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951.
Wickramasinghe NP Shaibat MA Jones CR Casabianca LB de Dios AC Harwood JS Ishii Y 《The Journal of chemical physics》2008,128(5):052210
High-resolution solid-state NMR (SSNMR) of paramagnetic systems has been largely unexplored because of various technical difficulties due to large hyperfine shifts, which have limited the success of previous studies through depressed sensitivity/resolution and lack of suitable assignment methods. Our group recently introduced an approach using "very fast" magic angle spinning (VFMAS) for SSNMR of paramagnetic systems, which opened an avenue toward routine analyses of small paramagnetic systems by (13)C and (1)H SSNMR [Y. Ishii et al., J. Am. Chem. Soc. 125, 3438 (2003); N. P. Wickramasinghe et al., ibid. 127, 5796 (2005)]. In this review, we discuss our recent progress in establishing this approach, which offers solutions to a series of problems associated with large hyperfine shifts. First, we demonstrate that MAS at a spinning speed of 20 kHz or higher greatly improves sensitivity and resolution in both (1)H and (13)C SSNMR for paramagnetic systems such as Cu(II)(DL-alanine)(2)H(2)O (Cu(DL-Ala)(2)) and Mn(acac)(3), for which the spectral dispersions due to (1)H hyperfine shifts reach 200 and 700 ppm, respectively. Then, we introduce polarization transfer methods from (1)H spins to (13)C spins with high-power cross polarization and dipolar insensitive nuclei enhanced by polarization transfer (INEPT) in order to attain further sensitivity enhancement and to correlate (1)H and (13)C spins in two-dimensional (2D) SSNMR for the paramagnetic systems. Comparison of (13)C VFMAS SSNMR spectra with (13)C solution NMR spectra revealed superior sensitivity in SSNMR for Cu(DL-Ala)(2), Cu(Gly)(2), and V(acac)(3). We discuss signal assignment methods using one-dimensional (1D) (13)C SSNMR (13)C-(1)H rotational echo double resonance (REDOR) and dipolar INEPT methods and 2D (13)C(1)H correlation SSNMR under VFMAS, which yield reliable assignments of (1)H and (13)C resonances for Cu(Ala-Thr). Based on the excellent sensitivity/resolution and signal assignments attained in the VFMAS approach, we discuss methods of elucidating multiple distance constraints in unlabeled paramagnetic systems by combing simple measurements of (13)C T(1) values and anisotropic hyperfine shifts. Comparison of experimental (13)C hyperfine shifts and ab initio calculated shifts for alpha- and beta-forms of Cu(8-quinolinol)(2) demonstrates that (13)C hyperfine shifts are parameters exceptionally sensitive to small structural difference between the two polymorphs. Finally, we discuss sensitivity enhancement with paramagnetic ion doping in (13)C SSNMR of nonparamagnetic proteins in microcrystals. Fast recycling with exceptionally short recycle delays matched to short (1)H T(1) of approximately 60 ms in the presence of Cu(II) doping accelerated 1D (13)C SSNMR for ubiquitin and lysozyme by a factor of 7.3-8.4 under fast MAS at a spinning speed of 40 kHz. It is likely that the VFMAS approach and use of paramagnetic interactions are applicable to a variety of paramagnetic systems and nonparamagnetic biomolecules. 相似文献
952.
We use 40 fs, 780 nm laser pulses to transiently align HBr molecules. We study the temporal dynamics of the resultant rotational wavepacket to gain insight into the electronic properties of the molecule. We show that the HBr polarization anisotropy can be extracted by comparing the time dependence of the HBr alignment with both the analogous alignment behavior of N(2) and the predictions of a rigid-rotor model. 相似文献
953.
Christopher K. R. T. Jones Robert Marangell Peter D. Miller Ramón G. Plaza 《Bulletin of the Brazilian Mathematical Society》2016,47(2):417-429
In this contribution, we summarize recent results [8, 9] on the stability analysis of periodicwavetrains for the sine-Gordon and general nonlinearKlein-Gordon equations. Stability is considered both from the point of view of spectral analysis of the linearized problem and from the point of view of the formal modulation theory of Whitham [12]. The connection between these two approaches is made through a modulational instability index [9], which arises from a detailed analysis of the Floquet spectrum of the linearized perturbation equation around the wave near the origin. We analyze waves of both subluminal and superluminal propagation velocities, as well as waves of both librational and rotational types. Our general results imply in particular that for the sine-Gordon case only subluminal rotationalwaves are spectrally stable. Our proof of this fact corrects a frequently cited one given by Scott [11]. 相似文献
954.
955.
Since the discovery of the halogen dance (HD) reaction more than 60 years ago, numerous insights into the mechanism have been unveiled. To date however, the reaction has not been investigated from a theoretical perspective. Density functional theory (DFT) was used to model the potential energy surface linking the starting reagents to the lithiated products for each step in the mechanism using a thiophene substrate. It was found that the lithium‐halogen exchange mechanism is critical to understand the HD mechanism in detail and yielded the knowledge that SN2 transition states (TS) are favored over the four‐center type for the lithium‐bromine exchange steps. The overall driving force for the HD is thermodynamics, while the kinetic factors tightly control the reaction path through temperature. The SN2 lithium‐bromide TS are barrierless, except the second, which is the limiting step. Finally, the model for the HD is discovered to be a pseudo‐clock type, due to a highly favorable bromide catalysis step and the reformation of 2‐bromothiophene. © 2016 Wiley Periodicals, Inc. 相似文献
956.
J. N. Orce M. Kumar Raju N. A. Khumalo T. S. Dinoko P. Jones R. A. Bark E. A. Lawrie S. N. T. Majola L. M. Robledo B. Rubio M. Wiedeking J. Easton E. A. Khaleel B. V. Kheswa N. Kheswa M. S. Herbert J. J. Lawrie P. L. Masiteng M. R. Nchodu J. Ndayishimye D. Negi S. P. Noncolela S. S. Ntshangase P. Papka D. G. Roux O. Shirinda P. S. Sithole S. W. Yates 《The European Physical Journal A - Hadrons and Nuclei》2016,52(6):166
957.
Cesati RR Dwyer G Jones RC Hayes MP Yalamanchili P Casebier DS 《Organic letters》2007,9(26):5617-5620
Recently developed copper-catalyzed coupling methodology has been applied to the synthesis of amino acid derived enamides. Bond formation proved to be strongly influenced by protection strategy and vinyl iodide substitution while tolerant of limited side chain functionality. Assessment of aminopeptidase activity revealed a preference for (E)-1,2-disubstituted constructs. 相似文献
958.
959.
Simperler A Kornherr A Chopra R Jones W Motherwell WD Zifferer G 《Physical chemistry chemical physics : PCCP》2007,9(30):3999-4006
The lactonisation of a CCR1 inhibitor (CC chemokine receptor 1, involved in autoimmune diseases) featuring a hydroxyl group in a gamma-position (gamma-OH) with respect to an amide group has been investigated in silico. The two key steps of the lactonisation reaction are (i) rearrangement to an optimal conformation and (ii) the formation of the lactone (ring closure) and expulsion of NH3. Quantum chemical calculations in the gas phase were employed to identify conformers of the molecule with favorable starting geometries for a lactonisation reaction. In total, calculations of 1296 conformers revealed that it is energetically feasible for an inhibitor molecule to adopt a conformation where the carbon atom of the amide group (C(amide)) is suitably close to the oxygen atom of the gamma-OH (O(gamma)) to facilitate a successful lactonisation reaction. Additionally, molecular dynamics methods were used to show that rearrangement to a suitable conformer for lactonisation to occur happens to a lesser extent when the CCR1 inhibitor was embedded in an amorphous trehalose matrix (a model carbohydrate excipient). The mechanism of the actual lactonisation was investigated using the complete Linear Synchronous Transit/Quadratic Synchronous Transit (LST/QST) method. This was performed in both the gas phase and in water and was found to be a concerted reaction. 相似文献
960.
Giuliani JR Gjersing EL Chinn SC Jones TV Wilson TS Alviso CT Herberg JL Pearson MA Maxwell RS 《The journal of physical chemistry. B》2007,111(45):12977-12984
Thermal degradation of a filled, cross-linked siloxane material synthesized from poly(dimethylsiloxane) chains of three different average molecular weights and with two different cross-linking species has been studied by (1)H multiple quantum (MQ) NMR methods. Multiple domains of polymer chains were detected by MQ NMR exhibiting residual dipolar coupling () values of 200 and 600 Hz, corresponding to chains with high average molecular weight between cross-links and chains with low average molecular weight between cross-links or near the multifunctional cross-linking sites. Characterization of the values and changes in distributions present in the material were studied as a function of time at 250 degrees C and indicate significant time-dependent degradation. For the domains with low , a broadening in the distribution was observed with aging time. For the domain with high , increases in both the mean and the width in were observed with increasing aging time. Isothermal thermal gravimetric analysis reveals a 3% decrease in weight over 20 h of aging at 250 degrees C. Degraded samples also were analyzed by traditional solid-state (1)H NMR techniques, and off-gassing products were identified by solid-phase microextraction followed by gas chromatography-mass spectrometry. The results, which will be discussed here, suggest that thermal degradation proceeds by complex competition between oxidative chain scissioning and postcuring cross-linking that both contribute to embrittlement. 相似文献