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61.
S. Sarge H. K. Cammenga B. Becker R. Rohr-Aehle R. Tacke 《Journal of Thermal Analysis and Calorimetry》1988,33(4):1185-1192
Silanes of the type R1R2Si(H)CH2OEl(O)xR
y
3
[R=organyl; El=C (x=y=1), S (x=2,y=1), P (x=1y=2)] undergo a thermally induced rearrangement to give silanes of the type R1R2Si (CH3)OEl(O)xR
y
3
. The energetic (reaction enthalpy) and kinetic data (reaction order, enthalpy and entropy of activation) of this reaction were determined by means of differential scanning calorimetry. The results obtained are discussed in terms of mechanistic aspects.
相似文献
Zusammenfassung Silane des Typs R1R2Si(H)CH2OE10xR y 3 mit R=organyl; E1=C (x=y=1), S(x=2, y=1) oder P (x=1,y=2) zeigen eine thermisch induzierte Umlagerung zu Silanen des Typs R1R2Si(CH3)OE10xR y 3 . Energetische (Reaktionsenthalpie) und kinetische Daten (Reaktionsordnung, Aktivierungsenthalpie und -entropie) dieser Umlagerungsreaktion wurden mittels DSC ermittelt. Die mechanistischen Aspekte der Ergebnisse werden diskutiert.
R1R2Si(H)OE1(O)xR y 3 , R= , E1=C (x=y=1), S (x=2,y=1), P (x=1,y=2), R1R2Si(CH3)OE1(O)xR y 3 . ( ) ( , ) . .
相似文献
62.
Gastel M Breuer U Holzbrecher H Becker JS Dietze HJ Kubon M Wagner H 《Analytical and bioanalytical chemistry》1995,353(3-4):478-482
The determination of elemental distributions in thin film solar cells based on amorphous silicon using electron beam SNMS is possible by quantifying the measured ion intensities. The relative sensitivity factors (RSFs) for all elements measured have to be known. The RSFs have been determined experimentally using implantation and bulk standards with known concentrations of the interesting elements. The measured RSFs have been compared with calculated RSFs. The model used for the calculation of the RSFs takes into account the probability for electron impact ionization and the dwell time of the neutrals inside the postionization region. The comparison between measured and calculated RSF shows, that this model is capable to explain the RSFs for most elements. Differences between calculated and measured values can be explained by the formation of hydride and fluoride molecules (in case of H and F) and influences of the angular distribution of the sputtered neutrals in case of Al. The experimentally determined RSFs have been used for a quantification of depth profiles of the i-, buffer-, p- and front contact layers of a-Si solar cells. 相似文献
63.
Bead cellulose derivatives as supports for immobilization and chromatographic purification of proteins 总被引:3,自引:0,他引:3
H F Boeden K Pommerening M Becker C Rupprich M Holtzhauer F Loth R Müller D Bertram 《Journal of chromatography. A》1991,552(1-2):389-414
Characteristic data are presented for Divicell, a macroporous bead cellulose with excellent flow parameters. The preparation of Divicell derivatives and their properties are described with respect to their application as chromatographic supports. The ion exchangers Divicell DEAE and Divicell CM were manufactured in two types with different exclusion limits and an available capacity for proteins of up to 100 mg/ml gel. Divicell Blue is a bead cellulose with covalently bound Cibacron Blue F3G-A and was found to be a very suitable adsorbent for the selective separation and purification of human serum albumin. Activation of Divicell with sodium periodate, epichlorohydrin and 5-norbornene-2,3-dicarboximido carbonochloridate provided activated supports used for immobilization of ligands in organic solvents and in aqueous solutions. Coupling of amines, diamines, amino acids, carbohydrates and proteins is described. The immobilized ligands retained their biological activity as determined by their specific adsorption of proteins. Divicell alkyl derivatives were tested in hydrophobic interaction chromatography with bovine serum albumin as a model. Examples are presented of the application of Divicell derivatives to the purification of biomacromolecules such as immunoglobulins and lectins by affinity chromatography. The results were comparable to those obtained using the corresponding Sepharose-derived absorbents. 相似文献
64.
Douglas C. Miller Martin R. Johnson John J. Becker James A. Ibers 《Journal of heterocyclic chemistry》1993,30(6):1485-1490
The new 22-π, aromatic “pentaplanar” macrocycle, ozaphyrin ( 6 ), has been synthesized by a McMurry coupling of 5,5′-diformyl-4,4′-dipropyl-2,2′-bipyrrole ( 1 ) with 2,5-bis(5-formyl-4-propyl-2-pyrrolyl)furan ( 5 ). This synthetic pathway to ozaphyrin and its characterization by 1H nmr spectroscopy, uv-visible spectroscopy, cyclic voltammetry, and X-ray crystallography are described. The structure consists of layers of planar, staggered macrocycles stacked perpendicular to the α-axis. Ozaphyrin crystallizes with four formula units in the monoclinic space group C52h-P21/n in a cell of dimensions a = 10.481(7) Å, b = 17.353(17) Å, c = 18.726(12) Å, and β = 102.84(5)° (108 K). The structure has been refined on F2 (5171 unique reflections, 411 variables) to Rw(Fo2) = 0.165. The conventional agreement index R(F) is 0.074 for the 3289 reflections have Fo2>2o(Fo2). 相似文献
65.
D. A. Becker 《Journal of Radioanalytical and Nuclear Chemistry》1993,168(1):169-183
The ASTM Task Group on Nuclear Methods of Chemical Analysis (E10.05.12) has conducted a trace element intercomparison among some of its members over the past two years. Eight non-NIST laboratories submitted data using nuclear techniques, with a total of 111 values for the apple leaves and 116 values for the peach leaves, on 46 and 50 elements, respectively. This intercomparison provided a unique opportunity for the analytical laboratories, because the analytical values submitted could be later compared to the NIST certified values. For the seven elements which were certified by NIST and had three or more intercomparison values, the results showed that: 1) 61% of all 56 intercomparison values submitted had results whose stated uncertainty overlapped the uncertainty limits of the NIST certified values, and 2) less than 6% of the intercomparison values had means which fell outside ±20% of the NIST values. In general, the intercomparison values submitted showed excellent agreement with the NIST values. However, many reported uncertainties accompanying intercomparison values appeared overly optimistic. 相似文献
66.
Abstract— A systematic comprehensive consideration of the emission spectroscopy, emission lifetimes, transient spectroscopy, as well as quantum yields of fluorescence, triplet occupation and photoisomeriz-ation is given for a wide variety of polyene derivatives including retinyl and longer, as well as shorter chainlength homologs. Absorption spectral properties and the results and significance of theoretical calculations are also included. Chainlength, solvent and temperature effects on state order and photophysical as well as photoisomerization properties are evaluated. The mechanism for the primary light step in vision is considered in light of photophysical and photoisomerization data on model visual pigments and rhodopsin. 相似文献
67.
Retrobiosynthetic analysis of the allergenic sesquiterpene lactone, anthecotuloide, suggested that this natural product could be formed either by head to head condensation of geranyl diphosphate with dimethylallyl diphosphate, or from farnesyl diphosphate (FPP), the accepted regular sesquiterpene precursor via the rearrangement of a germacranolide precursor. Isotopic labelling of anthecotuloide has now been achieved by feeding [1-(13)C]-glucose, [U-13C6]-glucose and [6,6-(2)H2]-glucose to aseptically grown plantlets of Anthemis cotula(family Asteraceae). Analysis of labelling patterns and absolute 13C abundances using quantitative 13C NMR spectroscopy showed that the isoprene building blocks of this sesquiterpene are formed exclusively via the MEP terpene biosynthetic pathway. This was supported by results from an experiment using [U-13C6]-glucose. A deuterium labelling experiment using [6,6-(2)H2]-glucose supported the original proposal and showed that anthecotuloide is formed from a non FPP precursor. Isotope ratio mass spectrometry suggested that there were two pathways for sesquiterpene biosynthesis in A. cotula. 相似文献
68.
69.
Ault BS Becker TM Li GQ Orchin M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(11):2567-2572
The carbonyl stretching frequencies in the infrared spectra of 38 fac-tricarbonyl octahedral complexes of manganese(I) prepared in this laboratory were determined. These complexes may be grouped into three types: (a) neutral complexes of the structure (CO)(3)Mn(P-P)Z where P-P represents depe, dppe, or dppp, and Z represents various anionic functional groups bonded to the manganese; (b) ionic complexes of the structure [(CO)(3)Mn(P-P)Z](+)BF(4)(-) where Z represents various neutral molecules possessing one phosphorous, nitrogen, or oxygen atom coordinated to the manganese; (c) complexes of the structure (CO)(3)Mn(pn)Z where the chelating pn represents 1,1-diphenylphosphino-2,2-dimethylaminoethane, Ph(2)PCH(2)CH(2)NMe(2). All of these complexes show three carbonyl stretching modes (2A' + A"). The effects on the frequencies of these modes induced by both the various Z groups and the various ligands are discussed. Theoretical calculations (B3LYP/6-31G) with optimization of the full molecule make it possible to distinguish between the three stretching modes and to make unambiguous assignments of appropriate symmetry species to each. 相似文献
70.
A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure. 相似文献