(E)-Cycloalkenes and (E,E)-cycloalkadienes by ring closing diyne- or enyne-yne metathesis/semi-reduction

A concise, practical and stereoselective entry into macrocyclic (E)-alkenes is outlined comprising a sequence of ring closing alkyne metathesis (RCAM), trans-selective hydrosilylation of the resulting cycloalkynes catalyzed by [Cp^∗Ru(MeCN)₃]PF₆, and a protodesilylation of the ensuing vinylsilanes with AgF in aq. THF/MeOH. Moreover, the first examples of intramolecular enyne-yne metathesis reactions catalyzed by the Schrock alkylidyne complex (tBuO)₃WCCMe₃ are reported; the resulting cyclic enynes can be converted along similar lines into the corresponding (E,E)-configured 1,3-dienes in good overall yields. Cycloalkyne 4 and the (E)-configured cyclic olefins 6 and 21 were characterized by X-ray crystallography.     

P-type nitrogen-doped ZnO nanoparticles stable under ambient conditions

Zinc oxide is considered as a very promising material for optoelectronics. However, to date, the difficulty in producing stable p-type ZnO is a bottleneck, which hinders the advent of ZnO-based devices. In that context, nitrogen-doped zinc oxide receives much attention. However, numerous reviews report the controversial character of p-type conductivity in N-doped ZnO, and recent theoretical contributions explain that N-doping alone cannot lead to p-typeness in Zn-rich ZnO. We report here that the ammonolysis at low temperature of ZnO(2) yields pure wurtzite-type N-doped ZnO nanoparticles with an extraordinarily large amount of Zn vacancies (up to 20%). Electrochemical and transient spectroscopy studies demonstrate that these Zn-poor nanoparticles exhibit a p-type conductivity that is stable over more than 2 years under ambient conditions.     

A Luminescent and Sublimable Dy(III) -Based Single-Molecule Magnet

The reaction of [Ln(hfac)(3) ]?2?H(2) O and pyridine-N-oxide (PyNO) leads to isostructural dimers of the formula [Ln(hfac)(3) (PyNO)](2) (Ln=Eu, Gd, Tb, Dy). The Dy derivative shows a remarkable single-molecule magnet behavior with complex hysteresis at 1.4?K. The dynamics of the magnetization features are two relaxation regimes: a thermally activated one at high temperature (τ(0) =(5.62±0.4)×10(-11) s and Δ=(167±1)?K) and a quantum tunneling regime at low temperature with a tunneling frequency of 0.42?Hz. The analysis of the Gd derivative evidences intradimer antiferromagnetic interactions (J=(-0.034±0.001)?cm(-1) ). Moreover, the Eu, Tb, and Dy derivatives are luminescent with quantum yield of 51, 53, and 0.1?%, respectively. The thermal investigation of [Dy(hfac)(3) (PyNO)](2) shows that the dimers can be sublimated intact, suggesting their possible exploit as active materials for surface-confined nanostructures to be investigated by fluorimetry methods.     

Desymmetrization by direct cross-metathesis producing hitherto unreachable P-stereogenic phosphine oxides

Desymmetrization of prochiral di- and trialkenyl phosphine oxides by cross-metathesis with various olefinic partners allowed direct access to novel racemic P-stereogenic products featuring two or three different alkenyl groups. The excellent control of product selectivity and E/Z selectivity allowed the preparation of desymmetrized products in good yields from readily available precursors. These are the first examples of desymmetrization of prochiral substrates by direct cross-metathesis.     

Cyclic organohydroborate complexes of metallocenes: VIII. Triphenylsiloxy derivatives of Group IV organometallic systems, Cp2M(OSiPh3)X (M=Ti, Zr, Hf; X=Cl, {(μ-H)2BC8H14})

Group IV metallocene triphenylsiloxy chlorides, Cp₂MCl(OSiPh₃) (1, M=Ti; 2, M=Zr; 3, M=Hf), and cyclic organohydroborates, Cp₂M(OSiPh₃){(μ-H)₂BC₈H₁₄} (4, M=Zr; 5, M=Hf), were synthesized and characterized. The new hafnocene chloride derivative 3 was obtained by treating Cp₂HfCl₂ with triphenylsilanol and piperidine. The 18-electron cyclic organohydroborates 4 and 5 were afforded by reacting 2 and 3 with K[H₂BC₈H₁₄], the potassium salt of the 9-BBN dimer. Reaction of 1 with K[H₂BC₈H₁₄] causes reduction of the Ti(IV) center and produces the well-known Ti(III), 17-electron, paramagnetic dimer [Cp₂Ti(μ-Cl)₂TiCp₂] (6). Single-crystal X-ray diffraction structures of 3, 4, 5, and 6 were determined.     

Noncovalent functionalization of multi-walled carbon nanotubes by pyrene containing polymers

Multi-walled carbon nanotubes (MWNTs) have been solubilized in water and in various organic solvents by noncovalent side-wall functionalization by pyrene containing polymers.     

Sensitive determination of diuron on zinc oxide nanoparticles modified carbon paste electrode in soil and water samples

An electrochemical sensor based on Zinc oxide nanoparticles (ZnONPs) modified carbon paste electrode was designed for the toxic diuron pesticide detection. The ZnONPs were synthesized through the hydrothermal route and their structural properties were investigated via scanning electron microscopy (SEM) and X-ray diffraction powder (XRD). The designed ZnONPs-modified carbon paste electrode (ZnONPs-CPE) was characterized using cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly enhanced sensitivity on the diuron oxidation peak current, compared to the bare carbon paste electrode. Qualitative and quantitative analysis were performed using cyclic voltammetry (CV) and square wave voltammetry (SWV). Experimental parameters such as pH, amount of ZnONPs and frequency were evaluated and the optimized conditions were obtained with 0.1 M phosphate buffer solution at pH=8, a frequency of 50 Hz and a quantity of 5 mg of ZnONPs. Under these conditions, linear responses ranging from 1.3 to 7.7 μM and 8.6 to 30 μM of diuron were obtained, with correlation coefficients of R²=0.994 and 0.996 respectively. Detection and quantification limits of 0.22 μM and 0.84 μM (S/N=3) were respectively achieved based on the 3σ method. The interference of some ions on the oxidation peak of diuron on ZnONPs-CPE was also evaluated and no interference was observed, therefore demonstrating the selectivity of the sensor. The proposed sensor, designed with ecofriendly materials, is sensitive, selective and was effectively used for diuron determination in soils and water samples with recoveries ranging from 98 % to 101.5 %.