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111.
112.
A revised formalism of SBS is given based on a new optical nonlinear wave equation which explicitly accounts for the macroscopic spatial inhomogeneity resulting from the induced acoustic wave in the medium. The new equation applies to other scattering phenomena, and more generally to optical wave propagation and interaction in nanostructured media for which characteristic spatial scale lengths of material structures (existing or optically induced) are smaller than the optical wavelength. 相似文献
113.
In a previous paper we discussed co-crystallization in a LDPE/HDPE blend using TREF and DSC. As part of that study it was observed that pure HDPE showed an unexpected fractionation behavior when quench crystallized in TREF. The overall peak broadened and two peaks appeared instead of the previously observed single peak for slow cooled HDPE.The development of two peaks was observed for all commercial HDPEs investigated, independent of their melting indices and densities. TREF and GPC were used in an attempt to evaluate the origin of the two HDPE components.The authors appreciate support from CAPES-BRAZIL (C.A.F.). Additional thanks go to Dr. G. W. Knight in Dow Chemical Company for kindly providing the polymer samples and performing the GPC analysis. 相似文献
114.
Turan K. Yazicilar Omer Andac Yunus Bekdemir Halil Kutuk Veysel T. Yilmaz William T. A. Harrison 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):m21-m22
The title compound, alternatively named sodium 6‐nitro‐3H‐1,2,3‐benzoxathiazole 2,2‐dioxide monohydrate, Na+·C6H3N2O5S?·H2O, consists of chains of NaO7 units, with the seven donor‐O atoms coming from two water molecules and five p‐nitrobenzoxasulfamate anions. The seven‐coordinate geometry around the Na+ ion is described as monocapped trigonal prismatic, but with a large distortion from ideal geometry. Each triangular face is defined by one O atom each from a water molecule, a nitro group and a sulfonyl group. An O atom from a sulfonyl group caps one of the square faces of the trigonal prism in an unsymmetrical fashion. The water molecules and one sulfonyl O atom are involved in bridging adjacent units, as is the nitro group of the anion. The sulfamate ions adopt an antiparallel alignment between the NaO7 units and are connected to each other by C—H?O and π–π interactions. The three‐dimensional crystal structure is stabilized by a network of strong O—H?N hydrogen bonds. 相似文献
115.
Chrif F. Matta Christopher N. Cow Paul H. M. Harrison 《Journal of Molecular Structure》2003,660(1-3):81-97
X-ray crystallography and theoretical analysis were applied to explore the molecular basis for the efficient and selective Claisen-like condensations of diacylglycolurils. The crystal structures of 1-acetyl-6-benzoyl-3,4,7,8-tetramethylglycoluril (4b), and of 1-(3′-oxo-3′-phenylpropionyl)-3,4,7,8-tetramethylglycoluril (5b), the product of base-promoted intramolecular condensation of 4b, were obtained by X-ray diffraction. The acetyl (Ac) group in 4b is essentially coplanar with the attached tetrahydroimidazolone ring of the glycoluril core (τ=7°), while the benzoyl (Bz) group is twisted by τ=45° relative to a plane through the ring to which it is bonded. Product 5b contains a flat amide (τ=7°). Ab initio energy optimizations of the experimental structures for 4b and 5b give optimized geometries which are not dramatically altered, suggesting that crystal packing effects are small. An atoms-in-molecules study of the delocalization of the Fermi hole reveals that electrons in the Bz C=O group of 4b are delocalized into the phenyl ring as well as into the urea moiety of the glycoluril core. This effect stabilizes the Bz over the Ac carbonyl group, and accounts for selective twisting of the Bz group. The Laplacian of the electron density reveals a non-bonded valence shell charge concentration at O of the Ac group, corresponding to a lone-pair region, aligned with a charge depletion in the valence shell of the Bz C=O carbon [(C15–O16C18)=113°]. The angle of approach [(O16C18=O19)] is 100°, equal to the angle for ideal nucleophilic attack on a carbonyl group. Oxygen atom O16 is thus poised to attack C18; only the O16C18 distance (3.248 Å) seems to prevent reaction. These results suggest that the same distance restraint may prevent O-acylation in the enolate intermediate 6b derived from4b. By contrast, the transition state for C-acylation, leading from 6b towards product 5b requires a different geometry, which may explain the observed selectivity for C-acylation in this enolate. The results show that, as 4b is converted to 5b, amide torsional strain is relieved, which may account for the high reactivity of 4b and the efficiency and irreversibility of this condensation process. This study provides a starting point for quantitative correlation of substrate structure in diacylglycolurils with kinetic data for the rearrangement reaction. 相似文献
116.
Blindauer CA Polfer NC Keiper SE Harrison MD Robinson NJ Langridge-Smith PR Sadler PJ 《Journal of the American Chemical Society》2003,125(11):3226-3227
Using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, we show that one Zn2+ ion in the Zn4 cluster of cyanobacterial metallothionein is inert to exchange with 67Zn2+. We suggest that this is zinc in site A, which together with the surrounding alpha and beta secondary structure forms a zinc-finger fold. 相似文献
117.
Nathan J. Downs Damien P. Igoe Alfio V. Parisi Olivia Taylor Shari L. Lazzaroni Alex Rawlings Daniel R. Garzn‐Chavez Simone L. Harrison 《Photochemistry and photobiology》2019,95(4):1083-1093
The risk of keratinocyte skin cancer, malignant melanoma and ultraviolet radiation (UVR)‐induced eye disease is disproportionately higher in Australia and New Zealand compared to equivalent northern hemisphere latitudes. While many teachers are aware of the importance of reinforcing sun safety messages to students, many may not be aware of the considerable personal exposure risk while performing outdoor duties in locations experiencing high to extreme ambient UVR year‐round. Personal erythemally effective exposure of classroom teachers in tropical Townsville (19.3°S) was measured to establish seasonal extremes in exposure behavior. Mean daily personal exposure was higher in winter (91.2 J m‐2, 0.91 Standard Erythema Dose [SED]) than summer (63.3 J m?2, 0.63 SED). The range of exposures represents personal exposures that approximate current national guidelines for Australian workers at the study latitude of approximately 1.2 SED (30 J m?2 effective to the International Commission on Non‐Ionizing Radiation Protection). Similar proportions of teachers spent more than 1 h outdoors per day in winter (28.6%) and summer (23.6%) as part of their teaching duties with seasonal differences having little effect on the time of exposure. Personal exposures for teachers peaked during both seasons near school meal break times at 11:00 am and 1:00 pm, respectively. 相似文献
118.
Cammidge AN Goddard VH Gopee H Harrison NL Hughes DL Schubert CJ Sutton BM Watts GL Whitehead AJ 《Organic letters》2006,8(18):4071-4074
A conceptually and practically simple alternative approach to the use of arylboron species as the organometallic component in cross-coupling processes is described whereby trihydroxyborate salts are isolated and directly employed. The protocol derives practical benefit from the ease and convenience of the isolation and subsequent use of the discrete borate salts, eliminates the need for additional base, and aids the use of correct reaction stoichiometry. 相似文献
119.
Andreas Manz Elisabeth Verpoorte Carlo S. Effenhauser Norbert Burggraf Daniel E. Raymond D. Jed Harrison H. Michael Widmer 《Journal of separation science》1993,16(7):433-436
Miniaturization of separation columns implies equally reduced vol- umes of injectors, detectors, and the connecting channels. Planar chip technology provides a powerful means for the fabrication of micron-sized structures such as channels. This is demonstrated by two examples. An optical absorbance detector chip exhibits the expected behavior of a 1 mm optical path length cell despite its volume of 1 nL. A capillary electrophoresis device allows integrated injections of 100 pL samples, efficiencies of 70,000 to 160,000 theoretical plates in 10 to 20 seconds, and external laser-induced fluorescence detection at any capillary length of choice between 5 and 50 mm. 相似文献
120.
Martinez-Casado R Mallia G Harrison NM 《Chemical communications (Cambridge, England)》2011,47(15):4385-4387
A practical and efficient method for exploiting second order Rayleigh-Schr?dinger perturbation theory to approximate the correlation energy contribution to the London dispersion interaction is presented. The correlation energy is estimated as the M?ller-Plesset contribution computed using single particle orbitals from hybrid exchange density functional theory as the reference state. 相似文献