Optimization of Lithium Content and Sintering Aid for Maximized Li+ Conductivity and Density in Ta‐Doped Li7La3Zr2O12

Ta‐doped cubic phase Li₇La₃Zr₂O₁₂ (LLZ) lithium garnet received considerable attention in recent times as prospective electrolyte for all‐solid‐state lithium battery. Although the conductivity has been improved by stabilizing the cubic phase with the Ta⁵⁺ doping for Zr⁴⁺ in LLZ, the density of the pellet was found to be relatively poor with large amount of pores. In addition to the high Li⁺ conductivity, density is also an essential parameter for the successful application of LLZ as solid electrolyte membrane in all‐solid‐state lithium battery. Systematic investigations carried out through this work indicated that the optimal Li concentration of 6.4 (i.e., Li_6.4La₃Zr_1.4Ta_0.6O₁₂) is required to obtain phase pure, relatively dense and high Li⁺ conductive cubic phase in Li_7?xLa₃Zr_2?xTa_xO₁₂ solid solutions. Effort has been also made in this work to enhance the density and Li⁺ conductivity of Li_6.4La₃Zr_1.4Ta_0.6O₁₂ further through the Li₄SiO₄ addition. A maximized room‐temperature (33°C) total (bulk + grain boundary) Li⁺ conductivity of 3.7 × 10^?4 S/cm and maximized relative density of 94% was observed for Li_6.4La₃Zr_1.4Ta_0.6O₁₂ added with 1 wt% of Li₄SiO₄.     

Analysing green supply chain management practices in Brazil’s electrical/electronics industry using interpretive structural modelling

Industries need to adopt the environmental management concepts in the traditional supply chain management. The green supply chain management (GSCM) is an established concept to ensure environment-friendly activities in industry. This paper identifies the relationship of driving and dependence that exists between GSCM practices with regard to their adoption within Brazilian electrical/electronic industry with the help of interpretive structural modelling (ISM). From the results, we infer that cooperation with customers for eco-design practice is driving other practices, and this practice acts as a vital role among other practices. Commitment to GSCM from senior managers and cooperation with customers for cleaner production occupy the highest level.     

Nitroarenes as Antitubercular Agents: Stereoelectronic Modulation to Mitigate Mutagenicity

Nitroarenes are less preferred in drug discovery due to their potential to be mutagenic. However, several nitroarenes were shown to be promising antitubercular agents with specific modes of action, namely, nitroimidazoles and benzothiazinones. The nitro group in these compounds is activated through different mechanisms, both enzymatic and non‐enzymatic, in mycobacteria prior to binding to the target of interest. From a whole‐cell screening program, we identified a novel lead nitrobenzothiazole (BT) series that acts by inhibition of decaprenylphosphoryl‐β‐d ‐ribose 2′‐epimerase (DprE1) of Mycobacterium tuberculosis (Mtb). The lead was found to be mutagenic to start with. Our efforts to mitigate mutagenicity resulted in the identification of 6‐methyl‐7‐nitro‐5‐(trifluoromethyl)‐1,3‐benzothiazoles (cBTs), a novel class of antitubercular agents that are non‐mutagenic and exhibit an improved safety profile. The methyl group ortho to the nitro group decreases the electron affinity of the series, and is hence responsible for the non‐mutagenic nature of these compounds. Additionally, the co‐crystal structure of cBT in complex with Mtb DprE1 established the mode of binding. This investigation led to a new non‐mutagenic antitubercular agent and demonstrates that the mutagenic nature of nitroarenes can be solved by modulation of stereoelectronic properties.     

Synthesis of PEO-based di-block glycopolymers at various pendant spacer lengths of glucose moiety and their in-vitro biocompatibility with MC3T3 osteoblast cells

Di-block copolymers of poly(ethylene oxide) (PEO) and glycopolymers at three different pendant spacer lengths of glucose moiety were synthesized by deacetylation of pendant moieties of 2,3,4,6-tetra-O-acetyl-d-glucopyranosides which were prepared by reversible addition-fragmentation chain-transfer (RAFT) process. The water soluble deacetylated copolymers, PEO-b-poly(acryl-d-glucopyranoside) (PEO-b-PAG, 2a), PEO-b-poly[4′-(acryloxy)butyl-d-glucopyranoside] (PEO-b-PABG, 2b), and PEO-b-poly[6′-(acryloxy)hexyl-d-glucopyranoside] (PEO-b-PAHG, 2c) were characterized in comparison with acetylated copolymers by spectroscopic and gel permeation chromatography methods. In order to assess the biocompatibility of these three di-block copolymers, the adhesion (%), viability (%), and proliferation assays were carried out in MC3T3 cells in-vitro at different concentrations from 10 nM to 1000 μM. Qualitative analysis of cell cytoskeletal organization was obtained by immunostaining with talin and integrin α5. It was clearly indicative of well spreading of cells in the presence of all glycopolymers at lower concentrations but with an increase in the concentration (10 and 100 μM) showed significant change in the cell surface morphologies, despite having good cell adhesion and viability as compared to the control conditions. The use of di-block glycolpolymers at?≤?100 μM of the concentration showed very good osteoblast cells adhesion and viability response; however at higher concentrations (1000 μM) of glycopolymers > 80% of cells lost their viability.     

Entropy of Alloy Phases: A Macroscopic Perspective

This study presents a comprehensive analysis of the entropy of condensed phases, its temperature, pressure, and composition dependence on a macroscopic correlative platform. Two principal contributions to total nonconfiguration entropy (S_T) are outlined. They are: (i) the pure thermal (S_th) contribution arising from the isochoric temperature dependence of Gibbs energy (G_T) and (ii) the elastic contribution (S_el) representing the dilatational volume effects. It is then argued that entropy variation among a group of alloy phases can be exclusively related to molar volume, only when both thermal pressure (p_th) and thermal entropy terms assume common values for all members. This argument is extended to establish a linear relationship between transformation entropy (ΔS_tr) and transformation-induced volumetric strain (ΔV_tr/V). The temperature and pressure dependencies of entropy have been discussed in terms of the complementing roles of S_th and S_el and simple approximations to these effects are suggested. A macroscopic power law relation for systematizing the standard entropy variation using a composite scaling parameter (MV^2/3/T_m) has been proposed, and its validity is demonstrated for both solid and liquid metals. This power law correlation has been exploited to deduce the following outcome: (i) a simple approximation for the initial slope (dp/dT_m) of p–T_m melting curve, (ii) self-consistent correlation of entropy with specific heat and Debye temperature, (iii) estimation of entropy of metastable phases, and (iv) correlating dilute solution entropy with volume effects of alloying.

     

Studies on photo-crosslinkable polyphosphoramide esters containing divanillylidene cycloalkanone units

Two series of photo-crosslinkable polyphosphoramide esters were synthesized from 2,5-bis(4-hydroxy-3-methoxy benzylidene)cyclopentanone and 2,6-bis(4-hydroxy-3-methoxy benzylidene)cyclohexanone with various N-arylphosphoramide dichlorides by interfacial polycondensation using hexadecyl trimethylammonium bromide as phase transfer catalyst at ambient temperature. The resulting polymers were characterized by inherent viscosity, Fourier transform infra-red, ¹H and ¹³C nuclear magnetic resonance spectroscopy. The thermal stability of the polymers synthesized was evaluated by thermogravimetric analysis. These polymers were studied for their photo-chemical reactions. The divanillylidene cycloakanone groups in the polymer chain function as photo-active centres. Crosslinking proceeds via 2π + 2π cycloaddition reaction of the divanillylidene cycloalkanone moieties. The rate of crosslinking decreases with increase in the size of the cycloalkanone ring, while the thermal stability increases with increase in the size of the cycloalkanone ring.     

Self-Assembly and Neurotoxicity of β-Amyloid (21–40) Peptide Fragment: The Regulatory Role of GxxxG Motifs

The three GxxxG repeating motifs from the C-terminal region of β-amyloid (Aβ) peptide play a significant role in regulating the aggregation kinetics of the peptide. Mutation of these glycine residues to leucine greatly accelerates the fibrillation process but generates a varied toxicity profile. Using an array of biophysical techniques, we demonstrated the uniqueness of the composite glycine residues in these structural repeats. We used solvent relaxation NMR spectroscopy to investigate the role played by the surrounding water molecules in determining the corresponding aggregation pathway. Notably, the conformational changes induced by Gly³³ and Gly³⁷ mutations result in significantly decreased toxicity in a neuronal cell line. Our results indicate that G³³xxxG³⁷ is the primary motif responsible for Aβ neurotoxicity, hence providing a direct structure–function correlation. Targeting this motif, therefore, can be a promising strategy to prevent neuronal cell death associated with Alzheimer's and other related diseases, such as type II diabetes and Parkinson's.     

Open dumping site in Asian developing countries: a potential source of polychlorinated dibenz-p-dioxins and polychlorinated dibenzofurans

Open landfill dumping areas for municipal wastes in Asian developing countries have recently received particular attention with regard to environmental pollution problems. Because of the uncontrolled burning of solid wastes, elevated contamination by various toxic chemicals including dioxins and related compounds in these dumping sites has been anticipated. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (PCBs) were determined in soils from dumping sites in the Philippines, Cambodia, India, and Vietnam. Residue concentrations of PCDD/Fs and coplanar PCBs in dumping site soils were apparently greater than those in soils collected in agricultural or urban areas far from dumping sites, suggesting that dumping sites are potential sources of PCDD/Fs and related compounds. Observed PCDD/F concentrations in soils from dumping sites in the Philippines and Cambodia were comparable or higher than those reported for dioxin-contaminated locations in the world (e.g., near the municipal waste incinerators and open landfill dumping sites). Homologue profiles of PCDD/Fs in dumping site soils from the Philippines and, to a lesser extent, from Cambodia and India reflected patterns of samples representing typical emissions, while profiles of agricultural or urban soils were similar to those of typical environmental sinks. This result suggests recent formation of PCDD/Fs in dumping site areas and that open dumping sites are a potential source of dioxins in Asian developing countries. Uncontrolled combustions of solid wastes by waste pickers, generation of methane gas, and low-temperature burning can be major factors for the formation of dioxins in dumping sites. Elevated fluxes of PCDD/Fs to soils in dumping sites were encountered in the Philippines, Cambodia, India, and Vietnam-Hanoi, and these levels were higher than those reported for other countries. Considerable loading rates of PCDD/Fs in the dumping sites of these countries were observed, ranging from 20 to 3900 mg/yr (0.12-35 mg TEQ/yr). PCDD/F concentrations in some soil samples from the Philippines, Cambodia, India, and Vietnam-Hanoi exceeded environmental guideline values, suggesting potential health effects on humans and wildlife living near these dumping sites. The estimated intakes of dioxins via soil ingestion and dermal exposure for children were higher than those for adults, suggesting greater risk of dioxin exposure for children in dumping sites. To our knowledge, this is the first comprehensive study on PCDD/Fs contamination in open dumping sites of Asian developing countries. On the basis of the result of this study, we have addressed a new environmental issue that open dumping sites are potential sources of PCDD/Fs and related compounds, and dioxin contamination in dumping sites may become a key environmental problem in developing countries.     

Comparative assessment of human exposure to phthalate esters from house dust in China and the United States

Because of volatilization and leaching from their application in consumer and personal care products, phthalate esters are ubiquitous contaminants in the indoor environment. In this study, we measured concentrations and profiles of 9 phthalate esters in indoor dust samples collected from six cities in China (n = 75). For comparison, we also analyzed samples collected from Albany, New York, USA (n = 33). The results indicated that concentrations, except for dicyclohexyl phthalate (DCHP) and bis(2-ethylhexyl) phthalate (DEHP), and profiles of phthalate esters varied significantly between the two countries. Concentrations of diethyl phthalate (DEP), di-n-hexyl phthalate (DNHP), and benzyl butyl phthalate (BzBP) were 5 to 10 times higher in dust samples collected from Albany than those from the Chinese cities. In contrast, concentrations of di-iso-butyl phthalate (DIBP) in dust samples from Albany were 5 times lower than those from the Chinese cities. We estimated the daily intake (DI) of phthalate esters through the routes of dust ingestion and dermal dust absorption. The extent of contribution of indoor dust to human exposures varied, depending on the type of phthalate esters. The contribution of dust to DEHP exposure was 2-5% and 10-58% of the estimated total DIs in China and the USA, respectively. On the basis of the estimates of total DIs of phthalates, extrapolated from urinary metabolite concentrations, the contributions of inhalation, dermal absorption, and dietary intake to total DIs were estimated. The results indicated that dietary intake is the main source of exposure to DEHP (especially in China), whereas dermal exposure was a major source for DEP. This is the first study to elucidate sources of human exposure to phthalates among the general population in China.