Micellar chromatography of inorganic compounds

Micellar chromatography has been used to separate various compounds and to determine the partition coefficients of the compounds between aqueous bulk solution and a micellar pseudophase. The application of this method to inorganic analyses is less common than its application to organic analyses, albeit the former application gives fundamental aspects of the micellar partition of simple ions and promises developments of novel separation. In this review, we focus our attention on the fundamental aspects of micellar chromatography mostly in inorganic analysis of simple ions.     

Separation and purification of isorhamnetin 3-sulphate from Flaveria bidentis (L.) Kuntze by counter-current chromatography comparing two kinds of solvent systems

The first preparative separation of a flavonoid sulphate isorhamnetin 3-sulphate from Flaveria bidentis (L.) Kuntze by counter-current chromatography (CCC) was presented. Two kinds of solvent systems were used. A conventional organic/aqueous solvent system n-butanol-ethyl acetate-water (4:1:5, v/v) was used, yielding isorhamnetin 3-sulphate 2.0 mg with a purity of 93.4% from 83 mg of pre-enriched crude extract obtained from 553 mg ethanol extract by macroporous resin. A one-component organic/salt-containing system composed of n-butanol-0.25% sodium chloride aqueous solution (1:1, v/v) was also used, and the LC column packed with macroporous resin has been employed for desalination of the target compound purified from CCC. As a result, 2.1 mg of isorhamnetin 3-sulphate with a purity of over 97% has been isolated from 402 mg of crude extract without pre-enrichment. Compared with the conventional organic/aqueous system, the one-component organic/salt-containing aqueous system was more suitable for the separation of isorhamnetin 3-sulphate, and purer target compound was obtained from the crude extract without pre-enrichment using the new solvent system. The chemical structure was confirmed by ESI-MS and (1)H, (13)C NMR. In summary, our results indicated that CCC using one-component organic/salt-containing aqueous solution is very promising and powerful for high-throughput purification of isorhamnetin 3-sulphate from Flaveria bidentis (L.) Kuntze.     

Removal of Nitrobenzene,Isophorone, 2,6-Dinitrotoluene and 2,4-Dinitrotoluene from Aqueous Solution by Solvent Sublation

Nitrobenzene, isophorone, 2,6-dinitrotoluene and 2,4-dinitrotoluene were removed from aqueous solution by solvent sublation. The separation efficiencies of three solvents (4-methyl-2-pentanone, 1-octanol and paraffin oil) as the overlaying layer were compared. The rate of separation of these organic pollutants by solvent sublation depends strongly on the size of air bubbles, which is affected by the overlaying solvent, and concentrations of sodium dodecyl sulfate (NDS), inorganic and polar organic solute.     

Simultaneous separation of 17 anions by capillary electrophoresis with the addition of an organic solvent

Seventeen inorganic and organic anions, that normally are insufficiently separated via ion chromatography, were completely separated by the addition of an organic solvent to a solution of BGE combined with an adjustment of the apparent pH via CE in combination with indirect UV absorbance detection. Methanol, ethanol, and acetonitrile were examined for their utility in manipulating the selective separation of anions. Methanol and acetonitrile were better modifiers than ethanol at enhancing the resolution of anions comigrating in an aqueous solution of BGE. Methanol was selected as the modifier that provided the largest separation window that could achieve a complete separation of the target analytes. Via the use of methanol, manipulation of the selectivity between inorganic anions and that between inorganic and organic anions was enhanced, but the separation between organic anions remained difficult when only methanol was used. By varying the apparent pH of the BGE in the presence of 10% v/v methanol, however, the separation selectivity between organic anions was substantially improved. Eventually, 7 inorganic and 10 organic anions were simultaneously separated using BGE at a pH of 6.3 in the presence of 10% v/v methanol.     

Coupled reversed-phase and ion chromatographic system for the simultaneous identification of inorganic and organic explosives

There are many methods available to detect and positively identify either organic or inorganic explosives separately, however no one method has been developed which can detect both types of explosive species simultaneously from a single sample. In this work, a unique coupled-chromatographic system is reported for the simultaneous determination of both organic and inorganic explosive species and is used for pre-blast analysis/identification purposes. This novel approach is based on the combination of reversed-phase high performance liquid chromatography and ion chromatography which allows trace levels of organic and inorganic explosives to be determined simultaneously from a single sample. Using this procedure, a 20 min reversed-phase separation of organic explosives is coupled to a 16 min ion-exchange separation of anions present in inorganic explosives, providing a complete pre-blast analysis/identification system for the separation and detection of a complex mixture containing organic and/or inorganic explosive species. The total analysis time, including sufficient column re-equilibration between runs, was <25 min using the coupled system. By this method, the minimum resolution for the organic separation was 1.16 between nitroglycerin and tetryl and the detection limits ranged from 0.31 mg L(-1) for cyclotetramethylene tetranitramine (HMX) and 1.54 mg L(-1) for pentaerythrite tetranitrate (PETN), while the minimum resolution for the inorganic separation was 0.99 between azide and nitrate, and the detection limits ranged from 7.70 μg L(-1) for fluoride and 159.50 μg L(-1) for benzoate.     

Phase morphology of hydrolysable polyurethanes derived from aqueous dispersions

Biodegradable polyurethanes are an interesting alternative to many applications that involve plastics since they can minimize environmental problems caused by the low rates of natural degradation of synthetic polymers. In addition, since waterborne polyurethanes are based on aqueous dispersions, they restrict the use of organic solvents during processing and application of the polymer, thus contributing furthermore to reduce environmental damage. In this work, aqueous anionic polyurethane dispersions (PUD) with tailorable susceptibility for hydrolysis were synthesized by progressively replacing polypropylene glycol (PPG) with a biodegradable polycaprolactone diol (PCL) as soft segments. The hard segments were formed by extending isophorone diisocyanate (IPDI) with hydrazine (HZ). Dimethylol propionic acid (DMPA) was used as ionic center and triethyl amine (TEA) as neutralizer. The degree of phase separation was evaluated mainly by infrared spectroscopy (FTIR) and small angle X-ray scattering (SAXS). The results indicated that phase separation between hard and soft segments of poly(ester-urethane) is more significant than that of poly(ether-urethane). Data obtained from SAXS experiments indicated that phase separation within soft domains can also be present in samples containing both polyester and polyether soft segments. Hydrolytic degradation of the polymers in buffer solution of pH 7.4 and alkaline solution was performed as an initial test. The results showed that the fraction of polyester soft segments in the polyurethanes can be used to tailor the susceptibility of the materials to hydrolytic attack. Polyurethanes having higher contents of polyester were more promptly hydrolytically degraded than polyurethanes containing only polyether segments.     

磷酸钛离子交换薄层色谱分离无机离子(英文)

The chromatographic behavior of 30 inorganic cations has been studied on thin layers of titanium phosphate ion-exchanger using several aqueous,organic and mixed mobile phases.The separation of one ion from several other ions and also ternary and binary separations have been developed.Some important analytical separations are reported.The effect of pH of the mobile phase on retention factor(Rf)values of the cations in the presence of complex-forming anion along with the separation power of the ion-exchanger were studied.This ion-exchanger exhibits high sorption capacity and varying selectivity towards metal ions and makes it a suitable stationary phase in thin layer chromatography.     

Polymer-controlled, bio-inspired calcium phosphate mineralization from aqueous solution

Nowadays, the majority of the commercially available calcium phosphate materials is fabricated by 'classical' materials science approaches, i.e., from rather poorly defined slurries or from organic solvents, often at high temperatures and pressures. Bioinspired precipitation of inorganics with (polymeric) additives from aqueous solution, on the other hand, enables the synthesis of intriguing inorganic or organic/inorganic materials that are often much more closely related to biological structures. This article discusses approaches for the fabrication of bio-inspired calcium phosphate hybrid materials by precipitation from aqueous solution. The article focuses on polymers and related self-assembling structures for the design of CaP/organic hybrids and pure CaP with crystal structures and morphologies regulated by the respective additive.     

On-line coupling of counter-current chromatography and macroporous resin chromatography for continuous isolation of arctiin from the fruit of Arctium lappa L.

In this work, we have developed a novel hybrid two-dimensional counter-current chromatography and liquid chromatography (2D CCC × LC) system for the continuous purification of arctiin from crude extract of Arctium lappa. The first dimensional CCC column has been designed to fractionalize crude complex extract into pure arctiin effluent using a one-component organic/salt-containing system, and the second dimensional LC column has been packed with macroporous resin for on-line adsorption, desalination and desorption of arctiin which was effluent purified from the first CCC dimension. Thus, the crude arctiin mixture has been purified efficiently and conveniently by on-line CCC × LC in spite of the use of a salt-containing solvent system in CCC separation. As a result, high purity (more than 97%) of arctiin has been isolated by repeated injections both using the ethyl acetate–8% sodium chloride aqueous solution and butanol–1% sodium chloride aqueous solution. By contrast with the traditional CCC processes using multi-component organic/aqueous solvent systems, the present on-line CCC × LC process only used a one-component organic solvent and thus the solvent is easier to recover and regenerate. All of used solvents such as ethyl acetate, n-butanol and NaCl aqueous solution are low toxicity and environment-friendly. Moreover, the lower phase of salt-containing aqueous solution used as mobile phase, only contained minor organic solvent, which will save much organic solvent in continuous separation. In summary, our results indicated that the on-line hybrid 2D CCC × LC system using one-component organic/salt-containing aqueous solution is very promising and powerful tool for high-throughput purification of arctiin from fruits of A. lappa.     

双水相浮选过程中青霉素的分离行为

基于双水相浮选技术(ATPF)分离富集水相中青霉素的方法,研究了双水相浮选过程中青霉素的分离行为.在常温下,2.5 g/L青霉素水溶液300 mL、初始pH 7、(NH4)2SO4浓度350 g/L、浮选溶剂为50%(w/w)PEG1000水溶液10 mL条件下,分别研究了青霉素在双水相浮选过程中的动力学行为和分离后的...     

水溶液中金属增强荧光的研究进展

本文综述了水溶液中金属增强荧光的研究进展,重点阐明如何通过控制荧光物质与金属纳米粒子表面的距离,实现水溶液中的金属增强荧光。荧光物质与金属纳米粒子表面的距离主要通过有机分子和无机分子Si O2层控制,只有当距离合适才能达到最大的金属增强荧光。金属增强荧光提高了荧光检测的灵敏度,扩大了荧光技术的应用范围,已广泛应用到DNA、蛋白质检测、生物标记、生物成像和免疫分析中。     

Carbonyl and carboxylate crosslinked cyclodextrin as a nanocarrier for resveratrol: in silico,in vitro and in vivo evaluation

Recently, much attention has been devoted towards the development of methods for the capture and separation of inorganic gases and organic compounds with high selectivity and efficiency using nanoporous materials. Unlike metal–organic frameworks and covalent organic network polymer, nanoporous molecular crystals (NMCs) do not have extended network structures through coordination or covalent bonding. Instead, they are composed of discrete organic molecules with only weak noncovalent interactions between them. Calixarenes, used as artificial hosts for molecular recognition, constitute a representative class of NMCs that exhibit “porosity without pores.” Despite the absence of empty-channels, calixarene crystals can absorb various inorganic gases and organic compounds, thereby undergoing a guest-induced structural change. Thus, because of their ability to precisely discriminate between molecules of similar sizes and structures, such NMCs show great potential for application as separation materials. This review summarizes reports on the absorption and inclusion of inorganic gases and organic molecules with crystals of calixarenes and their derivatives and discusses their potential as separation materials.     

微量锌的分离与富集

就近年来国内外富集分离微量锌的方法进行了综述，着重介绍常用的萃取法、液膜分离法、浮选分离法、树脂分离法、泡沫塑料富集分离法。     

Molecular Recognition Based on Membrane Potential Changes Induced by Host–Guest Complexation with Inorganic and Organic Guests

Guest-induced changes in membrane potentials are one of the representative modes of electrochemical signal transduction by molecular recognition at the interface of an organic membrane and an aqueous solution. Recent approaches based on synthetic hosts capable of effecting membrane potential changes by host–guest complexation with inorganic and organic guests are described. Although the studies in this area have mainly been aimed at inorganic cations as the target guests, recent approaches for recognition of inorganic anions and further organic guests are also documented. Highly selective changes in membrane potentials can be achieved for inorganic cations by sophisticated design of crown ethers and related compounds. Hosts with complementary charge(s) or multiple hydrogen bonding sites are effective for the recognition of inorganic anions and also of the polar moieties of organic ions. On the other hand, the recognition of nonpolar moieties of organic guests can be achieved by inclusion into well-defined cavities of host molecules. Quaternary onium and protonated amine salts are recently found to be capable of effecting membrane potential changes by complexation with neutral phenolic guests.     

Novel imidazolium stationary phase for high-performance liquid chromatography

A new imidazolium anion-exchange phase immobilized on silica is synthesized. HPLC separations of common inorganic anions (IO3-, Cl-, NO2-, Br-, NO3-, I-, SCN-) have been performed using a HPLC column (200 mm x 4.6 mm I.D.) packed with this stationary phase, with a phosphate buffer solution as the mobile phase and UV detection at 200 nm. The effects of pH and concentration of eluent on the separation of anions have been studied. Chromatographic parameters are calculated and the results show that the new stationary phase is of significant potential for the analysis of these anions. Successful separations of some ordinary organic anions have also been achieved with the said stationary phase. Meaningfully, organic and inorganic anions can be determined simultaneously and satisfactorily with several neutral compounds using the column. The separation of some organic compounds including hydroxybenzenes, bases and amines by this stationary phase with only water as the eluent has been investigated.     

Influence of organic solvents in the mobile phase on the determination of carboxylic acids and inorganic anions in grape juice by ion chromatography

Investigations have been initiated to develop a sufficiently good separation of both major and minor organic acids and inorganic anions present in grape musts using a Dionex As11 column, a sodium hydroxide gradient elution and a suppressed conductivity detection. Separation was complicated in aqueous mobile phase by co-elutions and selectivity was optimized using organic modifiers that alter ion-exchange selectivity for hydrophobic ions. In this study, the influence of three different solvents (methanol, ethanol and acetonitrile) on the efficiency of column was compared. The best separation of all ions in a synthetic solution was achieved with an eluent containing 13% (v/v) methanol and 13% (v/v) ethanol in water, the run during only 20 min. This method was next applied to grape juices with success and has shown sensitivity and reproducibility. Moreover, sample preparation was a simple 20-fold dilution with 0.45 microm filtration and direct injection without prior sample clean-up.     

FT-IR and 2D-IR spectroscopic studies on the effect of ions on the phase separation behavior of PVME aqueous solution.

Thermosensitive phase transition behavior of poly(vinyl methyl ether) (PVME) in an aqueous solution and the effect of inorganic ions on the coil-globule transition have been investigated by Fourier transform infrared (FT-IR) spectroscopy with attenuated total reflection (ATR) accessory. ATR-IR spectra of PVME aqueous solution indicate that in water-PVME-inorganic salts system, the phase separation temperature of PVME aqueous solution decreased with the increase of ion concentration and the increase of anion electronegativity. Meanwhile, two-dimensional infrared (2D-IR) measurements have been made to clarify the microcosmic conformational changes of PVME during the coil-globule transition. Results show that the conformation changes of main chains occur earlier than those of ether groups during heating. Furthermore, the 2D correlation spectroscopy of PVME aqueous solution during heating and the increase of concentration of potassium chloride have been studied. The features of 2D-IR spectra during heating did not change compared to the features of PVME aqueous solution during the increase of concentration of potassium chloride. This result implies that, although the addition of inorganic ions shifts the phase separation temperature, it does not alter the internal mechanism of the coil-globule transition of PVME.     

Organic and inorganic selenium speciation in environmental and biological samples by nanometer-sized materials packed dual-column separation/preconcentration on-line coupled with ICP-MS

A novel, fast, and cheap nonchromatographic method for direct speciation of dissolved inorganic and organic selenium species in environmental and biological samples was developed by flow injection (FI) dual-column preconcentration/separation on-line coupled with ICP-MS determination. In the developed technique, the first column packed with nanometer-sized Al(2)O(3) could selectively adsorb the inorganic selenium [Se(IV), Se(VI)], and the retained inorganic selenium could be eluted by 0.2 mol l(-1) NaOH, while the organic Se [selenocystine (SeCys(2)) and selenomethionine (Se-Met)] was not retained. On the other hand, the second column packed with mesoporous TiO(2) chemically modified by dimercaptosuccinic acid (DMSA) could selectively adsorb Se(IV) and SeCys(2) and barely adsorb Se(VI) and Se-Met. When the sample solution was passed through the column 1, separation of inorganic selenium and organic selenium could be achieved first. Then, the effluent from column 1 was successively introduced into the column 2 and the speciation of organic selenium could be attained due to the different adsorption behaviors of Se-Met and SeCys(2) on DMSA modified TiO(2). After that, the eluent from column 1 contained Se(IV), and Se(VI) was adjusted to desired pH and injected into column 2, and the speciation of Se(IV) and Se(VI) could also be realized thanks to their different retention on column 2. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. The detection limits obtained for Se(IV), Se(VI), Se-Met and SeCys(2) were 45-210 ng l(-1) with precisions of 3.6-9.7%. The proposed method has been successfully applied for the speciation of dissolved inorganic and organic selenium in environmental and biological samples. In order to validate the methodology, the developed method was also applied to the speciation of selenium in certified reference material of SELM-1 yeast, and the determined values were in good agreement with the certified values.     

Comparison of liquid chromatographic behaviors on N-methylimidazolium functionalized ZrO(2)/SiO(2)-4 and N-methylimidazolium functionalized SiO(2) stationary phases

A new stationary phase N-methylimidazolium functionalized ZrO(2)/SiO(2)-4 (Zr/SilprMim) has been prepared. The chromatographic property of this stationary phase is investigated by ion chromatography (IC) with inorganic and organic anions, and normal phase HPLC with basic compounds and hydroxybenzenes. The effects of pH and the strength of Lewis base of eluent on separation of anions are studied. This new stationary phase is also compared with a N-methylimidazolium functionalized SiO(2) stationary phase (SilprMim). The results show that this new stationary phase can be used in analysis of inorganic anions with great prospects. At the same time, successful separations of some organic anions can be obtained by using phosphate buffer solution as mobile phase. This new stationary phase also has a distinct advantage in the separation of basic compounds in normal phase. But due to the presence of Lewis acid sites on the surface of ZrO(2)/SiO(2)-4, Lewis bases such as hydroxybenzenes adsorb very strongly on this new stationary phase, and Lewis acid sites can be masked or modified by the eluent that contain Lewis base groups.