Electronic spectroscopy of the A1A" <--> X1A' system of CDBr

We report fluorescence excitation and single vibronic level emission spectra of jet-cooled CDBr in the 450-750 nm region. A total of 32 cold bands involving the pure bending levels 2(0)n with n=3-10 and combination bands 2(0)n3(0)1 (n=2-10), 2(0)n3(0)2 (n=2-9), 1(0)(1)2(0)n (n=7-10), and 1(0)(1)2(0)n3(0)(1) (n=6,8-9) in the A1A" <-- X1A' system of this carbene were observed; most of these are reported and/or rotationally analyzed here for the first time. Rotational analysis yielded band origins and effective (B) rotational constants for both bromine isotopomers (CD79Br and CD81Br). The derived A1A" vibrational intervals are combined with results of Yu et al. [J. Chem. Phys. 115, 5433 (2001)] to derive barriers to linearity for the 2n, 2n3(1), and 2n3(2) progressions. The A1A" state C-D stretching frequency (2350 cm(-1)) is determined for the first time, in excellent agreement with theory, as are the 79Br-81Br isotope splittings in the excited state. Our emission spectra probe the vibrational structure of the X1A' and a3A" states up to approximately 9000 cm(-1) above the vibrationless level of the X1A' state; the total number of levels observed is around twice that previously reported. Unlike CHBr, where even the lowest bending levels are perturbed by spin-orbit interaction with the triplet origin, the term energy of every level save one below 3000 cm(-1) in CDBr is reproduced by a Dunham expansion to within a standard deviation of 1 cm(-1), and a spin-orbit coupling matrix element of approximately 330 cm(-1) is derived from a deperturbation analysis of the triplet origin. The multireference configuration interaction (MRCI) calculations of Yu et al. [J. Chem. Phys. 115, 5433 (2001)] well reproduce triplet perturbations in the pure bending manifold, and globally, the vibrational frequencies of X1A', a3A", and A1A" are in excellent agreement with theoretical predictions.     

Characterization of ornithine and glutamine lipids extracted from cell membranes of Rhodobacter sphaeroides

The identification and structural characterization of a series of ornithine lipids extracted from the cell membranes of wild-type Rhodobacter sphaeroides, as well as from a glycerophosphocholine-deficient strain, have been achieved by multistage tandem mass spectrometry of their protonated and deprotonated precursor ions in a linear quadrupole ion trap. Systematic examination of the multistage gas-phase fragmentation reactions of these ions, combined with the use of hydrogen/deuterium exchange, has enabled the pathways responsible for sequential losses of the 3-hydroxy linked fatty acyl chain and the amide linked 3-OH fatty acyl chain from these lipids, as well as for formation of the previously reported ornithine specific positively charged "fingerprint" ion at m/z 115, to be determined. Additionally, the fragmentation pathways responsible for formation of a previously unreported ornithine lipid head group-specific product ion at m/z 131 in negative ion mode have been examined. Based on these results, and by comparison with the fragmentation behavior of model lipoamino acid standard compounds, a series of novel glutamine containing lipids have also been identified, with analogous structures but with masses 14 Da higher than those of several of the ornithine lipids observed in this study. Characteristic "fingerprint" ions indicative of these glutamine lipids were found at m/z 147, 130, and 129 in positive ion mode and at m/z 145 and 127 in negative ion mode. The results from this study establish an experimental basis for future efforts aimed at the sensitive identification, characterization, and quantitative analysis of ornithine and glutamine lipids in complex unfractionated cellular extracts.     

On finite groups whose Sylow subgroups have a bounded number of generators

Let G be a finite non-nilpotent group such that every Sylow subgroup of G is generated by at most δ elements, and such that p is the largest prime dividing |G|. We show that G has a non-nilpotent image G/N, such that N is characteristic and of index bounded by a function of δ and p. This result will be used to prove that G has a nilpotent normal subgroup of index bounded in terms of δ and p.     

Role of community tolerance level (CTL) in predicting the prevalence of the annoyance of road and rail noise

Fidell et al. [(2011), J. Acoust. Soc. Am. 130(2), 791-806] have shown (1) that the rate of growth of annoyance with noise exposure reported in attitudinal surveys of the annoyance of aircraft noise closely resembles the exponential rate of change of loudness with sound level, and (2) that the proportion of a community highly annoyed and the variability in annoyance prevalence rates in communities are well accounted for by a simple model with a single free parameter: a community tolerance level (abbreviated CTL, and represented symbolically in mathematical expressions as L(ct)), expressed in units of DNL. The current study applies the same modeling approach to predicting the prevalence of annoyance of road traffic and rail noise. The prevalence of noise-induced annoyance of all forms of transportation noise is well accounted for by a simple, loudness-like exponential function with community-specific offsets. The model fits all of the road traffic findings well, but the prevalence of annoyance due to rail noise is more accurately predicted separately for interviewing sites with and without high levels of vibration and/or rattle.     

Phase behaviour of SMA/PMMA blends: the influence of processing at low and high deformation rates

The influence of processing parameters (deformations) on SMA/PMMA blend phase behaviour is studied. It is found that injection moulding does change polymer blend phase behaviour. Phase separation kinetics are important to understand the injection moulding experiments and the kinetics are probably influenced by the deformations caused by the injection moulding proces. Capillary flow causes a complex change of polymer blend phase behaviour showing both deformation induced mixing and redemixing. Short capillaries, causing almost only uniaxial elongation in combination with pressure, cause no change to polymer blend phase behaviour. This is probably due to the short time the deformation is imposed to the material: it is expected that elongation is a main parameter causing changes in polymer blend phase behaviour. Parallel plate rheometer experiments show that applying only shear causes a complex change of phase behaviour showing both shear induced mixing and redemixing.     

Vinyl Halide-Modified Unsaturated Cyclitols are Mechanism-Based Glycosidase Inhibitors

Suitably configured allyl ethers of unsaturated cyclitols act as substrates of β-glycosidases, reacting via allylic cation transition states. Incorporation of halogens at the vinylic position of these carbasugars, along with an activated leaving group, generates potent inactivators of β-glycosidases. Enzymatic turnover of these halogenated cyclitols (F, Cl, Br) displayed a counter-intuitive trend wherein the most electronegative substituents yielded the most labile pseudo-glycosidic linkages. Structures of complexes with the Sulfolobus β-glucosidase revealed similar enzyme-ligand interactions to those seen in complexes with a 2-fluorosugar inhibitor, the lone exception being displacement of tyrosine 322 from the active site by the halogen. Mutation of Y322 to Y322F largely abolished glycosidase activity, consistent with lost interactions at O5, but minimally affected (7-fold) rates of carbasugar hydrolysis, yielding a more selective enzyme for unsaturated cyclitol ether hydrolysis.