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81.
We extract a relatively precise value for the decay constant of the meson by measuring B(D+ --> mu+nu) = (4.40 +/-0.66(+0.09)(-0.12) x 10(-4) using 281 pb(-1) of data taken on phi(3770) the resonance with the CLEO-c detector. We find fD+ = (222.6 +/- 16.7(+2.8)(-3.4)) MeV, and compare with current theoretical calculations. We also set a 90% confidence upper limit on B(D+e+nu)< 2.4 x 10(-5) which constrains new physics models.  相似文献   
82.
Solandelactones A, B, E, and F were synthesized using Nozaki-Hiyama-Kishi coupling of iododiene 13 with aldehydes 14 and 99 obtained by oxidation of alcohols 92 and 94. Key steps in the synthesis of 92 and 94 were (i) a Nagao asymmetric acetate aldol reaction of aldehyde 77 with thionothiazolidine 78 to set in place an alcohol that becomes the (7 S) lactone center of solandelactones, (ii) a Simmons-Smith cyclopropanation of 80 directed by this alcohol, and (iii) Petasis methylenation of cyclic carbonate 90 in tandem with a Claisen rearrangement that generates the octenalactone portion of solandelactones. Synthesis of solandelactones A, B, E, and F confirmed their gross structure and absolute configuration at C7, 8, 10, and 14 but showed that alcohol configuration at C11 must be reversed in pairs, A/B and E/F, from the previous assignment made to these hydroid metabolites. Thus, solandelactones A and B are correctly represented by 2 and 1, respectively, whereas solandelactones E and F are 6 and 5. A biogenesis of solandelactones is proposed for these C 22 oxylipins that parallels a hypothesis put forward previously to explain the origin of C 20 cyclopropane-containing algal products.  相似文献   
83.
The electrophoretic mobility behavior of well-characterized polystyrene latex particles, carrying one type of surface functional endgroups, has been studied as a function of pH. At low pH, the interaction of protons with the functional endgroups increased in the order: Hydroxyl > carboxyl > sulfate; at high pH the order of interaction was reversed; and at intermediate pH no interactions were observed. The particles of the polystyrene latexes in their different forms at the intermediate pH range, dispersed in deionized water, all exhibited the same mobility irrespective of the functional endgroup. The origin of charge in these systems is explained as being the result of either the preferential adsorption of hydroxyl ions or an electron - injection mechanism due to the overlap of local intrinsic molecular - ion states in polystyrene and water. At low concentrations of functional endgroups, the surface properties of the polystyrene latexes are largely dependent upon the hydrophobic nature of the surface.  相似文献   
84.
    
Fluorogenic analogues of α‐tocopherol developed by our group have been instrumental in monitoring reactive oxygen species (ROS) within lipid membranes. Prepared as two‐segment trap‐reporter (chromanol‐BODIPY) probes, photoinduced electron transfer (PeT) was utilized to provide these probes with an off/on switch mechanism warranting the necessary sensitivity. Herein, we rationalize within the context of Marcus theory of electron transfer how substituents on the BODIPY core and linker length joining the trap and reporter segments, tune PeT efficiency. DFT and electrochemical studies were used to estimate the thermodynamic driving force of PeT in our constructs. By tuning the redox potential over a 400 mV range, we observed over an order of magnitude increase in PeT efficiency. Increasing the linker length between the chromanol and BODIPY by 2.8 angstroms, in turn, decreased PeT efficiency 2.7‐fold. Our results illustrate how substituent and linker choice enable “darkening” the off state of fluorogenic probes based on BODIPY fluorophores, by favoring PeT over radiative emission from the singlet excited state manifold. Ultimately, our work brings light to the sensitivity ceiling one may achieve in developing fluorogenic antioxidant analogues of α‐tocopherol. The work provides general guidelines applicable to those developing fluorogenic probes based on PeT.  相似文献   
85.
86.
The concept of Majorana and Dirac massive neutrinos is discussed for the case in which there are several types, or flavors, of leptons. Different varieties of Dirac neutrinos are possible, distinguised by their magnetic moments and anomalous interactions with probabilities proportional to (m/E)2.  相似文献   
87.
We recently reported that ruthenium complexes, with general structure [mu-bidppz(bipy)4Ru2](4+) (B) or [mu-bidppz(phen)4Ru2](4+) (P) (bidppz=11,11'-bi(dipyrido[3,2- a:2',3'-c]phenazinyl)), show extreme kinetic selectivity for long AT tracts over mixed-sequence calf thymus DNA (ct-DNA), a selectivity that also varies markedly with the size (between B and P) and sense of chirality of the complex. Earlier studies, exploiting the great increase in luminescence intensity when the compound intercalates, have yielded complex kinetics indicating the presence of both first- and second-order processes. Even with a homogeneous DNA sequence, such as poly(dAdT)2, the luminescence kinetics generally requires more than a single exponential for a satisfactory fit. We here reveal that at least part of the complexity is a result of the extreme sensitivity of the effective quantum yield of the complexes, so that the luminescence trajectories also reflect subtle variations in the environment and binding geometry that the complex is sampling on its path to its final binding site. By monitoring the rearrangement process using circular dichroism (CD), we show that threading of both enantiomers of B and P into poly(dAdT)2 is effectively a monoexponential process, as expected if the compounds are not affecting each other during the intercalation process. Thus, the complex luminescence trajectories may be explained by slow relaxations in the binding geometry (DNA conformation) and associated changes in the environment of the entering complexes. To further disentangle the intriguing features of the threading intercalation kinetics, and how they may depend on the flexibility and size of the ruthenium complexes, we have also designed and studied two new ruthenium complexes, [mu-dtpf(phen)4Ru2](4+) (F) (dtpf=4,5,9,12,16,17,21,25-octaaza-23 H-ditriphenyleno[2,3-b:2,3-h]fluorene), in which the bridging ligand is made totally rigid, and [mu-bidppz([12]aneS4) 2Ru2](4+) (S), which has less bulky, nonaromatic ancillary ligands. The threading of F into poly(dAdT)2, also found to be a monoexponential process, is about 3 times slower than for P, indicating that the flexibility of the bridging ligand is an important factor for the intercalation rate. Surprisingly, in contrast to all other compounds, S requires two exponentials to fit its binding kinetics as monitored by CD. Also surprisingly, in view of the smaller steric bulk, even the fastest phase is roughly 2 times slower for S than for B and P. Thus, not only the size of the ancillary ligand but also other properties that can influence the energy landscape of the threading path are rate-determining factors. With mixed-sequence ct-DNA, threading of B and that of P are both multiphasic processes when monitored with CD as well as with luminescence. The rate constants for threading into ct-DNA show much larger variations between complexes than for poly(dAdT)2, confirming earlier results based on luminescence data.  相似文献   
88.
Cyclodextrin [2]rotaxanes have been prepared by coupling dimethylanilines with dicarboxylic acids using DMT-MM, in aqueous solutions of alpha-cyclodextrin, and the example illustrated shows unusual fluorescence emission and other spectroscopic behavior characteristic of the formation of molecular wires in solution, similar to the fibers observed in the solid state.  相似文献   
89.
We measure the mass of the eta meson using psi(2S) --> etaJ/psi events acquired with the CLEO-c detector operating at the CESR e(+)e(-) collider. Using the four decay modes eta --> gamma gamma, 3pi(0), pi(+)pi(-)pi(0), and pi(+)pi(-)gamma, we find M(eta) = 547.785 +/- 0.017 +/- 0.057 MeV, in which the first uncertainty is statistical and the second systematic. This result has an uncertainty comparable to the two most precise previous measurements and is consistent with that of NA48, but is inconsistent at the level of 6.5 sigma with the much smaller mass obtained by GEM.  相似文献   
90.
Topological winding and unwinding in a quasi-one-dimensional metastable Bose-Einstein condensate are shown to be manipulated by changing the strength of interaction or the frequency of rotation. Exact diagonalization analysis reveals that quasidegenerate states emerge spontaneously near the transition point, allowing a smooth crossover between topologically distinct states. On a mean-field level, the transition is accompanied by formation of gray solitons, or density notches, which serve as an experimental signature of this phenomenon.  相似文献   
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