粉防己碱拮抗α-石英细胞毒性的机理

借助于单细胞阳离子测定系统研究了α-石英诱发细胞毒性过程中,不同外钙浓度时粉防己碱作用后,细胞存活率与胞浆游离钙浓度的变化关系。研究发现粉防己碱可以通过阻断细胞离子通道,拮抗α-石英的细胞毒性。     

硒酸酯多糖抗石英细胞毒性的研究

本文采用家兔肺泡巨噬细胞体外培养法，以ＡＲ－ＣＭ阳离子测定系统和荧光试剂Ｆｕｒａ－２，研究了石英细胞毒性与肺泡巨噬细胞胞胞浆游离Ｃａ＾２＋浓度（［Ｃａ＾２＋］ｉ）的关系，并以细胞存活率，乳酸脱氢酶活性和脂质过氧化物表征了由石英引起的ＡＭ毒性及硒酸酯多糖对其毒性的拮抗效应，初步讨论了硒酸酯多糖拮抗石英细胞毒性的可能机理。     

硅溶胶粒度与分布对高硅铝比镁碱沸石合成的影响机理

以硅溶胶为硅源, 在不同碱度的溶液中对其进行前处理, 制得不同粒度与分布的硅溶胶母液, 并以此为原料合成了高硅铝比镁碱沸石分子筛(FER zeolite). 通过激光粒度分析仪(LPSA)、 傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)、 扫描电子显微镜/能量色散X射线光谱(SEM-EDS)和X射线荧光(XRF)等对母液和产物进行了表征, 考察了碱度对硅溶胶粒度特性和分子筛晶化过程以及产物性质的影响. 结果表明, 随着碱度增加, 硅溶胶母液的粒径逐渐增大, 对应于溶液中更多的Q³硅单元向Q²硅单元转变. 在低碱度下, 高聚合度的Q³硅单元倾向于使晶化过程遵循固相转化机理, 生成大片纯相镁碱沸石, 且产物的相对结晶度和固体收率均较高; 而在高碱度下, 大量活性的Q²硅单元则易于使凝胶成块, 晶化过程遵循液相转化机制, 产物尺寸较小且含有杂晶, 相对结晶度和固体收率均较低.     

赖氨酸修饰聚酰胺-胺树枝状高分子的制备及性能

通过液相合成法, 用L-赖氨酸(L-Lys)对4代聚酰胺-胺(4.0G PAMAM)进行表面修饰, 制备了新型的PAMAM-Lys树枝状高分子. 采用FTIR、 ¹H NMR、 元素分析和粒径分析等手段进行了结构表征. PAMAM-Lys的C, H, N元素含量分别为53.43%, 9.58%和24.29%, 端氨基测定值为2.18, 接近于理论计算值; 平均粒径约6.35 nm, 多分散系数约0.09. 应用透射电子显微镜和噻唑蓝四氮唑溴化物(MTT)比色法, 探讨了PAMAM和PAMAM-Lys树枝状高分子载体/质粒DNA复合物的形态及体外细胞毒性. 当最佳电荷比R_+/-=4时, PAMAM-Lys与DNA形成复合物, 通过静电作用, 使DNA结构收缩, 质粒粒径介于50~100 nm之间, 分布较均匀, 形态规则; 作用于体外293T细胞时, PAMAM-Lys及其与DNA复合物的细胞毒性明显低于5代聚酰胺-胺(5.0G PAMAM). 研究结果表明, 制备的新型PAMAM-Lys树枝状高分子显著降低了高代数PAMAM树枝状高分子载体的细胞毒性, 具有良好的体外细胞相容性, 有望成为一种DNA疫苗的优良载体.     

N-苄氧羰基-甘氨酸水飞蓟宾单酯的合成及其抗氧化活性

以水飞蓟宾(1)与N-苄氧羰基-甘氨酸为起始原料,采用DCC/DMAP促进偶合法合成了新型的N-苄氧羰基-甘氨酸-3-水飞蓟宾酯(2),其结构经UV,1H NMR,IR和ESI-MS表征。采用化学和生物学模型考察了2的清除自由基能力和抗脂质过氧化能力。结果表明,在测定浓度范围内,2具有较好的清除自由基能力和抗脂质过氧化能力。     

脂氧合酶催化双高-γ-亚麻酸脂质过氧化产生的碳自由基的结构确证

采用液相色谱-电子自旋共振波谱(LC/ESR)联用技术、液相色谱-质谱(LC/MS)联用技术结合自旋捕集技术,研究了脂氧合酶(LOX)催化双高-γ-亚麻酸(DGLA)脂质过氧化过程中产生的碳自由基.以α-[4-吡啶基-1-氧]-N-叔丁基氮酮(POBN)为自旋捕集剂,在LOX-DGLA反应混合物中与碳自由基形成自旋加合物后,根据各加合物在LC/UV/ESR和LC/MS中对应的保留时间,确定加合物的分子量,进一步根据加合物质谱裂解方式确定其结构.结果表明,在LOX催化DGLA脂质过氧化过程中产生的碳自由基主要包括~·C_7H_(13)O_2,~·C_(10)H_(17)O_2和~·C_5H_(11),分别来自DGLA脂氧自由基(8-,11-,15-LO~·)的β-裂解.此结果有利于进一步研究DGLA在体内的脂质过氧化过程及该过程中产生的碳自由基的生理作用.     

壳交联pH响应型PLGA载药微球的制备与研究

首先采用一次乳化法制备出PLGA[聚(乳酸-羟基乙酸)]纳米微球,并通过静电吸附将阳离子聚合物壳聚糖修饰到PLGA微球表面,然后以香草醛为交联剂对壳聚糖进行化学交联,得到一种壳交联的p H响应型纳米微球(PCV),微球粒径为(277.60±38.01)nm,表面电位为(21.60±4.51)m V.微球稳定性评价结果显示微球在24 h内粒径变化较小;流式细胞仪检测显示细胞对PCV微球的摄取量比未经修饰的PLGA微球的摄取量高;空白微球细胞毒性实验表明在空白微球浓度小于80μg/m L时细胞的存活率达93.24%.以多西他赛(DTX)为模型药物进行包载,该纳米微球DTX的载药率为7.48%,包封率为34.98%;体外药物释放实验显示,该微球在p H=5.0环境下孵育90 h的药物积累释放率达58.66%,而在p H=7.4的环境下的药物积累释放率为50.63%;此外,载DTX微球毒性试验结果表明该载药微球对A549肺癌细胞有较强的杀伤作用,其IC50值可达0.0009μg/m L.     

低氧含量KAlF4:Ce3+制备、表征及荧光性质的研究

采用乙二醇回流法合成了复合氟化物KAlF4和KAlF4:Ce3+纳米粒子,并利用X射线衍射(XRD),透射电子显微镜(TEM),X射线光电子能谱(XPS)等技术对其结构、形貌、粒径大小以及表面含氧量进行了表征.结果表明,采用回流法在适当的反应条件下可制得单一晶相的KAJF4和KAlF4:Ce3+纳米粒子,其平均粒径为32.5nm.KAlF4的O1s的XPS分峰谱图表明,其表面只有一种氧种为化学吸附氧(α氧),且表面氧的含量小于5%.KAlF4:Ce3+的发射光谱中最大发射峰位于330nm处,归属于Ce3+的5d→4f跃迁.     

近红外荧光BSA-CdSeTe探针的制备及在生物学中的应用

本文用半胱氨酸作表面修饰剂,水相合成水溶性的近红外量子点CdSeTe,并偶联标记BSA,形成近红外BSA-CdSeTe探针。对CdSeTe QDs和BSA-CdSeTe探针进行荧光光谱分析,探讨了pH值、CdSeTe用量和反应时间这三个因素对近红外BSA-CdSeTe探针荧光强度的影响,对近红外BSA-CdSeTe探针进行了体外细胞成像实验和细胞毒性实验。结果表明,制得的CdSeTe粒径约5 nm,BSA-CdSeTe粒径约19 nm。当λex≈470 nm时,二者的λem均在750 nm左右。在pH=8、1m L CdSeTe和反应120 min时体系的荧光强度最大。当BSACdSeTe探针浓度在4~200μg·mL~(-1)范围之间,L929细胞的存活率均在85%之上。该探针在近红外荧光显微镜中可视,与L929细胞共孵育后可实现实时成像。因此,近红外荧光探针BSA-CdSeTe是一种可以进行实时细胞成像且生物相容性良好的纳米探针。     

基于四苯基乙烯的荧光纳米探针的合成及细胞成像研究

近年来,设计合成具有生物相容性好、光学性质稳定、细胞毒性低的荧光纳米探针是生物医学领域的研究热点.通过1,1,2-三苯基-2-(4-甲醛基苯)乙烯与2-(4-氧代-3-苯基-1,3-噻唑-2-亚基)丙二腈反应合成新型四苯基乙烯类荧光探针(TPE-Rho),考察其聚集诱导发光(AIE)特性;使用共沉淀法将TPE-Rho包裹于两亲性表面活性剂Pluronic F-127中得到粒径分布均匀的荧光纳米探针(TPE-Rho dots). TPE-Rho dots显示黄色荧光发射、良好的稳定性、长斯托克斯位移(约200nm)等光学性能,并且对细胞生长活性基本无影响,随后以人肝癌细胞SK-Hep1和人结肠癌细胞Lo Vo作为模型细胞进行细胞成像,观察染色部位和荧光强度.结果表明,TPE-Rhodots能够对活细胞进行染色,选择性作用于细胞质.由此可以确定TPE-Rho dots的生物相容性良好、细胞毒性小、细胞膜通透性高、光稳定性好,可作为一种活细胞染色剂.     

十七氟癸基修饰的有机-无机杂化二氧化硅膜材料的制备及气体分离性能

以十七氟癸基三乙氧基硅烷(PFDTES)和1,2-双(三乙氧基硅基)乙烷(BTESE)为前驱体, 通过溶胶-凝胶法制备了十七氟癸基修饰的SiO₂溶胶, 采用浸渍提拉法在γ-Al₂O₃/α-Al₂O₃多孔陶瓷支撑体上涂膜, 然后在N₂气氛保护下烧结成完整无缺陷的有机-无机杂化SiO₂膜. 利用扫描电子显微镜对膜材料的形貌进行观察, 通过动态光散射技术对溶胶粒径及分布进行测试, 利用视频光学接触角测量仪、 红外光谱仪和热分析仪表征了十七氟癸基修饰对有机-无机杂化SiO₂膜疏水性的影响. 结果表明, 十七氟癸基已经成功修饰到SiO₂膜材料中, 且随着PFDTES加入量的增大, 溶胶粒径和膜材料对水的接触角不断增大. 当n(PFDTES): n(BTESE)=0.25: 1时, 溶胶粒径分布较窄, 平均粒径为3.69 nm, 膜材料对水的接触角为(112.0±0.4)º. 在修饰后的有机-无机杂化SiO₂膜中H₂的输运遵循微孔扩散机理, 在300℃时, H₂的渗透率达到5.99×10^-7 mol·m^-2·Pa^-1·s^-1, H₂/CO和H₂/CO₂的理想分离系数分别达到9.54和5.20, 均高于Knudsen扩散的理想分离因子, 表明膜材料具有良好的分子筛分效应.     

Polymer approach to supported silica membranes

Polymeric silica sols were used to prepare membranes on commercial -Al₂O₃ supports with nominal support pore diameters of 4.0 nm. Aging of the silica sols was shown to be effective to form discrete membrane layers. He/N₂ selectivity factors exceeding ideal Knudsen values were observed when the sols were prepared under conditions in which the condensation rate was minimized. We propose that the average pore size of the membrane depends on the balance of capillary pressure and modulus during membrane deposition. The condensation rate might influence the breadth of the pore size distribution.     

Effect of Variant Counterions on Stability and Particle Size of Silica Sol

The effects of variant counterions with ionic strength of 0.05, 0.10, 0.20 and 0.25 mol·kg^-1 on the stability and particle size of silica sols have been studied using the traditional methods of Ubbelohde viscosity measurement, TEM and titration respectively, finding that the stability and particle size of the silica sols are all concerned with the acidic, positively electric properties and the sizes of the counterions, as well as the attraction between the counterions and surface silicon hydroxyl groups of the silica sols. The small positively charged counterions lead to the decrease in particle sizes, making the silica sol the most stable. But the larger weakly acidic counterions can restrict the particle sizes of the silica sols and easily make the sols coagulate. It was also found that there existed a linear relationship between log r and log η, which has not ever been reported. The effect of temperature on the stability and particle sizes was also discussed.     

Preparation of poly(methyl methacrylate) films containing silica particle array structure from colloidal crystals

The incorporation of monodisperse, polymer-modified silica into poly(methyl metharylate) to prepare polymer films containing particle array structure was investigated. The preparation was carried out by a two-step radical polymerization for gelation and solidification. The colloidal crystallization of poly(methyl metharylate)-modified silica, in 78 nm size, in acetonitrile and successive copolymerization of methyl methacrylate and 1,2-dimethacryloylethane by UV light irradiation gave the polymer gel containing the colloidal crystal structure. The exchange of acetonitrile in the gel with methyl methacrylate and further photo-radical polymerization gave the durable polymer film composed of silica particle array.     

Influence of Sol-Gel Synthesis Parameters on the Microstructure of Particulate Silica Xerogels

The influence of key sol-gel synthesis parameters on the pore structure of microporous silica xerogels was investigated. The silica xerogels were prepared using an acid-catalyzed aqueous sol-gel process, with tetraethoxysilane (TEOS) as the silicon-containing precursor. At high H2O : TEOS ratios, sols synthesized at pH 2–3 yielded minimum values of mean micropore diameter and micropore volume. Analysis of the resulting Type I nitrogen adsorption isotherms and the equilibrium adsorption of N(C4F9)3 indicated micropore diameters for these xerogels of less than approximately 10 Å.Xerogel micropore volumes corresponding to sols prepared at pH 3 and an H2O : TEOS ratio of r = 83 were consistent with nearly close packing of silica spheres in the xerogel. Xerogel microstructure was only weakly dependent upon H2O : TEOS ratio during sol synthesis for r > 10. Xerogel micropore volume increased rapidly with sol aging time during an initial induction period of particle formation. However, the xerogel microstructure changed only slowly with time after this initial period, suggesting potential processing advantages for the particulate sol-gel route to porous silica materials.Surface adsorption properties of the silica xerogels were investigated at ambient temperature using N2, SF6, and CO2. CO2 adsorbed most strongly, SF6 also showed measurable adsorption, and N2 adsorption was nearly zero. These results were consistent with the surface transport of CO2, and to a lesser extent SF6, observed in gas permeation studies performed through thin membrane films cast from similarly prepared silica sols.     

Silica nanoparticle sols 1. Surface chemical characterization and evaluation of the foam generation (foamability)

Surface characterization and foaming studies were carried out with nine industrially manufactured, colloidal silica dispersions with particles sizes from 5-40 nm. All the silica sols produced transient foams with short decay times and the dynamic foam generation (foamability) was found to vary according to the sol type with the greatest foamability occurring for the hydrophobically modified sol and the deionized hydrophilic sol. However, it was found that improved foamability of all the sols could be achieved by changing the pH to within the region of the pH(pzc) which corresponds to the region of lowest hydrophilicity. An increase in pH (and build-up of negative charge) enhances the surface hydrophilicity and caused a decrease in foamability. In addition, for selected hydrophilic sols, it was shown that the foamability (a) increased with decrease in particle size (within the 6-40 nm range) and (b) increased with particle concentration (within the range of 1-15 wt%). Overall, it was concluded that the foamability was primary controlled by hydrophobicity (and hence by pH) and also by the particle concentration, the particle size and the degree of agglomeration.     

Effect of non-ionic surface active agents on TEOS-derived sols,gels and materials

The sol-gel process, starting from tetraethylorthosilicate precursor, is a suitable technique for the preparation of silica thin films. The use of specific organic additives, like non ionic surface-active agents, drastically modifies the gelation process and allows the preparation of microporous materials with a high microporous volume. The effects of additives on the sol, gel and material characteristics have been investigated by several methods such as ²⁹Si NMR, QELS, SAXS (for sols and gels), and N₂ adsorption, FESEM (for fired materials). It appears that the interactions of surface active agents with TEOS derived species limit condensation reactions and particle growing. A brittle gel structure is generated which leads to highly porous microporous silica after the elimination of organic chains by thermal treatment at 450°C. The material porous texture (specific surface area, pore size distribution and porous volume) can be varied especially by varying the surface active agent chain length and quantity. This kind of sol-gel system is suitable to prepare microporous silica membranes candidate for gas separation or catalytic reactor applications.     

变色硅胶吸附脱除模拟柴油中各种碱性氮化物

研究了变色硅胶吸附脱除氮含量为960.56μg/g模拟柴油中的碱性氮化物喹啉、苯胺和吡啶。比较了氧化铝、硅藻土、硅胶及变色硅胶对模拟柴油中喹啉的吸附脱除效果。采用XRD、低温N_2吸附-脱附和NH_3-TPD等方法对硅胶和变色硅胶进行了表征。考察了粒径、吸附温度、吸附时间、剂油质量比及共存芳香化合物(萘、苯或甲苯)对变色硅胶吸附脱除各种碱性氮化物的影响。变色硅胶吸附脱除碱性氮化物的顺序均为苯胺吡啶喹啉。吸附时间对三种氮化物的吸附脱除没有影响;吸附温度、变色硅胶粒径和共存芳香化合物对苯胺和吡啶的吸附脱除效果影响不大,对喹啉的吸附脱除效果影响较为明显;剂油质量比对三种氮化物的吸附脱除影响均较大,尤其是对喹啉影响最大。结果表明,变色硅胶吸附各种氮化物时Co能够与其中的N原子形成配位络合吸附。经焙烧再生,变色硅胶几乎完全恢复了对喹啉和吡啶的吸附脱除能力,并可多次再生,但变色硅胶再生后对苯胺的吸附能力损失较大。     

Pd nanoparticles dispersed on solid supports: synthesis,characterization and catalytic activity on selective hydrogenation of olefins in aqueous media

Two types of Pd nanoparticle catalysts were prepared having 2–4 nm particle size using silica gel and porous polymer beads as solid supports. 2‐Pyridinecarboxaldehyde ligand was anchored on commercially available 3‐aminopropyl‐functionalized silica gel followed by Pd metal dispersion. Bead‐shaped cross‐linked poly(4‐vinylpyridine‐co‐styrene) gel was prepared by an emulsifier‐free emulsion polymerization of 4‐vinylpyridine, styrene and divinylbenzene in the presence of ammonium persulfate and subsequently dispersing the Pd metal on the synthesized polymer. These catalysts were characterized by SEM, TEM and ICP techiniques with respect to appearance, size and possible leaching out, respectively. Furthermore, the reactivity of these catalysts was tested on hydrogenation of various α,β‐unsaturated carbonyl compounds using aqueous solvent under a hydrogen balloon (1 atm). The results showed that the Pd dispersed on silica was a more efficient catalyst than Pd dispersed on polymer and the former could be recycled more than 10 times without considerable loss in activity. Copyright © 2010 John Wiley & Sons, Ltd.     

Covalent immobilization of glucose oxidase onto new modified acrylonitrile copolymer/silica gel hybrid supports

New polymer/silica gel hybrid supports were prepared by coating high surface area of silica gel with modified acrylonitrile copolymer. The concentrations of the modifying agent (NaOH) and the modified polymer were varied. GOD was covalently immobilized on these hybrid supports and the relative activity and the amount of bound protein were determined. The highest relative activity and sufficient amount of bound protein of the immobilized GOD were achieved in 10% NaOH and 2% solution of modified acrylonitrile copolymer. The influence of glutaraldehyde concentration and the storage time on enzyme efficiency were examined. Glutaraldehyde concentration of 0.5% is optimal for the immobilized GOD. It was shown that the covalently bound enzyme (using 0.5% glutaraldehyde) had higher relative activity than the activity of the adsorbed enzyme. Covalently immobilized GOD with 0.5% glutaraldehyde was more stable for four months in comparison with the one immobilized on pure silica gel, hybrid support with 10% glutaraldehyde and the free enzyme. The effect of the pore size on the enzyme efficiency was studied on four types of silica gel with different pore size. Silica with large pores (CPC-Silica carrier, 375 A) presented higher relative activity than those with smaller pore size (Silica gel with 4, 40 and 100 A). The amount of bound protein was also reduced with decreasing the pore size. The effect of particle size was studied and it was found out that the smaller the particle size was, the greater the activity and the amount of immobilized enzyme were. The obtained results proved that these new polymer/silica gel hybrid supports were suitable for GOD immobilization.