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61.
The electronic structure of the ground and low-lying states of the diatomic fluorides TiF, VF, CrF, and MnF was examined by multireference and coupled cluster methods in conjunction with extended basis sets. For a total of 34 states we report binding energies, spectroscopic constants, dipole moments, separation energies, and charge distributions. In addition, for all states we have constructed full potential curves. The suggested ground state binding energies of TiF(X (4)Phi), VF(X (5)Pi), CrF(X (6)Sigma(+)), and MnF(X (7)Sigma(+)) are 135, 130, 110, and 108 kcal/mol, respectively, with first excited states A (4)Sigma(-), A (5)Delta, A (6)Pi, and a (5)Sigma(+) about 2, 3, 23, and 19 kcal/mol higher. In essence all our numerical findings are in harmony with experimental results. For all molecules and states studied it is clear that the in situ metal atom (M) shows highly ionic character, therefore the binding is described realistically by M(+)F(-). 相似文献
62.
Criteria for aerosol synthesis of soft-agglomerate, hard-agglomerate, or even nonagglomerate particles are developed on the basis of particle sintering and coalescence. Agglomerate (or aggregate) particles are held together by weak, physical van der Waals forces (soft agglomerates) or by stronger chemical or sintering bonds (hard agglomerates). Accounting for simultaneous gas phase chemical reaction, coagulation, and sintering during the formation and growth of silica (SiO2) nanoparticles by silicon tetrachloride (SiCl4) oxidation and neglecting the spread of particle size distribution, the onset of hard-agglomerate formation is identified at the end of full coalescence, while the onset of soft-agglomerate formation is identified at the end of sintering. Process conditions such as the precursor initial volume fraction, maximum temperature, residence time, and cooling rate are explored, identifying regions for the synthesis of particles with a controlled degree of agglomeration (ratio of collision to primary particle diameters). 相似文献
63.
Temitope T. Abiola Nazia Auckloo Jack M. Woolley Christophe Corre Stphane Poigny Vasilios G. Stavros 《Molecules (Basel, Switzerland)》2021,26(24)
Plants, as with humans, require photoprotection against the potentially damaging effects of overexposure to ultraviolet (UV) radiation. Previously, sinapoyl malate (SM) was identified as the photoprotective agent in thale cress. Here, we seek to identify the photoprotective agent in a similar plant, garden cress, which is currently used in the skincare product Detoxophane nc. To achieve this, we explore the photodynamics of both the garden cress sprout extract and Detoxophane nc with femtosecond transient electronic absorption spectroscopy. With the assistance of liquid chromatography-mass spectrometry, we determine that the main UV-absorbing compound in garden cress sprout extract is SM. Importantly, our studies reveal that the photoprotection properties of the SM in the garden cress sprout extract present in Detoxophane nc are not compromised by the formulation environment. The result suggests that Detoxophane nc containing the garden cress sprout extract may offer additional photoprotection to the end user in the form of a UV filter booster. 相似文献
64.
Dror Bar-Natan Stavros Garoufalidis Lev Rozansky Dylan P. Thurston 《Israel Journal of Mathematics》2000,119(1):217-237
We conjecture an exact formula for the Kontsevich integral of the unknot, and also conjecture a formula (also conjectured
independently by Deligne [De]) for the relation between the two natural products on the space of uni-trivalent diagrams. The
two formulas use the related notions of “Wheels” and “Wheeing”. We prove these formulas ‘on the level of Lie algebras’ using
standard techniques from the theory of Vassiliev invariants and the theory of Lie algebras. In a brief epilogue we report
on recent proofs of our full conjectures, by Kontsevich [Ko2] and by DBN, DPT, and T. Q. T. Le, [BLT].
This paper is available electronically 相似文献
65.
W Wang Z Liu L Ma C Hao S Liu VG Voinov NI Kalinovskaya 《Rapid communications in mass spectrometry : RCM》1999,13(12):1189-1196
Electrospray ionization (ESI) combined with multiple-stage tandem mass spectrometry (MS(n)) was used to directly analyze the glycolipid mixture from bacteria Bacillus pumilus without preliminary separation. Full scan ESI-MS revealed the composition of picomole quantities of glycerolglycolipid species containing C(14)-C(19) fatty acids, some of which were monounsaturated. Two main components were identified from their molecular masses and fragmentation pathways. The fragmentation pathway of the known compound compared with the investigated compound verified the proposed structure as 1(3)-acyl-2-pentadecanoyl-3(1)-O-[beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl]-sn-glycerols. A comparison of the multiple tandem mass spectra of the different alkali-metal cation adducts indicates that the intensity of fragments and the dissociation pathways are dependent on the alkali-metal type. The basic structures of glycerolglycolipids were reflected clearly from the fragmentation patterns of the sodium cations. The intense fragments of the sugar residue from the precursor ions were obtained from the lithiated adduct ions. ESI-MS(n) spectra of [M + K](+) ions did not provide as much fragmentation as [M + Na](+) and [M + Li](+) adducts, but their spectra allow the position of glycerol acylation to be determined. On the basis of MS(2) spectra of [M + K](+) ions, it was established that all components have a C(15:0) fatty acid at the sn-2 position of the glycerol backbone and C(14)-C(19) acids at the sn-1 position of the glycerol backbone. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
66.
Roshni Malde Michael A. Parkes Michael Staniforth Jack M. Woolley Vasilios G. Stavros Vijay Chudasama Helen H. Fielding James R. Baker 《Chemical science》2022,13(10):2909
Thiomaleimides undergo efficient intermolecular [2 + 2] photocycloaddition reactions and offer applications from photochemical peptide stapling to polymer crosslinking; however, the reactions are limited to the formation of the exo head-to-head isomers. Herein, we present an intramolecular variation which completely reverses the stereochemical outcome of this photoreaction, quantitatively generating endo adducts which minimise the structural disturbance of the disulfide staple and afford a 10-fold increase in quantum yield. We demonstrate the application of this reaction on a protein scaffold, using light to confer thiol stability to an antibody fragment conjugate. To understand more about this intriguing class of [2 + 2] photocycloadditions, we have used transient absorption spectroscopy (electronic and vibrational) to study the excited states involved. The initially formed S2 (π1π*) excited state is observed to decay to the S1 (n1π*) state before intersystem crossing to a triplet state. An accelerated intramolecular C–C bond formation provides evidence to explain the increased efficiency of the reaction, and the impact of the various excited states on the carbonyl vibrational modes is discussed.Tethered bromomaleimides are described which undergo thiol conjugation and rapid regio- and stereoselective photocycloadditions to serve as disulfide staples; with the excited state intermediates observed by transient absorption spectroscopies. 相似文献
67.
68.
Stavros Iliadis 《Topology and its Applications》2008,156(1):76-82
In the present paper it is proved the existence of topologically universal elements in some classes of mappings and classes of G-spaces generalizing some results from [S.D. Iliadis, Universal Spaces and Mappings, North-Holland Math. Stud., vol. 198, Elsevier, 2005] and [S.D. Iliadis, Universal Borel mappings and Borel actions of groups, Topology Appl., in press, doi:10.1016/j.topol.2007.05.029]. 相似文献
69.
Ardie Walser Stavros Demos Michael Etienne Roger Dorsinville 《Optics Communications》2004,240(4-6):417-421
The presence of strong nonlinear absorption has been observed in laser modified fused silica. Intensity-dependent transmission measurements using 355, 532 and 1064 nm laser pulses were performed in pristine polished regions in fused silica substrates and in locations that were exposed to dielectric breakdown. The experimental results suggest that multiphoton absorption is considerably stronger in the modified regions compared to pristine sites and is strongly dependent on the excitation wavelength. 相似文献
70.
We emulate the ground state of a Bose–Einstein condensate in a time-dependent isotropic harmonic trap by constructing analytic simulacra of a transformed wavefunction in the regions around the origin and far from the origin. This transformed wavefunction is obtained through a pseudoconformal transformation and is a function of new spatial and temporal variables, while the simulacra are generalisations of asymptotic solutions of the nonlinear Schrödinger equation and they are matched by requiring continuity not only of the wavefunction and of its slope, but of its curvature as well. The resulting piecewise analytic simulacra coincide almost perfectly with the numerically obtained solutions of the time-dependent nonlinear Schrödinger equation and constitute an easy and accurate analytic method for describing fully the condensate ground state. 相似文献