Effect of electronic polarization on charge-transport parameters in molecular organic semiconductors

Theoretical investigations of charge transport in organic materials are generally based on the "energy splitting in dimer" method and routinely assume that the transport parameters (site energies and transfer integrals) determined from monomer and dimer calculations can be reliably used to describe extended systems. Here, we demonstrate that this transferability can fail even in molecular crystals with weak van der Waals intermolecular interactions, due to the substantial (but often ignored) impact of polarization effects, particularly on the site energies. We show that the neglect of electronic polarization leads to qualitatively incorrect values and trends for the transfer integrals computed with the energy splitting method, even in simple prototypes such as ethylene or pentacene dimers. The polarization effect in these systems is largely electrostatic in nature and can change dramatically upon transition from a dimer to an extended system. For example, the difference in site energy for a prototypical "face-to-edge" one-dimensional stack of pentacene molecules is calculated to be 30% greater than that in the "face-to-edge" dimer, whereas the site energy difference in the pentacene crystal is vanishingly small. Importantly, when computed directly in the framework of localized monomer orbitals, the transfer integral values for dimer and extended systems are very similar.     

Mode-dependent enhancement of photodissociation and photoionization in a seven atom molecule

We report the first experimental demonstration of vibrational mode-dependent enhancement in photodissociation and photoionization of a seven atom molecule, methylamine (CH(3)NH(2)). The fundamental C-H stretches and the overtones or combinations of CH(3) bends were prepared via stimulated Raman excitation (SRE) prior to their 243.135 nm one-photon dissociation or two-photon ionization. The photodissociation or photoionization of the vibrationally excited molecules was achieved via 10 ns delayed or temporally overlapping SRE and UV pulses, respectively. It is shown that bending modes are more effective than stretches in promoting photodissociation and photoionization, since their UV excitation is favored by larger Franck Condon factors. This behavior provides clear evidence for vibrational mode-dependence in a relatively large molecule with a torsional degree of freedom, indicating that these modes survive intramolecular vibrational redistribution on a time scale considerably longer than hitherto inferred from previous studies.     

Carbon-13 NMR of Some New Substituted 2-Amino Benzotheazoles

The carbon -13 chemical shift of nine new substituted 2-amino benzothiazole is presented. The calculated chemical shift, using substituent parameters, agrees with the observed one.     

Capturing sodium dodecyl sulfate-treated protein antigens by antibody affinity electrophoresis

Modifications to antibody affinity electrophoresis for improved detection of proteins have been developed. The bifunctional linker glutaraldehyde is added to the polyacrylamide gel solution for better incorporation of the bait antibody into a distinct region of a 10% w/v polyacrylamide gel. The addition of glutaraldehyde alleviates the need of an electrophoresis buffer with a specific pH. The protein sample to be analyzed is treated with 2% w/v sodium dodecyl sulfate (SDS) to ensure that they carry a negative charge. The negative charge will allow the proteins to migrate towards the cathode and hence pass through the area embedded with the bait antibody. It is observed that electrophoretic migration of bovine serum albumin (BSA) or protein G ceases upon encounter with anti-BSA whereas proteins ovalbumin, beta-lactoglobulin A, and myoglobin migrate freely. However, the addition of 0.1% w/v SDS in the native gel running buffer disrupts the antibody-antigen bond and neither BSA nor protein G can be captured by anti-BSA.     

Bioactive Molecules of Mandarin Seed Oils Diminish Mycotoxin and the Existence of Fungi

Mandarin is a favorite fruit of the citrus family. Mandarin seeds are considered a source of nontraditional oil obtained from byproduct materials. This investigation aimed to assess the biomolecules of mandarin seeds and evaluated their antimycotic and antimycotoxigenic impact on fungi. Moreover, it evaluated the protective role of mandarin oil against aflatoxin toxicity in cell lines. The two types of extracted oil (fixed and volatile) were ecofriendly. The fatty acid composition, tocopherol, sterols, and carotenoids were determined in the fixed oil, whereas volatiles and phenolics were estimated in the essential oil. A mixture of the two oils was prepared and evaluated for its antimicrobial impact. The reduction effect of this mixture was also investigated to reduce mycotoxin secretion using a simulated experiment. The protective effect of the oil was evaluated using healthy strains of cell lines. Fixed oil was distinguished by the omega fatty acid content (76.24%), lutein was the major carotenoid (504.3 mg/100 g) and it had a high β-sitosterol content (294.6 mg/100 g). Essential oil contained limonene (66.05%), α-pinene (6.82%), β-pinene (4.32%), and γ-terpinene (12.31%) in significant amounts, while gallic acid and catechol were recorded as the dominant phenolics. Evaluation of the oil mix for antimicrobial potency reflected a considerable impact against pathogenic bacteria and toxigenic fungi. By its application to the fungal media, this oil mix possessed a capacity for reducing mycotoxin secretion. The oil mix was also shown to have a low cytotoxic effect against healthy strains of cell lines and had potency in reducing the mortality impact of aflatoxin B₁ applied to cell lines. These results recommend further study to involve this oil in food safety applications.     

Molecular Complexes of Crown Ethers, Part 6: Complexes of Cryptand (2,2,2) and Kryptofix 5 with Some Acceptors

The UV-Visible spectra of Cryptand (2,2,2) and Kryptofix 5 as donors, and TCNE (tetracyanoethylene), DDQ (2,3-dichloro-5,6- dicyano-1,4 benzoquinone) and PA (picric acid) as acceptors were studied. Charge transfer (CT) spectra were obtained for these systems. It was found that potassium halides have little effect on the spectra. The major process was due to an electron transfer from the donor to the acceptor. This revealed itself in very high conductivity values for the CT solutions in comparison to that of the donor or the acceptor solutions. The infrared and proton NMR spectra of the complexes indicated a strong interaction between the donor and the acceptor.     

Mass spectrometric detection of biotinylated peptides captured by avidin functional affinity electrophoresis

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry was used to detect biotinylated peptides captured by avidin functional affinity electrophoresis (AFAEP). Peptide samples loaded onto AFAEP were heated with sodium dodecyl sulfate to ensure that the peptides are negatively charged, and thus migrate electrophoretically toward the cathode through the embedded avidin zone in the middle of the gel. To detect the biotinylated peptides, the band containing the avidin-biotinylated peptide complexes was excised from a 7.5% w/v native polyacrylamide gel, and biotinylated peptides were extracted with aqueous 95% v/v formamide (pH 8.2), aqueous 6 M guanidine HCl (pH 1.5), or water, at temperatures from 4 to 95 degrees C for periods from 5 min to 24 h. It was observed that all three solvents are capable of extracting biotinylated peptides and avidin from the gel, but the best results were obtained with aqueous 95% v/v formamide (pH 8.2) at 65 degrees C for 20 min. However, some AFAEP-captured biotinylated peptides are not stable and are extensively modified by formamide during extraction at too high a temperature or too long an extraction time.     

Inverse-scattering theory and the density perturbations from inflation

We show how to use inverse-scattering theory as the basis for the inflationary reconstruction program, the goal of which is to gain information about the physics which drives inflation. Inverse-scattering theory provides an effective and well-motivated procedure, having a sound mathematical basis and being of sufficient generality that it can be considered the foundation for a nonparametric reconstruction program. We show how simple properties of the power spectrum translate directly into statements about the evolution of the background geometry during inflation.     

Conformational preference in thiophene-2-carbaldehyde

The 100 MHz ¹H NMR spectra of thiophene-2-carbaldehyde have been obtained in different solvents and analysed. It was found that the SO-cis conformation is more stable in all solvents, and that the proportion of the SO-trans population increases with decreasing polarity of the solvent. CNDO/2 calculations predict that the SO-cis is more stable than the SO-trans conformation. The aldehyde coupling to the ring was calculated by the CNDO/2 method and compared with the experimental value.