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121.
Liu Y Bersuker IB Garcia-Fernandez P Boggs JE 《The journal of physical chemistry. A》2012,116(28):7564-7570
It is shown that the pseudo Jahn-Teller effect (PJTE) in combination with ab initio calculations explains the origin of instability of the planar configuration of tetrafluorocyclobutadiene, C(4)F(4), with respect to a puckered structure and square-to-rectangle distortion of the carbon ring, and rationalizes its difference from the planar-rectangular geometry of C(4)H(4) and nonplanar (puckered) structure of Si(4)H(4). The two types of instability and distortion of the high-symmetry D(4h) configuration in these systems emerge from the PJT coupling of the ground B(2g) state with the excited A(1g) term producing instability along the b(2g) coordinate (elongation of the carbon or silicon square ring), and with the excited E(g) term resulting in e(g) (puckering) distortion. A rhombic distortion b(1g) of the ring is also possible due to the coupling between excited A(1g) and B(1g) terms. For C(4)F(4), ab initio calculations of the energy profiles allowed us to evaluate the PJTE constants and to show that the two instabilities, square-to-tetragonal b(2g) and puckering e(g) coexist, thus explaining the origin of the observed geometry of this system in the ground state. The preferred cis-trans (e(g) type) puckering in C(4)F(4) versus trans-trans puckering (b(2u) distortion) in Si(4)H(4) follows from the differences in the energy gaps to their excited electronic E(g) and A(1u) terms causing different PJTE in these two cases. 相似文献
122.
By analysing the facet structure of the convex polytope generated by the twelve transformation strains of cubic to monoclinic-I martensite, we show that there are two different kinds of monoclinic-I martensite. These two kinds differ in the sign of a material parameter. While the symmetry properties of both kinds are the same, the geometrical structure of the set of recoverable strains is different. A key idea is to consider the convex polytope formed by the transformation strains and to study its facets. Another insight is to use invariant theory to exploit the fact that compatible cones are algebraic surfaces. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
123.
Xiaojun Wang Isaac Elishakoff Zhiping Qiu Changhe Kou 《International Journal of Solids and Structures》2009,46(13):2539-2546
Hybrid theoretical, experimental and numerical method is proposed for free vibration and buckling of composite shell with unavoidable scatter in elastic moduli. Based on the Goggin’s measurement techniques, the elastic moduli for material T300-QY8911 are measured, and a set of experimental points are obtained. The measurements of elastic moduli are quantified by either (1) the smallest ellipsoid and (2) the smallest four-dimensional uncertainty hyper-rectangle. Then uncertainty propagation in vibration and buckling problems of composite shell by ellipsoidal analysis and interval analysis are, respectively, studied from the theoretical standpoint. Comparison between these analyses is performed numerically. 相似文献
124.
Csar Leyva-Porras María Zenaida Saavedra-Leos Laura Araceli Lpez-Martinez Vicente Espinosa-Solis Yolanda Tern-Figueroa Alberto Toxqui-Tern Isaac Compen-Martínez 《Molecules (Basel, Switzerland)》2021,26(18)
The drying of fruit juices has advantages such as easy handling of powders, reduction in volume, and preservation of the characteristics of the fruit. Thus, in this work, the effect of the spray drying conditions of strawberry juice (SJ) with maltodextrin (MX) as a carrying agent on the microencapsulation of bioactive compounds and physicochemical properties was studied. The content of phenolic compounds and antioxidant activity showed higher values at low concentrations of MX, while the effect of drying temperature was negligible. The thermal characterization showed that the low molecular weight sugars in the juice decreased the glass transition temperature (Tg). The morphological analysis by scanning electron microscopy (SEM) indicated that at low concentrations of MX, the particles agglomerated, while at intermediate and high concentrations, the particles were observed as well separated. Through microstructural analysis by X-ray diffraction (XRD), the presence of amorphous state was confirmed in all the samples, which is beneficial for preventing chemical and biochemical reactions, and promoting the conservation of the microencapsulated bioactive compounds. 相似文献
125.
In engineering applications, probabilistic reliability theory appears to be presently the most important method, however, in many cases precise probabilistic reliability theory cannot be considered as adequate and credible model of the real state of actual affairs. In this paper, we developed a hybrid of probabilistic and non-probabilistic reliability theory, which describes the structural uncertain parameters as interval variables when statistical data are found insufficient. By using the interval analysis, a new method for calculating the interval of the structural reliability as well as the reliability index is introduced in this paper, and the traditional probabilistic theory is incorporated with the interval analysis. Moreover, the new method preserves the useful part of the traditional probabilistic reliability theory, but removes the restriction of its strict requirement on data acquisition. Example is presented to demonstrate the feasibility and validity of the proposed theory. 相似文献
126.
Emilio Bustelo Isaac de los Ríos Manuel J. Tenorio M. Carmen Puerta Pedro Valerga 《Monatshefte für Chemie / Chemical Monthly》2000,131(12):1311-1320
Summary. The solid-state tautomerization of the hydrido-alkynyl derivatives [Cp
*RuH(C&*CR)-(dippe)][BPh4] (Cp* = C5Me5; R = SiMe3, Ph, H; dippe = 1,2-bis-(diisopropylphosphino)-ethane) to their vinylidene isomers [Cp
*Ru*C*CHR(dippe)][BPh4] was studied by IR spectroscopy. Characteristic isothermic αvs. t curves for each individual rearrangement process were recorded. Their shape, and hence the isomerization mechanism, depends
strongly on the nature of the substituent R. The kinetic analysis of the above curves using the Avrami-Erofeev provided some mechanistic information about the isomerization process in the solid.
Received July 7, 2000. Accepted August 29, 2000 相似文献
127.
Isaac Pesenson 《Transactions of the American Mathematical Society》2000,352(9):4257-4269
We consider a generalization of entire functions of spherical exponential type and Lagrangian splines on manifolds. An analog of the Paley-Wiener theorem is given. We also show that every spectral entire function on a manifold is uniquely determined by its values on some discrete sets of points.
The main result of the paper is a formula for reconstruction of spectral entire functions from their values on discrete sets using Lagrangian splines.
128.
Cristina García‐Simón Marc Garcia‐Borràs Dr. Laura Gómez Dr. Isaac Garcia‐Bosch Dr. Sílvia Osuna Prof. Marcel Swart Dr. Josep M. Luis Prof. Concepció Rovira Prof. Manuel Almeida Dr. Inhar Imaz Prof. Daniel Maspoch Dr. Miquel Costas Dr. Xavi Ribas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1445-1456
The metal‐directed supramolecular synthetic approach has paved the way for the development of functional nanosized molecules. In this work, we report the preparation of the new nanocapsule 3? (CF3SO3)8 with a A4B2 tetragonal prismatic geometry, where A corresponds to the dipalladium hexaazamacrocyclic complex Pd‐1 , and B corresponds to the tetraanionic form of palladium 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin ( 2 ). The large void space of the inner cavity and the supramolecular affinity for guest molecules towards porphyrin‐based hosts converts this nanoscale molecular 3D structure into a good candidate for host–guest chemistry. The interaction between this nanocage and different guest molecules has been studied by means of NMR, UV/Vis, ESI‐MS, and DOSY experiments, from which highly selective molecular recognition has been found for anionic, planar‐shaped π guests with association constants (Ka) higher than 109 M ?1, in front of non‐interacting aromatic neutral or cationic substrates. DFT theoretical calculations provided insights to further understand this strong interaction. Nanocage 3? (CF3SO3)8 can not only strongly host one single molecule of M(dithiolene)2 complexes (M=Au, Pt, Pd, and Ni), but also can finely tune their optical and redox properties. The very simple synthesis of both the supramolecular cage and the building blocks represents a step forward for the development of polyfunctional supramolecular nanovessels, which offer multiple applications as sensors or nanoreactors. 相似文献
129.
Biomolecules such as serum proteins can interact with drugs in the body and influence their pharmaceutical effects. Specific and precise methods that analyze these interactions are critical for drug development or monitoring and for diagnostic purposes. Affinity capillary electrophoresis (ACE) is one technique that can be used to examine the binding between drugs and serum proteins, or other agents found in serum or blood. This article will review the basic principles of ACE, along with related affinity-based capillary electrophoresis (CE) methods, and examine recent developments that have occurred in this field as related to the characterization of drug–protein interactions. An overview will be given of the various formats that can be used in ACE and CE for such work, including the relative advantages or weaknesses of each approach. Various applications of ACE and affinity-based CE methods for the analysis of drug interactions with serum proteins and other binding agents will also be presented. Applications of ACE and related techniques that will be discussed include drug interaction studies with serum agents, chiral drug separations employing serum proteins, and the use of CE in hybrid methods to characterize drug binding with serum proteins. 相似文献
130.
Sztainbuch IW 《The Journal of chemical physics》2006,125(12):124707
We have identified empirically a relationship between the surface morphology of small individual aggregates (<100 Au nanoparticles) and surface-enhanced Raman scattering (SERS) enhancement. We have found that multilayer aggregates generated greater SERS enhancement than aggregates limited to two-dimensional (2D) or one-dimensional structures, independent of the number of particles. SERS intensity was measured using the 730 cm(-1) vibrational mode of the adsorbed adenine molecule on 75 nm Au particles, at an excitation wavelength of 632.8 nm. To gain insight into these relationships and its mechanism, we developed a qualitative model that considers the collections of interacting Au nanoparticles of an individual aggregate as a continuous single entity that retains its salient features. We found the dimensions of the modeled surface features to be comparable with those found in rough metal surfaces, known to sustain surface plasmon resonance and generate strong SERS enhancement. Among the aggregates that we have characterized, a three 75 nm nanoparticle system was the smallest to generate strong SERS enhancement. However, we also identified single individual Au nanoparticles as SERS active at the same wavelength, but with a diameter twice in size. For example, we observed a symmetric SERS-active particle of 180 nm in diameter. Such individual nanoparticles generated SERS enhancement on the same order of magnitude as the small monolayer Au aggregates, an intensity value significantly stronger than predicted in recent theoretical studies. We also found that an aspect of our model that relates the dimensions of its features to SERS enhancement is also applicable to single individual Au particles. We conclude that the size of the nanoparticle itself, or the size of a protrusion of an irregularly shaped single Au particle, will contribute to SERS enhancement provided that its dimensions satisfy the conditions for plasmon resonance. In addition, by considering the ratio of the generated intensities of typical 2D Au aggregates to the enhancement of individual SERS-active particles, a value of approximately 2 is determined. Its moderate value suggests that it is not the aggregation effect that is responsible for much of the observed SERS enhancement but the surface region associated with the SERS-active site. 相似文献