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.

应用于太赫兹波驱动的DNP-NMR传输线

太赫兹波驱动的动态核极化增强核磁共振波谱系统可大幅提高信号灵敏度和缩短检测时间。该系统需采用传输线在驱动源回旋管与谱仪之间进行太赫兹波传输。本文针对400 MHz增强核磁共振系统设计了由准光模式变换器和波纹波导组成的太赫兹传输线,并进行了相关实验测试,测试结果表明准光模式变换器可将263 GHz回旋管TE 03模式转换成准高斯波束,其高斯成份为97%,整个传输线最终输出波束的高斯成份为96.3%。

烟草果胶和纤维素含量^(13)C MultiCP/MAS NMR同时测量

果胶和纤维素是烟草细胞壁的重要组成成分,其含量对烟草品质与安全性产生重要影响。传统分析方法难以实现果胶和纤维素的同时定量。本文在优化核磁共振波谱序列条件的基础上,采用固体^(13)C多重交叉极化/魔角旋转核磁共振波谱分析技术(^(13)C MultiCP/MAS NMR)建立了烟草果胶和纤维素含量的同时测量新方法。方法以聚半乳糖醛酸和微晶纤维素为标准物质,以3-(三甲基甲硅烷基)丙酸-d4钠盐(TMSP)做为内标物质,分别建立内标法标准曲线,相关系数R2为0.999 0和0.998 2。果胶测量的检出限和定量限分别为0.38和1.28 mg·g^(–1),精密度(RSD,n=5)小于3.05%。纤维素测量的检出限和定量限为1.01和3.32 mg·g^(–1),精密度(RSD,n=5)小于2.74%。应用本方法测量烟梗、烟草薄片和烟叶等不同类型样品中的果胶和纤维素含量,并对比烟草行业标准方法的测量结果,果胶含量的相对误差在-0.95%至4.51%之间,纤维素含量的相对误差在0.77%至2.46%之间。表明^(13)C MultiCP/MAS NMR方法快速,准确,适合批量样品的分析测量,为果胶和纤维素等细胞壁类大分子的同时定量分析提供重要技术支持。

NMR、GPC和MALDI-TOF应用于聚乙二醇单甲醚的教学实验

将核磁共振(NMR)、凝胶渗透色谱(GPC)和基质辅助激光解吸/电离飞行时间质谱(MALDI-TOF)三种高级分析技术整合到本科《高分子材料研究方法》课程的实验教学中。通过分析聚乙二醇单甲醚样品,学生深入学习了高分子结构和分子量的表征方法,熟悉了这三种仪器的操作和原理。本实验显著提升了课程内容的深度和广度,激发了学生的学习兴趣,并且增强了学生的实践操作能力和创新思维。综合应用这些分析技术,使学生在高分子材料的研究中获得了更全面的理解和技能的提升。

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。

Postmortem ^(7)Li NMR analysis for assessing the reversibility of lithium metal electrodes in lithium metal batteries

Despite the proficiency of lithium(Li)-7 NMR spectroscopy in delineating the physical and chemical states of Li metal electrodes,challenges in specimen preparation and interpretation impede its progress.In this study,we conducted a comprehensive postmortem analysis utilizing ^(7)Li NMR,employing a stan-dard magic angle spinning probe to examine protective-layer coated Li metal electrodes and LiAg alloy electrodes against bare Li metal electrodes within Li metal batteries(LMBs).Our investigation explores the effects of sample burrs,alignment with the magnetic field,the existence of liquid electrolytes,and precycling on the ^(7)Li NMR signals.Through contrasting NMR spectra before and after cycling,we identi-fied alterations in Li^(0) and Li^(+) signals attributable to the degradation of the Li metal electrode.Our NMR analyses decisively demonstrate the efficacy of the protective layer in mitigating dendrite and solid elec-trolyte interphase formation.Moreover,we noted that Li*ions near the Li metal surface exhibit magnetic susceptibility anisotropy,revealing a novel approach to studying diamagnetic species on Li metal elec-trodes in LMBs.This study provides valuable insights and practical guidelines for characterizing distinct lithium states within LMBs.

Operando NMR methods for studying electrocatalysis

The combination of electrochemical measurements with spectroscopic characterizations provides valuable insights into reaction mechanisms.Nuclear magnetic resonance(NMR)spectroscopy,as a powerful technique due to its atomic specificity and versatility in studying gas,liquid,and solid,allows the study of electrolyte solution,catalyst and catalyst-adsorbate interfaces.When applied in operando,NMR can offer molecular-level insights into various electrochemical processes.Operando NMR has been applied extensively in battery research,but relatively underexplored for electrocatalysis in the past two decades.In this mini review,we first introduce the operando electrochemical NMR setups,categorized by different probe designs.Then we review the applications of operando NMR for monitoring the electrolyte solution and the catalyst-adsorbate interface.Considering the high environmental impact of electrochemical conversion of CO_(2)into value-added products,we zoom in to the use of operando NMR in studying electrochemical CO_(2)reduction.Finally,we provide our perspective on further developing and applying operando NMR methods for understanding the complex reaction network of Cu-catalyzed electrochemical CO_(2)reduction.

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.

高速魔角旋转下基于组合π脉冲的射频驱动重耦同核双量子固体NMR相关实验研究

该文提出了一种改进固体核磁共振(NMR)实验中射频驱动重耦(RFDR)序列的方法。以组合π脉冲替代传统的单一矩形π脉冲作为RFDR序列的基本构成单元,并选择若干个适用于高速魔角旋转条件的组合π脉冲,在RFDR双量子实验中进行全面研究,通过数值模拟分析了影响RFDR双量子实验性能的两个关键因素——共振偏置和射频场不均匀性,并根据模拟结果确定了性能最优的组合π脉冲。结合六氟硅酸钠和L-组氨酸的一维和二维^(19)F或1H固体NMR实验,验证了在高速魔角旋转条件下选择适当的组合π脉冲的RFDR序列的优势。该方法不仅能确保较高的同核双量子激发效率,还能提高激发带宽,并且对射频场不均匀性更加不敏感。稳定高效的RFDR同核双量子相关实验为采用固体NMR分析强自旋耦合体系的核间相互作用提供了重要的技术支持。

Solid-state NMR study on sodium intercalation at low voltage window for Na_(3)V_(2)(PO_(4))_(3) as an anode

In-situ XRD,^(31)P NMR and ^(23)Na NMR were used to analyze the interaction behavior of Na_(3)V_(2)(PO_(4))_(3) at low voltage,and then a new intercalation model was proposed.During the transition from Na_(3)V_(2)(PO_(4))_(3) to Na_(4)V_(2)(PO_(4))_(3),Na ions insert into M1,M2 and M3 sites simultaneously.Afterwards,during the transition of Na_(4)V_(2)(PO_(4))_(3)to Na_(5)V_(2)(PO_(4))_(3),Na ions mainly insert into M3 site.

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.

A review of ^(17)O isotopic labeling techniques for solid-state NMR structural studies of metal oxides in lithium-ion batteries

Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.

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。

ASSURE-NMR-HSQC实验检测保健食品中西地那非类物质

本研究通过使用灵敏度增强的带梯度形状脉冲进行异核单量子相干(HSQC)实验检测保健食品中违法添加的西地那非类物质。待测样品以甲醇溶解超声辅助提取,减压浓缩后以氘代DMSO溶解上机测试;利用Assure-NMR软件将得到的未知样品异核单量子相干(Heteronculear Single Quantum Coherence)谱图与已知西地那非类物质谱图进行模拟匹配。本方法检出限可以达到200μg·kg-1,能快速有效的对保健食品中西地那非类物质的违法添加侦察识别。该方法简便快捷,可以为食品安全监管部门提供一种新颖便捷的那非类物质监管稽查参考办法。