Laplace NMR谱图重建——从经典正则化到深度学习

拉普拉斯核磁共振(Laplace NMR)可以提供待测样品的扩散系数或弛豫时间等物理参数信息,是用于研究分子化学结构、动力学和相互作用的强大工具.Laplace NMR的适用性很大程度上取决于拉普拉斯逆变换相关的信号处理算法的性能.在本文中,我们首先讨论了Laplace NMR谱图重建问题的不适定性,接着回顾了经典的基于正则化约束的重建算法,并介绍了目前前沿的深度学习算法在处理Laplace反演问题方面的应用,最后总结了这些算法的优缺点,并对Laplace NMR信号处理方法未来改进方向进行了展望.

Experimental study on failure characteristics of single-sided unloading rock under different intermediate principal stress conditions

Investigation of unloading rock failure under differentσ_(2)facilitates the control mechanism of excavation surrounding rock.This study focused on single-sided unloading tests of granite specimens under true triaxial conditions.The strength and failure characteristics were studied with micro-camera and acoustic emission(AE)monitoring.Furthermore,the choice of test path and the effect ofσ_(2)on fracture of unloading rock were discussed.Results show that the increasedσ_(2)can strengthen the stability of single-sided unloading rock.After unloading,the rock’s free surface underwent five phases,namely,inoculation,particle ejection,buckling rupture,stable failure,and unstable rockburst phases.Moreover,atσ_(2)≤30 MPa,the b value shows the following variation tendency:rising,dropping,significant fluctuation,and dropping,with dispersed damages signal.Atσ_(2)≥40 MPa,the tendency shows:a rise,a decrease,a slight fluctuation,and final drop,with concentrated damages signal.After unloading,AE energy is mainly concentrated in the micro-energy range.With the increasedσ_(2),the micro-energy ratio rises.In contrast,low,medium and large energy ratios drop gradually.The increased tensile fractures and decreased shear fractures indicate that the failure mode of the unloading rock gradually changes from tensile-shear mode to tensile-split one.The fractional dimension of the rock fragments first increases and then decreases with an inflection point at 20 MPa.The distribution of SIF on the planes changes asσ_(2)increases,resulting in strengthening and then weakening of the rock bearing capacity.

基于小型化原子磁力计的零场NMR波谱仪搭建与测试

常规高场NMR波谱仪依托超导技术,其体积大、维护成本高,且存在样本磁化率不均匀导致的谱线展宽现象,零场或近零场NMR技术则可实现有效互补.本文自主搭建了一套基于小型原子磁力计的可移动零场NMR波谱仪,采用以多功能采集卡(National Instruments PCIe-6353)为核心的集成控制系统,仪器主磁场强度小于1nT,可实现高分辨率的J-耦合谱采集.为实现对自旋体系的有效操控,利用样品绝热初态的单脉冲激发实现对三轴脉冲线圈的精确标定.在此基础上,使用改进的组合脉冲序列实现了在^(13)C-^(1)H异核体系下的单自旋选择性操控,验证了零场NMR波谱仪的有效性.

舒肝宁注射液的^(1)H-NMR指纹图谱分析

目的对舒肝宁注射液的^(1)H-NMR指纹图谱进行分析,为其质量控制标准技术升级提供参考依据。方法使用Noesygppr1d脉冲序列[recycle delay(RD)-90°-t 1-90°-t_(m)-90°-ACQ]采集1H-NMR谱图,质子共振频率为600.13 MHz,实验温度为298 K,通过方法学考察验证分析方法可靠性,采用相关系数法和夹角余弦法评价不同批次舒肝宁注射液样品的相似度。结果对舒肝宁注射液的^(1)H-NMR指纹图谱进行分析,共鉴定出88种化学成分,且不同批次的舒肝宁注射液具有较高的相似度。结论建立了一种基于^(1)H-NMR的舒肝宁注射液质量控制方法,可为舒肝宁注射液技术升级提供参考依据。

Structure and ion transport properties of organic ionic compounds revealed by NMR

Organic ionic plastic crystals(OIPCs)are emerging as an important material family for solid-state electrolytes and many other applications.They have significant advantages over conventional electrolyte materials,such as high ionic conductivity,non-flammability,and plasticity.Various nuclear magnetic resonance(NMR)spectroscopy techniques including solid-state NMR,pulsed-field gradient(PFG)NMR,and magnetic resonance imaging(MRI)etc.,provide us a versatile toolkit to understand the fundamental level structures,molecular dynamics,and ionic interactions in these materials.This article reviews the commonly used NMR methods including solid-and solution-state NMR,PFG-NMR,dynamic nuclear polarization(DNP)and the application of these methods in revealing the microscopic level structures and ion-transport mechanisms in OIPC materials.

A study on the temperature sensitivity of NMR porosity in porous media based on the intensity of magnetization Dedicated to the special issue “Magnetic Resonance in Porous Media”

The measurement of nuclear magnetic resonance(NMR)porosity is affected by temperature.Without considering the impact of NMR logging tools,this phenomenon is mainly caused by variations in magnetization intensity of the measured system due to temperature fluctuations and difference between the temperature of the porous medium and calibration sample.In this study,the effect of temperature was explained based on the thermodynamic theory,and the rules of NMR porosity responses to temperature changes were identified through core physics experiments.In addition,a method for correcting the influence of temperature on NMR porosity measurement was proposed,and the possible factors that may affect its application were also discussed.

Matrix Assisted Laser Desorption Ionization Time of Flight(MALDI-TOF)-Mass Spectrometry and^(13)C-NMR-Identified New Compounds in Paraberlinia bifoliolata(Ekop-Beli)Bark Tannins

Extracts of plant origin,particularly tannins,are attracting growing interest for the sustainable development of materials in the industrial sector.The discovery of new tannins is therefore necessary.The aim of this work was to contribute to the understanding of the properties of Paraberlinia bifoliolata tannin by Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy MALDI-TOF/MS and Carbon 13 Nuclear Magnetic Resonance(13C NMR).The chemical composition of tannin extracted from Paraberlinia bifoliolata bark was determined,as was the mechanical strength of the resin hardened with Acacia nilotica extracts.Yield by successive water extraction was 35%.MALDI-TOF/MS analysis revealed the presence of three new compounds in this tannin,previously unknown in this family of extracts.These are 3-hydroxyproline acid,N-methyl-4-hydroxypipecolic acid and N-methyl-5-dihydroxypipecolic acid.The identification of the above molecules means that this tannin can be used for industrial applications,as a resin in the manufacture of particleboard and in the formulation of green corrosion inhibitors.This information is reinforced by 13C NMR spectrometry,which indicates the presence of several polyflavonoid units,confirming the condensed nature of the tannin.Thermomechanical analysis of the resin formed by the purified tannin of Paraberlinia bifoliolata to which a vegetal biohardener has been added provided a Modulus of Elasticity(MOE)value of 4840 MPa at 150℃,confirming its possible use as a binder resin in the manufacture of wood panels as well as for the formulation of a corrosion inhibitor.

HdeA在细菌外膜囊泡环境下的原位NMR研究

HdeA是一种定位于细菌周质的分子伴侣,在维持蛋白质稳态中起着重要的作用.以往对HdeA的研究主要是在体外条件下进行,限制了人们对HdeA在天然环境下发挥作用机制的理解.细菌外膜囊泡是细菌自发分泌到胞外环境的外膜囊泡,其内容物与周质环境相似.本研究将HdeA富集到细菌外膜囊泡(OMVs)中,通过核磁共振波谱研究HdeA在OMVs中的构象变化.结果表明,HdeA在其原位环境中表现出酸依赖性的构象变化.在低pH条件下HdeA主要通过S15、W16、T17、S27、T32、E36、G54、T57、C66、Q71、F74及D83等残基启动其分子伴侣功能.此外本研究也为原位研究其它周质分子伴侣的功能提供了新方法.

Experimental aspects of ^(14)N overtone RESPDOR solid-state NMR spectroscopy under MAS beyond 60 kHz

Nitrogen-14(^(14)N)overtone(OT)spectroscopy under fast magic angle spinning(MAS)conditions(>60 kHz)has emerged as a powerful technique for observing correlations and distances between ^(14)N and ^(1)H,owing to the absence of the first-order quadrupolar broadenings.In addition,^(14)N^(OT) allows selective manipulation of ^(14)N nuclei for each site.Despite extensive theoretical and experimental studies,the spin dynamics of ^(14)N^(OT) remains under debate.In this study,we conducted experimental investigations to assess the spin dynamics of ^(14)N^(OT) using the rotational-echo saturation-pulse double-resonance(RESPDOR)sequence,which monitors population transfer induced by a^(14)N^(OT) pulse.The ^(14)N^(OT) spin dynamics is well represented by a model of a two-energy-level system.Unlike spin-1/2,the maximum excitation efficiency of ^(14)N^(OT) coherences of powdered solids,denoted by p,depends on the radiofrequency field(rf-field)strength due to orientation dependence of effective nutation fields even when pulse lengths are optimized.It is also found that the p factor,contributing to the ^(14)N^(OT) spin dynamics,is nearly independent of the B0 field.Consequently,the filtering efficiency of RESPDOR experiments exhibits negligible dependence on B0 when the ^(14)N^(OT) pulse length is optimized.The study also identifies the optimal experimental conditions for ^(14)N^(OT)/^(1)H RESPDOR correlation experiments.

B21C7与DB21C7分子构象溶剂效应NMR研究

通过^(1)H NMR核磁波谱学方法研究了芳香冠醚B21C7和DB21C7构象的溶剂效应。结果表明,CD_(3)CN分子与两种芳香冠醚的苯环取代基存在CH^(+)…N相互作用,CD_(3)OD与冠醚环存在OH^(+)…O相互作用。由于不同溶剂分子的作用引起苯环取代基与冠醚环的相对位置改变,冠醚环在苯环取代基的屏蔽区域和去屏蔽区域间变化,产生了相应化学位移差异。

BPC6/t-BAMBP协同萃取铯机理的NMR研究

采用^(1)HNMR和^(133)CsNMR研究了BPC6和t-BAMBP协同萃取Cs^(+)的机理。结果表明,在氘代氯仿中,BPC6与Cs^(+)可形成配合物,t-BAMBP与Cs^(+)不发生配位。在BPC6/t-BAMBP与Cs^(+)进行协同萃取时,Cs^(+)首先通过与BPC6进行配位进入油相,随后由BPC6·Cs^(+)配合物向相互作用更强的t-BAMBP·Cs^(+)进行转移,且随着t-BAMBP加入量的增加,t-BAMBP的配位数增加,形成更稳定的t-BAMBP·Cs^(+)配合物。

基于NMR的粮仓多场耦合图形化探测系统研究

粮仓是一个复杂的生态系统,其内部生物、非生物以及环境的耦合关系复杂,且只能对温度等少数参数进行探测,粮仓生态近乎“黑箱”。为了便于研究粮仓复杂的耦合关系、核实其中的基本规律,研究提出了一种基于核磁共振(Nuclear Magnetic Resonance,NMR)的粮仓多场耦合图形化探测系统。该系统由核磁共振成像分析仪、粮仓模拟装置和数据采集处理系统三部分组成,可同时实现粮堆温度、湿度和水分三参数的真实精准探测,并能通过配套云图生成软件直观、形象地呈现粮堆温度场、湿度场和水分场分布云图。该系统首次将低场核磁共振成像技术应用于粮堆多场耦合作用研究领域,为探明粮仓生态复杂的耦合关系,进一步证实相关理论研究结论提供了一种新的技术手段。该系统的提出有助于深化行业正在致力发展的粮堆多场耦合及生物场理论。

Low-field, high-gradient NMR shows diffusion contrast consistent with localization or motional averaging of water near surfaces

Nuclear magnetic resonance(NMR)measurements of water diffusion have been extensively used to probe microstructure in porous materials,such as biological tissue,however primarily using pulsed gradient spin echo(PGSE)methods.Low-field single-sided NMR systems have built-in static gradients(SG)much stronger than typical PGSE maximum gradient strengths,which allows for the signal attenuation at extremely high b-values to be explored.Here,we perform SG spin echo(SGSE)and SG stimulated echo(SGSTE)diffusion measurements on biological cells,tissues,and gels.Measurements on fixed and live neonatal mouse spinal cord,lobster ventral nerve cord,and starved yeast cells all show multiexponential signal attenuation on a scale of b with significant signal fractions observed at b×Do>1 with b as high as 400 ms/um2.These persistent signal fractions trend with surface-to-volume ratios for these systems,as expected from porous media theory.An exception found for the case of fixed vs.live spinal cords was attributed to faster exchange or permeability in live spinal cords than in fixed spinal cords on the millisecond timescale.Data suggests the existence of multiple exchange processes in neural tissue,which may be relevant to the modeling of time-dependent diffusion in gray matter.The observed multi-exponential attenuation is from protons on water and not macromolecules because it remains proportional to the normalized signal when a specimen is washed with D20.The signal that persists to b×Do>1 is also drastically reduced after delipidation,indicating that it originates from lipid membranes that restrict water diffusion.The multiexponential or stretched exponential character of the signal attenuation at b×Do>1 appears mono-exponential when viewed on a scale of(b×Do)/3,suggesting it may originate from localization or motional averaging of water near membranes on sub-micron length scales.To try to disambiguate these two contributions,signal attenuation curves were compared at varying temperatures.While the curves align when normalizing them using the localization length scale,they separate on a motional averaging length scale.This supports localization as the source of non-Gaussian displacements,but this interpretation is still provisional due to the possible confounds of heterogeneity,exchange,and relaxation.Measurements on two types of gel phantoms designed to mimic extracellular matrix.one with charged functional groups synthesized from polyacrylic acid(PAC)and another with uncharged functional groups synthesized from polyacrylamide(PAM),both exhibit signal at b×Do>1,potentially due to water interacting with macromolecules.These preliminary finding motivate future research into contrast and attenuation mechanisms in tissue with low-field,high-gradient NMR。

Characteristics Investigation of Single-Sided Ironless PMLSM Based on Halbach Array for Medium-Speed Maglev Train

This paper investigates characteristics of ironless permanent magnet linear synchronous motor(PMLSM)based on Halbach array used for medium-speed(200km/h)maglev train.Long primary ironless coil is laid in the middle of track and the Halbach permanent magnet array is attached to the bottom of each bogie as a source of traction,U-shape electromagnets at the both sides of the train for levitation.Two dimensional analytical model of single-sided ironless PMLSM based on Halbach array is established,using linear overlay method,the no-load air gap magnetic field is calculated firstly,winding current density distribution is obtained for calculating the characteristics of thrust and normal force against power angle,including force characteristics with equal and unequal pole pitch,the influence of steel sleeper,etc.Besides,the mathematical model for this type motor is built by 3D finite element method,the traction characteristics of medium-speed maglev under maximum speed 200km/h are calculated.The characteristics of this type motor are satisfactory owing to there is no detent force in the motor and thrust force reach maximum meanwhile normal force can be eliminated.Calculation method is verified by comparing finite element results,experimental result on a 200kW type motor further validates the accuracy of calculation and some important conclusions are obtained.

基于^(1)H-NMR代谢组学的绝经期综合征血清代谢标志物研究

目的:基于核磁共振氢谱(1H-NMR)代谢组学分析,结合模式识别寻找女性进入围绝经期以及罹患绝经综合征疾病的特异性血清代谢标志物。方法:选择80例绝经综合征患者、40例同龄围绝经期和40例育龄期健康女性为对照,利用^(1)H-NMR技术进行血清样本检测,运用PLS-DA、OPLS-DA分析对体内代谢产物进行比较研究。结果:绝经综合征患者与围绝经期、育龄期健康女性三组之间具有统计学差异的血清代谢物包括:乳酸、醋酸、谷氨酸、丙酮酸、肌酸、氧化三甲胺(TMAO)、N-乙酰糖蛋白、丙氨酸和胆碱。其中,进入围绝经期的健康女性,较育龄期有乳酸、醋酸等6个血清代谢产物显著下调,但尚不具备诊断价值。与围绝经期健康女性比较,绝经综合征患者丙氨酸、TMAO上调,谷氨酸、丙酮酸、N-乙酰糖蛋白和胆碱下调趋势显著,且谷氨酸、丙酮酸、N-乙酰糖蛋白和胆碱的变化趋势具有一定的诊断价值。结论:围绝经期是女性从生殖期过渡到老年期的一个特殊生理阶段,健康女性虽然较育龄期存在一定特征性代谢物的变化,但尚不具有诊断价值;但绝经综合征患者在疾病状态下所呈现的差异性代谢标志物,具有一定的诊断价值,可以为临床宏微观结合诊断绝经综合征提供一定的客观依据。

Adaptive current compensation with nonlinear disturbance observer for single-sided linear induction motor considering dynamic eddy-effect

An adaptive current compensation control for a single-sided linear induction motor(SLIM) with nonlinear disturbance observer was developed. First, to maintain t-axis secondary component flux constant with consideration of the specially dynamic eddy-effect(DEE) of the SLIM, a instantaneously tracing compensation of m-axis current component was analyzed. Second,adaptive current compensation based on Taylor-discretization algorithm was proposed. Third, an effective kind of nonlinear disturbance observer(NDOB) was employed to estimate and compensate the undesired load vibrations, then the robustness of the control system could be guaranteed. Experimental verification of the feasibility of the proposed method for an SLIM control system was performed, and it showed that the proposed adaptive compensation scheme with NDOB could significantly promote speed dynamical response and minimize speed ripple under the conditions of external load coupled vibrations and unavoidable feedback control variables measured errors, i.e., current and speed.

用遗传算法优化灵敏度增强的定量^(13)C NMR实验

定量核磁共振(qNMR)是NMR分析的重要组成部分,在组分分析、化合物结构鉴定等方面发挥着重要作用.碳原子组成了有机物的框架,而^(13)C NMR具有化学位移分布范围宽、谱峰窄、可宽带去耦等优点,因此^(13)C NMR在有机物分析中具有独特优势.但^(13)C核天然丰度低、旋磁比小、纵向弛豫时间较长,阻碍了定量^(13)C NMR的更广泛应用.在此前的工作中,我们提出了Q-DEPT^(+)脉冲序列,设计了读脉冲翻转角和极化转移时间双重循环,使得CH、CH_(2)、CH_(3)三种碳核在较宽的^(1)J_(CH)范围内获得均匀的灵敏度增强,并可用于定量^(13)C NMR实验.在本文中,我们利用遗传算法进一步优化了Q-DEPT^(+)实验的极化转移时间和读取脉冲的脉宽,并将^(13)C通道的180°硬脉冲改为对频偏效应有补偿作用的G5组合脉冲,优化后的序列称为Q-DEPT^(++).对胆固醇乙酸酯的氘代氯仿溶液分别使用常规反门控去耦(zgig)、Q-DEPT^(+)和Q-DEPT^(++)脉冲序列进行了定量实验,并将三者的定量准确性和灵敏度进行了对比.结果显示Q-DEPT^(++)脉冲序列在定量准确性和灵敏度两方面均有明显提高.

Further discussion of CO_(2) huff-n-puff mechanisms in tight oil reservoirs based on NMR monitored fluids spatial distributions

Due to the poor physical properties of tight reservoirs,CO_(2) huff-n-puff(HNP)is considered a potential enhanced oil recovery(EOR)method after primary depletion.Optimization plays a critical role in the effective implementation of CO_(2) huff-n-puff.But the optimization requires a good understanding of the EOR mechanisms.In this work,the spatial distribution of oil saturation under different experimental conditions was analyzed by the NMR method to further discuss the HNP mechanisms.According to the variation of 1D frequency signal amplitude,we divided the core into the hardly movable area and movable area,the region with the obvious signal decline was defined as the movable area,and the hardly movable area was the region with limited signal decline.Based on that the recovery characteristics of different scenarios were evaluated.Firstly,the necessity of the soaking stage was studied,where three scenarios with different soaking times were carried out.Secondly,the injection pressure was adjusted to investigate the effect of the pressure gradient.The T_(2) spectra show that soaking has significantly improved the production of crude oil in small pores,and higher oil recovery in a single cycle is observed,but it is lower when the elapsed time(total operation time)is the same.31.03% of oil can be recovered after 3 cycles HNP,which increases to 33.8% and 37.06% for the 4 cycles and 6 cycles cases.As the pressure gradient increases,more oil is removed out of the matrix,and the oil in the deep part of the reservoir can be effectively recovered.During the CO_(2) huff-n-puff process,the oil distributions are similar to the solution gas drive,the residual oil is distributed at the close end of the core and the range that the oil can be efficiently recovered is limited.

^(1)H NMR ERETIC2结合多变量分析法定量分析生麻黄与蜜炙麻黄差异

目的利用^(1)H NMR ERETIC2定量方法对14个批次的生麻黄和6个批次的蜜炙麻黄进行定性和定量分析,并筛选出差异成分,为麻黄质量标准的提升提供科学依据。方法以特征性成分麻黄碱信号强度为优选指标,对提取方法和复溶溶剂进行优化;建立基于^(1)H NMR ERETIC2方法的生麻黄和蜜炙麻黄特征成分绝对定量方法;采用^(1)H NMR谱图结合多变量分析法寻找不同批次生麻黄和蜜炙麻黄潜在的差异成分。结果最佳样品前处理方法为以甲醇为溶剂,物料比为1∶5(g/mL),超声提取5 min,氘代甲醇作为复溶溶剂。^(1)H NMR图谱共鉴定了11个化学成分,其中8个共有成分被选作定量指标。定量结果显示,生麻黄和蜜炙麻黄中异亮氨酸、蔗糖、葡萄糖和丙氨酸的含量差异有统计学意义(P<0.05);多元统计分析结果也表明,生麻黄和蜜炙麻黄之间存在明显差异,葡萄糖和蔗糖是主要的差异贡献成分,且在蜜炙麻黄中含量较高,而蜜炙麻黄中丙氨酸和异亮氨酸的含量则明显下降(P<0.05)。结论本研究建立的^(1)H NMR ERETIC2定量方法结合多元统计分析,可筛选出生麻黄和蜜炙麻黄的差异成分,能够有效区分生麻黄和蜜炙麻黄,为后续麻黄质量标准的完善提供了科学依据。

A new NMR-data-based method for predicting petrophysical properties of tight sandstone reservoirs

Evaluating the permeability and irreducible water saturation of tight sandstone reservoirs is challenging.This study uses distribution functions to fit measured NMR T_(2)distributions of tight sandstone reservoirs and extract parameters for characterizing pore size distribution.These parameters are then used to establish prediction models for permeability and irreducible water saturation of reservoirs.Results of comparing the fit of the T_(2)distributions by the Gauss and Weibull distribution functions show that the fitting accuracy with the Weibull distribution function is higher.The physical meaning of the statistical parameters of the Weibull distribution function is defined to establish nonlinear prediction models of permeability and irreducible water saturation using the radial basis function(RBF)method.Correlation coefficients between the predicted values by the established models and the measured values of the tight sandstone core samples are 0.944 for permeability and 0.851 for irreducible water saturation,which highlight the effectiveness of the prediction models.