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.

     

Ultrasonic‐Assistance and Aging Time Effects on the Zeolitation Process of BZSM‐5 Zeolite

The isomorphic substitution of boron into ZSM‐5 zeolite under static hydrothermal condition was investigated. Evaluation of hydrothermal synthesis of BZSM‐5 was performed by treating the synthesis mixture by different aging processes, namely, ultrasonic, static, stirring, and microwave‐assisted aging prior to the conventional hydrothermal treatment. The synthetic processes with different techniques of aging prior to the onset of conventional hydrothermal crystallization were compared with a process without any prior aging. The obtained results showed that the ultrasonic and microwave assisted aging shortened the crystallization time and altered the crystal size and the morphology of the obtained products. The characteristics of the synthesized products were obtained by FT‐IR spectroscopic, XRD and SEM techniques.     

Combination of Dispersive Liquid‐Liquid Microextraction with Flame Atomic Absorption for Determination of Trace Ni and Co in Water Samples and Vitamin B12

A dispersive liquid‐liquid microextraction method based on the dispersion of 1,2‐dichlorobenzene as an extraction solvent into an aqueous phase in the presence of ethanol as a dispersive solvent for the preconcentration of Co²⁺ and Ni²⁺ ions is discussed. 1‐Nitroso 2‐naphtol was used as a chelating agent prior to the extraction and the preconcentrated analyte was determined by flame atomic absorption spectrometry. The effect of various experimental parameters including the extraction and dispersive solvent type and volume, pH, amount of the chelating agent, etc. on the microextraction and complex formation was investigated for finding the optimum conditions. The enhancement factors were about 61.9 and 51.8, the calibration graphs were linear in the range of 10‐150 μgL^?1 and 10‐250 μgL^?1 with detection limits of 2.42 μgL^?1 and 1.59 μgL^?1, and RSD (n = 5) of 3.08% and 2.17% for cobalt and nickel, respectively. The method was successfully applied to the determination of Co and Ni in water and vitamin B₁₂.     

Fabrication and characterization of copper nanoparticles using thermal reduction: The effect of nonionic surfactants on size and yield of nanoparticles

Thermal reduction has been applied to the preparation of copper nanoparticles (Cu-NPs) using three kinds of nonionic surfactants (Triton X-100, Tween-80, and dodecylamine). The Cu-NPs were formed by decomposition of copper(II) oxalate in presence of triphenylphosphine. The effect of the surfactants on the formation of the Cu-NPs was studied via X-ray diffraction, scanning electron microscopy, energy dispersive analysis of X-rays, transmission electron microscopy, thermogravimetric differential thermal analyses, and Fourier transform infra-red spectroscopy. It is shown that the Cu-NPs have an fcc crystal structure. Depending on the surfactant used, Cu-NPs with diameters between 8 and 20 nm can be prepared. The smallest Cu-NPs (8 nm) were formed in the presence of micelles of dodecylamine (yield 49%), while the largest particles (20 nm) were obtained with Triton X-100 (yield 99%). The use of Triton X-100 results in the highest yield and most uniform Cu-NPs.     

Synthesis of Polymer Nanoparticles in the Presence of Diatoms as Sustainable Bio-Templates

Colloid Journal - Preparation of complex nano- and micron-sized non-spherical particulate geometries still remains a challenge. One potential approach is the utilization of natural templates with...     

Label-free PSA electrochemical determination by seed-mediated electrochemically-deposited gold nanoparticles on an FTO electrode

Journal of Solid State Electrochemistry - A facile and sensitive approach is introduced to precisely determine trace amounts of prostate specific antigen (PSA) by gold nanostructures deposited on...     

A New Nanocomposite Based on Pt-rGO Embedded Polymelamine Formaldehyde Nanocomposite for Reduction of Carbon Dioxide

Here, polymelamine formaldehyde was decorated on the surface of reduced graphene oxide whose surface was then electrodeposited with a sub-monolayer of platinum nanoparticles. The nanocomposite thus prepared was characterized using several spectroscopic methods. Using the nanocomposite as a potential electrocatalyst for carbon dioxide reduction, the products were detected by Raman spectroscopy, gas chromatography, ¹³C-NMR spectroscopy, and gas chromatography-mass spectrometry. The analytical results identified methanol as the main product of CO₂ reduction. Moreover, analysis of the liquid products confirmed methanol as the predominant product with a current density of 0.4 mA/cm and a Faradaic efficiency of 93 %.