交联聚膦腈中空微球的可控制备

以分散聚合法制备的聚苯乙烯微球为模板,以六氯环三膦腈、4,4’-二羟基二苯砜为共聚单体,三乙胺为缚酸剂,室温条件下制备出了聚苯乙烯／聚膦腈（核／壳）复合微球,然后用四氢呋喃处理该复合微球,得到聚膦腈中空微球。利用红外光谱、元素分析、扫描电镜及投射电镜对所制备中空微球的结构及形貌进行了表征。结果表明,所制备聚膦腈中空微球...     

分散共聚法制备特殊形态高分子微球的研究

以聚乙二醇 (PEG)大分子单体为反应性稳定剂 ,在丙烯腈的分散共聚反应中添加少量苯乙烯以形成疏水性核 ,制备得到了亚微米级高分子微球 .透射电子显微镜研究表明 ,该高分子微球具有特异的形态结构 .同时研究了分散共聚体系中各种反应因素对微球形态和直径的影响 ,结果表明 ,苯乙烯单体的添加量、PEG大分子单体的浓度及分子量、混合溶剂的组成对微球直径和形态均有明显的影响 .X 射线光电子能谱 (XPS)研究结果表明 ,微球表面聚集有亲水性PEG链 ,核为疏水的聚 (丙烯腈 苯乙烯 ) ,即形成的特异形态的PEG接枝高分子微球亦为复合型结构     

ATRP合成大分子单体法制备核壳结构微球

以α-溴代丙酸乙酯(EPN-Br)为引发剂, N,N, N′,N″,N″-五甲基二亚乙基三胺(PMDETA)为配体,使甲基丙烯酸叔丁酯进行原子转移自由基聚合,合成了端基带溴原子的聚甲基丙烯酸叔丁酯(PtBMA-Br)大分子中间体,通过其与甲基丙烯酸的亲核取代反应,得到了末端C=C双键含量高的大分子单体（MAA-PtBMA）,其相对分子质量可控制在5400-12000g/mol的范围内,分子量分布≤1.20。以偶氮二异丁腈为自由基引发剂,在乙醇中使MAA-PtBMA大分子单体与苯乙烯（St）进行分散共聚,制得了甲基丙烯酸叔丁酯接枝聚苯乙烯（PtBMA-g-PSt）微米级共聚微球,该微球具有核壳结构。     

新型可生物降解医用高分子材料-聚膦腈

聚磷腈是一族由交替的氮、磷原子以交替的单键、双键构成无机主链的新型可生物降解聚合物。聚膦腈具有独特的性质和显著的合成多样性,降解产物为磷酸、氨、氨基酸和乙醇等无毒物质。通过改变聚膦腈侧链结构和组成,可调节聚膦腈的降解速度,控制药物释放的速度。本文主要综述了聚膦腈的合成、降解及其在药物控释系统中的应用。     

磺化聚磷腈微球的制备及其乳化性能

以六氯环三磷腈(HCCP)和4,4′-二羟基二苯砜(BPS)为单体,通过一步沉淀共聚法制备了环交联型聚磷腈(PZS)微球,然后利用浓硫酸对其进行改性得到磺化聚磷腈(SPZS)微球。通过红外光谱、X射线光电子能谱、水接触角测试和扫描电子显微镜对SPZS微球的结构、亲-疏水性和形貌进行了表征。通过数码照片、光学显微镜、荧光显微镜等方法研究了SPZS微球的乳化性能,并通过油相固化的方式考察了微球在油-水界面的形貌。结果表明:磺化改性有效改善了聚磷腈微球的亲水性;SPZS微球可长效稳定多种油-水体系,形成细腻的水包油型Pickering乳液;SPZS微球吸附于油-水界面上形成了致密的粒子膜,有效阻止了乳液滴的聚并;SPZS微球的浓度、油水体积比及NaCl浓度均会影响乳化效果。     

聚[(四氟丙氧基)2-x(三氟乙氧基)x]膦腈合成和气体分离性能研究

以六氯环三聚磷腈为原料通过真空热开环聚合制得线型聚二氯磷腈(PDCP),再通过对PDCP进行亲核取代合成制备了新的聚膦腈类高分子--聚[(四氟丙氧基)2-x(三氟乙氧基).]膦腈,聚合物经过四氢呋喃-苯反复溶解-沉淀得到纯化产物.通过31P-NMR、1H-NMR和FTIR对其结构进行了表征;DSC法测定其玻璃化转变温度...     

聚(环三磷腈-co-4,4'-(9-芴)二苯酚)微球的制备及其稳定液体弹珠的性能研究

以六氯环三磷腈和4,4'-(9-芴)二苯酚为共聚单体,三乙胺为缚酸剂,乙腈为溶剂,通过一步沉淀聚合制备了疏水性的交联聚(环三磷腈-co-4,4'-(9-芴)二苯酚)(PZHF)微球,通过傅立叶变换红外光谱仪(FTIR)、X射线光电子能谱仪(XPS)和扫描电子显微镜(SEM)对微球的化学结构和形貌进行了表征;进一步以该微球为稳定剂,通过包覆水滴成功制备了液体弹珠,研究了液体弹珠的静态稳定性以及共聚物微球在液体弹珠表面的分布情况,并考察了液体弹珠的气体透过性.结果表明,PZHF微球具有高度交联的有机-无机杂化结构,平均粒径为1.3μm,且微球表面较为粗糙,具有疏水性;用其包覆水滴可得到稳定的液体弹珠,微球在气-液界面上的排列较为疏松,使液体弹珠具有独特的气体透过性,外界气体可通过液体弹珠表面进入内部水相而不破坏弹珠自身的结构.     

生物可降解聚膦腈材料的功能化及研究进展

聚膦腈是一类主链由磷氮原子交替组成,每个磷原子带有两个有机官能团侧基的有机-无机杂化高分子,其化学结构强大的可设计性赋予了材料丰富的理化性能。作为生物学用途的聚膦腈材料,生物相容性、生物可降解性和功能化改性是实现其应用的关键因素。本文从数种功能化聚膦腈(如光致荧光、导电、聚膦腈-聚酯共聚物)的制备、聚膦腈的降解机理和降解行为调控,以及生物可降解聚膦腈作为组织工程支架材料、药物载体材料和基因转染材料等几个方面,较为全面地综述了聚膦腈生物医用高分子的研究进展。     

聚膦腈-g-聚己内酯共聚物的合成与表征

通过三甲基碘硅烷与聚二(2-甲氧基乙氧基)膦腈侧链上的醚键反应后水解得到侧链含部分羟基的聚膦腈,然后利用聚膦腈的侧链羟基在异辛酸亚锡催化作用下,引发己内酯单体开环聚合制备了聚膦腈-g-聚己内酯共聚物.该共聚物中聚己内酯链段的接枝率和侧链长度可通过改变三甲基碘硅烷和己内酯单体的投料来控制.     

静电喷雾法制备聚膦腈微球

用静电喷雾法制备了粒径窄分布的甘氨酸乙酯-苯丙氨酸乙酯取代聚膦腈的微球.主要探讨了溶剂、溶液浓度、流速、喷射电压及接收距离对微球形貌和粒径的影响.微球的表面形貌与溶剂性质和聚合物溶液浓度密切相关,微球粒径受聚合物溶液流速的影响比较显著,随流速增大粒径呈单调上升趋势.结果显示对于[η]=0.1 dL/g的(甘氨酸乙酯)0.3(苯丙氨酸乙酯)0.7取代聚膦腈,以0.25 g/mL的四氢呋喃溶液进行静电喷雾,可获得粒径分布窄(1~2μm)且近球形的微粒,其工艺条件可进一步用于载药聚膦腈微球的制备和控制释放研究.     

Polymeric spheres on substrates from a spin-coating process

Formation of polymeric spheres in nanometer to sub-micrometer is achieved through a spin-coating process with polyamide (from 4,4(')-(hexafluoroisopropylidene)dianiline and 4,4(')-dicarboxydiphenylether) solutions in N,N-dimethylformamide and N,N-dimethylacetamide. The formation of polymeric spheres and their sizes are dependent on the polymer solution concentrations and the rates in spin-coating. The polymeric spheres could be obtained on various substrates including silicon, mica, and glass.     

Rare earth dysprosium nickelate nanospheres for the selective electrochemical detection of antipsychotic drug perphenazine in biological samples

Currently, perphenazine (PPZ) is widely used to treat the symptoms of schizophrenia, namely, a mental illness that reasons strong or improper emotions, loss of interest in life, and disturbed or abnormal thinking. In addition, the PPZ is exploited to control acute nausea and vomiting in adults, and it acts by reducing unusual excitement in the brain. Accordingly, we report a novel dysprosium nickelate (DyNiO₃)-modified electrodes were used to detect PPZ. The DyNiO₃ nanospheres were synthesized via the coprecipitation method. The excellent electron transport behavior and electrocatalytic activity of DyNiO₃-modified screen-printed electrode (SPCE) were used in the electro-oxidation of PPZ. The constructed DyNiO₃-500°C/SPCE sensor has a broad linear range and a low detection limit of 0.04–761.6 μM and 0.006 μM, respectively. The resultant-modified sensor demonstrates appreciable reproducibility, selectivity, repeatability, cyclic, and storage stability toward PPZ detection. The practicability of the reported fabricated electrode was investigated in human biological samples (urine and serum) spiked with PPZ, and the correlated recoveries were acceptable.     

一锅法制备pH和热敏的P(NIPAM-co-AA)高分子空心球

基于N-异丙基丙烯酰胺(NIPAM)在高于PNIPAM的相转变温度时的沉淀聚合反应,利用在成核阶段形成的非交联的核为模板,然后在核的增长阶段加入交联剂N,N′-亚甲基双丙烯酰胺(BMA)和丙烯酸(AA)使得核周围形成一层交联的P(NIPAM-co-AA)共聚物壳层,降温至相转变温度以下使得非交联的PNIPAM核解散并自发地从交联的壳层扩散出来,得到具有温度和pH敏感性的P(NIPAM-co-AA)空心球.透射电镜结果表明该微球具有中空结构.利用光散射在不同pH值和温度条件下对该空心球进行了表征,结果表明,P(NIPAM-co-AA)空心球对pH值和温度具有良好的响应能力.     

哌嗪-二氧化硫电荷转移复合物引发的甲基丙烯酸甲酯光聚合

本文研究了哌嗪 (PPZ)与二氧化硫 (SO2 )电荷转移复合物 (CTC)的制备及其作为光引发剂引发甲基丙烯酸甲酯 (MMA)的聚合 ,发现PPZ/SO2 摩尔比对聚合速率影响甚大 .当PPZ/SO2 为 1∶2时 ,形成了具有潜在引发能力的复合物 (Ⅰ ) .Ⅰ引发MMA光聚合的动力学关系式为Rp =Kp [Ⅰ ] 0 .34[MMA] 1.0 6 ,表观活化能为 2 3 7kJ/mol.并对引发机理进行了探讨     

锑掺杂二氧化锡实心球和空心球的碳还原制备及其生长机理研究

通过在水平管式炉中用石墨还原锑掺杂二氧化锡(ATO)纳米颗粒的方法制备了ATO的实心球和空心球, 并用EDX和XRD等技术分析了产物的物相和元素组成; 用FE-SEM和TEM观察了其形貌; 用HRTEM分析了其晶格结构. 结果表明, 产物为直径0.2~5 μm的ATO实心球和直径为2~20 μm的ATO空心球. 通过控制Ar流速和沉积位置控制了ATO实心球的尺寸和产量, 用Ostwald Ripening分析了ATO实心球的生长过程. ATO空心球的制备在具有较高氧浓度、长度稍长于刚玉管的陶瓷管中进行, 对其生长机理进行了讨论, 分析了相同条件下使用不同材质的管子生成不同形貌产物的原因.     

Microstructural Characterization and Mechanical Property of Iridium Coating Produced by Double Glow Plasma

Ir is the most interesting as an effective oxygen diffusion barrier for super high-temperature structural materials. In this study, an Ir coating, approximately 7 μm thick, was deposited onto Mo substrate by double glow plasma at substrate temperature of about 1,120 K in an argon atmosphere. The crystal orientation, morphology and mechanical property of the Ir coating were investigated by XRD, SEM, AFM, TEM, nanoindentation and scratch test. The results indicated that the (220)-oriented Ir coating was composed of the columnar grains. The surface roughness of the Ir coating was higher than that of the substrate. The hardness and the elastic modulus of the Ir coating were about 9.5 and 340 GPa, respectively. The coating had a high hardness due to the sub-micrometer size grains. The coating had good scratch resistance due to the strong adhesion of the coating to the substrate.     

α-Fe_2O_3空心球的水热法制备及其对苯酚的吸附性能

以铁氰化钾、磷酸二氢铵等为反应物,采用水热法合成了α-Fe2O3空心球,并用XRD,TEM,FESEM(场发射扫描电镜)、UV-Vis和低温氮吸附脱附对其进行了表征。结果表明,α-Fe2O3空心球直径在200～560nm之间,其BET比表面积为80m2·g-1,平均孔径为8.5nm。考察了反应时间、反应物用量和反应温度等对α-Fe2O3空心球形貌和大小的影响,提出了其可能的形成机理。研究了室温下α-Fe2O3空心球吸附苯酚的性能,吸附达平衡时,其吸附苯酚的量达97mg·g-1。     

Simultaneous estimation of four proton pump inhibitors—lansoprazole,omeprazole, pantoprazole and rabeprazole: development of a novel generic HPLC‐UV method and its application to clinical pharmacokinetic study

A highly selective, sensitive and accurate HPLC method has been developed and validated for the estimation of four proton‐pump inhibitors (PPI), lansoprazole (LPZ), omeprazole (OPZ), pantoprazole (PPZ) and rabeprazole (RPZ), with 500 µL human plasma using zonisamide as an internal standard (IS). The sample preparation involved simple liquid–liquid extraction of LPZ, OPZ, PPZ and RPZ and IS from human plasma with ethyl acetate. The baseline separation of all the peaks was achieved with 0.1% triethylamine (pH 6.0):acetonitrile (72:28, v/v) at a flow rate of 1 mL/min on a Zorbax C₈ column. The total chromatographic run time was 11.0 min and the simultaneous elution of IS, OPZ, RPZ, PPZ and LPZ occurred at approximately 2.42, 4.45, 5.02 and 9.37 min, respectively. The method was proved to be accurate and precise at linearity range of 20.61–1999.79 ng/mL with a correlation coefficient (r) of ≥0.999. The limit of quantitation for each of the PPI studied was 20.61 ng/mL. The intra‐ and inter‐day precision and accuracy values were found to be within the assay variability limits as per the FDA guidelines. The developed assay method was applied to a pharmacokinetic study in human volunteers. Copyright © 2009 John Wiley & Sons, Ltd.     

新型氧化铝空心球的制备及表征

以胶体碳球为模板, 廉价的硝酸铝为铝源, 成功制备出了新型的大小可控的氧化铝空心球. 通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)、能量扩散X射线(EDX)、X射线粉末衍射(XRD)等手段对合成产品进行了表征, 并考察了不同合成条件对空心球形貌的影响. 实验结果表明, 合成的氧化铝空心球大小均一, 粒径及壁厚均可调节. 在该实验条件下, 硝酸铝浓度及吸附时间的改变对产品结果没有明显的影响, 而吸附温度的改变引起了产品表面光滑度及壁厚的改变.     

A microemulsion-template-interfacial-reaction route to copper sulfide hollow spheres

CuS hollow spheres have been successfully synthesized through a facile microemulsion-template-interfacial-reaction route using copper naphthenate as metal precursor and thioacetamide as the source of S(2-). In this way, hollow spheres could be obtained directly since the reaction of two reactants respectively dissolved in two different phases of an oil-in-water (o/w) microemulsion only occurs at the oil/water interface. Therefore, it is a key for forming hollow spheres to optimize the interfacial reaction rate by controlling reaction conditions. Furthermore, the size of the hollow spheres can be tailored by changing the content of oil phase. In this study, the average diameter of the CuS hollow spheres can be adjusted from 110 to 280 nm by changing the content of oil phase from 0.5 ml to 1.5 ml. In addition, the reaction temperature is a very important factor for forming CuS hollow spheres and the appropriate reaction temperature is about 50 °C.