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[reaction: see text] An unusually bridged epidithiodiketopiperazine, pretrichodermamide A (3), was isolated from the fungus Trichoderma sp. BCC 5926. During the extensive effort to crystallize 3 for X-ray crystallographic analysis, conversion of this compound to trichodermamide A with coproduction of S(8) occurred.
[reaction: see text] Allylic ethers are converted to the corresponding alcohol or phenol in virtually quantitative yield at temperatures below ambient simply by stirring a hydrocarbon solution of the ether with 1 molar equiv of tert-butyllithium. The reaction, which produces 4,4-dimethyl-1-pentene as a coproduct, most likely involves an S(N)2' attack of the organolithium on the allyl ether.
Deacetoxycephalosporin-C synthase (DAOCS) is a mononuclear ferrous enzyme that transforms penicillins into cephalosporins by inserting a carbon atom into the penicillin nucleus. In the first half-reaction, dioxygen and 2-oxoglutarate produce a reactive iron-oxygen species, succinate and CO2. The oxidizing iron species subsequently reacts with penicillin to give cephalosporin and water. Here we describe high-resolution structures for ferrous DAOCS in complex with penicillins, the cephalosporin product, the cosubstrate and the coproduct. Steady-state kinetic data, quantum-chemical calculations and the new structures indicate a reaction sequence in which a 'booby-trapped' oxidizing species is formed. This species is stabilized by the negative charge of succinate on the iron. The binding sites of succinate and penicillin overlap, and when penicillin replaces succinate, it removes the stabilizing charge, eliciting oxidative attack on itself. Requisite groups of penicillin are within 1 A of the expected position of a ferryl oxygen in the enzyme-penicillin complex.
(1) l-citrulline, a coproduct of nitric oxide synthase (NOS)-catalysed metabolism of l-arginine to nitric oxide (NO), is an important intermediate of the urea cycle and a precursor for l-arginine biosynthesis in vascular cells. (2) In the present study, we have examined the characteristics of l-citrulline transport, regulation by lipopolysaccharide (LPS) and interferon-gamma (IFN-gamma) and the ability of l-citrulline to sustain NO synthesis in rat cultured aortic smooth muscle cells. (3) l-citrulline transport was saturable with an apparent Km=1.6+/-0.2 mm and Vmax=5.9+/-0.6 pmol microg-1 protein min-1. Transport was pH-insensitive, partially Na+-dependent and markedly inhibited by substrates selective for amino-acid transport systems L and N but not by l-arginine or substrates for systems A, ASC, xc- or XAG. Moreover, transport was not altered in cells treated with LPS (100 microg ml-1) and IFN-gamma (50 U ml-1) for 0-24 h. (4) Unlike l-arginine, l-citrulline could not sustain maximal NO production in cells expressing iNOS. (5) Our findings provide the first evidence in vascular smooth muscle cells that l-citrulline transport is mediated via a low-affinity carrier with characteristics resembling systems L and N. Moreover, in l-arginine-deprived rat aortic smooth muscle cells, l-citrulline cannot sustain maximal NO release via iNOS.
The crystalline compounds [Mg(Br)(L)(thf)].0.5Et2O [L = {N(R)C(C6H3Me2-2,6)}2SiR, R = SiMe3] (1), [Mg(L){N=C=C(C(Me)=CH)2CH2}(D)2] [D = NCC6H3Me2-2,6 (2), thf (3)] and [{Mg(L)}2{mu-OSO(CF3)O-[mu}2] (4) were prepared from (a) Si(Br)(R){C(C6H3Me2-2,6)=NR}2 and Mg for (1), (b) [Mg(SiR3)2(thf)2] and 2,6-Me2C6H3CN (5 mol for (2), 3 mol for (3)), and (c) (2) + Me3SiOS(O)2CF3 for (4); a coproduct from (c) is believed to have been the trimethylsilyl ketenimide Me3SiN=C=C{C(Me)=CH}2CH2 (5).
Adult listeners are sensitive to the acoustic variations that result from a speaker's coarticulation (or coproduction) of phonetic segments. The present study charted the development of such sensitivity in young children by examining their responses to coarticulatory effects in fricative-vowel syllables. Children, at each of the ages 3, 4, 5, and 7 years, and adults identified tokens from a synthetic /sh/-/s/ continuum followed by one of four natural vocalic portions: /i/ and /u/, produced with transitions appropriate for either /sh/ or /s/. Children demonstrated larger shifts in fricative phoneme boundaries as a function of vocalic transition than did adults, but relatively smaller shifts as a function of vowel quality. Responses were less consistent for children than for adults, and differences between children and adults decreased as children increased in age. Overall, these results indicate that perceptual sensitivity to certain coarticulatory effects is present at as young as 3 years of age. Moreover, the decrease in the sensitivity to vocalic transitions with age suggests that, contrary to a commonly held view, the perceptual organization of speech may become more rather than less segmental as the child develops.
Syntrophus gentianae is a strictly anaerobic bacterium which ferments benzoate to acetate, CO2 and H2 in the presence of hydrogen-utilizing partner bacteria. Benzoate is activated by a benzoyl CoA ligase enzyme which forms AMP and pyrophosphate as coproducts. Pyrophosphatase activity was found to be largely membrane bound. Pyrophosphate hydrolysis was associated with proton translocation across the cytoplasmic membrane. Proton translocation could be abolished by the protonophor carbonylcyanide p-chlorophenylhydrazone, and could also be coupled to ATP formation in membrane vesicle preparations. The ratio of ATP formation/pyrophosphate hydrolysis was 1:3. The reverse reaction, ATP-dependent pyrophosphate synthesis, was possible with the same coupling stoichiometry. Pyrophosphatase was 90% saturated at 1 mM pyrophosphate; pyrophosphate concentrations higher than 5 mM inhibited enzyme activity. Inhibition studies with ATP and EDTA indicated that MgPPi- was probably the physiological substrate. The optimum temperature was 35 degrees C. In the presence of Mg2+, the enzyme was remarkably heat stable, with 50% of its maximum activity after 10 min at 60 degrees C. Exogenously added pyrophosphate could not be used for energy conservation.
The work presented here uses photofragment translational spectroscopy to investigate the primary and secondary dissociation channels of acryloyl chloride (CH2==CHCOCl) excited at 193 nm. Three primary channels were observed. Two C-Cl fission channels occur, one producing fragments with high kinetic recoil energies and the other producing fragments with low translational energies. These channels produced nascent CH2CHCO radicals with internal energies ranging from 23 to 66 kcal/mol for the high-translational-energy channel and from 50 to 68 kcal/mol for the low-translational-energy channel. We found that all nascent CH2CHCO radicals were unstable to CH2CH + CO formation, in agreement with the G3//B3LYP barrier height of 22.4 kcal/mol to within experimental and computational uncertainties. The third primary channel is HCl elimination. All of the nascent CH2CCO coproducts were found to have enough internal energy to dissociate, producing CH2C: + CO, in qualitative agreement with the G3//B3LYP barrier of 39.5 kcal/mol. We derive from the experimental results an upper limit of 23 +/- 3 kcal/mol for the zero-point-corrected barrier to the unimolecular dissociation of the CH2CHCO radical to form CH2CH + CO.
The title reaction was studied in a crossed-beam experiment by imaging of state-selected products. The rotational state selection of the CD(3) products was achieved using (2+1) resonance-enhanced multiphoton ionization. The coincident information on the DF coproducts was revealed in a state-resolved manner from time-sliced velocity map images. Significant dependences of both the correlated differential cross sections and the DF vibrational branching ratios on the "tagged" CD(3) rotation states were found. The dynamical implications of one of the major findings are discussed.
The product state-resolved dynamics of the reactions H+H(2)O/D(2)O-->OH/OD((2)Pi(Omega);v',N',f )+H(2)/HD have been explored at center-of-mass collision energies around 1.2, 1.4, and 2.5 eV. The experiments employ pulsed laser photolysis coupled with polarized Doppler-resolved laser induced fluorescence detection of the OH/OD radical products. The populations in the OH spin-orbit states at a collision energy of 1.2 eV have been determined for the H+H(2)O reaction, and for low rotational levels they are shown to deviate from the statistical limit. For the H+D(2)O reaction at the highest collision energy studied the OD((2)Pi(3/2),v'=0,N'=1,A') angular distributions show scattering over a wide range of angles with a preference towards the forward direction. The kinetic energy release distributions obtained at 2.5 eV also indicate that the HD coproducts are born with significantly more internal excitation than at 1.4 eV. The OD((2)Pi(3/2),v'=0,N'=1,A') angular and kinetic energy release distributions are almost identical to those of their spin-orbit excited OD((2)Pi(1/2),v'=0,N'=1,A') counterpart. The data are compared with previous experimental measurements at similar collision energies, and with the results of previously published quasiclassical trajectory and quantum mechanical calculations employing the most recently developed potential energy surface. Product OH/OD spin-orbit effects in the reaction are discussed with reference to simple models.
We present state-resolved crossed beam scattering results for the reaction Cl+C2H6-->HCl+C2H5, obtained using direct current slice imaging. The HCl (v=0,J=2) image, recorded at a collision energy of 6.7+/-0.6 kcalmol, shows strongly coupled angular and translational energy distributions revealing features of the reaction not seen in previous studies. The overall distribution is mainly forward scattered with respect to the Cl beam, with a translational energy distribution peaking near the collision energy. However, there is a substantial backscattered contribution that is very different. It shows a sharp peak at 8.0 kcalmol, but extends to much lower energy, implying substantial internal excitation in the ethyl radical coproduct. These results provide new insight into the reaction, and they are considered in terms of alternative models of the dynamics. This work represents the first genuine crossed-beam study in which a product other than the methyl radical was detected with quantum state specificity, showing the promise of the approach generally for high resolution state-resolved reactive scattering.
The product pair correlation of the title reaction was measured with rotational selection for both the vibrationally ground CD3(nu = 0) and umbrella-excited CD3(nu2 = 2) products. A striking linear relationship was found between the rotational energy of the selected CD3 product and the correlated kinetic energy release (or the average vibrational energy of the DF coproduct). Such a linearly correlated (or anticorrelated) dependence appears to be stronger for CD3(nu2 = 2,N) than for CD3(nu = 0,N). The mechanistic implication of the observation is that the rotational motion N of the CD3 product tends to lie antiparallel to the orbital angular momentum l' of the two departing products. The dependency on the K quantum number--the projection of N on the top axis--is, on the other hand, less significant yet noticeable.
Velocity-map ion imaging has been applied to the photodissociation of NO(2) via the first absorption band at 308 nm using (2 + 1) resonantly enhanced multiphoton ionization detection of the atomic O((3)P(J)) products. The resulting ion images have been analyzed to provide information about the speed distribution of the O((3)P(J)) products, the translational anisotropy, and the electronic angular momentum alignment. The atomic speed distributions were used to provide information about the internal quantum-state distribution in the NO coproducts. The data were found to be consistent with an inverted NO vibrational quantum-state distribution, and thereby point to a dynamical, as opposed to a statistical dissociation mechanism subsequent to photodissociation at 308 nm. Surprisingly, at this wavelength the O-atom electronic angular momentum alignment was found to be small. Probe-only ion images obtained under a variety of molecular-beam backing-pressure conditions, and corresponding to O atoms generated in the photodissociation of either the monomer, NO(2), or the dimer, N(2)O(4), at 226 nm, are also reported. For the monomer, where 226 nm corresponds to excitation into the second absorption band, the kinetic-energy release distributions are also found to indicate a strong population inversion in the NO cofragment, and are shown to be remarkably similar to those previously observed in the wavelength range of 193-248 nm. Mechanistic implications of this result are discussed. At 226 nm it has also been possible to observe directly O atoms from the photodissociation of the dimer. The O-atom velocity distribution has been analyzed to provide information about its production mechanism.
A modified and recalibrated potential energy surface for the gas-phase Cl+CH4-->HCl+CH3 reaction is reported and tested. It is completely symmetric with respect to the permutation of the four methane hydrogen atoms and is calibrated with respect to updated experimental and theoretical stationary point properties and experimental forward thermal rate constants. From the kinetics point of view, the forward and reverse thermal rate constants and the activation energies were calculated using the variational transition-state theory with semiclassical transmission coefficients over a wide temperature range of 150-2500 K. The theoretical results reproduce the available experimental data, with a small curvature of the Arrhenius plot which indicates the role of tunneling in this hydrogen abstraction reaction. A dynamics study was also performed on this PES using quasiclassical trajectory (QCT) calculations, including corrections to avoid zero-point energy leakage along the trajectories. First, we found a noticeable internal energy in the coproduct methyl radical, both in the ground-state [CH4 (v=0)] and vibrationally excited [CH4 (v=1)] reactions. This CH3 internal energy was directly precluded in some experiments or oversimplified in previous theoretical studies using pseudotriatomic models. Second, our QCT calculations give HCl rotational distributions slightly hotter than those in experiment, but correctly describing the experimental trend of decreasing the HCl product rotation excitation in going from HCl (v'=0) to HCl (v'=1) for the CH4 (v=1) reaction. Third, the state specific scattering distributions present a reasonable agreement with experiment, although they tend to make the reaction more forward and backward scattered than found experimentally probably because of the hotter rotational distribution and the deficiencies of the QCT methods.
An ab initio interpolated potential energy surface (PES) for the Cl+CH(4) reactive system has been constructed using the interpolation method of Collins and co-workers [J. Chem. Phys. 102, 5647 (1995); 108, 8302 (1998); 111, 816 (1999); Theor. Chem. Acc. 108, 313 (2002)]. The ab initio calculations have been performed using quadratic configuration interaction with single and double excitation theory to build the PES. A simple scaling all correlation technique has been used to obtain a PES which yields a barrier height and reaction energy in good agreement with high level ab initio calculations and experimental measurements. Using these interpolated PESs, a detailed quasiclassical trajectory study of integral and differential cross sections, product rovibrational populations, and internal energy distributions has been carried out for the Cl+CH(4) and Cl+CD(4) reactions, and the theoretical results have been compared with the available experimental data. It has been shown that the calculated total reaction cross sections versus collision energy for the Cl+CH(4) and Cl+CD(4) reactions is very sensitive to the barrier height. Besides, due to the zero-point energy (ZPE) leakage of the CH(4) molecule to the reaction coordinate in the quasiclassical trajectory (QCT) calculations, the reaction threshold falls below the barrier height of the PES. The ZPE leakage leads to CH(3) and HCl coproducts with internal energy below its corresponding ZPEs. We have shown that a Gaussian binning (GB) analysis of the trajectories yields excitation functions in somehow better agreement with the experimental determinations. The HCl(v'=0) and DCl(v'=0) rotational distributions are as well very sensitive to the ZPE problem. The GB correction narrows and shifts the rotational distributions to lower values of the rotational quantum numbers. However, the present QCT rotational distributions are still hotter than the experimental distributions. In both reactions the angular distributions shift from backward peaked to sideways peaked as collision energy increases, as seen in the experiments and other theoretical calculations.
The cholera toxin genes of Vibrio cholerae are encoded by the filamentous phage, CTXphi. Chromosomal CTXphi prophage DNA is often found flanked by copies of a related genetic element designated RS1, and RS1 DNA can be packaged into filamentous phage particles (designated RS1phi) by using the CTXphi morphogenesis genes. RS1phi is a satellite phage that further controls expression and dissemination of CTXphi. Here we describe a CTXphi-independent mechanism for production of RS1phi. A nontoxigenic environmental V. cholerae strain (55V71) was identified that supports production of RS1phi. However, newly infected CTX-negative strains did not produce RS1phi, indicating that additional 55V71 genes were involved in production of RS1phi. Analysis of nucleic acids from phage preparations of 55V71 revealed a 7.5-kb single-stranded DNA, whose corresponding replicative form was found in plasmid preparations. This DNA likely corresponds to the genome of a new filamentous phage, which we have designated KSF-1phi. The replicative form DNA of KSF-1phi was cloned into pUC18, and the resulting construct pKSF-1.1 supported the production of RS1phi particles by CTX-negative V. cholerae strains. RS1phi particles produced in this way infect recipient V. cholerae strains by a mechanism that is independent of the CTXphi receptor, the toxin-coregulated pilus. Thus, KSF-1phi is capable of facilitating the transfer of the RS1 element to strains that do not express toxin coregulated pilus. Given that RS1phi can enhance coproduction of CTXphi particles, KSF-1phi-mediated dissemination of RS1 may indirectly promote the spread of toxin genes among V. cholerae strains. This study also shows that filamentous phages can package diverse DNA elements and thus may play a role in horizontal transfer of more genes than previously appreciated.
Let X be a Spin manifold with boundary, such that the Spin structure is defined near the boundary by an almost complex structure, which is either strictly pseudoconvex or pseudoconcave (and hence contact). Using generalized Szego projectors, we define modified partial differential-Neumann boundary conditions, Reo, for spinors, which lead to subelliptic Fredholm boundary value problems for the Spin-Dirac operator, eth(eo). To study the index of these boundary value problems we introduce a generalization of Fredholm pairs to the "tame" category. In this context, we show that the index of the graph closure of (eth(eo), Reo) equals the tame relative index, on the boundary, between Reo and the Calderon projector. Let X0 and X1 be strictly pseudoconvex, Spin manifolds, as above. Let phi : bX1 --> bX0, be a contact diffeomorphism, S0, S1 denote generalized Szego projectors on bX0, bX1, respectively, and R0(eo), R1(eo), the subelliptic boundary conditions they define. If X1 is the manifold X1 with its orientation reversed, then the glued manifold X = X0 coproduct operator(phi) X1 has a canonical Spin structure and Dirac operator, ethX(eo). Applying these results we obtain a formula for the relative index, R-Ind(S0, phi*S1), [formula: see text]. As a special case, this formula verifies a conjecture of Atiyah and Weinstein [(1997) RIMS Kokyuroku 1014:1-14] for the index of the quantization of a contact transformation between cosphere bundles.
Leukocyte preparations convert the hydroperoxy icosatetraenoic acids 5(S)-HPETE and 15(S)-HPETE to the unstable leukotriene epoxides LTA4 and 14,15-LTA4. In several ways, the conversion of 5- or 15-HPETE to leukotriene epoxide bears a formal mechanistic resemblance to the reaction catalyzed by the 12-lipoxygenase in the conversion of arachidonic acid to 12(S)-HPETE. Points of similarity include enzymatic removal of a hydrogen at carbon 10, double bond isomerization, and formation of a new carbon-to-oxygen bond. In the case of 15(S)-HPETE, two 8,15- and an erythro-14,15-dihydroxy acid (8,15- and 14,15-DiHETEs), which result from incorporation of molecular oxygen into each hydroxyl group, are coproducts in the formation of 14,15-LTA4. These facts prompted us to test the hypothesis that the biosynthesis of 14,15-LTA4 and of 8,15- and 14,15-DiHETEs from 15(S)-HPETE occurs by a mechanism similar to that observed in lipoxygenase reactions. Based on the results presented here, we conclude that the biosynthesis of 14,15-LTA4 and of 8,15- and 14,15-DiHETEs from 15(S)-HPETE occurs via a common intermediate and that, moreover, the formation of these metabolites from 15(S)-HPETE is catalyzed by an enzyme with many mechanistic features in common with the 12-lipoxygenase.