Computer-aided design of chiral ligands. Part I. Database search methods to identify chiral ligand types for asymmetric reactions

The utility of database searching to identify chiral ligand motifs is outlined. The key elements of three known chiral ligands have been described as bond vectors. The CAVEAT program was then used to screen the Cambridge Structural Database (CSD), portions of the Chemical Abstracts Services three-dimensional database (CAS-3D), and the TRIAD tricyclic structure database for scaffolds containing these elements. Scaffolds corresponding to the known starting points were identified indicating that this method can be used to identify chiral ligand structural motifs. In addition, alternate structural motifs were found that suggested alternative possible ligands.     

Second generation waste package design and storage concept for the Yucca Mountain Repository

The reference waste package design and operating mode to be used in the Yucca Mountain Repository is reviewed. An alternate (second generation) operating concept and waste package design is proposed to reduce the risk of localized corrosion of waste packages and to reduce repository costs. The second generation waste package design and storage concept is proposed for implementation after the initial licensing and operation of the reference repository design. Implementation of the second generation concept at Yucca Mountain would follow regulatory processes analogous to those used successfully to extend the design life and uprate the power of commercial light water nuclear reactors in the United States. The second generation concept utilizes the benefits of hot dry storage to minimize the potential for localized corrosion of the waste package by liquid electrolytes. The second generation concept permits major reductions in repository costs by increasing the number of fuel assemblies stored in each waste package, by eliminating the need for titanium drip shields and by fabricating the outer container from corrosion resistant low alloy carbon steel.     

Wrapper–Filter Feature Selection Algorithm Using a Memetic Framework

This correspondence presents a novel hybrid wrapper and filter feature selection algorithm for a classification problem using a memetic framework. It incorporates a filter ranking method in the traditional genetic algorithm to improve classification performance and accelerate the search in identifying the core feature subsets. Particularly, the method adds or deletes a feature from a candidate feature subset based on the univariate feature ranking information. This empirical study on commonly used data sets from the University of California, Irvine repository and microarray data sets shows that the proposed method outperforms existing methods in terms of classification accuracy, number of selected features, and computational efficiency. Furthermore, we investigate several major issues of memetic algorithm (MA) to identify a good balance between local search and genetic search so as to maximize search quality and efficiency in the hybrid filter and wrapper MA     

Synthesis and characterization of soluble narrow band gap conducting polymers based on diketopyrrolopyrrole and propylenedioxythiophenes

A series of novel electro-active conjugated polymers containing 2,5-dialkyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-diones (DPPs) and 3,4-dihydro-3,3-dialkyl-2H-thieno[3,4-b][1,4]dioxepines (dialkyl-ProDOTs) were synthesized using Stille coupling reaction in presence of CuO. The molecular weights of the synthesized polymers were found to be in the range of 18,000–45,000. Incorporation of the electron deficient DPP units and the electron rich dialkyl-ProDOT units in the conjugated backbone leads to low band gap polymers. All the polymers were found to be highly soluble in most chlorinated organic solvents as well THF and toluene with excellent film forming properties. From the UV–vis spectra, the band gap of the polymers was determined as 1.40–1.42 eV which is lower than the poly(dialkylProDOT)s. From the electrochemical study, highest occupied molecular orbital (HOMO) energy levels of the synthesized polymers were found to be in the range of 5.54–5.51 eV. Because of such high HOMO level, the resulting polymers were found to be more oxidatively stable. Polymers are thermally stable till 325–346 °C with only 5% weight loss which was confirmed from thermogravimetric analysis (TGA). The polymers were found to be moderately conducting with maximum conductivity up to 0.2–6.0 S/cm.     

Cu-doped TiO(2) nanoparticles enhance survival of Shewanella oneidensis MR-1 under ultraviolet light (UV) exposure

It has been shown that photocatalytic TiO₂ nanoparticles (NPs) can be used as an efficient anti-microbial agent under UV light due to generation of reactive oxygen species (ROS), while Shewanella oneidensis MR-1 is a metal-reducing bacterium highly susceptible to UV radiation. Interestingly, we found that the presence of Cu-doped TiO₂ NPs in the cultural medium dramatically increased the survival rates (based on colony-forming unit) of strain MR-1 by over 10,000-fold (incubation without shaking) and ~ 200 fold (incubation with shaking) after a 2-h exposure to UV light. Gene expression results (via qPCR measurement) indicated that the DNA repair gene recA in MR-1 was significantly induced by UV exposure (indicating cellular damage under UV stress), but the influence of NPs on recA expression was not statistically evident. Plausible explanations to NP attenuation of UV stresses are: 1. TiO₂ based NPs are capable of scattering and absorbing UV light and thus create a shading effect to protect MR-1 from UV radiation; 2. more importantly, Cu-doped TiO₂ NPs can co-agglomerate with MR-1 to form large flocs that improves cells' survival against the environmental stresses. This study improves our understanding of NP ecological impacts under natural solar radiation and provides useful insights to application of photocatalytic-NPs for bacterial disinfection.     

Chemical compositions and source identification of PM₂.₅ aerosols for estimation of a diesel source surrogate

Exposure to traffic-related pollution during childhood has been associated with asthma exacerbation, and asthma incidence. The objective of the Cincinnati Childhood Allergy and Air Pollution Study (CCAAPS) is to determine if the development of allergic and respiratory disease is associated with exposure to diesel engine exhaust particles. A detailed receptor model analyses was undertaken by applying positive matrix factorization (PMF) and UNMIX receptor models to two PM_2.5 data sets: one consisting of two carbon fractions and the other of eight temperature-resolved carbon fractions. Based on the source profiles resolved from the analyses, markers of traffic-related air pollution were estimated: the elemental carbon attributed to traffic (ECAT) and elemental carbon attributed to diesel vehicle emission (ECAD).Application of UNMIX to the two data sets generated four source factors: combustion related sulfate, traffic, metal processing and soil/crustal. The PMF application generated six source factors derived from analyzing two carbon fractions and seven factors from temperature-resolved eight carbon fractions. The source factors (with source contribution estimates by mass concentrations in parentheses) are: combustion sulfate (46.8%), vegetative burning (15.8%), secondary sulfate (12.9%), diesel vehicle emission (10.9%), metal processing (7.5%), gasoline vehicle emission (5.6%) and soil/crustal (0.7%). Diesel and gasoline vehicle emission sources were separated using eight temperature-resolved organic and elemental carbon fractions. Application of PMF to both datasets also differentiated the sulfate rich source from the vegetative burning source, which are combined in a single factor by UNMIX modeling. Calculated ECAT and ECAD values at different locations indicated that traffic source impacts depend on factors such as traffic volumes, meteorological parameters, and the mode of vehicle operation apart from the proximity of the sites to highways. The difference in ECAT and ECAD, however, was less than one standard deviation. Thus, a cost benefit consideration should be used when deciding on the benefits of an eight or two carbon approach.     

Mechanical,thermal and dynamic‐mechanical behavior of banana fiber reinforced polypropylene nanocomposites

Natural fiber‐reinforced nanocomposites based on polypropylene/nanoclay/banana fibers were fabricated by melt mixing in a twin‐screw extruder followed by compression molding in this current study. Maleic anhydride polypropylene copolymer (MA‐g‐PP) was used as a compatibilizer to increase the compatibility between the PP matrix, clay, and banana fiber to enhance exfoliation of organoclay and dispersion of fibers into the polymer matrix. Variation in mechanical, thermal, and physico‐mechanical properties with the addition of banana fiber into the PP nanocomposites was investigated. It was observed that 3 wt% of nanoclay and 5 wt% of MA‐g‐PP within PP matrix resulted in an increase in tensile and flexural strength by 41.3% and 45.6% as compared with virgin PP. Further, incorporation of 30 wt% banana fiber in PP nanocomposites system increases the tensile and flexural strength to the tune of 27.1% and 15.8%, respectively. The morphology of fiber reinforced PP nanocomposites has been examined by using scanning electron microscopy and transmission electron microscopy. Significant enhancement in the thermal stability of nanocomposites was also observed due to the presence of nanoclay under thermogravimetric analysis. Dynamic mechanical analysis tests revealed an increase in storage modulus (E′) and damping factor (tan δ), conforming the strong interaction between nanoclay/banana fiberand MA‐g‐PP in the fiber‐reinforced nanocomposites systems. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Effect of silane treated fly ash on physico-mechanical,morphological, and thermal properties of recycled poly(vinyl chloride) composites

The silane treatment on properties of fly ash (FA) and development of its composite using recycled poly(vinyl chloride) (r-PVC) material retrieve from waste wires and cable insulation are investigated in this work. The use of (3-aminopropyl)triethoxysilane was employed as a coupling agent with some other essential additives. The composites sheet was prepared by means of the melt mixing process and go along with the compression molding process. The superior properties on compatibility between silane-modified FA (FA(Si)) and r-PVC were successfully studied using rheological, thermomechanical, morphological, and water absorption analysis. Primary analysis of r-PVC and FA was employed using Fourier transform infrared spectroscopy analysis. The thermal stability of composites was stable up to 187°C. In addition, significant enhancement on tensile strength as well as young's modulus of composite as compared to untreated r-PVC/FA composites. Morphological properties of silane treated FA based composites presented the good distribution and excellent uniformity with higher wettability of FA particles within r-PVC matrix. The water absorption test showed decrease in water absorption with increase silane treatment concentration FA in the r-PVC matrix. It was remarkable to note that silane treated FA can be prepared as a composite using r-PVC matrix with further modified properties.