Hydrophobicity-induced drying transition in alkanethiol self-assembled monolayer—water interface

During the course of our investigation of the electron transfer properties of some redox species through highly hydrophobic long chain alkanethiol molecules on gold in aqueous and non-aqueous solvents, we obtained some intriguing results such as unusually low interfacial capacitance, very high values of impedance and film resistance, all of which pointed to the possible existence of a nanometer size interfacial gap between the hydrophobic monolayer and aqueous electrolyte. We explain this phenomenon by a model for the alkanethiol monolayer—aqueous electrolyte interface, in which the extremely hydrophobic alkanethiol film repels water molecules adjacent to it and in the process creates a shield between the monolayer film and water. This effectively increases the overall thickness of the dielectric layer that is manifested as an abnormally low value of interfacial capacitance. This behaviour is very much akin to the ‘drying transition’ proposed by Lum, Chandler and Weeks in their theory of length scale dependent hydrophobicity. For small hydrophobic units consisting of apolar solutes, the water molecules can reorganize around them without sacrificing their hydrogen bonds. Since for an extended hydrophobic unit, the existence of hydrogen bonded water structure close to it is geometrically unfavourable, there is a net depletion of water molecules in the vicinity leading to the possible creation of a hydrophobic interfacial gap.     

On linear and nonlinear Rossby waves in an ocean

This paper deals with recent developments of linear and nonlinear Rossby waves in an ocean. Included are also linear Poincaré, Rossby, and Kelvin waves in an ocean. The dispersion diagrams for Poincaré, Kelvin and Rossby waves are presented. Special attention is given to the nonlinear Rossby waves on a β-plane ocean. Based on the perturbation analysis, it is shown that the nonlinear evolution equation for the wave amplitude satisfies a modified nonlinear Schrödinger equation. The solution of this equation represents solitary waves in a dispersive medium. In other words, the envelope of the amplitude of the waves has a soliton structure and these envelope solitons propagate with the group velocity of the Rossby waves. Finally, a nonlinear analytical model is presented for long Rossby waves in a meridional channel with weak shear. A new nonlinear wave equation for the amplitude of large Rossby waves is derived in a region where fluid flows over the recirculation core. It is shown that the governing amplitude equations for the inner and outer zones are both KdV type, where weak nonlinearity is balanced by weak dispersion. In the inner zone, the nonlinear amplitude equation has a new term proportional to the 3/2 power of the difference between the wave amplitude and the critical amplitude, and this term occurs to account for a nonlinearity due to the flow over the vortex core. The solution of the amplitude equations with the linear shear flow represents the solitary waves. The present study deals with the lowest mode (n=1) analysis. An extension of the higher modes (n?2) of this work will be made in a subsequent paper.     

Asymptotic behavior of solutions of forced nonlinear neutral delay differential equations with impulses

Sufficient conditions for asymptotic behavior of the solutions of nonlinear forced neutral delay differential equations with impulses are found. The results given in [2,4,6,7] are generalized and improved.     

Thiol-mediated radical cyclization: regioselective formation of indole-annulated sulfur heterocycles by tandem cyclization

Indole-2-yl-prop-2-ynyl sulfides, under thiophenol-mediated alkenyl radical cyclization conditions, afforded exclusively 4-thiophenyl-2,3,4,9-tetrahydrothiopyrano[2,3-b]indoles or 3-thiophenylmethyl-2,3,8-trihydrothieno[2,3-b]indoles depending on the substituent at the indole nitrogen.     

Existence of a hydrophobic gap at the alkanethiol SAM-water interface: an interfacial capacitance study

The highly hydrophobic neat alkanethiol-coated SAM on evaporated gold shows an unusually low interfacial capacitance in aqueous media. This result cannot be explained by a simple parallel plate model of the double layer with the alkanethiol monolayer as a sole dielectric separator. Interestingly, a hydrophilic SAM prepared from a neat hydroxy thiol does not show any such capacitance lowering in aqueous media. Our results suggest the existence of a "hydrophobic gap" between the alkanethiol SAM-water interface. Such a model is also very much consistent with the predictions of Lum, Chandler, and Weeks theory of length scale dependent hydrophobicity.     

Highly efficient water promoted allylation and propargylation of arylepoxides via rearrangement-carbonyl addition

A simple and highly efficient one-pot procedure for allylation and propargylation of arylepoxides has been developed. A combination of SnCl₂ and catalytic Pd(0) or Pd(II) promotes the reaction of organic halides and epoxides in DMSO with controlled water addition, leading to the regioselective formation of the corresponding homoallyl and homopropargyl alcohols in good yields.     

Natures of Statefinder Parameters and Om Diagnostic for Cardassian Universe in Ho?ava-Lifshitz Gravity

In this work, we have considered Cardassian Universe in Ho?ava-Lifshitz gravity. Four types of Cardassian Universe models i.e., polytropic/power law, modified polytropic, exponential and modified exponential models have been considered for accelerating models. The natures of statefinder parameters, deceleration parameter, Om diagnostic and EoS parameters have been investigated for all types of Cardassian models in Ho?ava-Lifshitz gravity.     

Wilker-type inequalities for hyperbolic functions

Using classical analytic techniques, the Wilker–Anglesio inequality and parameterized Wilker inequality for hyperbolic functions are proved. The main result is then applied to deriving a hyperbolic analogue of the Sándor–Bencze inequality.     

One Way Traffic: Base-to-Backbone Hole Transfer in Nucleoside Phosphorodithioate

The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S⁻)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G^.+-P(S⁻)=S. The ionization potential of G-P(S⁻)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G^.+ to P(S⁻)=S led to dithiyl radical (P-2S^.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S^. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S⁻)=S concentrations showed a bimolecular conversion of P-2S^. to the σ²-σ*¹-bonded dimer anion radical [-P-2S 2S-P-]⁻ [ΔG (150 K, DFT)=−7.2 kcal mol⁻¹]. However, [-P-2S 2S-P-]⁻ formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol⁻¹]. Neither P-2S^. nor [-P-2S 2S-P-]⁻ oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate.