Visible‐Light‐Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster

Photosynthetic water oxidation in plants occurs at an inorganic calcium manganese oxo cluster, which is known as the oxygen evolving complex (OEC), in photosystem II. Herein, we report a synthetic OEC model based on a molecular manganese vanadium oxide cluster, [Mn₄V₄O₁₇(OAc)₃]^3?. The compound is based on a [Mn₄O₄]⁶⁺ cubane core, which catalyzes the homogeneous, visible‐light‐driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V₄O₁₃]^6? polyoxovanadate and three acetate ligands. When combined with the photosensitizer [Ru(bpy)₃]²⁺ and the oxidant persulfate, visible‐light‐driven water oxidation with turnover numbers of approximately 1150 and turnover frequencies of about 1.75 s^?1 is observed. Electrochemical, mass‐spectrometric, and spectroscopic studies provide insight into the cluster stability and reactivity. This compound could serve as a model for the molecular structure and reactivity of the OEC and for heterogeneous metal oxide water‐oxidation catalysts.     

Synthesis,Characterization and Investigation of Electrochemical and Spectroelectrochemical Properties of Peripherally Tetra Diethoxypropan Substituted Phthalocyanines

In this study novel peripherally tetra 1,3-diethoxy-2-propanol substituted Co(II), Cu(II), Mg(II), Ni(II) Zn(II) phthalocyanine derivatives were prepared. The characterization of the novel compounds was made by FT-IR, ¹H-NMR, UV-vis and MALDI-TOF mass. Electrochemical, in-situ spectroelectrochemical and electrocolorimetric measurements have been carried out with the aim to determine the redox properties, to illuminate reaction mechanism and the effect of substituent and metal center. Moreover, the color properties and aggregation tendency of compounds were also investigated.     

Cloud-point extraction of rhodamine 6G by using Triton X-100 as the non-ionic surfactant

Cloud-point extraction (CPE) using the non-ionic surfactant Triton X-100 was used successfully to remove a highly toxic dye, rhodamine 6G (R6G), from water and wastewater. The effects of different analytical parameters such as pH, concentration of Triton X-100 (TX-100) and salts, equilibrium temperature, and incubation time on the efficiency of the extraction of R6G were studied in detail, and optimum conditions for dye extraction were obtained. Thermodynamic parameters including changes in Gibbs free energy, enthalpy, and entropy were also calculated, and these parameters indicated that the CPE of R6G was feasible, spontaneous, and endothermic in the temperature range of 75-95 degrees C. The equilibrium solubilization capacity of TX-100 was found to be 1.10 mmol/mol by using Langmuir isotherm models. No significant interference effects were observed in the presence of phenol and its derivatives, some acidic and basic dyes and most of the anions and cations. It was concluded that the CPE process described in this paper can be an alternative technique for removal of dyes and other pollutants from waters and wastewaters.     

Towards near-infrared photosensitisation: a photosensitising hydrophilic non-peripherally octasulfanyl-substituted Zn phthalocyanine

A Zn(II) phthalocyanine substituted with eight hydroxylated sulfanyl moieties in non-peripheral positions was designed to exhibit properties desired for photodynamic therapy: hydrophilicity, isomeric purity and near-infrared absorption in addition to high singlet oxygen generation. Photophysical and photochemical studies proved to be promising.     

Form-stable electrospun nanofibrous mats as a potential phase change material

A series of Poly vinyl butyral–Poly (acrylic acid) (PVB-PAA) based form-stable phase change materials (PCMs) have been prepared for the use of thermal energy storage applications. Six types of formulations containing five different fatty alcohols were prepared by adding PVB to PAA. Using electrospinning to fabricate nanofibrous mats, our aim was to investigate their properties as form-stable PCMs. Fatty alcohols, 1-Tetradecanol, 1-Hexadecanol, 1-Octadecanol, 1-Eicosanol and 1-Docosanol, were added separately to base formulation. The structural characterization tests were performed by ATR-FTIR spectroscopy. Morphological tests were conducted using Scanning Electron Microscope (SEM). Thermal performances and phase change behaviors were tested by thermogravimetric analysis system (TGA) and differential scanning calorimetry (DSC). The heating cycle phase change enthalpy is measured between 223 and 241?J/g, and the freezing cycle phase change enthalpy is found between 215 and 239?J/g. The main decomposition PVB-PAA based PCMs started at 220?°C. This study suggested that PVB-PAA based PCMs possess well phase change properties and they were found to have an applicable temperature range. With the presented results these materials promise a great potential in thermal energy storage applications.     

Determination of chromatographic dissociation constants of some carbapenem group antibiotics and quantification of these compounds in human urine

The dissociation constant values (_s^spK_a) of some carbapenem group drugs (ertapenem, meropenem, doripenem) in different percentages of methanol–water binary mixtures (18, 20 and 22%, v/v) were determined from the mobile phase pH dependence of their retention factor. Evaluation of these data was performed using the NLREG program. From calculated pK_a values, the aqueous pK_a values of these subtances were calculated by different approaches. Moreover, the correlation established between retention factor and the pH of the water–methanol mobile phase was used to determine the optimum separation conditions. In order to validate the optimized conditions, these drugs were studied in human urine. The chromatographic separation was realized using a Gemini NX C₁₈ column (250 × 4.6 mm i.d., 5 µm particles) and UV detector set at 220 and 295 nm. Copyright © 2013 John Wiley & Sons, Ltd.     

Modeling the free radical polymerization of acrylates

Acrylates have gained importance because of their ease of conversion to high‐molecular‐weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well‐known monomer for free radical polymerization, but its α‐methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl α‐hydroxymethylacrylate (MHMA), methyl α‐methoxymethylacrylate (MC₁MA), methyl α‐acetoxymethylacrylate (MAcMA) show even better conversions to high‐molecular‐weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl α‐hydroxymethylacrylate (EHMA) and t‐butyl in t‐butyl α‐hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6‐31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC₁MA, MAcMA, EHMA, TBHMA, MC₁AN (α‐methoxymethyl acrylonitrile), and MC₁AA (α‐methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Synthesis of Smart Food Packaging from Poly (Gelatin-co-Dimethyl Acrylamide) / Citric Acid-Red Apple peel Extract

ABSTRACT

A novel and smart hydrogel was synthesized from N, N dimethyl acrylamide (DMAAm), gelatin, and citric acid (CA) red apple peel extract (RApE) to be utilized as a multi-functional food packaging material. The p(Gelatin-co-DMAAm)/CA-RApE was prepared through a redox polymerization technique in film form in petri dishes. Mechanical and water resistance of the p(Gelatin-co-DMAAm)/CA-RApE was improved by the addition of citric acid and N, N, methylenebisacrylamide (MBA) as cross linker. The characterization of p(Gelatin-co-DMAAm)/CA-RApE was carried out by Fourier transform infrared spectroscopy (FT-IR), thermo gravimetric analyzer (TGA), scanning electron microscopy (SEM), and dynamic and mechanical analyzer (DMA). FT-IR revealed the existence of bonding interactions between the functional group of RApE and gelatin, carbonyl groups of DMAAm, and carboxylic acid groups of CA. TGA results found that p(Gelatin-co-DMAAm)/CA-RApE was stable up to 565°C. It was observed that RApE improved thermal stability and decreased the elasticity of the p(Gelatin-co-DMAAm)/CA-RApE. When tested against Escherichia coli, Bacillus subtilis and Staphylococcus aureus, p(Gelatin-co-DMAAm)/CA-RApE was observed to have antimicrobial activity. Total antioxidant and anthocyanin effect of p(Gelatin-co-DMAAm)/CA-RApE was analyzed. Additionally, to monitor the color changes of p(Gelatin-co-DMAAm)/CA-RApE, it was studied at different pH values. Furthermore, p(Gelatin-co-DMAAm)/CA-RApE was applied to real samples such as whole pasteurized milk and cheese. It was found to have a good color indicator and antimicrobial activity for pasteurized whole milk and cheese. It was concluded that p(Gelatin-co-DMAAm)/CA-RApE is a very good candidate to be used in food packaging and biomedical materials, along with other potential applications.