Wave simulations of Gray‐Scott reaction‐diffusion system

In this work, we study the numerical simulation of the one‐dimensional reaction‐diffusion system known as the Gray‐Scott model. This model is responsible for the spatial pattern formation, which we often meet in nature as the result of some chemical reactions. We have used the trigonometric quartic B‐spline (T4B) functions for space discretization with the Crank‐Nicolson method for time integration to integrate the nonlinear reaction‐diffusion equation into a system of algebraic equations. The solutions of the Gray‐Scott model are presented with different wave simulations. Test problems are chosen from the literature to illustrate the stationary waves, pulse‐splitting waves, and self‐replicating waves.     

One-pot tuning of Au nucleation and growth: from nanoclusters to nanoparticles

We describe a simple and effective method to obtain colloidal surface-functionalized Au nanoparticles. The method is primarily based on irradiation of a gold solution with high-flux X-rays from a synchrotron source in the presence of 11-mercaptoundecanoic acid (MUA). Extensive tests of the products demonstrated high colloidal density as well as excellent stability, shelf life, and biocompatibility. Specific tests with X-ray diffraction, UV-visible spectrometry, visible microscopy, Fourier transform infrared spectroscopy, dark-field visible-light scattering microscopy, and transmission electron microscopy demonstrated that MUA, being an effective surfactant, not only allows tunable size control of the nanoparticles, but also facilitates functionalization. The nanoparticle sizes were 6.45 ± 1.58, 1.83 ± 1.21, 1.52 ± 0.37 and 1.18 ± 0.26 nm with no MUA and with MUA-to-Au ratios of 1:2, 1:1, and 3:1. The MUA additionally enabled functionalization with l-glycine. We thus demonstrated flexibility in controlling the nanoparticle size over a large range with narrow size distribution.     

Nonvolatile rewritable memory effects in graphene oxide functionalized by conjugated polymer containing fluorene and carbazole units

A new polymer, poly[{9,9-di(triphenylamine)fluorene}(9,9-dihexylfluorene)(4-aminophenylcarbazole)] (PFCz) was synthesized and used in a reaction with graphene oxide (GO) containing surface-bonded acyl chloride moieties to give a soluble GO-based polymer material GO-PFCz. A bistable electrical switching effect was observed in an electronic device in which the GO-PFCz film was sandwiched between indium-tin oxide (ITO) and Al electrodes. This device exhibited two accessible conductivity states, that is, a low-conductivity (OFF) state and a high-conductivity (ON) state, and can be switched to the ON state under a negative electrical sweep; it can also be reset to the initial OFF state by a reverse (positive) electrical sweep. The ON state is nonvolatile and can withstand a constant voltage stress of -1 V for 3 h and 10(8) read cycles at -1 V under ambient conditions. The nonvolatile nature of the ON state and the ability to write, read, and erase the electrical states, fulfill the functionality of a rewritable memory. The mechanism associated with the memory effects was elucidated from molecular simulation results and in-situ photoluminescence spectra of the GO-PFCz film under different electrical biases.     

Electrochemical Determination and in silico Studies of Fludarabine on NH2 Functionalized Multiwalled Carbon Nanotube Modified Glassy Carbon Electrode

A sensitive voltammetric technique has been developed for the determination of Fludarabine using amine‐functionalized multi walled carbon nanotubes modified glassy carbon electrode (NH₂‐MWCNTs/GCE). Molecular dynamics simulations, an in silico technique, were employed to examine the properties including chemical differences of Fludarabine‐ functionalized MWCNT complexes. The redox behavior of Fludarabine was examined by cyclic, differential pulse and square wave voltammetry in a wide pH range. Cyclic voltammetric investigations emphasized that Fludarabine is irreversibly oxidized at the NH₂‐MWCNTs/GCE. The electrochemical behavior of Fludarabine was also studied by cyclic voltammetry to evaluate both the kinetic (k_s and E_a) and thermodynamic (ΔH, ΔG and ΔS) parameters on NH₂‐MWCNTs/GCE at several temperatures. The mixed diffusion‐adsorption controlled electrochemical oxidation of Fludarabine revealed by studies at different scan rates. The experimental parameters, such as pulse amplitude, frequency, deposition potential optimized for square‐wave voltammetry. Under optimum conditions in phosphate buffer (pH 2.0), a linear calibration curve was obtained in the range of 2×10^?7 M–4×10^?6 M solution using adsorptive stripping square wave voltammetry. The limit of detection and limit of quantification were calculated 2.9×10^?8 M and 9.68×10^?8 M, respectively. The developed method was applied to the simple and rapid determination of Fludarabine from pharmaceutical formulations.     

Evidence for the interfacial reaction between Ni adatoms and H-Si(001) surface

Hydrogen termination of Si surfaces (H-Si) does not stop the interfacial reaction between Ni adatoms and H-Si(001) surface at room temperature. At low Ni coverage of 0.1% (equivalent to 0.02 ML), X-ray photoelectron spectroscopy (XPS) reveals a binding energy shift of Ni 2p_3/2 to 854.0 eV, which corresponds to the formation a NiSi-like environment. As the coverage of Ni increases, the Ni 2p_3/2 eventually shifts to 852.8 eV, indicative of formation of metallic Ni. XPS intensity vs Ni coverage analysis reveals a growth process akin to pseudo-layer-by-layer growth mode, thereby suggesting the formation of bulk-Si(001)/NiSi-like/Ni-rich-silicide-like/metallic Ni structure as growth proceeds. For Ni coverage not more that 33% (equivalent to 12.68 ML), Ni remains protected by the silicide environment and no oxidation of Ni to form Ni-oxides was observed even after exposing the samples to air for 400 days. For samples with Ni coverage above 41%, oxidation of Ni is observed by presence of NiO and NiSiO₃ peaks at 854.5 and 857.0 eV, respectively. The current studies suggest that there is reaction between Ni adatoms and Si at the growth front on H-Si(001) surfaces upon Ni deposition at room temperature and hydrogen termination does not suppress the interface reaction between Ni and Si.     

1,1‐Organoboration of silylethynyltin compounds studied by multinuclear magnetic resonance spectroscopy: isomerization at the CC bonds and electron‐deficient Si?H?B bridges

1,1‐Organoboration, using triethyl‐, triallyl‐ and triphenyl‐borane (BEt₃, BAll₃, BPh₃), of dimethysilylethynyl(trimethyl)stannane, Me₃Sn? C?C? Si(H)Me₂ ( 1 ), affords alkenes bearing three different organometallic groups at the C?C bond. For BEt₃ and BPh₃, the first products are the alkenes 4 with boryl and stannyl groups in cis‐positions. These rearrange by consecutive 1,1‐deorganoboration and 1,1‐organoboration into the isomers 5 as the final products, where boryl and silyl groups are in cis‐positions linked by an electron‐deficient Si? H? B bridge. 1,1‐Ethylboration of bis(dimethylsilylethynyl)dimethylstannane, Me₂Sn[C?C? Si(H)Me₂]₂ ( 2 ), leads to the stannacyclopentadiene 6 along with non‐cyclic di(alkenyl)tin compounds 7 and 8 . 1,1‐Ethylboration of ethynyl(trimethylstannylethynyl)methylsilane, Me(H)Si(C?C? SnMe₃)C?C? H ( 3 ), leads selectively to a new silacyclopentadiene 13 as the final product. The reactions were monitored and the products were characterized by multinuclear magnetic resonance spectroscopy (¹H, ¹¹B, ¹³C, ²⁹Si and ¹¹⁹Sn NMR). Copyright © 2005 John Wiley & Sons, Ltd.     

Aminoethynyl‐silanes, ‐germanes and ‐stannanes: novel organometallic‐substituted enamines via 1,1‐organoboration

The reactions of diethylaminoethynyl(trimethyl)silane (1), bis(diethylaminoethynyl)methylsilane (2), diethylaminoethynyl(trimethyl)germane (3), dimethylaminoethynyl(triethyl)germane (4), diethylaminoethynyl(trimethyl)stannane (5) and methyl(phenyl)aminoethynyl(trimethyl)stannane (6) with trialkylboranes [BEt₃ (7b), BPr₃ (7c), BⁱPr₃ (7d) and 9‐alkyl‐9‐borabicyclo[3.3.1]nonanes 9‐Me‐9‐BBN (8a) and 9‐Et‐9‐BBN (8b)] were studied. The alkynes 1 and 2 did not react even with boiling BEt₃, whereas the reactions of 3–6 afforded mainly novel enamines [(E)‐1‐amino‐1‐trialkylgermyl‐2‐dialkylboryl‐alkenes (9, 10), (E)‐1‐diethylamino‐1‐trimethylstannyl‐2‐dialkylboryl‐alkenes (11, 12), (E)‐1‐methyl(phenyl)amino‐1‐trimethylstannyl‐2‐dialkylboryl‐alkenes (13, 14)]. This particular stereochemistry is unusual for products from 1,1‐organoboration reactions, indicating a special influence of the amino group. The starting materials and products were characterized by multinuclear magnetic resonance spectroscopy (¹H, ¹¹B, ¹³C, ¹⁵N, ²⁹Si, ¹¹⁹Sn NMR). Copyright © 2003 John Wiley & Sons, Ltd.     

Stable exo-nido-metallacarboranes (M = Os(IV)) that incorporate meta-carborane-based dicarbollide ligands

Reactions of the [K]+ salts of the [nido-7,9-C2B9H12]- anion (2) and its C-phenylated derivative [7-Ph-nido-7,9-C2B9H11]- (4) with [OsCl2(PPh3)3] (3) proceed in benzene at ambient temperature with the formation of 16-electron chlorohydrido-Os(IV) exo-nido complexes, [exo-nido-10,11-{(Ph3P)2OsHCl}-10,11-(mu-H)2-7-R-7,9-C2B9H8] (5: R = H; 6: R = Ph), along with the small amounts of the charge-compensated nido-carboranes [nido-7,9-C2B9H11PPh3] (7) and [7-Ph-nido-7,9-C2B9H10PPh3] (8) as byproducts. However, when carried out under mild heating in ethanol, the reaction of 2 with 3 selectively afforded a 16-electron dihydrido-Os(IV) exo-nido complex [exo-nido-10,11-{(Ph3P)2OsH2}-10,11-(mu-H)2-7,9-C2B9H9] (9). Structures of both complexes 5 and 9 have been confirmed by single-crystal X-ray diffraction studies, which revealed that nido-carboranes in these species function as a bidentate dicarbollide ligands [7-R-nido-7,9-C2B9H10]2- linked to the Os(IV) center via two B-H...Os bonds involving adjacent B-H vertices in the upper CBCBB belt of the carborane cage. Thus, compounds 5 and 9 represent the first structurally characterized exo-nido-metallacarboranes based on meta-dicarbollide-type ligands. Variable-temperature 1H and 31P{1H} NMR experiments indicate that complex 9 is fluxional in solution and shows an unusual exchange between terminal Os-(H)2 and bridging {B-H}2...Os hydrogen atoms. Upon heating in d8-THF at 65 degrees C, complex 9 converts irreversibly to its closo isomer [2,2-(PPh3)2-2,2-H2-closo-2,1,7-OsC2B9H11] (13), which could thus be obtained as a pure crystalline solid. The structure of 13 has been established on the basis of analytical and multinuclear NMR data and a single-crystal X-ray diffraction study.     

Reassessment of the molecular mechanisms for H2 thermal desorption pathways from Si(1-x)Gex(001)-(2x1) surfaces

One of the aims of temperature-programmed desorption experiments is to facilitate identification of molecular pathways for desorption. The authors provide a rigorous assessment of the difficulty of doing this for H(2)/Si((1-x))Ge(x)(100)-(2x1). An extensive series of density functional calculations using both cluster and slab methods is performed. The resulting desorption barriers are used to compute thermal desorption spectra. A mean-field approximation is used to treat the populations of the various adsites present on the surface. The authors find a number of significant results. First, slab and cluster calculations do not appear to predict consistent differences in desorption barriers between intradimer and interdimer channels. Second, they find that a germanium atom affects the desorption barrier significantly only if it is present at the adsite. A germanium atom adjacent to an adsite or in the second layer influences the desorption barrier negligibly. Both cluster and slab calculations consistently predict a decrease of approximately 0.3-0.4 eV per germanium atom at the adsite. Third, current analysis of thermal desorption spectra in the literature, although yielding good fits to experimental data, is not rigorous. The authors' calculated spectra can be fitted rather well by assuming, as in current analysis of experimental data, three independent second-order channels, even though the underlying molecular pathways used to calculate the spectra are considerably different. Fourth, the authors' results highlight the importance of treating the rearrangement of hydrogen and germanium atoms at the surface during the thermal desorption process. This is generally not taken into account in kinetics modeling of desorption spectra.