Novel polymer synthesis methodologies using combination of thermally and photochemically-induced nitroxide mediated polymerisation

The combination of thermally- and photochemically-induced polymerization using light sensitive alkoxyamines was investigated. The thermally driven polymerizations were performed via the cleavage of the alkoxyamine functionality, whereas the photochemically-induced polymerizations were carried out either by nitroxide mediated photo-polymerization (NMP2) or by a classical type II mechanism, depending on the structure of the light-sensitive alkoxyamine employed. Once the potential of the various structures as initiators of thermally- and photo-induced polymerizations was established, their use in combination for block copolymer syntheses was investigated. With each alkoxyamine investigated, block copolymers were successfully obtained and the system was applied to the post-modification of polymer coatings for application in patterning and photografting.

Photocytotoxic Oxovanadium(IV) Complexes Showing Light-Induced DNA and Protein Cleavage Activity

Oxovanadium(IV) complexes [VO(L)(B)]Cl-2 (1-3), where L is bis(2-benzimidazolylmethyl)amine and B is 1,10-phenanthroline(phen),dipyrido[3,2-d:2',3'-f]quinoxaline(dpq) or dipyrido[3,2-a:2',3'-c]phenazine (dppz), have been prepared, characterized, and their photo-induced DNA and protein cleavage activity studied. The photocytotoxicity of complex 3 has been studied using adenocarcinoma A549 cells, The phen complex 1, structurally characterized by single-crystal X-ray crystallography, shows the presence of a vanadyl group in six-coordinate VON5 coordination geometry. The ligands L and phen display tridentate and bidentate N-donor chelating binding modes, respectively. The complexes exhibit a d-d band near 740 nm in 15% DMF-Tris-HCl buffer (pH 7.2). The phen and dpq complexes display an irreversible cathodic cyclic voltammetric response near -0.8 V in 20% DMF-Tris-HCl buffer having 0.1 M KCl as supporting electrolyte. The dppz complex 3 exhibits a quasi-reversible voltammogram near -0.6 V (vs SCE) that is assignable to the V(IV)-V(III)couple. The complexes bind to calf thymus DNA giving binding constant values in the range of 6.6 x 10(4)-2.9 x 10(5) M-1. The binding site size, thermal melting and viscosity binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes show poor ``chemical nuclease'' activity in dark in the presence of 3-mercaptopropionic acid or hydrogen peroxide. The dpq and dppz complexes are efficient photocleavers of plasmid DNA in UV-A light of 365 nm via a mechanistic pathway that involves formation of both singlet oxygen and hydroxyl radicals. The complexes show significant photocleavage of DNA in near-IR light (>750 nm) via hydroxyl radical pathway. Among the three complexes, the dppz complex 3 shows significant BSA and lysozyme protein cleavage activity in UV-A light of 365 nm via hydroxyl radical pathway. The dppz complex 3 also exhibits photocytotoxicity in non-small cell lung carcinoma/human lung adenocarcinoma A549 cells giving IC50 value of 17 mu M in visible light(IC50 = 175 mu M in dark).

Polymer based photo detectors

Recent developments in our laboratory related to polymer-based light sensors are reviewed. The inherent processibility of the active polymer medium is utilized in the implementation of different designs for the opto-electronic applications. The utility of these devices as sensitive photodetectors, image sensors and position sensitive detectors is demonstrated. The schottky-type layer formation at interfaces of polymers such as polyalkylthiophenes and aluminum accompanied by the enhanced photo-induced charge separation due to high local electric field is tapped for some of these device structures. The sensitivity of polymer-based field effect transistors to light also provides a convenient lateral geometry for efficient optical-coupling and control of the transistor state. ne range of these polymer-detectors available with the option of operating in the diode and transistor modes should be an attractive feature for many potential applications.

Light Induced Optical Properties Change in Sb20S40Se40 Thin Films

Thin films of Sb20S40Se40 of thickness 800 nm were prepared by thermal evaporation method. The as-prepared and illuminated thin films were studied by X-ray diffraction, Fourier Transform Infrared Spectroscopy and X-ray Photoelectron Spectroscopy and Raman spectroscopy. The optical band gap was reduced due to photo induced effects along with the increase in disorder. These optical properties changes are due to the change of homopolar bond densities. The core level peak shifting in XPS and Raman spectra supports the optical changes happening in the film due to light exposure.

Reversible shear-induced crystallization above equilibrium freezing temperature in a lyotropic surfactant system

We demonstrate a unique shear-induced crystallization phenomenon above the equilibrium freezing temperature (T-K(o)) in weakly swollen isotropic (L-i) and lamellar (L-alpha) mesophases with bilayers formed in a cationic-anionic mixed surfactant system. Synchrotron rheological X-ray diffraction study reveals the crystallization transition to be reversible under shear (i.e., on stopping the shear, the nonequilibrium crystalline phase L-c melts back to the equilibrium mesophase). This is different from the shear-driven crystallization below T-K(o), which is irreversible. Rheological optical observations show that the growth of the crystalline phase occurs through a preordering of the L-i phase to an L-alpha phase induced by shear flow, before the nucleation of the Lc phase. Shear diagram of the L-i phase constructed in the parameter space of shear rate ((gamma)) over dot vs. temperature exhibits L-i -> L-c and L-i -> L-alpha transitions above the equilibrium crystallization temperature (T-K(o)), in addition to the irreversible shear-driven nucleation of L-c in the L-i phase below T-K(o). In addition to revealing a unique class of nonequilibrium phase transition, the present study urges a unique approach toward understanding shear-induced phenomena in concentrated mesophases of mixed amphiphilic systems.

Laser- induced optical properties change in Sb10S40Se50 chalcogenide thin films: An investigation through FTIR and XPS measurements

Chalcogenide glasses are interesting materials for their infrared transmitting properties and photo-induced effects. This paper reports the influence of light on the optical properties of Sb10S40Se50 thin films. The amorphous nature and chemical composition of the deposited film was studied by X-ray diffraction and energy dispersive X-ray analysis (EDAX). The optical constants, i.e., refractive index, extinction coefficient, and optical band gap as well as film thickness are determined from the measured transmission spectra using the Swanepoel method. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. The dispersion energy parameter was found to be less for the laser-irradiated film, which indicates the laser-irradiated film is more microstructurally disordered as compared to the as-prepared film. It is observed that laser-irradiation of the films leads to decrease in optical band gap (photo-darkening) while increase in refractive index. The decrease in the optical band gap is explained on the basis of change in nature of films due to chemical disorderness and the increase in refractive index may be due to the densification of films with improved grain structure because of microstructural disorderness in the films. The optical changes are supported by X-ray photoelectron spectroscopy data. (C) 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Remarkable Selectivity and Photo-Cytotoxicity of an Oxidovanadium(IV) Complex of Curcumin in Visible Light

Oxidovanadium(IV) complexes of 2-(2'-pyridyl)-1,10-phenanthroline (pyphen), viz. VO(pyphen)(acac)](ClO4) (1), VO(pyphen)(anacac)](ClO4) (2) and VO(pyphen)(cur)](ClO4) (3), where acac is acetylacetonate (in 1), anacac is anthracenylacetylacetonate (in 2) and cur is curcumin monoanion (in 3) were synthesized, characterized and their photo-induced DNA cleavage activities and photo-cytotoxicities studied. The complexes are 1: 1 electrolytes in DMF. The one-electron paramagnetic complexes show a d-d band near 760 nm in DMF. Complexes 2 and 3 are blue and green emissive, respectively, in DMSO. The complexes exhibit irreversible V-IV/V-III reductive responses near -1.1 V and V-V/V-IV oxidative responses near 0.85 V vs. SCE in DMF-0.1 M TBAP. Complexes 2 and 3 display significant and selective photo-cytotoxicity upon irradiation with visible light giving an IC50 value of about 5 mu M against HeLa and MCF-7 cancer cells; they are significantly less-toxic against normal 3T3 control cells and in the absence of light. Complex 1 was used as a control. Both cytosolic and nuclear localization of the complexes were observed on the basis of fluorescence imaging. The complexes, avid binders to calf thymus (ct) DNA, were found to photocleave supercoiled pUC19 DNA upon irradiation with near-IR light (785 nm) by generating hydroxyl radical (OH) as the reactive oxygen species (ROS). Cell death events noted with HeLa and MCF-7 cell lines likely are attributable to apoptotic pathways involving light-assisted generation of intracellular ROS.

Effect of Te Addition into As2Se3 Thin Film: Optical Property Study by FTIR and XPS.

In the present work, we report the effect of Te deposition onto As2Se3 film which affects the optical properties. The Te/As2Se3 film was illuminated with 532 nm laser to study the photo induced diffusion. The prepared As2Se3, Te/As2Se3 films were characterized by X-ray diffraction which show a completely amorphous nature. On the basis of optical transmission data carried out by Fourier Transform infrared Spectroscopy, a non direct transition was found for these films. The optical bandgap is found to be decreased with Te deposition and photo darkening phenomena is observed for the diffused film. The change in the optical constants are also supported by the corresponding change in different types of bonds which are being analyzed by X-ray photoelectron spectroscopy.

飞秒激光与晶体和玻璃的相互作用

总结了飞秒激光与晶体和玻璃相互作用产生的新现象，如光致折射率改变、光致晶体相变、光还原稀土离子及光致发光等。并分析了它们可能的应用。同时简要的介绍了各种现象产生的机理，展望了飞秒激光与其它物质相互作用可能的研究方向及可能出现的新现象。指出了进行这些研究时可能采用的新方法。

Fe-diffusion-induced defects in InP annealed in iron phosphide ambient

Photoluminescence (PL) and photo induced current transient spectroscopy (PICTS) have been used to study deep levels in semi-insulating (SI) InP prepared by annealing undoped InP in pure phosphorus (PP) and iron phosphide (IP) ambient. Defects are much fewer in IP SI-InP than in PP SI-InP. Deep-level-related PL emission could only be detected in IP SI-InP. The results indicate that Fe diffusion inhibits the thermal formation of a number of defects in annealed InP. A complex defect has been formed in the annealing process in the presence of Fe.

Characterisation of bifunctional ruthenium(ii) complexes, potential DNA photo-probes. Presence of folded and unfolded conformers

Novel bifunctional ruthenium(n) complexes, [Ru(TAP)2(POQ-Nmet)]2+ and [Ru(BPY)2(POQ-Nmet)]2+(la, 2a), containing a metallic and an organic moiety, have been prepared as photoprobes and photoreagents of DNA(TAP = 1,4,5,8-tetraazaphenanthrene, POQ-Nmet = 5-[6-(7-chloroquinolin-4-yl)-3-thia-6-azaheptanamido]-l,10phenanthroline). The ES mass spectrometry and 'H NMR data in organic solvents indicate that the quinoline moiety exists in both the protonated and non-protonated form. Moreover, the comparison of the NMR data with those of the corresponding monofunctional complexes(without quinoline) evidences that [Ru(TAP).2(POQ-Nmet)]2+ and [Ru(BPY)J(POQ-Nmet)]2+ are unfolded when the quinoline unit is protonated whereas deprotonation permits folding of the molecule. In the folded state the spatial proximity of the electron donor(the organic moiety) and electron acceptor(the metallic moiety) in [Ru(TAP)2(POQ-Nmet)]2+ favours intramolecular photo-induced electron transfer, which has been shown in a previous study to be responsible for the very low luminescence of la in non-protonating solutions. The restoration of the luminescence by protonation of the quinoline moiety as observed previously is in agreement with the unfolding of the molecule demonstrated in this work. The existence of such folding-unfolding processes related to protonation is crucial for studies of la with DNA. © The Royal Society of Chemistry 2000.

Femtosecond dynamics of molecular and cluster ionization and fragmentation

The real-time dynamics of molecular (Na_2 . Na_3) and cluster Na_n (n=4-2l) multiphoton ionization and -fragmentation has been studied in beam experiments applying femtosecond pump-probe techniques in combination with ion and electron spectroscopy. Wave packet motion in the dimer Na_2 reveals two independent multiphoton ionization processes while the higher dimensional motion in the trimer Na_3 reflects the chaotic vibrational motion in this floppy system. The first studies of cluster properties (energy, bandwidth and lifetime of intermediate resonances Na^*_n) ) with femtosecond laser pulses give a striking illustration of the transition from "molecule-like" excitations to "surfaceplasma"-like resonances for increasing cluster sizes. Time-resolved fragmentation of cluster ions Na_n^* indicate that direct photo-induced fragmentation processes are more important at short times than the statistical unimolecular decay.

Light-induced electric dipole relaxation in synthetic and natural alexandrite

We present results of thermally stimulated depolarization current (TSDC) measurements in synthetic and natural alexandrite, which show TSDC bands related to the presence of electric dipoles in both types of samples. Synthetic material shows a wide TSDC band with a peak at 179 K, which can be fitted by two distinct relaxing dipole distributions. For natural alexandrite the TSDC band has a maximum around 195 K and can be fitted by three different distributions. Both samples present one of the calculated curves with a peak about 179 K, with activation energy of 0.57 eV and constant relaxation time of 1 × 10-14 sec. Photo-induced TSDC shows that TSDC bands can also be generated by simultaneous application of light and an electric field at 77 K.

Investigação das propriedades ópticas, elétricas e estruturais em ametista

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Photoelectrochemical properties of FTO/p-NiO electrode induced by UV light irradiation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)