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21.
R. Broda P. J. Daly Z. W. Grabowski H. Helppi M. Kortelahti J. McNeill R. V. F. Janssens R. D. Lawson D. C. Radford J. Blomqvist 《Zeitschrift für Physik A Hadrons and Nuclei》1985,321(2):287-295
The level structure of theN=81 nucleus147Dy has been studied byγ-ray spectroscopy following reactions of 230–250 MeV58,60Ni beams on89Y and90,92Zr targets. Yrast and near-yrast levels in147Dy above the known 59-s 11/2? state are established up to ~3.7 MeV; they include isomeric levels at 2,681, 3,407 and 3,650 keV. Guided by the results of shell model calculations, we interpret most of the observed level as senioritythree states arising from the coupling ofs 1/2,d 3/2, andh 11/2 neutron holes withπh 11/2 2. 相似文献
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The detection of lines in both the gas phase EPR spectrum at 9 GHz and the far-infrared LMR spectrum of the DO2 radical is reported. The measurements are fitted with an appropriate Hamiltonian and several parameters for the molecule in the state are determined. The majority of the transitions in the EPR spectrum are K-type doubling transitions and involve the a-component of the electric dipole moment. However the observation of one b-type transition (505-414) permits the determination of the off-diagonal component of the spin-rotation tensor, ?ab, and an estimate of the relative magnitudes of the a- and b-components of the dipole moment. A combination of the parameters for HO2 with those for DO2 leads to a better understanding of the properties of the molecule. In particular, the r0 molecular geometry has been determined more reliably than previously to be , , ∠HOO = 104.15°. 相似文献
24.
Harrison E. Radford F.David Wayne John M. Brown 《Journal of Molecular Spectroscopy》1983,99(1):209-220
The detection of the free radicals ClSO and FSO by the technique of far infrared laser magnetic resonance is reported. Observations of the former have been made with several laser lines; the spectra are complicated and have not been assigned but are attributed to ClSO on the basis of several chemical tests. The FSO radical was generated by the reaction of carbon disulphide with the products of a discharge through CF4 + O2. Spectra have been observed with laser lines at 394, 419 and 513 μm. Using the results of a subsequent microwave study of FSO, the rotational transitions involved in these spectra have been identified. The spectrum at 513 μm has been studied in detail and is shown to arise through level anticrossings between the levels 145,Kc (the lower levels involved in the transition) and 154,Kc+2. All aspects of this spectrum are reproduced quantitatively by the parameters determined from the microwave spectrum. It is thought that the other two FSO spectra arise in a similar manner. Such anticrossing signals are likely to be widespread in LMR experiments, causing intense narrow lines to occur at high magnetic fields even for molecules with weakly coupled electron spin. 相似文献
25.
Radford M. Neal 《Journal of computational and graphical statistics》2013,22(2):249-265
Abstract This article reviews Markov chain methods for sampling from the posterior distribution of a Dirichlet process mixture model and presents two new classes of methods. One new approach is to make Metropolis—Hastings updates of the indicators specifying which mixture component is associated with each observation, perhaps supplemented with a partial form of Gibbs sampling. The other new approach extends Gibbs sampling for these indicators by using a set of auxiliary parameters. These methods are simple to implement and are more efficient than previous ways of handling general Dirichlet process mixture models with non-conjugate priors. 相似文献
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Dr. Samuel F. Haysom Jonathan Machin Dr. James M. Whitehouse Dr. Jim E. Horne Dr. Katherine Fenn Dr. Yue Ma Dr. Hassane El Mkami Dr. Nils Böhringer Prof. Dr. Till F. Schäberle Prof. Dr. Neil A. Ranson Prof. Dr. Sheena E. Radford Prof. Dr. Christos Pliotas 《Angewandte Chemie (International ed. in English)》2023,62(34):e202218783
The β-barrel assembly machinery (BAM complex) is essential for outer membrane protein (OMP) folding in Gram-negative bacteria, and represents a promising antimicrobial target. Several conformational states of BAM have been reported, but all have been obtained under conditions which lack the unique features and complexity of the outer membrane (OM). Here, we use Pulsed Electron-Electron Double Resonance (PELDOR, or DEER) spectroscopy distance measurements to interrogate the conformational ensemble of the BAM complex in E. coli cells. We show that BAM adopts a broad ensemble of conformations in the OM, while in the presence of the antibiotic darobactin B (DAR-B), BAM′s conformational equilibrium shifts to a restricted ensemble consistent with the lateral closed state. Our in-cell PELDOR findings are supported by new cryoEM structures of BAM in the presence and absence of DAR-B. This work demonstrates the utility of PELDOR to map conformational changes in BAM within its native cellular environment. 相似文献
28.
Smith DP Giles K Bateman RH Radford SE Ashcroft AE 《Journal of the American Society for Mass Spectrometry》2007,18(12):2180-2190
The precise mechanism of protein folding remains elusive and there is a deficiency of biophysical techniques that are capable of monitoring the individual behavior of copopulated protein conformers during the folding process. Herein, an ion mobility spectrometry (IMS) device integrated with electrospray ionization mass spectrometry (ESI-MS) has been used to successfully separate and analyze protein conformers differing in cross section and/or charge state. In an initial test, an ensemble of folded and partially folded conformers of the protein cytochrome c was separated. A detailed study undertaken on the amyloidogenic protein beta(2)-microglobulin (beta(2)m), which forms fibrils by protein unfolding followed by self-aggregation and is responsible for the disease dialysis-related amyloidosis, has generated important insights into its folding landscape. Initially, a systematic titration of beta(2)m over the pH range 2 to 7 using ESI-IMS-MS allowed individual conformers to be monitored and quantified throughout the acid denaturation process. Furthermore, a comparison of wild-type beta(2)m with single and double amino acid variants with a range of folding stabilities and propensities for amyloid fibril formation has provided illuminating evidence of the role of different conformers in protein stability and amyloidogenic aggregation. The ESI-IMS-MS data presented here not only demonstrate an important and informative further dimension to ESI-MS, but also illustrate the potential of the ESI-IMS-MS technique for unravelling protein folding enigmas in general and studying protein misfolding diseases in particular. 相似文献
29.
DC Muddiman AP Null JC Hannis 《Rapid communications in mass spectrometry : RCM》1999,13(12):1201-1204
Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
30.
DC Bassett 《Macromolecular Symposia》1997,114(1):121-126
Molecular cilia, the uncrystallized portions of chains already partly attached to polymer crystals, exert a profound influence on the course of polymeric crystallization with ultimate responsibility for the divergence of adjacent lamellae which leads to spherulitic growth. Their effective size and pressure have been measured, in α-polypropylene, from electron microscopic measurements of the separation and maximum curvature of lamellae in row structures. That cilia exist and extend the effective region occupied by a lamella beyond the geometrical confines of its fold surfaces is important for crystallization theory and may well have implications for the connection of lamellae into networks and for gelation. 相似文献