离子液体修饰的杂化硅整体柱的制备及其电色谱性能

合成了含有烯丙基的离子液体氯化1-烯丙基-3-甲基咪唑(AMIMCl),采用自由基聚合反应将其固定到含有乙烯基的杂化硅整体柱表面,制备了离子液体修饰的杂化硅整体柱.在酸性环境下,利用该整体柱分离了核苷酸、酚类物质和苯甲酸类化合物,与未进行修饰的整体柱相比,离子液体修饰的杂化硅整体柱的电渗流反向,分离选择性明显提高,这可...     

Mini Review: Electroanalytical Sensors of Mesoporous Silica Materials

Mesoporous silica materials are promising substrates for electroanalytical sensors and electrocatalysis. Their characteristics include uniform pore sizes, surface areas in excess of 1000 m² g^?1, and long-range ordering of the packing of pores. The size scale, aspect ratio, and properties of mesoporous silica provide advantages in a variety of sensor applications. To improve performance, miniaturize platforms, and expand applications for trace analysis, novel materials with high sensitivity and rapid response have been developed and employed in recent years. These materials include pure mesoporous silica, mesoporous silica functionalized with organic groups, and composite or hybrid mesoporous silica. In this review, recent advances are outlined involving the application of mesoporous silica-based materials in electroanalytical sensors.     

水-乙醚二元溶剂体系中制备放射虫状介孔氧化硅

在水-乙醚双溶剂体系中合成了一种新型的放射虫状介孔氧化硅微球. 通过SEM、TEM、XRD以及孔分布测试技术对其进行了表征. 分析结果表明, 这种氧化硅产物反映了在不稳定的水-油界面合成的形貌特征, 具有多级孔结构和空的内腔以及两种类型径向取向的介孔结构外壳.     

以阴离子手性模板合成螺旋形貌的介孔分子筛

本文首次以具有手性的药物分子布洛芬(Ibuprfen, 2-(4-异丁基苯基)丙酸)为模板剂, 以3-氨丙基-3-乙氧基硅烷为共模板剂, 合成了具有新颖螺旋形貌的介孔分子筛, 并用XRD, FTIR, TEM 和SEM对其结构进行了表征.     

Synthesis and Characterization of Mesoporous Silica Templated by Amphiphilic RTILs

This article reports a novel preparation of mesoporous silica with series of 1-alky-3-methylimidazolium bromide (C_nMIM)Br (n = 12, 14, 16), a kind of amphiphilic room-temperature ionic liquids (RTILs), as a template via a sol-gel nanocasting technique. The pore morphology and structures of these mesoporous silica were characterized by Transmission electron microscopy (TEM). The results show that the RTIL bearing longer alkyl chain is preferred to form the mesoporous silica material with bigger pores. (C₁₆MIM)Br has been chosen to study how the various influencing factors affect the synthesis and structure of the mesoporous silica material, such as the acid concentration, the solling time, the gelling time and the calcination time. N₂ adsorption-desorption isotherms measurement was used to characterize the pore size distribution and BET surface area. The results indicate that all of the factors can make an influence on the preparation of the mesoporous silica, which is more sensitive to the concentration of the acid.     

功能化离子液体修饰的SBA-15固定化Burkholderia cepacia脂肪酶

采用含不同碳链长度咪唑环的烷基功能化离子液体修饰介孔材料SBA-15,并通过X-射线衍射、元素分析、N2吸附-脱附、红外光谱和扫描电镜等方法研究了离子液体修饰对SBA-15结构的影响.以三乙酸甘油酯的水解为探针反应,考察了甲基、丁基、辛基等不同链长烷基取代咪唑类离子液体修饰的SBA-15固定化Burkholderia cepacia脂肪酶(BCL)的酶活、最适反应条件及稳定性等酶学性质.结果表明,离子液体修饰后材料保持了原有的介孔结构,其固定化酶对温度及低pH的敏感度降低,比活力及稳定性均显著提高.其中甲基功能化离子液体修饰的SBA-15固定化酶的比活力最高,是原粉SBA-15固定化酶的2.4倍;辛基功能化离子液体修饰的SBA-15固定化酶的热稳定性、储存稳定性、重复使用性及有机溶剂耐受性最佳.     

Application of Ionic Liquid Modified Silica for Solid-Phase Extraction of Polysaccharides from Laminaria japonica

Silica-confined ionic liquids were synthesized for solid-phase extraction of polysaccharides, which was determined by high-performance liquid chromatography coupled with RI detection. The sorbent with amino-imidazolium groups was found to be the optimal material by a comparison of the adsorption capacity of fucoidan and laminarin onto different synthetic sorbents. The proper elution solvents for both laminarin and fucoidan were decided from practical tests. The sorbent performed stably and selectively, demonstrating potential applications in the separation of hydrophilic biomacromolecules, such as polysaccharides.     

模板技术制备单块介孔分子筛

模板技术与溶胶 -凝胶过程结合是合成介孔分子筛的有效方法 .模板通常采用表面活性剂在一定条件下自组装形成超分子结构 ,在不同条件下 ,此超分子结构具有不同聚集形态 ,合成出的介孔分子筛也具有不同的孔道排列方式 [1～ 4 ] .溶胶 -凝胶过程是通过硅源体的水解缩合并缓慢蒸发除去溶剂实现的 .此过程及产物受体系的 p H值影响很大 .在碱性体系中制备的介孔材料通常为粉末状 ,不利于实际应用 ,因此人们更加重视合成具有规则外形的介孔材料[5] .目前报道大多是在酸性体系中制备不同形状的介孔材料 [6～ 12 ] .有关合成单块介孔分子筛的报道…     

以阴离子表面活性剂/阳离子聚铵复合胶束为模板合成有序介孔二氧化硅

基于静电作用, 阴离子表面活性剂可与阳离子聚铵组装形成复合胶束. 借助阳离子聚铵,复合胶束可以作为模板与硅源协同组装, 形成高度有序的介孔二氧化硅. 本文通过调变不同种类阴离子表面活性剂、合成体系pH值、合成温度及阳离子聚铵和硅源用量等因素, 合成了具有不同介观结构和形貌的介孔二氧化硅. 实验证实阴离子表面活性剂/阳离子聚铵复合胶束模板法是合成介孔二氧化硅的一种通用方法.     

Synthesis of Highly ordered Large Size Mesoporous Silica and Effect of Stabilization as Enzyme Supports in Organic Solvent

ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅｔｅｃｈｎｉｑｕｅｆｏｒｅｎｖｉｒｏｎｍｅｎｔｐｒｏｔｅｃｔｉｏｎｈａｓｂｅ ｃｏｍｅｉｎｃｒｅａｓｉｎｇｌｙｉｍｐｏｒｔａｎｔ .Ｔｈｅｃｌｅａｒｂｉｏｄｅｃｏｍｐｏｓｉ ｔｉｖｅｍｅｔｈｏｄｓｈａｖｅｂｅｅｎｎｏｔｅｄｉｎｒｅｃｅｎｔｙｅａｒｓ ,ａｎｄｐｅｒｏｘｉｄａｓｅｓ(ｈｅｍｅｅｎｚｙｍｅ)ｈａｖｅｂｅｅｎｗｉｄｅｌｙｕｔｉｌｉｚｅｄｉｎｓｏｍｅａｐｐｌｉｃａｔｉｏｎｓｓｕｃｈａｓｄｅｐｏｌｙｍｅｒｉｚａｔｉｏｎｏｆｌｉｇｎｉｎｏｒｃｏａｌ[1,2 ] ,ａｎｄｔｈｅｎ…     

铝膜腔体内高度有序的介孔硅SBA-16的合成

在阳极铝膜腔体内, 以三嵌段聚合物F127为表面活性剂合成出一维纳米介孔二氧化硅材料. 采用压力诱导合成方法能使纳米纤维沿着铝膜腔体有序生长排列, 并且只存在于铝膜的腔体内, 在铝膜表面没有残留. 在纳米纤维的两侧可以清楚地观察到具有六边形结构的孔道, 直径为12 nm. 考察了正硅酸乙酯的水解时间以及化合物的不同配比对材料形貌的影响.     

二元阴、 阳离子表面活性剂调控合成不同形貌的介孔二氧化硅

经过简单的水热处理, 以二元阴、 阳离子表面活性剂[十六烷基三甲基溴化铵(CTAB)和十二烷基磺酸钠(SDS)分别作为阳离子表面活性剂和阴离子表面活性剂]为模板剂合成了不同形貌的介孔二氧化硅. 通过调控2种表面活性剂摩尔分数R(R=n(SDS)/[n(SDS)+n(CTAB)]), 合成了多种形貌的介孔二氧化硅. 对合成的不同形貌样品通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线粉末衍射仪(XRD) 及比表面和孔隙分析仪进行了表征. 结果表明, 随着R值从0.01变化到0.50, 介孔二氧化硅的形貌经历了一系列规律性的变化, 出现了二维六方、 层状相和反相堆积的形貌: 在R=0.01~0.18之间, 主要产物为六方相棒状结构, 且长径比随着R值增大而增大; 在R=0.20~0.28之间主要得到空心泡状结构且具有明显的演变过程; 在R=0.32~0.40之间发生了多层囊泡到单层囊泡的结构转变; 当R值超过一定范围时会产生反相堆积的形貌. 分析认为, SDS在加入过程中通过影响堆积参数g影响胶束的形貌变化, 调控了不同形貌介孔二氧化硅的合成. 各阶段产物形貌和R值的变化有直接关系, 可通过改变R值来合成特定形貌的产物.     

Characterization Studies on the Ionic Liquid-Templated Mesoporous Silica with Wormlike Pores

This article reports a novel preparation of wormlike mesoporous silica with 1-hexadecane-3-methylimidazolium bromide (C₁₆MIM)Br, a kind of room-temperature ionic liquids (RTILs), as a template via a sol-gel nanocasting technique. The characterization studies were carried out in contrast with that of the mesoporous silica with cetyltrimethylammonium bromide (CTAB), a usually used template, which has the same alkyl chain length with (C₁₆MIM)Br. The structures of the silica materials have been characterized by Transmission electron microscopy (TEM), High-resolution TEM (HRTEM) and N₂ adsorption-desorption measurements. The results show that both the mesoporous materials prepared with different templates respectively can form regular wormlike mesopores with ca. 2 nm in pore diameter. They also have large BET surface areas with narrow size distribution. Compared to the CTAB-template mesoporous silica, the material with (C₁₆MIM)Br as a template has highly uniform pore size and larger surface area. In addition, the formation mechanism of the wormlike mesopores with RTIL has been proposed by an electrostatic charge matching assembly-pathway and steric factor.     

酸诱导介观相转变硅基介孔材料的合成机理及其改性

采用两步法以三嵌段共聚物P104(PEO27-PPO61-PEO27)为模板剂合成介孔材料, 研究了介孔材料结构随体系pH 值的变化, 探讨了体系中介观相转变的机理. 研究表明,随着pH 的升高, 发现体系中无机物种和模板剂所组成的介观相发生了转变,由P6mm 的SBA-15(pH=1.51-2.67)2D六角孔道结构转变为3D 蠕虫状孔道的MSU-X(pH=3.93-4.56)结构. 对所得的两种不同种类的硅基材料以γ-胺丙基三乙氧基硅烷(APTES: NH2(CH2)3Si(C2H5O)3)进行表面烷基化改性结果表明, 在同样的条件下, 经过改性后MSU-X类介孔材料孔壁上接枝的烷基数目要远超过SBA-15 类介孔材料.     

Synthesis of Mesoporous Silica Molecular Sieves via a Novel Templating Scheme

ThediscoveryofM41SfamilyofmesoporousmolecularsievesbyMobilresearchersI'2hasstimulatedconsiderableinterestintheuseofthesematerialsascatalysts,catalystsupports,aswellasadsorbents3'#.Intheoriginalreport=,MCM-41waspreparedfromaself-assemblyprocesswhichinvolveselectrostaticinteractionsbetweenpositivelychargedquaternaryammoniummicelles(S )andinorganicanions(l-)usedasframeworkprecursors.Huoetal5extendedtheelectrostaticassemblyapproachesbyproposingfourcomplementarysynthesisschemes(S l-,S-I ,S X-…     

Polymerization of Methyl Methacrylate with Samarocene Complex Supported on Mesoporous Silica

Synthesis of polymers with controlled molecular weight and narrow polydispersity is of both fundamental interest and practical importance. In recent years, high molecular weight poly (methyl methacrylate) (PMMA) having an unusually narrow polydispersity has been synthesized by using the unique initiating property of (C5Me5)2LnⅢR (R=H, Me, Ln=Sm, Yb) complexes1,2. Herein we report the results of the first example of the polymerization of methyl methacrylate (MMA) with samarocene complex …     

Carbon Paste Electrode Modified with Carbamoylphosphonic Acid Functionalized Mesoporous Silica: A New Mercury‐Free Sensor for Uranium Detection

This study reports a new approach for developing a uranium electrochemical sensor that is mercury‐free, solid‐state, and has less chance for ligand depletion than existing sensors. A carbon‐paste electrode modified with carbamoylphosphonic acid self‐assembled monolayer on mesoporous silica was developed for uranium detection based on an adsorptive square‐wave stripping votammetry technique. Voltammetric responses for uranium detection are reported as a function of pH, preconcentration time, and aqueous phase uranium concentration. The uranium detection limit is 25 ppb after 5 minutes preconcentration and improved to 1 ppb after 20 minutes preconcentration. The relative standard deviations are normally less than 5%.     

Encapsulation of Organic Pigment Particles with Silica via Sol-Gel Process

This paper presented a novel preparation method of silica coated organic pigment. In this approach, the surfaces of the organic pigment were first orderly modified by poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), then coated by silica via sol-gel process of tetraethylorthosilicate (TEOS). The results showed that PVP, pH value, water and TEOS contents had significant influence on the morphology of the silica encapsulated organic pigment. Organic pigments coated silica by this approach could scatter UV ray with wavelength less than 270 nm, and this scattering property increased with more silica coated.     

pH对两步法非离子模板合成MSU-X类硅基介孔结构的影响

采用两步法以非离子型表面活性剂Tween 20为模板剂合成硅基介孔材料, 研究了pH对介孔材料结构的影响. 结果表明, 没有氟离子存在且模板剂浓度较低(约为2%(w))的条件下, 在弱酸性环境中(pH=3.32-4.26)可以制备有序的MSU-X类硅基介孔材料, 本研究中的简单合成体系有助于查明MSU-X合成机理. 对所得介孔材料测试表明, 在同样的合成体系中, 随着体系pH的变化, 所得硅基介孔材料的形貌和孔壁结构都发生了变化.