Photophysical and photocatalytic properties of nanosized copper-doped titania sol–gel catalysts

The effect of doping the TiO₂ lattice with copper was studied. TiO₂–Cu semiconductors (0.1, 0.5, 1.0 and 5.0 Cu wt.%) were synthesized by the sol–gel method by incorporating Cu (NO₃)₂ into the titanium alkoxide solution. In the samples thermally treated at 500 °C, mesoporous materials (9.5–12 nm) with specific surface areas of 90–52 m²/g were obtained. The X-ray diffraction (XRD) patterns of the annealed samples present anatase as the sole nanocrystalline phase (28 nm). The UV–vis diffuse reflectance spectra of the Cu-doped samples show a shift in the band gap to lower energy levels. The X-ray photoelectron spectroscopy (XPS) reveals a reduction in the oxidation state of the copper precursor, Cu(II), stabilizing Cu(0) and Cu(I) in the annealed solids. The photocatalytic test for the 2,4-dichlorophenoxyacetic acid degradation showed high efficiency and mineralization up to 92% (total organic carbon, TOC) in the Cu-doped sol–gel materials. The enhancement of the photocatalytic activity was discussed as an effect due to the Cu content as well as to the formation of stable Cu(I) in the Cu-doped TiO₂ semiconductors.     

Dynamic modelling of the response of UK forest soils to changes in acid deposition using the SAFE model

Both observed and modelled data have been examined from the ten UN-ECE Level II forest intensive monitoring sites in the UK to determine the changes and potential impact on soil solution chemistry resulting from changes in acid deposition inputs. The sites represent a range of forest tree types, soil sensitivities and pollutant deposition inputs found in the UK. The dynamic biogeochemical SAFE model was used to explore temporal changes in soil and soil solution chemical parameters that have been used as indicators for potential forest ecosystem and tree damage in national and international assessments of critical loads. The observed data and model results show that there is significant inter-site variation. The model indicates that the historical pollutant inputs have resulted in significant soil acidification at most of the sites. Model predictions generally match current day observations. Recently declining pollutant inputs have reduced and in some cases reversed the trend of increasing soil acidification. A discussion of the results in terms of critical loads, recovery, their wider implications and uncertainty is presented.     

Synthesis and antimicrobial activities of gold(I) sulfanylcarboxylates

Reaction of NaAuCl₄·H₂O and thiodiglycol (1:3 molar ratio) with 3-(aryl)-2-sulfanylpropenoic acids, H₂ xspa = [x:p = 3-phenyl-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, o-py = 3-(2-pyridyl)-, Clp = 3-(2-chlorophenyl)-, -o-mp = 3-(2-methoxyphenyl)-, -p-mp = 3-(4-methoxyphenyl)-, -o-hp = 3-(2-hydroxyphenyl)-, -p-hp = 3-(4-hydroxyphenyl)-, diBr-o-hp = 3-(3,5-dibromo-2-hydroxyphenyl)] and 2-cyclopentylidene-2-sulfanylacetic acid (H₂cpa) in a 1:1 metal/ligand molar ratio gave compounds of the type [Au(Hxspa)] or [Au(Hcpa)]. These compounds were reacted with diisopropylamine to afford [HQ][Au(xspa)] or [HQ][Au(cpa)] (HQ = diisopropylammonium) and with NaOH to afford Na[Au(xspa)]·H₂O and Na[Au(cpa)]·H₂O. All of the new compounds were isolated and characterised by IR and ¹H and ¹³C NMR spectroscopy. The antimicrobial activities of the complexes against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, Candida albicans, Pseudomonas aeruginosa and carbapenem-resistant P. aeruginosa were evaluated and compared to those of the equivalent silver(I) complexes. The comparison shows that the gold compounds generally show better activity than the silver analogues against S. aureus and B. subtilis, but low sensitivity against E. coli, P. aeruginosa and C. albicans, suggesting a different mode of antimicrobial action for equivalent silver and gold compounds.     

工艺与合金元素对镁锶系合金微观组织的影响

采用"熔-浸"热还原法,制备了具有优良组织结构的镁锶系列(Mg-Sr、Mg-Sr-Y、Mg-Sr-Zn、Mg-Sr-Zn-Y)镁合金。借助OM、SEM和XRD等测试技术,研究了工艺与合金元素对镁锶系合金微观组织结构的影响。结果表明:较低温下加入SrO有助于镁锶合金中Mg17Sr2相的形成;随镁锶合金冷却速度的增大,晶界处长条状Mg17Sr2相变成颗粒状和短条状;锶、钇和锌的加入均细化了镁锶合金的显微组织,多种元素的复合效果优于添加单一元素的作用;在镁锶形成共晶组织的基础上,Mg-Sr-Y合金在枝晶内和枝晶间形成了Mg24Y5相,在Mg-Sr-Zn-Y合金中形成了Mg12YZn相。     

Upon the characterization of semi-synthetic hydrogels based on poly (NIPAM) inserted onto collagen sponge

The preparation of a semi-synthetic hydrogel based on poly(N-isopropyl acrylamide-co-diethylene glycol diacrylate) inserted onto a collagen porous membrane, it was previous presented. The synthesis of the hydrogels was performed through radical copolymerization of N-isopropyl acrylamide (NIPAM) with diethylene glycol diacrylate (DEGDA) also as crosslinking agent, using ammonium persulfate as initiator and N,N,N′,N′-tetramethylethylene diamine activator, and it was achieved in the presence of the collagen matrix. In this paper the thus prepared hydrogels are characterized by Differential Scanning Calorimetry, Scanning Electron Microscopy and for their swelling capacities. A kinetic model was studied to investigate the swelling mechanism of the semi-interpenetrated polymeric network. The swelling behavior was found dependent on the hydrogel composition and to the external stimuli such as temperature and pH of environment. This manner of acting recommends these materials as smart materials with potential applications in tissue engineering and pharmaceutical field as for example bioproducts carrier matrices.     

Detection of nano-oxidation sites on the surface of hemoglobin crystals using tip-enhanced Raman scattering

Hemoglobin nanocrystals were analyzed with tip-enhanced Raman scattering (TERS), surface-enhanced resonance Raman scattering (SERRS) and conventional resonance Raman scattering (RRS) using 532 nm excitation. The extremely high spatial resolution of TERS enables selective enhancement of heme, protein, and amino acid bands from the crystal surface not observed in the SERRS or RRS spectra. Two bands appearing at 1378 and 1355 cm(-1) assigned to the ferric and ferrous oxidation state marker bands, respectively, were observed in both TERS and SERRS spectra but not in the RRS spectrum of the bulk sample. The results indicate that nanoscale oxidation changes are occurring at the hemoglobin crystal surface. These changes could be explained by oxygen exchange at the crystal surface and demonstrate the potential of the TERS technique to obtain structural information not possible with conventional Raman microscopy.     

Green Synthesis of Acetals/Ketals: Efficient Solvent-Free Process for the Carbonyl/Hydroxyl Group Protection Catalyzed by SBA-15 Materials

Acetals/ketals derived from the aldehydes/ketones are easily prepared under solventless conditions. The process is heterogeneously catalysed using acid or basic mesoporous molecular sieves Al-SBA-15 and (Cs)Al-SBA-15. The catalytic procedure herein reported is applied to the preparation of the key intermediates for the synthesis of {3-[(2R,3R,4R,5R)-(2,3,4,5-tetrahydroxyhexane-1,6-diyl)]}di-1H-imidazole 2 with potential biomedical applications.     

Optoelectronic properties of chemically deposited Bi2S3 thin films and the photovoltaic performance of Bi2S3/P3OT solar cells

Thin films of bismuth sulfide (Bi₂S₃), prepared on conductive tin-doped indium oxide (ITO)-glass substrates by chemical deposition showed a variation of optical band gap with thickness: 1.8 eV for a 50 nm film (deposited at 40 °C for 30 min) to 1.5 eV for a 200 nm film deposited for 2 h. The electronegativity for Bi₂S₃ compound is 5.3 eV, as estimated from the ionization energy and electron affinity of elemental Bi and S, and thus the electron affinity of chemically deposited Bi₂S₃ film was deduced to be 4.5 eV. In the energy level analysis of ITO/Bi₂S₃/P3OT/Au structure, Bi₂S₃ was established as an electron acceptor. To produce ITO/Bi₂S₃/P3OT/Au solar cell structures, poly3-octylthiophene (P3OT), prepared in the laboratory was dissolved in toluene and was drop-cast on the Bi₂S₃ film and a gold film was thermally evaporated. Under 100 mW/cm² tungsten-halogen irradiation incident from the ITO-side, the cell using a Bi₂S₃ film with thickness of 50 nm has the highest open circuit voltage (V_oc) of 440 mV and short-circuit current density (J_sc) of 0.022 mA/cm². The addition of a CdS thin film (90 nm) between ITO and B₂S₃ would increase V_oc to 480 mV, and J_sc to 0.035 mA/cm². The role of surface morphology and optoelectronic properties of the Bi₂S₃ film in the photovoltaic performance of the junction is discussed.     

Optical vortices in twisted elliptical optical fibers with torsional stress

In the present paper we have derived the analytical expressions for the modes of twisted elliptical fibers with torsional mechanical stress at various relationships of the fiber parameters. It was shown that circularly polarized optical vortices with the topological charges ±1 can propagate in elliptical fibers as generic modes if ellipticity and the twist-induced circular birefringence suppress the spin-orbit interaction. A comparison of the obtained results with the corresponding results for spun elliptical fibers is made.     

Analysis of the scatter growth in dispersive media with the use of dynamic light scattering

Analysis of the structure functions of intensity fluctuations of scattered laser light was applied to monitor the phase separation in probed disperse media. UV-cured mixtures of a liquid crystal and prepolymer were studied during the formation of the structure of dispersive polymer-liquid crystal (DPLC) composites. The experimentally observed features of light beating induced by dynamic light scattering in DPLC systems (the scaling properties of the structure functions, the narrowing of the beating spectrum for certain weight fractions of the liquid-crystalline component) were interpreted in terms of the discrete scattering model using the results of statistical modeling.