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21.
The relationship between the CD spectra of the chiral biaryls and their stereochemical configuration, as a function of the dihedral angle between the molecular planes of the aromatic moieties, has been investigated for biphenyl, 1,1′-binaphthyl, 1,1′-bianthryl and 9,9′-bianthryl in the exciton approximation and, for the 1,1′-binaphthyls, in the π-SCF approximation. Both methods provide unambiguous assignments of absolute configuration except for biaryls with a critical dihedral angle of π/2 in those with effective Ddata2 chromophoric symmetry, or 100–110° in the case of the 1,1′-binaphthyls. 相似文献
22.
Liliana N. Trevani Jenene C. Roberts Peter R. Tremaine 《Journal of solution chemistry》2001,30(7):585-622
The spectra of copper(II)–ammonia solutions in 2 mol-kg–1 NH4NO3(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH3)n
2+, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH4NO3(aq). The formation constants of Cu(NH3)n
2+ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg–1 CF3SO3H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH3)4
2+ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu2+ and the Cu(NH3)n
2+ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes. 相似文献
23.
Rogers PH Michel E Bauer CA Vanderet S Hansen D Roberts BK Calvez A Crews JB Lau KO Wood A Pine DJ Schwartz PV 《Langmuir : the ACS journal of surfaces and colloids》2005,21(12):5562-5569
The directed three-dimensional self-assembly of microstructures and nanostructures through the selective hybridization of DNA is the focus of great interest toward the fabrication of new materials. Single-stranded DNA is covalently attached to polystyrene latex microspheres. Single-stranded DNA can function as a sequence-selective Velcro by only bonding to another strand of DNA that has a complementary sequence. The attachment of the DNA increases the charge stabilization of the microspheres and allows controllable aggregation of microspheres by hybridization of complementary DNA sequences. In a mixture of microspheres derivatized with different sequences of DNA, microspheres with complementary DNA form aggregates, while microspheres with noncomplementary sequences remain suspended. The process is reversible by heating, with a characteristic "aggregate dissociation temperature" that is predictably dependent on salt concentration, and the evolution of aggregate dissociation with temperature is observed with optical microscopy. 相似文献
24.
Detailed analyses of crystalline, hydrated, and precipitated strontium compounds and an aqueous strontium solution by synchrotron extended X-ray absorption fine structure (EXAFS) were used to quantify local thermal and static disorder and to characterize strontium coordination in a variety of oxygen-ligated bonding environments. Analysis of anharmonic vibrational disorder (i.e., significant contribution from a third cumulant term (C(3)) in the EXAFS phase-shift function) in compounds with low and high static disorder around strontium showed that first-shell anharmonic contributions were generally not significant above experimental error in the EXAFS fits (R+/-0.02 ? with and without C(3)). The only case in which a significant apparent decrease in Sr-O distance was observed with increasing temperature, and for which a third cumulant term was significant, was for dilute strontium in aqueous solution. Empirical parameterization of Debye-Waller factor (sigma(2)) for strontium compounds as a function of backscatterer atomic number (Z), interatomic Sr-Z distance, and temperature of spectral data collection showed systematic increases in sigma(2) as a function of increasing temperature and Sr-Z bond length. At values of sigma(2) greater than approximately 0.025 ?(2) (for N<12 and R(Sr)-Z>3 ?), backscattering was generally not significant above noise levels in spectra of compounds of known crystal structure. Comparison of the EXAFS spectra of freshly precipitated SrCO(3) (spectra collected wet) to that of dry, powdered strontianite (SrCO(3)(s)) indicated no significant differences in the local atomic structure around strontium. Analysis of partially hydrated strontium in natural Ca-zeolite (heulandite) showed that strontium is substituted only in the calcium (Ca2) site. Backscattering from aluminum and silicon atoms in the zeolite framework were apparent in the EXAFS spectra at low and room temperature at distances from central strontium of <4.2 ?. Comparison of strontium structural coordination determined in this and previous studies suggests that previous EXAFS determinations of hydrated strontium may have underestimated first-shell interatomic distances and coordination numbers because minor contributions to the EXAFS phase-shift and amplitude functions were not accounted for, either theoretically or empirically. Copyright 2000 Academic Press. 相似文献
25.
Roberts RW 《Chemistry & biology》2004,11(11):1475-1476
Ostermeier, Guntas, and Mitchel describe a new approach to design enzymes that are allosterically regulated by an unrelated ligand . The resulting protein, constructed by nonhomologous recombination and genetic screens, displays switch-like behavior. 相似文献
26.
Artuso M Gao M Goldberg M He D Horwitz N Moneti GC Mountain R Muheim F Mukhin Y Playfer S Rozen Y Stone S Xing X Zhu G Bartelt J Csorna SE Egyed Z Jain V Gibaut D Kinoshita K Pomianowski P Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Würthwein F Asner DM Athanas M Bliss DW Brower WS Masek G Paar HP Gronberg J Korte CM Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Roberts D Ryd A Tajima H Witherell MS Balest R Cho K 《Physical review letters》1995,75(5):785-789
27.
28.
Bartelt J Csorna SE Egyed Z Jain V Gibaut D Kinoshita K Pomianowski P Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ Würthwein F Asner DM Athanas M Bliss DW Brower WS Masek G Paar HP Gronberg J Korte CM Kutschke R Menary S Morrison RJ Nakanishi S Nelson HN Nelson TK Qiao C Richman JD Roberts D Ryd A Tajima H Witherell MS Balest R Cho K Ford WT Lohner M Park H Rankin P Smith JG Alexander JP Bebek C Berger BE Berkelman K Bloom K Browder TE Cassel DG Cho HA 《Physical review D: Particles and fields》1995,52(9):4860-4867
29.
Battle M Ernst J Kwon Y Roberts S Thorndike EH Wang CH Dominick J Lambrecht M Sanghera S Shelkov V Skwarnicki T Stroynowski R Volobouev I Wei G Zadorozhny P Artuso M Goldberg M He D Horwitz N Kennett R Mountain R Moneti GC Muheim F Mukhin Y Playfer S Rozen Y Stone S Thulasidas M Vasseur G Zhu G Bartelt J Csorna SE Egyed Z Jain V Kinoshita K Edwards KW Ogg M Britton DI Hyatt ER MacFarlane DB Patel PM Akerib DS Barish B Chadha M Chan S Cowen DF Eigen G Miller JS O'Grady C Urheim J Weinstein AJ 《Physical review letters》1994,73(8):1079-1083
30.
Weaver M Arisaka K Roberts D Slater W Briere RA Cheu E Harris DA Roodman A Schwingenheuer B Wah YW Winstein B Winston R Barker AR Swallow EC Bock GJ Coleman R Crisler M Enagonia J Ford R Hsiung YB Jensen DA McFarland KS Ramberg E Tschirhart R Collins EM Gollin GD Nakaya T Yamanaka T Gu P Haas P Hogan WP Kim SK Matthews JN Myung SS Schnetzer S Somalwar SV Thomson GB Zou Y 《Physical review letters》1994,72(24):3758-3761