核壳结构Boc-氨基酸分子印迹分离介质的研究

将硅胶表面硅羟基与γ-（甲基丙烯酰氧）丙基三甲氧基硅烷反应合成具有CC端基的改性硅胶核,进一步以N-Boc-L-色氨酸为模板分子,采用分子印迹技术在改性后的硅胶表面包覆印迹聚合物,制备出核壳结构氨基酸分子印迹分离介质。这种印迹分离介质对模板N-Boc-L-色氨酸具有良好的吸附性,最大饱和吸附量可达到85.96 mg/...     

硅胶自环己烷中吸附环己酮和苯甲酸

用经不同温度处理的亲水硅胶(表面总羟基浓度不同)和甲基化硅胶(只含有缔合羟基或不同表面浓度的自由羟基的硅胶)为吸附剂, 测定了自环己烷中吸附环己酮和苯甲酸的等温线, 以及几种硅胶样品的红外光谱图, 探讨了表面自由羟基和缔合羟基在溶液吸附中的作用.     

改性固体表面的吸附作用——甲基化硅胶的热稳定性和吸附性能

本文利用三甲基氯硅烷与硅胶表面羟基反应的方法制备了甲基化硅胶。测定了亲水硅胶和甲基化硅胶的热处理对其自四氯化碳中吸附乙酸的等温线的影响,并配合有热重分析(TG)和红外光谱(IR)的测定。结果表明:(1)甲基化后的硅胶对乙酸的吸附能力大大下降;(2)甲基化硅胶的热处理温度达500℃时吸附能力完全恢复到甲基化前的硅胶的水平,甲基化层明显开始破坏的温度为450℃;(3)甲基化硅胶高温处理后吸附能力得以恢复的主要原因是重新形成表面自由羟基。     

热处理对憎水硅胶吸附水蒸气的影响

用甲基氯硅烷蒸气或溶液处理硅胶,均可制成憎水硅胶。关于憎水硅胶的吸附性能和热稳定性的研究,文献中时有报道。本文主要探讨以下3个问题:(1)在水蒸气吸附中,硅胶表面自由羟基和缔合羟基究竟哪种起主要作用;(2)从吸附水蒸气等数据讨论硅胶表面有机基团—OSi(CH_3)_3的热稳定性;(3)用二甲基二氯硅烷(DMCS)和三甲基氯硅烷(TMCS)处理的憎水硅胶,哪种硅胶的热稳定性较高。这些基本问题,不仅具有学术意义,对研究氧化物表面改性也有参考价值。     

酯化硅胶的物理结构和表面性质的研究

本文利用正庚醇或正辛醇与硅胶表面羟基反应制备了酯化硅胶。测定了酯化硅胶的物理结构、水蒸气吸附等温线、润湿热、差热分析和红外光谱。结果表明: (1)所有酯化硅胶的真密度(dT)、比表面(S)和比孔体积(V)均减少, 而有观密度(dA)增加, 但平均孔半径(r)变化不大; (2)酯化硅胶是憎水的, 其对水蒸气吸附, 以及对水和环己烷的润湿热均显著减少; (3)酯化硅胶的表面酯基在空气中于235-350℃破坏; (4)酯化反应是可逆的, 硅胶表面酯基在水中大约可水解41-47%。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载（英文）

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性,红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升,改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型,吸附等温线服从Langmuir等温线规律,由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性,红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升,改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型,吸附等温线服从Langmuir等温线规律,由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

硅胶的表面硫醇化改性及对水溶液中罗丹明B的固载

运用γ-巯丙基三乙氧基硅烷对硅胶表面硫醇化修饰改性, 红外及拉曼光谱分析表明硅胶的表面硫醇化借助硅胶表面羟基与γ-巯丙基二乙氧基硅烷间的化学键联实现。实验条件下改性硅胶对水体罗丹明B的吸附性能明显提升, 改性硅胶表面罗丹明B的吸附动力学符合准二级动力学模型, 吸附等温线服从Langmuir等温线规律, 由等温吸附计算得到的热力学函数变化表明吸附系自发、放热过程。吸附动力学、热力学及光谱表征均表明改性硅胶上罗丹明B的吸附主要为其在改性硅胶表面借助电价和共价键联的化学吸附。     

层层纳米自组装锆基色谱填料的表面性质研究

硅胶具备了许多色谱载体应具有的合适的表面物理化学参数.但硅基填料可使用的pH值范围较窄及其表面裸露的硅羟基对碱性物质和含N生物大分子的不可逆吸附等缺点限制了其在一些重要领域中的应用.氧化锆由于其优异的化学稳定性,特别是对碱性化合物和生物大分子的分离适应性而在色谱应用方面受到极大的关注[1,2],极有可能成为通用的色谱基质填料之一[3].本文旨在制备具有良好表面性质的锆基色谱填料,结合硅胶和氧化锆的优点,采用层层纳米自组装方法(LbL)[4]在微米硅胶球模板表面包覆多层纳米氧化锆颗粒,制备了新型氧化锆基质填料ZrO2/SiO2,…     

磁性二氧化硅微球的表面修饰及其在植物基因组核酸纯化中的应用

在利用自主研发的专利技术制备球形磁性硅胶微球的基础上,对磁性硅胶微球进行表面改性,使其表面分别键合硅羟基、环氧基、邻二醇基和羧基等官能团,并对表面官能团进行了定量研究。以小牛胸腺基因组脱氧核糖核酸(DNA)为模型化合物,研究了核酸在不同表面官能团的磁性硅胶上的吸附和脱附行为,发现表面具有硅醇基的磁球对DNA的回收率最高。将改性后磁性微球应用于玉米DNA的提取,得到了平均长度大于8kb的高纯度基因组DNA。与传统的有机溶剂抽提法相比,基于磁性微球的核酸固相萃取法具有快速简便、省时省力、易于自动化的特点,适合于大规模植物基因组DNA的样品制备。     

An improved methodology for adsorption characterization of unmodified and modified silica gels

An improvement in the adsorption characterization of the surface and structural properties of unmodified and modified mesoporous silica gels is presented. This improvement was achieved by selection of proper macroporous silica as the reference solid for adsorption characterization of porous silica gels. Experimental illustration is provided for unmodified and n-octyl-modified silica gels of different bonding density. The surface and structural properties of these silica gels were characterized by utilizing the standard adsorption data for both unmodified and octyl-modified LiChrospher Si-1000 macroporous silica gels. It was shown that the standard nitrogen adsorption data have an appreciable influence on the analysis of the pore size and surface properties of silica gels. This analysis can be improved by selecting the reference solid of the surface properties close to those of the silica gel studied.     

The Thermal Stability and Adsorbability of the Mechylated Silica Gel

The methylated silica gel has been produced by the reaction between the surface silanol groups and Clsi(CH3)3 vapor.The adsorption isotherms of acetic acid from carbon tetrachloride onto silica gel and emthylated silica gel heated at various temperatures have been determined at 25℃,and the above mentioned silica gels have been studied by TC and IR.The results indicate:(1) The adsorption of acetic acid from carbon tetrachloried onto methylated silica gel decreased greatly,probably because the concentration of the free hydroxyl groups for methylated silica gel decreased greatly as the IR shows.(2) As the methylated surface was destroyed at 450℃,the adsorption ability was restored when the methylated silica gel treated at>500℃.(3) So long as the methylated silica gel was treated at high temperature,the adsorption ability could be restored owing to that surface free hydroxyl groups were reproduced.     

Synthesis and Characterization of Microporous Silica Prepared with Sodium Silicate and Organosilane Compounds

Microporous silica gels were prepared in the pH range of 3–4 using sodium silicate as a silica source. Surface polarity of these gels was modified by grafting hydrophobic groups into the silica gel matrix with the help of hydrophilic solvents (acetone, acetonitrile, ethanol and methanol) and alkoxysilane compounds containing nonhydrolyzable alkyl groups. The porous framework and hydrophobicity of the silica gels were evaluated using nitrogen adsorption/desorption and water adsorption measurement techniques. All the measured isotherms were found to be type I which is indicative of microporosity. The surface area and microporosity of these samples were estimated by analyzing the measured nitrogen adsorption/desorption data using BET, Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The micropore size distribution was determined from their nitrogen adsorption isotherms using the slit-pore model of the Horvath-Kawazoe equation. Silica gels with high surface area (over 500 m²/g) as well as high microporosity (over 0.2 cc/g) were obtained at gelation pH of 3.50 from the water-solvent system.     

Liquid chromatography of benzene derivatives on a porous methacrylate copolymer containing epoxy groups

Summary The retention of benzene derivatives with nonpolar and polar substituents on a porous methacrylate copolymer containing epoxy groups using both nonpolar and polar eluents was investigated. When n-hexane is used as the eluent, the retention of n-alkylbenzenes and polymethylbenzenes is weaker than that of benzene. In the case of benzene derivatives containing polar functional groups their capacity ratios (k) on this porous polymer increases approximately linearly with the increase of the adsorbate molecules dipole moment. The retention characteristics of the methacrylate copolymer were compared with that of a styrene-divinylbenzene copolymer and silica gels with a hydroxylated surface and with a surface modified by chemically bonded alkylsilyl groups.     

Diffusion into and adsorption of polyethylenimine on porous silica gel

The polyethyleneimine (PEI)–water–silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI–cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.     

Structures and chromatographic characteristics of capsule-type silica gels coated with hydrophobic polymers in reversed-phase liquid chromatography

Summary Silicone polymer-coated silica gels modified with octadecyl and octyl groups (S/S-C₁₈, S/S-C₈), or “capsule-type silica gels” were developed as packing materials for reversed-phase liquid chromatography. They were obtained by coating the surface of totally porous silica gel with a homogeneous silicone polymer film, and thereafter modifying the coating polymer with octadecyl or octyl groups. Retaining the advantages of silica-based packings, they show strong resistance of alkali-like organic porous polymeric materials.     

苯基化硅胶的物理结构和表面性质的研究

本文利用苯基三氯硅烷和硅胶表面羟基反应制备了苯基化硅胶。测定了苯基化硅胶的物理结构、水蒸气吸附等温线、润湿热、差热分析(DTA)和红外光谱(IR)。结果表明,所有苯基化硅胶的真密度(dT)、比表面(S)和比孔体积(V)均减少, 而表观密度(dA)增加, 但苯基化对不同硅胶的平均孔半径(r)有不同的影响; 苯基化硅胶对水蒸气吸附, 对水、苯和环己烷的润湿热均显著减少; 苯基化硅胶的热稳定性大于甲基化硅胶, 甲基化硅胶的表面是高度憎水的, 但苯基化硅胶的憎水性则很弱。     

表面自由基链转移反应制备聚合物修饰的固定相

 利用巯丙基修饰硅胶的自由基链转移反应 ,在硅胶表面原位引发自由基聚合 ,制备了聚甲基丙烯酸甲酯修饰的反相高效液相固定相。通过红外吸收光谱 (FTIR)、拉曼光谱、热失重 (TGA)和元素分析对该固定相进行了表征。该固定相对含氧芳香化合物、多环芳烃等均有良好的分离能力。     

Surface Chemistry and Structure of Silicon Oxycarbide Gels and Glasses

In this study, the surface chemistry and structure of methyl-substituted silica gels and porous oxycarbide glasses were investigated. FTIR was used to measure the relative concentration of Si−CH₃ and Si−OH as a function of the degree of methyl-substitution and the pyrolysis temperature. The gels and glasses were further heated, dehydrated or hydrated, in situ, within the FTIR spectrometer. In the temperature range of 800–850°C, high surface area oxycarbide glasses were created with no detectable surface hydroxyl groups. Oxycarbide glasses synthesized in argon at 700°C displayed a weak band for surface hydroxyl groups and reversible physisorption of water, while those synthesized at 850/900°C showed a complete absence of surface hydroxyl groups and the formation of vicinal silanols upon chemisorption of water. Isolated silanols were observed upon heat treatment in vacuum. Formation of aromatic carbon species was found to correlate with the decomposition of the methyl groups. The oxycarbide surface is quite stable to densification (presumably due to elemental carbon on the pore surfaces). In the absence of oxygen, porous silicon oxycarbide glass powders maintain surface areas >200 m²/g at 1200°C. However, oxidizing species in the atmosphere deplete the aromatic carbon species, and the glasses lose surface area.