The use of sample rotation for minimizing convection effects in self-diffusion NMR measurements.

Undesirable temperature gradients in a NMR sample tube are usually generated by an inappropriate temperature regulation system. We have shown that such convection effects can greatly distort the measurement of translational self-diffusion coefficients. The use of sample spinning helps to minimize such undesirable effects by disruption of convection fluxes due to resulting Coriolis forces that have a strongly stabilizing effect on the conducting state of the system (J. Lounila et al., J. Magn. Reson. A 118, 50 (1996)). This simple trick allows the accurate measurement of diffusion coefficients for a wide range of temperatures and solvents without the need for a convection-compensated NMR pulse sequences or more sophisticated temperature control units. Experimental data obtained for some target compounds dissolved in several common deuterated solvents at different temperatures are reported and discussed.     

Convection-compensating PGSE experiment incorporating excitation-sculpting water suppression (CONVEX)

We present a new diffusion experiment which provides simultaneous suppression of an on-resonance solvent peak and compensation for convection. The experiment, which we name CONVEX, exploits similarities between two functionally different pulse sequences to enable the same sequence to be used simultaneously for two different purposes. The CONVEX pulse sequence combines a double-echo PGSE with double excitation-sculpting water suppression, using unequal gradient pulse-pair amplitudes (g1 and g2) and unequal diffusion intervals (Delta1 and Delta2). Convection compensation is achieved by setting g1:g2 = Delta2:Delta1. The new experiment provides the spectral quality, flat baseline, and water-suppression power characteristic of excitation-sculpting experiments, combined with excellent compensation for convection. The resulting Stejskal-Tanner plots are linear over a greater range of signal attenuation than in the absence of water suppression. Possible applications include protein NMR; NMR of cellular or colloidal systems; and the monitoring of technological processes.     

Solvent-localized NMR spectroscopy using the distant dipolar field: a method for NMR separations with a single gradient

Solvent-localized NMR (SOLO) is a new method which allows the separation of NMR spectra of substances dissolved in different solvents. It uses the selective HOMOGENIZED pulse sequence to produce a two-dimensional NMR spectrum resulting from intermolecular zero-quantum coherences in one distinct solvent. The detected signal is locally refocused by the action of the distant dipolar field, which is created by a frequency selective pulse only in regions containing the selected solvent. The prerequisites are that the different solvents have sufficiently different chemical shifts to be excited separately and that compartments with different solvents are spatially separated by more than the typical diffusion distance. Here, the method is demonstrated for the solvents water and DMSO on a length scale of 0.5 mm. Because signal in the spectra is refocused locally, SOLO is insensitive to variations in the magnetic field which may result from inhomogeneities or structures in the sample. This makes applications in strongly structured samples possible. SOLO is the first method that achieves localization of NMR signal with a single gradient pulse. Therefore, it can be used in conventional NMR spectrometers with one-axis gradient systems and lends itself to a wide range of applications including in vivo NMR.     

基于WATERGATE的双溶剂峰抑制方法

WATERGATE（W3/W5）是NMR实验中使用较为广泛的溶剂峰抑制方法,但该方法通常仅能对一个溶剂信号进行有效抑制. 本文对WATERGATE的脉冲序列进行修饰、优化,发展了两种新的双溶剂峰抑制方法. 实验结果表明,经过修饰、优化后的WATERGATE,实验的设立非常简单,不需要复杂的优化过程就能够对双（多）溶剂峰进行有效抑制, 可用于常规1D & 2D NMR 实验、HPLC NMR实验,以及天然产物粗提取物的分析中.     

Assessment of diffusion coefficients of general solvents by PFG-NMR: investigation of the sources error

Accurate measurements of the diffusion coefficients, including an estimate of uncertainty, of various solvent molecules using the PFG-NMR method were performed in this study. Accurate diffusion coefficients were obtained using the Shigemi NMR tube. The relative combined standard uncertainties of the diffusion coefficients were found to be within approximately 0.4%. The three uncertainty sources (signal decay of the standard and the solvent, and diffusion coefficient of standard) equally affect the combined standard uncertainties. Unreliable data were obtained using a normal NMR tube, indicating that convection and background gradient effects significantly affected the accurate measurement of the diffusion coefficients.     

The Solvent Effect on Spin Exchange in Long-Chain Nitroxide Biradicals

Intramolecular electron spin exchange, as a function of temperature and the solvent viscosity, polarity and relaxation properties of the solvent molecules, has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two long-chain flexible nitroxide biradicals existing in fluid solutions in three spectroscopically different spatial conformations. Certain thermodynamic parameters of the conformational rearrangements were calculated from the EPR spectra. Spin exchange in two biradicals dissolved in five different alcohols was compared with that in a nonpolar solvent (toluene), polar protic (water) and aprotic (acetonitrile), and with thermodynamic characteristics of the solvents. Distinct correlations were found between macroscopic (solvent viscosity, polarity) and microscopic (solvent longitudinal relaxation time) characteristics of solvents, and thermodynamic parameters of the intramolecular conformational transitions. Authors' address: Van Anh Tran, Institute of Physical and Theoretical Chemistry, Graz University of Technology, Technikerstrasse 4, 8010 Graz, Austria     

Glycerol and glycerol carbonate as ultraviscous solvents for mixture analysis by NMR

NMR of weakly polar analytes in an apolar ultraviscous solvent has recently been proposed for mixture analysis as a pertinent alternative to the DOSY experiment. The present article reports the first use of glycerol and glycerol carbonate as polar solvents for the NMR analysis of a model mixture of dipeptides. This work demonstrates the high potentiality of these solvents for the analysis of mixtures made of polar and potentially bioactive compounds. Medium-sized molecules slowly reorient in glycerol and glycerol carbonate under particular temperature conditions, so that solute resonances may show spin diffusion in NOESY spectra, thus opening the way to mixture analysis. Glycerol and glycerol carbonate have turned out to be ultraviscous solvents of choice for the individualization of four structurally close mixed dipeptides: Leu-Val, Leu-Tyr, Gly-Tyr and Ala-Tyr by means of 1D and 2D NOESY experiments. Selective sample excitation and signal detection were implemented to eliminate the intense proton signals of the non-deuterated solvents. Moreover, the recording of a multiplet selective 2D NOESY-TOCSY has shown that the analytical power of NMR in highly viscous solvents is not limited to the extraction of mixture component 1D subspectra but may also yield some supplementary information about atom connectivity within components.     

Convection-compensating diffusion experiments with phase-sensitive double-quantum filtering

We present a design scheme for phase-sensitive, convection-compensating diffusion experiments with gradient-selected homonuclear double-quantum filtering. The scheme consists of three blocks: a 1/2J evolution period during which antiphase single-quantum coherences are created; a period of double-quantum evolution; and another 1/2J period, during which antiphase single-quantum coherences are converted back into an in-phase state. A single coherence transfer pathway is selected using an asymmetric set of gradient pulses, and both diffusion sensitization and convection compensation are built into the gradient coherence transfer pathway selection. Double-quantum filtering can be used either for solvent suppression or spectral editing, and we demonstrate examples of both applications. The new experiment performs well in the absence of a field-frequency lock and does not require magnitude Fourier transformation. The proposed scheme may offer advantages in diffusion measurements of spectrally crowded systems, particularly small molecules solubilized in colloidal solutions or bound to macromolecules.     

Diffusion-broadened velocity spectra of convection in variable-temperature BP-LED experiments

When NMR diffusion experiments are performed at temperatures different from ambient temperature, temperature gradients due to probe design can cause thermal convection and therefore significantly affect the signal amplitude. Fourier transformation of the signal amplitude gives rise to a diffusion-broadened velocity spectrum, which contains information about the convection velocity. It is shown that when the diffusion broadening factor is smaller than the maximum velocity, the broadening has little effect on the determination of the maximum velocity. Thus, convection velocity can be determined in the presence of diffusion.     

Selective detection of the proton NMR spectra of molecules containing rare spins at natural abundance in liquid crystalline samples

It is shown that the proton NMR spectra of molecules containing rare spins at natural abundance dissolved in a liquid crystalline solvent can be obtained free from the strong lines from the spectrum of the abundant isotopomer by the 2D HSQC NMR experiment. The technique can also give the individual chemical shifts of the rare spins, and, for a molecule containing another abundant nucleus, such as fluorine, the rare spin--(19)F total anisotropic couplings are also obtained. The usefulness of the technique is demonstrated for molecules containing (13)C as the rare spins.     

Measurement of Convection and Temperature Profiles in Liquid Samples

This paper describes a method for measuring the rate of convective flow in a liquid sample used for high-resolution NMR. The measurement is straightforward and achieves a clean separation of convection from other effects such as diffusion and relaxation. Convection results from temperature gradients within the sample, and it is shown how these can be measured with the aid of a simple chemical shift imaging experiment of a sample whose spectrum shows a strong and well characterized temperature dependence. The use of these two methods is illustrated by showing how the rate of convection and the temperature profile depend on the solvent, temperature, and gas flow rate of the temperature regulating system. It is also shown that broadband (13)C decoupling results in significant temperature gradients and associated convection.     

量子分子动力学模拟液体钚的输运性质

采用第一原理分子动力学（QMD）方法模拟液体钚的输运性质.计算的粘性和扩散系数在较低温度时与文献有明显差异,在实验测量范围内,模拟结果与实验一致,温度升高时数值模拟结果趋于一致.利用QMD的模拟结果计算了应力自相关函数和速度自相关函数,结果表明：在温度较低时,液体钚呈现明显的强关联特性.对于具有强关联特性的液体,利用较短时间的QMD模拟结果,通过简单e指数拟合外推到t→∞得到的扩散系数和粘性具有较大偏差,这是造成本文模拟结果与文献结果出现差异的主要原因.通过增加QMD模拟时间步数,获得了更为准确的输运性质.     

Viscosity Effect Study on Quenching of Photoinduced Excited Triplet Duroquinone by TEMPO

ABSTRACT

Quenching dynamics of excited quinone molecules are given much attention in photochemistry and biochemistry. In order to study the viscosity effect on the quenching of triplet excited state of duroquinone (³DQ?) by stable radical, 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO), this study measured chemically induced dynamic electron polarization (CIDEP) spectra and transient absorptive spectra in various solvents. The solvents used were ethylene glycol, 1,2-propanol and their mixtures with different ratio in volume. The Stern-Volmer plot was obtained form CIDEP spectra of photolysis of DQ with different TEMPO concentrations. Combining the slope of the Stern-Volmer plot with lifetime of ³DQ?, determined from the ³DQ? transient absorbance decay curve, the quenching rate constants of ³DQ? by TEMPO were calculated in each solvent. The results indicate that the quenching rate constant is viscosity-dependent, and that it decreases linearly with the increase in solvent viscosity in the range used in our experiment.     

PGSTE-WATERGATE: an STE-based PGSE NMR sequence with excellent solvent suppression

A new stimulated-echo based pulsed gradient spin-echo NMR diffusion sequence incorporating WATERGATE solvent suppression, PGSTE-WATERGATE, is presented. The sequence provides superb solvent suppression without any phase distortions. The sequence is simple to set up and particularly suited to measuring diffusion coefficients in aqueous solution such as is commonly required in pharmaceutical and combinatorial applications. The utility of the sequence is demonstrated on samples containing lysozyme and sucrose. Importantly, the high degree of phase-distortion suppression allows more complicated selective pi pulses to be used to enhance the selectivity of solvent suppression.     

Molecular oxygen spin-lattice relaxation in solutions measured by proton magnetic relaxation dispersion

Proton spin-lattice relaxation rate constants have been measured as a function of magnetic field strength for water, water-glycerol solution, cyclohexane, methanol, benzene, acetone, acetonitrile, and dimethyl sulfoxide. The magnetic relaxation dispersion is well approximated by a Lorentzian shape. The origin of the relaxation dispersion is identified with the paramagnetic contribution from molecular oxygen. In the small molecule cases studied here, the effective correlation time for the electron-nuclear coupling may include contributions from both translational diffusion and the electron T(1). The electron T(1) for molecular oxygen dissolved in several solvents was found to be approximately 7.5 ps and nearly independent of solvent or viscosity.     

Determination of sample temperature and temperature stability with 129Xe NMR

The (129)Xe chemical shift of xenon dissolved in isotropic liquids is very sensitive to solvent density, which in turn is dependent on the sample temperature. Therefore, the (129)Xe chemical shift can be used as the basis of a thermometer for measuring actual sample temperatures in NMR experiments. Good accuracy can be achieved, but the thermometer is particularly useful in monitoring temperature stability. In the present case, carbon tetrachloride (CCl(4)), ethylbromide (C(2)H(5)Br), and deuterated chloroform (CDCl(3)) were chosen as solvents because of their large thermal expansion coefficient.     

Influence of solvent basicity on DMABN photophysics

¹H‐NMR resonance measurements of 4‐(dimethylamino)benzonitrile (DMABN), dissolved in dichloromethane at temperatures over the range 300–195 K, confirm that the electronic charge transfer from its dimethylamino group to its cyano group increases with increasing dipolarity of the solvent and hence that the twisted internal charge transfer form of DMABN can be directly created by excitation of its electronic ground state. However, in tetrahydrofuran and 1,4‐dioxane, the DMABN molecules form complexes with the solvent, hindering charge transfer and reducing the electron‐releasing capability of the dimethylamino group. Irradiating a dilute solution of DMABN with an intensity as low as 7.8 × 10¹³ photons/s causes the formation of 4‐(methylamino)benzonitrile as photoproduct. The emission spectra of DMABN exhibit an isoemission point at a wavelength that is shifted with an increase in solvent dipolarity. The high efficiency with which the photoproduct is obtained seems to depend on the basicity of the solvent and challenges some former photophysical conclusions not considering this fact and drawn by using stronger irradiation sources, as well as the potential use of DMABN‐like compounds as solvent viscosity probes. Copyright © 2016 John Wiley & Sons, Ltd.     

Theoretical analysis of solvent effects on nitrogen NMR chemical shifts in oxazoles and oxadiazoles

Using quantum chemistry methods we have evaluated the solvent effects on the ¹⁴N NMR chemical shifts in five oxa- and oxadiazoles dissolved in twelve solvents. These solvents differ in their polarity with the dielectric constants varying from 2 to 80. Moreover, three of them have a hydrogen-bond donor character. All possible hydrogen-bonding in the water solution with the oxygen and nitrogen (hydrogen-acceptor) centers in oxazoles (2) and oxadiazoles (3) have been considered in our studies. It has been shown that both the pure solvent and hydrogen-bonding effects are significant and result in ¹⁴N magnetic shielding increase. In water solutions the pure solvent effect is larger than the hydrogen-bonding effect. In addition, the solvent effect has been analyzed in terms of its direct and indirect contributions. It should be emphasized that our theoretical results for ¹⁴N chemical shifts in oxa- and oxadiazoles remain in a very good agreement with the accurate experimental data.     

Intramolecular spin exchange in flexible short-chain biradicals in solutions with various viscosity

Intramolecular electron spin exchange as a function of temperature and solvent viscosity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two short-chain flexible nitroxide biradicals. Certain thermodynamic parameters of the conformational rearrangements were calculated from the EPR spectra. The process of spin exchange in these biradicals dissolved in six different alcohols is compared with that in a nonpolar solvent (toluene) and with the thermodynamic characteristics of the solvents. No correlation is found on a macroscopic level (solvent viscosity) but on a microscopic level (solvent longitudinal relaxation times) a distinct correlation is seen. The original results are compared with literature data.