色谱固定相的超支化和聚酰胺-胺树状大分子接枝修饰方法研究进展

随着色谱固定相制备技术深入发展,固定相填料的修饰方法日渐成熟,主要包括固定相表面直接化学反应、表面附聚、共价接枝和超支化修饰。其中,以缩聚反应为主的超支化修饰方法自提出以来备受研究者的青睐,已经被应用于多种阴离子交换色谱固定相填料的制备。近些年来,和超支化聚合物具有相似结构的树状大分子由于其独特的物理性能、完美的树状结构和大量活性官能团,也逐渐被应用于各种色谱固定相填料的修饰,并有望进一步完善固定相填料的结构和分离性能。该文主要总结了超支化修饰方法和以聚酰胺-胺为主的树状大分子接枝修饰方法在色谱固定相填料制备中的应用,并对其未来发展进行展望。     

以枝形大分子聚酰胺-胺(PAMAM)为键合固定相的开管毛细管电色谱柱的制备及评价

用3-氨丙基三乙氧基硅烷(KH550)作偶联剂, 在毛细管内壁上逐步合成树枝形大分子聚酰胺-胺(PAMAM), 制得了1, 2和3代PAMAM键合的开管毛细管电色谱柱, 并对其性能进行了研究. 结果表明, 随着大分子代数的增加, 毛细管电渗流(EOF)逐步下降. 利用制得的1, 2和3代PAMAM修饰的开管毛细管电色谱柱对丙氨酸和脯氨酸的分离进行对比, 结果显示, 随着大分子PAMAM代数的增加, 分离度逐步增大, 丙氨酸和脯氨酸可在3代树枝状大分子PAMAM修饰的开管毛细管电色谱柱上达到基线分离. 采用非衍生化法和3代PAMAM修饰的开管毛细管电色谱柱成功地分析了精氨酸、 丙氨酸、 脯氨酸、 甲硫氨酸和组氨酸. 结果表明, 键合毛细管柱具有良好的重现性和稳定性.     

脱氧核糖核酸—聚胺基酰胺树状间隔臂—（二氧化锆—脲醛树脂）亲和色谱和固定相的合成及其应用

报道了一种高效液相亲和色谱固定相的合成方法。以3-5μm的非多孔二氧化锆与脲醛树脂（UFR）复合物微球用作高效液相亲和色谱固定相的基体，并用扫描电子显微镜检验该基体的结构和粒径。用此基体末端的酰胺基团为核心，分别与丙烯酸甲酯、乙二胺重复进行三次马氏加成反应和胺化反应，就开成末端为胺基的聚胺基酰胺（PAMAM）星型树状间隔臂。用^13C固体核磁共振检测了树状间隔臂的拓扑结构。此间隔臂用丁二酰亚胺（NHS）活化，最后与配位体脱氧核糖核酸（DNA）键合，并用紫外分光光度法测定了配位本容量。从而制备了一种[DNA-（PAMAM）-ZrO2-UFR)]高效液相亲和色谱固定相。通过优化色谱柱操作参数，其已用于蛋白质的分析和核糖核酸（RNA）碎片的分离。     

树状大分子PAMAM(1G)-FCD的合成及荧光性能

合成了外围由小分子2-芴醛修饰的树状大分子PAMAM(1G)-FCD, 用IR, 1H NMR, MALDI-TOF-MS等手段表征了其结构, 并对其荧光性能及Sn2+对该性能的影响进行了研究, 结果表明, Sn2+能使化合物荧光显著增强. 紫外光谱表明, 随着PAMAM(1G)-FCD溶液中Sn2+浓度的增加, 体系在360 nm处出现了新的吸收峰, 表明二者之间存在化学反应. 故该树状分子有望作为难得的蓝光区荧光材料及金属-树状大分子杂化材料.     

聚酰胺-胺树状大分子的应用

聚酰胺-胺(PAMAM)树状大分子是目前树状大分子化学中研究较为成熟的一类，是三种已经商品化的树状大分子之一，其功能化和应用是目前树状大分子领域的热点。PAMAM已在多个领域显示出良好的应用前景。本文主要对PAMAM在表面活性剂、催化剂、纳米复合材料、金属纳米材料、膜材料、导电材料等方面的应用进行评述。     

Cu2+对树状大分子PAMAM-FCD荧光性能的影响

以小分子2-芴醛(FCD)修饰树状大分子聚酰胺-氨PAMAM, 合成了1~3代树状大分子PAMAM-FCD, 用IR, 1H NMR和MALDI-TOF-MS等手段表征了化合物结构, 研究了Cu2+浓度对其荧光及紫外性能的影响. 结果表明, Cu2+可使其荧光强度和紫外吸收不同程度地增强. 在紫外光谱中, Cu2+自身的吸收峰消失, 表明Cu2+参与配位. PAMAM-FCD有望成为蓝光区荧光材料及树状大分子-铜杂化材料.     

聚酰胺-胺树状大分子修饰硅胶固定化胰蛋白酶的研究

以聚酰胺-胺(PAMAM)树状大分子修饰的硅胶为载体,胰蛋白酶为模型,考察了PAMAM的代数和固定化条件对酶的固载量及活力的影响.实验结果表明:选用3.0代PAMAM树状大分子修饰硅胶为载体固定化胰蛋白酶,酶促反应最适pH值为9.0,最适温度为60℃,对酪蛋白表现米氏常数K<,m>为7.76mg/mL,固定化胰蛋白酶表...     

核壳型二氧化硅色谱填料的研究进展

复杂样品的高效快速分离分析是分离科学家所面临的挑战。近年来,核壳型二氧化硅色谱填料以其高效、快速和低背压的特点被广泛用于小分子、大分子和复杂样品的快速分离分析。该文系统综述了二氧化硅核壳色谱固定相快速分离的机理,制备方法及其在小分子、多肽和生物大分子快速分离分析方面的应用,同时对核壳型色谱固定相的发展进行了展望。     

金属有机框架色谱固定相的研究进展

金属有机框架(MOFs)是由金属离子或金属簇与有机配体通过配位作用自组装形成的一类新型多孔材料. MOFs具有独特的拓扑结构、丰富的孔隙结构、可调的孔道尺寸、巨大的比表面积以及灵活的表面修饰等特征,是色谱分离领域颇受关注的一类新型固定相. 综述了近几年MOFs材料作为固定相在气相色谱、液相色谱及手性拆分等领域应用的研究进展,展现MOFs材料在色谱分离领域的优异性能和应用潜力,并对MOFs材料在色谱固定相领域今后的发展进行了展望.     

微波辅助合成法制备聚酰胺-胺树枝状分子修饰的开管毛细管电色谱柱

采用微波辅助合成技术,快速制备以聚酰胺-胺(poly(amidoamine),PAMAM)树枝状分子为固定相的开管毛细管电色谱柱.与常规合成方法相比,微波辅助合成法可以提高反应速度,极大地缩短制备周期.在pH 5.7～8.0范围内, 随着PAMAM树枝状分子代数的增加,毛细管电渗流(EOF)逐步下降.对丙氨酸和脯氨酸进行分离的实验结果表明,随着PAMAM树枝状分子代数的增加,分离度逐步增大,3代PAMAM树枝状分子修饰的毛细管柱具有良好的分离效果.以丙酮标记物连续测定10 d,柱效下降3.85%, 表明采用微波辅助合成技术制得的PAMAM树枝状分子修饰的毛细管柱具有良好的稳定性.     

Molecularly imprinted polymers: towards highly selective stationary phases in liquid chromatography and capillary electrophoresis

Molecularly imprinted polymers (MIPs) are synthetic polymers with a predetermined selectivity for a given analyte, or group of structurally related compounds, that make them ideal materials to be used in separation processes. In this sense, it is not surprising that the first applications of MIPs were as tailor-made chiral stationary phases in liquid chromatography. However, peak broadening and tailing, especially of the more retained enantiomers, were observed. Accordingly, this paper gives an overview of the attempts carried out during the recent years to improve the chromatographic performance of MIPs in liquid chromatography and capillary electrophoresis as well as the more recent applications. We conclude that MIPs are very promising materials to be used as selective stationary phases in chromatography although further developments are necessary in order to fully exploit their potential.     

新型碳纳米管色谱固定相制备的研究进展

碳纳米管（CNTs）作为一种新型的功能材料,具有优异的物理、化学和机械性能,已经在分析化学领域得到了广泛的关注和应用。通过填充法或原位化学气相沉积法,可制备CNTs气相色谱固定相;将CNTs沉积在硅胶微球或有机聚合物基质微球表面,可制备填充式CNTs液相色谱固定相;通过包埋共聚法将CNTs嵌入聚合物整体柱内,可制备毛细管CNTs液相色谱整体柱。本文主要综述了近年来CNTs（单壁碳纳米管和多壁碳纳米管）用于色谱固定相制备的研究现状,包括气相色谱及液相色谱,并对该领域今后的发展进行展望。     

C18-磺酸基双改性液相色谱固定相的制备与评价

以十八烷基三氯硅烷和3-巯丙基三甲氧基硅烷为改性剂,采用一锅法对硅胶表面加以修饰,进一步将巯基氧化制备成C18-磺酸基双改性液相色谱固定相.在优化的反应条件下得到了十八烷基和磺酸基摩尔比为3∶7的固定相,分别采用扫描电镜、元素分析、红外光谱对固定相的形貌和特征加以表征.针对制备的固定相,在不同的分离模式下,系统考察其色谱分离性能.在反相色谱模式下,成功分离了5种烷基苯化合物;在亲水模式下,分离了3种核苷;进一步应用于牛血清白蛋白酶解产物的分离,得到了较好的结果.实验结果表明,制备的混合模式固定相同时具有多种分离机理,在分离复杂样品、调整选择性方面具有潜在的优势.     

Protein separation using a novel silica-based RPLC/IEC stationary phase modified with N-methylimidazolium ionic liquid

Ionic liquids (ILs) immobilized on silica as novel high performance liquid chromatography (HPLC) stationary phases have attracted considerable attention. However, it has not been applied to protein separation. In this paper, N-methylimidazolium IL-modified silica-based stationary phase (SilprMim) was prepared and investigated as a novel multi-interaction stationary phase charged positively for protein separation. The results indicate that all of the basic proteins tested cannot be absorbed on this novel stationary phase, whereas all of the acidic proteins tested can be retained, and the baseline separation of eight kinds of acidic protein standards can be achieved when performed in reversed phase/ ion-exchange chromatography (RPLC/IEC) mode. Compared with commonly used commercial octadecylated silica (ODS) column, the novel stationary phase can show selectivity and good resolution to acidic proteins, which has a promising application in the separation and analyses of acidic proteins from the complex samples in proteomics. In addition, the chromatographic behavior of proteins, the effect of the ligand structure and the retention mechanism on this stationary phase were also investigated.     

Recent development trends for chiral stationary phases based on chitosan derivatives,cyclofructan derivatives and chiral porous materials in high performance liquid chromatography

The separation of enantiomers by chromatographic methods, such as gas chromatography, high‐performance liquid chromatography and capillary electrochromatography, has become an increasingly significant challenge over the past few decades due to the demand of pharmaceutical, agrochemical, and food analysis. Among these chromatographic resolution methods, high‐performance liquid chromatography based on chiral stationary phases has become the most popular and effective method used for the analytical and preparative separation of optically active compounds. This review mainly focuses on the recent development trends for novel chiral stationary phases based on chitosan derivatives, cyclofructan derivatives, and chiral porous materials that include metal‐organic frameworks and covalent organic frameworks in high‐performance liquid chromatography. The enantioseparation performance and chiral recognition mechanisms of these newly developed chiral selectors toward enantiomers are discussed in detail.     

Immobilized metallacarborane as a new type of stationary phase for high performance liquid chromatography

A new type of high performance liquid chromatography (HPLC) stationary phase was prepared, and its chromatographic properties were evaluated. The sorbent was composed of metallacarborane covalently bound to silica. Because of the chemical structure of the immobilized metallacarborane, the synthesized stationary phase was able to interact with nonpolar analytes via hydrophobic interactions. The chromatographic behavior of several low-molecular-weight hydrocarbons on the sorbent under typical reversed-phase conditions was compared with octadecyl-, sulfo phenyl- and aminopropyl-modified silica stationary phases. Moreover, as a consequence of the synthetic protocol employed, the immobilization of the metallacarborane led to the development of a zwitterionic chemically bonded phase, which demonstrated excellent resistance to "phase collapse" in a 100% aqueous environment. Finally, preliminary experiments indicated that the new stationary phase has the potential for utilization in hydrophilic interaction chromatography (HILIC) mode for the separation of polar compounds.     

Lewis碱改性氧化锆基质色谱固定相的研究进展

综述了Lewis碱改性氧化锆(或其复合氧化物)基质高效液相色谱填料的研究进展,涉及的改性剂包括氟离子、磷酸盐、有机膦酸、羧酸、酚类化合物、蛋白质和环糊精衍生物等。简要介绍了Lewis碱改性氧化锆固定相在毛细管电色谱中的应用。 引用文献51篇。     

高效液相色谱技术在代谢组学研究中的应用

高效液相色谱技术逐渐广泛应用于代谢组学的研究中。迄今为止,该技术已经在不同生理状态的生物体液的代谢指纹谱分析中得到了应用。本文评述了传统高效液相色谱技术、毛细管技术和超高效液相色谱等技术在代谢组学的应用。     

A new type of triptycene-based stationary phases with alkylated benzimidazolium cations for gas chromatographic separations

The new type of triptycene-based stationary phases with alkylated benzimidazolium cations shows high selectivity towards aromatic isomers.     

Supercritical ammonia as mobile phase in capillary chromatography

Instrumentation was assembled that allows the use of supercritical ammonia as mobile phase in capillary supercritical fluid chromatography. Several modifications of the typical chromatographic system were necessary, especially with respect to injection and detection. In addition, the stabilities of various polysiloxane stationary phases were studied. The chromatography of polarizable and polar basic materials was demonstrated using a nonpolar polysiloxane stationary phase.