Estimation of the lateral dimensions of cellulose crystallites using 13C NMR signal strengths

Differences in proton rotating-frame spin relaxation rates were exploited to edit the 13C NMR spectra of solid lignocellulosics, separating signals assigned to cellulose crystallites from signals assigned to amorphous material. Clusters of signals at 89 and 85 ppm were assigned to C-4 in the interiors and on the surfaces of cellulose crystallites, respectively. Relative signal areas were used to estimate the weight-averaged lateral dimensions of crystallites, using a model in which crystallites have approximately square cross sections. The same 10 samples were also characterized by wide-angle X-ray scattering (WAXS). There was a strong correlation (r2 = 0.988) between the two sets of lateral dimensions, but those estimated by WAXS were typically 10% lower than those estimated by NMR. The deviations were attributed to differences in molecular conformations between interior and surface chains, causing broadening of the WAXS peaks. In the case of an eleventh sample containing well-ordered xylan, the NMR and WAXS methods were in good agreement only after exclusion of a xylan signal at 82.6 ppm from the NMR data.     

'q-Titration' of long-chain and short-chain lipids differentiates between structured and mobile residues of membrane proteins studied in bicelles by solution NMR spectroscopy

'q-Titration' refers to the systematic comparison of signal intensities in solution NMR spectra of uniformly (15)N labeled membrane proteins solubilized in micelles and isotropic bicelles as a function of the molar ratios (q) of the long-chain lipids (typically DMPC) to short-chain lipids (typically DHPC). In general, as q increases, the protein resonances broaden and correspondingly have reduced intensities due to the overall slowing of protein reorientation. Since the protein backbone signals do not broaden uniformly, the differences in line widths (and intensities) enable the narrower (more intense) signals associated with mobile residues to be differentiated from the broader (less intense) signals associated with "structured" residues. For membrane proteins with between one and seven trans-membrane helices in isotropic bicelles, we have been able to find a value of q between 0.1 and 1.0 where only signals from mobile residues are observed in the spectra. The signals from the structured residues are broadened so much that they cannot be observed under standard solution NMR conditions. This q value corresponds to the ratio of DMPC:DHPC where the signals from the structured residues are "titrated out" of the spectrum. This q value is unique for each protein. In magnetically aligned bilayers (q>2.5) no signals are observed in solution NMR spectra of membrane proteins because the polypeptides are "immobilized" by their interactions with the phospholipid bilayers on the relevant NMR timescale (～10(5)Hz). No signals are observed from proteins in liposomes (only long-chain lipids) either. We show that it is feasible to obtain complementary solution NMR and solid-state NMR spectra of the same membrane protein, where signals from the mobile residues are present in the solution NMR spectra, and signals from the structured residues are present in the solid-state NMR spectra. With assigned backbone amide resonances, these data are sufficient to describe major features of the secondary structure and basic topology of the protein. Even in the absence of assignments, this information can be used to help establish optimal experimental conditions.     

Application of the NMR-MOUSE to food emulsions

The application of the NMR-MObile Universal Surface Explorer (NMR-MOUSE) to study food systems is evaluated using oil-in-water emulsions, and the results are compared to those obtained using a conventional low-field NMR (LF-NMR) instrument. The NMR-MOUSE is a small and portable LF-NMR system with a one-sided magnet layout that is used to replace the conventional magnet and probe on a LF-NMR instrument. The high magnetic field gradients associated with the one-sided MOUSE magnet result in NMR signal decays being dominated by molecular diffusion effects, which makes it possible to discriminate between the NMR signals from oil and water. Different data acquisition parameters as well as different approaches to the analysis of the NMR data from a range of oil-in-water emulsions are evaluated, and it is demonstrated how the concentration of oil and water can be determined from the NMR-MOUSE signals. From these model systems it is concluded that the NMR-MOUSE has good potential for the quantitative analysis of intact food products.     

Determination of structural and dynamic characteristics of biodegradable polymers by the NMR relaxation method

A theory of the NMR spectra of heterogeneous polymer systems is proposed that makes it possible to simulate signals observed over a wide temperature range with account of spectral diffusion. Based on this theory, a technique of rapid analysis of molecular structure parameters, including the degree of crystallinity and NMR line shape, is developed. The degree of crystallinity is demonstrated to be a linear function of the area under the NMR spectrum. It is shown that this dependence, universal for a given substance, makes it possible to reliably determine the degree of crystallinity over a wide temperature range (or the fraction of low-molecular additives in composites). The NMR spectra of chitosan is simulated and compared to experimental data. The universal dependence of the degree of crystallinity on the area under the spectrum of chitosan is calculated. A comparison with experimental signals allowed determining the degree of crystallinity.     

宽带磁共振T/R开关的设计与实现

磁共振系统中的发射/接收（transmit/receive,T/R）开关用于收发通路的切换,要求在隔离大功率信号的同时具有较小的插入损耗;另外,在宽带磁共振谱仪中,一般的窄带T/R开关也不再适用.本文基于PIN（positive-intrinsic-negative）二极管设计了工作频率为10~100 MHz的宽带磁共振T/R开关.通过减小电平跳变、优化开关过冲和解决二极管被动导通等问题,获得了插入损耗小于1 dB、大功率信号隔离度大于75 dB、开关时间1 μs的整体性能.用本文设计的宽带T/R开关替代一般探头中的窄带T/R开关,在0.5 T核磁共振（NMR）波谱仪上测得了氢核和氟核两个不同频率的磁共振信号,验证了宽带T/R开关的宽带性能.     

应用2D NMR技术研究羌活苷的结构

从传统中药羌活中分离得到1个香豆素类化合物,应用1D和脉冲梯度场反相2D NMR检测技术 (gCOSY, gNOESY, gHMQC, gHMBC) 研究了其结构,鉴定为6′-O-(反式阿魏酰基)-紫花前胡苷,命名为羌活苷（Forbesoside）. 本文对其碳氢NMR信号进行了全归属. 对从伞形花内酯衍生化为7-去甲基软木花椒素、紫花前胡苷元和6′-O-(反式阿魏酰基)-紫花前胡苷的NMR信号变化规律以及糖残基NMR信号归属方法进行了讨论和总结.     

Applications of DOSY NMR in the Chemical IndustryApplications of DOSY NMR in the Chemical Industry

DOSY(diffusion ordered spectroscopy)NMR is a technique that separates NMR signals of different species according to their diffusion coefficients.It is a powerful technique to provide solid characterization evidence for various applications in the chemical industry.Encapsulation and functional polymer grafting are two important capabilities in the chemical industry for new product development with challenging characterization requirements.Model systems of encapsulation and grafted polymer were studied and the characterization methods were set up by DOSY NMR.     

Ultra-low field NMR measurements of liquids and gases with short relaxation times

Interest in nuclear magnetic resonance measurements at ultra-low magnetic fields (ULF, approximately microT fields) has been motivated by various benefits and novel applications including narrow NMR peak-width, negligible susceptibility artifacts, imaging of samples inside metal containers, and possibility of directly imaging neuronal currents. ULF NMR/MRI is also compatible with simultaneous measurements of biomagnetic signals. However the most widely used technique in ULF NMR-prepolarization at high field and measurement at lower field-results in large transient signals which distort the free induction decay signal. This is especially severe for the measurement of signals from samples and materials with short T1 time. We have devised an approach that largely cancels the transient signals. The technique was successfully used to measure NMR signals from liquids and gases with T1 in the range 1-4 ms.     

超强磁场中核磁共振信号与屏蔽效应的理论研究

研究了超强磁场对于核磁共振样品中双原子分子中电子系统的哈密顿量的影响,并且给出了磁共振信号中由于外磁场与氢原子电子系统相互作用所产生的含有B02的修正项.基于核磁共振原理,获得了利用氢的NMR谱对超强磁场进行精确测量的理论依据,推导出了一种基于核磁共振技术的超强磁场测量公式,从而在理论上证明了对超强磁场进行精确测量是可行的.     

吲哚衍生物NMR数据归属及其溶剂效应研究

吲哚及其衍生物具有独特的生理活性,该文主要应用1D NMR 和2D NMR技术(COSY, HSQC, HMBC, NOESY)对合成的吲哚衍生物的¹H NMR、¹³C NMR谱信号进行了全归属. 用变温NMR研究了N-叔丁氧羰基吲哚（化合物m）中C-N键的旋转受阻对氢谱和碳谱的影响,计算了融合温度下C-N键旋转速率为175 Hz,此温度下活化自由能为12 kcal/mol. 研究了化合物m的溶剂效应,发现在低极性溶剂中的C-N键的旋转阻力大于极性溶剂.     

己二酮糖硝基甲烷加合产物的结构确定

立体选择性地合成了1, 2∶4, 5-二-O-异亚丙基-3-C-硝基甲基-β-D-核-己-2-吡喃酮糖，确证了其绝对构型. 并用gCOSY、gHSQC、gHMBC、ROESY等2D NMR技术对它的¹H和¹³C NMR谱峰进行了全归属.     

基于过抽样Gabor变换的核磁共振FID信号增强算法

基于作者先前提出的过抽样实值离散Gabor变换,本文提出了一有效的算法用于核磁共振自由感应衰减（NMR FID）信号的减噪. 由于NMR FID信号在时域中是一短暂的振荡衰减信号,使得变换后的NMR FID信号能量在时频域中集中在少数变换系数上,而噪声则遍布在整个变换系数上,因此通过对变换系数幅度进行阈值限制方法可达到明显地增强NMR FID信号的目的. 文中在理论和模拟实验上分析表明,过抽样Gabor变换比临界抽样Gabor变换更适宜于NMR FID信号的减噪,因为在过抽样条件下比在临界抽样条件下的综合窗及其对应的分析窗,无论是在时域中还是在频域中都可具有更好的局域分布集中性,同时,Gabor变换在过抽样条件下也比在临界抽样条件下具有更高的时频精度.     

High-resolution NMR with resistive and hybrid magnets: deconvolution using a field-fluctuation signal

A method for compensating effect of field fluctuation is examined to attain high-resolution NMR spectra with resistive and hybrid magnets. In this method, time dependence of electromotive force induced for a pickup coil attached near a sample is measured synchronously with acquisition of NMR. Observed voltage across the pickup coil is converted to field fluctuation data, which is used to deconvolute NMR signals. The feasibility of the method is studied by (79)Br MAS NMR of KBr under a 30T magnetic field of a hybrid magnet. Twenty single-scan NMR signals were accumulated after the manipulation, resulting in a high-resolution NMR spectrum.     

Enhancement of SQUID-detected NMR signals with hyperpolarized liquid 129Xe in a 1 microT magnetic field

We report an enhancement of proton NMR signals by a factor of 10(6) by cross polarization with hyperpolarized liquid 129Xe in an ultralow magnetic field of 1 microT. The NMR signals from cyclopentane, acetone, and methanol are detected using a commercial high-T(c) SQUID magnetometer with a signal-to-noise ratio of up to 1000 from a single 90 degrees tipping pulse. This technique allows a wide range of low-field NMR measurements and is promising for the detection of intermolecular scalar spin-spin couplings. Scalar intermolecular couplings can produce a shift of the average NMR frequency in a hyperpolarized sample even in the presence of rapid chemical exchange.     

吉士脱酮的1H及13C NMR研究

Gestodene是避孕药物18甲基炔诺酮的衍生物,动物实验表明它的孕激素活性为18甲基炔诺酮的3~5倍.本文采用各种2D NMR技术,包括:¹H-¹H COSY,¹H-¹³C COSY和HMBC等,归属了它的¹H和¹³C的谱线,并得到了有关质子间的偶合常数.     

吴茱萸内酯的NMR研究

从吴茱萸Evodia Rutaecarpa (Juss.) Benth.中分离得到并鉴定了化合物吴茱萸内酯, 我们应用二维核磁技术首次对化合物吴茱萸内酯的核磁信号进行了准确归属, 并纠正了文献中部分氢信号归属的错误。     

Selective detection of hyperpolarized NMR signals derived from para-hydrogen using the Only Para-hydrogen SpectroscopY (OPSY) approach

A new family of NMR pulse sequences is reported for the recording of para-hydrogen enhanced NMR spectra. This Only Para-hydrogen SpectroscopY (OPSY) approach uses coherence selection to separate hyperpolarized signals from those of fully relaxed and thermally equilibrated protons. Sequence design, performance, practical aspects and applicability to other hyperpolarization techniques are discussed.     

用2D NMR研究凯林内酯酰化物的相对构型

用2D NMR对钙离子拮抗活性成分Pd-Ia的结构进行了深入研究,确切归属了全部碳氢信号,纠正了文献中甲基信号归属的错误。并以此为参考,指定了这类化合物母核碳信号的归属,从而修正了文献中用角甲基碳化学位移值之差决定其C-3'和C-4'相对构型的有关内容,发现在顺式构型中,连接在C-2'的两个角甲基碳化学位移差值大于或等于2ppm,而在反式构型中,这个差值小于或等于2ppm,且△(δC-3'trans-δC-3'cis)>1ppm。     

Application of the Raman heterodyne technique for the detection of EPR and ENDOR

Raman heterodyne detection is a coherent optical-RF double resonance technique where the optical and RF fields induce coherence within a three level system and a resultant Raman field is measured using heterodyne detection. This approach has been used previously to detect NMR and more recently EPR. In this paper the parameters that affect the amplitude and signal to noise ratio of the Raman heterodyne signals are considered. The power levels in relation to the oscillator strength and dephasing times, the amplitude and spectrum of the laser frequency jitter in relation to the optical homogeneous linewidths and holeburning rates, and the sample properties such as absorption strength and optical quality, are all factors that affect the Raman signal. The presentation is focused on the Raman heterodyne detected EPR of the nitrogen-vacancy pair centre in diamond making comparisons with Raman heterodyne detected NMR signals obtained for rare earth ion systems. RF-RF double resonance studies, RF holeburning and ENDOR, which give information about the hyperfine levels are also reported for the nitrogen-vacancy centre. The resonance frequencies are in agreement with those predicted from the spin Hamiltonian. The factors affecting the lineshapes and relative intensities of the double resonance signals are discussed.     

Degradation of historical paper: nondestructive analysis by the NMR-MOUSE

The NMR-MOUSE is a mobile sensor for single-sided NMR inspection of organic materials which takes advantage of the principles of magnetic resonance and inside-out-NMR. Historical books dating from the 17th century were measured at different points by positioning the NMR-MOUSE on the paper. Different degrees of paper degradation can be discriminated from the regularized inverse Laplace transform of the envelope of the acquired echo signals. For the first time the degradation of historical paper was characterized entirely nondestructively by NMR. As a contribution to current preservation efforts, NMR shows great promise for future use in damage assessment of historical documents.