固体核磁共振技术在高分子表征研究中的应用

基于核自旋探针的核磁共振(NMR)波谱技术可以在非常宽广的时间和空间尺度上提供重要的微观结构和动力学信息.固体NMR已成为阐明高分子中化学键变化、链间相互作用、多尺度结构与动力学演化,及其与宏观物理化学性质关系的有力工具.本文从基础原理、实验方法与技巧、典型应用与研究进展等几方面进行简要综述.在基础原理部分介绍了化学位...     

固体核磁共振技术在固体酸催化剂表征及催化反应机理研究之应用进展

固体酸催化剂广泛应用于现代石油与化学工业中,其反应活性与其酸性密切相关.与传统的酸性表征方法(红外光谱、程序升温脱附、滴定等)相比,利用先进的探针分子技术、双共振和二维相关谱等核磁共振(NMR)技术可以获取固体催化剂酸种类、酸分布、酸浓度和酸强度等完整信息.同时,原位固体NMR实验可跟踪反应分子在催化剂活性中心吸附状态和转换的中间体物种,为揭示反应机理提供了最直接的实验证据.本文详细介绍了固体NMR的原理和一系列相关新技术,着重综述了固体NMR技术在酸催化剂结构、活性中心特性以及催化反应机理方面的应用进展.     

固体核磁共振定量表征方法及其在高分子结构研究中的应用

高分子材料拥有众多优良的特性,使其广泛应用于现代社会的生产、生活及高新科技等领域。对于高分子特性的研究离不开微观物理、化学结构的定量表征。在众多表征高分子结构定量信息的实验技术中,固体核磁共振（SSNMR）发挥着重要的作用。它可以定量表征高分子的化学结构、材料体系的相成分及共混组分等,从而实现了难溶高分子产物的结构鉴定,以及高分子微观物理、化学结构关联材料性能的研究。然而,传统的SSNMR定量方法（直接激发法,DD）往往需要耗费十几个小时甚至数天的实验时间。交叉极化方法（CP）虽然大大缩短了实验时间,却往往无法提供定量的信息。基于此,研究者们提出了多个定量CP的实验方法,同时满足了方法定量性和实验耗时短的需求。本文综述了传统SSNMR定量方法及几种定量的CP方法,简单介绍了每个方法的基本原理,并平行阐述了实验方法的应用范围及特点,通过部分实例展示了SSNMR定量方法在高分子材料领域的应用价值,为研究者研发新型的高分子材料提供可靠并有效的结构表征手段。     

固体样品的高分辨核磁共振方法

核磁共振法(NMR)是研究分子结构、分子构型及分子的动力学现象不可缺少的有力工具。近十多年来NMR所研究的对象已经不再局限于液体样品,固体样品也可以研究。过去对于固体样品只能得到宽线的谱图,而今天可     

固体核磁共振研究分子筛的新进展

分子筛由于具有独特的孔道及可调控酸碱性等特征,被作为离子交换剂、吸附剂及催化剂而广泛应用于石油化工的各种催化过程中。固体核磁共振是研究分子筛结构、酸性及主客体相互作用的强有力谱学手段之一。简单概述了固体核磁共振研究分子筛的最近进展。     

自制固体液体两用核磁共振谱仪

描述了研制的固体液体两用２００ＭＨｚ高分辨率核磁共振仪的基本结构,功能和一些重要的技术指标。实验结果表明,作为经济型的仪器,该仪器性能优良,功能较全,达到了预期的设计要求。     

多学科交叉研究中的固体核磁共振

<正>自1946年发现核磁共振现象以来,核磁共振(NMR)在现代基础研究和工业应用中都产生了广泛且重要的影响。固体NMR是一种研究固体材料的重要分析技术,与X射线衍射相比,它对体系中的近程有序变化更为敏感,能够在原子分子水平上研究各类非晶固体材料的微观结构和动力学行为。固体NMR已被广泛应用于多相催化、聚合物、     

峰峰肥煤的固体高分辨核磁共振研究

用固体,ＣＰ,ＣＰ／ＭＡＳＴＯＳＳ和偶极去相等实验技术对我国峰峰肥煤在不同处理阶段所得的三个固体样品进行了分析,得到了十二种煤的结构参数,并计算了三个样品的芳得族团大小,获得了各个样品的结构特点２及变化规律。     

固体表面的化学表征

第二次世界大战以后,材料科学的发展集中于固态性质的研究。经过几十年的努力,人们对固体本体性质的认识渐臻完善,但对影响     

固体核磁共振法测定硫化丁苯橡胶中的苯乙烯

采用魔角旋转固体核磁碳谱法(MAS–~(13)CNMR)测定硫化丁苯橡胶中的苯乙烯含量。通过固体核磁碳谱解析,对丁苯橡胶中苯乙烯、1,2-乙烯基、1,4-丁二烯的特征峰进行归属分析,以固体核磁外标法定量。对已知苯乙烯含量的标准样品进行测定,绘制校正曲线,结果显示理论苯乙烯含量与固体核磁法计算结果成良好的线性关系,线性相关系数(r~2)为0.97。经标准曲线校正后的苯乙烯含量接近于真实值,计算结果的相对误差小于5%,测定结果的相对标准偏差为0.31%(n=6)。该方法适用于单一胶种的硫化丁苯橡胶中苯乙烯含量的检测。     

Solid State NMR of Drugs: Soluble Aspirin

Abstract

Natural abundance ¹³C NMR spectra of a soluble aspirin and model mixtures of acetylsalicylic acid with buffering components have been recorded in the solid state by using the combined techniques of cross polarization, high-power decoupling and magic-angle spinning. The solid-state spectrum of the soluble aspirin tablet showed more resonances than the solution spectrum. These multiplicities were originated in the buffer mixture containing citric and tartaric acid, as well as their salts. Solid-state ¹³C NMR was therefore found to provide information that is lost in the solution spectrum due to the fast proton exchange between the organic acids and their conjugated salts.     

P-31 Solid State Nuclear Magnetic Resonance Investigations on Cyclophosphazenes

Abstract

The present study deals with solid state NMR investigations on cyclophosphazeaes wah the following substituents: -NH₂, -OMe, -F, -Cl, -Br, at which the substituent atoms are elements of the 2^nd period (N, O, and F) or elements of the 7^th main group (F, Cl, and Br). The NMR spectra were obtained by a BRUKER MSL 300 spectrometer using a resonance frequenacy of 121.496 MHz. With each compound a static powder spectrum, a hgh speed MAS spectrum, and several side band spectra were recorded.     

Structural Characterization of Non-Oxide Chalcogenide Glasses using Solid State NMR

In spite of the long-standing importance of non-oxide chalcogenide glasses in infrared optics and semiconductor technology, concepts describing the structural principles governing glass formation in these systems are just emerging. Most recently, modern quantitative solid state NMR techniques have offered new unique insights into the structural organization of these systems. In this review, we discuss the basic principles of various experimental approaches and their application to boron-silicon, -and phosphorus chalcogenide glasses.     

聚苯乙烯纳米复合材料的制备与固体核磁共振

根据功能化有机蒙脱土概念,采用磁力搅拌和超声搅拌两种不同的搅拌方法,分别制得了插层型和剥离型聚苯乙烯纳米复合材料。XRD和TEM测试结果显示,通过超声方法制得的聚苯乙烯复合材料具有很好的分散性,并且具有完全剥离的结构。另外,根据蒙脱土中Fe3+对复合材料中聚合物质子驰豫大小的影响,利用固体NMR质子弛豫的计算方法定量表征了聚苯乙烯纳米复合材料中有机土的分散性。结果证明,随着有机土在聚合物中的分散度增加,质子弛豫时间(T1H)逐渐减小。同时,通过NMR质子驰豫时间测量得到的结果和电镜结果相吻合。     

Solid State NMR Characterisation of Encapsulated Molecules in Mesoporous Silica

Ibuprofen molecules have been encapsulated in mesoporous MCM-41 type-silica functionalised or not by amino groups. They have been characterised by ¹³C and ¹H solid state NMR spectroscopy. The ¹³C MAS single pulse or cross polarization NMR spectra, as well as the ¹H MAS NMR spectra demonstrate an extremely high mobility of the ibuprofen molecules when the matrix is not functionalised. On the contrary, when the silica matrix is functionalized by amino groups, the ¹³C NMR response shows less mobility suggesting the existence of interactions between the amino groups and the carboxylic groups. Benzoic acid as well as benzamide have also been encapsulated and their NMR responses compared to that of ibuprofen.     

Solid State NMR and Fluorescence Studies of Conjugated Polymer Nanocomposties

^13C spin-lattice relaxation times （T1） of a conjugated polymer MEH-PPV in polymer/ layered silicate nanocomposites together with the steady state fluorescence emission and transient fluorescence decay measurements have been investigated. The T1 values of the conjugated carbons decrease dramatically according to the reduction of polymer concentration in the nano composites, while the fluorescence life times （τ） show a linear prolonging tendency. The results are explained from the point of view of molecular dynamics.     

NMR Investigations of the Inclusion of Thyroxine and Derivatives in Natural Cyclodextrins

Thyroxine T4 and its derivatives (T3, T2) are very sparingly soluble in aqueous solutions even in the form of salts. In the presence of or -cyclodextrins and in buffered basic solution, their solubilities are increased by inclusion in the cavity. The inclusion of these hormones in cyclodextrins was investigated by 1H-NMR in order to derive the influence of the number and position of the iodine atoms, and of the ionization state of the phenol group on the inclusion geometries.