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91.
1,3-Dimethylated hydrocarbon segments occur frequently as structural elements in polyketide natural products. The (13)C NMR chemical shifts of a series of model compounds containing such segments can be well reproduced by a combination of molecular mechanics and SOS-DFPT/IGLO calculations. (13)C NMR chemical shifts are calculated on MM3 geometries and are Boltzmann weighted according to the MM3 energies. On the basis of the resulting thermally averaged chemical shifts, all diastereomers of the model compounds can be unequivocally distinguished. Significant differences in chemical shifts occur at methyl groups and methylene groups that are adjacent to a single stereogenic center. The method is applied to predict the relative configuration of two stereocenters in the side chains of two natural products, sambutoxin and the bradykinin inhibitor L-755,897. 相似文献
92.
Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring. 相似文献
93.
Summary A simple procedure for the determination of salicylanilide and paratoluene sulphonamide in paints has been worked out. Salicylanilide is determined by ethanol extraction and subsequent measuring of the UV-absorption spectrum, and also by determining the nitrogen content according to Kjeldahl. For the determination of para-toluene sulphonamide three different methods are employed, viz., the Kjeldahl determination of the nitrogen content, the determination of the sulphur content by burning the sample in an oxygen flask and subsequent determination of sulphate, and also by measuring the UV-absorption spectrum, the last method being only a semi-quantitative check.
Part II: Hoffmann, E., B. Bursztyn, and A. Saracz: Z. analyt. Chem. 207, 432 (1965). 相似文献
Zusammenfassung Ein einfaches Verfahren zur Bestimmung von Salicylanilid und p-Toluolsulfonamid in Anstrichfarben wird beschrieben. Die Salicylanilidbestimmung erfolgt durch Äthanolextraktion und anschließende Messung des UV-Absorptionsspektrums sowie durch Stickstoffbestimmung nach Kjeldahl. Zur Bestimmung von p-Toluolsulfonamid dient ebenfalls die Stickstoffbestimmung nach Kjeldahl, sowie die Schwefelbestimmung durch Verbrennung in Sauerstoff mit anschließender Sulfatbestimmung und auch die UV-Absorptionsspektrometrie, letztere jedoch nur als halb quantitative Kontrollmethode.
Part II: Hoffmann, E., B. Bursztyn, and A. Saracz: Z. analyt. Chem. 207, 432 (1965). 相似文献
94.
The etch rate ofn-type Si in diluted HF solutions was investigated as a function of the bias voltage applied to the Si/electrolyte interface in the dark and under illumination. It was observed that the etch rate depends very sensitively on the minority carrier flow through this interface. For an illumination intensity of 5.3×1016 photons/cm2 s (=550nm) and the depleted Si/electrolyte interface biased slightly (less than 1 V) in reverse, the etch rate is increased by a factor of more than 1000 as compared to the etch rate under open-circuit condition. This effect can be used to create etch patterns during device processing without prior masking the semiconductors. Using the same effect it should be possible to trim the thickness of Si layers on (semi-) insulating substrates for the fabrication of enhancement-mode FETs. 相似文献
95.
Treatment of methyl 2-(1-hydroxyalkyl)prop-2-enoates 1 with conc. HBr solution afforded methyl (Z)-2-(bromomethyl)alk-2-enoates 2 , which were transformed regioselectively into N-substituted methyl (E)-2- (aminomethyl)alk-2-enoates 3 (SN2 reaction) and into N-substituted methyl 2-(1-aminoalkyl)prop-2-enoates 4 (SN2′ reaction). Regiocontrol of nucleophilic attack by amine was accomplished simply by choice of solvent, the SN2 reaction occurring in MeCN and the SN2′ reaction in petroleum ether. Hydrolysis and lactamization afforded β-lactams 7 and 8 , containing an exocyciic alkylidene and methylidene group at C(3), respectively. 相似文献
96.
Knez M Sumser MP Bittner AM Wege C Jeske H Hoffmann DM Kuhnke K Kern K 《Langmuir : the ACS journal of surfaces and colloids》2004,20(2):441-447
We studied the adsorption behavior and surface chemistry of the tobacco mosaic virus (TMV) on well-defined metal and insulator surfaces. TMV serves as a tubular supramolecular model system with precisely known surface termination. We show that if the surface chemistry of the substrate and the pH-dependent chemistry of the molecular surface match, for example, by hydrogen bonding, a strong adsorption occurs, and lateral movement is impeded. Due to the immobilization, the virion can be imaged by atomic force microscopy (AFM) in contact mode. We also used self-assembled monolayers with an acyl chloride group to induce covalent bonding via ester formation. Noncontact AFM proved that TMV keeps its cylindrical cross section only under weak adsorption conditions, that is, on hydrophobic surfaces, while on hydrophilic substrates a deformation occurs to maximize the number of interacting chemical groups. 相似文献
97.
Speciation of arsenic in environmental samples gains increasingly importance, as the toxic effects of arsenic are related to its oxidation state. A method was developed for the determination of trace amounts of arsenic (III) and total arsenic by flow injection hydride generation coupled with an in-house made non-dispersive AAS device. The total arsenic is determined after prereduction of arsenic (V) to arsenic (III) with L-cysteine in a low concentration of hydrochloric, acetic or nitric acid. The conditions for the prereduction, hydride generation and atomization were systematically investigated. A quartz tube temperature of 800 degrees C was found to be optimum in view of peak shape and baseline stability. Pb(II), Ni(II), Fe(III), Cu(II), Ag(I), Al(III), Ga(II), Se(IV), Bi(III) were checked for interfering with the 2 microg/L As(V) signal. A serious signal depression was only observed for Se(IV) and Bi(III) at a 150-fold excess. With the above system, arsenic was determined at a sampling frequency of about 1/min with a detection limit (3sigma) of 0.01 microg/L using a 0.5 mL sample. The reagent blank was 0.001+/-0.0003 absorbance units and the standard deviation of 10 measurements of the 2 microg/l As signal was found to be 1.2%. Results obtained for standard reference materials and water samples are in good agreement with the certified values and those obtained by ICP-MS 相似文献
98.
Small angle neutron scattering experiments (SANS) were carried out with solutions of the Lithium salt of Perfluoroctanoic acid (LIPFO) in pure D2O and mixtures of D2O and H2O and Diethylammoniumperfluorononanoate (DEAFN). For LIPFO the scattering intensity as a function of the scattering angles could be fitted with calculated scattering functions for spheres. The contrast variation method allowed us to extract accurate values for the radius, the concentrations of the micelles and the aggregation number. For DEAFN the observed scattering function could be fitted on the basis of spherical vesicles with an appreciable variance in diameter. For several solutions these parameters and the concentration of the vesicles could be evaluated. 相似文献
99.
Ute Ch.?Rodewald Mar’yana?Lukachuk Rolf-Dieter?Hoffmann Rainer?P?ttgenEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(12):1985-1991
Summary. The gadolinium–rhodium–indide Gd3Rh1.940(7)In4 was prepared by arc-melting of the elements and subsequent annealing in a corundum crucible in a sealed silica tube. Gd3Rh1.940(7)In4 adopts the hexagonal Lu3Co1.87In4 type, space group
, a = 781.4(5), c = 383.8(3) pm, wR2 = 0.0285, BASF = 0.375(1) (merohedric twinning via a twofold axis (xx0)), 648 F2 values, 22 variables. The structure is derived from the well known ZrNiAl type through an ordering of rhodium and indium
atoms on the Ni2 sites. The Rh/In ordering forces a reduction of the space group symmetry from
to
, leading to merohedric twinning for the investigated crystal. The Rh1 site has an occupancy of only 94.0(7)%. The investigated
crystal had a composition Gd3Rh1.940(7)In4. The main geometrical motif are three types of centered, tricapped trigonal prisms, i.e., [Rh1In26Gd3], [Rh2Gd6In23], and [In1Gd6In23]. The shortest interatomic distances occur for Rh–In (276–296 pm) followed by In–In (297 pm). Together, the rhodium and indium
atoms build up a three-dimensional [Rh1.940(7)In4] network, in which the gadolinium atoms fill slightly distorted pentagonal channels. The crystal chemistry of Gd3Rh1.940(7)In4 is discussed on the basis of a group-subgroup scheme. 相似文献
100.
Self-assembly of amphiphilic hexapyridinium cations at the air/water interface and on HOPG surfaces.
Haofei Gong Dr. Björn Bredenkötter Dr. Christoph Meier Carola Hoffmann‐ Richter Dr. Ulrich Ziener Dr. Dirk G. Kurth Dr. Dirk Volkmer Prof. Dr. 《Chemphyschem》2007,8(16):2354-2362
Mono- and multilayers of a novel amphiphilic hexapyridinium cation with six eicosyl chains (3) are spread at the air/water interface as well as on highly ordered pyrolytic graphite (HOPG). On water, the monolayer of 3 is investigated by recording surface pressure/area and surface potential/area isotherms, and by Brewster angle microscopy (BAM). Self-organized tubular micelles with an internal edge-on orientation of molecules form at the air/water interface at low surface pressure whereas multilayers are present at high surface pressure, after a phase transition. Packing motifs suggesting a tubular arrangement of the constituting molecules were gleaned from atomic force microscopy (AFM) investigations of Langmuir-Blodgett (LB) monolayers being transferred on HOPG at different surface pressures. These LB film structures are compared to the self-assembled monolayer (SAM) of 3 formed via adsorption from a supersaturated solution, which is studied by scanning tunnelling microscopy (STM). On HOPG the SAM of 3 consists of nanorods with a highly ordered edge-on packing of the aromatic rings and an arrangement of alkyl chains which resembles the packing of molecules at the air/water interface at low surface pressure. Additional details of the molecular packing were gleaned from single-crystal X-ray structure analysis of the hexapyridinium model compound 2b, which possesses methyl instead of eicosyl residues. 相似文献