Structural evolution of (Ca0.35Sr0.65)TiO3 perovskite at high pressures

Lattice parameters of a synthetic powder sample of Ca_0.35Sr_0.65TiO₃ perovskite have been determined by the method of Le Bail refinement, using synchrotron X-ray diffraction patterns collected at pressures up to 15.5 GPa with a membrane-driven diamond anvil cell. At ambient conditions, diffraction data were consistent with the I4/mcm structure reported previously in the literature for the same composition. Diffraction data collected at high pressures were consistent with tetragonal (or, at least, pseudo-tetragonal) lattice geometry, and no evidence was found for the development of any of the orthorhombic structures identified in other studies of (Ca, Sr)TiO₃ perovskites. Additional weak reflections, which could not be accounted for by the normal I4/mcm perovskite structure, were detected in diffraction patterns collected at pressures of 0.9-2.5 GPa, and above ∼13.5 GPa, however. Small anomalies in the evolution of unit cell volume and tetragonal strain were observed near 3 GPa, coinciding approximately with breaks in slope with increasing pressure of bulk and shear moduli for a sample with the same composition which had previously been reported. The anomalies could be due either to new tetragonal↔tetragonal/pseudo-tetragonal phase transitions or to subtle changes in compression mechanism of the tetragonal perovskite structure.     

导数振荡与应变能极小的平面分段三次参数Hermite插值

由于分段三次参数Hermite插值的切矢往往被作为变量,故可对其进行优化以使得构造的插值曲线满足特定的要求.为了构造兼具保形性与光顺性的平面分段三次参数Hermite插值曲线,给出了一种通过同时极小化导数振荡和应变能来确定切矢的方法.首先以导数振荡函数和应变能函数为双目标建立了切矢满足的方程系统;然后证明了方程系统存在唯一解,并给出了解的具体表达式;最后给出了误差分析,并通过数值算例表明方法的有效性.结果表明,相对于导数振荡极小化方法和应变能极小化方法,所提出的导数振荡和应变能极小化方法同时兼顾了平面分段三次参数Hermite插值曲线的保形性和光顺性.     

Exponential distributions on semigroups

Three fundamental characterizations of the standard exponential distribution on [0, ) are the remaining life, memoryless and constant failure properties. Analogs of these properties are studied for distributions on a class of semigroups in which the semigroup operation replaces addition, a compatible partial order replaces the ordinary order, and a left-invariant measure replaces Lebesgue measure. Partial characterizations of exponential distributions on such semigroups are obtained and the semigroup formulation provides new characterizations of certain aging properties studied in reliability-increasing failure rate, new better than used, and increasing failure rate average.     

Retrieval and chaos in extremely dilutedQ-Ising neural networks

Using a probabilistic approach, the deterministic and the stochastic parallel dynamics of aQ-Ising neural network are studied at finiteQ and in the limitQ. Exact evolution equations are presented for the first time-step. These formulas constitute recursion relations for the parallel dynamics of the extremely diluted asymmetric versions of these networks. An explicit analysis of the retrieval properties is carried out in terms of the gain parameter, the loading capacity, and the temperature. The results for theQ network are compared with those for theQ=3 andQ=4 models. Possible chaotic microscopic behavior is studied using the time evolution of the distance between two network configurations. For arbitrary finiteQ the retrieval regime is always chaotic. In the limitQ the network exhibits a dynamical transition toward chaos.     

On the extreme spectral properties of Toeplitz matrices generated byL 1 functions with several minima/maxima

In this paper we are concerned with the asymptotic behavior of the smallest eigenvalue ₁ ⁽ⁿ⁾ of symmetric (Hermitian)n ×n Toeplitz matricesT _n (f) generated by an integrable functionf defined in [–, ]. In [7, 8, 11] it is shown that ₁ ⁽ⁿ⁾ tends to essinff =m _f in the following way: ₁ ⁽ⁿ⁾ –m _f 1/n ^2k . These authors use three assumptions:A1)f –m _f has a zero inx =x ₀ of order 2k.A2)f is continuous and at leastC ^2k in a neighborhood ofx ₀.A3)x =x ₀ is the unique global minimum off in [–, ]. In [10] we have proved that the hypothesis of smoothnessA2 is not necessary and that the same result holds under the weaker assumption thatf L ¹[–, ]. In this paper we further extend this theory to the case of a functionf L ¹[–, ] having several global minima by suppressing the hypothesisA3 and by showing that the maximal order 2k of the zeros off –m _f is the only parameter which characterizes the rate of convergence of ₁ ⁽ⁿ⁾ tom _f .     

Theoretical study of structure and stability of fullerene derivative: C50O

A total of eight possible isomers of C₅₀O, an oxide of fullerene C₅₀ (D_5h), have been investigated by B3LYP/3‐21G calculations. The isomer, which has an annulene‐like structure with oxygen bridging across a [5,6] type C? C bond at the site between the pole and the equatorial belt, is found being the ground state of C₅₀O. Four isomers are relatively more stable and the energy differences between them are not large. This result indicates that more than one C₅₀O isomer will coexist once C₅₀O is synthesized. The relative stabilities of the C₅₀O isomers may be determined mainly by the strain release and by the formation of the cyclic phenylene substructure at the equatorial belt of the cage. The calculated nucleus independent chemical shifts (NICS) of the C₅₀O isomers will be useful because from them one can expect outstanding NMR properties that can lead to their identification and characterization. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Norvancomycin-capped silver nanoparticles: Synthesis and antibacterial activities against E. coli

The synthesis of norvancomycin (NVan)-capped silver nanoparticles (Ag@NVan) and their notable in vitro antibacterial activities against E. coli, a Gram-negative bacterial strain (GNB), are reported here. Mercaptoacetic acid-stabilized spherical silver nanoparticles with a diameter of 16±4 nm are prepared by a simple chemical reaction. The formation process of the silver nanoparticles is investigated by UV-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM). NVan is then grafted to the terminal carboxyl of the mercaptoacetic acid in the presence of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDAC). The TEM images of single bacteria treated with Ag@NVan show that plenty of Ag@NVan aggregate in the cell wall of E. coli. A possible antibacterial mechanism is proposed that silver nanoparticles may help destroy the stability of the outer membrane of E. coli, which makes NVan easier to bind to the nether part of the peptidoglycan structure. The antibacterial activities of silver nanoparticles on their own, together with the rigid polyvalent interaction between Ag@NVan and cell wall, enables Ag@NVan to be an effective inhibitor of GNB. This kind of bionanocomposites might be used as novel bactericidal materials and we also provide an effective synthesis method for preparing functional bioconjugated nanoparticles here. Supported by the National Natural Science Foundation of China (Grant No. 50373036) and Fok Ying Tung Education Foundation (Grant No. J20040212)     

橡胶中简单剪切与纯剪切的关系

研究了简单剪切与纯剪切的关系，得出了：（１）简单剪切可看成纯剪切加转动，转动角θ有；（２）若简单剪切椭圆的长轴与坐标轴Ｘ的夹角为φ，相应的纯剪椭圆长袖与坐标轴ｙ的夹角为β０，则φ＝β０；（３）橡胶在双向拉伸时剪应变γ的一般表达式为，对简单剪切而言即为     

Synthesis,Structure, and Fluxionality of Strained Hypercoordinate Silicon‐Bridged [1]Ferrocenophanes

The first hypercoordinate sila[1]ferrocenophanes [fcSiMe(2‐C₆H₄CH₂NMe₂)] ( 5 a ) and [fcSi(CH₂Cl)(2‐C₆H₄CH₂NMe₂)] ( 5 b ) (fc=(η⁵‐C₅H₄)Fe(η⁵‐C₅H₄)) were synthesized by low‐temperature (?78 °C) reactions of Li[2‐C₆H₄CH₂NMe₂] with the appropriate chlorinated sila[1]ferrocenophanes ([fcSiMeCl] ( 1 a ) and [fcSi(CH₂Cl)Cl] ( 1 d ), respectively). Single‐crystal Xray diffraction studies revealed pseudo‐trigonal bipyramidal structures for both 5 a and 5 b , with one of the shortest reported Si???N distances for an sp³‐hybridized nitrogen atom interacting with a tetraorganosilane detected for 5 a (2.776(2) Å). Elongated Si? C_ipso bonds trans to the donating NMe₂ arms (1.919(2) and 1.909(2) Å for 5 a and 5 b , respectively) were observed relative to both the non‐trans bonds ( 5 a : 1.891(2); 5 b : 1.879(2) Å) and the Si? C_ipso bonds of the non‐hypercoordinate analogues ([fcSiMePh] ( 1 b ): 1.879(4), 1.880(4) Å; [fcSi(CH₂Cl)Ph] ( 1 e ): 1.881(2), 1.884(2)). Solution‐state fluxionality of 5 a and 5 b , suggestive of reversible coordination of the NMe₂ group to silicon, was demonstrated by means of variable‐temperature NMR studies. The ΔG^≠ of the fluxional processes for 5 a and 5 b in CD₂Cl₂ were estimated to be 35.0 and 37.6 kJ mol^?1, respectively (35.8 and 38.3 kJ mol^?1 in [D₈]toluene). The quaternization of 5 a and 5 b by MeOTf, to give [fcSiMe(2‐C₆H₄CH₂NMe₃)][OTf] ( 7 a‐ OTf) and [fcSi(CH₂Cl)(2‐C₆H₄CH₂NMe₃)][OTf] ( 7 b‐ OTf), respectively, supported the reversibility of NMe₂ coordination at the silicon center as the source of fluxionality for 5 a and 5 b . Surprisingly, low room‐temperature stability was detected for 5 b due to its tendency to intramolecularly cyclize and form the spirocyclic [fcSi(cyclo‐CH₂NMe₂CH₂C₆H₄)]Cl ( 9 ‐Cl). This process was observed in both solution and the solid state, and isolation and Xray characterization of 9 ‐Cl was achieved. The model compound, [Fc₂Si(2‐C₆H₄CH₂NMe₂)₂] ( 8 ), synthesized through reaction of [Fc₂SiCl₂] with two equivalents of Li[2‐C₆H₄CH₂NMe₂] at ?78 °C, showed a lack of hypercoordination in both the solid state and in solution (down to ?80 °C). This suggests that either the reduced steric hindrance around Si or the unique electronics of the strained sila[1]ferrocenophanes is necessary for hypercoordination to occur.     

An approach to sequence-specific antibody proteases

We describe here a novel strategy for the isolation of antibodies with sequence-specific protease activity: the synthesis of dipeptide haptens in which the targeted peptide bond has been replaced by a ring-strained or torsionally strained hydroxyethylene transition-state analog. Thus, the analogs mimic both a peptide bond in a distorted, reactive conformation and the transition state for peptide bond hydrolysis. In order to obtain sequence-specific antibody proteases, these analogs have been flanked with additional amino acid residues in preparation for immunization. In particular, we have synthesized peptides containing analogs such as 2-cis-amino-3-cis-hydroxycyclobutane carboxylic acid andendo-(3-amino-2-hydroxy)bicyclo[2.2.1]heptane-7-anti-carboxylic acid. We have also prepared a series of peptide derivatives containing analogs, such as 2-[3-amino-2-oxo-1-azetidinyl]-3-methylbutanoic acid, in which the targeted peptide bond has been incorporated into a β-lactam ring. Since the “peptide bond” has been left intact, these species mimic only a distorted ground state. At present, antibodies are being elicited against a number of the above peptide derivatives.