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121.
O. V. Shishkin 《Russian Chemical Bulletin》1997,46(9):1510-1512
The molecular geometries and inversion barriers of the rings in 2-oxo-1,2,3,4-tetrahydropyridine and its alkyl-substituted
(Me, Et, Pri, or But) and phenyl-substituted derivatives were calculated by the molecular mechanics method. The introduction of substituents has
no substantial effect on the equilibrium conformation of the heterocycle (a distorted sofa). For 4-alkyl- and 3-alkyl-substituted
derivatives (except for 4-Me and 4-Et derivatives), an axial orientation of the alkyl group is more favorable. The phenyl
substituents have equatorial and axial orientations at postions 4 and 3, respectively.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1584–1586, September, 1997. 相似文献
122.
From the de Broglie matter wave hypothesis and Planck’s energy quantization law, and assuming conservation of energy in the
absorption of a photon and its consequent conversion to kinetic energy of motion by a material particle initially at rest,
one can deduce a simple mathematical relationship between the wavelength λ (or frequency ν), of the photon absorbed by the
particle at rest, and the resulting de Broglie matter wave length, λD, of the particle with kinetic energy of motion of mv2/2. The relationship so deduced, λD∝√λ, suggests that visible wavelengths of light, from about 4000 ?, in the violet, to beyond about 7000 ?, in the red, on
absorption by an electron at rest, lead to material electron wavelengths, λD, of the order of the size of the electron transfer proteins seen in the photosynthetic reaction centers of photosynthesizing
organisms, at about a size of 50–100 ?. In addition to understanding the mechanism of photosynthesis as a material wave mediated
phenomenon, further areas of importance of the relations pointed out in this paper are in the design of experiments to gain
a deeper understanding of the basic tenets of wave mechanics, and in the use of tunable lasers to probe various properties
of material waves, and to precisely control their properties for applications including lithography. 相似文献
123.
A new series of photoactivated DNA oxidizing agents in which an acridine moiety is covalently linked to viologen by an alkylidene spacer was synthesized, and their photophysical properties and interactions with DNA, including DNA cleaving properties, were investigated. The fluorescence quantum yields of the viologen-linked acridines were found to be lower than that of the model compound 9-methylacridine (MA). The changes in free energy for the electron transfer reactions were found to be favorable, and the fluorescence quenching observed in these systems is explained by an electron transfer mechanism. Intramolecular electron transfer rate constants were calculated from the observed fluorescence quantum yields and singlet lifetime of MA and are in the range from 1.06x10(10) s(-1) for 1 a (n=1) to 6x10(8) s(-1) for 1 c (n=11), that is, the rate decreases with increasing spacer length. Nanosecond laser flash photolysis of these systems in aqueous solutions showed no transient absorption, but in the presence of guanosine or calf thymus DNA, transient absorption due to the reduced viologen radical cation was observed. Studies on DNA binding demonstrated that the viologen-linked acridines bind effectively to DNA in both intercalative and electrostatic modes. Results of PM2 DNA cleavage studies indicate that, on photoexcitation, these molecules induce DNA damage that is sensitive to formamidopyrimidine DNA glycosylase. These viologen-linked acridines are quite stable in aqueous solutions and oxidize DNA efficiently and hence can be useful as photoactivated DNA-cleaving agents which function purely by the co-sensitization mechanism. 相似文献
124.
Teik-Cheng Lim 《Journal of mathematical chemistry》2003,33(3-4):279-285
The van der Waals forces for non-bonded interaction can be expressed either by the Exponential-6 or by the Lennard-Jones(m-n) potential functions, whereby m > n. Hitherto a relationship exists between the Exponential-6 and the Lennard-Jones(12-6) potential functions, with a scaling factor = 13.772 at or near the equilibrium and = 12.0 for long range interaction. This paper attempts to develop relationships between Exponential-6 and a more generalized Lennard-Jones(m-n). Analysis reveals that the relationship exists only when n = 6 and that two sets of scaling factors (as functions of index m) applies for the relationship between Exponential-6 and the Lennard-Jones(m-6), whereby m > 6. 相似文献
125.
It is proposed that in molecular mechanics calculation points belonging to various stable or meta-sta-ble conformtrs are mixed up and form fractal structures in conformation space.The calculation results show the following two phenomena:(i)Two levels of structure with fractal feature were observed.Around the conformer without mirror symmetry points belonging to the conformer and its enantiomer are mixed up and form the first level of fractal structure; on the boundary of the attractive basin o{ each atlractor,points belonging to different attractors form the second level of fractal structure.(ii) The variation of molecular mechanics parameters will influence the structure and area of each attractive basin significantly The above phenomena may become the basis of a new method for solving the troublesome multi-minimum-point problem in molecular mechanics calculation. 相似文献
126.
为研究不同渗透压力条件下的岩石卸荷力学特性,选取砂岩为研究对象,开展了不同渗透压力和不同应力路径下的三轴卸荷试验,并与常规三轴试验进行对比,比较了不同应力路径下的岩石强度特性,分析了渗透压力对岩石变形和强度参数的影响。试验结果表明:渗透压力的增大会弱化岩石强度,岩石的峰值强度随渗透压力的增大而降低,而轴向变形随渗透压力增大而增加,渗透压力越大,岩石的压密段特征越明显;针对两种不同的卸荷应力路径,恒轴压卸围压路径条件下,岩石的黏聚力不断降低,内摩擦角不断增加,而加轴压卸围压路径条件下,岩石的黏聚力不断增加,内摩擦角逐渐降低。 相似文献
127.
为了阐明循环加卸载路径对六边形蜂窝能量演化的影响规律,设计了3种不同分级循环加卸载试验,揭示了不同分级循环加卸载模式下外界输入总能量、弹性变形能、耗散能、塑性变形能等参数的演化特征及相互关系,研究结果表明:不同分级循环加卸载作用下,蜂窝的初始峰值强度和平台应力与卸载过程蜂窝弹性能的释放程度有关;3种不同分级循环加卸载模式下外界输入总能量、蜂窝的弹性变形能和塑性变形能随着加卸载梯级增大呈现非线性增加的趋势,耗散能在前三级循环作用下随着加载次数增加而减小,在最后一级循环中循环载荷上限较大,扰动效应强于强化效应,耗散能呈现相反趋势;提升循环载荷上限,蜂窝内部损伤增加,且越接近蜂窝初始峰值强度,蜂窝的损伤越严重;同时提升循环载荷下限,蜂窝弹性能释放较少,损伤加剧。 相似文献
128.
利用断裂力学的概念和方法,研究水工混凝土结构中多裂纹系应力强度因子的计算,根据“释放应力”的概念和修正cauchy型奇异积分方程组,获得Fredholm积分方程组,并考虑裂纹之间,裂纹与边界间的相互作用的基础上,提出了虚拟荷载方法。最后,由所求得的应力强度因子和全场应力分析,判断出最危险裂纹扩展的位置,对带有多裂纹系的试样进行了实验,结果与计算值的吻合良好。 相似文献
129.
In this paper, minimax principles are explored for elliptic mixed hemivariational–variational inequalities. Under certain conditions, a saddle-point formulation is shown to be equivalent to a mixed hemivariational–variational inequality. While the minimax principle is of independent interest, it is employed in this paper to provide an elementary proof of the solution existence of the mixed hemivariational–variational inequality. Theoretical results are illustrated in the applications of two contact problems. 相似文献
130.
A mathematical method to solve structural problems, using parameter-transfer finite elements (P-TFE) was recently proposed by the authors [1] [2] [3]. The proposed transfer finite element approach is able to create a mathematical model of a structure, taking into account directly the whole behaviour of the structure under dynamic, aerodynamic, and thermal actions, and not by assembling, in a separate fashion, the stiffness and the mass matrix on one side and the external load vector as performed by the classical finite element procedure.The purpose of this paper is to apply the above methodology to optimization problems, in particular to obtain the minimum structural weight for a beam, under primary constraints on buckling load or natural frequencies.The use of P-TFE in the field of structural optimization overcomes most difficulties of the usual techniques of solution and the element is particularly useful in the evaluation of the sensitivity matrix.The formulation of the optimization problem based on P-TFE is presented and some applications are studied. The numerical results obtained are compared with other existing methodologies and briefly discussed.
List of Symbols {B} m vector of the generalized state variables - {C} m vector of integration constants - [I] unit matrix - EI bending stiffness - A cross-sectional area - u adimensional thickness - l beam length - M,M bending moment - [N] m shape function ofm-th order - [N*] shape function atx 0 - P axial load - [R] i transfer matrix of thei-th element - T,T shear force - w transverse displacement - x adimensional independent variable - x 0 value ofx at the left of the element - {Y} vector of state variables - {Y*} imposed condition atx 0 - 0m Kronecker delta with the first pedix always set equal to zero - normalized eigenfrequency - normalized buckling load - mass density 相似文献
Sommario Gli autori hanno già proposto un metodo per studiare problemi strutturali [1] [2] [3], introducendo una nuova metodologia di discretizzazione, basata sull'impiego di elementi finiti di trasferimento, funzioni esplicite di un parametro, indicati come P-TFE. Tali elementi sono in grado di rappresentare, in similitudine alla funzione di trasferimento, il comportamento completo dell'elemento strutturale in esame, soggetto ad azioni dinamiche, aerodinamiche e termiche; sono parimenti in grado di produrre, in similitudine al metodo degli elementi finiti, un modello matematico discreto di un continuo.Scopo del presente lavoro è di applicare detta metodologia a problemi di ottimizzazione, in particolare alla ricerca del minimo peso per una trave che mantenga inalterate le sue caratteristiche di carico critico o le frequenze naturali di vibrazione.Vengono quindi presentati alcuni risultati numerici dei casi esaminati e confrontati con quelli ottenuti da altri autori con l'impiego di altre metodologie.
List of Symbols {B} m vector of the generalized state variables - {C} m vector of integration constants - [I] unit matrix - EI bending stiffness - A cross-sectional area - u adimensional thickness - l beam length - M,M bending moment - [N] m shape function ofm-th order - [N*] shape function atx 0 - P axial load - [R] i transfer matrix of thei-th element - T,T shear force - w transverse displacement - x adimensional independent variable - x 0 value ofx at the left of the element - {Y} vector of state variables - {Y*} imposed condition atx 0 - 0m Kronecker delta with the first pedix always set equal to zero - normalized eigenfrequency - normalized buckling load - mass density 相似文献