Polymer fractionation using chromatographic column packed with novel regenerated cellulose beads modified with silane

Novel microporous beads with the particle size of about 90 microm were prepared, for the first time, from cellulose and konjac glucomannan (RC/KGM3) in 1.5 M NaOH/0.65 M thiourea aqueous solution by emulsification method. The microporous beads were then modified with silane to avoid the adsorption of polymers containing hydroxyl groups, coded as RC/KGM3-Si. A preparative size-exclusion chromatographic (SEC) column (500 mm x 20 mm) was packed with RC/KGM3-Si, and its exclusion limit and fractionation range of the stationary phase were, respectively, weight-average molecular masses (Mw) of 4.8 x 10(5) g/mol and 5.3 x 10(3)-4.8 x 10(5) g/mol for polystyrene in tetrahydrofuran. The preparative SEC column was used to fractionate poly(epsilon-caprolactone) (PCL, Mw = 8.31 x 10(4) g/mol polydispersity index d= 1.55) in tetrahydrofuran and a polysaccharide PC3-2 (Mw = 1.21 x 10(5) g/mol, d= 1.70) in 0.05 M NaOH aqueous solution, respectively. The Mw values of the fractions determined by analytical SEC combined with laser light scattering were from 1.2 x 10(4) to 1.84 x 10(5) for PCL and from 8.5 x 10(4) to 2.13 x 10(5) for PC3-2, as well as d from 1.2 to 1.5. The results indicated that the preparative SEC has good fractionation efficiency in both organic solvent and alkaline aqueous solution for the various polymers.     

Capillary electrochromatography of peptides on a column packed with tentacular weak cation-exchanger particles

Silica-based, tentacular weak cation-exchanger particles were prepared for use as the stationary phase in the separation of positively charged sample components by capillary electrochromatography (CEC). Silica beads were first silanized with 3-(trimethoxysilyl) propyl methacrylate that served as a heterobifunctional linker, which reacted with 2-acrylarmidoglycolic acid in a second step by radical polymerization in aqueous solution. Baseline separation of basic peptides with good column efficiency was obtained on packed capillary columns by isocratic elution CEC with NaCl as the mobile phase modulator. The retention mechanism in the electrochromatographic process was studied by examining the effect of salt concentration on the migration behavior of the peptides. The chromatographic retention factor k'(lc) for charged sample components in the electrochromatographic process was estimated on the assumption that the overall migration rate of a charged migrant can be taken as the sum of the rate of chromatographic elution and the rate of electrophoretic migration. The estimated k(lc) values from experimental results were plotted against the molal salt concentration on a double logarithmic scale. The linear correlation is in good agreement with the prediction by the theory on the basis of traditional ion-exchange chromatography. The comparison of CEC results, obtained with open tubular and packed capillary columns having the same retentive functions as the stationary phase, supports the notion that variation of the phase ratio in the column offers an additional means to modulate the electrochromatographic migration behavior.     

Ultrahigh-pressure liquid chromatography using a 1-mm id column packed with 1.5-microm porous particles

The evolution of chromatography has led to the reduction in the size of the packing materials used to fabricate HPLC columns. The increase in the backpressure required has led to this technique being referred to as ultrahigh-pressure liquid chromatography (UHPLC) when the column backpressure exceeds 10000 psi (approximately 700 bar). Until recently, columns packed with sub-2-microm materials have generally fitted into two classes; either short (less than 5 cm) columns designed for use on traditional HPLC systems at pressures less than 5000 psi (350 bar), or capillary columns (inner diameters less than 100 microm). By using packing materials with diameters <2 microm to fabricate UHPLC columns, there is an increase in efficiency and a decrease in the analysis time that are directly proportional to the size of the packing material. In order to realize and exploit the increase in efficiency, however, the columns must maintain lengths typically associated with analytical columns (15-25 cm). We have packed 1 mm diameter, 150 mm in length columns with 1.5 microm packing material, and evaluated their performance in UHPLC. The pressure required to achieve optimum linear velocities in plots of plate height versus linear velocity was in the vicinity of 1104 bar (16000 psi). The 1.5 microm particle-packed column was compared with the more traditional 150 mm long analytical columns packed with 3 microm materials. This column showed an efficiency that was approximately twice that observed with the 3 microm packed column and a concomitant reduction in the analysis time, theoretically predicted.     

Fast analysis of isoflavones by high-performance liquid chromatography using a column packed with fused-core particles

The recent development of fused-core technology in HPLC columns is enabling faster and highly efficient separations. This technology was evaluated for the development of an fast analysis method for the most relevant soy isoflavones. A step-by-step strategy was used to optimize temperature (25-50 °C), flow rate (1.2-2.7 mL/min), mobile phase composition and equilibration time (1-5 min). Optimized conditions provided a method for the separation of all isoflavones in less than 5.8 min and total analysis time (sample-to-sample) of 11.5 min. Evaluation of chromatographic performance revealed excellent reproducibility, resolution, selectivity, peak symmetry and low limits of detection and quantification levels. The use of a fused-core column allows highly efficient, sensitive, accurate and reproducible determination of isoflavones with an outstanding sample throughout and resolution. The developed method was validated with different soy samples with a total isoflavone concentration ranging from 1941.53 to 2460.84 μg g⁻¹ with the predominant isoflavones being isoflavone glucosides and malonyl derivatives.     

Preparative high-performance liquid chromatography with reversed phase packed glass columns

An efficient system for preparative reversed-phase separations with packed glass columns is described. The advantage of this system is the use of relatively simple and inexpensive equipment. Column performance, load capacity, effect of the feed volume and the feed concentration on peak broadening are shown. The influence of the selectivity and the capacity factors on column load have been measured. The effect of the column dimensions is demonstrated by means of practical applications. The loading capacity of a column depends on the thermodynamic proporties of the separation system used. It is therefore not expedient in preparative chromatography to correlate the loading capacity of a column by means of grams dissolved per grams of adsorbent.     

End-functionalized polyethylene oxide coated silica particles for packed capillary column supercritical fluid chromatography

Summary Polyethylene oxide (PEO)-based polymers with hydroxy, methoxy, and aminopropoxy terminal groups were coated on diol functionalized and hexamethyldisilazane end-capped silica particles. Proton-donor and proton-acceptor test solutes, including carboxylic acids, hydroxy-containing compounds, arylamines, and alkylamines were used to evaluate the chromatographic performances of these polymer coated particles under SFC conditions with neat CO₂ as mobile phase. It was found that the particles coated with hydroxy-terminated PEO were suitable for the separation of proton-donor compounds such as hydroxy-containing compounds and carboxylic acids, and the particles coated with aminopropoxy-terminated PEO could be used for the separation of amines. That is, the proton-accepting stationary phase is suitable for the separation of proton accepting solutes, including strong basic alkylamines (pK_b4), using neat CO₂ as mobile phase, while the protondonating stationary phase is suitable for the separation of proton-donating compounds such as carboxylic acids (pK_a4). Hydrogen bond basicity was found to be a critical factor for the chromatography of basic amines. Low volatility acidic and basic drugs were chromatographed using the new stationary phases. The stability of the PEO coated particles was determined by measuring the loss of organic carbon under SFC conditions. It was found that approximately 18 % of the coating (average molecular weight of 15,000) was washed out of the particles by supercritical CO₂ after 7 h at 350 atm and 50°C     

Polymethylhydrosiloxane surface deactivation of silica particles for packed capillary column supercritical fluid chromatography

Summary Spherical porous silica particles (10 μm diameter, 300 ? and 80 ? pores), spherical nonporous silica particles (10 μm diameter), and irregular porous silica particles (≈ 10 μm diameter, 80 ? pores) were deactivated with polymethylhydrosiloxane (PS). The surface activities of the deactivated silica particles were investigated using various polar compounds under supercritical fluid chromatography (SFC) conditions (neat CO₂), and compared with a commercial C₁₈-bonded phase. The small pore (80 ?) silica particles could be more completely deactivated than larger pore (300 ?) and nonporous silica particles. The success of the PS deactivation method is ascribed to the excellent match between the reactive groups on the polymer backbone and the silica surface, and the formation of a highly crosslinked polymeric layer over the surface. Physical processes, such as adsorption and desorption of the deactivation reagent on the surface and diffusion from the surface, were found to have important effects on the deactivation. Using capillary columns packed with PS deactivated silica particles, typical polar organic compounds, including hydroxyl-containing compounds, carbonyl-containing compounds, free amines, and free carboxylic acids, were separated by SFC and compared with results from a commercial C₁₈-bonded phase. While the results clearly show that the PS deactivated particles were more inert than the C₁₈-bonded phase, better deactivation methods are still needed for separation of free acids and alkylamines.     

Development of capillary column packed with thiol-modified gold-coated polystyrene particles and its selectivity for aromatic compounds

Three types of thiol compounds (n-octadecanethiol, thiophenol, and 2-phenylethanethiol) were used to modify the gold-coated polystyrene particles (dp. 5microm) to prepare a stationary phase for capillary liquid chromatography through the formation of self-assembled monolayer. The column with n-octadecanethiol-modified gold-coated polystyrene particles (C18-Au) demonstrated the higher affinity to phenanthrene and anthracene than small aromatics compared to the ODS column. In addition, the shape selectivity between phenanthrene and anthracene in the C18-Au column was much higher than that in the ODS column (separation factors: 1.82 and 1.14, respectively). The relationship between the retention factor and acetonitrile content in the mobile phase revealed that the retention behaviors in the C18-Au column was more sensitive on the acetonitrile content than those in the ODS column. Relatively higher affinity for phenanthrene and anthracene was commonly observed in all the three thiol-modified Au columns than that for the conventional ODS column, whereas separations of benzene and nitro- and chlorobenzenes were quite different among the three thiol-modified Au and ODS columns.     

Films prepared from electrosterically stabilized nanocrystalline cellulose

Electrosterically stabilized nanocrystalline cellulose (ENCC) was modified in three ways: (1) the hydroxyl groups on C2 and C3 of glucose repeat units of ENCC were converted to aldehyde groups by periodate oxidation to various extents; (2) the carboxyl groups in the sodium form on ENCC were converted to the acid form by treating them with an acid-type ion-exchange resin; and (3) ENCC was cross-linked in two different ways by employing adipic dihydrazide as a cross-linker and water-soluble 1-ethyl-3-[3-(dimethylaminopropyl)] carbodiimide as a carboxyl-activating agent. Films were prepared from these modified ENCC suspensions by vacuum filtration. The effects of these three modifications on the properties of films were investigated by a variety of techniques, including UV-visible spectroscopy, a tensile test, thermogravimetric analysis (TGA), the water vapor transmission rate (WVTR), and contact angle (CA) studies. On the basis of the results from UV spectra, the transmittance of these films was as high as 87%, which shows them to be highly transparent. The tensile strength of these films was increased with increasing aldehyde content. From TGA and WVTR experiments, cross-linked films showed much higher thermal stability and lower water permeability. Furthermore, although the original cellulose is hydrophilic, these films also exhibited a certain hydrophobic behavior. Films treated by trichloromethylsilane become superhydrophobic. The unique characteristics of these transparent films are very promising for potential applications in flexible packaging and other high-technology products.     

Peroxyoxalate chemiluminescence detection with packed column supercritical fluid chromatography

Summary A detection scheme based upon peroxyoxalate chemiluminescence, which utilizes two post-column pumps and two stages of depressurization is investigated. The chemiluminescent detection limit for perylene is 23 times lower than determined by fluorescence, and is in the attomole range. This detection technique is investigated for packed column supercritical fluid chromatography (SFC). Due to the interface design used and the chemical band narrowing effects of chemiluminescence, an apparent increase in efficiency is observed. The interface design affords a wide range of pressures to be used for a separation. During pressure programming the column effluent changes flow rate. Because of a back-pressure regulator, the reaction and detection take place at nearly constant pressure. Therefore pressure gradient work is possible without concern for post-column reagent solubility (which is a concern for high-performance liquid chromatography). The effects of the expanded CO₂ from the SFC on the chemiluminescence signal and background are studied. The post-column detection is optimized for pH, photomultiplier voltage, concentrations and flow rates of the peroxide and oxalate ester.     

以纤维素/AmimCl溶液制备纤维素气凝胶

利用离子液体AmimCl溶解结合超临界CO2干燥的方法制备了纤维素气凝胶材料.研究了不同初始浓度的纤维素溶液及其在不同凝固浴中制备的纤维素凝胶的流变行为,进一步考察了纤维素溶液浓度和凝固浴种类对纤维素气凝胶材料结构的影响.结果表明,随着初始纤维素溶液浓度的增大,气凝胶的孔结构逐渐致密,比表面积随之减小;凝固浴的组成对纤维素气凝胶的结构也有较大影响.采用适当的制备条件,可以制备出高比表面积的纤维素气凝胶材料.对纤维素气凝胶的热性能进行了表征,结果表明所得到的气凝胶材料具有较好的热稳定性和较高的炭残余含量.     

Adsorption in a stratified column bed packed with porous particles having partially fractal structures and a distribution of particle diameters

Stratified column bed systems whose sections are formed by packing adsorbent particles with a partially fractal structure are proposed and studied. The simulation results clearly show that the breakthrough times and the shape of the breakthrough curves obtained from stratified column beds are significantly larger and sharper than those obtained from conventional columns. The stratified column beds provide, to the designer and user of chromatographic column systems, more degrees of freedom with respect to the number of parameters and variables that could be controlled in the design, construction, and operation of efficient chromatographic adsorption systems. Furthermore, the results suggest that the stratified column beds could provide a higher dynamic adsorptive capacity than conventional columns when it is required to increase the column throughput.     

羟甲基丙烯酰胺交联纤维素高吸水材料及其应用

研究了羧甲基纤维素经N-羟甲基丙烯酰胺交联制取的高吸水材料的产品性能，及交联剂用量对吸附性能的影响．将吸水材料与透析法结合用于蛋白质溶液的脱水浓缩，一般6小时可浓缩2．9～3．7倍，若在中间换过两次吸水剂，则在4小时内可浓缩5．6倍。     

Electrochromatography in microchips packed with conventional reversed-phase silica particles

This paper shows the applicability of a disposable and inexpensive microfluidic chip for electrochromatographic separations. The chip, recently developed by us for chip-based LC, was fabricated from PDMS incorporating conventional chromatographic RP silica particles (C18) without the use of frits. Three cephalosporin antibiotics were used to demonstrate the applicability of the chip-based chromatographic packing for electrochromatographic determinations. The used sample injection method utilizes hydrodynamic pressure, thereby, reducing the propensity for sample bias during the injection.     

分子印迹聚合物填充色谱柱的研究与发展

本文评述了分子印迹聚合物发展历史、制备方法、聚合体系的选择、性能表征及作用机理。主要介绍了其作为色谱固定相方面的应用,并对需解决的问题提出了建议。     

Characteristics of a new HPLC column packed with octadecyl-bonded polymer gel

Summary The chromatographic efficiency and stability of a new octadecyl-bonded polymer (ODP) gel, developed for reversed phase liquid chromatography (RPLC) by substitution of stearate ester groups for the hydroxyl groups of vinyl alcohol copolymer particles, were investigated and compared with those of conventional gels. The efficiency of the column packed with the ODP gel was practically unaffected by repeated alternating passages of distilled water and acetonitrile, apparently because the gel volume was affected similarly by both solvents. Like conventional ODS columns, the ODP column demonstrated a close correlation between log k’ (capacity factor) and carbon atom number in alkyl alcohols in accordance with Martin’s rule and H ∼ 4 dp, thus indicating a high column efficiency for these alcohols. The capacity factor of the ODP column for pyridine with acidic eluent was smaller than that of ODS columns, and the pyridine peak was sharp and symmetrical.     

High resolution liquid chromatography with a packed micro glass capillary column

Single, long columns (1–5 m) can be prepared efficiently using reversed phase packings (3–10 μm particle diameter). 1-m columns packed with 3 and 10 μm packing provide 110 000 and 50 000 theoretical plates, respectively. Very efficient columns can resolve highly complex mixtures and difficult-to-separate compounds. Temperature gradient elution is a powerful technique for LC with microbore columns.     

纤维素燃料乙醇废液与煤的成浆性能研究

提出了一种纤维素燃料乙醇废液大规模资源化利用的新方法—将纤维素燃料乙醇废液与煤共混制备废液煤浆作燃料用。借助旋转黏度计对废液煤浆(WLCS-CEF)进行流变性测定,研究了成浆浓度、废液加入量和添加剂对煤浆流变性的影响。结果表明,废液煤浆的表观黏度随成浆浓度及废液加入量的增加而增大,添加剂的加入明显改善废液煤浆的流变特性。废液中大分子量的木质素及未水解完全的纤维素和半纤维素能起到稳定煤浆的作用,同浓度下的废液煤浆比水煤浆稳定性高,且煤浆稳定性随浓度增大而增强,合适的添加剂也能改善稳定性。当选择添加剂A,成浆浓度为62%,废液添加量为煤量的2.5%时,制得的废液煤浆比较适合气化。