Room temperature synthesis of PbSe quantum dots in aqueous solution: stabilization by interactions with ligands

An aqueous route of synthesis is described for rapid synthesis of lead selenide quantum dots (PbSe QDs) at room temperature in an attempt to produce water-soluble and stable nanocrystals. Several thiol-ligands, including thioglycolic acid (TGA), thioglycerol (TGC), 3-mercaptopropionic acid (MPA), 2-mercaptoethylamine hydrochloride (MEA), 6-mercaptohexanoic acid (MHA), and l-cysteine (l-cys), were used for capping/stabilization of PbSe QDs. The effects of the ligands on the stability of PbSe QDs were evaluated for a period of two months at room temperature under normal light conditions and at 4 °C in the dark. The TGA- and MEA-capped QDs exhibited the highest stability prior to purification, almost two months when kept in the dark at 4 °C. However, the stability of TGA-capped QDs was reduced substantially after purification to about 5 days under the same conditions, while MEA-capped QDs did not show any significant instability. The stabilization energies of Pb-thiolate complexes determined by theoretical DFT simulations supported the experimental results. The PbSe QDs capped with TGA, MPA and MEA were successfully purified and re-dispersed in water, while those stabilized with TGC, MHA and l-cys aggregated during purification attempts. The purified PbSe QDs possess very susceptible surface resulting in poor stability for about 30-45 min after re-dispersion in water. In the presence of an excess of free ligand, the stability increased up to 5 days for TGA-capped QDs at pH 7.19, 9-12 days for MPA-capped QDs at pH 7.3-7.5 and 45-47 days for MEA-capped QDs at pH 7.35. X-Ray diffraction (XRD) results showed that the QDs possess a cubic rock salt structure with the most intense peaks located at 2θ = 25.3° (200) and 2θ = 29.2° (100). TEM images showed that the size of the QDs ranges between 5 and 10 nm. ICP-MS results revealed that Pb?:?Se ratios were 1.26, 1.28, 3.85, 1.18, and 1.31 for the QDs capped with TGA, MPA, MEA, l-cys, and TGC, respectively. The proposed method is inexpensive, simple and utilizes environmentally friendly chemicals and solvents.     

Nanoconfinement of spider silk fibrils begets superior strength, extensibility, and toughness

Silk is an exceptionally strong, extensible, and tough material made from simple protein building blocks. The molecular structure of dragline spider silk repeat units consists of semiamorphous and nanocrystalline β-sheet protein domains. Here we show by a series of computational experiments how the nanoscale properties of silk repeat units are scaled up to create macroscopic silk fibers with outstanding mechanical properties despite the presence of cavities, tears, and cracks. We demonstrate that the geometric confinement of silk fibrils to diameters of 50 ± 30 nm is critical to facilitate a powerful mechanism by which hundreds of thousands of protein domains synergistically resist deformation and failure to provide enhanced strength, extensibility, and toughness at the macroscale, closely matching experimentally measured mechanical properties. Through this mechanism silk fibers exploit the full potential of the nanoscale building blocks, regardless of the details of microscopic loading conditions and despite the presence of large defects. Experimental results confirm that silk fibers are composed of silk fibril bundles with diameters in the range of 20-150 nm, in agreement with our predicted length scale. Our study reveals a general mechanism to map nanoscale properties to the macroscale and provides a potent design strategy toward novel fiber and bulk nanomaterials through hierarchical structures.     

Influence of Eriophyid mites (Aculus olearius Castagnoli and Aceria oleae (Nalepa) (Acarina: Eriophyidae)) on some physical and chemical characteristics of Ayvalık variety olive fruit

BACKGROUND: Aculus olearius Castagnoli is a recently recorded species that damages olive fruits in the Mediterranean basin of Turkey. Thus, the effects of Eriophyid mites (Aculus olearius Castagnoli and Aceria oleae (Nalepa) (Acarina: Eriophyidae) on the olive fruits from Ayval?k variety in southern Turkey were studied for the first time in terms of some physical parameters and chemical constituents including some individual phenolics. RESULTS: The Eriophyid damaged fruits had higher L* values (lighter colour) and tyrosol level (37.53 mg kg^?1) than the undamaged fruits (28.51 mg kg^?1) in August. In contrast, Eriophyid damaged fruits were darker in colour and had lower levels (25.77 mg kg^?1) of tyrosol than those of undamaged fruits (79.14 mg kg^?1) in October. Eriophyid damaged samples had higher values of vanillic acid than the undamaged samples. An increase in the average concentrations of hydroxytyrosol and p‐coumaric acid was observed in the fruits harvested in August, whilst the oleuropein content decreased. CONCLUSION: The harvest in October can be recommended regarding the higher dimensional values, total oil, dry matter and oleuropein contents. But the interaction between harvest time and Eriophyid damage was found effective in terms of tyrosol content and skin colour; as tyrosol values were lower in the fruits harvested in October and the fruits were darker. The resistance of undamaged fruits against Eriophyid damage can be linked to high tyrosol content of these fruits. Copyright © 2010 Society of Chemical Industry     

Preparation and application of glycidyl methacrylate and methacrylic acid monomer mixture‐grafted poly(ethylene terephthalate) fibers for removal of methylene blue from aqueous solution

A novel fibrous adsorbent that grafts glycidyl methacrylate (GMA) and methacrylic acid (MAA) monomer mixture onto poly(ethylene terephthalate) (PET) fibers was used for removal of methylene blue (MB) in aqueous solutions by a batch equilibration technique. The operation parameters investigated included, pH of solution, removal time, graft yield, dye concentration, and reaction temperature. The adsorption rate of MB is much higher on the MAA/GMA‐grafted PET fibers than on the ungrafted PET fibers. MB was removed 99% the initial dye concentration at 10 mg L⁻¹ and 93% at 200 mg L⁻¹ by monomers mixture‐grafted PET fibers. Pseudofirst order and pseudosecond order kinetic equations were used to examine the experimental data of different graft yield. It was found that the pseudosecond order kinetic equation described the data of dye adsorption on fibrous adsorbent very well. The experimental isotherms data were analyzed using Langmuir and Freundlich isotherm models. The data was that Freundlich isotherm model fits the data very well for the dyes on the fibers adsorbent. The dye adsorbed was easily desorbed by treating with acetic acid/methanol mixture (50% V/V) at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Oxygen permeability and the mechanical and thermal properties of (low‐density polyethylene)/poly (ethylene‐co‐vinyl acetate)/organoclay blown film nanocomposites

Various (low‐density polyethylene)/poly(ethylene‐co‐vinyl acetate) (LDPE/EVA) nanocomposites containing organoclay were prepared by one‐ and two‐step procedures through melt blending. The resultant nanocomposites were then processed via the film blowing method. From the morphological point of view, X‐ray diffraction and optical microscopy studies revealed that although a prevalent intercalated morphology was evident in the absence of EVA, a remarkable increase of organoclay interlayer spacing occurred in the EVA‐containing systems. The advantages of the addition of EVA to the LDPE/organoclay nanocomposites were confirmed in terms of oxygen barrier properties. In other words, the oxygen transmission rates of the LDPE/EVA/organoclay systems were significantly lower than that of the LDPE/organoclay sample. The LDPE/EVA/organoclay films had better mechanical properties than their counterparts lacking the EVA, a result which could be attributed to the improvement of the organoclay reinforcement efficiency in the presence of EVA. Differential scanning calorimetry and thermogravimetric analysis experiments were performed to follow the effects of the EVA and/or organoclay on the thermal properties of LDPE. Finally, the films produced from the two‐step‐procedure compound showed enhanced oxygen barrier properties and mechanical behavior as compared to the properties of the films produced via the one‐step procedure. J. VINYL ADDIT. TECHNOL., 19:132–139, 2013. © 2013 Society of Plastics Engineers     

Dynamic Fault-Tolerant three-dimensional cellular genetic algorithms

This paper proposes a new dynamic and algorithm-based approach to achieve fault tolerance using 3D cellular genetic algorithms (Dynamic Fault-Tolerant 3D-cGA). The proposed algorithm is an improved version of our previous algorithm (Fault-Tolerant 3D-cGA) that introduces and utilizes a dynamic adaptation feature to achieve further improvement. In Dynamic Fault-Tolerant 3D-cGA, faulty individuals are isolated and the maximum number of fitness evaluations is recalculated to adapt to faults encountered. To improve the performance of the algorithm, a mitigation technique is integrated into our algorithm by introducing an explicit migration operator. A benchmark of well-known real-world and test problems is used to test the effectiveness of the algorithm in order to investigate the influence of adaptation schemes and migration on algorithm performance. Faulty critical system data is tackled in conjunction with various fault ratios. To illustrate the improvement achieved, Dynamic Fault-Tolerant 3D-cGA is compared with Fault-Tolerant 3D-cGA, the previously proposed algorithm. The overall results demonstrate the ability of Dynamic Fault-Tolerant 3D-cGA to maintain system’s functionality despite an increasing number of faults with up to 40% of processing elements (PEs), and clearly illustrate the importance of migration. Significant improvements in the performance of the algorithm, measured as efficiency, efficacy, and speed, are achieved, especially when migration is employed.     

A Chemometric Approach to Assess the Frying Stability of Cottonseed Oil Blends During Deep-Frying Process: I. Polar and Polymeric Compound Analyses

The main goal of the present study was (i) to determine the formation of degradation products in cottonseed oil (CSO) blends during deep frying process by adsorption and high performance size exclusion chromatography techniques and (ii) to evaluate the impacts of food additives on total polar (TPC) and polymeric compound (PTAG) formation using a chemometric approach. In order to prepare the frying CSO blends; ascorbic palmitate, mixed tocopherols, dimethylpolysiloxane, lecithin and sesame oils were used as additives. To determine the real impacts of additives, a quarter-fraction factorial experimental design with two levels and five factors was used. The changes in TPC and PTAG data were carefully evaluated during 10 h of frying at 170 ± 5 °C with normal distribution (ND) graphs and analyzed using a one-way analysis of variance (ANOVA), followed by Tukey’s Post-hoc test (α = 0.05). The results indicated that the increasing values for TPC and PTAG during the frying processes for all blends, TPC and PTAG contents reached maximum levels of 16.37 and 6.01 % respectively, which are below the limit values stated by official authorities for the quality assessment of frying oils. The ANOVA test results were in good agreement with ND graphs and data indicated that the impact of mixed tocopherols was significant for TPC formation, meanwhile the impact of lecithin and ascorbic palmitate × dimethylpolysiloxane were significant for PTAG formation. Thus, the present study should be considered to be a very useful guide for developing new frying oil formulations based on CSO by using food additives.