Growth of Ge nanofilms using electrochemical atomic layer deposition, with a "bait and switch" surface-limited reaction

Ge nanofilms were deposited from aqueous solutions using the electrochemical analog of atomic layer deposition (ALD). Direct electrodeposition of Ge from an aqueous solution is self-limited to a few monolayers, depending on the pH. This report describes an E-ALD process for the growth of Ge films from aqueous solutions. The E-ALD cycle involved inducing a Ge atomic layer to deposit on a Te atomic layer formed on Ge, via underpotential deposition (UPD). The Te atomic layer was then reductively stripped from the deposit, leaving the Ge and completing the cycle. The Te atomic layer was bait for Ge deposition, after which the Te was switched out, reduced to a soluble telluride, leaving the Ge (one "bait and switch" cycle). Deposit thickness was a linear function of the number of cycles. Raman spectra indicated formation of an amorphous Ge film, consistent with the absence of a XRD pattern. Films were more stable and homogeneous when formed on Cu substrates, than on Au, due to a larger hydrogen overpotential, and the corresponding lower tendency to form bubbles.     

Novel carbohydrate-based bifunctional organocatalysts for nucleophilic addition to nitroolefins and imines

Glucosamine has been selected as a cheap and readily available chiral scaffold for the synthesis of a series of novel enantiomerically pure bifunctional organocatalysts bearing a tertiary amino group in proximity to a (thio)urea group. The catalytic behaviour of these compounds, both as neutral and N-protonated species, was investigated using the addition of acetylacetone to β-nitrostyrene as a model reaction. Under optimized experimental conditions, chemical yields up to 93% and enantioselectivities up to 89% were obtained. Semiempirical (AM1) computational studies allowed to find a theoretical rationale for the chemical and stereochemical behaviour of the catalyst of choice. These catalysts were also preliminarily investigated as promoters in the addition of diethyl malonate to the N-Boc imine of benzaldehyde, affording the product in up to 81% ee.     

Fast carbon dioxide fixation by 2,6-pyridinedicarboxamidato-nickel(II)-hydroxide complexes: influence of changes in reactive site environment on reaction rates

The planar complexes [Ni(II)(pyN(2)(R2))(OH)](-), containing a terminal hydroxo group, are readily prepared from N,N'-(2,6-C(6)H(3)R(2))-2,6-pyridinedicarboxamidate(2-) tridentate pincer ligands (R(4)N)(OH), and Ni(OTf)(2). These complexes react cleanly and completely with carbon dioxide in DMF solution in a process of CO(2) fixation with formation of the bicarbonate product complexes [Ni(II)(pyN(2)(R2))(HCO(3))](-) having η(1)-OCO(2)H ligation. Fixation reactions follow second-order kinetics (rate = k(2)'[Ni(II)-OH][CO(2)]) with negative activation entropies (-17 to -28 eu). Reactions were monitored by growth and decay of metal-to-ligand charge-transfer (MLCT) bands at 350-450 nm. The rate order R = Me > macro > Et > Pr(i) > Bu(i) > Ph at 298 K (macro = macrocylic pincer ligand) reflects increasing steric hindrance at the reactive site. The inherent highly reactive nature of these complexes follows from k(2)' ≈ 10(6) M(-1) s(-1) for the R = Me system that is attenuated by only 100-fold in the R = Ph complex. A reaction mechanism is proposed based on computation of the enthalpic reaction profile for the R = Pr(i) system by DFT methods. The R = Et, Pr(i), and Bu(i) systems display biphasic kinetics in which the initial fast process is followed by a slower first order process currently of uncertain origin.     

Confluence of fuchsian second-order differential equations

Ordinary linear homogeneous second-order differential equations with polynomial coefficients including one in front of the second derivative are studied. Fundamental definitions for these equations: of s-rank of the singularity (different from Poincaré rank), of s-multisymbol of the equation, and of s-homotopic transformations are proposed. The generalization of Fuchs' theorem for confluent Fuchsian equations is proved. The tree structure of types of equations is shown, and the generalized confluence theorem is proved.Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 104, No. 2, pp. 233–247, August, 1995.     

Synthesis and Pharmacological Activity of 20-Keto-29-norlupane Derivatives

New 20-oxo- and hydroxyimino-derivatives of betulin that exhibit immunotropic and antiviral activities were synthesized. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 582–584, November–December, 2005.     

Temperature and pressure sensitivities of the highly birefringent photonic crystal fiber with core asymmetry

We investigated a particular design of a highly birefringent PCF with attractive features for pressure sensing applications. A plane-wave method together with the finite element method were used to numerically calculate phase and group modal birefringence, pressure and temperature sensitivities of our fiber. The simulation results together with the experiments demonstrate a considerable difference between a very high phase birefringence (B ∼ 10⁻³) and a very low negative group birefringence (G −10⁻³). Our fiber exhibits a low and positive temperature sensitivity (K_T < 0.1 rad/(K⋅m)), and relatively high and negative mechanical (pressure) sensitivity (K_p ≤ −10 rad/(MPa⋅m)), which supports its possible use as a mechanical sensor that does not require any temperature compensation.     

The source of trimuon events in neutrino scattering

A comprehensive study indicates that equally likely sources for trimuon events neutrino scattering are (a) charged heavy lepton production (with decay to three muons) and (b) simultaneous production of a neutral lepton (with decay to two muons) and a heavy quark (with decay to one muon). The sequential decay of a heavy quark to two muons is less likely. An intriguing model yielding simultaneous M⁰ and b quark production is proposed.     

Stability analysis of impulsive control systems

This paper studies impulsive control systems. Several stability criteria are established by employing the method of Lyapunov functions. These criteria may be used for impulsive feedback control design. As an application, impulsive control of the Lorenz chaotic system is discussed. Numerical experiments are carried out for the control of the Lorenz system. It is shown that small and frequent impulses need to be used in order to stabilize the Lorenz system.