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951.
A small series of ruthenium(II) tris(2,2'-bipyridine) complexes has been synthesized in which ethynylated thiophene residues are attached to one of the 2,2'-bipyridine ligands. The photophysical properties depend on the conjugation length of the thiophene-based ligand, and in each case, dual emission is observed. The two emitting states reside in thermal equilibrium at ambient temperature and can be resolved by emission spectral curve-fitting routines. This allows the properties of the two states to be evaluated in both fluid butyronitrile solution and a transparent KBr disk. It is concluded that both emitting states are of metal-to-ligand charge-transfer (MLCT) character, and despite the presence of conjugated thiophene residues, there is no indication for a low-lying pi,pi*-triplet state that promotes nonradiative decay of the excited-state manifold. A key feature of these systems is that the conjugation length imposed by the thiophene-based ligand helps to control the rate constants for both radiative and nonradiative decay from the two MLCT triplet states. 相似文献
952.
Sampathkumar SG Jones MB Meledeo MA Campbell CT Choi SS Hida K Gomutputra P Sheh A Gilmartin T Head SR Yarema KJ 《Chemistry & biology》2006,13(12):1265-1275
Short-chain fatty acid (SCFA)-carbohydrate hybrid molecules that target both histone deacetylation and glycosylation pathways to achieve sugar-dependent activity against cancer cells are described in this article. Specifically, n-butyrate esters of N-acetyl-D-mannosamine (But4ManNAc, 1) induced apoptosis, whereas corresponding N-acetyl-D-glucosamine (But4GlcNAc, 2), D-mannose (But5Man, 3), or glycerol (tributryin, 4) derivatives only provided transient cell cycle arrest. Western blots, reporter gene assays, and cell cycle analysis established that n-butyrate, when delivered to cells via any carbohydrate scaffold, functioned as a histone deacetylase inhibitor (HDACi), upregulated p21WAF1/Cip1 expression, and inhibited proliferation. However, only 1, a compound that primed sialic acid biosynthesis and modulated the expression of a different set of genes compared to 3, ultimately killed the cells. These results demonstrate that the biological activity of butyrate can be tuned by sugars to improve its anticancer properties. 相似文献
953.
Arce VB Della Védova CO Downs AJ Parsons S Romano RM 《The Journal of organic chemistry》2006,71(9):3423-3428
The conformational properties of gaseous trichloromethyl chloroformate (or "diphosgene"), ClC(O)OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the C=O double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol(-1) (B3LYP) or 7.06 kcal mol(-1) (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P2(1)/n, a = 5.5578(5) angstroms, b = 14.2895(12) angstroms, c = 8.6246(7) angstroms, beta = 102.443(2) degrees, Z = 4] likewise consists only of molecules in the syn form. 相似文献
954.
Van Ham R Van Vaeck L Adriaens A Adams F Hodges B Gianotto A Avci R Appelhans A Groenewold G 《Talanta》2006,69(1):91-96
The feasibility of static secondary ion mass spectrometry (S-SIMS) for the detection of molecule specific information from complex materials, such as natural clay and soil samples, has been investigated. Ion trap (IT), as well as triple quadrupole (TQ) instruments, have been used for mass analysis. Secondary ion images have been acquired using time-of-flight (TOF) S-SIMS. The generation of molecular adduct ions from thin and thick layers on the mineral substrates has been investigated using KBr as a simple model system. Results show that molecular adducts of KBr can be indeed detected from the spiked materials. However, the concentrations of the spiking solutions have to be significantly larger than expected from the surface area measured by gas adsorption techniques. In addition imaging analysis has evidenced that the detection of adduct ions in the mass spectra directly relates to the presence of local micro-crystallites. 相似文献
955.
A new convenient synthesis of substituted 2,6,9-trioxabicyclo[3.3.1]-nona-3,7-dienes is described. These new ‘bridged bis-dioxines’ were obtained in moderate to good yields by dimerization of the corresponding arylmalondialdehydes in the presence of 0.5 equiv of TMSOTf. The structure of the nitro derivative 1e has been proven by X-ray crystallography. A mechanism for this reaction is proposed. 相似文献
956.
Anthony D. Sercel Vladimir G. Beylin Mark E. Marlatt Boguslawa Leja H. D. Hollis Showalter Andr Michel 《Journal of heterocyclic chemistry》2006,43(6):1597-1604
Short, efficient pathways are described for the synthesis of racemic 2‐nitroimidazole radiation sensitizer RB‐6145 ( 2a ) and each of its corresponding (R)‐ and (S)‐enantiomers ( 2b and 2c , respectively). The synthesis of each enantiomer commences with the appropriate chiral epichlorohydrin and utilizes a novel application of 3‐trimethylsilyl‐2‐oxazolidinone ( 3b ) as a mild, safe surrogate for highly toxic aziridine. The synthesis of the (R)‐enantiomer ( 2b ) has been successfully scaled up to provide multi‐kilo quantities of material for early stage preclinical evaluation. 相似文献
957.
Maiti NC Zhu Y Carmichael I Serianni AS Anderson VE 《The Journal of organic chemistry》2006,71(7):2878-2880
The strength of the H-bond donation by alcohols is reflected in the carbon-hydrogen bond of the H-C-O-H functional group. The one-bond 13C-1H spin-spin coupling constant of hexafluoroisopropanol (HFIP) correlates with the strength of the H-bond in various HFIP-amine complexes with a slope of approximately -0.2 Hz in 1JCH per approximately 1 kJ mol(-1) increase in the H-bond enthalpy. The decrease in 1JCH is attributed to an increased overlap of the H-bonding sigma orbital with the antibonding sigma orbitals of the vicinal C-H bonds. 相似文献
958.
Scattering of plane guided waves obliquely incident on a straight feature with uniform cross-section
Wilcox PD Velichko A Drinkwater BW Croxford AJ Todd MD 《The Journal of the Acoustical Society of America》2010,128(5):2715-2725
A frequency-domain finite element (FE) method is presented for modeling the scattering of plane guided waves incident on an infinitely-long, straight feature with uniform cross-section in a planar host waveguide. The method utilizes a mesh of 2-dimensional finite elements with harmonic shape functions in the perpendicular direction. The model domain comprises a cross-section through the feature and short lengths of the adjoining host waveguide. A spatial frequency equal to the wavenumber of the desired incident mode multiplied by the sine of the desired incidence angle is prescribed for the element shape functions. An integral representation of the incident mode is used to determine a suitable system of harmonic forces to uniquely excite that mode. These are applied at nodes through the thickness of the host waveguide on one side of the feature. The displacement field is measured at nodes through the thickness of the host waveguide on either side of the feature and decomposed into reflected and transmitted modes. The cases of guided wave transmission in a featureless waveguide and the reflection of guided waves from a free-edge are examined as validation cases. Finally, the results for transmission at an adhesively-bonded stiffener are presented and compared with experimental measurements. 相似文献
959.
Gee KL Atchley AA Falco LE Shepherd MR Ukeiley LS Jansen BJ Seiner JM 《The Journal of the Acoustical Society of America》2010,128(5):EL211-EL216
Bicoherence analysis has been used to characterize nonlinear effects in the propagation of noise from a model-scale, Mach-2.0, unheated jet. Nonlinear propagation effects are predominantly limited to regions near the peak directivity angle for this jet source and propagation range. The analysis also examines the practice of identifying nonlinear propagation by comparing spectra measured at two different distances and assuming far-field, linear propagation between them. This spectral comparison method can lead to erroneous conclusions regarding the role of nonlinearity when the observations are made in the geometric near field of an extended, directional radiator, such as a jet. 相似文献
960.
Duncan Hanson Anthony Challinor Antony Lewis 《General Relativity and Gravitation》2010,42(9):2197-2218
The cosmic microwave background (CMB) represents a unique source for the study of gravitational lensing. It is extended across
the entire sky, partially polarized, located at the extreme distance of z = 1,100, and is thought to have the simple, underlying statistics of a Gaussian random field. Here we review the weak lensing
of the CMB, highlighting the aspects which differentiate it from the weak lensing of other sources, such as galaxies. We discuss
the statistics of the lensing deflection field which remaps the CMB, and the corresponding effect on the power spectra. We
then focus on methods for reconstructing the lensing deflections, describing efficient quadratic maximum-likelihood estimators
and delensing. We end by reviewing recent detections and observational prospects. 相似文献