Synthesis, characterization and catalytic oxyfunctionalization of cyclohexene with tert-butylhydroperoxide over a manganese(II) complex covalently anchored to multi-wall carbon nanotubes (MWNTs)

The chemical modification of multi-wall carbon nanotubes (MWNTs) is an emerging area in material science. In the present study, an hydroxyl functionalized manganese(II) Schiff-base has been covalently anchored on modified MWNTs. The new modified MWNTs have been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron (XPS), thermal analysis, UV–Vis, diffuse reflectance (DRS), FT-IR spectroscopy and elemental analysis. The results suggest that the symmetrical Schiff-base; N,N-bis(4-hydroxysalicylidene)-ethylene-1,2-diamine; H₂[(OH)₂-salen]; is a bivalent anion with tetradentate N₂O₂ donors derived from the phenolic oxygens and azomethine nitrogens. The formulae was found to be [Mn((OH)₂-salen)] for the 1:1 non-electrolytic complex. The multi-wall carbon nanotubes covalently anchored manganese(II) complex ([Mn((OH)₂-salen)]@MWNTs) catalyze the oxidation of cyclohexene with TBHP. Oxidation of cyclohexene catalyzed by this complex gave 2-cyclohexene-1-ol, 2-cyclohexene-1-one and 1-(tert-butylperoxy)-2-cyclohexene as the major products. The manganese(II) complex covalently anchored on MWNTs shows significantly higher catalytic activity than [Mn((OH)₂-salen)]. The activity of the immobilized catalyst remains nearly the same after three cycles, suggesting the true heterogeneous nature of the catalyst. This catalyst is more selective towards 2-cyclohexene-1-one.     

An efficient one-pot synthesis of pyrimido[2,1-b][1,3]thiazine derivatives by reaction of activated acetylenes, thiouracils, and isocyanides

The reactive 1:1 zwitterionic intermediate, formed by the addition of isocyanides to dialkyl acetylenedicarboxylates, was trapped by thiouracils to yield a ketenimine intermediate, which cyclized and then rearranged to afford pyrimido[2,1-b][1,3]thiazines in good yields.     

Substituted six-membered ring carbenes: the effects of amino and cyclopropyl groups through DFT calculations

DFT calculations are employed to compare and contrast six-membered ring carbenes including 1,3-dimethyltetrahydropyrimidin-2-ylidene (1a), 1-methyl-3-cyclopropyltetrahydropyridine-2-ylidene (2a), and 1,3-dicyclopropylcyclohexane-2-ylidene (3a) as well as their unsaturated analogues 1b, 2b, 3b, and 2c. The amino groups exert singlet-triplet energy separation (?E_s−t) of 60.9 kcal/mol to 1a while cyclopropyls induce a ?E_s−t of 14.8 kcal/mol to 3a. The simultaneous presence of amino and cyclopropyl in 2a leads to a ?E_s−t of 43.3 kcal/mol. Unsaturation slightly increases the ?E_s−t of 1a and 3a but not that of 2a. Our thermodynamic, kinetic, and reactivity results are compared with those of synthetic five-membered ring N-heterocyclic carbenes.     

Preparation of ethylene/α-olefins copolymers using (2-RInd)2ZrCl2/MCM-41 (R:Ph,H) catalyst,microstructural study

(2-RInd)₂ZrCl₂ (R:Ph,H) catalyst was supported on MCM-41 and ethylene copolymerization behavior as well as microstructure of copolymers were studied. A steady rate–time profile behavior was observed for homo and copolymerization of ethylene using supported catalysts. It was noticed that increasing the comonomer content can result in lower physical properties. The obtained results indicated that (2-PhInd)₂ZrCl₂/MCM-41 had higher ability of comonomer incorporation than the non-substituted supported catalysts. The CCC, CCE, and ECC (C: comonomer, E: ethylene) triad sequence distribution in backbone of copolymers were negligible, that means no evidence could be detected for comonomer blocks. The polymer characterization revealed that utilizing 1-octene instead of 1-hexene as the comonomer leads to more heterogeneous distribution of chemical composition. The heterogeneity of the chemical composition distribution and the physical properties were influenced by the type of comonomer and catalyst. (2-PhInd)₂ZrCl₂/MCM-41 produced copolymers containing narrower distribution of lamellae (0.3–1 nm) than the copolymer produce using Ind₂ZrCl₂/MCM-41 (0.3–1.6 nm).     

Quantum chemical study of the host-guest inclusion complexes of the local anaesthetic drugs, procaine hydrochloride and butacaine hydrochloride, with α- and β-cyclodextrins

Quantum mechanical (QM) calculations were carried out in order to study the host-guest inclusion complexes of procaine hydrochloride (Pro-H) and butacaine hydrochloride (But-H) with α- and β-cyclodextrins (α- and β-CDs) by PM3 and AM1 methods. The systems were studied by a 1:1 (α-CD/Pro-H, α-CD/But-H, β-CD/Pro-H, and β-CD/But-H) stoichiometric ratio. In this work we calculated the energy of complex formation in vacuo, and this investigation was carried out on the basis of the host-guest approach. The stabilization energy results for the 1:1 host-guest inclusion complexes indicate that the β-CD/Pro-H complex is more stable than the α-CD/Pro-H complex. Furthermore, stabilization energy for the 1:1 inclusion complex of α-CD with But-H is lower than that for the 1:1 inclusion complex of β-CD with But-H. The calculation results show that all complexation processes for the four complexes are exothermic. Enthalpy changes for the α-CD/But-H and β-CD/Pro-H host-guest inclusion complexes are more negative than those for the other ones. ΔG ^o values for both the β-CD/Pro-H and α-CD/But-H complexes are negative. Correspondence: S. M. Hashemianzadeh, Department of Physical Chemistry, College of Chemistry, Iran University of Science and Technology, Tehran, Iran.     

Parametric instability of a magnetic pendulum in the presence of a vibrating conducting plate

Nonlinear Dynamics - A pendulum with an attached permanent magnet swinging in the vicinity of a conductor is a typical experiment for the demonstration of electromagnetic braking and Lenz’...     

Pool boiling heat transfer performance of Newtonian nanofluids

Experimental measurements were carried out on the boiling heat transfer characteristics of γ-Al₂O₃/water and SnO₂/water Newtonian nanofluids. Nanofluids are liquid suspensions containing nanoparticles with sizes smaller than 100 nm. In this research, suspensions with different concentrations of γ-Al₂O₃ and SnO₂ nanoparticles in water were studied under nucleate pool boiling heat transfer conditions. Results show that nanofluids possess noticeably higher boiling heat transfer coefficients than the base fluid. The boiling heat transfer coefficients depend on the type and concentration of nanoparticles.     

A 3D-CMOS compatible silicon photo-sensor with a large vertical photosensitive area

This paper introduces design and simulation of a three-dimensional complementary metal–oxide–semiconductor CMOS compatible photo-sensor based on a silicon substrate. In the structure of photo-sensor, a vertical n+/p junction as a photosensitive area is formed on one side of a U-groove, and perpendicular to a lateral n-i-p structure on top-side of the silicon surface. This configuration enables a direct butt-coupling of a fiber-optic to the photosensitive area, which is a privilege for many remote monitoring applications. The device analysis is carried out by a two-dimensional simulation using SILVACO TCAD simulator. The thickness of the photo-sensitive area is investigated by considering the figures of merit for the two different thicknesses of 30 and 50 µm. The simulated results (according to the parameters defined for the Si substrate) show a very low dark current of 70 and 100 (fA/μm) for the 30 and 50 µm thicknesses, respectively. In addition, a high photo-current to dark current ratio of ~3000 is achieved under an intensity of 2 mW/cm² at 633 nm wavelength, according to the wavelength of red He–Ne laser. The sensor demonstrates a responsivity of 0.33 A/W corresponding to 65% external quantum efficiency and a ?3 dB frequency response of 0.2 GHz under a small signal of 2 mW/cm² at 633 nm wavelength for 10 V reverse bias.