Separation of short-chain branched polyolefins by high-temperature gradient adsorption liquid chromatography

A new separation principle was recently introduced into the analytical characterization of polyolefins by researchers from the German Institute for Polymers in Darmstadt. It was demonstrated that polyolefins can be selectively separated via high-performance liquid chromatography on the basis of their adsorption/desorption behaviours at temperatures as high as 160 °C. A Hypercarb? column packed with porous graphite gave the best results. The mobile phase consisted of a mixture of 1-decanol and 1,2,4-trichlorobenzene. In this work, the same chromatographic system is applied to the separation of ethylene/alkene and ethylene/norbornene copolymers. It was found that the elution volumes of the samples correlate linearly with the average chemical composition of samples. The elution volume is indirectly proportional to the concentration of branches in the ethylene/alkene copolymer. Branching shortens the length of continuous methylene sequences of the polymer backbone, thus decreasing the probability of orientation of a methylene sequence in a flat conformation on the graphite surface, which enables the most intensive van der Waals interactions between the methylene backbone and the carbon surface. An opposite trend in the elution order has been found for ethylene/norbornene copolymers. The elution volume of the ethylene/norbornene copolymers increased with the concentration of norbornene. It indicates pronounced attractive interactions between graphite and the cyclic comonomer.     

Separation of styrene-methacrylate copolymers by composition using normal and reversed-phase high-performance liquid chromatography

The separation of styrene-methacrylate copolymers by chemical composition was studied using high-performance liquid chromatography (HPLC). With the combination of acrylonitrile (polar) gel and nonpolar eluent or of styrene (nonpolar) gel and polar eluent, poly(styrene-co-methylmethacrylate) was separated by the adsorption mechanism. The former is designated as normal and the latter as reversed phase. With other combinations, the copolymer was separated mainly by fractional dissolution mechanism. The sample eluted slightly earlier as molecular weight decreased. The molecular weight effect on the reversed-phase HPLC was smaller than that on the normal phase. A gel with an exclusion limit of 3 × 10³ exhibited greater molecular weight dependence and worse resolution than a gel with an exclusion limit of 50 × 10⁴. Poly(styrene-co-n-butyl methacrylate) also was separated on the basis of chemical composition by normal and reverse-phase HPLC. However, poly(styrene-co-t-butyl methacrylate) was separated only by reverse-phase HPLC. When octadecyl methacrylate gel was used instead of styrene gel in reverse-phase HPLC, a good separation was not obtained. This indicates a specific interaction between the phenyl group of the styrene gel and the sample.     

Separation of iodine species by adsorption chromatography

Based on the different properties of iodide and iodate species in somesorption materials a new chromatographic method was developed to study thespeciation of iodine in a mangrove system. Two sorption materials, aluminaand silica, were investigated and several distribution coefficients for iodideand iodate were determined at different concentrations of NaOH, NaNO₃ and NaHCO₃ solutions. The best separation results wereobtained percolating sea water samples, containing iodine species, througha glass column filled with alumina. The iodide passed through the column afterwashing the column with 0.1M sodium nitrate solution, and the iodate was elutedwith a 0.5M sodium bicarbonate solution.     

Separation of copolymers using high-performance liquid chromatography with polymeric stationary phase and liquefied carbon dioxide as adsorption promoting solvent

Chromatographic separation of copolymers depending on the chemical composition was studied by a solvent gradient method using liquefied carbon dioxide (CO2) as an adsorption promoting solvent. As the high polar stationary phase, non-bonded silica gel, crosslinked acrylamide (AA) gel and crosslinked acrylonitrile (AN) gel were utilized. All columns showed the typical normal phase type of adsorption. Polymeric stationary phases showed the higher sample recovery for styrene-methyl methacrylate (St-MMAs) copolymers, indicating suitability for quantitative analyses. The separations of butyl methacrylate (BMA)-methyl methacrylate, and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (FBMA)-methy methacrylate copolymers were also carried out, and the latter copolymers were separated based on the CO2-philicity with acrylonitrile column.     

Separation of inorganic bromides by adsorption gas chromatography

Gas chromatography has been used to separate the volatile bromides of Zr, Nb, Mo, Te, In, Sn, Sb, Bi, Te and I. SiO(2), NaBr, KBr and CsBr have been used as stationary phases and Br(2)/N(2) and Br(2)/BBr(3)/N(2) as mobile phases. Temperature-programmed as well as isothermal gas chromatographic separations have been carried out.     

Two-dimensional liquid chromatography of diblock copolymers: Simulation at various adsorption interaction conditions

Diblock copolymers, which are heterogeneous in both molar mass and composition, can be fully characterized by using two-dimensional chromatography. Since the size-exclusion, the adsorption, and the critical interaction based modes of chromatography are possible for each of the polymers A and B, this leads to a variety of options for 2D-chromatography of copolymers AB. Using the theory of chromatography of block copolymers, 2D-chromatograms are simulated that correspond to the most interesting of these options. Orthogonal 2D-chromatograms are expected, if in the 1st dimension the critical condition is created for A, while in the 2nd dimension – for B. The situations, where A and B are both adsorbable, as well as those where the conditions of adsorption for A and SEC for B are created, are also considered. In particular, it is shown that the 2nd dimension combination of the critical condition for A and SEC – for B is preferable than that with SEC condition for both A and B. The simulated 2D-chromatograms of low- and high molar mass diblock copolymers, as well as of copolymers with one short block are compared with the reported real ones; it is concluded that the corresponding virtual and real 2D-chromatograms are qualitatively very similar.     

Characterization of copolymers by high performance liquid chromatography

Size exclusion chromatography (SEC) is capable of evaluating the molecular weight distribution (MWD) of a sample. Information about the chemical composition distribution can be gained by gradient high performance liquid chromatography (gradient HPLC), where a poor starting eluent is, in the course of the separation, substituted by another one of increasing elution strength. Both normal-phase and reversed-phase systems can be employed. The combination of SEC and gradient HPLC enables chromatographic cross-fractionation to be performed efficiently.     

Compositional characterization of styrene copolymers by non-exclusion liquid chromatography

Recent advances in high-performance liquid chromatography enable us to separate synthetic copolymers according to composition. Several techniques for non-exclusion liquid chromatography (NELC) for polymers and copolymers are reviewed, focusing on the technique developed in our laboratory. Size exclusion chromatography in combination with NELC makes possible the accurate determination of both molecular weight distribution and chemical composition distribution of copolymers at the same time.     

Separation of carbohydrates by liquid chromatography on silica gel,adding adsorption modificators to the eluent

Summary For the separation of carbohydrates by liquid chromatography, utilizing the intermolecular interaction with amino groups on the surface of the adsorbent, two types of adsorbents were used: silica gel modified by adding to the eluent a diamine, and a chemically bonded phase prepared by the reaction of -aminopropyl triethoxy silane with silica gel. Mono- di- and trisaccharides could be separated on silica gel modified by the adsorption of piperazin and ethylene diamine from the eluent. The separation capacity of columns packed with silica gel with bonded NH₂ groups and with silica gel having diamines adsorbed on its surface is similar. The retention volumes of 15 carbohydrates were measured on columns containing silica gel with hydroxylated surface and on silica gel modified with piperazin from the eluent consisting of acetone-water. Comparison of acetone-water and acetonitrile-water as the eluent showed that the former is also suitable for the analysis of carbohydrates.     

Separation of phenylthiohydantoin-amino acids by highpressure liquid chromatography

A method for the separation of all phenylthiohydantoin (PTH)-amino acids except PTH-arginine and PTH-histidine by high-pressure liquid chromatography on a silica column is described. Elution is performed with a concave solvent gradient from hexane—methanol—propanol (3980:9:11) to methanol—propanol (9:11). A complete run is achieved in 40 rain with a pressure drop of 1000 p.s.i. over the 250 mm × 2.1 mm column. Eluted peaks of 2–5 nmole are easily detected by their ultraviolet absorption at 254 nm. This method is superior to existing gas—liquid and thin-layer chromatographic techniques since all PTH-amino acids except PTH-arginine and PTH-histidine may be both separated and quantitated in a single run of 40 min.

The use of the technique in conjunction with an automated peptide sequence analyser is illustrated.     

Separation of nitroimidazoles by reversed-phase high-pressure liquid chromatography

A mixture of eight N-substituted and unsubstituted nitroimidazoles has been separated by high-pressure liquid chromatography with 5% ethanol as the eluent. Compounds with the same capacity ratios were selectively detected electrochemically by differential pulse polarography with a hanging mercury drop electrode. The HMDE detector had higher detection limits than the photometric detector set at 315 nm.     

Separation of porphyrin isomers by high-performance liquid chromatography

A high-speed reversed-phase high-performance liquid chromatographic method using an octadecylsilyl 3 cm long (3 microns particle size) column to separate the free acids of uroporphyrins I and III and coproporphyrins I and III from each other, and from the type I isomers of several other porphyrin carboxylic acids, is described. Separation of the porphyrins was achieved in less than 8 min, and injections were possible every 12 min. The detection limits of uroporphyrin, coproporphyrin, and mesoporphyrin were 75, 45, and 35 fmol (at a signal-to-noise ratio of 2), respectively. Application of the method to the determination of urinary and liver porphyrin patterns is shown.     

Separation of tetracyclines by high-speed liquid chromatography.

The separation of tetracycline and its four commoninpurities has been studied by high-speed liquid chromatography. A preliminary study of the effectiveness of ion-exchange, adsorption, liquid-liquid partition and reversed-phase ion-pair chromatography indicated that only the last method showed promise. By developing special hydrocarbon-bonded stationary phases a rapid and complete resolution of all five tetracyclines has been obtained within 10 min. Plate heights using a derivatised 18-mum partisil are in the range 0.15-0.3 mm. The method can be used to quantify the impurities in tetracycline at around the 1% level.     

Separation and identification of fullerenes by liquid chromatography

Summary The separation of fullerenes with a monomeric octadecylsilica bonded phase using n-hexane or toluene/methanol mobile phase systems is described. Analytical and preparative separations, incorporating on-line UV/VIS spectral measurements, confirmed the existence of large fullerenes such as C₇₆, C₇₈ and C₈₄. However, isomers of C₇₈ and C₈₄ were not conclusively found.     

Characterization of synthetic copolymers by interaction polymer chromatography: Separation by microstructure

Gradient elution of synthetic polymers has been studied both theoretically and experimentally using normal and reversed-phase HPLC systems. An accurate equation describing the gradient elution of polymer-homologous series in the context of continuous random-flight model of a flexible polymer chain interacting with attractive surface of the porous material has been derived and experimentally verified against a series of narrow polystyrene standards. Both the theory and the experiment predict the existence of molar mass-independent gradient elution at critical point of adsorption (CPA). The extension of the theory to synthetic copolymers predicts the existence of the CPA for statistical copolymers and describes its dependence on chemical composition and microstructure (blockiness) of the polymer chains. One of the important theoretical conclusions is that blockiness always increases the retention, so that blockier polymer chains elute later than their more random counterparts with the same chemical composition. This prediction has been confirmed experimentally using block and statistical styrene-methylmethacrylate copolymers. Block copolymers do not have CPA and always elute between critical points of the corresponding homopolymers. The retention depends on the polymer molar mass and increases with the length of the blocks from a stronger absorbing monomer. These findings provide theoretical and experimental bases for separation of statistical and block copolymers by chemical composition and microstructure of polymer chains.     

Separation of capsaicin from capsaicinoids by macroporous resin adsorption chromatography

The aim of present study is to develop an efficient and low‐cost method for capsaicin production isolated from capsaicinoids by macroporous resin adsorption chromatography. HZ816 resin has shown the best adsorption and desorption capacities for capsaicin among other resins. To optimize the operating parameters for separation, initial concentration, diameter‐to‐height ratio, mobile phase ratio, and crystallization method were investigated. When capsaicinoids solution (5 g/L) was loaded onto the column (diameter‐to‐height ratio = 1:12) with ethanol/1% w/w NaOH (4:6, v/v) as the mobile phase, capsaicin was purified most effectively. By using acid neutralization as the crystallization method, the purity of capsaicin improved from 90.3 to 99.5% with 82.3% yield. In conclusion, this study provides a simple and low‐cost method for the industrial‐scale production of high‐purity capsaicin.