Hydrothermal synthesis of ZnO/C microflowers for photocatalytic degradation of organic pollutants under visible light irradiation: kinetics,mechanism and recyclability

Journal of Materials Science: Materials in Electronics - We developed an improved hexagonal wurtzite ZnO and ZnO/C microflowers through the facile hydrothermal technique. The obtained...     

A systematic method for the targeted discovery of chemical attribution signatures: application to isopropyl bicyclophosphate production

Potential attribution signatures for the synthesis of a highly toxic bicyclophosphate, 4-isopropyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (Isopropyl Bicyclophosphate or IPBCP) were discovered using a trilateral synthetic, analytical, and statistical approach. Initially, five synthetic routes were confirmed to successfully produce IPBCP using a range of reaction solvents, reactant ratios, and reaction temperatures. Experimental design principles were subsequently used to guide a formal study specifically aimed at discovering attribution signatures that could be used to differentiate forensic samples. A comparison of three-dimensional scatter plots comprised of the detected ions, their relative retention times (RRTs) and intensities (from LC-MS analyses) identified: (1) signatures that were unique to a synthetic route; (2) signatures associated with a combination of synthetic route and reaction solvent; (3) signatures related to reaction solvent, and (4) signatures associated with reagent source. Top level analysis revealed that the majority of the signatures are related to the synthetic route or a combination of the synthetic route and reaction solvent. Deeper analysis utilizing high resolution mass spectrometry (HRMS) and MS(n) revealed that most of the signatures stem from impurities in the reagents or byproducts formed from incomplete reactions between the reagents used in a given synthetic route. Finally, a subsequent validation study was performed to assess the presence and absence of the key route dependent signatures.     

Direct patterning of polystyrene–polymethyl methacrylate copolymer by means of laser interference lithography using UV laser irradiation

The fabrication of functionalized surfaces on polymeric substrates is of importance in chemistry, biology, physics, and material science. Examples of functional surfaces are micro/nano periodic arrays that can be fabricated using different methods. However, many of these techniques require several fabrication steps. In this communication, we report the fabrication of advanced architectures in poly(methylmethacrylate)–polystyrene (PMMA–PS) copolymers using direct laser interference patterning. Because of the mixed optical properties of the copolymers, a different type of periodic architectures could be fabricated when compared with traditional pure polymers. This new type of periodic structures results from the local swelling of the copolymer due to the formation of gaseous products induced by the laser radiation. Additionally, relatively low laser fluences are necessary to initiate the ablation process of the copolymers. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Polyphenolic fractions improve the oxidative stability of microencapsulated linseed oil

The main objective of this study was to evaluate the effect of incorporating polyphenolic‐enriched fractions from murta leaves on the oxidative stability of linseed oil microencapsulated by spray drying. For this purpose, polyphenol‐enriched fractions from murta leaves were separated by gel permeation chromatography and chemically characterized. The oxidative stability of microencapsulated linseed oil (MLO) with antioxidants was evaluated in storage conditions at 25°C for 40 days. The antioxidant effects of the polyphenolic fractions and commercial antioxidants (BHT and trolox) on microencapsulated oil were evaluated by the value of conjugated dienes, peroxide, and p‐anisidine. In the initiation step of the oxidation, no significant oxidation delay (p>0.05) in MLO containing fractions F₆, F₈, or BHT and trolox was observed. However, in the termination step of the oxidation, the addition of fractions F₆, F₈, and BHT and trolox decreases significantly (p ≤ 0.05) the rancidity in MLO. Furthermore, the results of this study demonstrated the importance of the addition of natural antioxidants such as fractions of murta leaf extract in microencapsulated linseed oil to increase its resistance to oxidation. Practical applications: For incorporating linseed oil, a source of omega‐3 fatty acids, in the diet it is necessary to protect it against oxidative rancidity, the main cause of deterioration that affects food with a high unsaturated fat content. Microencapsulation is effective in retarding or suppressing the oxidation of unsaturated fatty acids and natural plants extracts are effective in inhibiting the lipid oxidation of microencapsulated oil. The use of process technology and a natural additive is expected to increase storage stability and enable its use in dry foods such as instant products. Linseed oil can be used in human nutrition as well as in animal feed as a replacement for fish oil.     

Functional properties and microstructure of cowpea cultivated in north-east Argentina

The goal of this work was to analyze the effect of different treatments on functional properties (Color parameters, water holding capacity, oil holding capacity, water imbibition capacity, protein solubility and apparent viscosity) and microstructure of three cowpea varieties. Proteins present in flours obtained from heat-treated seeds exhibited a significant increase in water and oil absorption values, water imbibition capacity, and apparent viscosity, whereas solubility decreased. Color determinations on flours showed a reduction in L* and H*, and an increment in C* with treatment intensity. Structural changes in seeds would explain the variations in the functionality of flours. This study shows that cooking and autoclaving affect significantly the functional properties of flours, while soaking had a lower impact. The knowledge about these changes will be very useful for developing and obtaining new preparations based on cowpea flour.     

One Step Lithography of Polypyrrole

Large areas of polypyrrole (PPy) thin films deposited onto inert polymeric substrates are structured by direct laser interference patterning (DLIP). Several square millimeter areas could be produced with one single (10 ns) pulse, at room temperature and atmospheric pressure. Nanometric arrays of lines (>600 nm) or grids of PPy deposited on dielectric polymers polypropilene or polypirrol (PP or PE) are fabricated by DLIP at 355 nm. The period of the lines structures, measured by white light interferometry (WLI), is 3.5 µm. Regular structures are analyzed using scanning electron microscope (SEM) and a focus ion beam (FIB) tomography. It is shown that only the PPy film is structured while the PP or PE substrate remains unaltered. Fourier transform infrared spectroscopy (FTIR) and UV‐vis spectroscopy, permit to ensure that PPy chemical structure remains unaltered after the structuration process. The width of PPy lines can be tailored by controlling the fluence of the laser beam. Contact angle measurement shows that the wettability is affected by the structuring, making the surface more hydrophobic. The structuring technique seems to be suitable for the fabrication of PPy regular structures over various substrates.     

Large face to face tetraphenylporphyrin/fullerene nanoaggregates. A DFT study

Large face to face tetraphenylporphyrin/fullerene nanoaggregates containing up six C60 units and six tetraphenylporphyrin (H2TPP) or tetraphenylporphyrinato-zinc (TPP-Zn) moieties have been studied using dispersion corrected PBE/def2-SVP level of theory. It has been found that most important contribution to the binding energy between fragments comes from dispersion interactions. The binding energies for Zn containing nanoaggregates are slightly higher than those for metal free ones what is not related to the difference in dispersion contributions to the binding energy but comes from DFT term. Center to center distances for large nanoaggregates are shorter than those for the complexes H2TPP/C₆₀ and TPP-Zn/C₆₀ and this effect is more obvious for metal free nanoaggregates. According to the calculations, the band gap of nanoaggregates barely depends on its size being close to 2 eV. The nature of electronic excitations in Zn containing nanoaggregates has strong charge transfer (CT) contribution and does not depend on nanoaggregate size, while for metal free nanoaggregate most of low energy excitations are not CT by nature. Ionization potentials and electron affinities of nanoaggregates depend strongly on their size. Polaron cations are uniformly delocalized over donor H2TPP or TPP-Zn units, while polaron anions are delocalized over acceptor C₆₀ units. The reorganization energies calculated for hole and electron transport decreased linearly with 1/n where n is the number of repeating units in nanoaggregate.     

Gelation,thermal and pasting properties of pigeon pea (Cajanus cajan L.), dolichos bean (Dolichos lablab L.) and jack bean (Canavalia ensiformis) flours

This study evaluated the rheological, thermal and pasting properties of pigeon pea (PP), dolichos bean (DB) and jack bean (JB) legume flours and gels. Starch and protein contents were also measured and its molecular weight distribution was determined by electrophoresis. PP and DB showed the highest viscosities while JB had the highest pasting temperature. The minimum flour concentrations for gel formation were estimated at 6–8% for DB and PP and 10% for JB. Above these concentrations all flour suspensions heated to 95 °C led to gels with a solid-like behavior. Differential scanning calorimetry showed two endothermic peaks in all flours at 80–89 °C and 96–100 °C. Avrami model was successfully fitted to the hardening kinetics of PP and DB gels stored at 4 °C. The half-life times were 22 and 6 h for PP and DB respectively. PP and DB flours were able to form self-supporting gels and could be applied in the formulation of gel-like foods.     

Recognizing Age at Slaughter of Cattle from Beef Samples Using GC/MS–SPME Chromatographic Method

Beef from cattle less than 30 months old at the point of slaughter are generally sold in meat markets. Though the age of the animal can generally be estimated by dentition, this method cannot be applied to a carcass or a piece of meat from which the teeth have been removed. Since gas chromatography of volatile organic compounds has been used to classify biological samples, this technique was used for classifying meat obtained from cattle aged over 30 months (OTM) at point of slaughter. Volatile organic compounds of fresh meat (M. longissimus dorsi) samples obtained from cattle of different age and dentition (two, four, and six teeth) at point of slaughter were analyzed using gas chromatography/mass spectrum (GC/MS). Six volatile organic compounds were selected (hexanoic acid, benzoic acid, octanoid acid, tridecane, tetradecane, and 4-formylbenzoic acid) and confirmed by using chemical standards and Kovat’s indexes. The chromatogram data were used to train two classifiers, one based on the partial least square (PLS) method and another based on support vector machine (SVM), but only SVM showed high accuracy. Data exploration based on the principal component analysis allowed for comprehension of the data distribution, proposing a new version of PLS in a parallel configuration. This modified version of the PLS algorithm showed better accuracy than the SVM classifier. In conclusion, volatile organic compounds analyzed by GC/MS–solid-phase microextraction can be used to recognize OTM beef.