Temperature-induced Evolution of Micro-structure and Chain Dynamics in Thermoplastic Polyurethane with Low Hard Segment Content as Studied by In Situ Synchrotron SAXS and Time-Domain NMR Experiments

The microstructural evolution of a thermoplastic polyurethane(TPU)with low hard segment content has been monitored utilizing in situ real-time synchrotron small angle X-ray scattering(SAXS)and time-domain nuclear magnetic resonance(NMR)measurements.The TPU is composed of 23 wt% of[4,4-methylenediphenyl diisocyanate(MDI)]-[1,4-butanediol(BD)]chain segments,which form hard domains,as[polytetrahydrofuran(PTHF)]forming soft domains.The number and distribution of monomer units in hard blocks is determined by the successive self-nucleation and annealing thermal fractionation technique.In situ SAXS method reveals heating-induced increase in the spacing of hard and soft domains,while time-domain ^(1)H-NMR characterizes the changes in the phase composition and chain dynamics in these domains.A glassy fraction of short MDI-BD chain segments in hard domains passes through T_(g) above ambient temperature.At higher temperatures,MDI-BD nanocrystals start to melt.Sequence length distribution of MDI-BD chain segments causes a distribution in crystal sizes and wide melting temperature range.The melting is accompanied by the mixing of MDI-BD with PTHF segments in soft domains,and by increase in segmental mobility in these domains.Above 180℃,the TPU melt is homogeneous on the scale above nanometers according to SAXS data.

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.

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。

Time-domain dynamic constitutive model suitable for mucky soil site seismic response

Soil nonlinear behavior displays noticeable effects on the site seismic response.This study proposes a new functional expression of the skeleton curve to replace the hyperbolic skeleton curve.By integrating shear modulus and combining the dynamic skeleton curve and the damping degradation coefficient,the constitutive equation of the logarithmic dynamic skeleton can be obtained,which considers the damping effect in a soil dynamics problem.Based on the finite difference method and the multi-transmitting boundary condition,a 1D site seismic response analysis program called Soilresp1D has been developed herein and used to analyze the time-domain seismic response in three types of sites.At the same time,this study also provides numerical simulation results based on the hyperbolic constitutive model and the equivalent linear method.The results verify the rationality of the new soil dynamic constitutive model.It can analyze the mucky soil site nonlinear seismic response,reflecting the deformation characteristics and damping effect of the silty soil.The hysteresis loop area is more extensive,and the residual strain is evident.

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.

Time-Domain Analysis of Body Freedom Flutter Based on 6DOF Equation

The reduced weight and improved efficiency of modern aeronautical structures result in a decreasing separation of frequency ranges of rigid and elastic modes.Particularly,a high-aspect-ratio flexible flying wing is prone to body freedomflutter(BFF),which is a result of coupling of the rigid body short-periodmodewith 1st wing bendingmode.Accurate prediction of the BFF characteristics is helpful to reflect the attitude changes of the vehicle intuitively and design the active flutter suppression control law.Instead of using the rigid body mode,this work simulates the rigid bodymotion of the model by using the six-degree-of-freedom(6DOF)equation.A dynamicmesh generation strategy particularly suitable for BFF simulation of free flying aircraft is developed.An accurate Computational Fluid Dynamics/Computational Structural Dynamics/six-degree-of-freedom equation(CFD/CSD/6DOF)-based BFF prediction method is proposed.Firstly,the time-domain CFD/CSD method is used to calculate the static equilibrium state of the model.Based on this state,the CFD/CSD/6DOF equation is solved in time domain to evaluate the structural response of themodel.Then combinedwith the variable stiffnessmethod,the critical flutter point of the model is obtained.This method is applied to the BFF calculation of a flyingwing model.The calculation results of the BFF characteristics of the model agree well with those fromthe modalmethod andNastran software.Finally,the method is used to analyze the influence factors of BFF.The analysis results show that the flutter speed can be improved by either releasing plunge constraint or moving the center ofmass forward or increasing the pitch inertia.

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。

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。

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.