Photoinduced cycloadditions of N-methyl-1,8-naphthalenedicarboximides with alkynes

Photoinduced cycloadditions of N-methyl-1,8-naphthalenedicarboximide 1 with phenylacetylenes 2a-2c, cyclopropylacetylene 2d, diphenylacetylenes 2e-2f and 1-phenylpropyne 2g were investigated. In the case of phenylacetylenes 2a, 2b and cyclopropylacetylene 2c, photoreaction with 1 takes place at the naphthalene C(1)C(2) bond to give the cyclobutene products. For 4-methoxyphenylacetylene 1c, the cyclobutene 3c is obtained together with the 4-benzo[a]thebenidinone 4c derived from a primary oxetene product formed by [2+2] addition of the imide carbonyl with the alkyne. Similar to 2c, photocycloaddition of 1 with 2e and 2f gave the cyclobutenes 7e, 7f, 8f and the 4-benzo[a]thebenidinone products 9e, 9f and 10f, respectively, derived from the corresponding oxetenes. Photoreaction of 1 with 2g gave cyclobutene 7g and benzo[a]thebenidinone 9g. Sensitization experiment and internal heavy atom effect study showed that these reactions proceed from the ππ* singlet excited state of 1. Estimation of the free energy change for electron transfer between ¹1* and the alkynes and the calculation of charge and spin density distribution in the anion radical of 1 and the cation radical of the alkynes suggested that the cyclobutene products are formed by direct [2+2] cycloaddition of ¹1* with the alkyne, while the formation of the oxetene products is the result of electron transfer interaction between ¹1* and the alkyne. The regioselectivity in the oxetene formation is accounted for by charge and spin density distribution in the anion radical of 1 and the cation radical of the alkyne.     

Raman and surface enhanced Raman microscopy of microstructured polyethylenimine/DNA multilayers

We analyze microstructured multilayer films of poly(ethyleneimine) (PEI) and DNA by employing Raman and surface enhanced Raman spectroscopy (SERS). The microstructuring of the samples allows a simultaneous measurement of signal and reference in a single analytic process. Silver nanoparticles are implemented in the microstructured multilayers for SERS measurements. The recorded SERS spectra of PEI/DNA are dominated by the Raman bands of the DNA bases which show a larger mean enhancement than bands belonging to DNA backbone vibrations. Our results show that the combination of SERS and microstructured multilayer films provides an adapted way to characterize the polyelectrolytes as well as to measure the enhancement factor and the distance dependence for the SERS active silver nanoparticles. Furthermore, microstructured polyelectrolyte films containing SERS active nanoparticles are used for sensing molecules.     

Directional dependence of the mean excitation energy and spectral moments of the dipole oscillator strength distribution of glycine and its zwitterion

In this contribution, we consider the interaction of glycine, a small, model biomolecule, and its zwitterion with fast ion radiation. The object of the study is to determine the differences in properties among various conformers and orientations of the neutral molecule and the zwitterion and to determine if these differences will have implications in terms of radiation protection and radiation therapy. To this end, quantum mechanical calculations were carried out on three conformers of the neutral molecule and two of the zwitterion to determine both the isotropic and directional components of the moments of the dipole oscillator strength distribution in each case. It is these moments that determine the interaction of swift radiation with a molecule.     

Analysis of wave packet motion in frequency and time domain: oxazine 1

Wave packet motion in the laser dye oxazine 1 in methanol is investigated by spectrally resolved transient absorption spectroscopy. The spectral range of 600-690 nm was accessible by amplified broadband probe pulses covering the overlap region of ground-state bleach and stimulated emission signal. The influence of vibrational wave packets on the optical signal is analyzed in the frequency domain and the time domain. For the analysis in the frequency domain an algorithm is presented that accounts for interference effects of neighbored vibrational modes. By this method amplitude, phase and decay time of vibrational modes are retrieved as a function of probe wavelength and distortions due to neighbored modes are reduced. The analysis of the data in the time domain yields complementary information on the intensity, central wavelength, and spectral width of the optical bleach spectrum due to wave packet motion.     

Conidial pigmentation is important to tolerance against solar-simulated radiation in the entomopathogenic fungus Metarhizium anisopliae

The importance of conidial pigmentation to solar UV radiation tolerance in the entomopathogenic fungus Metarhizium anisopliae var. anisopliae, was estimated by comparing the effects of exposure to simulated solar UV radiation on the wild-type parent strain U.S. Department of Agriculture (USDA)-Agricultural Research Service (ARS) Collection of Entomopathogenic Fungal Cultures (ARSEF) 23, which has dark green conidia, and three groups of color mutants with yellow, purple and white conidia. The comparisons included inactivation levels and the kinetics of germination of conidia exposed or not exposed to simulated solar UV radiation. In addition to significantly inactivating the conidia of different mutants, exposure to radiation delayed for several hours the germination of surviving conidia of the wild type and all mutants. In general, mutants with white conidia were more sensitive to simulated solar UV radiation than mutants with purple conidia, which were more sensitive than mutants with yellow conidia, which in turn were more sensitive than the green wild strain. A significant variation in tolerance to simulated solar radiation was observed among mutants within each color group, particularly among mutants with yellow conidia. Revertants with green conidia, DWR 179 and DWR 176, were obtained from the very sensitive UV mutants DWR 148 (yellow conidia) and DWR 149 (purple conidia), respectively. These revertants had levels of tolerance to simulated solar UV radiation similar to those of the wild-type ARSEF 23. This observation is strong evidence of the importance of green conidial pigmentation for tolerance to simulated solar UV radiation, a factor that could be manipulated to produce M. anisopliae strains with more tolerance to solar UV radiation.     

Theory and experiment agree: single-walled carbon nanotube caps grow catalyst-free with chirality preference on a SiC surface

High-temperature quantum chemical molecular dynamics simulations have been performed on model systems of thin SiC crystal surfaces with two graphene sheets placed on top of either C or Si face. In agreement with experiment, we find that (a) the C-face-attached graphene layer warps readily to form small diameter, stable nanocaps, suitable for further perpendicular growth of nanotubes, (b) the Si-face-attached graphene sheet does not readily wrap and forms more volatile Si-graphene bonds, and (c) C face nanocaps appear to anneal to dome-shape structures with zigzag chirality.     

Preparation of colloidal CdSe and CdS/CdSe nanoparticles from sodium selenosulfate in aqueous polymers solutions

Cadmium selenide nanoparticles formation at the interaction between CdCl2 and Na2SeSO3 in aqueous solutions of sodium polyphosphate and gelatin has been studied. Structural and optical properties of CdSe nanoparticles have been characterized. It has been shown that the temperature and the ratio of reagents concentrations are the basic parameters, controlling the size of CdSe nanoparticles. Photocatalytic activity of CdS nanoparticles in Na2SeSO3 reduction has been found and investigated; structural and optical properties of binary CdS/CdSe nanoparticles have been characterized. This photoreaction, when carried out in the presence of CdCl2, results in the formation of composite CdS/CdSe nanoparticles. It has been shown that slow interaction of adsorbed selenosulfate with surface-trapped CdS conduction band electrons is the limiting stage of the photocatalytic reaction.     

On-line tracking of the coating of nanoscaled silica with titania nanoparticles via zeta-potential measurements

Nanoscaled spherical silica particles were directly coated with the titania nanoparticles by means of a heterogenic coagulation. Silica was prepared by the Stöber method, titania by a hydrolysis–condensation reaction of tetrapropylorthotitanate under acidic conditions. The on-line tracking of the coating process was performed by measuring the change in zeta potential during the gradual addition of a titania sol to the spherical silica particles. Silica particles of various sizes were used to determine the consumption of the titania sol in the dependence upon the particle size. The coated and uncoated particles were characterized by zeta-potential measurements, acoustic attenuation spectroscopy, dynamic light scattering, and scanning electron microscopy.     

Synthesis and structural characterization of the first metal organic thallium antimonide

The first metal organic thallium antimonide, the heterocycle [Me2TlSb(SiMe3)2]3, was synthesized by reaction of [Me2AlSb(SiMe3)2]3 with the Lewis acid-base adduct dmap-TlMe3 (dmap = 4-dimethylaminopyridine). The analogous TlBi heterocycle [Me2TlBi(SiMe3)2]3 couldn't be isolated due to its limited thermal stability in solution.     

Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation

We describe efforts to understand the structure and reactivity of lithiated cyclohexanone N-cyclohexylimine. The lithioimine affords complex solvent-dependent distributions of monomers, dimers, and trimers in a number of ethereal solvents. Careful selection of solvent provides exclusively monosolvated dimers. Rate studies on the C-alkylations reveal chronic mixtures of monomer- and dimer-based pathways. We explore the factors influencing reactants and alkylation transition structures and the marked differences between lithioimines and isostructural lithium dialkylamides with the aid of density functional theory calculations.