Semiempirical and ab initio conformational analysis of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane with application of GIAO-SCF methods to NMR spectrum interpretation

The GIAO-SCF method for calculating isotropic nuclear magnetic shielding values has been utilized to explain certain features in the ¹H-NMR spectrum of 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane. Population distributions of the low-energy conformers based on their ab initio energies were used to produce weighting factors for the individual calculated shielding values to calculate the weighted average of the shielding values for a complete set of conformers. The differences in ¹H chemical shifts between the hydrogens of the two methyl groups and between the axial and equatorial hydrogens in 2-methylene-8,8-dimethyl-1,4,6,10-tetraoxaspiro[4.5] decane were shown to be due to energy differences between the chair and boat orientations of the six-membered ring and contribution from a twist-boat conformation. Results suggest a hypothesis that intramolecular differences in chemical shift might be calculated to a greater degree of accuracy than chemical shifts calculated relative to a standard.     

Correctness of concurrent processes

A new notion of correctness for concurrent processes is introduced and investigated. It is a relationship P sat S between process terms P built up from operators of CCS [24], CSP [18] and COSY [20] and logical formulas S specifying sets of finite communication sequences as in [38]. The definition of P sat S is based on a Petri net semantics for process terms [27]. The main point is that P sat S requires a simple liveness property of the net denoted by P. This implies that P is divergence free and externally deterministic. Process correctness P sat S determines a new semantic model for process terms and logical formulas. It is a modification ^* of the readiness semantics [28] which is fully abstract with respect to the relation P sat S. The model ^* abstracts from the concurrent behaviour of process terms and certain aspects of their internal activity. In ^* process correctness P sat S boils down to semantic equality: ^*P = ^*S. The modified readiness equivalence is closely related to failure equivalence [7] and strong testing equivalence [9].     

Computation of through-space NMR shielding effects in aromatic ring pi-stacked complexes

Aromatic compounds can form dimeric complexes in solution. Substituted aromatics tend to form parallel-stacked complexes, either aligned or offset. The HF-GIAO method in Gaussian 03 was employed to calculate the NMR isotropic shielding values of the proximal hydrogen of diatomic hydrogen probes above and below the center of the ring and above and below an unsubstituted ring carbon of 1,3,5-trimethylbenzene in a face-to-face pi-stacked aligned complex with 1,3,5-trinitrobenzene. The calculated isotropic shielding values for the aromatic hydrogens of each of the substituted rings were subtracted from the isotropic shielding values calculated for the comparable positions in the complex. Complexation results in each aromatic ring shielding the other ring. Also, the calculated isotropic shielding values for the proximal hydrogen of a diatomic hydrogen probe over (or under) each of the individual substituted benzenes were subtracted from the isotropic shielding values calculated for the comparable positions in the complex. The difference is the shielding increment due to complexation. Complexation results in increased NMR shielding of a hydrogen probe molecule on both sides of the pi-stacked complex, with slightly more shielding due to complexation on the side nearest 1,3,5-trimethylbenzene. The results are interpreted in terms of polarization of the pi cloud of the substituted benzenes by complexation and its NMR consequences. Finally, NMR shielding calculations were done on the optimized structure of N-phenylpyrrole dimer. The data were compared to concentration-dependent NMR shift data to estimate the percent dimer present.     

Spatially referenced methods of processing raster and vector data

The authors consider a general method of constructing addressing and arithmetic systems for two-dimensional image data using the hierarchy of ‘molecular’ tilings based on an original isohedral ‘atomic’ tiling. (Each molecular title at level k is formed from a constant number of tiles at level k−1; this is termed the ‘aperture’ property of the hierarchy.) In addition they present 11 objective criteria (which are of significance in cartographic image processing), by which these hierarchies and tilings may be described and compared.

Of the 11 topologically distinct types of isohedral tiling, three ([3⁶], [4⁴] and [6³]) are composed of regular polygons, and two of these ([3⁶] and[4⁴]) satisfy the condition that all tiles have the same ‘orientation’. In general, although each level in a hierarchy is topologically equivalent, the tiles may differ in shape at different levels and only [6³], [4⁴], [4.8²] and [4.6.12] are capable of giving rise to hierarchies in which the tiles at all levels are the same shape. The possible apertures of hierarchies obeying this condition are n² (for any n > 1)in the cases of [6³] and [4⁴]; n² or 2n² in the case of [4.8²]; and n² or 3n² in the case of [4.6.12].

In contrast the only tiling exhibiting the uniform ‘adjacency’ criterion is[3⁶]. However, hierarchies based on this atomic tiling generate molecular tiles with different shapes at every level. If these disadvantages are accepted, hierarchies based on first-level molecular tiles referred to as the 4-shape, 4′-shape, 7-shape and 9-shape are generated. Of these the 4-shape and the 9-shape appear to satisfy many of the cartographically desirable properties in addition to having an atomic tiling which exhibits uniform adjacency.

In recent years the generalized balanced ternary addressing system has been developed to exploit the image processing power of the 7-shape. The authors have generalized and extended this system as ‘tesseral addressing and arithmetic’, showing how it can be used to render a 4-shape into a spatially correct linear quadtree.     

重金属捕集剂二甲基二硫代氨基甲酸对6种重金属螯合固化性能的量子化学研究

为探讨二甲基二硫代氨基甲酸盐螯合重金属离子的作用机理,本文采用密度泛函理论,在B3LYP/6-31++G（d,p）和B3LYP/LanL2DZ混合基组水平上,分别计算了二甲基二硫代氨基甲酸离子（DDC^-）和铬、铜、钴、锌、铁、镉6种重金属离子形成配合物的前线轨道能级、配位能△E、考虑基组重叠误差后的配位能△E_BSSE、零点振动能校正后的配位能△E_ZPE及自然电荷分布。研究结果表明:上述二甲基二硫代氨基甲酸配合物的稳定性与能级差△ε及配位能△E_BSSE、△E_ZPE的绝对值密切相关,△ε及△E_BSSE、△E_ZPE的绝对值越大,配合物越稳定。6种二甲基二硫代氨基甲酸重金属配合物的稳定性由大到小的顺序为:[CrDDC]²⁺>[CuDDC]⁺>[CoDDC]⁺>[ZnDDC]⁺>[FeDDC]⁺>[CdDDC]⁺。在形成配合物的过程中,电子从配体DDC^-流向重金属离子,电荷转移越多,配位能的绝对值越大。     

Modeling through-space magnetic shielding over ethynyl,cyano, and nitro groups

In a strong magnetic field, covalently bonded hydrogen nuclei located over a pi bonded functional group experience magnetic shielding (or deshielding) that results from the combined effect of the magnetic anisotropy of the pi bond and various other intramolecular shielding effects. Gauge including atomic orbital (GIAO)-HF in Gaussian 98 was employed to calculate isotropic shielding values and to predict the net through-space proton NMR shielding increment for a simple model system: the proximate proton of methane held in various positions over simple molecules that contain a carbon-carbon triple bond, a carbon-nitrogen triple bond, or a nitro group. These net shielding increments of the proximate proton of methane, plotted against their Cartesian coordinates, led to the development of a single empirical equation for predicting the NMR shielding experienced by a covalently bonded proton over each group. The predictive capability of each equation has been validated by calculating shielding increments of protons over the functional group in known structures. These shielding increments are then used to adjust predicted chemical shifts for through-space shielding effects, and the adjusted values are compared to experimentally observed chemical shifts. The algorithms for predicting the shielding increment for a proton over these functional groups can be used in a spreadsheet or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. Their use can substantially improve the accuracy of the estimated chemical shift of a proton in the vicinity of these functional groups, and thus assist in spectral assignments and in correct structure determination.     

Petri net-based analysis on object assignment in distributed object-oriented systems

Object-oriented programming ^[9], which treats objects as processes in execution, has shown significant effectiveness in distributed systems. This effectiveness is greatly influenced by how objects are assigned to nodes. In this paper, we present a colored generalized stochastic Petri net (CGSPN) model to analyze the behavior of object invocations when an assignment strategy is applied. The effectiveness of an object assignment is also analyzed by our CGSPN model. Moreover, this analysis provides guidelines to develop an efficient object assignment strategy. ^[4–8]     

Thermal characterization of surface-micromachined silicon nitridemembranes for thermal infrared detectors

The aim of this work is to provide a thorough thermal characterization of membrane structures intended for thermal infrared detector arrays. The fabrication has been conducted at temperatures below 400°C to allow future post processing onto existing CMOS readout circuitry. Our choices of membrane material and processing technique were plasma enhanced chemical vapor deposited silicon nitride (SiN) and surface micromachining, respectively. The characterization gave for the thermal conductance (G) and thermal mass between the membrane and its surroundings 1.8·10^-7 W/K and 1.7·10^-9 J/K, respectively, which are close to the best reported values elsewhere. From these results the thermal conductivity and specific heat of SiN were extracted as 4.5±0.7 W/m.K and 1500±230 J/kg.K. The contribution to G from different heat transfer mechanisms are estimated. A model describing the pressure dependence of G was developed and verified experimentally in the pressure interval [5·10^-3, 1000] mbar. Finally, the influence of the thermal properties of the membrane on infrared detector performance is discussed     

Structural, electronic, and magnetic properties of heterofullerene C(58)Si with odd number of atoms and a near planar tetracoordinate Si atom

Density functional calculations and minimization techniques have been employed to characterize the structural and electronic properties of [5,6]-heterofullerene-C₅₈Si-C_2v. Since it has odd number of atoms and a near planar tetracoordinate Si atom on the skeleton of the cage, it has odd number of atoms assembling a cage and is a novel molecule. Vibrational frequencies of the molecule have been calculated at the B3LYP/6-31G* level of theory. The absence of imaginary vibrational frequency confirms that the molecule corresponds to a true minimum on the potential energy hypersurface. Sixteen ¹³C nuclear magnetic resonance (NMR) spectral signals of C₅₈Si are characterized, and its heat of formation was estimated in this work.     

Characteristics of a label-free piezoelectric immunosensor detecting Pseudomonas aeruginosa

A label-free immunosensor system detecting a psychrophylic bacterium, Pseudomonas aeruginosa was developed as follows. Four types of anti-P. aeruginosa antibody were individually chemisorbed onto one-side gold electrodes of piezoelectric quartz crystals according to a thiolated antibody coupling procedure initiated with a thiol-cleavable heterobifunctional cross-linker, sulfosuccinimidyl-6-[3-(2-pyridyldithio)propionamido]hexanoate. A flow-type biosensor system was operated optimally at 0.2 M sodium potassium phosphate, pH 7.2 with a minimal matrix effect and the selected flow rate for it was 0.155 ml/min. A biosensor response was detected by measuring a steady-state resonant frequency shift after the response time around 8 min. The frequency shifts obtained were quite specific according to the antibody types and P. aeruginosa strains. The biosensor responses to varying concentrations of the P. aeruginosa cells ranging from 1.3×10⁷ to 1.3×10⁸ CFU/ml were determined as 17–176 Hz and a linear calibration curve (r=0.942) was obtained by plotting the responses in a double-logarithmic scale. The selectivity of the biosensor between P. aeruginosa and Xanthomonas spp. which both belong to the aerobic pseudomonads was, however, not so good owing to the property of the antibody used. The sensor chip could be reused at least seven times without an appreciable decrease in sensitivity.     

An NMR shielding model for protons above the plane of a carbonyl group

Covalently bonded hydrogen nuclei located over the plane of a carbonyl group in a strong magnetic field experience magnetic shielding (or deshielding) that results from the combined effect of the magnetic anisotropy of the carbon-oxygen double bond and various other intramolecular shielding effects. GIAO-HF in Gaussian 98 was employed to calculate isotropic shielding values and to predict the net proton NMR shielding increment for a simple model system: the proximate proton of methane held in various positions over formaldehyde. The net shielding increments of the proximate proton of methane, plotted against its Cartesian coordinates relative to the center of the carbon-oxygen double bond, led to the development of a single empirical equation for predicting the NMR shielding experienced by a covalently bonded proton over the plane of a carbonyl group. The predictive capability of this equation has been validated by calculating the shielding increments of protons over the plane of a carbonyl group in known structures, using this as a correction to the chemical shift estimated by subtituent effects and comparing the result to experimentally observed chemical shifts. Shielding is predicted by this equation for protons located in the region from over the center of the carbon-oxygen double bond to beyond the carbon atom; deshielding is predicted for protons located above and beyond the oxygen atom. This prediction differs from those made by the long-held "shielding cone" model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the shielding increment for a proton over a carbonyl group can be used in a spreadsheet or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. Its use can improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon-oxygen double bond, and thus assist in spectral assignments and in correct structure determination.     

On application of differential geometry to computational mechanics

Developments in the fields of computational science—the finite element method—and mathematical foundations of continuum mechanics result in many new algorithms which give solutions to very complicated, complex, large scaled engineering problems. Recently, the differential geometry, a modern tool of mathematics, has been used more widely in the domain of the finite element method. Its advantage in defining geometry of elements [13–15] or modeling mechanical features of engineering problems under consideration [4–7] is its global character which includes also insight into a local behavior. This fact comes from the nature of a manifold and its bundle structure, which is the main element of the differential geometry.

Manifolds are generalized spaces, topological spaces. By attaching a fiber structure to each base point of a manifold, it locally resembles the usual real vector spaces; e.g. ³. The properties of a differential manifold M are independent of a chosen coordinate system. It is equivalent to say, that there exists smooth or C^r differentiable atlases which are compatible.

In this paper a short survey of applications of differential geometry to engineering problems in the domain of the finite element method is presented together with a few new ideas.

The properties of geodesic curves have been used by Yuan et al. [13–15], in defining distortion measures and inverse mappings for isoparametric quadrilateral hybrid stress four- and eight-node elements in ². The notion of plane or space curves is one of the elementary ones in the theory of differential geometry, because the concept of a manifold comes from the generalization of a curve or a surface in ³.

Further, the real global nature of differential geometry, has been used by Simo et al. [4,6,7]. A geometrically exact beam finite strain formulation is defined. The mechanical basis of such a nonlinear model can be found in the mathematical foundation of elasticity [18]. An abstract infinite dimensional manifold of mappings, a configuration space, is constructed which permits an exact linearization of algorithms, locally. A similar approach is used by Pacoste [5] for beam elements in instability problems.

Special attention is focused on quadrilateral hybrid stress membrane elements with curved boundaries which belong to a series of isoparametric elements developed by Yuan et al. [14]. The distortion measures are redefined for eight-node isoparametric elements in ² for which geodesic coordinates are used as local coordinates.     

An algorithm for predicting proton nuclear magnetic resonance deshielding over a carbon-carbon double bond

Hydrogen nuclei located over a carbon-carbon double bond in a strong magnetic field experience NMR shielding effects that result from the magnetic anisotropy of the nearby double bond and various other intramolecular shielding effects. We have used GIAO, a subroutine in Gaussian 98, to calculate isotropic shielding values and to predict the proton NMR shielding increment for a simple model system: methane held in various orientations, positions, and distances over ethene. The average proton NMR shielding increments of several orientations of methane have been plotted versus the Cartesian coordinates of the methane protons relative to the center of ethene. A single empirical equation for predicting the NMR shielding experienced by protons over a carbon-carbon double bond has been developed from these data. The predictive capability of this equation has been validated by comparing the shielding increments for several alkenes calculated using our equation to the experimentally observed shielding increments. This equation predicts the NMR shielding effects more accurately than previous models that were based on fewer geometries of methane over ethene. In fact, deshielding is predicted by this equation for protons over the center and within about 3 A of a carbon-carbon double bond. This result is in sharp contrast to predictions made by the long-held McConnell "shielding cone" model found in nearly every textbook on NMR, but is consistent with experimental observations. The algorithm for predicting the (de)shielding increment for a proton over an alkene can be used in a spreadsheet on a PC or incorporated into software that estimates chemical shifts using additive substituent constants or a database of structures. In either application its use can substantially improve the accuracy of the estimated chemical shift of a proton in the vicinity of a carbon-carbon double bond, and thus assist in spectral assignments and in correct structure determination.     

C6H6和SO3相互作用的理论研究（英文）

采用B3LYP和MP2方法在6-31G*、6-31+G*和6-311+G**基组下对C6H6…SO3复合物体系的4种可能结构进行自由优化,得3种。在考虑基组重叠误差校正基础上,得结合能,并用自然键轨道分析方法讨论其相互作用。结果表明,用B3LYP/6-31G*计算3种复合物的结合能分别为-17.75, -18.33, -18.80 kJ/mol,且C6H6和SO3结合时电子从苯环向SO3转移,形成电荷转移复合物,它们之间的作用包含π-p作用方式。     

An algorithm for predicting the NMR shielding of protons over substituted benzene rings

In a strong magnetic field, hydrogen nuclei located over an aromatic ring experience a reduced magnetic field as a result of the induced magnetic field associated with circulating pi electrons. We used GIAO-SCF, an ab initio subroutine in Gaussian 94 to calculate isotropic shielding values and to determine the proton nuclear magnetic resonance (NMR) shielding increment for a simple model system: methane held at various positions over a substituted benzene ring. The NMR shielding increments experienced by the proximal protons of methane have been mapped as a function of their position X, Y, and Z relative to the center of aniline and, separately, nitrobenzene. A mathematical function of the same form has been fit to the three-dimensional shielding increment surface at each of five distances from the face of each aromatic ring. In addition, a single mathematical equation has been developed for predicting the shielding caused by either substituted aromatic ring. The chemical shifts predicted by using the results of this equation in conjunction with additive substituent increments are compared to observed values.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate

Raman spectroscopy has exhibited the C–H stretch (A₁ mode) frequency ν₁ of hydrated methanes at 2915 cm⁻¹ for the 5¹² cage and 2905 cm⁻¹ for the 5¹²6² cage. These values are lower than the frequency of 2916.5 cm⁻¹ in gaseous methane. In this paper, we theoretically examine the Raman spectra observed in methane hydrate by normal mode analysis using the independent molecule model. By a breakdown of the symmetry, the four frequencies in modes A₁, E, T₂ and T₂ observed in gaseous methane are separated into nine frequencies in the hydrate. It is necessary to consider the anharmonic potential energy within methane and hydrogen bonding between methane hydrogen and water oxygen in order to get a result in qualitative agreement with experiment. The frequency in the 5¹²6² cage is shifted downward in comparison to the one in 5¹², and the frequencies in the both cages are also shifted downward compared with the frequencies in gas. Calculations are also reported for the isotopic methane (CD₄, ¹³CH₄) hydrates.     

Theoretical prediction of structural,vibrational and NMR parameters of plastic optical fiber (POF) material precursors. Cis and trans perhydro- and perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolanes

Density functional theory (DFT) prediction of cis and trans perhydro- and perfluoro-2-methylene-4,5-dimethyl-1,3-dioxolanes structure, supported by vibrational analysis and calculation of multinuclear isotropic nuclear magnetic resonance (NMR) shieldings and indirect spin–spin couplings (SSCCs) was performed. The performance of the used methodology was verified on 1,3-dioxolane selected as model compound. The structures of hydrogenated and fluorinated monomers of POF materials were calculated using B3LYP and BLYP density functionals combined with 6-311++G(3df,2pd) basis set. The BLYP/6-311++G(3df,2pd) level of theory was suggested for vibrational analysis. Gauge independent atomic orbitals (GIAO) calculations were applied to distinguish between cis and trans isomers of the title 1,3-dioxolanes. For obtaining both accurate nuclear shieldings and individual spin–spin coupling constants the BHandH/aug-pcJ-2 level of theory was chosen. The protocol used for the calculations nicely showed remarkable differences in vibrational spectra and NMR parameters of cis and trans isomers of the studied 1,3-dioxolane derivatives before and after fluorination.     

(E)-N-(4-氨基正丁基)-3-(3-羟基-4-甲氧基-苯基)丙烯酰胺顺反构象异构化的理论研究

在HF/6-31G(d)水平上寻找(E)-N-(4-氨基正丁基)-3-(3-羟基-4-甲氧基-苯基)丙烯酰胺的顺反构象异构化的过渡态,计算得到了顺反异构化的势垒,揭示其在常温下反式和顺式异构体可迅速转化,但顺式异构体占绝大部分。在B3LYP/6-311 G(2d,p)水平上用GIAO方法计算两种异构体的~1H和~(13)C NMR的化学位移,通过对理论计算值与实验值的统计分析,显示顺式构象的计算值与实验值较为接近,实验结果证实了理论推断的正确性。     

基于差分表的Blow-CAST-Fish算法的密钥恢复攻击

针对Blow-CAST-Fish算法攻击轮数有限和复杂度高等问题,提出一种基于差分表的Blow-CAST-Fish算法的密钥恢复攻击。首先,对S盒的碰撞性进行分析,分别基于两个S盒和单个S盒的碰撞,构造6轮和12轮差分特征;然后,计算轮函数f₃的差分表,并在特定差分特征的基础上扩充3轮,从而确定密文差分与f₃的输入、输出差分的关系;最后,选取符合条件的明文进行加密,根据密文差分计算f₃的输入、输出差分值,并查寻差分表找到对应的输入、输出对,从而获取子密钥。在两个S盒碰撞的情况下,所提攻击实现了9轮Blow-CAST-Fish算法的差分攻击,比对比攻击多1轮,时间复杂度由2^107.9降低到2⁷⁴;而在单个S盒碰撞的情况下,所提攻击实现了15轮Blow-CAST-Fish算法的差分攻击,与对比攻击相比,虽然攻击轮数减少了1轮,但弱密钥比例由{\mathrm{2}}^{-\mathrm{52.4}}提高到{\mathrm{2}}^{-\mathrm{42}},数据复杂度由2⁵⁴降低到2⁴⁷。测试结果表明,在相同差分特征基础上,基于差分表的攻击的攻击效率更高。     

Adaptive control of Markov chains, I: Finite parameter set

Consider a controlled Markov chain whose transition probabilities depend upon an unknown parameter α taking values in finite setA. To each α is associated a prespecified stationary control lawphi(alpha). The adaptive control law selects at each timetthe control action indicated byphi(alpha_{t})where αtis the maximum likelihood estimate of α. It is shown that αtconverges to a parameter α^*such that the "closed-loop" transition probabilities corresponding to α^*andphi(alpha^{ast})are the same as those corresponding to α⁰andphi(alpha)where α⁰is the true parameter. The situation when α⁰does not belong to the model setAis briefly discussed.