光谱法分析乙丙共聚物的序列结构及链节比

用FTIR, 1 H NMR和 13 C NMR分析乙丙共聚物的序列结构与链节比. 通过对乙丙共聚物 1 H NMR, 13 C NMR和 13 C-1 H二维核磁共振谱的综合分析, 提出了与前人不同的归属, 并提出了不同位置碳原子积分面积相关性分析方法, 该方法避免了烦琐的理论计算, 可简便地得到乙丙共聚物的主要序列结构. 通过比较 1 H NMR和 13 C NMR计算乙丙共聚物中乙烯、 丙烯链节比, 表明可以用 1 H NMR代替 13 C NMR完成对乙丙共聚物中乙烯、 丙烯链节比的定量计算.     

双核Pt(Ⅳ)配合物与Guanosine-5''''-Monophosphate和Glutathione反应的核磁共振光谱研究

合成了一个新型的双核Pt(Ⅳ)配合物{[cis-Pt(NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物1)及相应的 15N标记化合物{[cis-Pt(15NH3)2Cl(OH)2]2(4,4'-methylenedianiline)}(NO3)2(化合物15N-1).利用1H NMR和ESMS进行了结构表征,化合物15N-1的2D[1H,15N]HSQC NMR发现,该化合物在水溶液中存在同分异构体.2D[1H,15N]HSQC NMR技术跟踪了化合物15N-1与Guanosine-5'-Monophosphate(5'-GMP)和Glutathione(GSH)的反应.结果显示,5'-GMP能在0.5 h内将化合物1还原,而GSH在6 h以后才能够部分的将化合物1还原.化合物1所表现出来的反应性能将有利于提高其治疗效果和降低毒副作用.     

小果博落回对照物质及其核磁共振氢谱指纹图的创建

采用规范化的程序获取6个不同来源小果博落回样品的对照物质(CSPD)及其^1H NMR图谱;从小果博落回CSPD中分得6个单体成分,其结构分别被鉴定为二氢血根碱(1)、二氢白屈菜红碱(2)、6-甲氧基二氢血根碱(3)、6-甲氧基二氢白屈菜红碱(4)、齐墩果酸(5)和原阿片碱(6)。通过各单体化合物的^1H NMR图谱与CSPD的^1H NMR图谱的对比研究,实现了小果博落回的^1H NMR指纹图的解析。研究结果表明：6个不同来源的小果博落回样品,其^1H NMR指纹图有很好的重现性和高度的特征性,并主要显示以上生物碱类成分的特征共振信号,可做为其基源鉴定的参考。     

Natural-abundance solid-state 2H NMR spectroscopy at high magnetic field

High-resolution solid-state (2)H NMR spectroscopy provides a method for measuring (1)H NMR chemical shifts in solids and is advantageous over the direct measurement of high-resolution solid-state (1)H NMR spectra, as it requires only the application of routine magic angle sample spinning (MAS) and routine (1)H decoupling methods, in contrast to the requirement for complex pulse sequences for homonuclear (1)H decoupling and ultrafast MAS in the case of high-resolution solid-state (1)H NMR. However, a significant obstacle to the routine application of high-resolution solid-state (2)H NMR is the very low natural abundance of (2)H, with the consequent problem of inherently low sensitivity. Here, we explore the feasibility of measuring (2)H MAS NMR spectra of various solids with natural isotopic abundances at high magnetic field (850 MHz), focusing on samples of amino acids, peptides, collagen, and various organic solids. The results show that high-resolution solid-state (2)H NMR can be used successfully to measure isotropic (1)H chemical shifts in favorable cases, particularly for mobile functional groups, such as methyl and -N(+)H(3) groups, and in some cases phenyl groups. Furthermore, we demonstrate that routine (2)H MAS NMR measurements can be exploited for assessing the relative dynamics of different functional groups in a molecule and for assessing whole-molecule motions in the solid state. The magnitude and field-dependence of second-order shifts due to the (2)H quadrupole interaction are also investigated, on the basis of analysis of simulated and experimental (1)H and (2)H MAS NMR spectra of fully deuterated and selectively deuterated samples of the α polymorph of glycine at two different magnetic field strengths.     

模型药物毒性血清^1H NMR谱代谢组学的Fisher判别分析研究

基于核磁共振技术的代谢组学是近年发展起来的一种新的组学技术,主要利用生物体液的核磁共振谱提供生物体内全部小分子代谢物的丰富信息.然而,噪声的存在影响了模式识别方法分析的准确度.近年来小波变换以其多分辨率分析的特性、方法简单、快速等优点成为一种有效的去除分析信号噪声的方法.本实验通过运用小波变换去除噪声、校正基线后,再进行Fisher判别分析,得到了较传统分析更为清晰的代谢标识物,建立了良好的代谢模型.     

Novel determination of the total phenolic content in crude plant extracts by the use of 1H NMR of the -OH spectral region

A novel method for the determination of the total phenolic content using (1)H NMR spectroscopy in the -OH spectral region is presented. The use of DMSO-d(6), which is an aprotic and strongly hydrogen bonding solvent, allows the "appearance" of the relative sharp resonances of phenolic hydroxyl protons in the region of 8-14 ppm. The determination of the total phenolic -OH content requires three steps: (i) a 1D (1)H NMR spectrum is obtained in DMSO-d(6); (ii) a subsequent 1D (1)H NMR spectrum is recorded with irradiation of the residual water signal which results in the elimination or reduction of the phenolic -OH groups, due to proton exchange; and (iii) 1D (1)H NMR spectra are recorded with the addition of a progressively increased amount of salt, NaHCO(3), which results in extensive linebroadening of the COOH resonances thus allowing the discrimination of the phenolic from the carboxylic acid signals. Integration, with respect to the internal standard TSP-d(4), of the signal resonances between 14 and 8 ppm in spectrum (i) which are either eliminated or reduced in intensity in steps (ii) and (iii) allows the quantitation of the total phenolic content. The method was applied to model compounds, a mixture of them and several extracts of natural products. The results of the proposed (1)H NMR method were compared to the Folin-Ciocalteu (FC) reagent method. Additionally, since (1)H NMR refers to the total phenolic hydroxyl protons, a reaction factor, A(e), is proposed that corresponds to the hydroxyl reactivity. The (1)H NMR method is rapid and accurate bearing the inherent advantages of the NMR spectroscopy and can be applied directly in complex extracts. Furthermore, it can be applied in a wide range of matrixes from crude plant extracts and food products to biological samples.     

Insight on the NMR study of supramolecular gels and its application to monitor molecular recognition on self-assembled fibers

The 1H NMR study of supramolecular gels formed by two organogelators derived from valine is described. The analysis of the variation of chemical shift values and relaxation times in the gel samples reveals that in these systems only discrete species are observed by 1H NMR. The reduced T2 values and negative NOEs that are measured upon gel formation can be ascribed to an exchange between discrete organogelator species and the gel network. This process is found to be fast in the time scale of 1H NMR relaxation and slow in the NMR observation frequency time scale. It is shown here that other molecules, aside from the gelator itself, can interact with the gel network and this process can be monitored easily by measurement of relaxation times. As a proof of principle, the selective interaction of 2,2'-bis(hydroxymethyl)biphenyl over diphenylmethane with the self-assembled fibers formed by one of the gelators in benzene is described.     

强酸性环境中氧氟沙星的质子化模型研究

利用核磁共振波谱技术研究了不同浓度硫酸溶液中氧氟沙星(OFL)的1H,19F和13C核磁共振谱,对不同硫酸浓度引起的δH,δF,δC和JFC耦合常数的变化进行比较分析,由此推测其结构状态.综合1H,19F和13C核磁共振谱特点及其变化,提出OFL分子在强酸性环境中N1'被进一步质子化的结构模型.在浓硫酸溶液中,N1'被进一步质子化,并与F9形成氢键(N1'—H+┈F9),该结构使分子的共轭程度大幅降低,导致其荧光发射波长、荧光激发波长及紫外吸收波长均发生蓝移.硫酸溶液中氧氟酸和甲基氧氟沙星的荧光光谱行为进一步证明了OFL分子在浓硫酸溶液中质子化模型的合理性.     

31P and 1h NMR as probes of domain alignment in a rigid crystalline surfactant mesophase

A viscous reverse hexagonal surfactant mesophase containing bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water, was characterized by Fourier transform (31)P and (1)H NMR spectroscopy. Shear alignment was reflected through both (31)P NMR and (1)H NMR spectra. A complicated (31)P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures become macroscopically aligned after Couette shear. (31)P NMR chemical shift anisotropy characteristics are used to elucidate orientation of the hexagonal phase. Interestingly, (1)H NMR spectra exhibit spectral changes upon shear alignment closely corresponding with that of (31)P NMR spectra. These observations complement the findings of mesophase alignment obtained using SANS and imply that (31)P and (1)H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis.     

一种新的六氢嘧啶并嘧啶二酮衍生物的核磁共振分析

采用氢谱(1H NMR)、碳谱(13C NMR)、梯度场氢氢化学位移相关谱(1H-1H COSY)、梯度场质子检测异核单量子化学位移相关谱(HSQC)、梯度场质子检测异核多重键化学位移相关谱(HMBC)等多种NMR分析方法,确证了8a-对甲氧苯基-4,5-双(对氯苯基)六氢嘧啶[4,5-d]并嘧啶-2,7(1H,3H)-二酮的结构,对它的1H和13C NMR谱信号进行了归属,为其结构鉴定提供了重要依据。     

四(对烷氧苯基)卟啉及其金属络合物的光谱分析

利用IR、UV、1HNMR、MS、元素分析研究确证了38个卟啉类化合物及其金属络合物的结构。总结了卟啉类配体与金属络合的IR、UV、1HNMR判据。     

Aluminium complexes in methanol-water mixture as studied by 27Al NMR nuclear magnetic resonance

(27)Al NMR spectroscopy can be used for study of coordination and solvation in both aqueous and non-aqueous solutions. Various octahedral and tetrahedral aluminium complexes have been proved to exist in solution by (1)H and (27)Al NMR spectroscopy. (27)Al nuclear magnetic resonance (NMR) spectroscopy also can be used to determine thermodynamic properties of complexes in the solution. The formation of [Al(OH)(4-n)(CH(3)OH)(n)]((n-1)+) (n=1, 2, 3 and 4) species through the reaction of aluminate anion with methanol has been investigated by (27)Al NMR spectroscopy. (27)Al NMR spectra reveal evidence for Al bound to one, two, three and four CH(3)OH, the production of aluminate species is affected by the MeOH/H(2)O. Results obtained from 2D EXSY experiments clearly confirm there are exchanges among the species.     

Benzoxazine oligomers: evidence for a helical structure from solid-state NMR spectroscopy and DFT-based dynamics and chemical shift calculations

A combination of molecular modeling, DFT calculations, and advanced solid-state NMR experiments is used to elucidate the supramolecular structure of a series of benzoxazine oligomers. Intramolecular hydrogen bonds are characterized and identified as the driving forces for ring-shape and helical conformations of trimeric and tetrameric units. In fast MAS (1)H NMR spectra, the resonances of the protons forming the hydrogen bonds can be assigned and used for validating and refining the structure by means of DFT-based geometry optimizations and (1)H chemical-shift calculations. Also supporting these proposed structures are homonuclear (1)H[bond](1)H double-quantum NMR spectra, which identify the local proton-proton proximities in each material. Additionally, quantitative (15)N[bond](1)H distance measurements obtained by analysis of dipolar spinning sideband patterns confirm the optimized geometry of the tetramer. These results clearly support the predicted helical geometry of the benzoxazine polymer. This geometry, in which the N...H...O and O...H...O hydrogen bonds are protected on the inside of the helix, can account for many of the exemplary chemical properties of the polybenzoxazine materials. The combination of advanced experimental solid-state NMR spectroscopy with computational geometry optimizations, total energy, and NMR spectra calculations is a powerful tool for structural analysis. Its results provide significantly more confidence than the individual measurements or calculations alone, in particular, because the microscopic structure of many disordered systems cannot be elucidated by means of conventional methods due to lack of long-range order.     

Sites of hydroxyl radical reaction with amino acids identified by (2)H NMR detection of induced (1)H/(2)H exchange.

Hydroxyl radical reacts with the aliphatic C-H bonds of amino acids by H atom abstraction. Under anaerobic conditions inclusion of a (2)H atom donor results in (1)H/(2)H exchange into these C-H bonds [Goshe et al. Biochemistry 2000, 39, 1761--1770]. The site of (1)H/(2)H exchange can be detected and quantified by (2)H NMR. Integration of the (2)H NMR resonances within a single spectrum permits the relative rate of H atom abstraction from each position to be determined. Analysis of the aliphatic amino acid spectra indicates that the methine and methylene positions were more reactive than the methyl positions. The (2)H NMR spectra of isoleucine and leucine show that H-atom abstraction distal to the alpha-carbon occurs preferentially. Significant (1)H/(2)H exchange was observed into the delta positions of proline and arginine and into the epsilon-methylene of lysine, indicating that a positive charge on a geminal N does not inhibit the (1)H/(2)H exchange. Comparisons of (2)H NMR integrations between amino acid spectra indicated that (1)H/(2)H exchange occurred in the following descending order: L > I > V > R > K > Y > P > H > F >M> T > A > [C, S, D, N, E, Q, G, W]. The extent of (1)H/(2)H exchange into methionine, N-glycyl-methionine, and methionine sulfoxide suggests that a prominent solvent exchange pathway involving hydroxyl radical mediated oxidation of methionine exists to account for the large (2)H incorporation into the gamma-methylene of methionine sulfoxide that is absent for N-glycyl-methionine. Analysis of the (1)H NMR spectra of the reactions with phenylalanine and tyrosine indicated that hydroxyl radical addition to the phenyl ring under the anaerobic reductive reaction conditions did not result in either exchange or hydroxylation.     

Simultaneous quantification and identification of individual chemicals in metabolite mixtures by two-dimensional extrapolated time-zero (1)H-(13)C HSQC (HSQC(0))

Quantitative one-dimensional (1D) (1)H NMR spectroscopy is a useful tool for determining metabolite concentrations because of the direct proportionality of signal intensity to the quantity of analyte. However, severe signal overlap in 1D (1)H NMR spectra of complex metabolite mixtures hinders accurate quantification. Extension of 1D (1)H to 2D (1)H-(13)C HSQC leads to the dispersion of peaks along the (13)C dimension and greatly alleviates peak overlapping. Although peaks are better resolved in 2D (1)H-(13)C HSQC than in 1D (1)H NMR spectra, the simple proportionality of cross peaks to the quantity of individual metabolites is lost by resonance-specific signal attenuation during the coherence transfer periods. As a result, peaks for individual metabolites usually are quantified by reference to calibration data collected from samples of known concentration. We show here that data from a series of HSQC spectra acquired with incremented repetition times (the time between the end of the first (1)H excitation pulse to the beginning of data acquisition) can be extrapolated back to zero time to yield a time-zero 2D (1)H-(13)C HSQC spectrum (HSQC(0)) in which signal intensities are proportional to concentrations of individual metabolites. Relative concentrations determined from cross peak intensities can be converted to absolute concentrations by reference to an internal standard of known concentration. Clustering of the HSQC(0) cross peaks by their normalized intensities identifies those corresponding to metabolites present at a given concentration, and this information can assist in assigning these peaks to specific compounds. The concentration measurement for an individual metabolite can be improved by averaging the intensities of multiple, nonoverlapping cross peaks assigned to that metabolite.     

含9-丁基咔唑基二炔/聚炔汞及二炔金配合物的合成与性质

合成了9-丁基咔唑基聚炔汞聚合物[—HgC≡CRC≡C—]n及其二聚体[MeHgC≡CRC≡CHgMe]和金的二聚体[(PPh3)AuC≡CRC≡CAu(PPh3)](R=9-丁基咔唑基). 用 1H NMR, 13C NMR, 31P NMR, FTIR, FAB-MS, UV-Vis, Fluorescence及Phosphorescence 光谱对其进行了表征. 结果表明, 体系中金和汞产生的重原子效应可以促进单线激发态S1与三线激发态T1的系间跃迁, 使标题化合物产生有机三线态发光.     

Synthesis and solid-state NMR characterization of cubic mesoporous silica SBA-1 functionalized with sulfonic acid groups

Well-ordered cubic mesoporous silicas SBA-1 functionalized with sulfonic acid groups have been synthesized through in situ oxidation of mercaptopropyl groups with H(2)O(2) via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strong acidic conditions. Various synthesis parameters such as the amounts of H(2)O(2) and MPTMS on the structural ordering of the resultant materials were systematically investigated. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), multinuclear solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, (29)Si{(1)H} 2D HETCOR (heteronuclear correlation) NMR spectroscopy, thermogravimetric analysis (TGA), and nitrogen sorption measurements. By using (13)C CPMAS NMR technique, the status of the incorporated thiol groups and their transformation to sulfonic acid groups can be monitored and, as an extension, to define the optimum conditions to be used for the oxidation reaction to be quantitative. In particular, (29)Si{(1)H} 2D HETCOR NMR revealed that the protons in sulfonic acid groups are in close proximity to the silanol Q(3) species, but not close enough to form a hydrogen bond.     

Formation, isolation, spectroscopic properties, and calculated properties of some isomers of C(60)H(36)

Isomers of C(60)H(36) and He@C(60)H(36) have been synthesized by the Birch or dihydroanthracene reduction of C(60) and isolated by preparative high-pressure liquid chromatography. (3)He, (13)C, and (1)H NMR spectroscopic properties were then determined. A comparison of experimental chemical shifts against those computed using density functional theory (B3LYP) with polarized triple- and double-zeta basis sets for He and C,H, respectively, allowed provisional assignment of structure for several isomers to be made. Theoretical calculations have also been carried out to identify low-energy structures. The transfer hydrogenation method using dihydroanthracene gives a major C(60)H(36) isomer and a minor C(60)H(36) isomer with C(3) symmetry as determined by the (13)C NMR spectrum of C(60)H(36) and the (3)He NMR spectrum of the corresponding sample of (3)He@C(60)H(36). In view of the HPLC retention times and the (3)He chemical shifts observed for the Birch and dihydroanthracene reduction products, the two isomers generated by the latter procedure can be only minor isomers of the Birch reduction. A significant energy barrier apparently exists in the dihydroanthracene reduction of C(60) for the conversion of the C(3) and C(1) symmetry isomers of C(60)H(36) to the T symmetry isomer previously predicted by many calculations to be among the most stable C(60)H(36) isomers. Many of the (1)H NMR signals exhibited by C(60)H(36) (and C(60)H(18), previously reported) are unusually deshielded compared to "ordinary" organic compounds, presumably because the unusual structures of C(60)H(36) and C(60)H(18) result in chemical shift tensors with one or more unusual principal values. Calculations clearly show a relationship between exceptionally deshielded protons beta to a benzene ring in C(60)H(18) and C(60)H(36) and relatively long C-C bonds associated with these protons. The additional information obtained from 1D and 2D (1)H NMR spectra obtained at ultrahigh field strengths (up to 900 MHz) will serve as a critical test of chemical shifts to be obtained from future calculations on different C(60)H(36) isomers.     

1H NMR chemical shift calculations as a probe of supramolecular host-guest geometry

The self-assembled supramolecular host [Ga(4)L(6)](12-) (1; L = 1,5-bis[2,3-dihydroxybenzamido]naphthalene) can encapsulate cationic guest molecules within its hydrophobic cavity and catalyze the chemical transformations of bound guests. The cavity of host 1 is lined with aromatic naphthalene groups, which create a magnetically shielded interior environment, resulting in upfield shifted (1-3 ppm) NMR resonances for encapsulated guest molecules. Using gauge independent atomic orbital (GIAO) DFT computations, we show that (1)H NMR chemical shifts for guests encapsulated in 1 can be efficiently and accurately calculated and that valuable structural information is obtained by comparing calculated and experimental chemical shifts. The (1)H NMR chemical shift calculations are used to map the magnetic environment of the interior of 1, discriminate between different host-guest geometries, and explain the unexpected downfield chemical shift observed for a particular guest molecule interacting with host 1.     

Unsaturation Characterization of Polyolefins by NMR and Thermal Gradient NMR (TGNMR) with a High Temperature Cryoprobe

Summary: It is important to identify the types of unsaturation and to quantify the amount of unsaturation in polyolefins for understanding chain termination mechanisms of polymerization with different catalysts. Unsaturation is also closely related to processibility, weatherability of polyolefin products and the level of antioxidants to be added for stabilizing purposes. However, it can be very challenging to accurately measure samples with a low level of the unsaturation within a reasonable amount of NMR acquisition time, along with some challenging technical issues, such as dynamic range with ¹H NMR. This paper reports a new method to accurately quantify unsaturation by using multi peak presaturation ¹H NMR with a high temperature NMR cryoprobe. The limit of quantification can be less than 1 unsaturation/1,000,000 carbons with about 30 min NMR acquisition. This paper also introduces a new technique, temperature gradient NMR (TGNMR) with or without substrates, to characterize unsaturation distribution directly in NMR tube upon temperature change.