Acceleration of carbon-13 spin-lattice relaxation times in amino acids by electrolytes

Measurements of the enhancement, by various electrolytes, of the spin-lattice relaxation time of carbon-13 at different locations in a number of amino acids are reported. Spin-lattice relaxation times T1 of all the carbons in amino acids generally tend to decrease with increase in the concentration of electrolytes, the largest effects often being observed for the charged carboxylate groups of the amino acids. Carboxylic carbons in amino acids are the sensitive 'acceptor' of the 13C spin-lattice relaxation accelerating effects offered by electrolytes, and the 13C spin-lattice relaxation accelerating ability of electrolytes decreases in the order Mg(ClO4)2 > MgCl2 > CaCl2 > NaCl > KCl > LiClO4 > NaOH. The mechanisms of the observed phenomena are discussed in terms of intermolecular interaction, paramagnetic impurities in electrolytes and other mechanisms; large contributions of intermolecular interactions with electrolytes are present on complex formation between amino acids and metal ions and the incoming 'unsaturation' of the primary solvation shell of cations with the increase in electrolyte concentration.     

High-Resolution Solid-State NMR Characterization of Morphology in Annealed Polylactic Acid

Single-pulse ¹³C NMR spectra and spin-lattice relaxation times T₁(¹H), detected indirectly via ¹³C carbons, and T₁(¹³C) were measured at 31°C for virgin pelletized and annealed polylactic acid (PLA) samples using the magic-angle spinning technique. The structural relaxation resulting in more regular crystals with narrower conformation distribution and increase in the lamellae thickness and crystallinity brought about by annealing at 100°C was deduced from the narrowing of the ¹³C NMR lines and proton spin-lattice relaxation times T₁(¹H). The spin-lattice relaxation times T₁(¹³C) related to the respective carbons of the α-polymorph of PLA are also discussed in the study.     

Identification of halogen substituents in natural products by measurement of 13c spin-lattice relaxation times and integrated intensities

A method is proposed for differentiating brominated carbons from chlorinated carbons by means of natural-abundance ¹³C NMR spectroscopy. The basis of the method is that the spin-lattice relaxation behaviour of brominated carbons is influenced by carbon-bromine scalar interactions, which can lead to shortened ¹³C spin-lattice relaxation times and reduced values of the nuclear Overhauser enhancement. C-Cl scalar interactions make a negligible contribution to the spin-lattice relaxation of chlorinated carbons. These effects are illustrated by measurement of the ¹³C spin-lattice relaxation times and integrated intensities of chloro-, bromo and iodobenzene and chloro-, bromo- and iodocyclohexane. The method is then tested on four polyhalogenated marine natural products. The results indicate that ¹³C relaxation measurements can be used to distinguish brominated carbons from chlorinated carbons in the case of halogenated quaternary carbons, sp² hydridized methine carbons and some sp³ hydridized methine carbons, but not in the case of halogenated methylene carbons or gem-dihalo substituted methine carbons.     

Possible intermolecular association in triphenyltin chloride in the solution state as detected by NMR spectroscopy

NMR measurements ((119)Sn chemical shift, line width and (13)C relaxation) were made on triphenyltin chloride in two solutions, 2.5 and 0.75 mol% in CDCl(3), at several temperatures. The (13)C spin-lattice relaxation time and NOE data for the phenyl carbons provide the corresponding correlation times for the overall molecular reorientational motion and the internal rotation of the phenyl groups. The results are indicative of a weak intermolecular association of the triphenyltin chloride molecules in solution and are discussed with reference to a model for intermolecular phenyl ring π-π stacking interactions.     

1,2-聚丁二烯~(13)C-NMR弛豫的溶剂效应

本文测定了一系列具有不同微观结构的1,2-聚丁二烯样品在四种溶剂的50.3MHz ~(13)C自旋-晶格弛豫时间(T_1)和核Overhauser效应(NOE)值。并用Schaefer logx~2相关时间分布模型对实验数据进行了拟合。研究了1,2-聚丁二烯在溶液中的~(13)C-NMR弛豫的溶剂效应及其与结构的关系。发现聚合物与溶剂的溶解度参数之差△δ越大,聚合物在溶液中协同链段运动趋向越明显,~(13)C自旋-晶格弛豫速率(1/T_1)越大;1,2-链节较少,分子链较柔顺时,~(13)C-NMR弛豫受溶剂影响较显著。NMR弛豫参数对结构变化的反应在良溶剂中比在不良溶剂中敏感。     

13C NMR spectroscopy of 13C1-labeled octanethiol-protected Au nanoparticles: shifts,relaxations, and particle-size effect

We report here an investigation of metal-ligand interactions in nanoparticles with 13C NMR, using a labeled 13C1-octanethiol, a protecting ligand for self-assembled monolayer (SAM) systems, in which close proximity of the 13C1 to the metal surface serves as an effective probe for the changing electronic environment. Several remarkable results have been obtained: as the metal core size increases from 1.6 to 4.0 nm, the 13C1 spectrum is downshifted from 40.5 to 53 ppm, and the spin-spin relaxation rate, T2-1, increases while the spin-lattice relaxation ratio decreases. Although the spin-lattice relaxation may be due to particle tumbling and ligand motion in the liquid state, the main source of the spin-spin relaxation, and NMR shift, is most possibly due to the changing electronic properties of the metal core.     

Synthesis of macrocycles and their application as chiral solvating agents in the enantiomeric recognition of carboxylic acids and α-amino acid derivatives

The chiral macrocycles 1 and 2 with multiple binding sites have been synthesized from D-phenylalanine as chiral solvating agents (CSAs) for the enantiomeric discrimination and determination of the enantiomeric excess of carboxylic acids and a-amino acids derivatives by the ¹H NMR spectroscopy. The results show that chiral macrocycles 1 and 2 are effective CSAs towards the carboxylic acids and a-amino acids derivatives.     

Dynamic study of the noncrystalline phase of 13C-labeled polyethylene by variable-temperature 13C CP/MAS NMR spectroscopy

The ¹³C spin-lattice relaxation times T₁ of ¹³C-labeled polyethylene crystallized under different conditions were measured at temperatures from ?120 to 44°C by variable-temperature solid-state high-resolution ¹³C nuclear magnetic resonance (NMR) spectroscopy, in order to determine accurately the dynamics of the noncrystalline region of the polymer. From these results, it was found that the T₁ minimum for the CH₂ carbons in the noncrystalline region of solution-crystallized polyethylene with high crystallinity appears at higher temperature by about 20°C than that of melt-quenched polyethylene with low crystallinity. This means that the molecular motion of the CH₂ carbons in the noncrystalline regions is more constrained at a given temperature in the material of higher crystallinity. Furthermore, dynamics of the noncrystalline region is discussed in terms of the ¹³C dipolar dephasing times.     

High-resolution solid-state 13C NMR study of ethylcellulose films

Ethylcellulose films cast from concentrated solutions of chloroform, benzene, and carbon tetrachloride were subjected to the NMR relaxation measurements including ¹H spin-lattice relaxation time (T_1H), rotating-frame ¹H spin-lattice relaxation time (T_1ρH), and ¹³C spin-lattice relaxation time (T_1C). The values of T_1ρH for carbons in the glucose units of ethyl-cellulose were of the same order of magnitude as those reported for the crystalline and noncrystalline regions of ramie cellulose. The values of T_1C for unsubstituted C2, C3 carbons were smaller than those for the corresponding carbons in the noncrystalline region of native celluloses. The T_1C values for unsubstituted C2, C3, and substituted C6 carbons showed a small but definite dependence on the solvent from which the films were cast. © 1993 John Wiley & Sons, Inc.     

Chain behavior of an amphoteric cellulose derivative: O-carboxymethyl-O-2-hydroxy-3-(trimethylammonio) propylcellulose

The ¹³C NMR spin-lattice relaxation times (T₁) of anhydroglucose units vary with the number of substituents, and the T₁ values of unsubstituted anhydroglucose units of O-carboxymethylcellulose are longer than those of amylose. Those results indicate that in water, the rotational motions of anhydroglucose units of cellulose derivative are quite important local motions contributing to the ¹³C NMR spin-lattice relaxation, and within a cellulose chain, anhydroglucose units rotate with different degrees of freedom depending on their environment. Moreover, the ¹³C NMR spin-lattice relaxation data indicate that the mobilities of ionic substituents are dependent on substitution positions as well as their ionic interaction. © 1995 John Wiley & Sons, Inc.     

Carbon-13 spin-lattice relaxation study of linear polymers in solution

Proton-decoupled, partially relaxed, Fourier-transform NMR of ¹³C in natural abundance was used to determine spin-lattice relaxation times of individual carbons of polyisobutylene, polyacrylonitrile, poly(vinyl chloride), and poly(vinyl alcohol) in solution. It is shown that the relaxation times are independent of the difference in stereochemical configuration. From the values of the nuclear Overhauser enhancement factor it is shown that the relaxation times are independent of the difference in stereochemical configuration. From the values of the nuclear Overhauser enhancement factor it is shown that the excess spin energy from equilibration of all the ¹³C, even of quaternary carbons, in the polymers dealt with here is transferred to the lattice mainly through ¹³C-¹H dipolar interactions. It is shown that the segmental motions responsible for the spin-lattice relaxation of the polymer skeleton in solution can be described by the isotropic model within a good approximation, except for poly(vinyl alcohol) at low temperature. The activation energies of skeletal and internal methyl motions are estimated from the temperature dependence of the correlation time. Differences in the ¹³C line widths for individual carbons of polyisobutylene are discussed briefly.     

聚合物异核交叉弛豫及二维NOE谱

The heteronuclear cross-relaxation rates in polymers were determined by selective and conventional ~(13)C spin-lattice relaxation experiments, the proton-carbon distances were calculated by the theoretical formula, and two-dimensional NOE spectra of the polymers were also measured. The results showed that (1) the measured proton-carbon distances coincide with the distances from molecular models, (2) there is the observable dipolar cross-relaxation effect between the quaternary carbons and their neighboring protons, and (3) the optimum mixing times depend on the relaxation properties of the proton and carbon.     

PASADENA hyperpolarization of succinic acid for MRI and NMR spectroscopy

We use the PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) method to achieve 13C polarization of approximately 20% in seconds in 1-13C-succinic-d2 acid. The high-field 13C multiplets are observed as a function of pH, and the line broadening of C1 is pronounced in the region of the pK values. The 2JCH, 3JCH, and 3JHH couplings needed for spin order transfer vary with pH and are best resolved at low pH leading to our use of pH approximately 3 for both the molecular addition of parahydrogen to 1-13C-fumaric acid-d2 and the subsequent transfer of spin order from the nascent protons to C1 of the succinic acid product. The methods described here may generalize to hyperpolarization of other carboxylic acids. The C1 spin-lattice relaxation time at neutral pH and 4.7 T is measured as 27 s in H2O and 56 s in D2O. Together with known rates of succinate uptake in kidneys, this allows an estimate of the prospects for the molecular spectroscopy of metabolism.     

聚合物异核交叉弛豫及二维NOE谱

Kover和Batta首次采用选择性质子π脉冲来测定~(13)C自旋-晶格弛豫速率并与常规反转回复法测定的自旋-晶格弛豫速率相比较求出了交叉弛豫速率,并以此来计算异核间的距离,但他们的计算方法仅适用于满足极端窄化条件的刚性球状分子。二维异核NOE谱(HOESY)是1983年才发展起来的二维NMR技术,它可用来研究异核间的交叉弛豫作用及研究分子间相互作用。Kover和Batta在此方面作了许多     

SOLID-STATE HIGH RESOLUTION NMR STUDY ON POLY (2, 6-DIMETHYL-1,4-PHENYLENE OXIDE)

Experiments including ~(13)C spin-lattice relaxation, ~(13)C heteronuclear dipolar dephasing and~1H spin diffusion are performed on poly (2, 6-dimethyl-1, 4-phenylene oxide) (PPO). Theresults show that the rotation of the methyl groups in solid PPO is partially restricted, whichresults in a surprisingly efficient spin diffusion between the aromatic proton and methyl protoncharacterized by a diffusion time of 150μs. The results also show that the aromatic ring insolid PPO is rigid and twisted, which causes all aromatic carbons to be chemicallyunequivalent.     

Strategy for the study of paramagnetic proteins with slow electronic relaxation rates by nmr spectroscopy: application to oxidized human [2Fe-2S] ferredoxin

NMR studies of paramagnetic proteins are hampered by the rapid relaxation of nuclei near the paramagnetic center, which prevents the application of conventional methods to investigations of the most interesting regions of such molecules. This problem is particularly acute in systems with slow electronic relaxation rates. We present a strategy that can be used with a protein with slow electronic relaxation to identify and assign resonances from nuclei near the paramagnetic center. Oxidized human [2Fe-2S] ferredoxin (adrenodoxin) was used to test the approach. The strategy involves six steps: (1) NMR signals from (1)H, (13)C, and (15)N nuclei unaffected or minimally affected by paramagnetic effects are assigned by standard multinuclear two- and three-dimensional (2D and 3D) spectroscopic methods with protein samples labeled uniformly with (13)C and (15)N. (2) The very broad, hyperfine-shifted signals from carbons in the residues that ligate the metal center are classified by amino acid and atom type by selective (13)C labeling and one-dimensional (1D) (13)C NMR spectroscopy. (3) Spin systems involving carbons near the paramagnetic center that are broadened but not hyperfine-shifted are elucidated by (13)C[(13)C] constant time correlation spectroscopy (CT-COSY). (4) Signals from amide nitrogens affected by the paramagnetic center are assigned to amino acid type by selective (15)N labeling and 1D (15)N NMR spectroscopy. (5) Sequence-specific assignments of these carbon and nitrogen signals are determined by 1D (13)C[(15)N] difference decoupling experiments. (6) Signals from (1)H nuclei in these spin systems are assigned by paramagnetic-optimized 2D and 3D (1)H[(13)C] experiments. For oxidized human ferredoxin, this strategy led to assignments (to amino acid and atom type) for 88% of the carbons in the [2Fe-2S] cluster-binding loops (residues 43-58 and 89-94). These included complete carbon spin-system assignments for eight of the 22 residues and partial assignments for each of the others. Sequence-specific assignments were determined for the backbone (15)N signals from nine of the 22 residues and ambiguous assignments for five of the others.     

Arsenic containing heterocycles. II. Confirmation of the structure of benzo[a]-9-chlorophenarsazine 12-chloride by 13C-NMR spectroscopy and spin-lattice relaxation time studies: Possible evidence for the contribution of an 75as-13C mechanism to the relaxation of the arsenic bearing quarternary carbons in the phenarsazine ring system

The product of the reaction of (3-chlorophenyl)-2-naphthylamine with arsenic trichloride has been confirmed to be benzo(a)-9-chlorophenarsazine 12-chloride by ¹³C-nmr spectroscopy and spin-lattice (T₁) relaxation time measurements. A considerable shortening of the spin-lattice relaxation times of the arsenic bearing quaternary carbons, relative to the calculated relaxation times, was observed. This discrepancy has been interpreted in terms of an ⁷⁵As-¹³C dipolar contribution to quaternary carbon relaxation.     

1,2-聚丁二烯分子运动的~(13)C-NMR研究——Ⅱ.分子运动的温度依赖性

本文用200MHz脉冲傅利叶变换波谱仪测定了1,2-聚丁二烯样品在不同温度下的~(13)C-T_(19)NOE,线宽和化学位移等~(13)G自旋弛豫参数,研究了1,2-聚丁二烯分子运动的温度依赖性.结果发现,在-10—-30℃之间,样品中各碳核的NOE和谱线宽度随温度变化的曲线斜率增加,表明此时长程链运动冻结;各碳核nT_1随温度的变化均在-45℃左右出现极小值.     

固体核磁共振弛豫在高分子研究中的应用

本文综述了近年来固体核磁弛豫方法在高分子研究中的应用，共分５个部分加以介绍：（１）自旋－晶格弛豫过程；（２）在旋转坐标系中的＾１３Ｃ自旋－晶格弛豫过程；（３）交叉极化速率和旋转坐标系中的＾１Ｈ自旋－晶格弛豫过程；（４）自旋－自旋弛豫过程；（５）动态结构导致的线形变化。本文主要讨论磁性核的各种弛豫过程以及它们与分子结构和分子运动的关系。     

Solid-state NMR (19F and 13C) study of graphite monofluoride (CF)n: 19F spin-lattice magnetic relaxation and 19F/13C distance determination by Hartmann-Hahn cross polarization

Graphite monofluoride (CF)(n) was studied by solid-state NMR. (19)F spin-lattice relaxation time T(1) and second moment measurements of the (19)F line are presented. A "chair" conformation structure is found to be compatible with the experimental data. Relaxation is shown to be mainly due to paramagnetic oxygen. The presence of a molecular motion with an activation energy of 1.685 kJ.mol(-1) (202.7 K) is also evidenced. (19)F magic angle spinning (MAS) NMR and (13)C MAS NMR with (19)F to (13)C cross-polarization allows the determination of CF and CF(2) groups. Reintroduction of dipolar coupling by cross-polarization is used for C-F bond length determination (0.138 +/- 0.001 nm).