Influence of substitution on the strength and nature of CH···N hydrogen bond in XCCH···NH3 complexes

The effect of substitution on the strength and nature of CH···N hydrogen bond in XCCH···NH₃ (X = F, Cl, Br, OH, H, Me) and NCH···NH₃ complexes were investigated by quantum chemical calculations. Ab initio calculations were performed using MP2 method with a wide range of basis sets. With tacking into account the BSSE and ZPVE, the values of BEs decrease. Replacement of the nonparticipatory hydrogen atom of HCCH by the electronegative atoms (F, Cl, and Br), lead to the BEs increases. The BE corresponding to the replacement of the nonparticipatory hydrogen atom of HCCH by the OH and CH₃ groups decreases. A far greater enhancement of the interaction energy arises from replacement of HCCH by the more acidic HCN. The natural bond orbital analysis and the Bader's quantum theory of atoms in molecules were also used to elucidate the interaction characteristics of these complexes. The electrostatic nature of H‐bond interactions is predicted from QTAIM analysis. In addition, the relationship between the isotropic and anisotropic chemical shifts of the bridging hydrogen and binding energy of complexes as well as electron density at N···H BCPs were investigated. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Ab Initio Study of Structures,Metallotropic 1,2-Shifts and Prototropic 1,2-Shifts of Cyclopentadienyl(trimethyl)silane, -germane and -stannane

Molecular structures, metallotropic and prototropic shifts of cyclopentadienyl(trimethyl)silane ( 1 ), cyclopentadienyl(trimethyl)germane ( 2 ), and cyclopentadienyl(trimethyl)stannane ( 3 ) were investigated using ab initio molecular orbital and the Becke, Lee, Yang, and Parr density functional (B3LYP) methods. The results show that the most stable structure of compounds 1-3 has the (CH 3 ) 3 M fragment in the allylic position. The energy barrier of metallotropic shifts in compound 1 is higher than in 2 , and in compound 2 higher than in 3 , in good agreement with experimental data. The cyclopentadienyl rings in compounds 1-3 are found to be planar but this result contradicts the reported experimental data.     

Photoactivated Nitrene Chemistry to Prepare Gold Nanoparticle Hybrids with Carbonaceous Materials

Photolysis of organic solvent soluble aryl azide‐modified gold nanoparticles (N₃‐AuNPs) with a core size of 4.6±1.6 nm results in the generation of interfacial reactive nitrene intermediates. The high reactivity of the nitrenes is utilized to tether the AuNP to the native surface of carbon nanotubes, and reduce graphene oxide and micro‐diamond powder, likely via addition to π‐conjugated carbon skeleton or insertion into the functionalities at the surface, to yield the desired hybrid material without the need for pretreatment of the surface. The AuNP‐covalent hybrid materials are robust in that they survive vigorous washing and sonication. In the absence of photolysis no attachment occurs with the same N₃‐AuNP. The nanohybrid AuNP‐nanohybrid materials are characterized using a combination of TEM, powder XRD, XPS and UV/Vis and IR spectroscopies. All of the characterization studies confirm the uniform incorporation of the AuNP on the irradiated substrates.     

A Study on Transreactions of PET/PEN Reactive Blending in a Twin‐Screw Extruder Using an Axial Dispersion Model

Transreactions of PET and PEN melt‐mixed in a twin‐screw extruder are investigated. The extruder is modeled and characterized in the frame of a tubular system of closed type. The kinetic modeling is based on a modified second‐order reversible reaction equation, which allows the dispersion equation to be solved analytically. The analysis shows a good agreement between the model and experiment. The axial dispersion model is employed to predict the extent of transesterification reactions (X) and degree of randomness (RD). ¹H NMR measurements are performed to estimate X and RD. Theoretical and experimental data are in good agreement. The model can thus be exploited to describe the effects of processing parameters, mixing time, mixing temperature, and blend composition on X and RD.

     

以方沸石负载Ni(Ⅱ)催化剂修饰的电极电氧化甲醇(英文)

There is a high overvoltage in the oxidation of methanol in fuel cells,and so modified electrodes are used to decrease it.A modified electrode that used Ni(II) loaded analcime zeolite to catalyze the electrooxidation of methanol in alkaline solution was proposed.Analcime zeolite was synthesized by hydrothermal synthesis,and Ni(II) ions were incorporated into the analcime structure,which was then mixed with carbon paste to prepare modified electrode.The electrocatalytic oxidation of methanol on the surface of the modified electrode in alkaline solution was investigated by cyclic voltammetry and chronoamperometry.The effects of the scan rate of the potential,concentration of methanol,and amount of zeolite were investigated.The rate constant for the catalytic reaction of methanol was 6 × 103 cm3 mol-1 s-1 from measurements using chronoamperometry.The proposed electrode significantly improved the electron transfer rate and decreased the overpotential for methanol oxidation.     

Application of a dispersive micro‐solid‐phase extraction method for pre‐concentration and ultra‐trace determination of cadmium ions in water and biological samples

A method for the trace determination of cadmium ions in water, human urine and human blood serum samples using ultrasonic‐assisted dispersive micro‐solid‐phase extraction (UA‐D‐μSPE) was developed. Silica‐coated magnetic nanoparticles were coated with polythiophene, and the resulting sorbent was characterized using thermogravimetry, differential thermal analysis, scanning electron microscopy, Fourier transform infrared spectrometry and X‐ray diffraction. Following UA‐D‐μSPE, cadmium ions were quantified using graphite furnace atomic absorption spectrometry. A Box–Behnken design was used for optimization of important sorption and desorption parameters in UA‐D‐μSPE: in the sorption step, pH of solution, sorption amount and sonication time for sorption; in the desorption step, concentration of eluent, volume of eluent and sonication time. The optimum conditions for the method were: pH of solution, 7.5; sonication time for sorption, 3 min; sorption amount, 35 mg; type and concentration of eluent, HCl and 1.1 mol l^?1; volume of eluent, 360 μl; sonication time for desorption, 110 s. Under the optimized conditions the limit of detection and relative standard deviation for the detection of cadmium ions by UA‐D‐μSPE were found to be 0.8 ng l^?1 and <6%, respectively.     

Synergetic catalytic effect of rGO,Pd, Fe3O4 and PPy as a magnetically separable and recyclable nanocomposite for coupling reactions in green media

In this paper, rGO/Pd–Fe₃O₄@PPy as an efficient stable nanocomposite was synthesized. To understand the synergetic effects of rGO, Pd, Fe₃O₄ and PolyPyrrole, the performance of rGO/Pd–Fe₃O₄@PPy as a heterogeneous recyclable nanocatalyst in the green synthesis of C‐C and C‐O coupling products, as well as different conditions are studied. Synthesized rGO/Pd–Fe₃O₄@PPy was characterized by FT‐IR, XRD, FE‐SEM, EDS, TGA and AFM analysis. Best results are obtained under sonication in H₂O for C‐C coupling and by ball‐milling for C‐O coupling. The benefits of this method include: green solvents and conditions, absence of external base, low reaction times with high yield and easy work‐up method.     

Synthesis and characterization of a Ni nanoparticle stabilized on Ionic liquid‐functionalized magnetic Silica nanoparticles for tandem oxidative reaction of primary alcohols

In this research, preparation of the magnetic nanoparticle, coating by a silica shell using (3‐aminopropyl) triethoxysilane and synthesis of a novel sulfonic acid‐substituted imidazolium‐based ionic liquid onto the surface of these particles via a multi‐component reaction, is described. The functionalized nanoparticles was loaded by Ni nanoparticles and characterized by means of techniques such as XRD, FTIR, SEM, EDX, TEM, TGA and ICP‐OES. The nanostructures have spherical shapes that ranged in size from 80 to 100 nm. The catalytic activity of these nanoparticles was tested in aerobic oxidation of primary alcohols that showed good performance in the wide range of primary alcohols in water at mild reaction conditions. As a second step of this work, the tandem oxidative synthesis of alkylacrylonitriles and bisindolylmethanes were investigated using primary alcohols under oxidation conditions. This catalyst system can be recovered using external magnet and reused for five consecutive cycles without significantly less of its activity.     

Simultaneous voltammetric sensing of acetaminophen,epinephrine and melatonin using a carbon paste electrode modified with zinc ferrite nanoparticles

A highly selective electrochemical sensor was fabricated based on a modified carbon paste electrode with zinc ferrite nanoparticles (ZnFe₂O₄ NPs). The nanocomposite has attractive properties such as high surface-to-volume ratio and good electrocatalytic activity towards the drugs acetaminophen (AC), epinephrine (EP), and melatonin (MT), best at working voltages of 0.35, 0.09 and 0.55 V (vs. Ag/AgCl), respectively. The linear ranges (and detection limits) are 6.5–135 (0.4) μmol L^?1 for AC, 5–100 (0.7) μmol L^?1 for EP, and 6.5–145 (3) μmol L^?1 for MT.

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Graphical abstract A novel electrochemical sensor based on a modified carbon paste electrode with zinc ferrite nanoparticles (ZnFe₂O₄) for the simultaneous detection of the acetaminophen, epinephrine and melatonin was fabricated