纯位移核磁共振氢谱及其应用

J耦合引起的核磁共振(NMR)信号多重裂分的数目和耦合常数反映了磁性原子核之间的化学键数目和空间位置信息,是研究分子结构的重要依据之一.但是当分子中磁性原子核数目增加时,NMR谱图特别是一维核磁共振氢谱(1D ~1H NMR)中,J耦合所致的多重裂分造成谱图重叠,严重干扰结构指认和定量分析.利用纯位移(亦称宽带同核去耦)~1H NMR谱图可以消除J耦合效应(即将相邻质子间耦合所引起的多重裂分融合成一个单峰),得到与去耦碳谱相似的、只含化学位移信息的谱图.该文首先介绍了三种最受关注的获取纯位移核磁共振氢谱技术——BIRD、ZS和PSYCHE的基本原理,随后综述了纯位移~1H NMR谱图的典型应用.     

Anomalous Proton NMR Deshielding in Anilinopyrazoles

In connection with the synthesis of thienobenzodiazepines and certain heterocyclic analogues¹, a number of anilino heterocycle precursors were prepared. Their proton NMR spectra were generally unexceptional with the exclusion of one of the pyrazole isomers which showed a remarkable deshielding of one proton signal in the aniline ring. Further investigations have inferred that this low field shift can be attributed to through speace deshielding by a proximal pyrazole nitrogen lone pair.     

Automated Signal Detection as Tool to Evaluate Magnetic Field Homogeneity from Fourier Transformed Proton NMR Spectra

Off line analysis of proton nuclear magnetic resonance (NMR) spectra by computerized peak detection is used to determine the shim quality from Fourier transformed spectra. The method is designed to analyze spectra independently from any further information about the measurement. For this purpose, the number of maxima in a spectral region is determined and compared to the number of peaks identified by an automatic routine utilizing a curvature-based method. The resulting “shim quality quotient” represents a good indicator for the magnetic field homogeneity present during the measurement. This method can be applied to separated single signals as well as to entire spectral regions. Hence, its brought use as tool in automatic interpretation of NMR spectra is possible. An example is shown for an in situ proton NMR measurement of glucose mutarotation.     

The Proton NMR and Structures of Dimethyl and Diethyl Dichalcogenides

The proton NMR spectra of dimethyl dichalcogenides and diethyl dichalcogenides were measured. The experimental results do not show the evidence for the existence of rotational isomerism in each molecules.     

Proton NMR study of α-MnH0.06

Proton nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates for the solid solution α-MnH_0.06 have been measured over the temperature range 11-297 K and the resonance frequency range 20-90 MHz. A considerable shift and broadening of the proton NMR line and a sharp peak of the spin-lattice relaxation rate are observed near 130 K. These effects are attributed to the onset of antiferromagnetic ordering below the Néel temperature T_N≈130 K. The proton NMR line does not disappear in the antiferromagnetic phase; this suggests a small magnitude of the local magnetic fields at H-sites in α-MnH_0.06. The spin-lattice relaxation rate in the paramagnetic phase is dominated by the effects of spin fluctuations.     

Proton nuclear magnetic resonance spectra of brain tumors

Proton nuclear magnetic resonance (NMR) spectra were successfully measured in human brain tumor tissues and experimental rat brain tumors. The investigation was performed on clinical materials which consisted of tissue from one normal brain and 36 brain tumors. Normal rat brain tissue and rat glioma implanted in the brain were also analysed. NMR measurements were carried out at the resonance frequency of 99.54 MHz. The proton NMR spectrum of the normal brain consisted of one broad component and eight superimposed sharp peaks. The sharp peaks obtained from the brain tumors varied from those of the normal brain. A decrease in the signal intensity from N-acetyl aspartate was the most common finding in all tumors. Spectral patterns were similar within the same histological types, but varied among the different types. Therefore, ¹H-NMR spectra might indicate the metabolism characteristic of each tumor type which would be invaluable for clinical differential dagnosis of brain tumors.     

Spectroscopic Studies of Proton Transfer Equilibria In Hydrogen Bonded Complexes

Abstract

Recent studies on proton transfer equilibria for many hydrogen bonded complexes are discussed. These studies employ various spectroscopic techniques as infrared, ultraviolet, ¹H NMR, ¹³C NMR, ¹⁵N NMR and nuclear quadrupole resonance (NQR) spectroscopy. Special attention has been paid to Fourier transform infrared (FTIR), and it forms the main focus of this review, in particular for the study of proton transfer equilibria in proton sponges hydrogen bonded complexes. The influence of proton transfer equilibria on the physical, chemical and biological properties of hydrogen bonded complexes is shown. Some applications of proton transfer equilibria are also discussed.

     

NMR Study of Pentafluoroaniline - Hydrogen Bonding and Proton Exchange

The temperature and concentration dependence of ¹H NMR chemical shifts of pentafluoroaniline and aniline in acetone (Ac), dimethylsulphoxide (DMSO) and hexamethylphosphortriamide (HMPA) indicate that the effect of hydrogen bond formation, δ = δ_obs - δ_A' is similar for both anilines. The analysis of ¹H NMR spectra showed, that proton exchange of t-butyl alcohol (tBA) and 2,6-di-t-butylphenol (DTBPh) with pentafluoroaniline is slower than that with aniline.     

Proton Resonance Assignments in Oligosaccharides Containing Multiple Monosaccharide Residues of the Same Type

A technique is described for assisting the resonance assignment process in oligosaccharide proton NMR spectra, where multiple residues of the same type generate extreme resonance overlap in the spectrum. The approach involves the modification of a conventional HOHAHA experiment with constant-time acquisition in t₁, which effectively proton decouples the C-1 protons of residues whose resonances overlap, thus affording a significant increase in effective resolution in that dimension. For a sufficiently long spin-lock time, complete one-dimensional subspectra are obtained essentially free of cross talk from adjacent resonances. Further simplification of the assignment process is illustrated by incorporation of the constant-time modification into a three-dimensional HOHAHA-HOHAHA experiment.     

Proton dynamics in Rochelle salt

The investigation of the frequency spectra of Rochelle salt was performed by inelastic incoherent scattering of thermal neutrons using beryllium detector method. The neutron spectra were measured above the upper ferroelectric transition temperature at 307 K and in the polarized phase at 291 K, in the energy range 17–83 meV. Tentative conclusions concerning proton dynamics are drawn from the analysis of the spectra.     

Proton Nuclear Magnetic Resonance Spectroscopy: Significant Barriers to Rotation About N-N Bonds in 3-Acylaminoquinazolin-4(3H)-One Derivatives

Abstract

The proton NMR spectra of several 3-acylaminoquinazolin-4(3H)-one derivatives have been studied as a function of temperature. The changes, which were found to occur in the spectra at high temperatures, are discussed in terms of hindered rotation about the nitrogen-nitrogen bond. The free energies of activation for the rate-determining stereochemical process were calculated to be as high as (14.7～20.6 Kcal mol^?1) for hydrazine derivatives.     

质子化学位移各向异性的测量

测量质子化学位移各向异性（CSA）有助于表征分子结构与其动力学,但由于¹H-¹H同核偶极耦合相互作用很强及质子各向异性化学位移较小,测量质子化学位移各向异性仍具有巨大挑战,特别是对含有多种质子的生物大分子,如蛋白质.本文简要综述了测量质子化学位移各向异性的方法,包括同核去耦慢速魔角旋转方法、超快魔角旋转方法、对称重耦（RN_n^v）方法、xCSA方法以及量子化学计算方法.我们重点介绍了在高速魔角旋转条件下蛋白质氨基质子化学位移各向异性的测量及它们与氢键长度、蛋白质二级结构之间的关系.     

脑科学研究中的质子磁共振波谱方法

核磁共振（NMR）波谱作为一种操作简单、高效且重复性良好的技术手段,在脑科学领域的应用日益广泛,尤其是离体核磁共振氢谱（¹H NMR）和活体核磁共振氢谱（¹H MRS）.¹H NMR和¹H MRS在实验设计、样品预处理、数据处理等方面各有优劣、各擅胜场.本综述主要从适用范围、样品预处理、数据处理分析等方面,对二者在方法学层面的研究现状进行总结和讨论,以期为脑科学领域的研究者进行大脑代谢相关研究时提供一定的参考和帮助.     

A Multiple Scattering Theory for Proton Penetration

We extend the electron small-angle multiple scattering theory to proton penetration. After introducing the concept of narrow energy spectra,the proton energy loss process is included in the proton deep penetration theory. It precisely describes the whole process of proton penetration.Compared to the Monte Carlo method,this method maintains the comparable precision and possesses much higher computational efficiency. Thus, it shows the real feasibility of applying this algorithm to proton clinical radiation therapy.     

Spectroscopic Studies of Some Organic Compounds: Solvent Effects on 1H NMR Shift of Amine Proton of Morpholine

Abstract

The influence of the aprotic Solvents on the ¹H NMR spectra of the N-H proton has been studied. The chemical shift shows quite good correlation with the solvatochromic parameters, π?, β, and α, while a fair correlation with the Gutmann donor and acceptor numbers were obtained.     

Proton and deutron NMR study of PTFE ionomer membranes

Proton and deutron NMR have been conducted to investigate the ionic motion in perfluorinated ionomer membranes from Dow Chemical (XUS) and DuPont (Nafion^R). Two proton relaxation peaks were found in the XUS specimen absorbed with H₂O. The major (narrow) peak presented a spin-lattice relaxation time (T₁) of 107 ms while the minor (broader) one gave much longer T₁. While the former was attributed to the water molecules involved in restricted motion, the latter was expected to be associated with the protons located in the vicinity of the sulfonate groups. Similar to the previous results from the others, only a single peak was detected in Nafion^R in ¹H spectra, indicating that the protons in the different environments were engaging rapid exchange within NMR time scale. In contrast to the inverse proportion dependence of the linewidth on the water sorption in Nafion^R, the major line of the XUS membrane exhibited insensitive linewidth dependence on the variation of H₂O concentration. The difference was attributed to the existence of narrow breaths of the pores in XUS sample, such that free water contribution to the enhancement of proton mobility was limited. The ²H spectra of Nafion^R were found to possess a doublet, due to nuclear quadrupolar interaction. Dow (XUS) membrane treated in at 100% relative humidity (RH) D₂O presented a single peak with the linewidth insensitive to the amount of heavy water absorbed. An additional rise emerged on the “shoulder” of this single peak when treated at 33% RH. It is concluded that XUS membrane does not provide strong hydrogen bonding to eliminate the rapid motion average over the nuclear quadrupole interaction.     

The NMR Measurement of the Hydrogen Bonding of Proton Donors Having More Than one Equivalent Proton

In the hydrogen bonding of a protonic acid having more than one equivalent proton to a n-donor, the K, δH and δS parameters can be measured by NMR spectrometry without any ambiguity as in the case of a single-proton acid, but the measured hydrogen-bond chemical shift is reduced in magnitude as it is the weighted average of the chemical shift of the bonded proton and that of the proton(s) remaining free in the dimer-complex.     

Proton dynamics in calcium hydroxide. A NMR study

Proton NMR, T₁ measurements in Ca(OH)₂ in the temperature range 390-160K are reported. We present evidence for the existence of at least two-dynamically diferent types of protons. A localized proton fraction corresponding to hydroxyl groups which undergo an “umbrella”- type vibration and a mobile proton population diffusing by fast proton jumps. This latter fraction increases with temperature. At the highest temperatures more than 90% of the observed protons are highly mobile whereas the localized fraction assumes a different kind of motion presumably loosing its localized character.     

Dispersion Relations for Proton Relaxation in Solid Dielectrics

Russian Physics Journal - Frequency-temperature spectra of the complex permittivity are studied for proton semiconductors and dielectrics using the methods of a quasi-classical kinetic theory of...     

氘核破裂效应对质子出射能谱的贡献(英文)

基于连续离散化耦合道理论（CDCC）, 并在假设剩余核不仅可处于束缚态而且可处于一系列的激发态的基础上, 本工作论述了氘核破裂效应对质子出射能谱的贡献。计算结果可以基本解释质子出射能谱在大约氘核入射能量一半处出现峰值结构的实验现象。本工作的计算结果与C.Kalbach的经验公式基本保持一致。Based on the continuum discretized coupled channels(CDCC) theory, and the hypothesis that the residual nucleus locates not only in bound state but also in a series of excited states, the contribution of deuteron breakup effect in outgoing proton energy spectra are studied in the present work. And the results can basically explain the experimental results that a peak structure is appeared in the outgoing proton energy spectra at about half of the incident energy. The results of present calculation generally agree with those obtained from C. Kalbach’s empirical formulaum.