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81.
In this communication, we report enhancements of nuclear spin polarization by dynamic nuclear polarization (DNP) in static and spinning solids at a magnetic field strength of 9T (250 GHz for g=2 electrons, 380 MHz for 1H). In these experiments, 1H enhancements of up to 170+/-50 have been observed in 1-13C-glycine dispersed in a 60:40 glycerol/water matrix at temperatures of 20K; in addition, we have observed significant enhancements in 15N spectra of unoriented pf1-bacteriophage. Finally, enhancements of approximately 17 have been obtained in two-dimensional 13C-13C chemical shift correlation spectra of the amino acid U-13C, 15N-proline during magic angle spinning (MAS), demonstrating the stability of the DNP experiment for sustained acquisition and for quantitative experiments incorporating dipolar recoupling. In all cases, we have exploited the thermal mixing DNP mechanism with the nitroxide radical 4-amino-TEMPO as the paramagnetic dopant. These are the highest frequency DNP experiments performed to date and indicate that significant signal enhancements can be realized using the thermal mixing mechanism even at elevated magnetic fields. In large measure, this is due to the high microwave power output of the 250 GHz gyrotron oscillator used in these experiments.  相似文献   
82.
We present results of Monte Carlo simulations measuring the coherent structure function of a chain moving through an ordered lattice of fixed topological obstacles. Our computer experiments use chains up to 320 beads and cover a large range of wave vectors and a time range exceeding the reptation time. For additional information we also measured the coherent structure function of internal pieces of the chain. We compare our results i) to the predictions of the primitive chain model, ii) to an approximate form resulting from Rouse motion in a coiled tube, and iii) to our recent evaluation of the full reptation model. i) The primitive chain model can fit the data for times , where T 2 is the Rouse time of the chain. Besides some phenomenological amplitude factor this fit involves the reptation time T 3 as a second fit parameter. For the chain lengths measured, the asymptotic behavior is not attained. ii) The model of Rouse motion in a tube, which we have criticized before on theoretical grounds, is shown to fail also on the purely phenomenological level. iii) Our evaluation of the full reptation model yields an excellent fit to the data for both total chains and internal pieces and for all wave vectors and all times, provided specific micro-structure effects of the MC dynamics are negligible. Such micro-structure effects show up for wave vectors of the order of the inverse segment size and enforce the introduction of some phenomenological, wave-vector-dependent prefactor. For the dynamics of the total chain our data analysis based on the full reptation model shows the importance of tube length fluctuations. Universal (Rouse-type) internal relaxation, however, is unimportant. It can be observed only in the form of the diffusive motion of a short central subchain in the tube. Finally, we present a fit formula which in a large range of wave vectors and chain lengths reproduces the numerical results of our theory for the scattering from the total chain.Received: 9 July 2003, Published online: 11 November 2003PACS: 83.10.Kn Reptation and tube theories - 82.35.Lr Physical properties of polymers - 83.10.Rs Computer simulation of molecular and particle dynamics  相似文献   
83.
84.
Linear mechanisms of catalytic and noncatalytic chemical reactions which are theoretically feasible have been classified and coded using a detailed procedure for the unique numbering of cycles, edges, and vertices in the kinetic graphs. The following classification criteria are used in a hierarchical order: number of cycles and vertices, mutual connectivity of the cycles, manner of linking any pair of cycles, number of elements linking two cycles, mutual position of two cycles joined to a third one, orientation of edges, and presence of pendant vertices. All the types and classes of mechanisms are presented for reactions having up to five and four routes, respectively.  相似文献   
85.
86.
Polarized Raman spectra are reported for the high frequency intrachain modes in crystals of the metallic polymer (SN)x. The principal features observed (at 454, 621, 658 and 782 cm?1) are strong, very anisotropic, and sharper than in thin films. The strongest feature, at 658 cm?1, narrows but does not shift with decreasing temperature or increasing pressure. Some of the peaks vary in relative intensity as the laser frequency is varied from 4579 to 6005 Å through the plasma resonance.  相似文献   
87.
88.
A theory of generalized statical bases is developed for usein the flexibility methods as applied to skeletal structuralproblems. It is shown that any maximal linearly independentset of cycles of the integral cycle group of a linear graphmodel of the structure may be used in the formation of a staticalbasis. Such a set of simple cycles is found by embedding thisgraph into a two-dimensional polyhedron. Cell complexes areformed so that the simple cycles bounding the 2-cells correspondto substructures on which a statical basis may be constructed.Two methods are given for the construction of the embeddings.In one a collapsible complex is formed from a union of a setof disks; while in the other the embedding is into an orientablemanifold which is modified to form an admissible complex.  相似文献   
89.
额尔齐斯河(新疆段)水质评价   总被引:2,自引:0,他引:2  
对额尔齐斯河1993~1999年的水质污染数据用因子分析的方法进行分析,得到评价额尔齐斯河水质污染的有机污染因子,综合污染因子和金属污染因子,并以此对额尔齐斯河水质污染情况作出较客观的评价。  相似文献   
90.
本文主要讨论s.i.s.向量随机测度关于白噪声的积分的收敛性,我们得到了如下结果设X是具type2的Banach空间,{Fn}∞n=0是一列被μ所控制的X值s.i.s随机测度,对任意的E∈∑,E[Fn(E)]=0,E‖Fn(E)‖2<+∞,{Fn(E)}∞n=0是一致W弱可积,且{Fn}∞n=1弱几乎收敛到F0,则(1)对每个n≥0∫FndW是s.i.s向量随机测度;(2)∫FndWwp→∫F0dW.  相似文献   
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