Intermolecular interactions and geometry of non-rigid molecules in weak crystalline complexes: Vibrational spectra of 4,4′-dinitrobiphenyl complexes with biphenyl,biphenyl derivatives and p-terphenyl

Raman spectroscopy is used to study the complexes of 4,4′-dinitrobiphenyl with biphenyl, 4-hydroxybiphenyl, 4-bromobiphenyl and p-terphenyl, which crystallize in a highly unusual geometry. Their phonon spectra at 125 K and 18 K are compared and the effect of isotopic substitution of biphenyl on the phonon spectra of its complex is examined. Internal vibrations of the components in the crystalline complex are compared with those observed in the pure crystals of the components. The results from both phonon and intramolecular vibration studies show that these complexes form in fixed stoichiometries, are governed by geometrical factors, and are stabilized primarily by van der Waals interaction, although other kinds of interactions may provide additional stabilization. The 4,4′-dinitrobiphenyl molecule as well as biphenyl and p-terphenyl are centrosymmetric and remain so when the complexes are cooled from room temperature to 18 K. For biphenyl complex, this conclusion is supported by the observed IR spectra which show mutual exclusion between IR-active and Raman active vibrations. Crystal splitting is observed on the 410 cm^?1 vibration of 4,4′-dinitrobiphenyl. This splitting is attributed to the presence of more than one 4,4′-dinitrobiphenyl molecules in the complex unit.     

An a posteriori error estimator for plane-strain geotechnical analyses

In this paper, an a posteriori error estimator suitable for use in geotechnical engineering has been developed. This error criterion is based on the superconvergent patch recovery method with equilibrium and boundary conditions method, taking into account Biot's coupled consolidation theory. After testing on several problems, the introduction of pore pressures and other parameters into the error estimator was found to improve results significantly, providing a convergence rate of approximately two orders higher than the global rate.     

Highly efficient frequency doubling of high-energy Nd:YAG laser using a CsB3O5 crystal

We have demonstrated efficient frequency doubling of high-energy fundamental Nd:YAG laser pulse energy of the multi-joule (J) level at a high repetition rate using high optical-quality top-seeded solution growth CsB₃O₅(TSSG-CBO) crystal for the first time. Second-harmonic (532 nm) generation (SHG) output energy of 1.2 J at 10 Hz is obtained with a conversion efficiency of 60%. This result has been obtained at the multi-J level by the growth of high optical-quality TSSG-CBO crystal with the large effective nonlinear coefficient and high damage threshold. These results indicate that TSSG-CBO is a good candidate material for high-energy SHG of Nd-doped lasers at the several J level or more with high repetition rate.     

Graphitic encapsulation of catalyst particles in carbon nanotube production

A new model is proposed for the encapsulation of catalyst metal particles by graphite layers that are obtained, for example, in low-temperature chemical vapor deposition production of carbon nanotubes (CNTs). In this model graphite layers are primarily formed from the dissolved carbon atoms in the metal-carbide particle when the particle cools. This mechanism is in good agreement with molecular dynamics simulations (which show that precipitated carbon atoms preferentially form graphite sheets instead of CNTs at low temperatures) and experimental results (e.g., encapsulated metal particles are found in low-temperature zones and CNTs in high-temperature regions of production apparatus, very small catalyst particles are generally not encapsulated, and the ratio of the number of graphitic layers to the diameter of the catalyst particle is typically 0.25 nm(-1)).     

Compensation for source nonstationarity in multireference,scan-based near-field acoustical holography

Multireference, scan-based near-field acoustical holography is a useful measurement tool that can be applied when an insufficient number of microphones is available to make measurements on a complete hologram surface simultaneously. The scan-based procedure can be used to construct a complete hologram by joining together subholograms captured using a relatively small, roving scan array and a fixed reference array. For the procedure to be successful, the source levels must remain stationary for the time taken to record the complete hologram; that is unlikely to be the case in practice, however. Usually, the reference signal levels measured during each scan differ from each other with the result that spatial noise is added to the hologram. A procedure to suppress the effects of source level, and hence reference level, variations is proposed here. The procedure is based on a formulation that explicitly features the acoustical transfer functions between the sources and both the reference and scanning, field microphones. When it is assumed that source level changes do not affect the sources' directivity, a nonstationarity compensation procedure can be derived that is based on measured transfer functions between the reference and field microphones. It has been verified both experimentally and in numerical simulations that the proposed procedure can help suppress spatially distributed noise caused by the type of source level nonstationarity that is characteristic of realistic sources.     

Untersuchunz von Fetten

Ohne Zusammenfassung     

The metallation of imino(triphenyl)phosphorane by ethylmagnesium chloride: The synthesis, isolation and X-ray structure of [Ph3P=NMgCl·O=P(NMe2)3]2

Imino(triphenyl)phosphorane, Ph₃P=NH 1a, is metallated by ethylmagnesium chloride to give the N-magnesioiminophosphorane complex [Ph₃P=NMgCl·O=P(NMe₂)₃]₂ 4, whose X-ray structure has been determined.     

THE ASSOCIATION OF THE 5-METHYLPHENAZINIUM CATION AND THE 5-METHYL-10-HYDRO-PHENAZINIUM RADICAL CATION WITH MICELLES*

Abstract— 5-Methylphenazinium (MP⁺) cation salts are known to stimulate photophosphorylation in photosynthetic systems. The mechanism is thought to involve the translocation of protons across the thylakoid membrane although few details are known concerning the mechanism and the identity of the proton carrier. As there is some indication that the semireduced species, the 5-methyl-10-hydro-phenazinium (MPH⁺) cation radical, may be the proton carrier, we have studied the interaction of MPH⁺ with micelles as a model system for aqueouslipid interactions in a membrane. In this study we have used the techniques of NMR and EPR. In the presence of sodium dodecyl sulfate (NaLS) micelles the EPR spectrum of MPH ⁺ is broadened indicating specific binding of MPH⁺ to the micelle. A binding constant of -10⁵M^-1 was obtained. The 220 MHz NMR spectrum of a micellar solution with added MPH! shows specific broadening of the alkyl protons. The use of model paramagnetic adducts has allowed us to infer from the NMR results that the MPH⁺ ion penetrates the hydrocarbon part of the micelle to a considerable extent. This would indicate to us that MPH⁺ can indeed function as a proton carrier as it should be able to penetrate deeply into the lipid layer of the membrane. From these results, we conclude that:

• 1 Both MP⁺ and MPH⁺ interact strongly with NaLS micelles. MPH⁺ interacts more weakly with neutral Triton X-100 micelles while in this case, no evidence of interaction is seen for MP⁺. No binding of either MP⁺ or MPH⁺ is observed with cationic micelles from CTAB.
• 2 MP⁺ is adsorbed to NaLS micelles in a very hydrophilic region, probably In the Stern layer. MPH⁺, however, is much less hydrophilic than MP⁺ and appears to reside in the Palisade layer a few angstroms below the head groups.

On the basis of these results, we make the following proposals:

• 1 MPH⁺ is sufficiently hydrophobic to be a candidate for the reduced MP⁺ species which actually carries the proton across the thylakoid membrane.
• 2 The site at which MP⁺ is reduced by X must be anionic in nature in order for MP⁺ to be bound strongly.

     

Search for the standard model Higgs boson in the H→WW→lνq'q decay channel

We present a search for the standard model Higgs boson (H) in pp collisions at sqrt(s)=1.96 TeV in events containing a charged lepton (?), missing transverse energy, and at least two jets, using 5.4 fb(-1) of integrated luminosity recorded with the D0 detector at the Fermilab Tevatron Collider. This analysis is sensitive primarily to Higgs bosons produced through the fusion of two gluons or two electroweak bosons, with subsequent decay H→WW→?νq'q, where ? is an electron or muon. The search is also sensitive to contributions from other production channels, such as WH→?νbb. In the absence of a signal, we set limits at the 95% C.L. on the cross section for H production σ(pp→H+X) in these final states. For a mass of M(H)=160 GeV, the limit is a factor of 3.9 larger than the cross section in the standard model and consistent with an a priori expected sensitivity of 5.0.     

The Synthesis of 4-Amino-2-methyl-3-(1-oxo) Pent-4-ynyl-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-b]pyridine

The synthesis of ketone 1 from the ethyl ester of 4-amino-2-methyl-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-b]pyridine-3-carboxylic acid using β-ketosulfone methodology is described.