Effects of hyperbranched and linear architecture on properties of polymers composed of poly(ɛ-caprolactone) and hydroxycinnamic acid

Photoreactive and degradable polymers with linear and hyperbranched architectures which composed of poly(?-caprolactone) and hydroxycinnamic acid or its substituted derivatives were synthesized by thermal melt-polycondensation. The chemical structures of the polymers were confirmed by FTIR and ¹H NMR measurements. The polymers showed good photoreactivities and fluorescent properties, and the hyperbranched polymers showed higher photoreactive speed and weaker fluorescence properties. These polymers had excellent thermal stabilities due to the rigid conjugated structures and the π-π strcking interaction of the cinnamoyl group, especially for the hyperbranched polymer. Moreover, the hydrolysis experiments and the XRD results revealed that the hyperbranched and linear polymers are amorphous and crystalline, respectively, and the degradation rate of amorphous polymers are faster than crystalline samples.     

Formulation studies on a topical gel of tretinoin�Cdimethyl-beta-cyclodextrin complex

The aim of this work was to develop and characterize a 0.05% tretinoin hydrogel formulations in which tretinoin is free or complexed with dimethyl-beta-cyclodextrin in order to compare the main advantages of its complexation. Theoretically, the complexation will mainly allow to: overcome drug low solubility in water and low stability; enhance the drug release by promoting skin absorption and alleviate of drug inducing local irritation. The hydrogels prepared were both microbiological and physically stable during 30 days. However, the chemical stability was less encouraging. The complexed tretinoin gel had also a higher releasing profile than the free tretinoin gel. This study has demonstrated that it is possible to obtain a microbiological and physically stable gel formulation with good releasing profile.     

A study on sol–gel synthesis and characterization of SiC nano powder

Nano sized β-SiC particles were synthesized from sol–gel process. Mono dispersed β-SiC nano particles with semi spherical morphology were obtained by employing APC as a dispersant agent and adjusting pH in the range of 2.5–4. Phenolic resin and TEOS were employed as precursors and heat treatment was conducted up to 1500 °C. Different techniques such as XRD, DTA, FTIR, PSA, SEM and TEM were used to characterize the formation of β-SiC. The (Si–O-C) bonds were formed by hydrolysis and condensation reactions in the gel while the nucleation of crystalline β-SiC was found to be initiated at 1400 °C. The primary particles in the sol were found to be (< 10 nm) while the size distribution in the final product was recorded in the range of 30–50 nm.     

Adsorption and corrosion inhibition behavior of polyethylene glycol on α-brass alloy in nitric acid solution

The corrosion performance of α-brass in 1 M HNO₃ and in the presence of polyethylene glycol (PEG) has been investigated using AC impedance spectra (EIS), potentiodynamic polarization (PP), electrochemical frequency modulation (EFM), and mass reduction (MR) techniques. The outcome data of EIS showed a rise in the resistance charge transfer (R_ct) and a decrease in the capacitance double layer (C_dl). Protection efficiency (IE) of PEG has been obtained by varying the dose of the PEG and temperature. PEG adsorbed on α-brass in acidic solution follows isotherm Langmuir. The polarization curves displayed that PEG acts as a mixed-kind inhibitor. The parameters obtained from thermodynamic activation of corrosion α-brass in 1 M HNO₃ were obtained and debated. The results obtained from all tests were in excellent agreement.     

Preparation, crystal structure, and solid-state optical property of a disulfonic acid/amine fluorescent complex composed of 4,4′-biphenyldisulfonic acid and 2-naphthylethylamine

Solid-state disulfonic acid/amine fluorescent host complexes including methanol (MeOH) as guests were successfully prepared using 4,4′-biphenyldisulfonic acid and 2-naphthylethylamine as component molecules. Although the crystal structure of the obtained host complex is similar to that of the corresponding dicarboxylic acid/amine host complex, the solid-state photo-luminescence quantum yield of the disulfonic acid/amine fluorescent host complex is increased relative to those of the corresponding dicarboxylic acid/amine host complex.     

Quantum DFT and DF–DFT study of vibrational spectra of sulfuric acid,sulfuric acid monohydrate,formic acid and its cyclic dimer

Rigorous theoretical treatment of vibrational frequencies is critically important for the interpretation of unassigned experimental vibrational spectra and accurate determination of thermodynamic properties of molecular clusters. IR spectra of trans monomers of sulfuric and acetic acids, sulfuric acid monohydrate and cyclic dimer of the formic acid have been studied using DFT and DF–DFT methods using BLYP, B3LYP and PW91 with 12 different Pople and Dunning basis sets. New data for above-mentioned structures have been reported, scaling factors have been calculated and a comprehensive analysis of the performance of BLYP, B3LYP and PW91 methods has been performed. Comparison of the obtained results with experiments shows that results of pure PW91 and BLYP are better than predictions of well-established hybrid B3LYP method. Our analysis shows on the existence of the considerable difference in scaling factors weighted to high and low frequencies. In the case of formic acid dimer, the deviation the predicted low frequencies from the experimental data is considerable that leads to quite large (∼6–7 kcal mol⁻¹) uncertainties in the absolute values of the cluster Gibbs free energy. In order to determine an efficient computational strategy that comprises accuracy and reasonable computational costs, the effect of density fitting (DF) and basis set superposition error (BSSE) on the vibration frequencies has been investigated. We found that application of the DF that substantially (2.5–3.5 times) increases the performance of pure PW91 and BLYP methods gives excellent results, which are very close to those of conventional DFT. This suggests that DF–DFT is a viable low-cost alternative to conventional DFT in predicting vibrational spectra. It has been found that while vibrational spectra obtained using the counterpoise correction (CP) for the BSSE do not deviate much from uncorrected ones, the difference in absorption intensities between corrected and uncorrected spectra obtained using small and medium-sized basis sets is considerable. This suggests that application of DF–DFT uncorrected for the BSSE with large basis sets is a more efficient strategy of predicting vibrational spectra than the application of conventional DFT with small basis sets.     

Effect of sintering temperature on the structural, optical and electrical properties of sol–gel derived indium oxide thin films

Sol gel derived indium oxide, In₂O₃; films were prepared by spin coating technique. The films were dried and sintered at different sintering temperatures (300, 400, 450 and 500 °C) in air. The effect of sintering temperature on the structural, optical and electrical properties of In₂O₃ thin films was studied. The morphology and structure of the films were analyzed by scanning electron microscope and X-ray diffraction. The films showed a bcc structure that changes its 400-preferential orientation to 222 orientation as the sintering temperature increases from 300 to 500 °C. The optical behavior of the films was studied by measuring the transmission spectra in the wavelength range 200–2,500 nm. Different optical models have been proposed for fitting the transmittance data and simulate the optical constants as well as the film thickness of In₂O₃ films. The best fitting of the data was obtained by combining the classical Drude and OJL models coupled with the Bruggeman effective medium approximation. The optical parameters of Drude model (plasma frequency and damping constant) are used calculate the electrical properties of the films. The calculated values of the electrical sheet resistance were compared with those measured experimentally by four probes. The correlation between the film orientation change and its optical and electrical properties was discussed.     

Sol–gel synthesis of highly effective catalyst based on cobalt tetrasulfophthalocyanine complex and silicon oxide

New hybrid materials based on silicon oxide and water soluble cobalt phthalocyanine complex were synthesized and characterized. It was shown that synthesized material exhibit pronounced catalytic activity in the R–SH type of organic compounds oxidation reaction in comparison with the individual macroheterocycle. The influence of the synthetic route of the hybrid material preparation on its catalytic efficiency was determined.     

Microstructural and optical characterizations of sol–gel based antimony doped indium oxide coatings on glass

Thin films of antimony doped indium oxide on glass has been developed by sol–gel dipping process. Four different Sb: In atomic ratios, 1:99, 4:96, 7:93, 10:90 were selected for the precursors. Pressure flow curve of the precursors were Newtonian which apparently developed homogeneous films baking at 500 °C in air. The EDS study restricted to the study of the films of only two Sb: In atomic ratios, namely 7:93, 10:90 as antimony sublimes during baking. Polycrystalline nature of the nanostructured films were revealed by X-ray diffractogram and SAED analysis. Transmission electron microscopy study shows the presence of nanoclusters of maximum average size, ~11 nm. The band gap evaluation from the absorption spectra suggested the presence of bulk indium oxide, nanoclustered indium oxide and antimony doped indium oxide. Presence of Sb(V) in the system was evidenced from the characteristic absorption spectra in the UV region. Visible transmissivity and electrical resistivity suggested the films to be prospective transparent conducting oxide material. The photoluminescence study exhibited the characteristic emissions for defect centres.     

Atomic oxygen erosion resistance of sol–gel oxide films on Kapton

Silica, alumina and silica-alumina composite films were deposited on Kapton substrate via sol–gel method and their atomic oxygen (AO) erosion resistance was test in a ground-based AO simulator. The surface morphology and the structure of as-deposited films were investigated by scanning electronic microscope, X-ray photoelectron spectroscopy, and Fourier transformed infrared spectroscopy. After AO exposure, more cracks and micro-pores appear on the surface of silica and alumina films, respectively. For the silica-alumina composite films, their toughness and densification are good, and the stable interface is formed between the alumina and silica phases. Therefore, the silica-alumina composite-coated Kapton shows the best AO resistance and the erosion yield is two orders of magnitude less than that of pristine Katpon. Moreover, the composite-coated Kapton remains optically stable under AO exposure.     

Preparation,characterisation and electrochromic property of mesostructured tungsten oxide films via a surfactant templated sol–gel process from tungstic acid

A novel kind of mesoporous tungsten oxide films (TOFs) has been prepared via a non-ionic surfactant templated sol–gel route from cheap and easy handling tungstic acid. Characterisations by means of various techniques, including XRD, TEM, SEM, ATR and DTA, confirm that the obtained mesostructures are composed of fine mesopores (2–3 nm) and thin pore walls. Compared with previously reported surfactant templated mesoporous TOFs, our initial evaluation on the electrochromic properties showed that the derived TOFs show greatly enhanced colouration efficiency of 44 cm² C⁻¹ and faster colouration/bleaching speed of 10/2 s, respectively. Owing to the ordering of mesostructures delivered by our method, the mesostructural changes associated with the electrochemical reaction during the electrochromic cycling of such materials can be directly monitored by low-angle XRD measurements.     

Thermodynamic study on salt effects on complex formation of α-, β- and γ-cyclodextrins with p-aminobenzoic acid

The aim of this work was to gain a deeper understanding of salt effects in the inclusion complex formation of cyclodextrins. For this purpose, thermodynamic study of complex formation of α-, β- and γ-cyclodextrins with p-aminobenzoic acid was carried out in water and solutions of KCl, KBr, KH₂PO₄ and K₂SO₄ (0.2 mol/kg). Stability constants were calculated from the binding isotherms obtained on the basis of ¹H NMR measurements. Enthalpy and entropy of complex formation were estimated from the van’t Hoff plots. It was found that effects of KCl, KH₂PO₄ and K₂SO₄ are insignificant, while the influence of KBr on complex formation of cyclodextrins with p-aminobenzoic acid is more pronounced and results in a decrease of the stability constants. Specific action of Br⁻ is caused by the ability of these anions to penetrate into macrocyclic cavity. Coexistence of two complexation equilibria in KBr solution is accompanied by significant solvent reorganization originated from more intensive dehydration of the interacting species. This results in an increase of the enthalpy and entropy of complex formation. Manifestation of Br⁻ effect was found to be the same in the binding of p-aminobenzoic acid with α-, β- and γ-cyclodextrins.     

Energy and electron transfer reactions on silica gel and titania–silica mixed oxide surfaces

Research on Chemical Intermediates - The energy and electron transfer reactions of anthracene co-adsorbed with an electron donor on silica gel and titania–silica mixed oxides have been...     

Synthesis and characterization of semiconductor tin oxide thin films on glass substrate by sol–gel technique

In this study, synthesis and characterization of semiconductor tin oxide (SnO₂) thin films on glass substrate were systematically investigated by using sol–gel technique for gas sensing applications. Turbidity, pH values, wettability and rheological properties of solution were measured by turbidimeter, pH meter, contact angle goniometer and rheometer machines before coating process. The thermal, structural, microstructural and optical properties of the coatings and powders made from the sols were extensively characterized by using DTA-TG, FT-IR, XRD, SEM-EDS, refractometer and spectrophotometer. Four different solutions, including 6, 8, 10 and 14 mL methanol content, were prepared by sol–gel technique to determine solvent influence on microstructure and semiconducting properties of the thin films. Refractive indiceses, band gaps, absorbance and transmittance values of SnO₂ thin films, containing different methanol quantity, were determined and their variations depending on solvent content were obtained. It is concluded that solvent content influences microstructural and semiconducting properties of Sn based oxide thin films notably.     

Synthesis and characterization of nanocrystalline tin oxide by sol–gel method

Nanocrystalline SnO₂ particles have been synthesized by a sol–gel method from the very simple starting material granulated tin. The synthesis leads a sol–gel process when citric acid is introduced in the solution obtained by dissolving granulated tin in HNO₃. Citric acid has a great effect on stabilizing the precursor solution, and slows down the hydrolysis and condensation processes. The obtained SnO₂ particles range from 2.8 to 5.1 nm in size and 289–143 m² g⁻¹ in specific surface area when the gel is heat treated at different temperatures. The particles show a lattice expansion with the reduction in particle size. With the absence of citric acid, the precursor hydrolyzes and condenses in an uncontrollable manner and the obtained SnO₂ nanocrystallites are comparatively larger in size and broader in size distribution. The nanocrystallites have been characterized by means of TG-DSC, FT-IR, XRD, BET and TEM.     

Synthesis and characterization of lead oxide nano-powders by sol–gel method

Our goal in this research was to obtain lead oxide nano-powders by sol–gel method. In this method, lead oxide nano-powders were synthesized through the reaction of citric acid (C₆H₇O₈·H₂O) solution and lead acetate [Pb(C₂H₃O₂)₂] solution as stabilizer and precursor, respectively. The effect of different parameters including calcination temperature, (molar ratio of citric acid to lead acetate) and drying conditions were investigated. The prepared lead oxide nano-powders were characterized by FT-IR spectroscopy, X-ray diffraction, thermogravimetric analysis and scanning electron microscopy. The prepared PbO samples consist of the particles in the range of 50–120 nm or the thick plate like structures with thickness of 53 nm depending on the drying conditions.