Passive nonlinear reshaping towards parabolic pulses in the steady-state regime in optical fibers

The passive nonlinear reshaping in normally dispersive optical fibers in the steady-state regime is studied numerically. It is found that normal dispersion and self-phase modulation are able to provide pulse reshaping towards a parabolic pulse profile at the distances exceeding the optical wave breaking length. However, as compared to the similariton formation in active fibers the resulted pulse shape in passive fibers is strongly depended on the initial pulse parameters and nonlinear and dispersive fiber properties as well. The influence of initial pulse shape, initial chirp, third-order dispersion and loss on the parabolic pulse formation is studied consistently, and estimation of practical conditions which are needed for parabolic pulses formation in a passive fiber is provided.     

Enantioselective hydrogenations with chiral titanocenes

In this review article chiral titanocenes and their application for the enantioselective hydrogenations of different unsaturated compounds are discussed, with a special emphasis on the kinetics and the practicality of the developed systems. The nature of enantioselectivity and the hydrogenation mechanisms are reviewed as well. Catalyst immobilization and the different immobilization techniques are examined.     

Plasmon-assisted click chemistry at low temperature: an inverse temperature effect on the reaction rate

Plasmon assistance promotes a range of chemical transformations by decreasing their activation energies. In a common case, thermal and plasmon assistance work synergistically: higher temperature results in higher plasmon-enhanced catalysis efficiency. Herein, we report an unexpected tenfold increase in the reaction efficiency of surface plasmon-assisted Huisgen dipolar azide–alkyne cycloaddition (AAC) when the reaction mixture is cooled from room temperature to −35 °C. We attribute the observed increase in the reaction efficiency to complete plasmon-induced annihilation of the reaction barrier, prolongation of plasmon lifetime, and decreased relaxation of plasmon-excited-states under cooling. Furthermore, control quenching experiments supported by theoretical calculations indicate that plasmon-mediated substrate excitation to an electronic triplet state may play the key role in plasmon-assisted chemical transformation. Last but not least, we demonstrated the possible applicability of plasmon assistance to biological systems by AAC coupling of biotin to gold nanoparticles performed at −35 °C.

The decrease of reaction temperature can potentially lead to an increase of plasmon-assisted catalytic efficiency.     

Reactions at the solid-liquid interface: surface-controlled dissolution of solid particles. The dissolution of potassium bicarbonate in dimethylformamide

We present a mathematical model for the surface-controlled dissolution of solid particles. This is applied to the dissolution of a solid having different particle size distribution functions: those of a monodispersed solid containing particles of all one size, a two-size-particle distribution, and a Gaussian distribution of the particle sizes. The dissolution of potassium bicarbonate in dimethylformamide is experimentally studied indirectly at elevated temperatures. We monitor the dissolution via the homogeneous deprotonation of 2-cyanophenol by dissolved KHCO3. The loss of 2-cyanophenol was detected electrochemically at a platinum microdisk electrode, and separately, the formation of the 2-cyanophenolate anion was monitored via UV-visible spectroscopic analysis. The results presented show that the kinetics of the loss of 2-cyanophenol behaves on one hand as a homogeneous chemical process and on the other hand as a dissolution-rate-controlled process. Initially, predissolved KHCO3 in solution deprotonates the 2-cyanophenol and homogeneous reaction dominates the observed kinetics, and at longer times, the observed kinetics is controlled by the rate of KHCO3 dissolution. Modeling of the experimental results for the surface-controlled dissolution of KHCO3 in dimethylformamide (DMF) yielded a mean value for the dissolution rate constant, k, at elevated temperatures; k was found to have a value of (1.1 +/- 0.3) x 10(-8) mol cm(-2) s(-1) at 100 degrees C, and the activation energy for the dissolution was 34.4 +/- 0.4 kJ mol(-1) over the temperature range 60-100 degrees C.     

Dependence of the anticancer activity of 1,3‐oxazole derivatives on the donor/acceptor nature of his substitues

A series of new 1,3‐oxazole derivatives, containing in position 5 both donor and acceptor substituents were synthesized. These substances were considered as potentially active anticancer pharmacophores in the human tumor cell line panel derived from nine cancer types, including lung, colon, melanoma, renal, ovarian, brain, leukemia, breast, and prostate. Primary in vitro one‐dose anticancer screening was shown that compounds with acceptor substituents (such as –C(O)OMe, –CN) in the position 5 inhibit the growth of most cell lines, and compounds with donor substituents (such as –NHR, ?SR) in the position 5 do not practically inhibit the growth of cancer cell lines. It can be assumed that the pharmacological activity of 1,3‐oxazole derivatives depends on donor/acceptor nature of the substituents in position 5. It was proposed to evaluate the donor/acceptor ability of 1,3‐oxazole derivatives using the special parameter φ₀, which takes into account the relative position of the boundary levels (HOMO end LUMO). The quantum‐chemical modeling was performed; the special parameter φ₀ for 1,3‐oxazole derivatives correlates with the experimental results. Quantum‐chemical calculations of the special parameter φ₀ allow modeling the pharmacological activity of 1,3‐oxazole derivatives by introducing donor or acceptor substituents at position 2 or 5. This work may be useful for chemists to develop a target synthesis of potential biologically active compounds.     

Fiber coupling to BaTiO3 glass microspheres in an aqueous environment

Compact microspheres with high-quality (Q) whispering gallery modes are required for many applications involving liquid immersion, such as sensing nanoparticles and studying resonant radiative pressure effects. We show that high-index (1.9 and 2.1) barium titanate glass (BTG) microspheres are perfect candidates for these applications due to their high-Q (～10(4) in the 1100-1600 nm range) resonances evanescently excited in spheres with diameters of 4-15 μm. By reattaching the spheres at different positions along a tapered optical fiber, we show that the coupling constant exponentially increases with thinner fiber diameters. We demonstrate the close to critical coupling regime with intrinsic Q=3×10(4) for water immersed 14 μm BTG spheres.     

Visible-light photocurrent response of TiO2-polyheptazine hybrids: evidence for interfacial charge-transfer absorption

We investigated photoelectrodes based on TiO(2)-polyheptazine hybrid materials. Since both TiO(2) and polyheptazine are extremely chemically stable, these materials are highly promising candidates for fabrication of photoanodes for water photooxidation. The properties of the hybrids were experimentally determined by a careful analysis of optical absorption spectra, luminescence properties and photoelectrochemical measurements, and corroborated by quantum chemical calculations. We provide for the first time clear experimental evidence for the formation of an interfacial charge-transfer complex between polyheptazine (donor) and TiO(2) (acceptor), which is responsible for a significant red shift of absorption and photocurrent response of the hybrid as compared to both of the single components. The direct optical charge transfer from the HOMO of polyheptazine to the conduction band edge of TiO(2) gives rise to an absorption band centered at 2.3 eV (540 nm). The estimated potential of photogenerated holes (+1.7 V vs. NHE, pH 7) allows for photooxidation of water (+0.82 V vs. NHE, pH 7) as evidenced by visible light-driven (λ > 420 nm) evolution of dioxygen on hybrid electrodes modified with IrO(2) nanoparticles as a co-catalyst. The quantum-chemical simulations demonstrate that the TiO(2)-polyheptazine interface is a complex and flexible system energetically favorable for proton-transfer processes required for water oxidation. Apart from water splitting, this type of hybrid materials may also find further applications in a broader research area of solar energy conversion and photo-responsive devices.     

Understanding the mechanism of DNA deactivation in ion therapy of cancer cells: hydrogen peroxide action*

Changes in the medium of biological cells under ion beam irradiation has been considered as a possible cause of cell function disruption in the living body. The interaction of hydrogen peroxide, a long-lived molecular product of water radiolysis, with active sites of DNA macromolecule was studied, and the formation of stable DNA-peroxide complexes was considered. The phosphate groups of the macromolecule backbone were picked out among the atomic groups of DNA double helix as a probable target for interaction with hydrogen peroxide molecules. Complexes consisting of combinations including: the DNA phosphate group, H₂O₂ and H₂O molecules, and Na⁺ counterion, were considered. The counterions have been taken into consideration insofar as under the natural conditions they neutralise DNA sugar-phosphate backbone. The energy of the complexes have been determined by considering the electrostatic and the Van der Waals interactions within the framework of atom-atom potential functions. As a result, the stability of various configurations of molecular complexes was estimated. It was shown that DNA phosphate groups and counterions can form stable complexes with hydrogen peroxide molecules, which are as stable as the complexes with water molecules. It has been demonstrated that the formation of stable complexes of H₂O₂-Na⁺-PO₄ ^- may be detected experimentally by observing specific vibrations in the low-frequency Raman spectra. The interaction of H₂O₂ molecule with phosphate group of the double helix backbone can disrupt DNA biological function and induce the deactivation of the cell genetic apparatus. Thus, the production of hydrogen peroxide molecules in the nucleus of living cells can be considered as an additional mechanism by which high-energy ion beams destroy tumour cells during ion beam therapy.     

Controlling cooperativity of a metastable open system coupled weakly to a noisy environment

The notion of cooperativity comprises a specific characteristic of a multipartite system concerning its ability to demonstrate a sigmoidal-type response of varying sensitivities to input stimuli in transitions between states under controlled conditions.From a statistical physics viewpoint,in this work we attempt to describe the cooperativity by the stability of a metastable open system with respect to irreversibility.To treat the evolution of a system weakly coupled to the environment in a kinetic framework,we consider two fluctuating energy levels of different dimensionalities,initial population of one level,reversible transitions of population between the levels,and irreversible depopulation of another level.An average is made over level fluctuations and environment vibrations so that an inter-level transition rate can be obtained accounting for the influences of external control on level position and dimensionality.It is found that the cooperativity of the two-level system is bounded approximately between 0.736 and unity,with the lower bound indicating worsening system stability.