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31.
The fractional Stokes–Einstein relation postulates a direct relationship between conductivity and shear flow. Like viscosity, the electrical resistivity of a glass-forming liquid exhibits a non-Arrhenius scaling with temperature. However, while both viscosity and resistivity are non-Arrhenius, here we show that these two properties follow distinct functional forms. Through analysis of 821 unique silicate liquids, we show that viscosity is best represented using the Mauro–Yue–Ellison–Gupta–Allan (MYEGA) model, whereas the resistivity of the same compositions more closely follows the Avramov–Milchev (AM) equation. Our results point to two fundamentally different mechanisms governing viscous flow and conductivity and therefore cast doubt on the general validity of the fractional Stokes–Einstein relation. 相似文献
32.
We show, by computer simulation, that tapered or pear-shaped particles, interacting through purely repulsive interactions, can freely self-assemble to form the three-dimensionally periodic, gyroid cubic phase. The Ia3d gyroid cubic phase is formed by these particles on both compression of an isotropic configuration and expansion of a smectic A bilayer arrangement. For the latter case, it is possible to identify the steps by which the topological transformation from nonintersecting planes to fully interpenetrating, periodic networks takes place. 相似文献
33.
Fluorescence methodologies have been utilized to examine micropolarity, intramolecular motion, and singlet quenching in the intraparticle void volume of zeolites X, Y, and ultrastable Y (USY) interfaced with bathing polar solvents. Micropolarity was assessed from the 3-to-1 band ratio (III/I) of the fluorescence spectrum of pyrene (PY) and from lambda(max) of the fluorescence spectrum of 1-pyrenecarboxaldehyde (1-PCA). In zeolites bathed in anhydrous solvents, both PY and 1-PCA reported increased micropolarity according to the trend USY < bulk solvent < NaX approximately NaY. For example, in NaY (USY), III/I ranged from 0.44 (0.98) in acetonitrile to 0.52 (1.34) in n-hexanol, compared to 0.60, 1.06, and 1.62 in bulk acetonitrile (ACN), n-hexanol, and n-hexane, respectively. The polarity studies reveal that the ionic nature of NaX and NaY and the hydrophobic nature of USY strongly influence the microenvironment of the arene despite the presence of desorbing polar solvents. Constraints on intramolecular motion were examined in polar-solvated NaX through measurements of the fluorescence lifetime of trans-stilbene. Lifetimes ranged from 113 ps in NaX-ACN to 671 ps in NaX-tert-butyl alcohol. The latter value is close to that observed in bulk glycerol. Diffusion-controlled quenching of PY fluorescence by O2 and a series of nitrocompounds dissolved in solvents bathing the zeolite was examined by a time-resolved approach. For all of the quenchers and solvents studied, quenching was more efficient in USY compared to NaX and NaY. Interestingly, the rate of O2 quenching in USY-MeOH was only 12 times lower than that in bulk MeOH. In contrast, in NaY-MeOH and NaX-MeOH the rate of O2 quenching was too low to be measured. The rate constants in these systems were therefore taken as the rate constant for diffusion-controlled quenching of trapped electrons measured previously. These values were 600 times and 10(5) times lower than the rate of fluorescence quenching in USY-MeOH, respectively. The O2 quenching studies show that dispersive interactions of polar solvents with the cavity walls dominate in USY because of the hydrophobic nature of the USY surface. In NaX and NaY, stronger ion-dipole and hydrogen bonding interactions dominate and lead to more restricted access and lowered quenching efficiency. Perrin (or static) quenching of pyrene fluorescence was also examined to infer the concentration of nitromethane (NM) in the void volume of NaX and NaY bathed in MeOH, ACN, or H2O. The results indicate that access of NM to the interior of NaY is more inhibited in ACN compared to MeOH, presumably because of the higher dipole moment of ACN and its resulting stronger association with the zeolite surface. At similar levels of static quenching equated to a similar NM concentration in the zeolite, dynamic quenching by NM varied by no more than a factor of 2 in all systems compared. This implies that the rate of NM diffusion in solvated zeolite interiors is similar regardless of zeolite or solvent properties. In contrast to O2 diffusion in zeolites, NM exhibits a high dipole moment and can therefore migrate through polar-solvated zeolite apertures by adsorbing to the zeolite. Overall, the results of this study show a close relationship between the behavior of probes and quenchers in the confines of polar-solvated zeolite interiors and the chemical properties of the zeolite. Differences between weakly and strongly interacting surfaces are revealed clearly in the results. 相似文献
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35.
The Molecular Structure of gauche‐1,3‐Butadiene: Experimental Establishment of Non‐planarity
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Dr. Joshua H. Baraban Dr. Marie‐Aline Martin‐Drumel P. Bryan Changala Dr. Sandra Eibenberger Dr. Matthew Nava Prof. David Patterson Prof. John F. Stanton Prof. G. Barney Ellison Dr. Michael C. McCarthy 《Angewandte Chemie (International ed. in English)》2018,57(7):1821-1825
The planarity of the second stable conformer of 1,3‐butadiene, the archetypal diene for the Diels–Alder reaction in which a planar conjugated diene and a dienophile combine to form a ring, is not established. The most recent high level calculations predicted the species to adopt a twisted, gauche structure owing to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the double bonds. The structure cis‐1,3‐butadiene is unambiguously confirmed experimentally to indeed be gauche with a substantial dihedral angle of 34°, in excellent agreement with theory. Observation of two tunneling components indicates that the molecule undergoes facile interconversion between two equivalent enantiomeric forms. Comparison of experimentally determined structures for gauche‐ and trans‐butadiene provides an opportunity to examine the effects of conjugation and steric interactions. 相似文献
36.
D'Andrea TM Zhang X Jochnowitz EB Lindeman TG Simpson CJ David DE Curtiss TJ Morris JR Ellison GB 《The journal of physical chemistry. B》2008,112(2):535-544
We have studied the oxidation of self-assembled monolayers (SAMs) of alkanes and alkenes with a thermal beam of OH radicals. The target films were produced by bonding alkane thiols and alkene thiols to a gold surface and the SAMs are mounted in a vacuum chamber at a base pressure of 10-9 Torr. Hydroxyl radicals were produced by a corona discharge in an Ar/H2O2/water mixture. The resultant molecular beam was scanned by an electrostatic hexapole and the OH radicals [4 (+/- 1) x 1011 OH radicals cm-2 sec-1] were focused onto the target SAM. All of the hydroxyl radicals impinging on the SAM surface are rotationally (J' ' = 5/2) cold. The vibrational temperature of the radicals is estimated to be 1700-3400 K which implies that between 5% and 22% of the hydroxyl radical beam is OHv=1 and the remainder (95% to 78%) is OHv=1. The collision energy of the beam with the SAM is 333 cm-1 corresponding to a 485 K thermal beam. We employed reflection/absorption infrared spectroscopy (RAIRS) to monitor the reactivity of OH with an alkane and an alkene SAM. RAIRS demonstrated that a 10 min dose of OH radicals largely destroys the CH3- groups at the interface. This corresponds to a deposition of 2.4 x 1014 OH cm-2 or about 60% of the SAM monolayer. Oxidation of an undec-10-ene-1-thiol (HS(CH2)9HC=CH2) SAM with OH radicals proceeded more quickly with all the terminal alkenes, -CH=CH2, eliminated within 5 min following deposition of 1.2 x 1014 radicals. We believe that the OH radicals initiate a radical-induced polymerization of the alkene film. 相似文献
37.
Caravan P Parigi G Chasse JM Cloutier NJ Ellison JJ Lauffer RB Luchinat C McDermid SA Spiller M McMurry TJ 《Inorganic chemistry》2007,46(16):6632-6639
The amphiphilic gadolinium complex MS-325 ((trisodium-{(2-(R)-[(4,4-diphenylcyclohexyl) phosphonooxymethyl] diethylenetriaminepentaacetato) (aquo)gadolinium(III)}) is a contrast agent for magnetic resonance angiography (MRA). MS-325 consists of two slowly interconverting diastereoisomers, A and B (65:35 ratio), which can be isolated at pH > 8.5 (TyeklAr, Z.; Dunham, S. U.; Midelfort, K.; Scott, D. M.; Sajiki, H.; Ong, K.; Lauffer, R. B.; Caravan, P.; McMurry, T. J. Inorg. Chem. 2007, 46, 6621-6631). MS-325 binds to human serum albumin (HSA) in plasma resulting in an extended plasma half-life, retention of the agent within the blood compartment, and an increased relaxation rate of water protons in plasma. Under physiological conditions (37 degrees C, pH 7.4, phosphate buffered saline (PBS), 4.5% HSA, 0.05 mM complex), there is no statistical difference in HSA affinity or relaxivity between the two isomers (A 88.6 +/- 0.6% bound, r1 = 42.0 +/- 1.0 mM(-1) s(-1) at 20 MHz; B 90.2 +/- 0.6% bound, r1 = 38.3 +/- 1.0 mM(-1) s(-1) at 20 MHz; errors represent 1 standard deviation). At lower temperatures, isomer A has a higher relaxivity than isomer B. The water exchange rates in the absence of HSA at 298 K, kA298 = 5.9 +/- 2.8 x 10(6) s(-1), kB298 = 3.2 +/- 1.8 x 10(6) s(-1), and heats of activation, DeltaHA = 56 +/- 8 kJ/mol, DeltaHB = 59 +/- 11 kJ/mol, were determined by variable-temperature 17O NMR at 7.05 T. Proton nuclear magnetic relaxation dispersion (NMRD) profiles were recorded over the frequency range of 0.01-50 MHz at 5, 15, 25, and 35 degrees C in a 4.5% HSA in PBS solution for each isomer (0.1 mM). Differences in the relaxivity in HSA between the two isomers could be attributed to the differing water exchange rates. 相似文献
38.
39.
Hu C Barabanschikov A Ellison MK Zhao J Alp EE Sturhahn W Zgierski MZ Sage JT Scheidt WR 《Inorganic chemistry》2012,51(3):1359-1370
Nuclear resonance vibrational spectra have been obtained for six five-coordinate imidazole-ligated iron(II) porphyrinates, [Fe(Por)(L)] (Por = tetraphenylporphyrinate, octaethylporphyrinate, tetratolylporphyrinate, or protoporphyrinate IX and L = 2-methylimidazole or 1,2-dimethylimidazole). Measurements have been made on both powder and oriented crystal samples. The spectra are dominated by strong signals around 200-300 cm(-1). Although the in-plane and out-of-plane vibrations are seriously overlapped, oriented crystal spectra allow their deconvolution. Thus, oriented crystal experimental data, along with density functional theory (DFT) calculations, enable the assignment of key vibrations in the spectra. Molecular dynamics are also discussed. The nature of the Fe-N(Im) vibrations has been elaborated further than was possible from resonance Raman studies. Our study suggests that the Fe motions are coupled with the porphyrin core and peripheral groups motions. Both peripheral groups and their conformations have significant influence on the vibrational spectra (position and shape). 相似文献
40.
G B Richter-Addo R A Wheeler C A Hixson L Chen M A Khan M K Ellison C E Schulz W R Scheidt 《Journal of the American Chemical Society》2001,123(26):6314-6326
The six-coordinate nitrosyl sigma-bonded aryl(iron) and -(ruthenium) porphyrin complexes (OEP)Fe(NO)(p-C(6)H(4)F) and (OEP)Ru(NO)(p-C(6)H(4)F) (OEP = octaethylporphyrinato dianion) have been synthesized and characterized. Single-crystal X-ray structure determinations reveal an unprecedented bending and tilting of the MNO group for both [MNO](6) species as well as significant lengthening of trans axial bond distances. In (OEP)Fe(NO)(p-C(6)H(4)F) the Fe-N-O angle is 157.4(2) degrees, the nitrosyl nitrogen atom is tilted off of the normal to the heme plane by 9.2 degrees, Fe-N(NO) = 1.728(2) A, and Fe-C(aryl) = 2.040(3) A. In (OEP)Ru(NO)(p-C(6)H(4)F) the Ru-N-O angle is 154.9(3) degrees, the nitrosyl nitrogen atom is tilted off of the heme normal by 10.8 degrees, Ru-N(NO) = 1.807(3) A, and Ru-C(aryl) = 2.111(3) A. We show that these structural features are intrinsic to the molecules and are imposed by the strongly sigma-donating aryl ligand trans to the nitrosyl. Density functional-based calculations reproduce the structural distortions observed in the parent (OEP)Fe(NO)(p-C(6)H(4)F) and, combined with the results of extended Hückel calculations, show that the observed bending and tilting of the FeNO group indeed represent a low-energy conformation. We have identified specific orbital interactions that favor the unexpected bending and tilting of the FeNO group. The aryl ligand also affects the Fe-NO pi-bonding as measured by infrared and (57)Fe M?ssbauer spectroscopies. The solid-state nitrosyl stretching frequencies for the iron complex (1791 cm(-)(1)) and the ruthenium complex (1773 cm(-)(1)) are significantly reduced compared to their respective [MNO](6) counterparts. The M?ssbauer data for (OEP)Fe(NO)(p-C(6)H(4)F) yield the quadrupole splitting parameter +0.57 mm/s and the isomer shift 0.14 mm/s at 4.2 K. The results of our study show, for the first time, that bent Fe-N-O linkages are possible in formally ferric nitrosyl porphyrins. 相似文献