The reaction of carbanions with 2-substituted-2-nitropropanes : Substitution and dimerization occurring by radical chain processes involving electron transfer

The reaction of mono-enolate anions with O₂NCMe₂X where X = Cl, NO₂, p-MePhSO₂ yield coupling (RCOCH(R′)(CMe₂NO₂) and enolate dimerization products (RCOCH(R′)CH(R′)COR) by free radical chain mechanisms involving bimolecular substitution or electron transfer reactions between the enolate anion and the intermediate nitro alkane radical anion (XCMe₂NO₂^?).     

Polymerization of methylmethacrylate in presence of tetramethylthiuramdisulphide

The effect of TMTD on the polymerization of methyl methacrylate was studied. The plot of $\text{R}{}_{\mathrm{P}}\text{vs [TMTD]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ shows a maximum ascribed to participation of TMTD-radicals in cross (P′ + RS′) and mutual-termination (RS′ + RS′). The total polymerization rate is then well expressed by a derived relation. Study of the influence of TMTD on the molecular weight of polymethylmethacrylate allows characterization of the transfer process.     

Optimization of CuW alloy electrodeposition towards high-tungsten content

With the help of the factorial design of experiments, optimization of the deposition of the CuW alloy was successfully done. The important deposition parameters were identified as pH, current density, and—the most important one—copper ion concentration. All of them were examined in their wide ranges. Under optimal conditions, in a citrate bath, with copper ion concentration of 1.0 mM, at current density of −100 mA cm⁻² and at pH ca. 8.3, the alloy layer had the highest tungsten content (circa 30 wt.%), satisfactory adhesion and a smooth and crackless morphology. The structure of the electrodeposited alloy can be described as an amorphous solid solution of Cu in W with built-in Cu nanocrystals.

     

Activity changes of glassy carbon electrodes caused by their exposure to OH• radicals

GC electrodes were exposed to Fenton solutions. The surface changes produced by the OH^? radicals of these solution were inspected using SEM, XPS, Raman spectroscopy and electrochemistry. The OH^? radicals caused erosion and roughening of the surface, selective oxidation and dissolution of sp² carbon, and reduction of the number of nucleation sites for silver deposition.     

Hot embossing of PTFE: Towards superhydrophobic surfaces

Three types of reusable stamps with features in the form of 2D arrays of pits having lateral dimensions in the range of 2-80 μm and heights of 1.5-15 μm were successfully employed for the hot embossing of PTFE at temperatures up to 50 °C above the glass transition temperature of PTFE amorphous phase. Due to the softening of PTFE at the temperatures used in this study, we were able to decrease imprint pressure significantly when comparing with the imprint conditions reported by other authors. Impact of the imprint temperature, pressure and time on the fidelity of pattern transfer as well as on water repellency was tested. The best results of embossing were achieved by applying pressure of 10 kg/cm² for 2 min at 170 °C. In this case, flattening of a natural PTFE roughness and pretty accurate deep replicas of the stamp patterns were observable on the whole imprinted area. Improvement in water repellency was largest for the samples imprinted by Ni stamp patterned with a 2D array of 2 μm square pits spaced by the same dimension and having a depth of 1.5 μm. Cassie-Baxter wetting regime was observed for the deepest imprints with water contact angles up to the superhydrophobic limit.     

Early evolution of transversally thermalized partons

The idea that the parton system created in relativistic heavy-ion collisions (i) emerges in a state with transverse momenta close to thermodynamic equilibrium and (ii) its evolution at early times is dominated by the 2-dimensional (transverse) hydrodynamics of the ideal fluid is investigated. It is argued that this mechanism may help to solve the problem of early equilibration.     

Electroanalytical and spectroscopic procedures for examination of interactions between double stranded DNA and intercalating drugs

A method is presented for the electroanalytical characterization of interactions of dsDNA with a drug, under conditions that both agents are dissolved in the phosphate buffer solution and both are electroactive. Normal pulse, square wave, differential pulse, and cyclic voltammetries were employed in the measurements of the drug and dsDNA oxidation signals at carbon electrodes. UV–Vis spectroscopy was used as a non-electrochemical method to support the electroanalytical data. An anticancer drug, C-1311 (5-diethylaminoethyl-amino-8-hydroxyimidazoacridinone), has been selected for the examination. Normal pulse voltammetry was particularly useful in showing that under the conditions employed neither dsDNA nor the drug were adsorbed at the electrode surface. Necessary conditions for the appearance of the well-defined dsDNA voltammetric signal (guanine peak) are: rigorous chemical and biological purity in the cell and appropriate purity of DNA. An analysis of the obtained results confirmed that there were two modes of interaction between C-1311 and dsDNA: by intercalation and electrostatically. In the presence of excess NaCl the electrostatic interactions deteriorate. The binding constants (K ₁ and K ₂, respectively) and the number (n) of nucleic base pairs (bp) and the number (m) of phosphate groups (pg) interacting with one molecule of drug have been determined. For strong interactions (intercalation) the values of the binding constant, K ₁, and the binding-site size, n, equal 3.7 × 10⁴ M⁻¹ and 2.1, respectively. For the weak electrostatic interactions the K ₂ and m parameters equal 0.28 × 10⁴ M⁻¹ and 4.7. The intercalation process is rather slow and its rate (the conditions of pseudo-first-order reaction) was estimated to equal 7 × 10⁻⁴ s⁻¹. The possibility of independent determination of both interacting agents was very useful in the study. Figure Intercalation of C-1311 into a dsDNA fragment     

Oxime-induced reactivation of sarin-inhibited AChE: a theoretical mechanisms study

Oximes (especially oximate anions) are used as potential reactivators of OP-inhibited AChE due to their unique alpha-effect nucleophilic reactivity. In the present study, by applying the DFT approach at the B3LYP/6-311G(d,p) level and the M?ller-Plesset perturbation theory at the MP2/6-311G(d,p) level, the formoximate-induced reactivation patterns of the sarin-AChE adduct and the corresponding reaction mechanism have been investigated. The potential energy surface along the pathway of the reactivation reaction of sarin-inhibited AChE by oxime reveals that the reaction can occur quickly due to the relatively low energy barriers. A two-step process is a major pathway proposed for the studied reactivation reaction. Through the nucleophilic attack, the oximate first binds to the sarin-AChE adduct to form a relatively stable phosphorus complex. The regeneration of the serine takes place subsequently through an elimination step, which is expected to be competitive with the nucleophilic attacking process. The polarizable continuum model (PCM) has been applied to evaluate the solvate effects on the pathway. It is concluded that the reaction energy barriers are also low enough for the reaction to easily occur in solvent. The results derived from both the gas-phase model and the aqueous solvation model suggest that the studied oximate anion is an efficient antidote reagent for sarin-inhibited AChE.     

Control of single emitter radiation by polarization- and position-dependent activation of dark antenna modes

We study the modification of the decay rates of a single dipolar emitter positioned in the vicinity of metallic linear nanoantennas when higher-order plasmonic excitations are induced. We show that it is possible to effectively tune the enhancement or suppression of both the radiative and nonradiative decay processes by controlling the position and orientation of the dipole with respect to the antenna. Transverse polarization of a single emitter, with respect to the antenna axis, located at the center of the antenna activates dark antenna modes that modify dramatically both the intensity and the spectral features of the decay rates.