Reactivity of substituted copper(II) salicylates with tert‐butylperoxyl radical: Structure–reactivity relationships

Absolute rate constants (k_eff) for the chemical reactions of Cu(II)₂(3,5‐di‐iso‐propylsalicylate)₄(H₂O)₃, Cu(II)₂(3,5‐di‐tert‐butylsalicylate)₄, Cu(II)₂(3,5‐di‐tert‐butylsalicylate)₄(H₂O)₄, Cu(II)₂(3,5‐dimethylsalicylate)₄(H₂O)₃, Cu(II)₂(3‐ethylsalicylate)₄(H₂O), Cu(II)₂(3‐phenylsalicylate)₄, and Cu(II)(3,5‐di‐iso‐propylsalicylate)₂(pyridine)₂ with tert‐butylperoxyl radical were determined using kinetic electron paramagnetic resonance measurements in 10% toluene in the hexane medium at temperatures ranging from ?63°C to 2°C. These antioxidant (AO) chelates were ranked by their reactivity as follows: 2,6‐di‐tert‐butyl‐4‐methylphenol ? Cu(II)₂(3,5‐di‐tert‐butylsalicylate)₄ ? Cu(II)₂(3‐phenylsalicylate)₄ > Cu(II)₂(3,5‐di‐iso‐propylsalicylate)₄(H₂O)₃ ? Cu(II)₂(3,5‐di‐tert‐butylsalicylate)₄(H₂O)₄ ? Cu(II)₂(3,5‐dimethylsalicylate)₄(H₂O)₃ > Cu(II)₂(3‐ethylsalicylate)₄(H₂O) ? Cu(II)(3,5‐di‐iso‐propylsalicylate)₂(pyridine)₂ at 20°C. Differential pulse voltammetry was used to determine redox behavior of these chelates in CH₂Cl₂. Two types of salicylic OH groups were detected in these Cu(II) salicylates, characterized by the presence or absence of AO reactivity. One of them was coordinate covalently bonded to Cu(II) via the oxygen atoms of the salicylic OH groups, displaying oxidation peak potentials in the range from +650 to 970 mV versus Ag/Ag⁺. The second type was intramolecularly hydrogen bonded to carboxylate oxygens, with an oxidation peak potential in the range from +1100 to 1200 mV versus Ag/Ag⁺. It was concluded that non–hydrogen‐bonded salicylic OH groups are responsible for the antiperoxyl radical reactivity of these chelates, while neither Cu(II) nor salicylate ligands displayed reactivity with peroxyl radical. It has been established in this research that axially bonded electron pair donors such as pyridine and water decrease H‐donating reactivity of Cu(II) salicylates by promoting the formation of intramolecular hydrogen bonding between the salicylic OH hydrogen atoms and carboxylate oxygen atoms in the salicylic ligands. Dependences of log k_eff at 20°C and the anodic oxidation potential (E_pa) for the salicylic OH group on the difference between symmetric and asymmetric stretching frequencies of carboxylate groups (in Fourier transform infrared spectra) for the substituted Cu(II) salicylates were determined. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 56–67, 2010     

Synthesis of polyyne rotaxanes

Active-metal templating has been used to synthesize rotaxanes consisting of a phenanthroline-based macrocycle threaded around a C8, C12, or C20 polyyne chain. The crystal structure of the C12 rotaxane has been determined. In the rhenium(I) carbonyl complex of this rotaxane, with Re(CO)(3)Cl coordinated to the phenanthroline macrocycle, the proximity of the polyyne chain quenches the luminescence of the rhenium. These rotaxanes offer a new approach to controlling the environment and interactions of a polyyne chain.     

Laser-induced breakdown spectroscopy with laser irradiation on?mid-infrared hydride stretch transitions: polystyrene

An investigation of laser-induced breakdown spectroscopy (LIBS) of a polymer (polystyrene) with laser irradiation in the mid-infrared (mid-IR) spectral region is presented. A particular goal of this study is to determine whether the LIBS signals are enhanced when the laser wavelength is tuned to that of a vibrational transition of the polymer. Significant enhancements were indeed observed upon irradiation on the C–H stretch fundamental vibrational transitions. In addition, mode-specific effects were observed; the signals were stronger, compared to the relative intensities in the one-photon absorption spectrum, for irradiation on the aromatic (phenyl) C–H stretch transitions, rather than those involving aliphatic (backbone) C–H modes. The applicability of mid-IR resonance enhanced LIBS for detection of residues on surfaces is discussed.     

Properties of Black Silicon Layers Fabricated by Different Techniques for Solar Cell Applications

Black silicon (BS) layers coated with passivation films are widely used as antireflective frontal surfaces for solar cells. The most common BS fabrication techniques are reactive ion etching (RIE), metal-assisted chemical etching, and laser-induced processing. Herein, the structural and optical properties, as well as the minority carrier lifetime, of BS are compared with and without atomic layer deposited HfO₂ passivation films produced by the above formation methods. The antireflection behavior of the samples is discussed based on the light trapping effect and the change in the BS refractive index from air to the bulk of crystalline Si. Finally, test solar cells are manufactured, and their photovoltaic parameters are studied. The comparison results show that RIE is the most preferred in all technical respects. The features of using different BS fabrication techniques from the solar cell manufacturing point of view are analyzed.     

Determination of the internal state distribution of the SD product from the S(1D)+D2 reaction

The S(1D)+D2-->SD+D reaction has been studied through a photolysis-probe experiment in a cell. S(1D) reagent was prepared by 193 nm photolysis of CS2, and the SD(X 2Pi) product was detected by laser fluorescence excitation. The nascent rotational/fine-structure state distribution of the SD(X 2Pi) product was determined. This reaction, previously studied theoretically and in a crossed molecular beam experiment, is known to proceed through formation and decay of a long-lived collision complex involving the deep well in the H2S ground electronic state. The determined SD rotational state distribution in the v=0 vibrational level was found to be approximately statistical, with a small preference for formation of the F1 (Omega=3/2) fine-structure manifold over F2 (Omega=1/2). The branching into the Lambda doublet levels was also investigated, and essentially equal populations of levels of A' and A" symmetry were found. The present results are compared with previous investigations of this reaction and the analogous O(1D)+D2 reaction.     

Molecular dynamics simulations of inverse sodium dodecyl sulfate (SDS) micelles in a mixed toluene/pentanol solvent in the absence and presence of poly(diallyldimethylammonium chloride) (PDADMAC)

Well-aligned ZnO nanorods (NRs) were grown on indium-tin-oxide (ITO) slide by the hydrothermal method and used as templates for preparing ZnO/Au composite nanoarrays. The optical and morphological properties of ZnO/Au composites under various HAuCl(4) concentrations were explored via UV-vis absorption spectroscopy, photoluminescence (PL) and scanning electron microscopy (SEM). The density and size of gold nanoparticles (Au NPs) on ZnO NRs can be controlled by adjusting the concentration of HAuCl(4). The optimal ZnO/Au composites display complete photocatalytic degradation of methyl blue (MB) within 60 min, which is superior to that with pure ZnO NRs prepared by the same method. The reason of better photocatalytic performance is that Au NPs act as electron traps and it prevents the rapid recombination of electrons and holes, resulting in the improvement of photocatalytic efficiency. The photocatalytic performance of ZnO/Au composites is mainly controlled by the density of Au NPs formed on ZnO NRs. The application in rapid photodegradation of MB shows the potential of ZnO/Au composite as a convenient catalyst for the environmental purification of organic pollutants.     

Direct Visualization of Amlodipine Intervention into Living Cells by Means of Fluorescence Microscopy

Amlodipine, a unique long-lasting calcium channel antagonist and antihypertensive drug, has weak fluorescence in aqueous solutions. In the current paper, we show that direct visualization of amlodipine in live cells is possible due to the enhanced emission in cellular environment. We examined the impact of pH, polarity and viscosity of the environment as well as protein binding on the spectral properties of amlodipine in vitro, and used quantum chemical calculations for assessing the mechanism of fluorescence quenching in aqueous solutions. The confocal fluorescence microscopy shows that the drug readily penetrates the plasma membrane and accumulates in the intracellular vesicles. Visible emission and photostability of amlodipine allow confocal time-lapse imaging and the drug uptake monitoring.     

Introduction to the theory of functional differential equations and their applications. Group approach

In this work, we give an introduction to the theory of nonlinear functional differential equations of pointwise type on a finite interval, semi-axis, or axis. This approach is based on the formalism using group peculiarities of such differential equations. For the main boundary-value problem and the Euler-Lagrange boundary-value problem, we consider the existence and uniqueness of the solution, the continuous dependence of the solution on boundary-value and initial-value conditions, and the “roughness” of functional differential equations in the considered boundary-value problems. For functional differential equations of pointwise type we also investigate the pointwise completeness of the space of solutions for given boundary-value conditions, give an estimate of the rank for the space of solutions, describe types of degeneration for the space of solutions, and establish conditions for the “smoothness” of the solution. We propose the method of regular extension of the class of ordinary differential equations in the class of functional differential equations of pointwise type. __________ Translated from Sovremennaya Matematika. Fundamental’nye Napravleniya (Contemporary Mathematics. Fundamental Directions), Vol. 8, Functional Differential Equations, 2004.