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961.
The rate constants for the reactions of OH and OD with 2-methyl-3-buten-2-ol (MBO) have been measured at 2, 3, and 5 Torr total pressure over the temperature range 300-415 K using a discharge-flow system coupled with laser induced fluorescence detection of OH. The measured rate constants at room temperature and 5 Torr for the OH + MBO reaction in the presence of O2 and the OD + MBO reaction are (6.32 +/- 0.27) and (6.61 +/- 0.66) x 10(-11) cm3 molecule(-1) s(-1), respectively, in agreement with previous measurements at higher pressures. However, the rate constants begin to show a pressure dependence at temperatures above 335 K. An Arrhenius expression of k0 = (2.5 +/- 7.4) x 10(-32) exp[(4150 +/- 1150)/T] cm6 molecule(-2) s(-1) was obtained for the low-pressure-limiting rate constant for the OH + MBO reaction in the presence of oxygen. Theoretical calculations of the energetics of the OH + MBO reaction suggest that the stability of the different HO-MBO adducts are similar, with predicted stabilization energies between 27.0 and 33.4 kcal mol(-1) relative to the reactants, with OH addition to the internal carbon predicted to be 1-4 kcal mol(-1) more stable than addition to the terminal carbon. These stabilization energies result in estimated termolecular rate constants for the OH + MBO reaction using simplified calculations based on RRKM theory that are in reasonable agreement with the experimental values. 相似文献
962.
Pickering AL Mitterbauer C Browning ND Kauzlarich SM Power PP 《Chemical communications (Cambridge, England)》2007,(6):580-582
Capped boron nanoparticles have been synthesized at room temperature by a simple route that does not involve the use of flammable boranes. 相似文献
963.
Two cleft-like anion receptors have been synthesised that contain indole hydrogen-bond donors and show fluoride selectively in a DMSO-water solution with crystallographic studies showing a 'twisted' binding mode for fluoride in the solid state. 相似文献
964.
Selby JD Manley CD Feliz M Schwarz AD Clot E Mountford P 《Chemical communications (Cambridge, England)》2007,(46):4937-4939
Two broadly applicable strategies for extending the available ligand platforms of the virtually unexplored terminal Ti=N-NR2 functional group are described, along with the highly selective room temperature insertion of alkynes into the N-N bond of Ti{MeN(CH2CH2NSiMe3)2}(NNPh2)(py) and the catalytic cis-diamination of PhC[triple bond]CMe by diphenylhydrazine. 相似文献
965.
García-Garrido SE Caltagirone C Light ME Gale PA 《Chemical communications (Cambridge, England)》2007,(14):1450-1452
The interaction of a variety of acridinone derivatives containing hydrogen-bond donor groups in the 4- and 5-positions with anions demonstrate the potential of this new scaffold in anion receptor and sensor design. 相似文献
966.
Varghese HT Panicker CY Philip D Pazdera P 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(3-4):1055-1059
FT-Raman and FT-IR spectra of 2-cyanophenylisocyanid dichloride were recorded and analyzed. The vibrational frequencies of the title compound have been computed using the Hartree-Fock/6-31G* basis and compared with the experimental values. The prepared compound was identified by NMR and mass spectra. 相似文献
967.
Sibert JW Forshee PB Hundt GR Sargent AL Bott SG Lynch V 《Inorganic chemistry》2007,46(25):10913-10925
Two series of isomeric, redox-responsive azacrown ethers based on ortho- and para-phenylenediamine (Wurster's crowns) have been synthesized and their properties explored through 13C NMR spectroscopy, electrospray ionization mass spectrometry, cyclic voltammetry, and X-ray crystallography. These crowns display strong affinity for alkali metal cations while maintaining comparable selectivity profiles to the parent crown ethers from which they are derived. Like Wurster's reagent (N,N,N',N'-tetramethyl-p-phenylenediamine or para-TMPD), the para-Wurster's crowns undergo two reversible one-electron oxidations. The integrity of the alkali metal ion complexes is maintained in the neutral and singly oxidized ligand states but not after removal of two electrons. In contrast, the oxidation of ortho-Wurster's crowns is scan rate dependent, occurring at potentials substantially higher than their para counterparts, with their complexes oxidizing irreversibly. X-ray crystal structures of representative complexes show, in all cases, participation of the redox-active phenylenediamine subunits in complex formation via direct bonding to the guest cation. 相似文献
968.
Counter-current chromatography separation scaled up from an analytical column to a production column
Wood P Ignatova S Janaway L Keay D Hawes D Garrard I Sutherland IA 《Journal of chromatography. A》2007,1151(1-2):25-30
An analytical separation was performed on an analytical J-type counter-current chromatography (CCC) instrument using a 5.4 ml column, with a 1 ml/min mobile phase flow rate. This separation had a resolution of 0.69 and was achieved in 10 min. The same separation was performed using two 2300 ml columns connected in series at a flow rate of 850 ml/min using a production scale J-type centrifuge. This production scale separation was also obtained in 10 min with a resolution of 0.71. This represents an 850 times increase in productivity. This paper presents these separations and the underlying scale up theory. 相似文献
969.
There remains an unmet need for skin tissue-based assays for the measurement of the UVA protection and efficacy of sunscreens. Here we describe development of a novel electron paramagnetic resonance assay that uses the photogeneration of reactive melanin radical as a measure of UV light penetration to melanocytes in situ in skin. We have used areas of focal melanocytic hyperplasia in the skin of Monodelphis domestica to model the human nevus. We show that we are able to use this assay to determine the monochromatic protection factors (mPF) of research and commercial sunscreens at specific narrow wavebands of UVB, UVA and blue visible light. Both commercial sunscreens, a sun protection factor (SPF) 4 and an SPF 30 product, had mPFs in the UVB range that correlated well with their claimed SPF. However, their mPF in the UVA ranges were only about one-third of claimed SPF. This technique can be used to design and assay sunscreens with optimally balanced UVA and UVB protection. 相似文献
970.
Tull EJ Bartlett PN Ryan KR 《Langmuir : the ACS journal of surfaces and colloids》2007,23(14):7859-7873
Site-selective assembly of 5 microm amine-functionalized glass spheres from aqueous suspensions onto gold surfaces patterned with carboxylic acid and methyl-terminated thiols has been achieved through the introduction of a variable tilt flow cell. In situ microscope imaging has been employed to study the four phases of assembly independently, and the relative roles of electrostatic attraction and capillary emersion have been explored. In contradiction to the commonly recognized electrostatic assembly model, detailed theoretical analysis and experimental evidence are presented to support a mechanism where patterning occurs at the point of meniscus contact. Control of pattern quality is demonstrated through the comparison of results obtained from a variety of experiments, and the best conditions for the assembly of monolayer features are identified. Finally, evidence for the extension of this assembly method to the production of singlet sphere arrays is discussed. 相似文献