Accurate and efficient method for predicting thermochemistry of polycyclic aromatic hydrocarbons - bond-centered group additivity

A self-consistent estimation method for the thermochemical properties of polycyclic aromatic hydrocarbons (PAH) is presented. This method is based on enthalpies of formation (DeltaHf(degrees), entropies (S(degrees)298, and heat capacities (C(degrees)p obtained from B3LYP/6-31G(d) calculations of the total energies and frequencies for 139 PAHs, including C(60) and C(70) fullerenes. The enthalpies of formation were calculated using an optimized set of homodesmic reactions given the available experimental DeltaHf(degrees) of PAHs. The theoretical entropies were compared with the existing experimental entropies, and some inconsistencies in the experimental data were identified. The estimation method presented here is a systematic extension of the widely employed atom-centered group additivity method originally proposed by Benson. This new method is based on bond-centered groups that define bonds linking two atom-centered groups and specify the size of the rings to which they belong. In addition, a term to describe the resonance energy is included. The thermochemical properties of PAHs up to C(70) fullerene are estimated with a mean average deviation of 2.8 kcal mol(-1) in DeltaHf(degrees), 0.7 cal K(-1) mol(-1) in S(degrees)298, and about 0.5 cal K(-1) mol(-1) in the C(degrees)p. This bond-centered group additivity method for the thermochemical properties of PAHs significantly expands both the range of systems that can be estimated and the accuracy of the estimations. The results of this work also allow us to assess the quality of available experimental data. For example, there are strong indications that the literature DeltaHf(degrees)of benzo[k]fluoranthene is about 10 kcal mol(-1) too low.     

Spectral and electrochemical investigation of p-sulfonatocalix[4]arene-stabilized vitamin E aggregation

The host–guest interaction of α-tocopherol (vitamin E) with p-sulfonatocalix[4]arene (p-SC4) in solution state is studied using emission and cyclic voltammetric techniques. The lipid soluble α-tocopherol (α-T) forms a solid complex with p-SC4. FTIR and NMR spectral analysis of the solid complex reveals the tight packing of α-T inside the cavity of p-SC4. The structural deformation is confirmed by XRD analysis. SEM images differentiate the highly porous gel like structure of vitamin E aggregate and the solid structure of the host–guest complex prepared. NOESY spectra confirm the tight penetration of α-T within the hydrophobic cavity of p-SC4.     

Synthesis,Characterization, and Reactivity Ratios of Phenyl Methacrylate-N-vinyl-2-pyrrolidone Copolymers

Free radical solution copolymerization of phenyl methacrylate and N-vinyl-2-pyrrolidone was carried out using benzoyl peroxide in 2-butanone solution at 70°C. The composition of the copolymer was determined using ¹H-NMR spectra by comparing the intensities of aromatic protons to that of total protons. The results were used to calculaie the copolymerization reactivity ratios by both the Fineman-Ross (F-R) and Kelen-Tüdös (K-T) methods. The reactivity ratios are r ₁ = 4.49 ± 1.27 and r ₂ = 0.05 ± 0.09 as determined by the K-T method. These values are in good agreement with those determined by the F-R method. The FT-infrared and ¹³C-NMR spectra of the copolymer are discussed.     

经Opuntia dilenii haw植物提取液绿色合成制备的纳米铝酸锌的催化性质(英文)

Various nanosized zinc aluminate(ZnAl2O4) samples were prepared by a conventional and a mi- crowave method both with and without using Opuntia dilenii haw plant extract,and were charac- terized by X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),high resolution scanning electron microscopy(HRSEM),energy dispersion scanning(EDX),temperature dependent conductance measurements, thermoelectric power measurements, ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy,and photoluminescence spectroscopy.The formation of a pure ZnAl2O4 phase was confirmed by XRD and FT-IR.A change in morphology from nanosized plates to nanosized sheets with,respectively,the conventional and microwave heating methods was clearly shown by HRSEM.UV-Vis diffusion reflectance spectroscopy measured the band gaps of ZnAl2O4 nanosized plates and nanosized sheets as 3.5 and 3.9 eV,respectively.The synthesized ZnAl2O4 was single crystalline and has three photoluminescence emissions at 482,528,and 540 nm.ZnAl2O4 nanosized sheets prepared by the microwave method showed higher catalytic activity for the oxida- tion of benzyl alcohol(85% conversion) than ZnAl2O4 nanosized plates prepared by the convention- al method(60% conversion).     

Polarization of electronic transitions in aromatic hydorcarbon molecules and their mono- and di-valent ions

An overview of predictive chemical kinetics is presented, with an application to the simulation and design of homogeneous charge compression ignition (HCCI) engines. The engine simulations are sensitive to the details of hydroperoxyalkyl (QOOH) radical chemistry, which are only partially understood, and there is a significant discrepancy between the simulations and experiment that limits the usefulness of the simulations. One possible explanation is that QOOH decomposes by other channels not considered in existing combustion chemistry models. Rate constants for one of these neglected channels, the intramolecular radical attack on the QOOH peroxide linkage to form hydroxyalkoxyl (HOQO) radicals, are predicted using quantum chemistry (CBS-QB3), to test whether or not this proposed channel can explain the observed discrepancies in the engine simulations. Although this channel has a significant rate, the competing attack on the other O atom in the peroxide to form a cyclic ether+OH is computed to be an order of magnitude faster, so the HOQO channel does not appear to be fast enough to explain the discrepancy. Definitive judgement on the importance of this reaction channel will require a careful reconsideration of all the coupled chemically activated QOOH reaction channels using modern predictive chemical kinetics software.     

Photoinduced Copper‐Catalyzed Regioselective Synthesis of Indoles: Three‐Component Coupling of Arylamines,Terminal Alkynes,and Quinones

The first successful example of a visible‐light‐induced copper‐catalyzed process for C? H annulation of arylamines with terminal alkynes and benzoquinone is described. This three‐component reaction allows use of a variety of commercial terminal alkynes as coupling partners for the one‐step regioselective synthesis of functionalized indoles. Moreover, the current process represents a sustainable and atom‐economical approach for the preparation of complex indoles from easily accessible starting materials under visible‐light irradiation, without the need for expensive metals and harsh reaction conditions.     

Innovation algorithm in ARMA process

Most of the works in Time Series Analysis are based on the Auto Regressive Integrated Moving Average (ARIMA) models presented by Box and Jenkins(1976). If the data exhibits no apparent deviation from stationarity and if it has rapidly decreasing autocorrelation function then a suitable ARMA(p,q) model is fit to the given data. Selection of the orders of p and q is one of the crucial steps in Time Series Analysis. Most of the methods to determine p and q are based on the autocorrelation function and partial autocorrelation function as suggested by Box and Jenkins (1976). Many new techniques have emerged in the literature and it is found that most of them are of very little use in determining the orders of p and q when both of them are non-zero. The Durbin-Levinson algorithm and Innovation algorithm (Brockwell and Davis, 1987) are used as recursive methods for computing best linear predictors in an ARMA(p,q) model. These algorithms are modified to yield an effective method for ARMA model identification so that the values of order p and q can be determined from them. The new method is developed and its validity and usefulness is illustrated by many theoretical examples. This method can also be applied to any real world data.     

Slave fermion formalism for the tetrahedral spin chain

We use the SU(2) slave fermion approach to study a tetrahedral spin 1/2 chain, which is a one-dimensional generalization of the two dimensional Kitaev honeycomb model. Using the mean field theory, coupled with a gauge fixing procedure to implement the single occupancy constraint, we obtain the phase diagram of the model. We then show that it matches the exact results obtained earlier using the Majorana fermion representation. We also compute the spin-spin correlation in the gapless phase and show that it is a spin liquid. Finally, we map the one-dimensional model in terms of the slave fermions to the model of 1D p-wave superconducting model with complex parameters and show that the parameters of our model fall in the topological trivial regime and hence does not have edge Majorana modes.