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21.
The reaction paths for the formation of Si3O3 molecules have been investigated at high level ab initio quantum chemical calculations by using the QCISD method with the 6-311++G(d,p) basis set. The cis-Si2O2 isomer does not participate in the chemical mechanism for the formation of Si3O3 molecules. Although the SiO + cis-Si2O2 reaction is exothermic and spontaneous, it is not expected to explain the growth mechanism of Si3O3 in the interstellar silicate grains of circumstellar envelopes surrounding M-type giants. The reaction of SiO with cyclic Si2O2 molecules is exothermic, is spontaneous, and has a nonplanar transition state. The Gibbs free energy for the transition state formation, (DeltaG0#), is around 5.5 kcal mol-1 at 298 K. The bimolecular rate coefficient for this reaction, kT, is about 1 x 10-12 cm3 molecule-1 s-1 at 298 K and in the collision limit, 1.5 x 10-10 cm3 molecule-1 s-1, at 500 K. The activation energy, Ea, is about 8 kcal mol-1. The enthalpy of Si3O3 fragmentation is 53.9 kcal mol-1 at 298 K. The SiO + cyclic Si2O2 reaction is expected to be the most prominent reaction path for the Si3O3 formation in interstellar environment and fabrication of silicon nanowires. 相似文献
22.
The reverse α–α′ phase separation in Fe-20Cr-6Al alloys has been monitored by differential scanning calorimetry in as-hot rolled and recrystallized samples previously aged at 435?°C. The splitting in the position of the minima, and the increasing enthalpy change involved, might be explained in terms of dissolution of α′ particles with different compositions and volume fractions. These results are fully consistent with the α–α′ phase separation kinetics determined by atom probe tomography during ageing at 435?°C. The monitoring of activation energy for α′ dissolution indicates that it is faster in as-hot rolled samples. Finally, the activation energy evolution indicates that there is first a dissolution of β′ Fe(AlTi) phase followed by α′ dissolution. 相似文献
23.
An Immobilized‐Dirhodium Hollow‐Fiber Flow Reactor for Scalable and Sustainable C−H Functionalization in Continuous Flow
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Chun‐Jae Yoo Dr. Daniel Rackl Wenbin Liu Caroline B. Hoyt Brian Pimentel Prof. Ryan P. Lively Prof. Huw M. L. Davies Prof. Christopher W. Jones 《Angewandte Chemie (International ed. in English)》2018,57(34):10923-10927
A scalable flow reactor is demonstrated for enantioselective and regioselective rhodium carbene reactions (cyclopropanation and C?H functionalization) by developing cascade reaction methods employing a microfluidic flow reactor system containing immobilized dirhodium catalysts in conjunction with the flow synthesis of diazo compounds. This allows the utilization of the energetic diazo compounds in a safe manner and the recycling of the dirhodium catalysts multiple times. This approach is amenable to application in a bulk‐scale synthesis employing asymmetric C?H functionalization by stacking multiple fibers in one reactor module. The products from this sequential flow–flow reactor are compared with a conventional batch reactor or flow–batch reactor in terms of yield, regioselectivity, and enantioselectivity. 相似文献
24.
J. Socorro Luis O. Pimentel C. Ortiz M. Aguero 《International Journal of Theoretical Physics》2009,48(12):3567-3585
Using the ADM formalism in the minisuperspace, we obtain the commutative and noncommutative exact classical solutions and
exact wave function to the Wheeler-DeWitt equation with an arbitrary factor ordering, for the anisotropic Bianchi type I cosmological
model, coupled to a scalar field, cosmological term and barotropic perfect fluid. We introduce noncommutative scale factors,
considering that all minisuperspace variables q
i
do not commute, so the symplectic structure was modified. In the classical regime, it is shown that the anisotropic parameter
β
±nc
and the field φ, for some value in the λ
eff cosmological term and noncommutative θ parameter, present a dynamical isotropization up to a critical cosmic time t
c
; after this time, the effects of isotropization in the noncommutative minisuperspace seems to disappear. In the quantum regimen,
the probability density presents a new structure that corresponds to the value of the noncommutativity parameter. 相似文献
25.
Silveri MM Rohan ML Pimentel PJ Gruber SA Rosso IM Yurgelun-Todd DA 《Magnetic resonance imaging》2006,24(7):833-841
Rapid maturational brain changes occur during adolescence--a time associated with risk-taking behaviors and improvements in cognition. The present study examined the relationship between white matter (WM) microstructure, impulsive behavior and response inhibition in female and male adolescents. Twenty-one healthy adolescents underwent diffusion tensor imaging using a 3.0-T magnetic resonance imaging system. Impulse control was assessed using the Bar-On Emotional Quotient Inventory, Youth Version. Response inhibition was assessed using the Stroop Color-Word Interference Test. Fractional anisotropy (FA), a measure of WM coherence, and trace, a measure of overall diffusivity, were determined from voxels manually placed in the midline and in the left and right forward-projecting arms of the genu and the splenium of the corpus callosum. Sex-specific differences were observed for the relationship between FA and impulsive behavior in the right anterior callosum for males and in the splenium for females. Males, compared to females, displayed significantly higher FA in the left WM region. Although trace was not associated with impulse control, trace in the genu (for females) and splenium (males and females) was associated with Stroop performance. Regional differences in trace also were evident, with lower values in the splenium observed than in all other regions. Although the latter significantly improved with age, no sex differences in impulse control or in Stroop performance were detected. The present findings provide supporting evidence for sex-related differences in the development of WM microstructure during adolescence. These data further suggest a neurobiological mechanism underlying some of the emotional and cognitive changes commonly observed in males versus females during the adolescent period. 相似文献
26.
Busin CS Lima AP de Almeida Prado CP Strüssmann C Júnior SS Recco-Pimentel SM 《Micron (Oxford, England : 1993)》2006,37(4):355-362
Cytogenetic analysis were done on specimens from two populations of Lysapsus limellus limellus, three of L. l. bolivianus and of one of Lysapsus caraya. All animals showed a diploid chromosomal number of 2n=24. The karyotypes of the two L. limellus subspecies were very similar, differing only by the larger amount of telomeric heterochromatin and a small pericentromeric C-band on the short arms of pair 2 in L. l. limellus specimens. The karyotype of L. caraya differed from those of the two L. limellus subspecies in terms of chromosomal morphology, C-banding pattern and location of the main NOR on chromosomes 7 and 6, respectively. The karyotype of the L. l. bolivianus population from Guajará-Mirim/RO differed from those of the other populations of the same subspecies in morphology and heterochromatin pattern of chromosomes 7 and 8. Additional NORs were detected by silver staining and confirmed by FISH in one of the homologues of pairs 1 and 8 in L. l. bolivianus and in pair 7 in L. caraya. These results suggest that a reassessment of the taxonomic status of L. limellus subspecies, especially of the L. l. bolivianus populations, may be necessary. 相似文献
27.
We consider the Hammersley interacting particle system starting from a shock initial profile with densities \(\rho ,\lambda \in {\mathbb R}\) (\( \rho < \lambda \)). The microscopic shock is taken as the position of a second-class particle initially at the origin, and the main results are: (i) a central limit theorem for the shock; (ii) the variance of the shock equals \(2[\lambda \rho (\lambda - \rho )]^{-1}t + O(t^{2/3})\). By using the same method of proof, we also prove similar results for first-class particles. 相似文献
28.
C.A. Parra Vargas J.L. Pimentel Jr. P. Pureur D.A. Landínez Téllez J. Roa-Rojas 《Physica B: Condensed Matter》2012,407(16):3128-3130
The irreversibility properties of high-Tc superconductors are of major importance for technological applications. For example, a high irreversibility magnetic field is a more desirable quality for a superconductor [1]. The irreversibility line in the H–T plane is constituted by experimental points, which divides the irreversible and reversible behavior of the magnetization. The irreversibility lines for series of La1.5+xBa1.5+x−yCayCu3Oz polycrystalline samples with different doping were investigated. The samples were synthesized using the usual solid estate reaction method. Rietveld-type refinement of x-ray diffraction patterns permitted to determine the crystallization of material in a tetragonal structure. Curves of magnetization ZFC–FC for the system La1.5+xBa1.5+x−yCayCu3Oz, were measured in magnetic fields of the 10–20,000 Oe, and allowed to obtain the values for the irreversibility and critical temperatures. The data of irreversibility temperature allowed demarcating the irreversibility line, Tirr(H). Two main lines are used for the interpretation of the irreversibility line: one of those which suppose that the vortexes are activated thermally and the other proposes that associated to Tirr a phase transition occurs. The irreversibility line is described by a power law. The obtained results allow concluding that in the system La1.5+xBa1.5+x−yCayCu3Oz a characteristic bend of the Almeida–Thouless (AT) tendency is dominant for low fields and a bend Gabay–Toulouse (GT) behavior for high magnetic fields. This feature of the irreversibility line has been reported as a characteristic of granular superconductors and it corroborates the topological effects of vortexes mentioned by several authors 1 and 2. 相似文献
29.
Tendons are formed by dense connective tissue composed of an abundant extracellular matrix (ECM) that is constituted mainly of collagen molecules, which are organized into fibrils, fibers, fiber bundles and fascicles helicoidally arranged along the largest axis of the tendon. The biomechanical properties of tendons are directly related to the organization of the collagen molecules that aggregate to become a super-twisted cord. In addition to collagen, the ECM of tendons is composed of non-fibrillar components, such as proteoglycans and non-collagenous glycoproteins. The capacity of tendons to resist mechanical stress is directly related to the structural organization of the ECM. Collagen is a biopolymer and presents optical anisotropies, such as birefringence and linear dichroism, that are important optical properties in the characterization of the supramolecular organization of the fibers. The objective of this study was to present a review of the composition and organization of the ECM of tendons and to highlight the importance of the anisotropic optical properties in the study of alterations in the ECM. 相似文献
30.
A strict proof of the equivalence of the Duffin-Kemmer-Petiau and Klein-Gordon-Fock theories is presented for physical S-matrix
elements in the case of charged scalar particles minimally interacting with an external or quantized electromagnetic field.
The Hamiltonian canonical approach to the Duffin-Kemmer-Petiau theory is first developed in both the component and the matrix
form. The theory is then quantized through the construction of the generating functional for the Green's functions, and the
physical matrix elements of the S-matrix are proved to be relativistic invariants. The equivalence of the two theories is
then proved for the matrix elements of the scattered scalar particles using the reduction formulas of Lehmann, Symanzik, and
Zimmermann and for the many-photon Green's functions.
Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 124, No. 3, pp. 445–462, September, 2000. 相似文献