Where does the planar-to-nonplanar turnover occur in small gold clusters?

Several levels of theory, including both Gaussian-based and plane wave density functional theory (DFT), second-order perturbation theory (MP2), and coupled cluster methods (CCSD(T)), are employed to study Au6 and Au8 clusters. All methods predict that the lowest energy isomer of Au6 is planar. For Au8, both DFT methods predict that the two lowest isomers are planar. In contrast, both MP2 and CCSD(T) predict the lowest Au8 isomers to be nonplanar.     

Multireference second-order perturbation theory: how size consistent is "almost size consistent"

A systematic study of the deviation from size consistency of the multireference second-order Moller-Plesset perturbation theory (MRMP2) method is presented. The size-consistency error is shown to depend on the number of monomers in a supermolecule calculation, size of basis set, number of correlated valence electrons, and size of active space. HF, F(2), and N(2) are used as test cases, with stretched bonds, to include simple, well-defined multireference character. This is essential in ensuring that MRMP2 is being tested as a multireference method. It is concluded that the MRMP2 and other multireference perturbation theory methods can exhibit significant size-consistency errors, and that the size of the error depends on the manner in which the perturbation theory is implemented.     

Facility for non-destructive analysis for major and trace elements using neutron-capture gamma-ray spectrometry

A facility for neutron-capture γ-ray spectroscopy for analytical purposes has been developed and tested at the National Bureau of Standards reactor. The system consists of an internal beam tube with collimators, an external beam tube and irradiation station, a Compton-suppressed Ge(Li) γ-ray detection system, and a minicomputer-based data-collection and-analysis system. Detection limits have been established for many elements and errors arising from neutron self shielding, γ-ray peak overlap, neutron beam variations, and sample matrix evaluated.     

Optically active polymer carbon nanotube composite

A completely soluble optically active polyaniline-multiwalled carbon nanotube composite was investigated by spectroscopic and microscopic techniques. It was found that the polymer's optical activity was retained in the presence of carbon nanotubes. Solutions were found to be easily processable into thin films, which exhibited dendritic structures only in the presence of nanotubes.     

A laser induced fluorescence study of vibrational energy transfer processes in cyclopropane

Results of infrared laser induced fluorescence studies on cyclopropane are presented. Molecules were excited from the ground state to the v₁₀ level of cyclopropane using a Q-switched CO₂ laser operating on either the P(14) or P(20) transition of the 9.6 μ branch. Fluorescence was observed from the v₆, v₈, v₁₀ + v₁₁ and v₅ + v₁₀ levels of cyclopropane. The self-deactivation of vibrationally excited cyclopropane through V → T/R processes was found to have a rate of 8.0 ± 1.5 ms^?1 torr^?1. Deactivation by rare gas collisions was also studied with comparison to simple V → T and V → R theories. V → V equilibration processes are discussed involving the v₆, v₈, v₁₀, v₁₁, and v₁₀ + v₁₁ levels.     

INACTIVATION OF CELL SURFACE RECEPTORS BY PHEOPHORBIDE a, A GREEN PIGMENT ISOLATED FROM Psychotria acuminata

Abstract— The inhibition of cytokine and monoclonal antibody binding to cell surfaces caused by an extract of Psychotria acuminata, a medicinal plant used in the traditional medicine of the people of Belize (Central America), was attributed to the presence of pheophorbide a and pyropheophorbide a Since the binding of tumor necrosis factor-alpha, interleukin-8, complement factor 5a as well as epidermal growth factor to target cells was dramatically reduced, the inhibition was not receptor or cytokine specific. In addition, the respective binding of radiolabeled monoclonal antibodies CL203 and R15.7 to the cell surface antigens intracellular cell adhesion molecule-1 and lymphocyte function-associated antigen-1 ß-chain was decreased by pretreatment of cells with pheophorbide a as well. In all cases, the inhibition by pheophorbides was dependent on the simultaneous presence of light, indicating causative involvement of a photodynamic process. These observations are not unique to pheophorbides and can be extended to porphyrins as well as to other photodynamic agents. Cytotoxicity resulting from photodynamic therapy (PDT) has been documented by many studies. Our investigations suggest that the inactivation of cell surface receptors contributes not only to the antitumor effect of PDT but also to the systemic immunosuppression, a serious side effect of PDT.     

Benzohydrazides,benzothiohydrazides, and benzamidrazones as sources of 1,3,4(2H)-oxadiazolenones, 1,3,4(2H)-thiadiazolenones,and 1,2,4(5H)-triazolenones

Benzohydrazides, benzothiohydrazides, and benzamidrazones have been converted to 1,3,4(2H)-oxadiazolenones, 1,3,4(2H)-thiadiazolenenones, and 1,2,4(5H)-triazolenones respectively by reaction with ethyl chloroformate, with ethyl thiolchloroformate, and with phenyl isocyanate. In some reactions, a carbamate or urea has been isolated as intermediate.     

Model discrimination for rotational energy transfer in the Ar-N2 system

The jackknife test of Rothstein et al. is applied to discrimination between several different models used to compute the rotationally inelastic cross sections for the Ar-N₂ system. The modified exponential models are the best models, except for the case where the energy gap is small, when power laws are best.     

Solar ultraviolet-B radiation in urban environments: the case of Baltimore, Maryland

Ultraviolet-B radiation (UV-B, 280-320 nm) has important effects in urban areas, including those on human health. Broadband UV-B radiation is monitored in Baltimore, MD, as part of the Baltimore Ecosystem Study, a long-term ecological research program. We compare broadband UV-B irradiance in Baltimore with UV-B at two nearby locations: a more rural station 64 km southeast and a suburban station 42 km southwest. The monitoring station in Baltimore is on the roof of a 33-m-tall building; there are no significant obstructions to sky view. The U.S. Department of Agriculture UV-B Monitoring and Research Program provided all sensors, which were calibrated at the National Oceanic and Atmospheric Administration Central UV Calibration Facility. UV-B irradiances at the three sites generally were similar. Over all conditions, Baltimore and the suburban site measured 3.4% less irradiance than the rural site. This difference is within the anticipated +/-3% calibration uncertainty of the pyranometers. On 59 days with cloud-free conditions at all three sites, average differences in measured UV-B among the three sites were even smaller; Baltimore measured 1.2% less irradiance than the rural site. High aerosol optical thickness strongly reduced daily UV-B dose, whereas [SO2] had no influence. Surface O3 increased with increasing UV-B dose when [NO2] exceeded 10 ppb.     

Biodegradation of mixed wastes in continuously operated cyclic reactors

The problem of simultaneous biodegradation of two dissimilar substrates in a continuously operated cyclic reactor was studied both at the theoretical and experimental levels using a simple model system. The system involved media containing mixtures of glucose and phenol as carbon sources. A pure culture ofPseudomonas putida (ATCC 17514) was employed. Independent kinetic experiments have revealed that glucose and phenol are involved in a crossinhibitory uncompetitive kinetic interaction. The dynamics of a cyclically operated reactor were analyzed using the principles of bifurcation theory for forced systems. Experimental results have confirmed the theoretical predictions. Implications of the results for the design of waste-treating facilities are discussed.