The effects of anticalcification treatments and hydration on the molecular dynamics of bovine pericardium collagen as revealed by (13)C solid-state NMR

This article describes a solid-state NMR (SSNMR) investigation of the influence of hydration and chemical cross-linking on the molecular dynamics of the constituents of the bovine pericardium (BP) tissues and its relation to the mechanical properties of the tissue. Samples of natural phenetylamine-diepoxide (DE)- and glutaraldehyde (GL)-fixed BP were investigated by (13)C cross-polarization SSNMR to probe the dynamics of the collagen, and the results were correlated to the mechanical properties of the tissues, probed by dynamical mechanical analysis. For samples of natural BP, the NMR results show that the higher the hydration level the more pronounced the molecular dynamics of the collagen backbone and sidechains, decreasing the tissue`s elastic modulus. In contrast, in DE- and GL-treated samples, the collagen molecules are more rigid, and the hydration seems to be less effective in increasing the collagen molecular dynamics and reducing the mechanical strength of the samples. This is mostly attributed to the presence of cross-links between the collagen plates, which renders the collagen mobility less dependent on the water absorption in chemically treated samples. Copyright (C) 2010 John Wiley & Sons, Ltd.

Characterization of organic matter in sediment cores of the Todos os Santos Bay, Bahia, Brazil, by elemental analysis and (13)C NMR

The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by elemental analysis and (13)C Nuclear Magnetic Resonance ((13)C NMR). This article reports a study of six sediment cores collected at different depths and regions of Todos os Santos Bay. The elemental profiles of cores collected on the eastern side of Frades Island suggest an abrupt change in the sedimentation regime. Auto-regressive Integrated Moving Average (ARIMA) analysis corroborates this result. The range of depths of the cores corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects in the region. Principal Component Analysis of the (13)C NMR spectra clearly differentiates sediment samples closer to the Subae estuary, which have high contents of terrestrial organic matter, from those closer to a local oil refinery. The results presented in this article illustrate several important aspects of environmental impact of human activity on this bay. (C) 2011 Elsevier Ltd. All rights reserved.

Complete assignment of (1)H and (13)C NMR spectra of alpha-phenylsulfinyl-N-methoxy-N-methylpropionamide and some p-substituted derivatives

The complete assignment of the (1)H and (13)C NMR spectra of the diastereomeric pairs of some alpha-arylsulfinyl-substituted N-methoxy-N-methylpropionamides with the substituents methoxy, methyl, chloro, nitro is reported. Copyright (C) 2008 John Wiley & Sons, Ltd.

Fast Acquisition of (13)C NMR Spectra using the Steady-state Free Precession Sequence

In this paper, we show that the steady-state free precession sequence can be used to acquire (13)C high-resolution nuclear magnetic resonance spectra and applied to qualitative analysis. The analysis of brucine sample using this sequence with 60 degrees flip angle and time interval between pulses equal to 300 ms (acquisition time, 299.7 ms; recycle delay, 300 ms) resulted in spectrum with twofold enhancement in signal-to-noise ratio, when compared to standard (13)C sequence. This gain was better when a much shorter time interval between pulses (100 ms) was applied. The result obtained was more than fivefold enhancement in signal-to-noise ratio, equivalent to more than 20-fold reduction in total data recording time. However, this short time interval between pulses produces a spectrum with severe phase and truncation anomalies. We demonstrated that these anomalies can be minimized by applying an appropriate apodization function and plotting the spectrum in the magnitude mode.

Optimised polyolefin branch quantification by 13 C NMR spectroscopy

Quantitative branch determination in polyolefins by solid- and melt-state 13C NMR has been investigated. Both methods were optimised toward sensitivity per unit time. While solid-state NMR was shown to give quick albeit only qualitative results, melt-state NMR allowed highly time efficient accurate branch quantification. Comparison of spectra obtained using spectrometers operating at 300, 500 and 700 MHz 1H Larmor frequency, with 4 and 7~mm MAS probeheads, showed that the best sensitivity was achieved at 500 MHz using a 7 mm 13C-1H optimised high temperature probehead. For materials available in large quantities, static melt-state NMR, using large diameter detection coils and high coil filling at 300 MHz, was shown to produce comparable results to melt-state MAS measurements in less time. While the use of J-coupling mediated polarisation transfer techniques was shown to be possible, direct polarisation via single-pulse excitation proved to be more suitable for branch quantification in the melt-state. Artificial line broadening, introduced by FID truncation, was able to be reduced by the use of π pulse-train heteronuclear dipolar decoupling. This decoupling method, when combined with an extended duty-cycle, allowed for significant improvement in resolution. Standard setup, processing and analysis techniques were developed to minimise systematic errors contributing to the measured branch contents. The final optimised melt-state MAS NMR method was shown to allow time efficient quantification of comonomer content and distribution in both polyethylene- and polypropylene-co-α-olefins. The sensitivity of the technique was demonstrated by quantifying branch concentrations of 8 branches per 100,000 CH2 for an industrial ‘linear’ polyethylene in only 13 hours. Even lower degrees of 3–8 long-chain branches per 100,000 carbons were able to be estimated in just 24 hours for a series of γ-irradiated polypropylene homopolymers.

Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

Three centered hydrogen bonds of the type C=O...H(N)...X-C in diphenyloxamide derivatives involving halogens and a rotating CF3 group: NMR, QTAIM, NCI and NBO studies

The existence of three centered C=O...H(N)...X-C hydrogen bonds (H-bonds) involving organic fluorine and other halogens in diphenyloxamide derivatives has been explored by NMR spectroscopy and quantum theoretical studies. The three centered H-bond with the participation of a rotating CF3 group and the F...H-N intramolecular hydrogen bonds, a rare observation of its kind in organofluorine compounds, has been detected. It is also unambiguously established by a number of one and two dimensional NMR experiments, such as temperature perturbation, solvent titration, N-15-H-1 HSQC, and F-19-H-1 HOESY, and is also confirmed by theoretical calculations, such as quantum theory of atoms in molecules (QTAIM), natural bond orbital (NBO) and non-covalent interaction (NCI).

Intramolecular hydrogen bonds involving organic fluorine in the derivatives of hydrazides: an NMR investigation substantiated by DFT based theoretical calculations

The rare examples of intramolecular hydrogen bonds (HB) of the type the N-H center dot center dot center dot F-C, detected in a low polarity solvent in the derivatives of hydrazides, by utilizing one and two-dimensional solution state multinuclear NMR techniques, are reported. The observation of through-space couplings, such as, (1h)J(FH), and (1h)J(FN), provides direct evidence for the existence of intra-molecular HB. Solvent induced perturbations and the variable temperature NMR experiments unambiguously establish the presence of intramolecular HB. The existence of multiple conformers in some of the investigated molecules is also revealed by two dimensional HOESY and N-15-H-1 HSQC experiments. The H-1 DOSY experimental results discard any possibility of self or cross dimerization of the molecules. The derived NMR experimental results are further substantiated by Density Function Theory (DFT) based Non Covalent Interaction (NCI), and Quantum Theory of Atom in Molecule (QTAIM) calculations. The NCI calculations served as a very sensitive tool for detection of non-covalent interactions and also confirm the presence of bifurcated HBs.

Organic fluorine involved intramolecular hydrogen bonds in the derivatives of imides: NMR evidence corroborated by DFT based theoretical calculations

The rare occurrence of intramolecular hydrogen bonds (HBs) of the type N-H center dot center dot center dot F-C is detected in the derivatives of imides in a low polarity solvent by using multi-dimensional and multinuclear NMR experiments. The observation of (1h)J(FH), (2h)J(FN), and (2h)J(FF), where the spin magnetization is transmitted through space among the interacting NMR active nuclei, provided strong and unambiguous evidence for the existence of intra-molecular HBs. The variation in the chemical shifts of labile protons depending on physical conditions, such as the solvent dilution and the systematic alteration of temperature confirmed the presence of weak interactions through intramolecular HBs in all the investigated fluorine substituted molecules. The self or cross dimerization of molecules is unequivocally discarded by the analysis of the rates of diffusion obtained using pseudo-two dimensional DOSY experiments. The Density Function Theory (DFT) calculations based on the Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings.

含硒抗体酶及酶法合成~（13）C尿苷二磷酸葡萄糖

胞质谷胱甘肽过氧化物酶（cGPX）是生物体内重要的抗氧化含硒酶，在保护机体免受活性氧损伤方面起着重要作用，因此利用抗体酶技术进行cGPX的人工模拟具有重要意义。本文在疏水腔修饰法指导下，设计合成了两种新的具有GSH特征的半抗原Hp4和Hp5。通过单克隆抗体及化学诱变技术制备得到三种针对半抗原Hp4的含硒抗体酶和两种针对Hp5 特异的含硒抗体酶。其中SeHB5(1867 U/μmol)和SeIA7（3567U/μmol）活力达到和天然酶同一数量级，进一步验证了疏水腔修饰法。本文还对含硒抗体酶SeHB5和SeIA7的酶学性质进行了系统的研究。生物活性实验表明含硒抗体酶对不同浓度H_2O_2损伤的小鼠心肌细胞均有一定程度的保护作用。本文同时报道了三种硒代β-环糊精作为cGPX模拟物的活力，其中6,6'-(O-亚苯基）二硒基桥联-β-环糊精二聚体的活力超过目前被认为最理想的补硒试剂Ebselen。~（13）C标记UDPG在利用核磁手段发现新的UDPG依赖糖基转移酶和检测新的糖基化合物，确定糖基间连接方式，合成同位素标记寡糖和多糖等方面具有广阔的应用前景。本文首次从植物培养细胞Rauvolfia serpentina经四步纯化得到具有一定纯度的UDPG焦磷酸化酶，并应用该酶建立了经济，简便，高产率的从葡萄糖出发，酶法大量合成UDPG的方法。利用该方法首次合成得到0.5克级的UDP-[4-~（13）C]-glucose，产率高达～70%。在NMR谱学方面确定了UDPG中葡萄糖基上4位C的归属，从而纠正了文献中关于UDPG核磁谱归属中的部分错误。

3~C-NMR 研究糠醇和糠醇与三■2—羟乙基■异氰尿酸酯缩聚磺化反应

80年代初,Kurihara 等开发的 PEC—1000复合膜,首次实现了工业规模的海水一级淡化,并在无机和有机水溶液的分离和浓缩方面显示了巨大潜力。据分析这种高效分离膜的功能分离层的主要结构成分是糠醇(FA)和三(?)2一羟乙基(?)异氰尿酸酯(THEIC)

Determining adsorbate configuration on alumina surfaces with 13C nuclear magnetic resonance relaxation time analysis

Relative strengths of surface interaction for individual carbon atoms in acyclic and cyclic hydrocarbons adsorbed on alumina surfaces are determined using chemically resolved 13C nuclear magnetic resonance (NMR) T1 relaxation times. The ratio of relaxation times for the adsorbed atoms T1,ads to the bulk liquid relaxation time T1,bulk provides an indication of the mobility of the atom. Hence a low T1,ads/T1,bulk ratio indicates a stronger surface interaction. The carbon atoms associated with unsaturated bonds in the molecules are seen to exhibit a larger reduction in T1 on adsorption relative to the aliphatic carbons, consistent with adsorption occurring through the carbon-carbon multiple bonds. The relaxation data are interpreted in terms of proximity of individual carbon atoms to the alumina surface and adsorption conformations are inferred. Furthermore, variations of interaction strength and molecular configuration have been explored as a function of adsorbate coverage, temperature, surface pre-treatment, and in the presence of co-adsorbates. This relaxation time analysis is appropriate for studying the behaviour of hydrocarbons adsorbed on a wide range of catalyst support and supported-metal catalyst surfaces, and offers the potential to explore such systems under realistic operating conditions when multiple chemical components are present at the surface.

(1)H, (15)N and (13)C assignments of the Rhipicephalus (Boophilus) microplus anti-microbial peptide microplusin

Microplusin, a Rhipicephalus (Boophilus) microplus anti-microbial peptide (AMP) is the first member of a new family of cysteine-rich AMPs with histidine-rich regions at the N- and C-termini, which is being fully characterized by biophysical and biochemical methods. Here we report the NMR resonance assignments for (1)H, (15)N, and (13)C nuclei in the backbone and side chains of the microplusin as basis for further studies of structure, backbone dynamics and interactions mapping.