Electronic structure and optical properties of an alternated fluorene-benzothiadiazole copolymer: interplay between experimental and theoretical data

The donor-acceptor copolymer containing benzothiadiazole (electron acceptor), linked to functionalized fluorene (electron donor), [poly[9,9-bis(3'-(tert-butyl propanoate))fluorene-co-4,7-(2,1,3-benzothiadiazole)] (LaPPS40), was synthesized through the Suzuki route. The polymer was characterized by scanning electron microscopy, gel permeation chromatography, NMR, thermal analysis, cyclic voltammetry, X-ray photoelectron spectroscopy, UV-vis spectrometry, and photophysical measurements. Theoretical calculations (density functional theory and semiempirical methodologies) used to simulate the geometry of some oligomers and the dipole moments of molecular orbitals involved were in excellent agreement with experimental results. Using such data, the higher energy absorption band was attributed to the π-π* (S(0) → S(4)) transition of the fluorene units and the lower lying band was attributed to the intramolecular (ICT) (S(0) → S(1)) charge transfer between acceptor (benzothiadiazole) and donor groups (fluorene) (D-A structure). The ICT character of this band was confirmed by its solvatochromic properties using solvents with different dielectric properties, and this behavior could be well described by the Lippert-Mataga equation. To explain the solvatochromic behavior, both the magnitude and orientation of the dipole moments in the electronic ground state and in the excited state were analyzed using the theoretical data. According to these data, the change in magnitude of the dipole moments was very small for both transitions but the spatial orientation changed remarkably for the lower energy band ascribed to the ICT band.     

Stereoselective Plasmonic Interaction in Peptide-tethered Photopolymerizable Diacetylenes Doped with Chiral Gold Nanoparticles

Designing polymeric systems with ultra-high optical activity is instrumental in the pursuit of smart artificial chiroptical materials, including the fundamental understanding of structure/property relations. Herein, we report a diacetylene ( DA ) moiety flanked by chiral D - and L -FF dipeptide methyl esters that exhibits efficient topochemical photopolymerization in the solid phase to furnish polydiacetylene ( PDA ) with desired control over the chiroptical properties. The doping of the achiral gold nanoparticles provides plasmonic interaction with the PDA s to render asymmetric shape to the circular dichroism bands. With the judicious design of the chiral amino acid ligand appended to the AuNPs, we demonstrate the first example of selective chiral amplification mediated by stereo-structural matching of the polymer-plasmonic AuNP hybrid pairs. Such ordered self-assembly aided by topochemical polymerization in peptide-tethered PDA provides a smart strategy to produce soft responsive materials for applications in chiral photonics.     

Laser-driven synthesis and magnetic properties of iron nanoparticles

Nanoparticles of iron have been prepared by laser-driven decomposition of iron pentacarbonyl vapor. In this method, an infrared laser rapidly heats a dilute mixture of precursor vapors to decompose the precursor and initiate particle nucleation. It was found that when using SF₆ as a photosensitizer during the synthesis, ferrous fluoride (FeF₂) was produced as an undesired byproduct in the product powder. The particle size, composition, and crystalline structure have been characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and X-ray photoelectron spectroscopy (XPS). Results of magnetization measurements for small iron nanoparticles (about 5 nm diameter) are also presented, showing superparamagnetic behavior at room temperature, and a blocking temperature near 125 K.     

Synthesis,characterization, crystal structures, in vitro and in vivo antitumor activity of palladium(II) and zinc(II) complexes with 2-formyl and 2-acetyl pyridine N(4)-1-(2-pyridyl)-piperazinyl thiosemicarbazone

The present paper includes synthesis and spectral characterization of the novel prepared palladium(II) and zinc(II) complexes with 2-formyl pyridine N(4)-1-(2-pyridyl)-piperazinyl thiosemicarbazone, HFo4Npypipe, 1 and the 2-acetyl pyridine N(4)-1-(2-pyridyl)-piperazinyl thiosemicarbazone, HAc4Npypipe, 2. The Pd(II) complexes [PdCl(Fo4Npypipe)], 3, [PdCl(Ac4Npypipe)], 4 and the Zn(II) complexes [ZnCl₂(Fo4Npypipe)], 5 and [ZnCl₂(Ac4Npypipe)], 6 have been characterized by elemental analyses and spectroscopic studies. The crystal structure of the complexes [PdCl(Fo4Npippy)], 3 and [PdCl(Ac4Npippy)], 4, have been solved by single-crystal X-ray diffraction. The electronic, IR, UV/Vis, and NMR spectroscopic data of the complexes are reported. The results of the cytotoxic activity of 1–6 have been evaluated in vitro against the cells of three human cancer cell lines: MCF-7, T24, A-549 and a mouse L-929 (a fibroblast-like cell line cloned from strain L). For selected compounds 2 and 6 the acute toxicity and antitumor activity were evaluated on leukemia P388-bearing mice. The Zn(II) compounds 5 and 6 are considered as agents with potential antitumor activity, and can therefore be candidates for further stages of screening in vitro and/or in vivo.     

A process for the rapid removal of dialkylamino-substituents from aromatic rings. Application to the expedient synthesis of (R)-tolterodine

A range of N,N-dialkylanilines have been successfully converted to the parent substituted benzenes by a novel two-step pathway. The products are obtained in good yields and optical purity of adjacent stereocenters is maintained. This technology has been applied toward the synthesis of (R)-tolterodine.     

Linear and nonlinear optical studies in photonic crystal alloys

We report on linear transmittance and reflectance as well as on third-harmonic generation in photonic crystal alloys formed by various compositions of polystyrene and poly (methyl methacrylate) colloidal spheres of the same size. These photonic crystal alloys are structurally ordered but contain refractive-index disorder and thus provide a random variation of scattering potential. The stopgap shows a monotonic shift in wavelength as a function of composition that can be fitted by assuming an effective dielectric constant for the colloidal spheres. In each alloy a dramatic enhancement of third-harmonic generation is observed, always on the short-wavelength side of the stopgap.     

Photorefractive inorganic organic polymer-dispersed liquid-crystal nanocomposite photosensitized with cadmium sulfide quantum dots

We report on a new photorefractive medium consisting of a hole-transporting polymer composite matrix, electro-optically active nanodroplets of liquid crystals, and cadmium sulfide quantum dots as photosensitizers. This medium exhibits greater than 90% internal diffraction efficiency and a net two-beam coupling gain of 22.5 cm(-1) with a response time of <1 min . Data on optical transmission are also presented.