Hyphenation of gas chromatography to microcoil 1H nuclear magnetic resonance spectroscopy

Whereas the hyphenation of gas chromatography (GC) with mass spectrometry is of great importance, little is known about the coupling to nuclear magnetic resonance spectroscopy (NMR). The investigation of this technique is an attractive proposition because of the valuable information given by NMR on molecular structure. The experiments shown here are to our knowledge the first hyphenating capillary GC to microcoil NMR. In contrast to liquids, gases have rarely been investigated by NMR, mainly due to the experimental difficulties in handling gases and the low signal-to-noise-ratio (SNR) of the NMR signal obtained at atmospheric pressure. With advances in NMR sensitivity (higher magnetic fields and solenoidal microprobes), this limitation can be largely overcome. In this paper, we describe the use of a custom-built solenoidal NMR microprobe with an active volume of 2 microL for the NMR detection of several compounds at 400 MHz, first in a mixture, and then with full coupling to capillary GC to identify them separately. The injected amounts of each analyte in the hyphenated experiments are in the range of 15-50 micromol, resulting in reasonable SNR for sample masses of 1-2 microg.     

Modelling of the hydration of tricalcium silicate

A previously developed mathematical procedure is used to illustrate the kinetics and mechanism of cement hydration. By using the experimentally obtained degree of hydration against time curve and the weight percentage particle size distribution (PSD) of a cement, the procedure can isolate an individual cement particle and characterize its different regimes or modes of hydration reaction. Specifically, one can identify an accelerating mode followed by a decelerating mode of reaction, and the changeover period, maxima, from one mode to the other.     

Hexavalent chromium in tricalcium silicate: Part II Effects of CrVI on the hydration of tricalcium silicate

The composition and structure of hydrated tricalcium silicate (C3S) pastes admixed with CrVI have been studied. The resultant mixture simulates CrVI waste forms stabilized in ordinary Portland cement. Scanning electron microscopy and transmission electron microscopy were used to identify the microstructural changes accompanying the addition of CrVI solutions to C3S. Energy-dispersive X-ray spectroscopy was used to probe the distribution of chromium in the phases within the hazardous waste forms. Elucidation of the molecular structure of the reaction products was accomplished with Fourier transform infrared and nuclear magnetic resonance spectroscopies.CrVI was found to be contained in the waste form as soluble Ca2CrO5·3H2O and partially chemically bonded within the calcium silicate hydrate (C–S–H) phase. CrVI was also found to increase the condensation of C–S–H and porosity of the waste form.     

Effect of CaCl2 on the hydration of tricalcium silicate

The hydration of tricalcium silicate has been studied at 30° C in the presence and absence of 2 wt % CaCl₂ with a water∶solid ratio of 0.8. Free lime determinations, X-ray diffraction analysis, thermal analysis, infra-red spectroscopy, scanning electron microscopy and zeta potential measurements were used for hydration studies. The results indicate that the accelerating action of CaCl₂ is due to higher diffusivity of chloride ions.     

Pre-induction and induction hydration of tricalcium silicate: an environmental scanning electron microscopy study

Environmental scanning electron microscopy (ESEM) has been used to study the very early pre-induction, and induction physical processes that occur in the hydration of tricalcium silicate. An in situ experimental technique is described which allows direct, real-time observation of the sub-micrometre morphological changes that take place during this reaction. The results of this investigation are correlated with kinetic data obtained by differential scanning calorimetry (DSC). In this way, microstructural evolution has been identified with the stages of very early hydration. Upon first contact with water, a gelatinous coating was seen to form at grain surfaces and a crystalline secondary product was observed at the end of an extensive dormant period. These findings are viewed in the light of previous wet and dry microscopy studies, and are discussed within the framework of ordinary Portland cement as a possible explanation of induction. Comment is made as to the suitability of environmental SEM for analysis of such materials.     

Characterisation of products of tricalcium silicate hydration in the presence of heavy metals

The hydration of tricalcium silicate (C(3)S) in the presence of heavy metal is very important to cement-based solidification/stabilisation (s/s) of waste. In this work, tricalcium silicate pastes and aqueous suspensions doped with nitrate salts of Zn(2+), Pb(2+), Cu(2+) and Cr(3+) were examined at different ages by X-ray powder diffraction (XRD), thermal analysis (DTA/TG) and (29)Si solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). It was found that heavy metal doping accelerated C(3)S hydration, even though Zn(2+) doping exhibited a severe retardation effect at an early period of time of C(3)S hydration. Heavy metals retarded the precipitation of portlandite due to the reduction of pH resulted from the hydrolysis of heavy metal ions during C(3)S hydration. The contents of portlandite in the control, Cr(3+)-doped, Cu(2+)-doped, Pb(2+)-doped and Zn(2+)-doped C(3)S pastes aged 28 days were 16.7, 5.5, 5.5, 5.5, and <0.7%, respectively. Heavy metals co-precipitated with calcium as double hydroxides such as (Ca(2)Cr(OH)(7).3H(2)O, Ca(2)(OH)(4)4Cu(OH)(2).2H(2)O and CaZn(2)(OH)(6).2H(2)O). These compounds were identified as crystalline phases in heavy metal doping C(3)S suspensions and amorphous phases in heavy metal doping C(3)S pastes. (29)Si NMR data confirmed that heavy metals promoted the polymerisation of C-S-H gel in 1-year-old of C(3)S pastes. The average numbers of Si in C-S-H gel for the Zn(2+)-doped, Cu(2+)-doped, Cr(3+)-doped, control, and Pb(2+)-doped C(3)S pastes were 5.86, 5.11, 3.66, 3.62, and 3.52. And the corresponding Ca/Si ratios were 1.36, 1.41, 1.56, 1.57 and 1.56, respectively. This study also revealed that the presence of heavy metal facilitated the formation of calcium carbonate during C(3)S hydration process in the presence of carbon dioxide.     

29Si MAS NMR study of the hydration of tricalcium silicate in the presence of finely divided silica

²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy has been used to investigate the effect of finely divided silica on the hydration of tricalcium silicate (C₃S). In order to reduce the time needed to obtain quantitative results, low levels of paramagnetic iron oxide were added to materials to increase the nuclear relaxation rate. The reactions of the C₃S and the finely divided silica could then be monitored separately and without chemical modification. The results were correlated with data from microcalorimetry, thermogravimetric analysis and electron microscopy. Under the conditions used here the presence of the silica accelerates greatly the hydration process, and results in a markedly increased degree of polymerization in the resulting gel, without significantly affecting the induction period of the reaction. The significance of these results for understanding the hydration process of C₃S in the presence of silica is outlined.     

核磁共振技术在茶叶生化成分鉴定中的应用

核磁共振(NMR)在化合物结构鉴定中有着无可比拟的优势.文中就NMR技术在茶叶品质成分、有害成分及品质鉴定中的运用状况进行了阐述与分析,指出了NMR在茶叶鉴定中的技术特点及急待攻克的局限性,提出NMR与其他仪器的联用可为茶叶生化成分研究提供更加全面准确的信息.该文对从事茶叶生化组分鉴定及其生理活性机理研究的工作者有一定借鉴作用.     

Solid state spatially resolved 1H and 19F nuclear magnetic resonance spectroscopy of dental materials by stray-field imaging

As part of a program to evaluate the use of stray-field magnetic resonance microimaging (STRAFI) in dental materials research spatially resolved nuclear magnetic resonance (NMR) for solid dental cements has been investigated. By applying a quadrature echo pulse sequence to a specimen positioned in the stray-field of a NMR spectrometer superconducting magnet the magnetic resonance within a thin slice was obtained. The specimen was stepped through the field in 500 m increments to record ¹ and ¹⁹F profiles and T₂ values at each point. The specimens were fully cured cylinders made from four types of restorative material (glass ionomer, resin modified glass ionomer, compomer, composite). The values for F¹⁹T₂ varied with material type and reflected the nature of the matrix structure. For all materials containing ¹⁹F in the glass two values were calculated for ¹⁹F T₂, one short and one long. These were relatively invariant. Solid state magic angle spinning (MAS)-NMR showed that they came from the glass. This suggests that a proportion of the element is relatively mobile (in a glass phase) and the remainder is more tightly bound (in a compound dispersed in the glass). This demonstration, that NMR microimaging of both ¹H and ¹⁹F in solid dental cements is possible, opens up exciting new possibilities for investigating the distribution of these elements (in particular fluorine) in solid dental materials. ©©1999©Kluwer Academic Publishers     

The effect of a retarder on the early stages of the hydration of tricalcium silicate

Cement is used in the oil industry to line oil wells. The major component of oilwell cement is tricalcium silicate (C₃S), which is responsible for the initial thickening of the cement slurry. It is important to control the time that it takes for this slurry to thicken, and this is achieved in practice by the addition of chemical retarders, which delay the onset of thickening. In this paper, the action of a retarder whose main effect is to form a complex with calcium ions is investigated by use of a model for the hydration of C₃S previously investigated by Preece, Billingham and King (2001). It is found that such a retarder can significantly increase the thickening time of pure tricalcium silicate.     

Possible states of chloride in the hydration of tricalcium silicate in the presence of calcium chloride

Calcium chloride may be present in the free, adsorbed or interlayer state in hydrating tricalcium silicate. Attempts have been made to study these states to correlate some of the physical, chemical and mechanical properties.     

Low-temperature fabrication of macroporous scaffolds through foaming and hydration of tricalcium silicate paste and their bioactivity

A low-temperature fabrication method for highly porous bioactive scaffolds was developed. The two-step method involved the foaming of tricalcium silicate cement paste and hydration to form calcium silicate hydrate and calcium hydroxide. Scaffolds with a combination of interconnected macro- and micro-sized pores were fabricated by making use of the decomposition of a hydrogen peroxide (H₂O₂) solution that acted as a foaming agent and through the hydration of tricalcium silicate cement. It was found possible to control the porosity and pore sizes by adjusting the concentration of the H₂O₂ solution. The in vitro bioactivity of the highly porous scaffolds was investigated by immersion in simulated body fluid (SBF) for 7 days. Hydroxyapatite (HAp) was formed on the surface of the scaffolds. Their bioactivity could be expected to be as good as that of tricalcium silicate cement, making the material competent for the bone tissue engineering application.     

17O quantitative nuclear magnetic resonance spectroscopy of gasoline and oxygenated additives

17O Nuclear magnetic resonance (NMR) spectroscopy allows exclusive detection and direct quantification of oxygenates in gasoline unaffected by its hydrocarbon content, using the internal standard quantitative NMR (QNMR) method. Chemical shifts of 24 oxygen-containing compounds as potential additives and contaminants have been measured in gasoline and corrected values of deltaO 18.1 and 3.9 determined for neat methyl tert-butyl ether (MTBE) and neat di-n-butyl ether, respectively. Quantification of ethanol in gasoline can be readily achieved by 17O QNMR with dimethyl sulfone as an internal standard reference material, at the levels currently used in retail gasolines (1-20%). In addition, the simultaneous detection and quantification of the oxygenates methanol, ethanol, 2-propanol, tert-butyl alcohol, and MTBE in gasoline has been established to further demonstrate the specificity of the method. 17O NMR has distinct advantages over 1H and 13C QNMR methods, and although it cannot reliably differentiate 1-propanol, 1-butanol, 1-pentanol, and isopentyl alcohol, 17O NMR does allow the rapid and unambiguous identification of unexpected oxygenates such as acetates and ketones found as contaminants in some retail gasoline.     

Microinhomogeneity of high-alkali aluminosilicate glasses studied by nuclear magnetic resonance spectroscopy

The structure of quenched aluminosilicate glasses with Na₂O/Al₂O₃ > 1 has been studied by high-resolution nuclear magnetic resonance spectroscopy. The aluminum in the structure of the glasses is shown to be in fourfold coordination. Increasing the sodium oxide content of the glasses reduces the degree of polymerization in their structure and leads to a nonuniform nonbridging oxygen distribution over the aluminosilicate glass network. The glasses have a locally microinhomogeneous structure due to the presence of both highly polymerized aluminosilicate anion groups and relatively depolymerized silicate anions.     

Reversed-phase high-performance liquid chromatography combined with on-line UV diode array, FT infrared, and 1H nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry: application to a mixture of nonsteroidal antiinflammatory drugs

A prototype multiply hyphenated system has been applied to the analysis of a mixture of nonsteroidal antiinflammatory drugs separated by reversed-phase HPLC. Characterization of the model NSAIDs was achieved via a combination of diode array UV, 1H NMR, FT-IR spectroscopy, and time-of-flight mass spectrometry. This combination of spectrometers allowed the collection of UV, 1H NMR, IR, and mass spectra together with atomic composition data enabling almost complete structural characterization to be performed.     

Metabolite profiling of human amniotic fluid by hyphenated nuclear magnetic resonance spectroscopy

The metabolic profiling of human amniotic fluid (HAF) is of potential interest for the diagnosis of disorders in the mother or the fetus. In order to build a comprehensive metabolite database for HAF, hyphenated NMR has been used, for the first time, for systematic HAF profiling. Experiments were carried out using reverse-phase (RP) and ion-exchange liquid chromatography (LC), in order to detect less and more polar compounds, respectively. RP-LC conditions achieved good separation of amino acids, some sugars, and xanthines. Subsequent NMR and MS analysis enabled the rapid identification of 30 compounds, including 3-methyl-2-oxovalerate and 4-aminohippurate identified in HAF for the first time, to our knowledge. Under ion-exchange LC conditions, a different set of 30 compounds was detected, including sugars, organic acids, several derivatives of organic acids, and amino acids. In this experiment, five compounds were identified for the first time in HAF: D-xylitol, amino acid derivatives (N-acetylalanine, N-acetylglycine, 2-oxoleucine), and isovalerate. The nonendogenous nature of some metabolites (caffeine, paraxanthine, D-xylitol, sorbitol) is discussed. Hyphenated NMR has allowed the rapid detection of approximately 60 metabolites in HAF, some of which are not detectable by standard NMR due to low abundance (microM) and signal overlap thus enabling an extended metabolite database to be built for HAF.     

Interactions between chemical evolution (hydration) and physical evolution (setting) in the case of tricalcium silicate

This paper describes recent experimental results concerning investigation of the parameters which determine, on the one hand, the kinetics of hydration of tricalcium silicate and the thermodynamic, morphological and structural characteristics of C-S-H and, on the other hand, the evolution of the particle interactions at the origin of setting. It is shown that, in both cases, lime concentration in solution is the most important parameter. As a consequence, the chemical evolution of the system, which controls the lime concentration in solution, determines the nature of particle interactions and the physical evolution of the suspension or paste. In return, the contacts, between particles, resulting from the coagulation of the suspension, seem to have a role in the kinetics of the chemical reaction.     

Protein structure determination in solution by two-dimensional and three-dimensional nuclear magnetic resonance spectroscopy

Over the last decade, nuclear magnetic resonance (NMR) spectroscopy has evolved into a powerful method for determining structures of biological macromolecules. This has opened a unique opportunity for obtaining high-resolution three-dimensional structures in solution, in contrast to the well-established methods of X-ray diffraction, which are applicable only to solids and in particular single crystals. This rapid development has been spurred by several key advances in the field, especially the introduction of two- and three-dimensional NMR experiments, high field spectrometers (500 and 600 MHz), and computational algorithms for converting NMR derived restraints into three-dimensional structures. This review outlines the methodology employed for solving protein structures in solution, describing the basic NMR experiments necessary as well as introducing the concepts upon which the computational algorithms are founded. A variety of examples is discussed, illustrating the present state of the art, and future possibilities are indicated.