ELISE NMR: experimental liquid sealing of NMR samples

We present a simple, generally applicable approach to prevent sample evaporation when working at elevated temperatures in high resolution NMR. It consists of experimentally sealing the NMR sample by a second liquid (Experimental Liquid Sealing, ELISE). For aqueous samples, we identified the mineral oil commonly used in PCR application as the best candidate, because it contains only a very limited amount of water-soluble contaminants, is stable over time and heat resistant. The procedure does not interfere with shim settings, and is compatible with a wide variety of samples, including oligosaccharides and proteins. For chloroform samples, a simple drop of water allows to efficiently seal the sample, avoiding solvent evaporation even over lengthy time periods.     

Quantitative NMR monitoring of liquid ingress into repellent heterogeneous layered fabrics

Fabrics which are water repellent and repellent to other liquids are often constructed using multiple layers of material. Such a construction is preferable to a single layer of a liquid-repellent textile because, under the action of an applied pressure, ingress of a liquid through the first layer can be halted by the second or subsequent layers. In the quantitative investigation of this problem, current techniques provide limited information on the progress and distribution of the liquid as it ingresses into a fabric. Moreover, many techniques require that the material is delaminated prior to analysis, and cannot be conducted in real time to measure the progress of a liquid through the textile substrate. In this work we demonstrate that unilateral NMR, which allows signal to be collected from a volume of interest in a material residing above the instrument, can be a powerful tool to quantitatively monitor the ingress of a liquid through a layered sample exhibiting pronounced heterogeneities in repellency. A known volume of oil was placed on the top of a model textile sample composed of three 80 microm thick layers. Spatially resolved one dimensional vertical NMR profiles of the system were acquired as a function of the pressure vertically applied to the top of the sample. These profiles show that the absolute liquid volume present in each layer of textile can routinely be measured within 4 min with a spatial resolution of 15 microm. If each individual layer exhibits different repellency to the test liquid, the complexity of the dynamics of the ingress can be investigated in great detail. An elegant application of the unilateral instrument was obtained in which the sensitive volume matched the region of interest of the individual layers of the textile under investigation.     

Reducing the NMR sample volume using a single organic liquid: Increased sensitivity for mass-limited samples with standard NMR probes

A simple inexpensive protocol for confining an aqueous sample to the active region of a standard NMR probe is examined for high-resolution NMR. The aqueous sample is sandwiched between an inert perfluorinated organic liquid that has been exploited in the design of micro-coil NMR probes. The procedure is demonstrated with 3 mm NMR tubes at ambient and elevated temperatures but should be equally applicable to smaller diameter tubes. It is shown that confinement has minimal effects on line shape and provides at least a two fold increase in sensitivity over a conventional sample, for the same mass of solute.     

Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

Construction and performance of an NMR tube with a sample cavity formed within magnetic susceptibility-matched glass

We describe the construction and performance of an NMR tube with a magnetic susceptibility matched sample cavity that confines the solution within the detection zone in the axial direction and in a quasi-rectangular region in the radial direction. The slot-like sample cavity provides both good sample volume efficiency and tolerance to sensitivity loss in the sample space. The signal-to-noise ratio per unit volume of the constructed tube was 2.2 times higher than that of a cylindrical tube of 5mm outer diameter with a sample containing 300 mM NaCl at a static magnetic field of 14.1T. Even the overall signal-to-noise ratio of the slot tube was 35% higher than that of the conventional 5mm tube for a sample containing 300 mM NaCl. Similar improvements over existing sample tube geometries were obtained at 950 MHz. Moreover the temperature rise resulting from RF heating was found to be significantly lower for the slot tube even when compared to 3 and 4mm outer diameter cylindrical tubes as measured in a 5mm cryoprobe. A further advantage of this type of tube is that a sample cavity of any desired size and shape can be formed within a cylindrical tube for use in a single cryogenic probe.     

High resolution nuclear magnetic resonance spectroscopy in liquids and gases at pressures up to 2500 bar: I. High pressure NMR spectrometer and experimental technique

This article is the first in a series of four papers, which deal with the effect of hydrostatic pressure on the high resolution proton magnetic resonance spectra of methane, ethylene, methanol and ethanol. The present paper describes the spectrometer in which high resolution spectra can be recorded at pressures up to 2500 bar. The most essential part of the spectrometer is a beryllium copper high pressure vessel in which the sample can be rotated under pressure. The positions of the spectral lines are referred to an external reference of benzene, contained in a sealed glass capillary. Frequency modulation of the transmitter is used in the measurement of the line positions. The paper describes how the apparatus can also be used for the measurement of the density dependence of the diamagnetic volume susceptibility.     

Optimal electric fields for different sample shapes in high resolution NMR spectroscopy

For many applications, reducing sample resistance, rather than increasing probe Q or filling factor, is the only way to further improve the signal-to-noise ratio of cryogenically cooled NMR probes. In this paper, bounds are calculated for the minimum sample resistance that can be achieved for various sample geometries. The sample resistance of 100 mM NaCl in H(2)O in 5 mm sample tubes was measured on a 600 MHz cold probe to be within 14% of the optimum value. The minimum sample resistance can however be lowered by altering the tube cross section. Rectangular tubes oriented with the long axis along the RF magnetic field are particularly favourable.     

Precision and sensitivity optimization of quantitative measurements in solid state NMR

This work presents a methodology for optimizing the precision, accuracy and sensitivity of quantitative solid state NMR measurements based on the external reference method. It is shown that the sample must be exclusively located within and completely span the coil region where the NMR response is directly proportional to the sample amount. We describe two methods to determine this "quantitative" coil volume, based on whether the probe is equipped or not with a gradient coil. In addition, to improve the sensitivity and the accuracy, an optimum rotor packing design is described, which allows the sample volume of the rotor to be matched to the quantitative coil volume. Experiments conducted on adamantane and NaCl, which are representative of a soft and hard material, respectively, show that one order of magnitude increase in experimental precision can be achieved with this methodology. Interestingly, the precision can be further improved by using the ERETIC method in order to compensate for most instrumental instabilities.     

Multibore sample cell increases EPR sensitivity for aqueous samples

We have performed calculations, verified by experiment, to explain why the sensitivity of biological EPR can be dramatically increased by dividing the aqueous sample into separate compartments. In biological EPR, the major factor affecting sensitivity is the number of spins in the sample. For an aqueous sample at ambient temperature, this is limited by the requirement for a small volume, due to strong non-resonant absorption of microwaves by water. However, recent empirical studies have shown that this volume limitation can be greatly relieved by dividing the aqueous sample into separate volumes, which allows much more aqueous sample to be loaded into a resonant cavity without significant degradation of the cavity quality factor. Calculations, based on the Bruggeman mixing rule, show quantitatively that the composite aqueous sample has a permittivity much less than that of bulk water, depending on the aqueous volume fraction f. Analysis for X-band EPR spectroscopy shows that the optimal volume fraction of an aqueous composite sample, producing maximum sensitivity, is f=0.15, increasing the sensitivity by a factor of 8.7, compared with an aqueous sample in a single tube.     

Diffusion and spatially resolved NMR in Berea and Venezuelan oil reservoir rocks.

Conventional and spatially resolved proton NMR and relaxation measurements are used in order to study the molecular motions and the equilibrium and nonequilibrium diffusion of oils in Berea sandstone and Venezuelan reservoir rocks. In the water-saturated Berea a single line with T*2 congruent to 150 microseconds is observed, while the relaxation recovery is multiexponential. In an oil reservoir rock (Ful 13) a single narrow line is present while a distribution of relaxation rates is evidenced from the recovery plots. On the contrary, in the Ful 7 sample (extracted at a deeper depth in a different zone) two NMR components are present, with 3.5 and 30 KHz linewidths, and the recovery plot exhibits biexponential law. No echo signal could be reconstructed in the oil reservoir rocks. These findings can be related to the effects in the micropores, where motions at very low frequency can occur in a thin layer. From a comparison of the diffusion constant in water-saturated Berea, D congruent to 5*10(-6) cm2/sec, with the ones in model systems, the average size of the pores is estimated around 40 A. The density profiles at the equilibrium show uniform distribution of oils or of water, and the relaxation rates appear independent from the selected slice. The nonequilibrium diffusion was studied as a function of time in a Berea cylinder with z axis along H0, starting from a thin layer of oil at the base, and detecting the spin density profiles d(z,t) with slice-selection techniques. Simultaneously, the values of T1's were measured locally, and the distribution of the relaxation rates was observed to be present in any slice.(ABSTRACT TRUNCATED AT 250 WORDS)     

Design, construction, and validation of a 1-mm triple-resonance high-temperature-superconducting probe for NMR

We report a 600-MHz 1-mm triple-resonance high-temperature-superconducting (HTS) probe for nuclear magnetic resonance spectroscopy. The probe has a real sample volume of about 7.5 microl, an active volume of 6.3 microl, and appears to have the highest mass sensitivity at any field strength. The probe is constructed with four sets of HTS coils that are tuned to 1H, 2H, 13C, and 15N, and there is a z-axis gradient. The coils are cooled with a conventional Bruker CryoPlatform to about 20 K, and the sample chamber can be regulated above or below room temperature over a moderate range using a Bruker variable temperature unit. The absolute S/N for 0.1% ethylbenzene is approximately 1/3 that of a conventional 5mm probe with just 1/70 of the sample volume. We demonstrate the utility of this probe for small molecules and proteins with 2D spectra of just 1.7 microg of ibuprofen and 400 microM 15N-labeled ubiquitin.     

Experimental method for low-temperature reaction studies in sealed samples by 13C CP/MAS NMR

A new, simple, and inexpensive technique is presented for monitoring high-resolution solid-state NMR of ¹³C at temperatures ranging between 85 and 450 K. In this procedure, the reaction conditions are controlled by preparing samples at 77 K in 5 mm NMR tubes, while attached to a vacuum system. The NMR tubes are prefitted with a rotor for spinning. After preparation, the samples are sealed, transferred to the double-resonance MAS NMR probe, and analyzed, all while the sample temperature is maintained as low as 85 K. The spinning rates vary from 3.0 kHz at 85 K to 5.2 kHz at 300 K using nitrogen drive gas. Probe design and performance, sample-preparation procedure, and details of the low-temperature experiment are described. In general, the technique may be applied in studies of low-temperature reaction mechanisms and kinetics. ¹³C CP/MAS spectra of ethylene adsorbed on silica-supported ruthenium catalyst are presented to illustrate its performance and possible application.     

地塞米松棕榈酸酯的NMR数据解析

参考地塞米松在D₂O中检测的的¹H、¹⁹F NMR数据、棕榈酸的¹H、¹³C NMR标准图谱数据和Lindeman-Adams经验公式,对地塞米松棕榈酸酯进行了¹H和¹³C MNR检测,通过DEPT和¹H-¹H COSY、HMQC、HMBC等2D NMR技术对该化合物所有的¹H和¹³C NMR信号进行了全归属和详细解析.     

Susceptibility corrections in solid state NMR experiments with oriented membrane samples. Part II: theory

In solid state NMR analysis of oriented biomembranes the samples typically have the shape of a rectangular block, formed by stacking a number of glass slides coated with the membranes under investigation. Reference material may be provided internally in the volume of the block or as an external layer on its surface, as described in the accompanying paper [J. Magn. Reson. 164 (2003) 104-114]. The demagnetizing field resulting in such non-spheroidal samples is inhomogeneous. It shifts and broadens the NMR lines of both the sample and of the reference, as compared to the ideal of a spherical sample. The magnitude of these effects is typically of the order of a few ppm. To determine the necessary corrections, a general analysis is presented here for the demagnetizing field of a layered sample of rectangular block geometry, with the normal of the layers parallel to the main field or tilted about an axis of the block. The correction to the line position of the block sample is found to be approximately equal to that of the spheroid which can be inscribed into the block, and for which the correction is well known. For an external reference layer, placed on top of the block, the correction can be found by the same approximation, invoking a simple mirror concept. The layered structure of the block can be accounted for by using an average magnetic susceptibility. Sample and support materials contribute to that average according to their volume filling factors. If the sample material is anisotropic at the molecular level, as e.g. lipid bilayers are, the resulting anisotropy of the block is reduced by the filling factor of the sample material.     

4.5 GPa静水压活塞圆筒式高压装置的压力检测分析及压力校正

 本文提供了提高现有活塞圆筒式高压装置流体静压强的一种实验方法。成功地制作了锰铜丝压力计，并利用铋丝相变准确地做了压力校正。各箍的应力检测分析和相对位移测量都表明：无论压腔空载或充液时，在0.000 1~3.08 GPa均不显示出同步箍紧作用；上下缸的压强差偏大带来高压暴露的危险。为把流体静压强提高到3.08 GPa以上，建议改进设计；（1）内箍中箍合二为一，外箍分为上下二层，将增加箍力；（2）调整各箍之间接触圆锥面的面积，将有助于同步箍紧；（3）增大密封套圈的无支承面，将减少上下缸压差，有利于安全运行。     

One micrometer resolution NMR microscopy

We obtained a magnetic resonance image of 1 microm resolution and 75 microm(3) voxel volume for a phantom filled with hydrocarbon oil within an hour at 14.1 T. For this work, a specially designed probe with a high sensitivity RF coil and gradient coils generating over 1000 G/cm was built. The optimal pulse sequence was analyzed in consideration of the bandwidth, diffusion coefficients, and T(1) and T(2) relaxations of the medium. The system was applied to the in vivo imaging of a geranium leaf stem to get the images of 2 microm resolution and 200 microm(3) voxel volume.     

In situ fluid typing and quantification with 1D and 2D NMR logging

In situ nuclear magnetic resonance (NMR) fluid typing has recently gained momentum due to data acquisition and inversion algorithm enhancement of NMR logging tools. T(2) distributions derived from NMR logging contain information on bulk fluids and pore size distributions. However, the accuracy of fluid typing is greatly overshadowed by the overlap between T(2) peaks arising from different fluids with similar apparent T(2) relaxation times. Nevertheless, the shapes of T(2) distributions from different fluid components are often different and can be predetermined. Inversion with predetermined T(2) distributions allows us to perform fluid component decomposition to yield individual fluid volume ratios. Another effective method for in situ fluid typing is two-dimensional (2D) NMR logging, which results in proton population distribution as a function of T(2) relaxation time and fluid diffusion coefficient (or T(1) relaxation time). Since diffusion coefficients (or T(1) relaxation time) for different fluid components can be very different, it is relatively easy to separate oil (especially heavy oil) from water signal in a 2D NMR map and to perform accurate fluid typing. Combining NMR logging with resistivity and/or neutron/density logs provides a third method for in situ fluid typing. We shall describe these techniques with field examples.     

荧光光谱智能监测水中矿物油浓度的研究

为便于环保部门实时准确监测水体油污染情况,研制了一套基于紫外荧光和物联网技术在线监测水中矿物油浓度的系统。该系统采用非对称Czemy-Turner光路的高精度单色器,提高了分辨率;光路增加了一束参考光,用于修正光源波动对探测结果的影响;光路增添光纤传输激发光和荧光,减小系统因仪器振动造成的光路偏差;探头采用特殊设计光纤束,大幅提高光纤耦合效率和信号输出;系统集成了控制模块和无线通讯模块,实现系统的实时测量、数据处理和远程控制。该系统集成度高、探测精度高、稳定性好。利用化学计量学方法中的平行因子算法和化学校正分析理论,降低矿物油不同成分差异带来的计算误差,精确计算出未知样品的浓度。使用该系统测定了柴油、机油、原油三种样品溶液在10,25,50和100 mg·L-1的荧光光谱。用光栅光谱仪测得这三种油的最佳吸收波长分别为256,365和397 nm;用荧光分光光度计测量了上述三种油的吸光度分别为0.028,0.036和0.041;它们的最佳发射波长分别为355,419和457 nm。利用该装置测得柴油、机油和原油的检出限分别为0.03,0.04和0.06 mg·L-1,相对误差分别为2.1%,1.0%和2.8%。     

NMR properties of petroleum reservoir fluids

NMR well logging of petroleum reservoir require the measurement of the NMR response of water, oil, and gas in the pore space of rocks at elevated temperatures and pressures. The viscosity of the oil may range from less than 1 cp to greater than 10,000 cp. Also, the oil and gas are not a single component but rather a broad distribution of components. The log mean T1 and T2 relaxation time of dead (gas free) crude oils are correlated with viscosity/temperature and Larmor frequency. The relaxation time of live oils deviate from the correlation for dead crude oils. This deviation can be correlated with the methane content of the oil. Natural gas in the reservoir has components other than methane. Mixing rules are developed to accommodate components such as ethane, propane, carbon dioxide, and nitrogen. Interpretation of NMR logs uses both relaxation and diffusion to distinguish the different fluids present in the formation. Crude oils have a broad spectrum of components but the relaxation time distribution and diffusion coefficient distribution are correlated. This correlation is used to distinguish crude oil from the response of water in the pores of the rock. This correlation can also be used to estimate viscosity of the crude oil.     

Application of nmr spectroscopy to determine the thermodynamic characteristics of water bound to OX-50 nanosilica

We have used low-temperature 1H NMR spectroscopy to determine the thermodynamic characteristics of water bound to OX-50 nanosilica (SBET ≈ 50 m2/g) in different media: aqueous, air, chloroform medium, and gaseous methane. We demonstrate the difference between the hydration parameters of silica OX-50 on going from an aqueous suspension to a hydrated powder. We present the water cluster size distributions in the studied systems, calculated from the Gibbs–Thomson equation. We found that the average water cluster size in suspension is considerably larger than the cluster sizes in hydrated powders.