Time-Resolved Fluorescence and Transient Spectroscopy in Determining Photochemical and Photophysical Channels in Reacting Systems in Solutions and Microheterogeneous Media

Abstract— Characterization of short-lived intermediates in homogeneous and microheterogeneous systems has been carried out using time-resolved spectroscopic techniques. The data obtained from these techniques have been analyzed in a relatively unconventional manner to elucidate complex transient behavior for two reactive systems. The highly nonexponential fluorescence decay for a series of fraws-stilbene-derivatized amphiphiles that readily form bilayer systems in aqueous media has been analyzed using a distribution of lifetimes analysis (DLA). The utility of DLA for quantitative studies was first determined by simulation of artificial decay data. Despite some limitations in DLA, qualitative conclusions as to the nature of the fluorescing species may be drawn when supplementary information such as steady-state spectroscopic data are also considered. The results indicate that the observed fluorescence originates from different types of excited-state species that consist of two or more trans-stilbene units; one of the emissions is attributed to the excited state of a ground-state aggregate while the other is assigned to an excimer that may arise from a 'defect'in the bilayer. The nonexponential nature of the decays is attributed to distributions of environments experienced by the fluorescing species. Electron transfer (ET) reactions between several excited pinacols and carbon tetrachloride in solution have been found to yield products with quantum yields that are higher than unity in the presence of oxygen, suggesting a chain mechanism for product formation. In these systems both the donor and the acceptor undergo bond fragmentation following the initial ET step. The individual steps involved in the proposed mechanism for these systems have been investigated in part using different steady-state and time-resolved laser spectroscopic techniques. However, it was also necessary to utilize pulse radiolysis in order to confirm the involvement of certain radical intermediates that were not observable by the usual flash photolysis techniques.     

Photocatalytic ozonation degradation of ciprofloxacin using ZnO nanoparticles immobilized on the surface of stones

Ciprofloxacin is used in the treatment of bacterial infections. Because ciprofloxacin is not effectively degraded by biological processes, advanced oxidation processes such as photocatalytic ozonation are applied to remove this antibiotic from wastewater. The aim of this study was to investigate photocatalytic ozonation for the removal of ciprofloxacin from aquatic environments and optimization of the effective parameters of the process. For this purpose, ZnO nanoparticles were synthesized using the thermal method and immobilized on the surface of stones. The structural properties of the nanoparticles were determined by XRD, TEM, Photoluminescence (PL) and SEM. Experiments were carried out in a Plexiglas reactor supported with the continuous injection of ozone. The effective parameters for removal efficiency were reaction time, initial concentration of ciprofloxacin, pH, photocatalyst concentration and reaction kinetics. The highest ciprofloxacin removal efficiency occurred at the following optimal conditions: pH of 7, reaction time of 30?min, photocatalyst concentration of 3?g/L and initial ciprofloxacin concentration of 10?mg/L. Removal efficiency of 96% was obtained under these conditions. Linear kinetic models showed that the process followed pseudo-first order and Langmuir-Hinshelwood kinetics. This process had a high removal efficiency and suitable for removal of ciprofloxacin from aquatic environments.GRAPHICAL ABSTRACT     

Dynamic headspace liquid-phase microextraction of alcohols

A method was developed using dynamic headspace liquid-phase microextraction and gas chromatography-mass spectrometry for extraction and determination of 9 alcohols from water samples. Four different solvents, hexyl acetate, n-octanol, o-xylene and n-decane were studied as extractants. The analytes were extracted using 0.8 microl of n-octanol from the headspace of a 2 ml sample solution. The effect of sampling volume, solvent volume, sample temperature, syringe plunger withdrawal rate and ionic strength of the solution on the extraction performance were studied. A semiautomated system including a variable speed stirring motor was used to ensure a uniform movement of syringe plunger through the barrel. The method provided a fairly good precision for all compounds (5.5-9.3%), except methanol (16.4%). Detection limits were found to be between 1 and 97 microg/l within an extraction time of approximately 9.5 min under GC-MS in full scan mode.     

Application of high-field NMR and cryogenic probe technologies in the structural elucidation of poecillastrin a,a new antitumor macrolide lactam from the sponge poecillastra species

Poecillastrin A (1), a new polyketide-derived macrolide lactam, was isolated from a deep-water collection of the marine sponge Poecillastra species. The structure of poecillastrin A (1) was assigned using NMR data acquired at 500 MHz with an inverse-detection cryogenic probe and at 800 MHz with a room-temperature probe.     

Si-tolerance of iron doped Pt/alumina catalyst in the total oxidation of VOC

Summary In the present study the effects of addition of iron on the catalytic activity and Si tolerability of Pt/g-Al₂O₃in the total oxidation of volatile organic compounds were investigated. Preliminary results showed that there is a noticeable improvement effect on Si-tolerance of catalyst, particularly for short term poison exposure. Bulk analysis of deposited silicon on the catalyst surface indicated that both Pt/g-Al₂O₃and iron-doped pellets had roughly the same silicone uptakes. Deactivation of catalyst was reversible and much faster for iron doped sample. The promoting effects of iron were related to its electronegativity and, to blocking of fewer Pt sites when iron is present at the surface of the catalyst.     

A study of peroxyoxalate-chemiluminescence of acriflavine

The chemiluminescence arising from the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of acriflavine has been studied. The relationship between the chemiluminescence intensity and concentrations of TCPO, H2O2, acriflavine and the base sodium salicylate are reported. The kinetic parameters for the peroxyoxalate-chemiluminescence (PO-CL) of acriflavine were evaluated from the computer fitting of the corresponding chemiluminescence intensity-time plots.     

Identification of the function of gene lndM2 encoding a bifunctional oxygenase-reductase involved in the biosynthesis of the antitumor antibiotic landomycin E by Streptomyces globisporus 1912 supports the originally assigned structure for landomycinone

The angucycline antibiotic family of the landomycins displays potent antitumor activity. To elucidate early post polyketide synthase (PKS) tailoring steps of the landomycin E biosynthetic pathway in Streptomyces globisporus 1912, the mutant S. globisporus M12 was prepared through gene replacement experiment of lndM2. It encodes an enzyme with putative oxygenase and reductase domains, according to sequencing of the gene and its counterpart lanM2 from S. cyanogenus S136 landomycin A biosynthetic gene cluster. The isolation of the novel shunt products 11-hydroxytetrangomycin and 4-hydroxytetrangomycin along with the well-known angucyclines tetrangomycin and tetrangulol from the culture of S. globisporus M12 provides evidence for the involvement of lndM2 in the early biosynthetic pathway of the landomycins, in particular in the formation of the alicyclic 6-hydroxy function of the landomycin aglycon. We therefore propose LndM2 to be responsible for both hydroxylation of the 6-position and its subsequent reduction. These reactions are necessary before the glycosylation reactions can occur. The results are in agreement with the originally published structure of landomycin but do not support the recently suggested revised structure.     

Synthesis and characterization of adducts of dichlorosulphato bis(1,3-propylenediamine)metal(II) complexes with dialkyltin dichlorides

Summary Adducts of dichlorosulphato bis(1,3-propylenediamine)-metal(II) complexes with dialkyltin dichlorides, [R₂Sn(MeCN) ₂]₂[M(NH(CH₂)₃NH)₂(SO₃Cl)₂] (M = Cr, Fe, Co, Ni or Cu; R = Me or n-Bu) have been prepared. The positive shift in the symmetric SO₃ stretch and splitting of the doubly degenerate (E) modes in their i.r. spectra suggest a covalent linkage for the SO₃Cl^– group. The adducts are non-electrolytes; magnetic moments and ligand field data suggest that each SO₃Cl^– group is monodentate, generating an octahedral geometry around the metal ions, except for Ni^II where tetragonal distortion is observed.Author to whom all correspondence should be directed.     

Ethylenediamine complexes of transition metalbis(chlorosulphates)

Summary The number and positions of the i.r. active modes in ethylenediamine complexes of M(SO₃Cl)₂ (M = Mn, Fe, Co, Ni or Cu) suggest that the SO₃Cl^– anion is covalently bound in these non-electrolytic complexes. Magnetic moments and ligand field data suggest that each SO₃Cl^– group is monodentate, giving an octahedral geometry around the metal ions.     

Growth promotion of HepG2 hepatoma cells by antisense-mediated knockdown of glypican-3 is independent of insulin-like growth factor 2 signaling

Glypican-3 (GPC3) encodes a cell-surface heparan- sulfate proteoglycan and its expression is frequently silenced in ovarian cancer, mesotheliomas, and breast cancer cell lines and ectopic expression of GPC3 inhibited the growth of these cells, suggesting that GPC3 plays a negative role in cell proliferation. In contrast, up-regulation of GPC3 is often observed in hepatoma, neuroblastoma, and Wilms' tumor. Whether GPC3 plays the same growth inhibitory role in these tumors remains to be studied. Here we report that antisense-mediated knockdown of GPC3 in the HepG2 hepatoma cells significantly promotes the growth of hepatoma cells. In addition, we show that this growth promotion is independent of insulin-like growth factor 2 (IGF2) signaling. Our data suggest that GPC3 plays a growth-suppressing role in hepatoma and provide cell biological evidence inconsistent with the hypothesis that GPC3 acts as a growth suppressor by downregulating IGF2.