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141.
The molecular structure of gaseous 2-cyclopentene-1,4-dione has been studied by electron diffraction. The molecule is planar to within the experimental error. The results obtained for some of the more important parameters with estimated uncertainties of 2σ are r(C-H) = 1.093 Å (0.013), r(C0) = 1.208 Å (0.002), r(CC) = 1.341 Å (0.005), r(CH-CO) = 1.493 Å (0.005), r(CO-CH2) = 1.525 Å (0.005), ∠CC-C = 110.4° (0.3), ∠CH-CO = 124.9° (1.1), ∠CC-H. = 118.7° (5.8), ∠H-C-H = 113.2° (8.7) l(C-H) = 0.0853 A (0.0113), l(CO) = 0.0428 Å (0.0021), l(CC) = 0.0448 Å (0.0037) and l(C-C) = 0.0561 Å (0.0029). The structure is discussed in connection with the structures of related molecules. 相似文献
142.
Journal of Thermal Analysis and Calorimetry - 相似文献
143.
The influence of the water concentration in the water—n-octane—sodium dodecyl sulfate—n-pentanol microemulsions on the polarity index I
1/I
3, the efficiency of formation of the fluorescent probe (pyrene) excimers I
ex/I
m, and the conductivity of the system in a wide interval of water—oil ratios was studied. Analysis of changes in the polarity index shows that in all types of the microemulsions pyrene is solubilized in the hydrophobic part of the water—oil interface between the surfactant hydrocarbon radicals. Depending on the water—oil ratio, the site of its localization changes, and the effective permittivity of the medium eff varies from 5 to 11. Variations of the conductivity and polarity index allow one to observe three structures in the mucroemulsion, viz., water—oil, bicontinual region, and oil—water. Variation of the I
ex/I
m ratio reveals only the transition from the water—oil microemulsion to the oil—water microemulsion. 相似文献
144.
Bhurruth-Alcor Y Røst T Jorgensen MR Kontogiorgis C Skorve J Cooper RG Sheridan JM Hamilton WD Heal JR Berge RK Miller AD 《Organic & biomolecular chemistry》2011,9(4):1169-1188
Peroxisome proliferator activated receptors (PPARs) have been shown to have critical roles in fatty acid oxidation, triglyceride synthesis, and lipid metabolism - making them an important target in drug discovery. Here we describe the in silico design, synthesis and in vitro characterisation of a novel series of 2,5-disubstituted indoles as PPARα/γ dual agonists. PPAR activation assays are performed with known agonists diazabenzene (WY14.643), aminopyridine (BRL49653) and bisaryl (L165.041), as positive controls. All the indole compounds synthesized are found to be active PPARα and PPARγ agonists, with particular efficacy from those with 2-naphthylmethyl substitution. This is a useful demonstration of a new de novo design methodology implemented by the protobuild program and its ability to rapidly produce novel modulators for a well characterized drug target. 相似文献
145.
Salvatore P Hansen AG Moth-Poulsen K Bjørnholm T Nichols RJ Ulstrup J 《Physical chemistry chemical physics : PCCP》2011,13(32):14394-14403
We have studied self-assembled molecular monolayers (SAMs) of complexes between Os(II)/(III), Fe(II)/(III), and Ru(II)/(III) and a 2,2',6',2'-terpyridine (terpy) derivative linked to Au(111)-electrode surfaces via a 6-acetylthiohexyloxy substituent at the 4'-position of terpy. The complexes were prepared in situ by first linking the terpy ligand to the surface via the S-atom, followed by addition of suitable metal compounds. The metal-terpy SAMs were studied by cyclic voltammetry (CV), and in situ scanning tunnelling microscopy with full electrochemical potential control of substrate and tip (in situ STM). Sharp CV peaks were observed for the Os- and Fe complexes, with interfacial electrochemical electron transfer rate constants of 6-50 s(-1). Well-defined but significantly broader peaks (up to 300 mV) were observed for the Ru-complex. Addition of 2,2'-bipyridine (bipy) towards completion of the metal coordination spheres induced voltammetric sharpening. In situ STM images of single molecular scale strong structural features were observed for the osmium and iron complexes. As expected from the voltammetric patterns, the surface coverage was by far the highest for the Ru-complex which was therefore selected for scanning tunnelling spectroscopy. These correlations displayed a strong peak around the equilibrium potential with systematic shifts with increasing bias voltage, as expected for a sequential two-step in situ ET mechanism. 相似文献
146.
Henriette N. Tobiesen Dr. Lars A. Leth Marc V. Iversen Dr. Line Næsborg Dr. Søren Bertelsen Prof. Dr. Karl Anker Jørgensen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18648-18652
The first stereoselective, near-equimolar, and metal-free oxidative bioconjugation of amino acids and oligopeptides to aldehydes is presented. Based on a newly developed organocatalytic oxidative concept, the C-terminal and side-chain carboxylic acid functionalities of amino acids and oligopeptides are shown to couple in a stereoselective manner to α-branched aldehydes catalyzed by a chiral primary amine and a quinone as oxidizing agent. The oxidative coupling generally proceeds in high yield. For aspartic acid, selective coupling of the side-chain, or the C-terminal carboxylic acid, is demonstrated depending on the protection strategy. The stereoselective, oxidative bioconjugation concept is extended to a series of oligopeptides where coupling to carboxylic acid functionalities is presented. Bioorthogonal linker molecules for further functionalization are obtained by merging the oxidative coupling strategy with the click concept. It is demonstrated that the configuration of the new stereocenter is determined exclusively by the organocatalyst. 相似文献
147.
Pawlas J Vedsø P Jakobsen P Huusfeldt PO Begtrup M 《The Journal of organic chemistry》2000,65(26):9001-9006
1-Hydroxypyrazolo[3,4-c]quinoline (22), 1-hydroxypyrazolo[4, 3-c]quinoline (21), 1-hydroxypyrazolo[3,4-c]isoquinoline (20), and 1-hydroxypyrazolo[4,3-c]isoquinoline (19) were prepared from 1-benzyloxypyrazole (6), establishing the pyridine B-ring in the terminal step. The pyridine ring of pyrazoloquinolines 14 and 18 was formed via cyclization of a formyl group at C-4 or C-5 and an amino group of a 2-aminophenyl substituent at C-5 or C-4 in 1-benzyloxypyrazole. The pyridine ring of pyrazoloisoquinolines 5 and 9 was created via cyclization of a formyl group in a 2-formylphenyl substituent at C-4 or C-5 with an iminophosphorane group installed at C-5 or C-4 of 1-benzyloxypyrazole by lithiation followed by reaction with tosyl azide and then with tributylphoshine utilizing the Staudinger/aza-Wittig protocol. The 2-aminophenyl and the 2-formylphenyl substituent were introduced at C-5 or C-4 by regioselective metalation followed by transmetalation to the pyrazolylzinc halide and subsequent palladium-catalyzed cross-coupling with 2-iodoaniline or 2-bromobenzaldehyde. The order of reactions and use of protecting groups in the individual sequences have been optimized. The 1-benzyloxy-substituted pyrazoloquinolines and isoquinolines thus obtained were debenzylated by strong acid to the corresponding 1-hydroxy-substituted pyrazoloquinolines and isoquinolines 19-22. 相似文献
148.
Red and yellow dichroistic crystals of a vanadium(V) compound, potassium (mu-oxo, di-mu-sulfato)bis(oxodisulfatovanadate), K(8)(VO)(2)O(SO(4))(6), have been obtained from the ternary catalytic model melt system K(2)S(2)O(7)[bond]K(2)SO(4)[bond]V(2)O(5). By slow cooling of the melt from 420 to 355 degrees C, crystal growth occurred, using solid V(2)O(5) crystals present in the melt as nucleation promoter. The compound crystallizes in the monoclinic space group P2(l) with a = 13.60(9) A, b = 13.93(9) A, c = 14.05(9) A, beta = 90.286(10) degrees, and Z = 2. It contains two VO(6) octahedra linked together by a mu-oxo and two mu-sulfato bridges. Furthermore, each octahedron has two monodentate sulfate ligands, making the dimeric entity coordinatively saturated. IR spectroscopy shows bands arising from V[bond]O[bond]V and V[double bond]O stretches as well as splitting of sulfate bands due to the different degrees of freedom present for different conformations of sulfate ligands. The coordination of vanadium in K(8)(VO)(2)O(SO(4))(6) is discussed in relation to the reaction mechanism of SO(2) oxidation catalysis. 相似文献
149.
A fast and sensitive high performance liquid chromatography method for quantitative determination of rosiglitazone in human plasma has been developed. The extraction from plasma was performed using solid-phase extraction (SPE) on C4 silica (100 mg) disposable extraction cartridges (DEC). The separation of rosiglitazone and two metabolites was achieved on a Phenomenex® Synergi 4 µm MAX-RP (150 × 4.6 mm) column, protected by a guard column. The mobile phase was 0.01 M ammonium acetate, pH 7.0 - acetonitrile (65:35, v/v). (3S)-3-OH-quinidine was used as internal standard. The analytes were detected using fluorescence detection. The method was validated. The limit of quantitation was 1 ng mL−1 and the detection limit was 0.25 ng mL−1 for rosiglitazone in human plasma. The recovery was 90% for rosiglitazone. Linearity was observed over a range of 1-1000 ng mL−1 (r2=0.9959). The intra- and inter-day precision (C.V.) did not exceed 8.7 %. Applicability of the method was demonstrated by a clinical pharmacokinetic study. A healthy volunteer received in two separate phases 4 mg and 8 mg rosiglitazone maleate as a single oral dose. Plasma concentrations were measured for 24 h in both phases. 相似文献
150.
Detection of autofluorescence at the skin surface is highly influenced by melanin and hemoglobin. Epidermal absorption and scattering may also be an influencing factor and is represented in this article as a quantitative parameter, epidermal thickness. To examine this parameter we measured the 370 nm fluorescence in vivo after excitation with 330 nm and the 455 nm fluorescence after excitation with 330 and 370 nm. Measurements were performed on sun-exposed skin at the dorsal aspect of the forearm and shoulder and on nonexposed buttock skin. Skin pigmentation and redness of the same body sites were measured by reflectance spectroscopy. The thickness of the stratum corneum and the cellular part of epidermis was quantified by light microscopy of skin biopsies. Multiple regression analysis was used to find correlations between autofluorescence and the potential influencing factors. We found a highly significant correlation of skin autofluorescence with pigmentation and redness for both emission wavelengths (Em). A small but significant correlation to epidermal thickness was found only for excitation wavelength (Ex) 370 nm and Em455 nm if body site was included in the analysis. No correlation between Ex330:Em370 and Ex330:Em455 and thickness of epidermis was found. For practical use, correction of skin autofluorescence for pigmentation is essential, correction for redness is of less importance and correction for epidermal thickness is unnecessary. 相似文献