光谱法分析乙丙共聚物的序列结构及链节比

用FTIR, 1 H NMR和 13 C NMR分析乙丙共聚物的序列结构与链节比. 通过对乙丙共聚物 1 H NMR, 13 C NMR和 13 C-1 H二维核磁共振谱的综合分析, 提出了与前人不同的归属, 并提出了不同位置碳原子积分面积相关性分析方法, 该方法避免了烦琐的理论计算, 可简便地得到乙丙共聚物的主要序列结构. 通过比较 1 H NMR和 13 C NMR计算乙丙共聚物中乙烯、 丙烯链节比, 表明可以用 1 H NMR代替 13 C NMR完成对乙丙共聚物中乙烯、 丙烯链节比的定量计算.     

Flow injection analysis NMR (FIA–NMR): a novel flow NMR technique that complements LC–NMR and direct injection NMR (DI–NMR)

Details of a new flow NMR technique, flow injection analysis NMR (FIA–NMR), are presented for the first time. This method blends some aspects of both liquid chromatography–NMR and direct injection NMR, and complements both. FIA‐NMR is shown to be useful as an analytical technique, especially for repetitive analyses, and may also prove useful in the analysis of combinatorial chemistry libraries. The feasibility of FIA‐NMR is demonstrated by the quantitative analysis of an over‐the‐counter pharmaceutical. Copyright © 2003 John Wiley & Sons, Ltd.     

13C and 15N NMR studies of iron-bound cyanides of heme proteins and related model complexes: sensitive probe for detecting hydrogen-bonding interactions at the proximal and distal sides

Studies of the 13C and 15N NMR paramagnetic shifts of the iron-bound cyanides in the ferric cyanide forms of various heme proteins containing the proximal histidine and related model complexes are reported. The paramagnetic shifts of the 13C and 15N NMR signals of the iron-bound cyanide are not significantly affected by the substitution of the porphyrin side chains. On the other hand, the paramagnetic shifts of both the 13C and 15N NMR signals decrease with an increase in the donor effect of the proximal ligand, and the 13C NMR signal is more sensitive to a modification of the donor effect of the proximal ligand than the 15N NMR signal. With the tilt of the iron-imidazole bond, the paramagnetic shift of the 13C NMR signal increases, whereas that of the 15N NMR signal decreases. The hydrogen-bonding interaction of the iron-bound cyanide with a solvent decreases the paramagnetic shift of both 13C and 15N NMR signals, and the effect is more pronounced for the 15N NMR signal. Data on the 13C and 15N NMR signals of iron-bound cyanide for various heme proteins are also reported and analyzed in detail. Substantial differences in the 13C and 15N NMR shifts for the heme proteins can be explained on the basis of the results for the model complexes and structures around the heme in the heme proteins. The findings herein show that the paramagnetic shift of the 13C NMR signal of the iron-bound cyanide is a good probe to estimate the donor effect of the proximal imidazole and that the ratio of 15N/13C NMR shifts allows the hydrogen-bonding interaction on the distal side to be estimated.     

NMR Studies of polymeric materials - an overview

NMR has been used extensively in studies of synthetic polymers. The approaches employed may require solution NMR, solid state NMR, or NMR imaging. In each case, different techniques and analytical methodologies have been devised to facilitate experimentation or to maximize information output. These techniques are not mutually exclusive and often provide complementary information. A selective review is made herewith of polymer/NMR studies, with emphasis on the contributions made at NMR symposia held in Detroit in October, 1993 as part of the 20th FACSS meeting.     

1.5T核磁共振弛豫时间分析仪的研制及其潜在应用

介绍了国产1.5T核磁共振弛豫时间分析仪的基本组成、性能指标,研发过程中攻克的技术难题。该仪器主要由磁体部分、电子部分、软件部分组成,具有体积小、信噪比高、检测无损、使用和维护简便和造价低廉等优点。同时对该系统磁体频率和磁信号的稳定性进行了相关的测试,结果表明该系统稳定可靠。该仪器的磁场强度增加到1.5T,在同等外界条件和环境下,信噪比增加约为0.5T系统的10倍,检测灵敏度大幅度提高;该仪器为食品品质鉴定、食品安全检测、医学诊断、生物标志物的大规模筛选等生化分析提供一个全新的途径。     

NMR位移试剂Eu(fod)~4^-对锍盐^1H和^1^3C NMR的影响

合成了八种新的四氟硼酸二甲基苯基锍，用元素分析和核磁共振对其结构进行了表征。研究了以CDCl~3为溶剂，NMR位移试剂Eu(fod)~4^-对所合成锍盐的^1H和^1^3C NMR的影响。结果表明，Eu(fod)~4^-是一个对锍盐非常有效的位移试剂，且Eu(fod)~4^-对二甲基苯基锍盐之甲基的^1H和^1^3C NMR的位移呈线性关系。     

µ-NMR at the point of care testing

NMR shows strong analytical capability for obtaining molecular information on materials and is used in a variety of fields. Micro-NMR (µNMR) is mainly based on low-field NMR (LF-NMR), which makes NMR detection portable and inexpensive. Point-of-care testing (POCT) has gradually become an area of major concern, and scientists have made much progress in applying µNMR systems for POCT. To the best of our knowledge, this is the first review of the latest development in miniaturization of µNMR systems. Then, we discuss cutting-edge µNMR-based applications in POCT and the outlook for future developments.     

RNA unrestrained molecular dynamics ensemble improves agreement with experimental NMR data compared to single static structure: a test case

Nuclear magnetic resonance (NMR) provides structural and dynamic information reflecting an average, often non-linear, of multiple solution-state conformations. Therefore, a single optimized structure derived from NMR refinement may be misleading if the NMR data actually result from averaging of distinct conformers. It is hypothesized that a conformational ensemble generated by a valid molecular dynamics (MD) simulation should be able to improve agreement with the NMR data set compared with the single optimized starting structure. Using a model system consisting of two sequence-related self-complementary ribonucleotide octamers for which NMR data was available, 0.3 ns particle mesh Ewald MD simulations were performed in the AMBER force field in the presence of explicit water and counterions. Agreement of the averaged properties of the molecular dynamics ensembles with NMR data such as homonuclear proton nuclear Overhauser effect (NOE)-based distance constraints, homonuclear proton and heteronuclear ¹H–³¹P coupling constant (J) data, and qualitative NMR information on hydrogen bond occupancy, was systematically assessed. Despite the short length of the simulation, the ensemble generated from it agreed with the NMR experimental constraints more completely than the single optimized NMR structure. This suggests that short unrestrained MD simulations may be of utility in interpreting NMR results. As expected, a 0.5 ns simulation utilizing a distance dependent dielectric did not improve agreement with the NMR data, consistent with its inferior exploration of conformational space as assessed by 2-D RMSD plots. Thus, ability to rapidly improve agreement with NMR constraints may be a sensitive diagnostic of the MD methods themselves.     

Fragment Screening and Fast Micromolar Detection on a Benchtop NMR Spectrometer Boosted by Photoinduced Hyperpolarization

Fragment-based drug design is a well-established strategy for rational drug design, with nuclear magnetic resonance (NMR) on high-field spectrometers as the method of reference for screening and hit validation. However, high-field NMR spectrometers are not only expensive, but require specialized maintenance, dedicated space, and depend on liquid helium cooling which became critical over the recurring global helium shortages. We propose an alternative to high-field NMR screening by applying the recently developed approach of fragment screening by photoinduced hyperpolarized NMR on a cryogen-free 80 MHz benchtop NMR spectrometer yielding signal enhancements of up to three orders in magnitude. It is demonstrated that it is possible to discover new hits and kick-off drug design using a benchtop NMR spectrometer at low micromolar concentrations of both protein and ligand. The approach presented performs at higher speed than state-of-the-art high-field NMR approaches while exhibiting a limit of detection in the nanomolar range. Photoinduced hyperpolarization is known to be inexpensive and simple to be implemented, which aligns greatly with the philosophy of benchtop NMR spectrometers. These findings open the way for the use of benchtop NMR in near-physiological conditions for drug design and further life science applications.     

Hyphenation of capillary separations with nuclear magnetic resonance spectroscopy

The hyphenation of small-volume separations to information-rich detection offers the promise of unmatched analytical information on the components of complex mixtures. Nuclear magnetic resonance (NMR) spectroscopy provides information about molecular structure, although sensitivity remains an issue for on-line NMR detection. This is especially true when hyphenating NMR to capillary separations as the observation time and analyte mass are decreased to the point where reduced information is obtained from the eluting analytes. Because of these limitations, advances in instrumental performance have a large impact on the overall performance of a separation–NMR system. Instrumental aspects and the capabilities of cLC–NMR, CEC–NMR and CE–NMR are reviewed, and applications that have used this technology highlighted. Recent trends towards small volume capillary scale separations are emphasized, as is the recent success of capillary-isotachophoresis (cITP)–NMR.     

High‐field 95Mo and 183W static and MAS NMR study of polyoxometalates

The potential of high‐field NMR to measure solid‐state ⁹⁵Mo and ¹⁸³W NMR in polyoxometalates (POMs) is explored using some archetypical structures like Lindqvist, Keggin and Dawson as model compounds that are well characterized in solution. NMR spectra in static and under magic angle spinning (MAS) were obtained, and their analysis allowed extraction of the NMR parameters, including chemical shift anisotropy and quadrupolar coupling parameters. Despite the inherent difficulties of measurement in solid state of these low‐gamma NMR nuclei, due mainly to the low spectral resolution and poor signal‐to‐noise ratio, the observed global trends compare well with the solution‐state NMR data. This would open an avenue for application of solid‐state NMR to POMs, especially when liquid‐state NMR is not possible, e.g., for poorly soluble or unstable compounds in solution, and for giant molecules with slow tumbling motion. This is the case of Keplerate where we provide here the first NMR characterization of this class of POMs in the solid state. Copyright © 2017 John Wiley & Sons, Ltd.     

NOAH: NMR Supersequences for Small Molecule Analysis and Structure Elucidation

Nested NMR experiments combining up to five conventional NMR pulse sequences into one supersequence are introduced. The core 2D NMR techniques routinely employed in small molecule NMR spectroscopy, such as HSQC, HMQC, HMBC, COSY, NOESY, TOCSY, and similar, can be recorded in a single measurement. In this way the data collection time may be dramatically reduced and sample throughput increased for basic NMR applications, such as structure elucidation and verification in synthetic, medicinal, and natural product chemistry.     

From single to multiple microcoil flow probe NMR and related capillary techniques: a review

Nuclear magnetic resonance (NMR) spectroscopy is one of the most important and powerful instrumental analytical techniques for structural elucidation of unknown small and large (complex) isolated and synthesized compounds in organic and inorganic chemistry. X-ray crystallography, neutron scattering (neutron diffraction), and NMR spectroscopy are the only suitable methods for three-dimensional structure determination at atomic resolution. Moreover, these methods are complementary. However, by means of NMR spectroscopy, reaction dynamics and interaction processes can also be investigated. Unfortunately, this technique is very insensitive in comparison with other spectrometric (e.g., mass spectrometry) and spectroscopic (e.g., infrared spectroscopy) methods. Mainly through the development of stronger magnets and more sensitive solenoidal microcoil flow probes, this drawback has been successfully counteracted. Capillary NMR spectroscopy increases the mass-based sensitivity of the NMR spectroscopic analysis up to 100-fold compared with conventional 5-mm NMR probes, and thus can be coupled online and off-line with other microseparation and detection techniques. It offers not only higher sensitivity, but in many cases provides better quality spectra than traditional methods. Owing to the immense number of compounds (e.g., of natural product extracts and compound libraries) to be examined, single microcoil flow probe NMR spectroscopy will soon be far from being sufficiently effective as a screening method. For this reason, an inevitable trend towards coupled microseparation–multiple microcoil flow probe NMR techniques, which allow simultaneous online and off-line detection of several compounds, will occur. In this review we describe the current status and possible future developments of single and multiple microcoil capillary flow probe NMR spectroscopy and its application as a high-throughput tool for the analysis of a large number of mass-limited samples. The advantages and drawbacks of different coupled microseparation–capillary NMR spectroscopy techniques, such as capillary high-performance liquid chromatography–NMR spectroscopy, capillary electrophoresis–NMR spectroscopy, and capillary gas chromatography–NMR spectroscopy, are discussed and demonstrated by specific applications. Another subject of discussion is the progress in parallel NMR detection techniques. Furthermore, the applicability and mixing capability of tiny reactor systems, termed “microreactors” or “micromixers,” implemented in NMR probes is demonstrated by carbamate- and imine-forming reactions.     

“CLASSIC NMR”: An In‐Situ NMR Strategy for Mapping the Time‐Evolution of Crystallization Processes by Combined Liquid‐State and Solid‐State Measurements

A new in‐situ NMR strategy (termed CLASSIC NMR) for mapping the evolution of crystallization processes is reported, involving simultaneous measurement of both liquid‐state and solid‐state NMR spectra as a function of time. This combined strategy allows complementary information to be obtained on the evolution of both the solid and liquid phases during the crystallization process. In particular, as crystallization proceeds (monitored by solid‐state NMR), the solution state becomes more dilute, leading to changes in solution‐state speciation and the modes of molecular aggregation in solution, which are monitored by liquid‐state NMR. The CLASSIC NMR experiment is applied here to yield new insights into the crystallization of m‐aminobenzoic acid.     

两种立体构型的1,3,5,-三-α-萘基苯的合成

通过Adole反应和Grigard反应合成了相应的两种立体异构的1,3,5-三-α-萘基苯. 报道了它们的UV, IR, FD-MS和NMR . 论了两种异构体的^1H NMR 和^1^3C NMR的区别.     

Nuclear magnetic resonance coupled microseparations

The increased separation efficiency afforded by reducing the size of the separation column has resulted in 'microseparations' becoming an important component in many chemical and biochemical applications. The coupling of microseparations with NMR detection is an area of increasing interest owing to the high structural information of NMR. In order to couple efficiently with the separation, the NMR detector must be reduced in size to correspond to that of the separation peak. This paper summarizes some of the approaches used in coupling NMR detection with pressure-driven and electrophoretic microseparations, the design of small NMR detectors and applications of this technology.     

Billion‐Fold Enhancement in Sensitivity of Nuclear Magnetic Resonance Spectroscopy for Magnesium Ions in Solution

β‐nuclear magnetic resonance (NMR) spectroscopy is highly sensitive compared to conventional NMR spectroscopy, and may be applied for several elements across the periodic table. β‐NMR has previously been successfully applied in the fields of nuclear and solid‐state physics. In this work, β‐NMR is applied, for the first time, to record an NMR spectrum for a species in solution. ³¹Mg β‐NMR spectra are measured for as few as 10⁷ magnesium ions in ionic liquid (EMIM‐Ac) within minutes, as a prototypical test case. Resonances are observed at 3882.9 and 3887.2 kHz in an external field of 0.3 T. The key achievement of the current work is to demonstrate that β‐NMR is applicable for the analysis of species in solution, and thus represents a novel spectroscopic technique for use in general chemistry and potentially in biochemistry.     

Reconstructing Reliable Powder Patterns from Spikelets (Q)CPMG NMR Spectra: Simplification of UWNMR Crystallography Analysis

Spikelets NMR spectra are very popular as they enable the shortening of experimental time and give the possibility to obtain required NMR parameters for nuclei with ultrawide NMR patterns. Unfortunately, these resulted ssNMR spectra cannot be fitted directly in common software. For this reason, we developed UWNMRSpectralShape (USS) software which transforms spikelets NMR patterns into single continuous lines. Subsequently, these reconstructed spectral envelopes of the (Q)CPMG spikelets patterns can be loaded into common NMR software and automatically fitted, independently of experimental settings. This allows the quadrupole and chemical shift parameters to be accurately determined. Moreover, it makes fitting of spikelets NMR spectra exact, fast and straightforward.     

1H, 13C, NH, HH, CH COSY, HH NOESY NMR and UV-vis studies of Solophenyl red 3BL dye azo-hydrazone tautomerism in various solvents

Azo-hydrazone tautomeric behavior of polyazo Solophenyl red 3BL (C.I. Direct 80) dye in different solvents (water, methanol and DMSO) was investigated using 1H, 13C, NH, HH, CH COSY, HH NOESY NMR techniques and UV-vis spectroscopy. Two-dimensional NMR experiments were used to assign 1H, 13C and 15N NMR lines unambiguously. Results showed that the hydrazone-form proton NMR signal appeared in the weakest field with respect to tetramethylsilane, in comparison with the amide and phenolic proton NMR signals. UV-vis absorption spectroscopic evidences showed that azo-hydrazone mixture exists in water and DMSO solvents, but in methanol, only azo tautomer was dominant, which was in a good agreement with NMR spectroscopic results.     

Dry‐cured ham tissue characterization by fast field cycling NMR relaxometry and quantitative magnetization transfer

Fast field cycling (FFC) and quantitative magnetization transfer (qMT) NMR methods are two powerful tools in NMR analysis of biological tissues. The qMT method is well established in biomedical NMR applications, while the FFC method is often used in investigations of molecular dynamics on which longitudinal NMR relaxation times of the investigated material critically depend. Despite their proven analytical potential, these two methods were rarely used in NMR studies of food, especially when combined together. In our study, we demonstrate the feasibility of a combined FFC/qMT‐NMR approach for the fast and nondestructive characterization of dry‐curing ham tissues differing by protein content. The characterization is based on quantifying the pure quadrupolar peak area (area under the quadrupolar contribution of dispersion curve obtained by FFC‐NMR) and the restricted magnetization pool size (obtained by qMT‐NMR). Both quantities correlate well with concentration of partially immobilized, nitrogen‐containing and proton magnetization exchanging muscle proteins. Therefore, these two quantities could serve as potential markers for dry‐curing process monitoring. Copyright © 2016 John Wiley & Sons, Ltd.