双模板法制备介孔／大孔复合孔结构硅胶独石

采用双模板法,向正硅酸甲酯的水解体系中同时引入聚乙二醇和三嵌段共聚物,成功制备出具有双连续大孔、同时孔壁中分布着有序介孔的复合孔结构硅胶独石材料. 产物的比表面积高达880 m2/g, 大孔孔径为0.2～5 μm, 介孔高度集中地分布在 5 nm. 结合物理吸附、扫描电镜、粉末X射线衍射和透射电镜等表征手段,发现合成条件如原料组成、反应温度和pH值等对反应体系中凝胶化转变和相分离发生的相对速度有重要影响,进而影响产物复合孔结构的生成. 此外,通过对合成条件的优化,一方面增强了无机骨架的强度,另一方面降低了湿凝胶干燥过程中的毛细管压力降,有效缓和了凝胶结构在干燥过程中的开裂和变形,使复合孔结构硅胶独石在厘米尺度内具有良好的整体性能.     

Carbon monolith: Preparation,characterization and application as microextraction fiber

A carbon monolith was synthesized via a polymerization–carbonization method, styrene and divinylbenzene being adopted as precursors and dodecanol as a porogen during polymerization. The resultant monolith had bimodal porous substructure, narrowly distributed nano skeleton pores and uniform textural pores or throughpores. The carbon monolith was directly used as an extracting fiber, taking place of the coated silica fibers in commercially available solid-phase microextraction device, for the extraction of phenols followed by gas chromatography–mass spectrometry. Under the studied conditions, the calibration curves were linear from 0.5 to 50 ng mL⁻¹ for phenol, o-nitrophenol, 2,4-dichlorophenol and p-chlorophenol. The limits of detection were between 0.04 and 0.43 ng mL⁻¹. The recoveries of the phenols spiked in real water samples at 10 ng mL⁻¹ were between 85% and 98% with the relative standard deviations below 10%. Compared with the commercial coated ones (e.g. PDMS, CW/DVB and DVB/CAR/PDMS), the carbon monolith-based fiber had advantages of faster extraction equilibrium and higher extraction capacity due to the superior pore connectivity and pore openness resulting from its bimodal porous substructure.     

基于硅胶整体材料研磨颗粒的多功能聚乙二醇键合固定相的制备及其在高效液相色谱多模式分离中的应用

研究通过对溶胶-凝胶法制备的硅胶整体材料进行研磨、浮选、假晶相转换和水热处理，最终获得了粒径为2~5 μm、孔径为20~60 nm的硅胶颗粒。利用部分含氟的阴离子表面活性剂Capstone FS-66和常用的阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）组成的双胶束模板体系对硅胶基质进行假晶相转换处理；再采用碳酸钠溶液水热处理的方式，进一步扩大孔径。用扫描电镜（SEM）和N₂吸附-解吸等温线测量对扩孔处理前后的硅胶整体材料研磨颗粒进行表征，结果清楚地显示了处理前后的形貌变化和差异。随后将含有长链聚乙二醇（PEG）的硅烷键合到扩孔后的硅胶颗粒表面，分别利用元素分析、红外光谱以及热重分析对固定相进行表征，并对固定相进行色谱性能评价。对键合固定相的元素分析和热重分析数据进行分析表明，硅胶表面键合PEG的含量约为8%。研究揭示了利用假晶相转换法与碳酸钠溶液水热处理和长链PEG硅烷修饰的硅胶整体材料颗粒在尺寸排阻色谱分离蛋白质方面的良好分离效果。同时进一步的高效液相色谱评价结果表明，该键合固定相还可用于疏水作用色谱模式分离核糖核酸酶A和溶菌酶，以及可用于亲水作用色谱模式分离吡啶甲酸、左旋多巴、三聚氰胺和邻苯二酚等极性比较强的化合物。研究显示了PEG键合固定相具有多功能性，及其在多模式高效液相色谱分离中的应用潜力。     

基于巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱用于糖蛋白的选择性富集

发展了以巯基-烯点击反应制备有机-无机杂化硼酸亲和整体柱的新方法。首先以四甲氧基硅烷(TMOS)和巯丙基三甲氧基硅烷(MPTMS)作为反应单体,采用溶胶-凝胶反应制备表面含巯基的硅胶整体柱。然后利用巯基-烯(thiol-ene)的点击反应在整体柱上修饰硼酸配基3-丙烯酰胺基苯硼酸(AAPBA),制成AAPBA-硅胶杂化亲和整体柱。对影响硼酸亲和整体柱性能的条件如TMOS与MPTMS的比例、聚乙二醇和甲醇的用量等进行了优化。并采用扫描电镜、红外光谱等分析仪器对整体柱形貌和机械稳定性能进行了表征。研究了AAPBA-硅胶杂化亲和整体柱的分离性能,结果表明,其在中性条件下对含有顺式二醇的生物小分子核苷具有良好的特异亲和能力,并已成功地应用于卵清蛋白、辣根过氧化物酶等糖蛋白的分离。基于巯基-烯反应的制备方法新颖、可靠,可用于制备多种不同类型的硼酸亲和整体柱,具有较大的应用前景。     

Post‐polymerization modification of a new reactive monolith for reversed phase and hydrophilic interaction capillary electrochromatography of neutral,polar, and biologically active compounds

A reactive monolith based on the polymerization of 3‐chloro‐2‐hydroxypropyl methacrylate, (HPMA‐Cl), with a crosslinking agent, ethylene glycol dimethacrylate (EDMA), was synthesized and post‐functionalized with a macromolecular ligand polyethyleneimine. Monolithic columns with controlled permeability and pore structure were prepared by free radical polymerization in the presence of a binary porogenic mixture of isopropanol and decanol. The presence of chloropropyl functionality in the pristine monolith allowed the synthesis of a post‐fuctionalized monolith carrying cationic groups that was used to control the magnitude of electroosmotic flow (EOF) in electrochromatographic separation. In the synthesis of pristine monoliths, the feed concentration of functional monomer (ie, HPMA‐Cl) was changed between 30 and 60 v/v % for obtaining cationic monoliths providing satisfactory electrochromatographic separation. The best electrochromatographic performance was obtained with the polyethyleneimine functionalized monolith prepared by using the pristine monolith obtained by 60% (v/v) monomer concentration. This monolith was used in reversed phase and hydrophilic interaction capillary electrochromatography modes for the separation of alkylbenzenes, polycyclic aromatic hydrocarbons, phenols, and nucleosides, using mobile phases with low acetonitrile (ACN) contents ranging between 20% and 35% (v/v). This ACN range was remarkably lower than the content of ACN used on the hydrophilic polymethacrylate‐based monoliths reported previously (ie, >90%). The plate heights up to 5.3 μm were obtained for the separation of nucleosides with the environmental friendly mobile phases whose ACN contents were also remarkably lower than that of similar polymethacrylate‐based monoliths.     

金纳米粒子修饰毛细管硅胶整体柱的制备及其电色谱性能研究

通过毛细管硅胶整体柱表面修饰十八烷基硫醇金纳米粒子,制备了一种新型毛细管电色谱固定相.制备金纳米粒子修饰整体柱时,采用溶胶-凝胶法制备毛细管硅胶整体柱,并在其表面化学修饰3-巯基丙基三甲氧基硅烷;通过巯基基团固载金纳米粒子于整体柱上,再共价键合十八烷基硫醇于金纳米粒子表面.以甲苯为探针,对理论塔板高度与流动相线速度之间...     

原位合成的活性脲醛树脂作为模板剂制备二氧化硅介孔材料

利用酸性条件下正硅酸乙酯的水解和脲醛树脂的聚合反应同时一步原位进行的方法合成了二氧化硅复合粉体(包括核壳微球结构和网状结构)和块体凝胶材料. 液氮吸附BET分析结果证明复合材料焙烧后得到的二氧化硅孔径分布均匀, 大小在介孔范围内. 改变反应性单体尿素. 甲醛及正硅酸乙酯等的初始浓度可对二氧化硅块体材料的孔径大小进行调节. 扫描电子显微镜观测结果显示, 随着原料单体初始浓度的变化复合粉体材料的微米级形貌可以是多孔网状结构或核壳结构. 从红外光谱和差热分析的结果推测, 高甲醛/尿素摩尔比[n(甲醛)∶n(尿素)≥2]条件下形成的支链脲醛树脂可作为块体二氧化硅理想的孔结构导向剂.     

Preparation of C60–Silica Hybrid Monolith by Sol-Gel Process

A C₆₀–silica hybrid monolith was prepared by the hydrosilylation of C₆₀ in the presence of platinum catalyst followed by sol-gel process with tetraethoxysilane. The hydrosilylation with trichlorosilane, triethoxysilane, chlorodiphenylsilane, and dichlorophenylsilane gave silylated C₆₀s as a brown pasty liquid. The formula was estimated to be C₆₀{Si(OEt)₃}_2.6H_2.6 or C₆₀(SiPh₂Cl)_3.2H_3.2 based on the proton nuclear magnetic resonance spectrum. A C₆₀–silica hybrid gel monolith was obtained by sol-gel process of the silylates and tetraethoxysilane in ethanol followed by aging for 3 weeks at room temperature. The monolith was brown and transparent with a diameter of 25 mm. On the other hand, the sol-gel reaction of tetraethoxysilane, trimethoxyphenylsilane, and C₆₀ provided a heterogeneous gel with a phase separation of C₆₀.     

金纳米粒子修饰的氨基硅胶整体柱的制备及超灵敏表面增强拉曼散射检测

采用溶胶-凝胶法结合超分子模板技术, 以四乙氧基硅烷(TEOS)和3-氨丙基三乙氧基硅烷(APTES)作为反应前体, 以十六烷基三甲基溴化铵(CTMAB)为超分子模板, 简单快速地制备了一种新型氨基硅胶整体柱, 通过氨基将金纳米粒子组装在整体柱材料孔表面并用于表面增强拉曼散射(SERS)光谱分析. 以对巯基苯胺(PATP)和结晶紫(CV)为拉曼探针, 考察了金纳米粒子修饰的氨基硅胶整体柱用作SERS活性基底的性能. 结果表明, 该整体柱基底具有良好的SERS增强效应, 可检测到的PATP和CV的最低浓度分别为10^-9和10^-11 mol/L. 与金溶胶SERS基底相比, 本文制备的整体柱基底的检测灵敏度显著提高, 并具有良好的信号均一性, 是一种具有现场痕量检测应用潜力的SERS活性基底.     

A thermosensitive monolithic column as an artificial antibody for the on-line selective separation of the protein

The main objective of this study was to develop a new methodology for the preparation of a protein (antigen) that is a molecularly imprinted polymer (MIP, an artificial antibody) modified onto the surface of a silica skeleton in which the resulting stationary phase is thermosensitive. The silica monolithic skeleton with vinyl groups was synthesized in a stainless-steel column by using a mild one-step sol-gel process with two types of precursor: methyltrimethoxysilane (MTMS) and γ-methacryloxypropyltrimethoxysilane (γ-MAPS). Subsequently, three types of the thermosensitive protein MIP were anchored onto the surface of the silica skeleton to prepare the MIP monoliths, which were systematically investigated for back pressure and separation ability at different temperatures to establish good imprinting conditions. Under the optimized imprinting conditions, the chromatographic behavior of the thermosensitive MIP monolith exhibited strong retention ability for the lysozyme template (target antigen) in relation to the nonimprinting monolith (NIP monolith). The imprinting factor (IF) for lysozyme reached 3.48 at 20 °C. Moreover, this new type of artificial antibody displayed favorable binding characteristics for lysozyme over competitive proteins and was further evaluated to selectively separate lysozyme in a real sample by using an on-line method. The run-to-run and column-to-column repeatability measurements of the thermosensitive MIP monoliths were also satisfactory.     

Incorporation of carbon nanotubes in porous polymer monolithic capillary columns to enhance the chromatographic separation of small molecules

Multiwalled carbon nanotubes have been entrapped in monolithic poly(glycidyl methacrylate-co-ethylene dimethacrylate) capillary columns to afford stationary phases with enhanced liquid chromatographic performance for small molecules in the reversed phase. While the column with no nanotubes exhibited an efficiency of only 1800 plates/m, addition of a small amount of nanotubes to the polymerization mixture increased the efficiency to over 15,000 and 35,000 plates/m at flow rates of 1 and 0.15 μL/min, respectively. Alternatively, the native glycidyl methacrylate-based monolith was functionalized with ammonia and, then, shortened carbon nanotubes, bearing carboxyl functionalities, were attached to the pore surface through the aid of electrostatic interactions with the amine functionalities. Reducing the pore size of the monolith enhanced the column efficiency for the retained analyte, benzene, to 30,000 plates/m at a flow rate of 0.25 μL/min. Addition of tetrahydrofuran to the typical aqueous acetonitrile eluents improved the peak shape and increased the column efficiency to 44,000 plates/m calculated for the retained benzene peak.     

Capillary electrochromatography with monolithic silica columns. IV. Electrochromatographic characterization of polar bonded monolithic stationary phases having surface-bound cyano functionalities

Two polar ligands, namely 3-hydroxypropionitrile and 1H-imidazole-4,5-dicarbonitrile (IDCN) were covalently attached to epoxy-activated silica-based monolithic capillary columns via an epoxide ring-opening reaction to yield CN-OH-Monolith and 2CN-OH-Monolith, respectively. The silica monolith was prepared by a sol-gel process, and the resulting "rod-like" stationary phase was subjected to pore tailoring with an alkaline solution to convert small pore domains to mesopore domains, thus yielding a monolith with bimodal pore structure consisting of flow through pores (i.e., flow channels for mobile-phase flow) and mesopores that provide most of the adsorption capacity of the monolith toward the separated solutes. The two polar monoliths, CN-OH-Monolith and 2CN-OH-Monolith, were evaluated in normal-phase CEC with organic-rich mobile phases less polar than the stationary phase. The 2CN-OH-Monolith bearing more polar functions than the CN-OH-Monolith exhibited more retention and improved selectivity toward model polar solutes.     

Preparation of a Hybrid Cation-Exchange Monolith and Its Application for the Separation of Proteins by High Performance Liquid Chromatography

A hybrid cation-exchange monolith for high performance liquid chromatography (HPLC) was prepared by a one-pot synthesis with reverse-atom transfer radical polymerization, in which sodium bisulfite was used as the inorganic material, methyl methacrylate was used as organic material, 2, 2'-Azobisisobutyronitrile as initiator, and ferric trichloride as the inorganic catalyst. Moreover, sodium bisulfite was used to provide the sulfonic group. The conditions of polymerization were optimized. The chemical groups of the monolith were assayed by Fourier transform infrared spectroscopy; the morphology of monolithic material was investigated by scanning electron microscopy; the pore size distribution was determined by a mercury porosimeter; and the mechanical stability and permeability of the monolith were investigated by the back-pressure drop at several linear velocities. Finally, the monolith was used to separate human serum albumin from human plasma in conjunction with HPLC in 5 min, and the influences of buffer concentration and pH value on the elution of human serum albumin were investigated. In addition, the monolith was applied to separate lysozyme from egg whites in a short time (4 min) and separate a mixture of aromatic compounds.     

Preparation and evaluation of a macroporous molecularly imprinted hybrid silica monolithic column for recognition of proteins by high performance liquid chromatography

A novel type of macroporous molecularly imprinted hybrid silica monolithic column was first developed for recognition of proteins. The macroporous silica-based monolithic skeleton was synthesized in a 4.6 mm i.d. stainless steel column by a mild sol–gel process with methyltrimethoxysilane (MTMS) as a sole precursor, and then vinyl groups were introduced onto the surface of the silica skeleton by chemical modification of γ-methacryloxypropyltrimethoxysilane (γ-MAPS). Subsequently, the molecularly imprinted polymer (MIP) coating was copolymerized and anchored onto the surface of the silica monolith. Bovine serum albumin (BSA) and lysozyme (Lyz), which differ greatly in molecular size, isoelectric point, and charge, were representatively selected for imprinted templates to evaluate recognition property of the hybrid silica-based MIP monolith. Some important factors, such as template–monomer molar ratio, total monomer concentration and crosslinking density, were systematically investigated. Under the optimum conditions, the obtained hybrid silica-based MIP monolith showed higher binding affinity for template than its corresponding non-imprinted (NIP) monolith. The imprinted factor (IF) for BSA and Lyz reached 9.07 and 6.52, respectively. Moreover, the hybrid silica-based MIP monolith displayed favorable binding characteristics for template over competitive protein. Compared with the imprinted silica beads for stationary phase and in situ organic polymer-based hydrogel MIP monolith, the hybrid silica MIP monolith exhibited higher recognition, stability and lifetime.     

Octyl-functionalized hybrid silica monolithic column for reversed-phase capillary electrochromatography

Hybrid silica monolithic stationary phase functionalized with octyl groups was synthesized by a two-step acid/base-catalyzed hydrolysis/co-condensation of tetraethoxysilane (TEOS) and n-octyltriethoxysilane (C(8)-TEOS). The influences of determining factors in the sol-gel process such as the monomer ratio and water content on the monolith formation were systematically investigated. An increase in the TEOS/C(8)-TEOS ratio in the polymerization mixture shifted the pore size distribution towards smaller pore diameter with larger pore volume. The optimal TEOS/C(8)-TEOS volume ratio was found to be 90/50, under which condition the median pore diameter of the monolith was around 1.0 microm with pore volume of 3.25 cm(3)/g. The chromatographic characteristics of the monolithic column prepared with the optimized fabrication condition were studied. Some aromatic compounds including alkylbenzenes, polycyclic aromatic hydrocarbons (PAHs) and phenols were successfully separated on the octyl-functionalized silica monolithic column with high column efficiency up to 180,000 plates/m.     

Efficient Removal of Pb(II) from Aqueous Medium Using Chemically Modified Silica Monolith

The adsorptive removal of lead (II) from aqueous medium was carried out by chemically modified silica monolith particles. Porous silica monolith particles were prepared by the sol-gel method and their surface modification was carried out using trimethoxy silyl propyl urea (TSPU) to prepare inorganic–organic hybrid adsorbent. The resultant adsorbent was evaluated for the removal of lead (Pb) from aqueous medium. The effect of pH, adsorbent dose, metal ion concentration and adsorption time was determined. It was found that the optimum conditions for adsorption of lead (Pb) were pH 5, adsorbent dose of 0.4 g/L, Pb(II) ions concentration of 500 mg/L and adsorption time of 1 h. The adsorbent chemically modified SM was characterized by scanning electron microscopy (SEM), BET/BJH and thermo gravimetric analysis (TGA). The percent adsorption of Pb(II) onto chemically modified silica monolith particles was 98%. An isotherm study showed that the adsorption data of Pb(II) onto chemically modified SM was fully fitted with the Freundlich and Langmuir isotherm models. It was found from kinetic study that the adsorption of Pb(II) followed a pseudo second-order model. Moreover, thermodynamic study suggests that the adsorption of Pb(II) is spontaneous and exothermic. The adsorption capacity of chemically modified SM for Pb(II) ions was 792 mg/g which is quite high as compared to the traditional adsorbents. The adsorbent chemically modified SM was regenerated, used again three times for the adsorption of Pb(II) ions and it was found that the adsorption capacity of the regenerated adsorbent was only dropped by 7%. Due to high adsorption capacity chemically modified silica monolith particles could be used as an effective adsorbent for the removal of heavy metals from wastewater.     

Preparation and characterization of temperature-responsive poly(N-isopropylacrylamide-co-N,N'-methylenebisacrylamide) monolith for HPLC

A temperature-responsive poly(N-isopropylacrylamide-co-N,N'-methylenebisacrylamide) [poly(NIPAAm-co-BIS)] monolith was prepared via a free-radical polymerization technique using an aqueous redox initiator in solution at -12°C. The effect of the % T (total monomer concentration/100 mL) and % C (cross-linker concentration/100 mL) on the visual form was investigated. The effect of the porogen on the pore structure was characterized by SEM. Under the optimum condition, the monolith for HPLC was successfully prepared and its mechanical strength and permeability have been studied. Furthermore, a temperature-dependent resolution of aromatic ketones was achieved using only water as mobile phase. The increasing interaction between solutes and the monolith was observed when temperature increased. The theoretical plate number of every analyte was more than 10(4).     

Selective sample pretreatment by molecularly imprinted polymer monolith for the analysis of fluoroquinolones from milk samples

Water-compatible pefloxacin-imprinted monoliths synthesized in a water-containing system were used for the selective extraction of fluoroquinolones (FQs). The MIP monolith was synthesized by using methacrylic acid as the functional monomer, di(ethylene glycol) dimethacrylate as a cross-linker and methanol–water (10:3, v/v) as the porogenic solvent. The ability of the derivated MIP for selective recognition of FQs (ciprofloxacin, difloxacin, danofloxacin and enrofloxacin) and quinolones (flumequine, and oxolinic acid) was evaluated. The derivated monolith showed high selectivity and was able to distinguish between FQs and quinolones. A simple rapid and sensitive method using polymer monolith microextraction (PMME) based on the MIP monolith combined with HPLC with fluorescence detection was developed for the determination of four FQs from milk samples. Owing to the unique porous structure and flow-through channels in the network skeleton of the MIP monolith, phosphate buffer diluted milk samples were directly supplied to PMME; allowing non-specific bound proteins and other biological matrix to be washed out, and FQs to be selectively enriched. The limit of detection of the method was 0.4–1.6 ng/mL and recovery was 92.4–98.2% with relative standard deviations less than 5.9%.     

三维有序大孔-介孔二氧化硅的可控制备及表征

以聚甲基丙烯酸甲酯(PMMA)胶晶为大孔模板、嵌段共聚物P123为介孔模板,利用双模板剂法进行了三维有序大孔-介孔二氧化硅材料的制备研究。采用SEM、TEM、低角XRD以及N₂吸脱附技术对样品进行了表征。结果表明,通过简单的调控PMMA胶晶模板的组装过程,就可以调变合成材料中的大孔结构,从而轻松地实现可控的制备出具有网状或者层状结构的三维有序大孔-介孔二氧化硅材料,并提出了其可能的形成机理。此外,所制备的三维有序大孔-介孔二氧化硅样品均具有较大的BET比表面积(>550m₂·g^-1),大孔孔径200nm左右,介孔孔径分布集中于3.5nm左右。     

Novel separation medium spongy monolith for high throughput analyses

Sponge-like material was utilized as novel chromatographic media for high throughput analyses. The pore size of the sponge-like material was several dozen micrometer, and was named spongy monolith because it consists of continuous structured copolymers, which was made of poly(ethylene-co-vinyl acetate), such as monolithic materials including silica monoliths and organic polymer monoliths. The spongy monolith was packed into a stainless steel column (100 mm × 4.6 mm I.D.) and evaluated in liquid chromatography (LC) with an on-line column-switching LC concentration system. The results indicate that the packed column could be used with high flow rates and low back pressure (9.0 mL/min at 0.5 MPa). Furthermore, bisphenol A was quantitatively recovered by on-line column-switching LC concentration with the spongy monolithic column. Additionally, the adsorption capacity and physical strength of the media was enhanced via chemical modification of spongy monoliths using glycerol dimethacrylate. The results compared with original spongy monolith demonstrated that a higher adsorption capacity was achieved on a shorter column, and a stable low back pressure was obtained at high throughput elution even with a longer column.