The photoelectron spectra of D2d and C2ν hydrocarbons containing two norbornadiene or quadricylane groups

The photoelectron spectra of the hydrocarbons 1 to 4 have been recorded and interpreted by qualitative correlation with the spectra of their subsystems norbornadiene, quadricyclane, allene and cyclopropane. It has been shown that the interactions of the symmetry adapted orbitals of the subsystems are governed not only by their symmetry behaviour with respect to D_2d in 1 and 2 , or C_2ν in 3 and 4 , but also by the local symmetry at the points of attachment of the subsystems.     

Development and Certification of NIST Standard Reference Materials for Relative Raman Intensity Calibration

In analytical Raman spectroscopy it becomes increasingly important to employ a procedure for the correction of the relative intensity of Raman spectra. The determination of the intensity response function of a Raman instrument traditionally has been carried out through a white light source that has been calibrated for its relative spectral irradiance. While this method will furnish a correction curve to yield spectra corrected to relative Raman intensity, it is often cumbersome and fraught with experimental difficulties that can profoundly affect the reliability of the correction procedure. An alternate methodology that permits a simplified calibration of the Raman instrument response function is based on the use of luminescent glass standards that transfer a white light calibration onto the Raman measurement system. In this procedure, a measurement of the luminescence of an intensity standard, whose relative irradiance has been determined, provides a means to establish the instrument response function. Correction of measured spectra by this function furnishes spectra that are free of instrumental intensity artifacts. Based on this approach, NIST is developing a series of Standard Reference Materials (SRMs) for the calibration of Raman intensity. This process, and the results obtained thereby, is described for Raman spectroscopy measurements employing 785nm excitation. The procedure is valid for both macro-sampling and micro-sampling Raman work.     

Demonstration-scale evaluation of a novel high-solids anaerobic digestion process for converting organic wastes to fuel gas and compost

Early evaluations of the bioconversion potential for combined wastes such as tuna sludge and sorted municipal solid waste (MSW) were conducted at laboratory scale and compared conventional low-solids, stirred-tank anaerobic systems with the novel, high-solids anaerobic digester (HSAD) design. Enhanced feedstock conversion rates and yields were determined for the HSAD system. In addition, the HSAD system demonstrated superior resiliency to process failure. Utilizing relatively dry feedstocks, the HSAD system is approximately one-tenth the size of conventional low-solids systems. In addition, the HSAD system is capable of organic loading rates (OLRs) on the order of 20-25 g volatile solids per liter digester volume per d (gVS/L/d), roughly 4-5 times those of conventional systems

Current efforts involve developing a demonstration-scale (pilot-scale) HSAD system. A two-ton/d plant has been constructed in Stanton, CA and is currently in the commissioning/startup phase. The purposes of the project are to verify laboratory- and intermediate-scale process performance; test the performance of large-scale prototype mechanical systems; demonstrate the long-term reliability of the process; and generate the process and economic data required for the design, financing, and construction of full-scale commercial systems. This study presents conformational fermentation data obtained at intermediate-scale and a snapshot of the pilot-scale project

     

Kristallstruktur von Monosilber(I)amidosulfat,AgSO3NH2

A crystal structure analysis of the colourless AgSO₃NH₂ was carried out at room temperature:M=203.95, orthorhombic, Pcab,a=7.809 (2) Å,b=8.067 (2) Å,c=11.682 (3) Å,V=735.9 ų,Z=8,d _x=3.681 Mgm^–3,F(000)=760, Mo K, =0.71069 Å (graphite monochromator), =5.77 mm^–1,R=4.36% (509 reflections, 56 parameters). The ionic structure shows approximate trigonal bipyramidal coordination around the Ag⁺-ions.

     

High-speed and high-accuracy DNA sequencing by capillary gel electrophoresis in a simple, low cost instrument Two-color peak-height encoded sequencing at 40°C

A low-cost DNA sequencer was constructed based on a single helium-neon laser. The two-color peak-height encoded sequencing protocol, based on the use of T7 DNA polymerase in a manganese buffer, was used to generate samples. Two termination reactions were performed. In the first, a TAMRA (applied Biosystems)-labeled primer was extended in the presence of ddATP and ddCTP. The amounts of dideoxynucleotides were adjusted to produce a 3:1 peak height ratio. Similarly, a ROX (Applied Biosystems)-labeled primer was extended in the presence of ddGTP and ddTTP; the amounts of dideoxynucleotides was adjusted to produce a 3:1 peak height ratio. The pooled fragments were separated on a 4% T LongRanger gel operated at 39°C. Over 500 bases of sequence were generated in 50 min.     

New Models for the Study of the Racemization Mechanism of Carbodiimides. Synthesis and Structure (X-ray Crystallography and (1)H NMR) of Cyclic Carbodiimides

The crystal and molecular structure of carbodiimides 2 (5,6,18,19-tetradehydro-5,12,13,18,25,26-hexahydrotetrabenzo[d,h,m,q][1,3,10,12]tetraazacyclooctadecine) and 3 (8,10,22,24-tetraazapentacyclo[23.3.1.1(3,7).1(11,15).1(17,21)]dotriaconta-1(29),3,5,7(32),8,9,11,13,15(31),17,19,21(30),22,23,25,27-hexadecaene) have been determined. The activation barriers for the racemization of carbodiimides 1 (6,7-dihydrodibenzo[d,h][1,3]diazonine), 2, and 3 have been determined. While 1 presents a relatively high barrier (17.4 kcal mol(-)(1)), 2 and 3 have very low activation barriers (between 5 and 7 kcal mol(-)(1)). We tentatively conclude that open-chain and large-ring carbodiimides racemize by nitrogen inversion or trans-rotation while medium-size cyclic carbodiimides racemize by cis-rotation.     

Photoelectron Spectra of Unsaturated Oxides. I. 1,4-Dioxin and related systems

The He (Iα) photoelectron spectra of the four unsaturated oxides 3,4-dihydropyran ( 6 ), γ-pyran ( 7 ), 2, 3-dihydro-1, 4-dioxin ( 9 ) and 1, 4-dioxin ( 10 ) are reported and analysed. Band assignments are based on ab-initio calculations, using the STO-3G basis set. The proposed orbital sequences (with reference to the coordinate systems given in Table 1) are, for the top three orbitals: 6 , π, nσ, nπ; 7 , 3b₁(π), 1a₂(π), 11a₁(σ); 9 , 11b(π), 12a(σ), 11a(π); 10 , 2b_3u(π), 1b_1g(π), 6a_g(σ). Finally the (almost) localized π-orbitals have been computed by the Foster-Boys localization procedure.     

Analysis of individual platelet-derived microparticles,comparing flow cytometry and capillary electrophoresis with laser-induced fluorescence detection

Platelet-derived microparticles (PMPs) formed by vesiculation during platelet activation seem to play a role in blood coagulation and in pathological disease states. Flow cytometry is currently the gold standard to characterize platelets and PMPs. Using this technique we distinguished between platelets and PMPs based on size and the presence of phosphatidyl serine (PS); PMPs were arbitrarily defined to be smaller than one micrometer and capable of forming a stable complex with fluorescently-labeled Annexin V, a protein that forms a calcium-dependent complex with PS. Further confirmation of PMP and platelet identity was done by use of fluorescently-labeled antibodies against CD41a, a glycoprotein found on the surface of both platelets and PMPs. In this report we also introduce the use of capillary electrophoresis with post-column laser-induced fluorescence detection (CE-LIF) for the analysis of fluorescently labeled platelets and PMPs. While both flow cytometry and CE-LIF can measure individual fluorescent events, only CE-LIF allowed us to calculate individual electrophoretic mobilities of activated platelets and PMPs that were then represented as distributions. A comparison between distributions suggests that PMPs have less negative mobilities. The fact that activated platelet preparations include PMPs partially obscure the interpretation of the data. While PMP and platelet number ml(-1) determined by flow cytometry is lower than the same parameter determined by CE-LIF, signal-to-noise ratio was 20 fold better for flow cytometry than for CE-LIF. This is the first time that a direct comparison between these two techniques is reported.     

Application of the Equivalent Bond Orbital Model to the C2s-Ionization Energies of Saturated Hydrocarbons

It is shown that the ab initio STO-3G treatment applied to simple saturated linear, branched and cyclic hydrocarbons, assuming standard geometries, yields orbital energies ? for their canonical orbital φ_j which correlate perfectly with the observed C_2s ionization energies I, if Koopmans' approximation is accepted. Applying the Foster-Boys localization procedure to these canonical orbitals φ_j leads to localized orbitals λμ and their corresponding Hartree-Fock matrix F_λ = (F_λ,μv). An examination of the matrix elements F_λ,μv, i.e. of the self-energies A_μ = F_λ,μμ of the localized CC- and CH-orbitals λ_μ and of the cross terms F_{λ, μv} (μ ≠ v) between them, leads to the conclusion that a satisfactory approximation should be obtained by setting A_μ = A for all μ, F_λ,μv = B if λ_μ and λ_v are vicinal and neglecting all other cross terms. The resulting model is nothing but the well-known equivalent bond orbital model of Lennard-Jones & Hall, which however can now be calibrated using the known C_2s-ionization energies of hydrocarbons. Due to the discrete structure and the wider range (∽ 8 eV) of the C_2s band systems in the photoelectron spectra of these molecules this leads to a more satisfactory parametrization than using the narrower and badly resolved C_2p band system. Comparison of calculated band positions using the calibrated model with observed C_2s-band ionization energies for a series of hydrocarbons reveals that the simple equivalent bond orbital model is better than one might have expected.     

Über Tris[(trialkylphosphan)gold(I)]oxonium-tetrafluoroborate und Tris[(triphenylphosphan)gold(I)]sulfonium-tetrafluoroborat

On Tris[(trialkylphosphine)gold(I)]oxonium Tetrafluoroborates and Tris[(triphenylphosphine)gold(I)]sulfonium Tetrafluoroborate [Et₃PAu]⁺BF, obtained from Et₃PAuCl and AgBF₄ in tetrahydrofuran, reacts with KOH (molar ratio 3:1) to give the oxonium salt [(Et₃P)Au]₃O⁺BF ( 1 ). The homologous [^t(Bu₃P)Au]₃O⁺BF ( 2 ) is generated similarly from ^tBu₃PAuCl and Ag₂O in the presence of NaBF₄ in THF. The composition and identity of these two first tris[(tri alkyl phosphine)gold(I)]oxonium salts have been confirmed by analytical and spectroscopic data. The compounds are useful aurating agents. From the corresponding triphenylphosphine complex and (Me₃Si)₂S quantitative yields of the sulfonium salt [(Ph₃P)Au]₃S⁺BF ( 3 ) are obtained. Its crystal structure features monomeric cations, and in these small Au? S? Au angles indicate significant metal-metal bonding.