Wet chemical functionalization of III-V semiconductor surfaces: alkylation of gallium arsenide and gallium nitride by a Grignard reaction sequence

Crystalline gallium arsenide (GaAs) (111)A and gallium nitride (GaN) (0001) surfaces have been functionalized with alkyl groups via a sequential wet chemical chlorine activation, Grignard reaction process. For GaAs(111)A, etching in HCl in diethyl ether effected both oxide removal and surface-bound Cl. X-ray photoelectron (XP) spectra demonstrated selective surface chlorination after exposure to 2 M HCl in diethyl ether for freshly etched GaAs(111)A but not GaAs(111)B surfaces. GaN(0001) surfaces exposed to PCl(5) in chlorobenzene showed reproducible XP spectroscopic evidence for Cl-termination. The Cl-activated GaAs(111)A and GaN(0001) surfaces were both reactive toward alkyl Grignard reagents, with pronounced decreases in detectable Cl signal as measured by XP spectroscopy. Sessile contact angle measurements between water and GaAs(111)A interfaces after various levels of treatment showed that GaAs(111)A surfaces became significantly more hydrophobic following reaction with C(n)H(2n-1)MgCl (n = 1, 2, 4, 8, 14, 18). High-resolution As 3d XP spectra taken at various times during prolonged direct exposure to ambient lab air indicated that the resistance of GaAs(111)A to surface oxidation was greatly enhanced after reaction with Grignard reagents. GaAs(111)A surfaces terminated with C(18)H(37) groups were also used in Schottky heterojunctions with Hg. These heterojunctions exhibited better stability over repeated cycling than heterojunctions based on GaAs(111)A modified with C(18)H(37)S groups. Raman spectra were separately collected that suggested electronic passivation by surficial Ga-C bonds at GaAs(111)A. Specifically, GaAs(111)A surfaces reacted with alkyl Grignard reagents exhibited Raman signatures comparable to those of samples treated with 10% Na(2)S in tert-butanol. For GaN(0001), high-resolution C 1s spectra exhibited the characteristic low binding energy shoulder demonstrative of surface Ga-C bonds following reaction with CH(3)MgCl. In addition, 4-fluorophenyl groups were attached and detected after reaction with C(6)H(4)FMgBr, further confirming the susceptibility of Cl-terminated GaN(0001) to surface alkylation. However, the measured hydrophobicities of alkyl-terminated GaAs(111)A and GaN(0001) were markedly distinct, indicating differences in the resultant surface layers. The results presented here, in conjunction with previous studies on GaP, show that atop Ga atoms at these crystallographically related surfaces can be deliberately functionalized and protected through Ga-C surface bonds that do not involve thiol/sulfide chemistry or gas-phase pretreatments.     

Butylated hydroxytoluene analogs: synthesis and evaluation of their multipotent antioxidant activities

A computer-aided predictions of antioxidant activities were performed with the Prediction Activity Spectra of Substances (PASS) program. Antioxidant activity of compounds 1, 3, 4 and 5 were studied using 1,1-diphenyl-2-picrylhydrazyl (DPPH) and lipid peroxidation assays to verify the predictions obtained by the PASS program. Compounds 3 and 5 showed more inhibition of DPPH stable free radical at 10?? M than the well-known standard antioxidant, butylated hydroxytoluene (BHT). Compound 5 exhibited promising in vitro inhibition of Fe2?-induced lipid peroxidation of the essential egg yolk as a lipid-rich medium (83.99%, IC?? 16.07 ± 3.51 μM/mL) compared to α-tocopherol (α-TOH, 84.6%, IC?? 5.6 ± 1.09 μM/mL). The parameters for drug-likeness of these BHT analogues were also evaluated according to the Lipinski’s “rule-of-five” (RO5). All the BHT analogues were found to violate one of the Lipinski’s parameters (LogP > 5), even though they have been found to be soluble in protic solvents. The predictive polar surface area (PSA) and absorption percent (% ABS) data allow us to conclude that they could have a good capacity for penetrating cell membranes. Therefore, one can propose these new multipotent antioxidants (MPAOs) as potential antioxidants for tackling oxidative stress and lipid peroxidation processes.     

Average scattered field from a random PEC cylinder buried below a slightly rough surface

Scattering from a perfect electric conducting cylinder with random radius buried below a half space dielectric homogenous interface is studied. The cylindrical wave scattered by cylinder is expanded in terms of plane wave spectrum. Small perturbation method is used to study the interaction of each plane wave with the interface. The zeroth order term yields solution for a flat interface, whereas scattering from a rough surface is given by first-order term. Results are obtained for both TM and TE polarizations. Analytical expressions of the average scattered field are obtained and verified using numerical evaluation. Different scattering scenarios are simulated by varying the distribution of the radius. It is observed that average scattering cross section of an ensemble with normal/uniform distribution is almost equal to that of a cylinder with mean radius.     

Probabilistic analysis of three-player symmetric quantum games played using the Einstein-Podolsky-Rosen-Bohm setting

This Letter extends our probabilistic framework for two-player quantum games to the multiplayer case, while giving a unified perspective for both classical and quantum games. Considering joint probabilities in the Einstein-Podolsky-Rosen-Bohm (EPR-Bohm) setting for three observers, we use this setting in order to play general three-player noncooperative symmetric games. We analyze how the peculiar non-factorizable joint probabilities provided by the EPR-Bohm setting can change the outcome of a game, while requiring that the quantum game attains a classical interpretation for factorizable joint probabilities. In this framework, our analysis of the three-player generalized Prisoner's Dilemma (PD) shows that the players can indeed escape from the classical outcome of the game, because of non-factorizable joint probabilities that the EPR setting can provide. This surprising result for three-player PD contrasts strikingly with our earlier result for two-player PD, played in the same framework, in which even non-factorizable joint probabilities do not result in escaping from the classical consequence of the game.     

Effect of some trace elements on the nucleic acid metabolising enzymes level of germinating wheat seeds

Wheat seeds were grown in the presence and absence of some trace elements like Co, Cu, Fe, Mn, Mo and Zn in non-toxic limits. The level of enzyme activities involved in nucleic acid metabolism were measured by spectrophotometric methods. The level of certain RNA metabolising enzymes increased manyfold in trace element-treated seeds, while the level of AMP-deaminase was increased manyfold in Co-treated seeds.     

Direct versus indirect H atom elimination from photoexcited phenol molecules

The active role of the optically dark pi sigma* state, following UV absorption, has been implicated in the photochemistry of a number of biomolecules. This work focuses on the role of the pi sigma* state in the photochemistry of phenol upon excitation at 200 nm. By probing the neutral hydrogen following UV excitation, we show that hydrogen elimination along the dissociative pi sigma* potential energy surface occurs within 103 +/- 30 fs, indicating efficient coupling at the S1/S2 and S0/S2 conical intersections, with no identifiable role of statistical unimolecular decay of vibronically excited (S0) phenol in the timeframe of our measurements.     

Pavonin: a new five-membered lactone from Adenanthera pavonina Linn. (Mimoaceae)

A new five-membered lactone named pavonin with an exo-cyclic double bond has been isolated from the methanol soluble part of Adenanthera pavonina Linn. belonging to the family Mimoaceae. The structure of pavonin has been established with the aid of spectroscopic techniques including decoupling and HMBC experiments.     

The effect of cobalt addition on sintering and microstructural behaviour of silver–tungsten (Ag–W) composite

The present investigation has been revealed that homogeneous silver-tungsten (Ag–W) composite powders doped with cobalt as sinter aid can be produced by the two-stage reduction of co-precipitated tungstate. The sintering of the powders has been studied using dilatometry and the results showed that the critical level for activated sintering is of the order of 0.3 mass percent cobalt with respect to the tungsten content of the compact powder. This critical level is equivalent to approximately six to seven atomic layer coverage of the tungsten particles by cobalt. The levels of cobalt addition above the critical amount leads to the formation of cobalt tungsten (CoW₃) intermetallic compound precipitates, which become trapped within the silver phase in the sintered composite material. Microstructural evaluation of sintered specimens has been carried out using optical and electron microscopy. Transmission electron microscopy results revealed the neck formation between adjacent tungsten particles along with the presence of silver around the tungsten particles. Energy dispersive X-ray (EDX) analysis also confirmed that amounts of cobalt was 0.3 mass percent, in the region containing the silver at the tungsten particle interface which agreed with the level of activated sintering.     

Controlled synthesis of trifluoropropylmethylsiloxane–dimethylsiloxane gradient copolymers by anionic ROP of cyclotrisiloxanes

Kinetics of the anionic ring opening copolymerization of 2,4,6‐tris(3,3,3‐trifluoropropyl)‐2,4,6‐trimethylcyclotrisiloxane (F₃) with hexamethylcyclotrisiloxane (D₃) was studied in THF using BuLi as the initiator. The apparent reactivity ratios were estimated by computer simulation to r = 0.10 ± 0.02, r = 51.8 ± 5.5, which were used to predict the copolymer composition. As a result of so much different reactivities, simultaneous copolymerization leads to copolymers of blocky structure containing a narrow intermediate fragment with gradient distribution of siloxane units. Polymers having more uniform distribution of the trifluoropropyl groups along the chain were obtained by the semibatch process, adding F₃ to the polymerization of less reactive D₃. The resulted copolymers were characterized by SEC chromatography, ²⁹Si NMR, DSC, DMA, and SAXS. Thermal and mechanical properties of the copolymers obtained by simultaneous copolymerization were similar to those of block copolymers. Only the copolymers obtained by semibatch method showed properties typical for gradient copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1204–1216, 2009