Theoretical investigation of the atmospheric chemistry of methyl difluoroacetate: reaction with Cl atoms and fate of alkoxy radical at 298 K

A theoretical study on the mechanism of the reactions of methyl difluoroacetate (MDFA) CF₂HC(O)OCH₃ with Cl atoms is presented. Two conformers relatively close in energy have been identified for MDFA. Geometry optimization and frequency calculations have been performed at the MPWB1K/6-31+G(d,p) level of theory, and energetic information is further refined by calculating the energy of the species using G2(MP2) theory. Transition states (TSs) are searched on the potential energy surface involved during the reaction channels, and each of the TSs is characterized by the presence of only one imaginary frequency. The existence of TSs on the corresponding potential energy surface is ascertained by performing intrinsic reaction coordinate calculation. Our calculations reveal that hydrogen abstraction from the –CH₃ group is thermodynamically and kinetically more facile than that from the –CF₂H group. Theoretically calculated rate constants at 298 K using the canonical transition state theory are found to be in good agreement with the experimentally measured ones. The atmospheric lifetime of CF₂HC(O)OCH₃ was estimated to be 16 years. The atmospheric fate and the main degradation process of alkoxy radical CF₂HC(O)OCH₂O are also discussed for the first time. Our calculation indicates that the fluorine atoms substitution has deactivating effect for the α-ester rearrangement.     

Weak Galerkin finite element methods for electric interface model with nonhomogeneous jump conditions

In this paper, the weak Galerkin finite element method (WG-FEM) is applied to a pulsed electric model arising in biological tissue when a biological cell is exposed to an electric field. A fitted WG-FEM is proposed to approximate the voltage of the pulsed electric model across the physical media involving an electric interface (surface membrane), and heterogeneous permittivity and a heterogeneous conductivity. This method uses totally discontinuous functions in approximation space and allows the usage of finite element partitions consisting of general polygonal meshes. Optimal pointwise-in-time error estimates in L²-norm and H¹-norm are shown to hold for the semidiscrete scheme even if the regularity of the solution is low on the whole domain. Furthermore, a fully discrete approximation based on backward Euler scheme is analyzed and related optimal error estimates are derived.     

Eisenstein series and Ramanujan-type series for 1/π

Using certain representations for Eisenstein series, we uniformly derive several Ramanujan-type series for 1/π.     

Generalized Frobenius partitions with 6 colors

We present the generating function for \(c\phi _6(n)\), the number of generalized Frobenius partitions of \(n\) with \(6\) colors, in terms of Ramanujan’s theta functions and exhibit \(2\), and \(3\)-dissections of it that yield the congruences \(c\phi _6(2n+1)\equiv 0~(\text {mod}~4)\), \(c\phi _6(3n+1)\equiv 0~(\text {mod}~3^2)\) and \(c\phi _6(3n+2)\equiv 0~(\text {mod}~3^2)\).     

A New On-fluorescent Probe for Manganese (II) Ion

A new fluorescent probe for Mn²⁺ ion, (6E)-N-((E)-1,2-diphenyl-2-(pyridin-2-ylimino)ethylidene)pyridin-2-amine (L), has been synthesized from benzil and 2-amino pyridine and characterized. In 1:1 (v/v) CH₃CN:H₂O (pH 4.0, universal buffer) L exhibits fluorescent intensity with emission peak at λ_max 360 nm on excitation with photons of 310 nm. Fluorescent intensity of L increases distinguishingly on interaction with Mn²⁺ ion compared to metal ions—Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺ and Ag⁺ individually or all together. The enhancement in fluorescent intensity is due to snapping of photoinduced electron transfer (PET) prevailed in free L. Fluorescence and UV/visible spectral data analysis shows that binding stoichiometry between Mn²⁺ and L is 1:1 with log β?≈?3.0. Both L and its Mn²⁺ complex were optimised using density functional theory (DFT) and vibrational frequency calculations confirm that both are at local minima on the potential energy surfaces.     

Microwave Assisted Catalytic Protection and Deprotection of Alcohols with 3,4-Dihydro-2H-Pyran

Protection of alcohols as their 2-tetrahydropyranyl ethers and their subsequent hydrolysis can be easily achieved through a microwave irradiated reaction catalysed by iodine.     

Synthesis,Bifunctionalization, and Remarkable Adsorption Performance of Benzene‐Bridged Periodic Mesoporous Organosilicas Functionalized with High Loadings of Carboxylic Acids

Highly ordered benzene‐bridged periodic mesoporous organosilicas (PMOs) that were functionalized with exceptionally high loadings of carboxylic acid groups (COOH), up to 80 mol % based on silica, have been synthesized and their use as adsorbents for the adsorption of methylene blue (MB), a basic dye pollutant, and for the loading and release of doxorubicin (DOX), an anticancer drug, is demonstrated. These COOH‐functionalized benzene? silicas were synthesized by the co‐condensation of 1,4‐bis(triethoxysilyl) benzene (BTEB) and carboxyethylsilanetriol sodium salt (CES), an organosilane that contained a carboxylic acid group, in the presence of non‐ionic oligomeric surfactant Brij 76 in acidic medium. The materials thus obtained were characterized by a variety of techniques, including powder X‐ray diffraction (XRD), nitrogen‐adsorption/desorption isotherms, TEM, and ¹³C and ²⁹Si solid‐state NMR spectroscopy. Owing to the exceptionally high loadings of COOH groups, their high surface areas, and possible π? π‐stacking interactions, these adsorbents have very high adsorption capacities and extremely rapid adsorption rates for MB removal and for the controlled loading/release of DOX, thus manifesting their great potential for environmental and biomedical applications.     

Catalytic Activities of Au6, , and Clusters for CO oxidation: A density functional study

We have studied the CO oxidation over neutral, anionic, and cationic gold hexamer clusters using density functional theory which elucidates the effect of cluster charge state on the catalytic activity. Herein, we have considered the conventional bimolecular Langmuir–Hinshelwood mechanism with coadsorbed CO and O₂ at the neighboring sites in all the clusters. Among the three clusters, entails lower barriers during the various steps of the oxidation mechanism. The stability of all the species including the transition states with respect to the interacting species in indicates no thermal activation. Our study suggests better catalytic activity of as compared to the neutral and cationic counterparts. © 2014 Wiley Periodicals, Inc.