The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer*

ABSTRACT

The reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH₂) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10^?13?cm³?molecule^?1?s^?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10^?13?cm³?molecule^?1?s^?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH₂ is 1.71?×?10^?15?cm³?molecule^?1?s^?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH₃.     

Newton trajectories for the tilted Frenkel–Kontorova model

ABSTRACT

Newton trajectories are used for the Frenkel–Kontorova model of a finite chain with free-end boundary conditions. We optimise stationary structures, as well as barrier breakdown points for a critical tilting force were depinning of the chain happens. These special points can be obtained straight forwardly by the tool of Newton trajectories. We explain the theory and add examples for a finite-length chain of a fixed number of 2,?3,?4,?5 and 23 particles.     

Novel thionin-functionalised core shell magnetic nanoparticles for dispersive solid-phase extraction of Hg(II) in food and water samples

To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L^?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g^?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%.     

Some extensions of the operator entropy type inequalities

In this paper, we define the generalised relative operator entropy and investigate some of its properties such as subadditivity and homogeneity. As application of our result, we obtain the information inequality. In continuation, we establish some reverses of the operator entropy inequalities under certain conditions by using the Mond–Pe?ari? method.     

Dynamic analysis on generalized linear elastic body subjected to large scale rigid rotations

The dynamic analysis of a generalized linear elastic body undergoing large rigid rotations is investigated. The generalized linear elastic body is described in kine-matics through translational and rot...     

A novel chaotic image encryption scheme using DNA sequence operations

In this paper, we propose a novel image encryption scheme based on DNA (Deoxyribonucleic acid) sequence operations and chaotic system. Firstly, we perform bitwise exclusive OR operation on the pixels of the plain image using the pseudorandom sequences produced by the spatiotemporal chaos system, i.e., CML (coupled map lattice). Secondly, a DNA matrix is obtained by encoding the confused image using a kind of DNA encoding rule. Then we generate the new initial conditions of the CML according to this DNA matrix and the previous initial conditions, which can make the encryption result closely depend on every pixel of the plain image. Thirdly, the rows and columns of the DNA matrix are permuted. Then, the permuted DNA matrix is confused once again. At last, after decoding the confused DNA matrix using a kind of DNA decoding rule, we obtain the ciphered image. Experimental results and theoretical analysis show that the scheme is able to resist various attacks, so it has extraordinarily high security.     

A novel hyperchaotic system and its circuit implementation

A four-dimensional hyperchaotic system with five parameters is proposed. Its dynamical properties such as dissipativity, equilibrium points, Lyapunov exponent, Lyapunov dimension, bifurcation diagrams and Poincare maps are analyzed theoretically and numerically. Theoretical analyses and simulation tests indicate that the new system's dynamics behavior can be periodic attractor, chaotic attractor and hyperchaotic attractor as the parameter varies. Finally, the circuit of this new hyperchaotic system is designed and realized by Multisim software. The simulation results confirm that the chaotic system is different from the existing chaotic systems and is a novel hyperchaotic system. The system is recommendable for many engineering applications such as information processing, cryptology, secure communications, etc.     

Two-scale image fusion of visible and infrared images using saliency detection

Military, navigation and concealed weapon detection need different imaging modalities such as visible and infrared to monitor a targeted scene. These modalities provide complementary information. For better situation awareness, complementary information of these images has to be integrated into a single image. Image fusion is the process of integrating complementary source information into a composite image. In this paper, we propose a new image fusion method based on saliency detection and two-scale image decomposition. This method is beneficial because the visual saliency extraction process introduced in this paper can highlight the saliency information of source images very well. A new weight map construction process based on visual saliency is proposed. This process is able to integrate the visually significant information of source images into the fused image. In contrast to most of the multi-scale image fusion techniques, proposed technique uses only two-scale image decomposition. So it is fast and efficient. Our method is tested on several image pairs and is evaluated qualitatively by visual inspection and quantitatively using objective fusion metrics. Outcomes of the proposed method are compared with the state-of-art multi-scale fusion techniques. Results reveal that the proposed method performance is comparable or superior to the existing methods.     

Coupling nanoliter high‐performance liquid chromatography to inductively coupled plasma mass spectrometry for arsenic speciation

Nanoliter high‐performance liquid chromatography shows low consumption of solvents and samples, offering one of the best choices for arsenic speciation in precious samples in combination with inuctively coupled plasma mass spectrometry. A systematic investigation on coupling nanoliter high‐performance liquid chromatography to inductively coupled plasma mass spectrometry from instrument design to injected sample volume and mobile phase was performed in this study. Nanoflow mobile phase was delivered by flow splitting using a conventional high‐pressure pump with reuse of mobile phase waste. Dead volume was minimized to 60 nL for the sheathless interface based on the previously developed nanonebulizer. Capillary columns for nanoliter high‐performance liquid chromatography were found to be sensitive to sample loading volume. An apparent difference was also found between the mobile phases for nanoliter and conventional high‐performance liquid chromatography. Baseline separation of arsenite, arsenate, monomethylarsenic, and dimethylarsenic was achieved within 11 min on a 15 cm C₁₈ capillary column and within 12 min on a 25 cm strong anion exchange column. Detection limits of 0.9–1.8 μg/L were obtained with precisions variable in the range of 1.6–4.2%. A good agreement between determined and certified values of a certified reference material of human urine (GBW 09115) validated its accuracy along with good recoveries (87–102%).     

LIMITATIONS ON PRESCRIBING THE HOPF DIFFERENTIAL FOR MINIMAL SURFACES IN H3

ABSTRACT

The Hopf map from minimal surfaces in H ³ to holomorphic quadratic differentials on H ² is considered. Whether or not a given quadratic differential is in the image of this map is determined by the global existence/non-existence of solutions to a certain quasi-linear PDE. It is shown that this map is not surjective.