Two-dimensional nuclear magnetic resonance spectroscopy

Great spectral simplification can be obtained by spreading the conventional one-dimensional nuclear magnetic resonance (NMR) spectrum in two independent frequency dimensions. This so-called two-dimensional NMR spectroscopy removes spectral overlap, facilitates spectral assignment, and provides a wealth of additional information. For example, conformational information related to interproton distances is available from resonance intensities in certain types of two-dimensional experiments. Another method generates 1H NMR spectra of a preselected fragment of the molecule, suppressing resonances from other regions and greatly simplifying spectral appearance. Two-dimensional NMR spectroscopy can also be applied to the study of 13C and 15N, not only providing valuable connectivity information but also improving sensitivity of 13C and 15N detection by up to two orders of magnitude.     

Multiple-quantum nuclear magnetic resonance spectroscopy

A nuclear magnetic resonance (NMR) event is popularly viewed as the flip of a single spin in a magnetc field, stimulated by the absorption or emission of only one quantum of radio-frequency energy. Nevertheless, resonances between nuclear spin states that differ by more than one unit in the Zeeman quantum number also can be induced in systems of coupled spins by suitably designed sequences of radio-frequency pulses. Pairs of states excited in this way oscillate coherently at the frequencies of the corresponding multiple-quantum transitions and produce a response that may be monitored indirectly in a two-dimensional time-domain experiment. The pattern of multiple-quantum excitation and response, influenced largely by the concerted interactions of groups of coupled nuclei, simplifies the NMR spectrum in some instances and provides significant new information in others. Applications of multiple-quantum NMR extend to problems in many different areas, ranging from studies of the structure and function of proteins and nucleic acids in solution to investigations of the arrangements of atoms in amorphous semiconductors. The specific spectroscopic techniques are varied as well and include methods designed, for example, to simplify spectral analysis for liquids and liquid crystals, eliminate inhomogeneous broadening, study interatomic connectivity in liquid-state molecules, identify clusters of atoms in solids, enhance the spatial resolution in solid-state imaging experiments, and probe correlated molecular motions.     

Protein structure determination in solution by nuclear magnetic resonance spectroscopy

Knowledge of three-dimensional protein structures is one of the foundations of protein design and protein engineering. Nuclear magnetic resonance spectroscopy was recently introduced as a second method for protein structure determination, in addition to the well-established diffraction techniques with protein single crystals. This new approach enables one to carry out detailed structural studies of proteins in solution and other noncrystalline states, which may be similar or identical to the physiological environment, and promises new insights into the dynamics of protein molecules and the protein-folding problem.     

Effects of pulse shaping in laser spectroscopy and nuclear magnetic resonance

Pulsed excitation fields are routinely used in most laser and nuclear magnetic resonance (NMR) experiments. In the NMR case, constant amplitude (rectangular) pulses have traditionally been used; in laser spectroscopy the exact pulse shape is often unknown or changes from shot to shot. This article is an overview of the effects of radio-frequency and laser pulse shapes and the instrumental requirements for pulse shaping. NMR applications to selective excitation, solvent suppression, elimination of phase roll, and reduced power dissipation are discussed, as are optical applications to soliton generation, velocity selective excitation, and quantitative population transfer.     

High-resolution nuclear magnetic resonance spectroscopy in a circularly polarized laser beam

Nuclei in a fluid subjected to a continuous wave circularly polarized light beam are predicted to experience a static magnetic field proportional to E(+/-) x E(+/-), where E(+/-) is the electric vector of the right or left circularly polarized wave and the dot denotes a time derivative. The field strongly depends on the local electronic structure and is present in all atoms. For an intensity of 10 watts per square centimeter propagating in the direction of the field of a magnetic resonance spectrometer, the general theory presented here predicts shifts of +/- 4 x 10(-8) hertz for protons and +/- 10(-5) hertz for fluorine-19. Larger shifts are predicted if the laser frequency is near an optical absorption.     

Protein-metal ion binding site: determination with proton magnetic resonance spectroscopy

Proton magnetic resonance spectra of aqueous gelatin were analyzed with respect to composition and molecular interactions. Aqueous gelatin complexes cobaltous ions in the pD range of approximately 3.5 to 7.5. Glutamyl and aspartyl side chains are shown to be the sites of binding.     

3．0T质子磁共振波谱在阿尔兹海默病的应用

目的观察3．0T氢质子磁共振波谱（IH—MRS）检测阿尔茨海默病（AD）的代谢变化及其临床意义。方法对30例临床确诊轻度AD组患者（AD组）和30名健康对照者（对照组）的1H—MRS进行分析,对两组颞叶海马区行1H—MRS检测,得到N-乙酰天门冬氨酸（N—acetyl aspartate,NAA）峰、肌酸（creatine,Cr）峰、胆碱（choline,Cho）．峰的积分值及计算出NAA／Cr、Cho／Cr和MI／Cr,并将两组数据进行对比。结果AD组患者颞叶海马区的NAA／Cr值为（1．47±0．15）、Cho／Cr值为（0．79±0．18）、MI／Cr值为（0．77±0．15）,与对照组比较差异均有统计学意义（P〈0．01）。结论1H—MRS检测颞叶海马区的NAA／Cr比值降低及MI／Cr比值升高对轻度AD临床辅助诊断有一定提示价值。     

Nuclear magnetic resonance spectroscopy in the Earth sciences: structure and dynamics

Detailed knowledge of the structure and dynamics of the materials that make up the earth is necessary for fundamental understanding of most geological processes. Nuclear magnetic resonance spectroscopy is beginning to play an important role in investigations of inorganic solid materials, as well as of liquids and organic compounds; it has already contributed substantially to our knowledge of minerals and rocks, compositionally simplified analogs of magmas, and the surfaces of silicate crystals. The technique is particularly useful for determining local structure and ordering state in crystals, glasses, and liquids, and is sensitive to atomic motion at the time scales of diffusion and viscosity in silicates. New techniques offer promise for increased resolution for quadrupolar nuclei and for extension of experiments to high temperature and pressure.     

Study of aldose reductase inhibition in intact lenses by 13C nuclear magnetic resonance spectroscopy

Carbon-13 nuclear magnetic resonance spectroscopy has been used in the study of glucose metabolism, specifically aldose reductase inhibition, in intact rabbit lenses maintained in organ culture. This technique provides an effective method of screening potential inhibitors of aldose reductase under conditions that more closely approximate in vivo conditions than do earlier methods. The aspirin substitutes acetaminophen and ibuprofen were studied as aldose reductase inhibitors and were found to be effective in reducing sorbitol accumulation in lenses exposed to high glucose stress. Results of this work with various inhibitors of aldose reductase are discussed in terms of lens metabolism and implications regarding diabetic complications such as cataract formation.     

Monitoring the time course of cerebral deoxyglucose metabolism by 31P nuclear magnetic resonance spectroscopy

The phosphorylation of 2-deoxyglucose by the mammalian brain is used as an index of the brain's energy metabolism. The results of phosphorus-31 nuclear magnetic resonance (31P NMR) monitoring of conscious animals in vivo showed rapid phosphorylation of 2-deoxyglucose by brain tissue. The rate of phosphorylation as determined by 31P NMR was consistent with results achieved by tracer methods using carbon-14-labeled 2-deoxyglucose. However, the disappearance of 2-deoxyglucose-6-phosphate was shown to be faster than that reported by tracer studies and occurred without alterations of intracellular pH and energy homeostasis. These results were confirmed by gas chromatography and mass spectroscopy. It is postulated that 2-deoxyglucose may be metabolized in several ways, including dephosphorylation by a hexose phosphatase.     

核磁共振技术在枯草芽孢杆菌的抗菌物质结构鉴定中的应用

核磁共振(NMR)技术是化合物结构鉴定的一种重要的方法。该文简单介绍了NMR技术的基本原理,及NMR技术在枯草芽孢杆菌所产的多肽、脂肽类抗菌物质结构鉴定中的运用概况,进一步阐述了NMR联用技术的发展现状,展望了其在枯草芽孢杆菌抗菌物的结构鉴定方面的应用前景。     

Electron nuclear double resonance spectroscopy

Precise information about the molecular structure, stereochemistry, and environment of paramagnetic species can be obtained by electron nuclear double resonance (ENDOR) spectroscopy. This technique has been applied in a wide range of disciplines to liquid-phase, single-crystal, and powder samples. In some cases-the study of defects in ionic single crystals, for instance-the volume and complexity of data obtained by ENDOR can hinder interpretation. Such difficulties have been overcome by the use of supplemental ENDOR techniques that simplify the assignment of ENDOR lines. The increased use of computers for the automation of instrumentation, the design of experiments, and the analysis of data has made possible the study of a wider range of problems. With these improvements, as well as with the increased sensitivity provided by optically detected ENDOR, it is now feasible to study polycrystalline and amorphous materials, such as thin-film semiconductors and biological samples in vivo.     

In vivo determination of the pyridine nucleotide reduction charge by carbon-13 nuclear magnetic resonance spectroscopy

An intracellular coenzyme has been observed by carbon-13 nuclear magnetic resonance spectroscopy. The pyridine nucleotides in Escherichia coli were specifically labeled with carbon-13 from the biosynthetic precursor, nicotinic acid. The intracellular redox status and metabolic transformations of the pyridine nucleotides were examined under a variety of conditions. A highly reduced nicotinamide adenine dinucleotide pool was observed under anaerobic conditions only in cells that were cultured aerobically on glycerol.     

All-optical magnetic resonance in semiconductors

A scheme is proposed wherein nuclear magnetic resonance (NMR) can be induced and monitored using only optical fields. In analogy to radio-frequency fields used in traditional NMR, circularly polarized light creates electron spins in semiconductors whose hyperfine coupling could tip nuclear moments. Time-resolved Faraday rotation experiments were performed in which the frequency of electron Larmor precession was used as a magnetometer of local magnetic fields experienced by electrons in n-type gallium arsenide. Electron spin excitation by a periodic optical pulse train appears not only to prepare a hyperpolarized nuclear moment but also to destroy it resonantly at magnetic fields proportional to the pulse frequency. This resonant behavior is in many ways supportive of a simple model of optically induced NMR, but a curious discrepancy between one of the observed frequencies and classic NMR values suggests that this phenomenon is more complex.     

High-resolution nuclear magnetic resonance of solids

The development of line-narrowing techniques, such as magic-angle spinning (MAS) and high-power decoupling, has led to powerful high-resolution nuclear magnetic resonance approaches for solid samples. In favorable cases (for instance, where high abundances of protons are present) cross polarization (CP) provides a means of circumventing the time bottleneck caused by inefficient spinlattice relaxation in many solids. The combined CP-MAS approach for carbon-13 with proton decoupling has become a popular and routine experiment for organic solids. For many nuclides with spin quantum number /> (1/2) the central nuclear magnetic resonance transition can be employed in high-resolution experiments that involve rapid sample spinning. A continuing stream of advances holds great promise for the use of high-resolution techniques for the characterization of solids by a wide range of nuclides.     

Force detection of nuclear magnetic resonance

Micromechanical sensing of magnetic force was used to detect nuclear magnetic resonance with exceptional sensitivity and spatial resolution. With a 900 angstrom thick silicon nitride cantilever capable of detecting subfemtonewton forces, a single shot sensitivity of 1.6 x 10(13) protons was achieved for an ammonium nitrate sample mounted on the cantilever. A nearby millimeter-size iron particle produced a 600 tesla per meter magnetic field gradient, resulting in a spatial resolution of 2.6 micrometers in one dimension. These results suggest that magnetic force sensing is a viable approach for enhancing the sensitivity and spatial resolution of nuclear magnetic resonance microimaging.     

Tumor detection by nuclear magnetic resonance

Spin echo nuclear magnetic resonance measurements may be used as a method for discriminating between malignant tumors and normal tissue. Measurements of spin-lattice (T(1)) and spin-spin (T(2)) magnetic relaxation times were made in six normal tissues in the rat (muscle, kidney, stomach, intestine, brain, and liver) and in two malignant solid tumors, Walker sarcoma and Novikoff hepatoma. Relaxation times for the two malignant tumors were distinctly outside the range of values for the normal tissues studied, an indication that the malignant tissues were characterized by an increase in the motional freedom of tissue water molecules. The possibility of using magnetic relaxation methods for rapid discrimination between benign and malignant surgical specimens has also been considered. Spin-lattice relaxation times for two benign fibroadenomas were distinct from those for both malignant tissues and were the same as those of muscle.     

Nuclear magnetic resonance at high pressure

Nuclear magnetic resonance relaxation measurements at high pressure provide unique information about the microscopic behavior of liquids. This article presents the principles of this technique; illustrates its usefulness by several specific examples of studies of molecular liquids, water, and supercritical dense fluids; and indicates the promising future of high-resolution nuclear magnetic resonance spectroscopy at high pressure with examples of studies of chemical exchange and homogeneous catalytic processes.