Macromolecular dimensions and mechanical properties of monolayer films of Sonorean mesquite gum

Mesquite gum sourced from Prosopis velutina trees and gum arabic (Acacia spp.) were characterized using light scattering and Langmuir isotherms. Both gum materials were fractionated by hydrophobic interaction chromatography, yielding four fractions for both gums: FI, FIIa, FIIb and FIII in mesquite gum and FI, FII, FIIIa and FIIIb in gum arabic. In mesquite gum, the obtained fractions had different protein content (7.18-38.60 wt.-%) and macromolecular dimensions (M approximately 3.89 x 10(5)-8.06 x 10(5) g.mol(-1), RG approximately 48.83-71.11 nm, RH approximately 9.61-24.06 nm) and architecture given by the structure factor (RG/RH ratio approximately 2.96-5.27). The mechanical properties of Langmuir monolayers at the air-water interface were very different on each gum and their fractions. For mesquite gum, the most active species at the interface were those comprised in Fractions IIa and IIb and III, while Fraction I the pi/A isotherm lied below that of the whole gum. In gum arabic only Fraction III developed greater surface pressure at the same surface per milligram of material than whole gum. This is rationalized in terms of structural differences in both materials. Mesquite gum tertiary structure seems to fit best with an elongated polydisperse macrocoil in agreement with the "twisted hairy rope" proposal for arabinogalactan proteoglycans.     

Identification and semi-quantitative determination of gum Arabic in wines by GC-MS and size exclusion chromatography

A method for the identification and the semi-quantitative determination of the food additive gum Arabic in wines is described. Tests carried out on solutions spiked with known amounts of wine and gum Arabic polysaccharides allowed to define the suitable conditions for their quantitative precipitation and size exclusion analysis. CG-MS analyses of the different recovered fractions allowed to discriminate between gum Arabic and wine polysaccharides through the identification of glucose and mannose present only in wine polysaccharides. The proposed method was based on the wine polysaccharides free peak area obtained by size exclusion chromatography. The same cut-off time was always used both in the preparation of the calibration plot and in the analysis of the real samples. Gum Arabic was determined in a ratio of 1/10 w/w with wine polysaccharides with a detection limit of 0.074 mg ml(-1) which is lower than the lowest gum Arabic amount usually added into wines. Owing to the moderately low natural variability of the gum Arabic standards the described procedure is suitable for a semi-quantitative analysis even if its accuracy allowed a quite reliable determination of the gum Arabic amount usually added to wine.     

RHEOLOGICAL PROPERTIES AND APPLICATIONS OF MESQUITE TREE (PROSOPIS JULIFLORA) GUM. 5. THE RHEOLOGICAL PROPERTIES AND STABILITY OF CORN OIL -IN-WATER EMULSIONS STABILISED BY BLENDS OF MESQUITE GUM AND TWEEN 60.

Corn oil-in-water emulsions were prepared using mesquite gum and Tween 60 in conjunction as emulsifier-stabilisers. The mesquite gum/ Tween 60 ratio influenced the viscoelasticity and stability of the emulsions. The viscoelasticity parameters decreased in magnitude, and the rate of drop coalescence increased, as the mesquite gum/Tween 60 ratio decreased. In addition, this ratio influenced the pattern of change in the viscoelasticity parameters when the emulsions were aged. Mixed films of mesquite gum and Tween 60 adsorbed at a flat corn oil-water interface exhibited viscoelasticity, the parameter magnitudes decreasing as the mesquite gum/ Tween 60 ratio decreased. The influence of the mesquite gum/Tween 60 ratio on both the emulsions and model interfacial films is attributed to the relative proportions of the two emulsifier-stabilisers adsorbed at the oil-water interface, their configuration in the adsorbed state and their ability to interlink to form a network.     

文物中多糖类胶结材料的热裂解-气相色谱/质谱识别

热裂解-气相色谱/质谱(Py-GC/MS)技术能够实现微量样品中有机组分的准确、快速检测,非常适用于文物中各类天然有机材料的定性分析。该研究以中国古代书画、建筑、器物等文化遗产中常用的淀粉、桃胶,以及西方文化遗产中常用的阿拉伯胶等多糖类胶结材料为研究对象,系统分析并总结各类材料的Py-GC/MS特征裂解组分及辨别方法。研究发现,淀粉、桃胶、阿拉伯胶在色谱保留时间前段的裂解产物基本一致,主要是小分子呋喃、酮类组分;在保留时间中段3类材料的裂解产物主要是呋喃型酮等组分,但不同材料的具体裂解组分差异明显;在保留时间后段,3类材料检出多种单糖衍生物以及单糖低聚体衍生物,其中桃胶与阿拉伯胶裂解组分较为接近,但与淀粉完全不同。因此,可根据不同保留时间段淀粉、桃胶、阿拉伯胶裂解产物的差异实现3类材料的辨别,其中1,6-脱水-β-D-吡喃葡萄糖只在淀粉中检出且色谱峰强度高,可以作为识别淀粉的特征组分;此外,可根据桃胶、阿拉伯胶在保留时间后段的裂解产物主要质谱碎片离子m/z 60、m/z 101的提取离子流图分布特征实现其辨别。基于所建立的Py-GC/MS方法,研究推断故宫旧藏清代剔红云龙纹天球瓶瓶口部位黏结材料含有面粉,旻宁御笔并蒂含芳贴落画心纸所用黏结材料为面粉糨糊。该研究所建立方法及所总结的数据易于推广,适用于我国文物中多糖类材料的准确、快速识别,研究结果能为相关文物材质工艺的研究以及保护修复方案的制定提供科学依据。     

Use of high-performance exclusion chromatography for analysis of the molecular mass of polysaccharides produced from buckwheat and sunflower wastes

High-performance exclusion chromatography was used to study polysaccharide samples obtained by successive extraction with water, ammonium oxalate, and alkali from waste produced in buckwheat and sunflower processing. The molecular-mass distribution of fractions (protein-polysaccharide complex, polysaccharides, and low-molecular-weight compounds) was analyzed in relation to sources of carbohydrates and methods of their production.     

Molecular weight determination of hyaluronic acid by gel filtration chromatography coupled to matrix-assisted laser desorption ionization mass spectrometry.

An analytical approach has been described for the molecular weight characterization of enzymatically degraded hyaluronic acid (HA). The approach involved the combined use of aqueous gel filtration chromatography (GFC) with matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). Microfractions were collected across an eluting peak from the chromatography system, followed by mass spectrometric analysis of these narrow fractions. The molecular mass determined by MALDI-MS and the signal obtained from the chromatography established a calibration curve for other hyaluronic acid samples analyzed by this GFC system. Results of one HA sample were obtained from both the calibration curve and direct fraction-by-fraction MALDI-MS analysis, and comparison of these results showed reasonable agreement. In contrast, molecular weights resulted from external calibration using dextran and pullullan standards showed drastically different numbers. Therefore, the GFC-MALDI-MS approach is a reliable method for the molecular weight characterization of polydisperse polysaccharides for which suitable calibration standards are unavailable for conventional GFC analysis.     

Application of pyrolysis-gas chromatography/mass spectrometry to study changes in the organic matter of macro- and microaggregates of a Mediterranean soil upon heating

The heating effect on the soil organic matter (SOM) of a Mediterranean soil was studied in two fractions (macro- and microaggregates) and in two environments (soil under canopy of Quercus coccifera and bare soil between plants). Samples were heated under laboratory conditions at different temperatures (220, 380 and 500°C) to establish their effects on the SOM quality and quantity by comparison with unheated control samples (25°C). The SOM content in the soil under canopy was higher than in the bare one and in the microaggregate fractions than in the macroaggregate ones. Increasing temperatures caused, in general, the decrease of SOM content in both soils as well as in both aggregate classes. The quality of SOM was determined after extraction with 0.1 M NaOH and analysed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Obtained pyrolysates were characterized by the presence of polyphenols and other aromatic pyrolysis products (lipids, polysaccharides, proteins and lignin derivatives). Some of the products in these control samples, and furthermore the presence of black carbon (BC) markers (e.g. benzene, pyridine and toluene), confirmed the occurrence of past wildfires in the study zone. The composition of the SOM extracted from the soils heated at 220°C, was quite similar to that obtained from unheated soils. The products derived from polysaccharides and lignin, and some coming from polyphenols, were not detected in the pyrolysates of the soil heated at 380 and 500°C.     

野菊花中性多糖CIP-C的分离纯化及结构解析

以野菊花为原材料, 经热水提取、乙醇沉淀、DEAE-Sepharose Fast Flow和Sephacryl S-200 凝胶柱层析分离纯化, 得到1个水溶性的中性多糖CIP-C. 采用GC-MS、部分酸水解及甲基化分析等对该多糖的结构进行了解析. 结果表明, 该多糖主要由D-Man, D-Glc和D-Gal组成, 并含有少量的D-Fuc, L-Ara和D-Xyl, 其主链由β(或α)-D-1,4-Man, β-D-1,6-Glc和β-D-1,4-Gal组成, 而阿拉伯糖通过α-L-T-Araf和α-L-1,5-Araf连接形成阿拉伯聚糖支链或与β-D-1,4-Galp的O3位相连形成阿拉伯半乳聚糖支链.     

RHEOLOGICAL PROPERTIES AND APPLICATIONS OF MESQUITE TREE (PROSOPIS JULIFLORA) GUM. 3. THE INFLUENCE OF MESQUITE GUM OH THE INTERFACIAL TENSION BETWEEN OIL AND WATER

The influence of mesquite gum on the interfacial tension between liquid paraffin and distilled water has been studied as a function of gum concentration, pH, and added NaCl or CaCl₂. The time dependence of the reduction in interfacial tension was influenced by all three variables. Diffusion to the oil-water interface was the dominant factor in the initial decrease of interfacial tension when low mesquite gum concentrations were used. Reconformation of molecules adsorbed at the oil-water interface controlled the reduction in interfacial tension at longer times when using more concentrated gum solutions.     

Quantification of major grape polysaccharides (Tempranillo v.) released by maceration enzymes during the fermentation process

The influence of commercial enzymes on wine polysaccharide content was studied. Tempranillo wines were made using commercial maceration enzyme preparations along with controls. The analytical method for the quantification of wine polysaccharides was carried out by a multistep procedure. Wine-soluble polysaccharides were isolated by wine concentration polysaccharides precipitation with an acid-alcohol medium and separation of each polysaccharide family by high resolution size-exclusion chromatography on a Superdex-75 HR column. The glycosyl-residue compositions of the fractions obtained were determined by gas chromatography with flame ionisation and mass spectrometry of their trimethylsilyl-ester O-methyl glycosides after acidic methanolysis and derivatization. The content of each fraction was estimated from the concentration of individual glycosyl residues that are characteristic of well-defined wine polysaccharides. The analytical method proposed had good sensitivity, repeatability, reproducibility and accuracy. Soluble polysaccharides in wine were essentially composed of grape cell wall polysaccharides: arabinogalactans and arabinogalactan-proteins (38-41%), and rhamnogalacturonans-II (38-46%). Yeast mannans and mannoproteins were also present but in smaller proportions (14-19%). Wines treated with commercial enzymes had larger concentrations of arabinogalactans, arabinogalactan-proteins and rhamnogalacturonans-II than control wines, but the content of mannans and mannoproteins was similar in both wines. This indicated that the commercial enzymes hydrolysed grape pectic polysaccharides during the maceration-fermentation stage but had no influence on yeast parietal polysaccharides.     

Two-dimensional liquid chromatography of PDMS-PS block copolymers

In this study, liquid chromatography at critical conditions of polystyrene (PS) and polydimethylsiloxane (PDMS) is used as the first dimension for the two-dimensional analysis of polydimethylsiloxane-block-polystyrene copolymers. Comprehensive two-dimensional liquid chromatography with size exclusion chromatography as the second dimension reveals information about the molar mass distributions of all separated fractions from the first dimension. Furthermore, fractions eluting at the critical conditions were collected and subjected to analysis in the second dimension at the critical adsorption point of the other block. These fractions were analyzed by Fourier transform infrared spectroscopy to determine their chemical compositions. The combination of the above approaches and the calibration of the evaporative light scattering detector for the first-dimension analysis yield deep insights into the molecular heterogeneity of the block copolymer samples. The composition of the samples and the chemical composition of the real block copolymer are also calculated by combining the results obtained at both critical conditions.     

The measurement of mass and size distributions,conformation, and branching of important food polymers by mals following sample fractionation

Three distinctive food polymers (ultra high molar mass amylopectin, guar gum, and hemi-cellulose) were chosen as model samples to illustrate the use of multi angle light scattering (MALS) detection in conjunction with size exclusion chromatography (SEC) separations for the characterization of such macromolecules. By combining SEC and MALS, absolute molar mass, rms radius and their distributions can be measured readily without reference to any molar mass standards and without the need to make structural assumptions. In addition, the conformation and branching of those polymers can be derived also.     

Off-line combination of reversed-phase liquid chromatography and laser desorption/ionization time-of-flight mass spectrometry with seamless post-source decay fragment ion analysis for characterization of square-planar nickel(II) complexes

Characterization of square-planar nickel(II) complexes of the Schiff base of (S)-N-benzylproline (2-benzoylphenyl)amide and various amino acids that are used as efficient alpha-amino acids synthons was carried out using laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) in off-line combination with liquid chromatography. A mixture of four square-planar nickel(II) complexes was separated using reversed-phase liquid chromatography (RPLC) and the separated fractions from the chromatographic run were spotted on the metal target directly from the column outlet using a lab-made sample deposition device. The separated fractions were then analyzed by LDI-TOF MS. Seamless postsource decay (sPSD) fragment ion analysis was used for their structural characterization, which made possible the confirmation of expected chemical structures of the analyzed compounds. The off-line combination of the separation by RPLC and analysis by LDI-TOF MS allowed successful separation, sensitive detection and structure elucidation of the square-planar nickel(II) complexes.     

Molecular Weight and Aggregation of Erwinia Gum in Aqueous Solutions

Erwinia(E) gum is composed of glucose, fucose, galactose and glucuronic acid. The weight-average molecular weights Mw, number-average molecular weights Mn and intrinsic viscosities[η] of the four fractions and the unfractionated E gum in aqueous solutions at desired temperatures were studied by light scattering, membrane osmometry, size exclusion chromatography(SEC) and viscometry. The experimental results prove that E gum formed aggregates in the aqueous solution at 25 ℃ and the aggregates were broken gradually with increasing temperature. The dissociation of the aggregates of E gum in the aqueous solution started at 36 ℃, and was completed at around 90 ℃. The [η] values of E gum and its fractions are much higher than those of the conventional polymers with the similar molecular weights, and decrease with increasing NaCl concentration.     

UPLC‐ESI‐MS study of the oxidation markers released from tannin depolymerization: toward a better characterization of the tannin evolution over food and beverage processing

Condensed tannins take an important part in the sensory quality of food and beverage. Sensory analyses are usually carried out with various tannin fractions isolated from food or beverage, and their interpretation are limited by the lack of knowledge in the fine and accurate molecular composition of the tannin fractions. Besides, the studies of the chemical reactivity conducted in model solutions with ‘simple’ flavanols allow a better understanding of their evolution pathways, but they cannot take into account their reactivity as polymers, specifically regarding oxidation. In particular, competition between intramolecular and intermolecular reactions may strongly impact on the tannin structures (size, branching and conformation) and consequently on their properties. An ultra‐performance liquid chromatography‐mass spectrometry electrospray ionization mass spectrometer analytical method was thus developed in order to identify oxidized tannins generated by autoxidation. Given the difficulties to separate and detect tannins with high DP, samples were depolymerized by chemical depolymerization prior to analysis. Since the linkages created by oxidation are not cleavable in the usual depolymerization conditions (contrarily to the original interflavanic linkages), specific oxidation residues are released from tannins structures after their autoxidation. Oxidation markers of both intermolecular and intramolecular mechanisms have been identified; these are mainly dimers and trimers, more or less oxidized, and some contain additional hydroxyl groups. Furthermore, the nature of the subunits (extension vs terminal) making up these dimers and trimers was clearly established. Copyright © 2012 John Wiley & Sons, Ltd.     

Pyrolysis/gas chromatography/mass spectrometry of asphaltene fractions

Two n-heptane-precipitated asphaltene samples, characterized by elemental analysis and nuclear magnetic resonance spectrometry, were fractionated according to relative molecular size by gel permeation chromatography (GPC). Both the whole asphaltene samples and their fractions were analysed by pyrolysis/gas chromatography/mass spectrometry. The data obtained from the pyrograms (average side-chain length, aromaticity index, sulphur compounds vs. aliphatic compounds, presence of SO₂ and CO₂) demonstrated that, in the case of asphaltenes, GPC fractionation results in the separation of different chemical structures ranging from lower molecular mass, highly aromatic and polar compounds to higher molecular mass, less polar and aromatic compounds.     

Molar mass distributions by gradient liquid chromatography: predicting and tailoring selectivity

Interactive liquid chromatography (iLC) for polymer analysis is usually applied to the characterisation of distributions other than molar mass. In particular, its use for the determination of chemical-composition, functionality-type and tacticity distributions has been demonstrated. The application of iLC for the determination of molar mass distributions (MMDs), however, has not yet been fully explored. An expanded version of the reversed-phase liquid chromatography model has been developed to describe and predict how the retention behaviour of polydisperse polystyrene samples changes with molar mass. The relationship between molar mass and the parameters of the model has been investigated in some detail and non-linear correlations were found. From the model and the relationships between the model parameters and molar mass, calibration curves (retention time versus molar mass) were constructed to predict changes in chromatographic selectivity across a given molar mass range. These calibration curves were compared to experimentally obtained curves and, in most cases, excellent agreement was found. The dramatic enhancement in selectivity that can be obtained with iLC in comparison to size-exclusion chromatography (SEC) was illustrated by measuring matrix-assisted laser desorption ionisation (MALDI) MS spectra of fractions collected during a gradient-LC separation. In the low-molar mass range, essentially monodisperse fractions were obtained. Calibration curves, predicted by the model and validated experimentally using narrow-dispersity standards and MALDI-MS spectra of fractions, were used to determine the molar mass distribution of some narrowly distributed polystyrene samples. Molar mass distributions for such standards were found to be somewhat lower than the values reported by the manufacturers. The results also deviated from those obtained by MALDI-MS.     

Planar chromatographic separation of petroleum residues and coal-derived liquids

Vacuum distillation residues from two petroleum crudes, a coal liquefaction extract and a coal tar pitch have been fractionated by planar chromatography (PC) using two solvent sequences: pyridine–acetonitrile and tetrahydrofuran (THF)–toluene. Fractions recovered from PC were examined by UV-fluorescence spectroscopy (UV-F), size-exclusion chromatography (SEC). UV-F and SEC of the whole samples showed differences in aromatic cluster size and molecular mass (MM) ranges which could be related to the different origins of the samples. The MM ranges indicated by SEC were greater for the vacuum residues than for coal-derived materials. However, the UV-F spectra of the fractions indicated that the petroleum residue fractions contained similar aromatic types, whereas the fractions from coal liquids contained significantly different aromatic types. SEC profiles of the fractions indicated a separation of coal-derived samples by increasing molecular size with increasing immobility in PC, whereas for petroleum fractions, the same trend was not apparent. MALDI-mass spectra of the set of original samples showed broadly similar ranges of MM distributions but additional work is necessary to identify appropriate matrices and procedures in order to improve the MALDI spectra.     

Pyrolysis-gas chromatography/mass spectrometry of a coal extract and its fractions separated by planar chromatography: correlation of structural features with molecular mass

The structural characterisation of a coal liquefaction extract and its three fractions separated by planar chromatography has been described. Size exclusion chromatography showed the molecular mass distributions to become progressively larger with decreasing mobility on the plate. UV-fluorescence spectroscopy of the fractions indicated parallel increases in the sizes of polynuclear aromatic ring systems. Analysis by probe-mass spectrometry of the 'whole' coal extract showed the expected array of small polynuclear aromatic groups extending to m/z 450. The probe mass spectra of the lightest fraction ('mobile in pyridine and acetonitrile') showed similar features, except for effects due to vacuum drying to remove solvent. In sharp contrast, the two heaviest fractions ('mobile in pyridine and immobile in acetonitrile' and 'immobile in pyridine') showed no significant ions other than those from residual NMP solvent (m/z 98 and 99). Pyrolysis-gas chromatography/mass spectrometry of these two heaviest fractions showed only traces of aromatic compounds or fragments. The aromatic pyrolysis products of these fractions were too large and involatile to pass through the GC column. The major components observed in the pyrolysis-gas chromatography/mass spectrometry of the two heavy fractions were alkanes and alkenes, ranging between C10-C25. Since none of the samples contained free alkanes, alkenes or cycloalkanes before pyrolysis, they were generated during the pyrolysis step. The shifts of UV-fluorescence spectral intensity to shorter wavelengths with decreasing size indicated by size exclusion chromatography (SEC) provide direct evidence of differences in structure with changing molecular mass. This evidence strongly suggests that species identified as being of large molecular mass in this extract sample are not composed of molecular aggregates. It remains difficult to establish whether and when it would be legitimate to invoke molecular aggregates to explain the large molecular masses (MMs) identified here and in other work. Copyright 2000 John Wiley & Sons, Ltd.     

碱溶性茶多糖的提取及其分析

在煎煮后的低档绿茶茶渣中提取碱溶性茶多糖,经HPGPC-ELSD法分析其含有3种均一性多糖组分,依出峰顺序其质量分数约为5.96%、78.99%和15.05%;GC-MS法测得组成碱溶性茶多糖的6种单糖:鼠李糖、阿拉伯糖、木糖、甘露糖、葡萄糖和半乳糖,并分析了其摩尔比例.紫外-可见吸收光谱分析显示,碱溶性茶多糖在250～290 nm区段有"波浪状"吸收.红外光谱表征了碱溶性茶多糖的特征,圆二色谱分析了其水溶液的cotton效应.结果表明,在190 nm有正cotton效应,在203 nm有负cotton效应.