Double proton transfer and one-electron oxidation behaviors in double H-bonded glycinamide-formamidine complex and comparison with biological base pair

The behaviors of double proton transfer (DPT) occurring in a representative glycinamide-formamidine complex have been investigated employing the B3LYP/6-311++G** level of theory. Computational results suggest that the participation of a formamidine molecule favors the proceeding of the proton transfer (PT) for glycinamide compared with that without mediator-assisted case. The DPT process proceeds with a concerted mechanism rather than a stepwise one since no zwitterionic complexes have been located during the DPT process. The barrier heights are 14.4 and 3.9 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 3.1 and 2.9 kcal/mol to 11.3 and 1.0 kcal/mol with further inclusion of zero-point vibrational energy (ZPVE) corrections, where the lower reverse barrier height implies that the reverse reaction should proceed easily at any temperature of biological importance. Additionally, the one-electron oxidation process for the double H-bonded glycinamide-formamidine complex has also been investigated. The oxidated product is characterized by a distonic radical cation due to the fact that one-electron oxidation takes place on glycinamide fragment and a proton has been transferred from glycinamide to formamidine fragment spontaneously. As a result, the vertical and adiabatic ionization potentials for the neutral double H-bonded complex have been determined to be about 8.46 and 7.73 eV, respectively, where both of them have been reduced by about 0.79 and 0.87 eV relative to those of isolated glycinamide due to the formation of the intermolecular H-bond with formamidine. Finally, the differences between model system and adenine-thymine base pair have been discussed briefly.

State-to-state dynamics of elementary chemical reactions using Rydberg H-atom translational spectroscopy

In this review, a few examples of state-to-state dynamics studies of both unimolecular and bimolecular reactions using the H-atom Rydberg tagging TOF technique were presented. From the H2O photodissociation at 157 nm, a direction dissociation example is provided, while photodissociation of H2O at 121.6 has provided an excellent dynamical case of complicated, yet direct dissociation process through conical intersections. The studies of the O(D-1) + H-2 --> OH+H reaction has also been reviewed here. A prototype example of state-to-state dynamics of pure insertion chemical reaction is provided. Effect of the reagent rotational excitation and the isotope effect on the dynamics of this reaction have also been investigated. The detailed mechanism for abstraction channel in this reaction has also been closely studied. The experimental investigations of the simplest chemical reaction, the H-3 system, have also been described here. Through extensive collaborations between theory and experiment, the mechanism for forward scattering product at high collision energies for the H+HD reaction was clarified, which is attributed to a slow down mechanism on the top of a quantized barrier transition state. Oscillations in the product quantum state resolved different cross sections have also been observed in the H+D-2 reaction, and were attributed to the interference of adiabatic transition state pathways from detailed theoretical analysis. The results reviewed here clearly show the significant advances we have made in the studies of the state-to-state molecular reaction dynamics.

Calorimetric study and thermal analysis of berberine sulphate

The heat capacities of berberine sulphate [(C20H18NO4)(2)SO4.3H(2)O] were measured from 80 to 390 K by means of an automated adiabatic calorimeter. Smoothed heat capacities,{H-T-H-298.15} and {S-T-S-298.15} were calculated. The loss of crystalline water started at about 339.3+/-0.2 K, and its peak temperature was 365.8+/-0.6 K. The peak temperature of decomposition for berberine sulphate was at about 391.4+/-0.4 K by DSC curve. TG-DTG analysis of this material was carried out in temperature range from 310 to 970 K. TG and DSC curves show that there is no melting in the whole heating process.

Investigation of thermodynamic properties of Co2O3 powder

The isobaric molar heat capacities of powder of Co2O3 were determined by an adiabatic calorimeter in the temperature range from 78 to 350 K. No phase transition takes place in this temperature range. The relationship of C-p,C-m with thermodynamic temperature T was established as C-p,C-m = -5 x 10(-6)T(3) + 0.0026T(2) + 0.0325T + 4.2592 (J K-1 mol(-1)), fitting coefficient R-2 = 0.9996. According to this relationship and the relationships between thermodynamic functions, the thermodynamic functions of powder of C2O3 were derived with 298.15 K as reference temperature. Thermal decomposition of Co2O3 powder was studied through thermogravimetry (TG). The possible mechanism of the thermal decomposition reaction was suggested according to the TG result. (C) 2003 Elsevier Science B.V. All rights reserved.

Heat capacities and thermodynamic functions of p-chlorobenzoic acid

The heat capacities of p-chlorobenzoic acid were measured in the temperature range from 80 to 580 K by means of an automatic adiabatic calorimeter equipped with a small sample cell of internal volume of 7.4cm(3). The construction and procedures of the calorimetric system were described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on alpha-Al2O3. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.28 per cent, while the inaccuracy is within +/-0.40 per cent, compared with the recommended reference data in the whole experimental temperature range. A fusion transition at T = 512.280 K was found from the C-p-T curve of p-chlorobenzoic acid. The enthalpy and entropy of the phase transition, as well as the thermodynamic functions {G((T)) - G((298.15))}, {H-(T) - H-(298.15)} and {S-(T) - S-298.15}, were derived from the heat capacity data. The mass fraction purity of p-chlorobenzoic acid sample used in the present calorimetric study was determined to be 0.99935 by fraction melting approach. (C) 2002 Elsevier Science Ltd. All rights reserved.

Low temperature heat capacity and thermal stability of nanocrystalline nickel

The heat capacity (C-p) of nanocrystalline nickel (nc-Ni, 40 mn crystallite size) has been measured over the temperature range of 78-370 K with a high-resolution automated adiabatic calorimeter. The measured results are compared with the C-p values of the corresponding coarse-grained crystal, and an enhancement of heat capacity of the nanocrystalline nickel was observed to be 2-4% in the temperature range between 100 and 370 K. The thermal stability of the nanocrystalline nickel sample was determined by a differential scanning calorimeter and a thermogravimetric system. The melting point of nc-Ni is the same as that of the corresponding coarse-grained crystalline nickel and the sample is stable at temperature lower than 500 K. (C) 2002 Elsevier Science B.V. All rights reserved.

Brazos River bar; a study in the significance of grain size parameters

A bar on the Brazos River near Calvert, Texas, has been analyzed in order to determine the geologic meaning of certain grain size parameters and to study the behavior of the size fractions with transport. The bar consists of a strongly bimodal mixture of pebble gravel and medium to fine sand; there is a lack of material in the range of 0.5 to 2 mm, because the source does not supply particles of this size. The size distributions of the two modes, which were established in the parent deposits, are nearly invariant over the bar because the present environment of deposition only affects the relative proportions of the two modes, not the grain size properties of the modes themselves. Two proportions are most common; the sediment either contains no gravel or else contains about 60% gravel. Three sediment types with characteristic bedding features occur on the bar in constant stratigraphic order, with the coarsest at the base. Statistical analysis of the data is based on a series of grain size parameters modified from those of Inman (1952) to provide a more detailed coverage of non-normal size curves. Unimodal sediments have nearly normal curves as defined by their skewness and kurtosis. Non-normal kurtosis and skewness values are held to be the identifying characteristics of bimodal sediments even where such modes are not evident in frequency curves. The relative proportions of each mode define a systematic series of changes in numerical properties; mean size, standard deviation and skewness are shown to be linked in a helical trend, which is believed to be applicable to many other sedimentary suites. The equations of the helix may be characteristic of certain environments. Kurtosis values show rhythmic pulsations along the helix and are diagnostic of two-generation sediments.

基于参数化求和不变量与特征重整的形状匹配

从特征提取和特征匹配两方面考虑,提出了一种鲁棒的形状匹配方法。首先,基于求和不变量,设计了基于面积的形状参数化和归一化方法,提出了参数化求和不变量,该不变量基于形状局部描述且采用积分算子计算,具有较好的鲁棒性和仿射不变性。然后,为进一步提高形状匹配的鲁棒性,在特征匹配上,分析了参数化求和不变量的先验信息,设计了基于特征重整的匹配距离函数,并通过动态规划进行实现。仿真实验表明了所提方法的有效性。

An integrated aurora image retrieval system: AuroraEye

With the digital all-sky imager (ASI) emergence in aurora research, millions of images are captured annually. However, only a fraction of which can be actually used. To address the problem incurred by low efficient manual processing, an integrated image analysis and retrieval system is developed. For precisely representing aurora image, macroscopic and microscopic features are combined to describe aurora texture. To reduce the feature dimensionality of the huge dataset, a modified local binary pattern (LBP) called ALBP is proposed to depict the microscopic texture, and scale-invariant Gabor and orientation-invariant Gabor are employed to extract the macroscopic texture. A physical property of aurora is inducted as region features to bridge the gap between the low-level visual features and high-level semantic description. The experiments results demonstrate that the ALBP method achieves high classification rate and low computational complexity. The retrieval simulation results show that the developed retrieval system is efficient for huge dataset. (c) 2010 Elsevier Inc. All rights reserved.

Geometric Distortion Insensitive Image Watermarking in Affine Covariant Regions

Feature-based image watermarking schemes, which aim to survive various geometric distortions, have attracted great attention in recent years. Existing schemes have shown robustness against rotation, scaling, and translation, but few are resistant to cropping, nonisotropic scaling, random bending attacks (RBAs), and affine transformations. Seo and Yoo present a geometrically invariant image watermarking based on affine covariant regions (ACRs) that provide a certain degree of robustness. To further enhance the robustness, we propose a new image watermarking scheme on the basis of Seo's work, which is insensitive to geometric distortions as well as common image processing operations. Our scheme is mainly composed of three components: 1) feature selection procedure based on graph theoretical clustering algorithm is applied to obtain a set of stable and nonoverlapped ACRs; 2) for each chosen ACR, local normalization, and orientation alignment are performed to generate a geometrically invariant region, which can obviously improve the robustness of the proposed watermarking scheme; and 3) in order to prevent the degradation in image quality caused by the normalization and inverse normalization, indirect inverse normalization is adopted to achieve a good compromise between the imperceptibility and robustness. Experiments are carried out on an image set of 100 images collected from Internet, and the preliminary results demonstrate that the developed method improves the performance over some representative image watermarking approaches in terms of robustness.

Local Feature Based Geometric-Resistant Image Information Hiding

Watermarking aims to hide particular information into some carrier but does not change the visual cognition of the carrier itself. Local features are good candidates to address the watermark synchronization error caused by geometric distortions and have attracted great attention for content-based image watermarking. This paper presents a novel feature point-based image watermarking scheme against geometric distortions. Scale invariant feature transform (SIFT) is first adopted to extract feature points and to generate a disk for each feature point that is invariant to translation and scaling. For each disk, orientation alignment is then performed to achieve rotation invariance. Finally, watermark is embedded in middle-frequency discrete Fourier transform (DFT) coefficients of each disk to improve the robustness against common image processing operations. Extensive experimental results and comparisons with some representative image watermarking methods confirm the excellent performance of the proposed method in robustness against various geometric distortions as well as common image processing operations.

Time-resolved synchrotron SAXS observations on sheared syndiotactic poly(propylene) crystallization process

The in situ crystallization kinetics of syndiotactic poly(propylene) (sPP) has been investigated by synchrotron small-angle X-ray scattering (SAXS). The structure evolutions during the isothermal crystallization of sPP with different shear rates have been observed. The results show that shear accelerates the process of crystallization kinetics. Even under low shear rate, the lamellae can be distinctly oriented. In contrast, the lamellar parameters such as the long period, lamellar thickness, and the scattering invariant 0 can change obviously only under high shear rate.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.

Microstructure analysis of nylon 66 by WAXD and SAXS

The analysis of the small angle X-ray scattering (SAXS) data was based upon particle characteristic function, one-dimensional electron-density correlation function and particle distribution function. The microstructure of nylon 66 with different degrees of crystallinity was studied by means of X-ray scattering method. The radius of gyration R-g, the Porod radius R-p, the thickness of crystalline region L-c the thickness of non-crystalline region L-n, the thickness of interphase region d(tr), the long period L, the semiaxises of particles (a, a, b), the distribution of the particle sizes and the scattering invariant were calculated. The results indicate that there was a significant interphase region between the crystalline region and the non-crystalline region. and its content (W-t,W-x) should not be neglected in comparison with that of crystalline region W-c,W-x. The morphology of nylon 66 prepared by isothermal crystallization at a high temperature was mainly a lamellar structure, while the spherical crystals dominated in the quenched sample. The size of the particles in the quenched sample was smaller than that of those in the isothermally crystallized sample. and the distribution of the particle sizes in the isothermally crystallized sample was wider.

Influence of annealing on structure of Nylon 11

Differential scanning calorimeter (DSC), wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and density techniques have been used to investigate the structural parameters of the solid state of Nylon 11 annealed at different temperatures. The equilibrium heat of fusion Delta H-m(0) and equilibrium melting temperature T-m(0) were estimated to be 189.05 J g(-1) and 202.85 degrees C respectively by using the Hoffman-Weeks approach. The degree of crystallinity (W-c,W-x) ranged approximately 24-42% was calculated by WAXD and compared with those by calorimetry (W-c,W-h) and density (W-c,W-d) measurements. The radius of gyration R-g, crystalline thickness L-c, noncrystalline thickness L-a, long period L, semiaxes of the particles (a, b), electron-density difference between the crystalline and noncrystalline regions eta(c) - eta(a), and the invariant Q increased with increasing annealing temperature. The analysis of the SAXS data was based upon the particle characteristic function and the one-dimensional electron-density correlation function. An interphase region existed between the crystalline and noncrystalline region with a clear dimension of about 2 nm for semicrystalline Nylon 11. Instead of the traditional two-phase model, a three-phase model has been proposed to explain these results by means of SAXS.