且难以 分解的磷酸酯消毒与防护。