Strain engineering of selective chemical adsorption on monolayer MoS2

Nanomaterials are prone to influence by chemical adsorption because of their large surface to volume ratios. This enables sensitive detection of adsorbed chemical species which, in turn, can tune the property of the host material. Recent studies discovered that single and multi-layer molybdenum disulfide (MoS2) films are ultra-sensitive to several important environmental molecules. Here we report new findings from ab inito calculations that reveal substantially enhanced adsorption of NO and NH3 on strained monolayer MoS2 with significant impact on the properties of the adsorbates and the MoS2 layer. The magnetic moment of adsorbed NO can be tuned between 0 and 1 μB; strain also induces an electronic phase transition between half-metal and metal. Adsorption of NH3 weakens the MoS2 layer considerably, which explains the large discrepancy between the experimentally measured strength and breaking strain of MoS2 films and previous theoretical predictions. On the other hand, adsorption of NO2, CO, and CO2 is insensitive to the strain condition in the MoS2 layer. This contrasting behavior allows sensitive strain engineering of selective chemical adsorption on MoS2 with effective tuning of mechanical, electronic, and magnetic properties. These results suggest new design strategies for constructing MoS2-based ultrahigh-sensitivity nanoscale sensors and electromechanical devices.

Toxic state–corporate crimes, Neo-liberalism and green criminology : the hazards and legacies of the oil, chemical and mineral industries

This paper uses examples from the history and practices of multi-national and large companies in the oil, chemical and asbestos industries to examine their legal and illegal despoiling and destruction of the environment and impact on human and non-human life. The discussion draws on the literature on green criminology and state-corporate crime and considers measures and arrangements that might mitigate or prevent such damaging acts. This paper is part of ongoing work on green criminology and crimes of the economy. It places these actions and crimes in the context of a global neo-liberal economic system and considers and critiques the distorting impact of the GDP model of ‘economic health’ and its consequences for the environment.

Estimation of biodiesel properties from chemical composition – An artificial neural network (ANN) approach

Biodiesel, produced from renewable feedstock represents a more sustainable source of energy and will therefore play a significant role in providing the energy requirements for transportation in the near future. Chemically, all biodiesels are fatty acid methyl esters (FAME), produced from raw vegetable oil and animal fat. However, clear differences in chemical structure are apparent from one feedstock to the next in terms of chain length, degree of unsaturation, number of double bonds and double bond configuration-which all determine the fuel properties of biodiesel. In this study, prediction models were developed to estimate kinematic viscosity of biodiesel using an Artificial Neural Network (ANN) modelling technique. While developing the model, 27 parameters based on chemical composition commonly found in biodiesel were used as the input variables and kinematic viscosity of biodiesel was used as output variable. Necessary data to develop and simulate the network were collected from more than 120 published peer reviewed papers. The Neural Networks Toolbox of MatLab R2012a software was used to train, validate and simulate the ANN model on a personal computer. The network architecture and learning algorithm were optimised following a trial and error method to obtain the best prediction of the kinematic viscosity. The predictive performance of the model was determined by calculating the coefficient of determination (R2), root mean squared (RMS) and maximum average error percentage (MAEP) between predicted and experimental results. This study found high predictive accuracy of the ANN in predicting fuel properties of biodiesel and has demonstrated the ability of the ANN model to find a meaningful relationship between biodiesel chemical composition and fuel properties. Therefore the model developed in this study can be a useful tool to accurately predict biodiesel fuel properties instead of undertaking costly and time consuming experimental tests.

Development route of the wind power industry in China

Wind power is one of the world's major renewable energy sources, and its utilization provides an important contribution in helping solve the energy problems of many countries. After nearly 40 years of development, China's wind power industry now not only manufactures its own massive six MW turbines but also has the largest capacity in the world with a national output of 50 million MW•h in 2010 and set to rise by eight times of that amount by 2020. This paper investigates this development route by analyzing relevant academic literature, statistics, laws and regulations, policies and research and industry reports. The main drivers of the development in the industry are identified as technologies, turbines, wind farm construction, pricing mechanism and government support systems, each of which is also divided into different stages with distinctive features. A systematic review of these aspects provides academics and practitioners with a better understanding of the history of the wind power industry in China and reasons for its rapid development with a view to enhancing progress in wind power development both in China and the world generally.

The acetal concept : regioselective access toortho,ortho-diphenols via dibenzo-1,3-dioxepines

Traditional methods are ill-suited for the synthesis of ortho,ortho-biphenols, a structural motif found in many polyphenolic natural products, as well as synthetically useful compounds such as the chiral ligands binol, vapol, and vanol. The new route consists of a radical-based reaction of an acetal-tethered biphenyl ether substrate and subsequent hydrolytic cleavage of the dibenzo-1,3-dioxepine intermediate.

The fragmentation pathways of protonated Amiton in the gas phase : towards the structural characterisation of organophosphorus chemical warfare agents by electrospray ionisation tandem mass spectrometry

Amiton (O,O-diethyl-S-[2-(diethylamino)ethyl]phosphorothiolate), otherwise known as VG, is listed in schedule 2 of the Chemical Weapons Convention (CWC) and has a structure closely related to VX (O-ethyl-S-(2-diisopropylamino)ethylmethylphosphonothiolate). Fragmentation of protonated VG in the gas phase was performed using electrospray ionisation ion trap mass spectrometry (ESI-ITMS) and revealed several characteristic product ions. Quantum chemical calculations provide the most probable structures for these ions as well as the likely unimolecular mechanisms by which they are formed. The decomposition pathways predicted by computation are consistent with deuterium-labeling studies. The combination of experimental and theoretical data suggests that the fragmentation pathways of VG and analogous organophosphorus nerve agents, such as VX and Russian VX, are predictable and thus ESI tandem mass spectrometry is a powerful tool for the verification of unknown compounds listed in the CWC. Copyright (c) 2006 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

A novel route in bone tissue engineering : magnetic biomimetic scaffolds

In recent years, interest in tissue engineering and its solutions has increased considerably. In particular, scaffolds have become fundamental tools in bone graft substitution and are used in combination with a variety of bio-agents. However, a long-standing problem in the use of these conventional scaffolds lies in the impossibility of re-loading the scaffold with the bio-agents after implantation. This work introduces the magnetic scaffold as a conceptually new solution. The magnetic scaffold is able, via magnetic driving, to attract and take up in vivo growth factors, stem cells or other bio-agents bound to magnetic particles. The authors succeeded in developing a simple and inexpensive technique able to transform standard commercial scaffolds made of hydroxyapatite and collagen in magnetic scaffolds. This innovative process involves dip-coating of the scaffolds in aqueous ferrofluids containing iron oxide nanoparticles coated with various biopolymers. After dip-coating, the nanoparticles are integrated into the structure of the scaffolds, providing the latter with magnetization values as high as 15 emu g�1 at 10 kOe. These values are suitable for generating magnetic gradients, enabling magnetic guiding in the vicinity and inside the scaffold. The magnetic scaffolds do not suffer from any structural damage during the process, maintaining their specific porosity and shape. Moreover, they do not release magnetic particles under a constant flow of simulated body fluids over a period of 8 days. Finally, preliminary studies indicate the ability of the magnetic scaffolds to support adhesion and proliferation of human bone marrow stem cells in vitro. Hence, this new type of scaffold is a valuable candidate for tissue engineering applications, featuring a novel magnetic guiding option.

A rapid transcriptional activation is induced by the dormancy-breaking chemical hydrogen cyanamide in kiwifruit (Actinidia deliciosa) buds

Budbreak in kiwifruit (Actinidia deliciosa) can be poor in locations that have warm winters with insufficient winter chilling. Kiwifruit vines are often treated with the dormancy-breaking chemical hydrogen cyanamide (HC) to increase and synchronize budbreak. This treatment also offers a tool to understand the processes involved in budbreak. A genomics approach is presented here to increase our understanding of budbreak in kiwifruit. Most genes identified following HC application appear to be associated with responses to stress, but a number of genes appear to be associated with the reactivation of growth. Three patterns of gene expression were identified: Profile 1, an HC-induced transient activation; Profile 2, an HC-induced transient activation followed by a growth-related activation; and Profile 3, HC- and growth-repressed. One group of genes that was rapidly up-regulated in response to HC was the glutathione S-transferase (GST) class of genes, which have been associated with stress and signalling. Previous budbreak studies, in three other species, also report up-regulated GST expression. Phylogenetic analysis of these GSTs showed that they clustered into two sub-clades, suggesting a strong correlation between their expression and budbreak across species.

Impact of a change in tillage and crop residue management practice on soil chemical and microbiological properties in a cereal-producing red duplex soil in NSW, Australia

The effect of a change of tillage and crop residue management practice on the chemical and micro-biological properties of a cereal-producing red duplex soil was investigated by superimposing each of three management practices (CC: conventional cultivation, stubble burnt, crop conventionally sown; DD: direct-drilling, stubble retained, no cultivation, crop direct-drilled; SI: stubble incorporated with a single cultivation, crop conventionally sown), for a 3-year period on plots previously managed with each of the same three practices for 14 years. A change from DD to CC or SI practice resulted in a significant decline, in the top 0-5 cm of soil, in organic C, total N, electrical conductivity, NH4-N, NO3-N, soil moisture holding capacity, microbial biomass and CO2 respiration as well as a decline in the microbial quotient (the ratio of microbial biomass C to organic C; P <0.05). In contrast, a change from SI to DD or CC practice or a change from CC to DD or SI practice had only negligible impact on soil chemical properties (P >0.05). However, there was a significant increase in microbial biomass and the microbial quotient in the top 0-5 cm of soil following the change from CC to DD or SI practice and with the change from SI to DD practice (P <0.05). Analysis of ester-linked fatty acid methyl esters (EL-FAMEs) extracted from the 0- to 5-cm and 5- to 10-cm layers of the soils of the various treatments detected changes in the FAME profiles following a change in tillage practice. A change from DD practice to SI or CC practice was associated with a significant decline in the ratio of fungal to bacterial fatty acids in the 0- to 5-cm soil (P <0.05). The results show that a change in tillage practice, particularly the cultivation of a previously minimum-tilled (direct-drilled) soil, will result in significant changes in soil chemical and microbiological properties within a 3-year period. They also show that soil microbiological properties are sensitive indicators of a change in tillage practice.

Formation and electron field emission of graphene films grown by hot filament chemical vapor deposition

Graphene films with different structures were catalytically grown on the silicon substrate pre-deposited with a gold film by hot filament chemical vapor deposition under different conditions, where methane, hydrogen and nitrogen were used as the reactive gases. The morphological and compositional properties of graphene films were studied using advanced instruments including field emission scanning electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The results indicate that the structure and composition of graphene films are changed with the variation of the growth conditions. According to the theory related to thermodynamics, the formation of graphene films was theoretically analyzed and the results indicate that the formation of graphene films is related to the fast incorporation and precipitation of carbon. The electron field emission (EFE) properties of graphene films were studied in a high vacuum system of ∼10-6 Pa and the EFE results show that the turn-on field is in a range of 5.2-5.64 V μm-1 and the maximum current density is about 63 μ A cm-2 at the field of 7.7 V μm-1. These results are important to control the structure of graphene films and have the potential applications of graphene in various nanodevices.

Microplasma-chemical synthesis and tunable real-time plasmonic responses of alloyed Aux Ag1−x nanoparticles

Tunable synthesis of bimetallic AuxAg1-x alloyed nanoparticles and in situ monitoring of their plasmonic responses is presented. This is a new conceptual approach based on green and energy efficient, reactive, and highly-non-equilibrium microplasma chemistry.

Nanoherding : plasma-chemical synthesis and electric-charge-driven self organization of SiO2 nanodots

We report on the chemical synthesis of the arrays of silicon oxide nanodots and their self-organization on the surface via physical processes triggered by surface charges. The method based on chemically active oxygen plasma leads to the rearrangement of nanostructures and eventually to the formation of groups of nanodots. This behavior is explained in terms of the effect of electric field on the kinetics of surface processes. The direct measurements of the electric charges on the surface demonstrate that the charge correlates with the density and arrangement of nanodots within the array. Extensive numerical simulations support the proposed mechanism and prove a critical role of the electric charges in the self-organization. This simple and environment-friendly self-guided process could be used in the chemical synthesis of large arrays of nanodots on semiconducting surfaces for a variety of applications in catalysis, energy conversion and storage, photochemistry, environmental and biosensing, and several others.

Surface chemical modification of carbon nanowalls for wide-range control of surface wettability

Carbon nanowalls (CNWs) are self-assembled, free-standing, few-layered graphenenano-structures with large surface area, and thin graphene edges. For their application to nanobiotechnology, the effects of chemisorbed species on surface wettability were investigated. The surfaces of as-grown CNWs obtained using CH4/H2 mixture were hydrophilic. After Ar atmospheric pressure plasma treatments for up to 30 s, the contact angles of water droplets on the CNWs decreased from 51° to 5°, owing to a result of oxidation only at edges and surface defects. They increased up to 147° by CF4 plasma treatment at low pressure. The wide-range control of surface wettability of CNWs was realized by post-growth plasma treatments. We also demonstrated detection of bovine serum albumin using surface-modified CNWs as electrodes.

Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Room-temperature photoluminescence from nitrogenated carbon nanotips grown by plasma-enhanced hot filament chemical vapor deposition

Nitrogenated carbon nanotips with a low atomic concentration of nitrogen have been synthesized by using a custom-designed plasma-enhanced hot-filament plasma chemical vapor deposition system. The properties (including morphology, structure, composition, photoluminescence, etc.) of the synthesized nitrogenated carbon nanotips are investigated using advanced characterization tools. The room-temperature photoluminescence measurements show that the nitrogenated carbon nanotips can generate two distinct broad emissions located at ∼405 and ∼507 nm, respectively. Through the detailed analysis, it is shown that these two emission bands are attributed to the transition between the lone pair valence and bands, which are related to the sp3 and sp2 C-N bonds, respectively. These results are highly relevant to advanced applications of nitrogenated carbon nanotips in light emitting optoelectronic devices.