The effectiveness of an intervention in reducing risk of dioxin exposure in Da Nang : changes in community knowledge, attitudes and prevention practices after 2.5 years

Introduction Environmental and biological samples taken around Da Nang Air Base have shown elevated levels of dioxin over many years [1-3]. A pre-intervention knowledge, attitudes and practices (KAP) survey (2009), a risk reduction program (2010) and a post intervention KAP survey (2011) were undertaken in four wards surrounding Danang Airbase. A follow-up evaluation was undertaken in 2013. Methods A KAP survey was implemented among 400 randomly selected food handlers. Eleven indepth interviews and four focus group discussions were also undertaken. Results The knowledge of respondents remained positive and/or improved at 2.5 years follow-up. There were no significant differences in attitudes toward preventing dioxin exposure across surveys; most respondents were positive in all three surveys. An increase in households (69.5%) undertaking measures to prevent exposure was observed, which was higher than in the pre-intervention survey (39.6%) and post- intervention survey (60.4%) (χ2 = 95.6; p < 0.001). The proportion of respondents practicing appropriate preventive measures was also significantly improved. Conclusions Despite most of the intervention program’s activities ceasing in 2010, the risk reduction program has resulted in positive outcomes over the longer-term, with many knowledge and attitude measures remaining stable or imporving. Some KAP indicators decreased, but these KAP indicators were still significantly higher than the pre-intervention levels.

ortho-Bromo(propa-1,2-dien-1-yl)arenes : substrates for domino reactions

o-Bromo(propa-1,2-dien-1-yl)arenes exhibit novel and orthogonal reactivity under Pd catalysis in the presence of secondary amines to form enamines (concerted Pd insertion, intramolecular carbopalladation, and terminative Buchwald–Hartwig coupling) and of amides to form indoles (addition, Buchwald–Hartwig cyclization, and loss of the acetyl group). The substrates for these reactions can be accessed in a reliable and highly selective two-step process from 2-bromoaryl bromides.

On the importance of an acid additive in the synthesis of pyrido[1,2-a]benzimidazoles by direct copper-catalyzed amination

Pyrido[1,2-a]benzimidazoles1, 2a are interesting compounds both from the viewpoint of medicinal chemistry2–7 (solubility,7 DNA intercalation3) and materials chemistry8 (fluorescence). Of note among the former is the antibiotic drug Rifaximin,5 which contains this heteroaromatic core. The classical synthetic approach for the assembly of pyrido[1,2-a]benzimidazoles is by [3+3] cyclocondensation of benzimidazoles containing a methylene group at C2 with appropriate bielectrophiles.2a However, these procedures are often low-yielding, involve indirect/lengthy sequences, and/or provide access to a limited range of products, primarily providing derivatives with substituents located on the pyridine ring (A ring, Scheme 1).2–4 Theoretically, a good alternative synthetic method for the synthesis of pyrido[1,2-a]benzimidazoles with substituents in the benzene ring (C ring) should be accessible by intramolecular transition-metal-catalyzed CN bond formation in N-(2-chloroaryl)pyridin-2-amines, based on chemistry recently developed in our research group.9 These substrates themselves are easily available through SNAr or selective Pd-catalyzed amination10 of 2-chloropyridine with 2-chloroanilines.11 If a synthetic procedure that eliminated the need for preactivation of the 2-position of the 2-chloroarylamino entity could be developed, this would be even more powerful, as anilines are more readily commercially available than 2-chloroanilines. Therefore the synthesis of pyrido[1,2-a]benzimidazoles (4) by a transition-metal-catalyzed intramolecular CH amination approach from N-arylpyridin-2-amines (3) was explored (Scheme 1).

Vibrational spectroscopy of the copper (II) disodium sulphate dihydrate mineral kröhnkite Na2Cu(SO4)2 · 2H2O

A natural single-crystal specimen of the kröhnkite from Chuquicamata, Chile, with the general formula Na2Cu(SO4)2 · 2H2O, was investigated by Raman and infrared spectroscopy. The mineral kröhnkite is found in many parts of the world's arid areas. Kröhnkite crystallizes in the monoclinic crystal system with point group 2/m and space group P21/c. It is an uncommon secondary mineral formed in the oxidized zone of copper deposits, typically in very arid climates. The Raman spectrum of kröhnkite dominated by a very sharp intense band at 992 cm−1 is assigned to the ν1 symmetric stretching mode and Raman bands at 1046, 1049, 1138, 1164, and 1177 cm−1 are assigned to the ν3 antisymmetric stretching vibrations. The infrared spectrum shows an intense band at 992 cm−1. The Raman bands at 569, 582, 612, 634, 642, 655, and 660 cm−1 are assigned to the ν4 bending modes. Three Raman bands observed at 429, 445, and 463 cm−1 are attributed to the ν2 bending modes. The observation that three or four bands are seen in the ν4 region of kröhnkite is attributed to the reduction of symmetry to C2v or less.

Protecting web 2.0 services from botnet exploitations

Recently, botnet, a network of compromised computers, has been recognized as the biggest threat to the Internet. The bots in a botnet communicate with the botnet owner via a communication channel called Command and Control (C & C) channel. There are three main C & C channels: Internet Relay Chat (IRC), Peer-to-Peer (P2P) and web-based protocols. By exploiting the flexibility of the Web 2.0 technology, the web-based botnet has reached a new level of sophistication. In August 2009, such botnet was found on Twitter, one of the most popular Web 2.0 services. In this paper, we will describe a new type of botnet that uses Web 2.0 service as a C & C channel and a temporary storage for their stolen information. We will then propose a novel approach to thwart this type of attack. Our method applies a unique identifier of the computer, an encryption algorithm with session keys and a CAPTCHA verification.

Enhancement of 1,2-dehydration of alcohols by alkali cations and protons : a model for dehydration of carbohydrates

We have used electronic structure calculations to investigate the 1,2-dehydration of alcohols as a model for water loss during the pyrolysis of carbohydrates found in biomass. Reaction enthalpies and energy barriers have been calculated for neat alcohols, protonated alcohols and alcohols complexed to alkali metal ions (Li + and Na +). We have estimated pre-exponential A factors in order to obtain gas phase rate constants. For neat alcohols, the barrier to 1,2-dehydration is about 67 kcal mol -1, which is consistent with the limited experimental data. Protonation and metal complexation significantly reduce this activation barrier and thus, facilitate more rapid reaction. With the addition of alkali metals, the rate of dehydration can increase by a factor of 10 8 while addition of a proton can lead to an increase of a factor of 10 23.

Unusual cross-ring S(N)2 reactions of M-H (-) ions of methoxyacetanilides

Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a 'cross-ring' internal S(N)2 reaction involving an incipient methyl anion. For example, p-CH3O-C6H4-N--CO-CH3--> [(p.CH3O-C6H4-N=C=O)CH3-]--> O---C6H4-N=C=O+C2H6.

Fragmentation pathways of 2,3-dimethyl-2,3-dinitrobutane cations in the gas phase

2,3-Dimethyl-2,3-dinitrobutane (DMNB) is an explosive taggant added to plastic explosives during manufacture making them more susceptible to vapour-phase detection systems. In this study, the formation and detection of gas-phase \[M+H](+), \[M+Li](+), \[M+NH(4)](+) and \[M+Na](+) adducts of DMNB was achieved using electrospray ionisation on a triple quadrupole mass spectrometer. The \[M+H](+) ion abundance was found to have a strong dependence on ion source temperature, decreasing markedly at source temperatures above 50 degrees C. In contrast, the \[M+Na](+) ion demonstrated increasing ion abundance at source temperatures up to 105 degrees C. The relative susceptibility of DMNB adduct ions toward dissociation was investigated by collision-induced dissociation. Probable structures of product ions and mechanisms for unimolecular dissociation have been inferred based on fragmentation patterns from tandem mass (MS/MS) spectra of source-formed ions of normal and isotopically labelled DMNB, and quantum chemical calculations. Both thermal and collisional activation studies suggest that the \[M+Na](+) adduct ions are significantly more stable toward dissociation than their protonated analogues and, as a consequence, the former provide attractive targets for detection by contemporary rapid screening methods such as desorption electrospray ionisation mass spectrometry. Copyright (C) 2009 Commonwealth of Australia. Published by John Wiley & Sons, Ltd.

A detailed investigation of nominally 2-D radical-farming scramjet combustion

This paper reports on an investigation of the flow/chemistry coupling inside a nominally two-dimensional inlet-fuelled scramjet configuration. The experiments were conducted at a freestream Mach number of 7.3 and a total flow enthalpy of 4.3MJ/kg corresponding to a Mach 9.7 flight condition. The phenomenon of radical-farming has been studied in detail using two-dimensional OH* chemiluminescence imaging and emission spectroscopy. High signal levels of excited OH (OH*) were detected behind the first shock reflections inside the combustion chamber upstream of any measurable pressure rise from combustion, which occurred towards the rear of the combustor. The production of OH in the first hot pocket initiates the ignition process and then accelerates the combustion process in the next downstream hot pocket. This was confirmed by numerical simulations of premixed hydrogen/air flow through the scramjet. Chemical kinetics analyses reveal that the ignition process is governed by the interaction between various reaction groups leading to a chainbranching explosion for low mean temperature and pressure combustion flowfields.

Breaking time-inversion invariance through decoherence : energetic consequences for attosecond neutron scattering

Nuclei and electrons in condensed matter and/or molecules are usually entangled, due to the prevailing (mainly electromagnetic) interactions. However, the "environment" of a microscopic scattering system (e.g. a proton) causes ultrafast decoherence, thus making atomic and/or nuclear entanglement e®ects not directly accessible to experiments. However, our neutron Compton scattering experiments from protons (H-atoms) in condensed systems and molecules have a characteristic collisional time about 100|1000 attoseconds. The quantum dynamics of an atom in this ultrashort, but ¯nite, time window is governed by non-unitary time evolution due to the aforementioned decoherence. Unexpectedly, recent theoretical investigations have shown that decoherence can also have the following energetic consequences. Disentangling two subsystems A and B of a quantum system AB is tantamount to erasure of quantum phase relations between A and B. This erasure is widely believed to be an innocuous process, which e.g. does not a®ect the energies of A and B. However, two independent groups proved recently that disentangling two systems, within a su±ciently short time interval, causes increase of their energies. This is also derivable by the simplest Lindblad-type master equation of one particle being subject to pure decoherence. Our neutron-proton scattering experiments with H2 molecules provide for the first time experimental evidence of this e®ect. Our results reveal that the neutron-proton collision, leading to the cleavage of the H-H bond in the attosecond timescale, is accompanied by larger energy transfer (by about 2|3%) than conventional theory predicts. Preliminary results from current investigations show qualitatively the same e®ect in the neutron-deuteron Compton scattering from D2 molecules. We interpret the experimental findings by treating the neutron-proton (or neutron-deuteron) collisional system as an entangled open quantum system being subject to fast decoherence caused by its "environment" (i.e., two electrons plus second nucleus of H2 or D2). The presented results seem to be of generic nature, and may have considerable consequences for various processes in condensed matter and molecules, e.g. in elementary chemical reactions.

High pressure in situ diffraction studies of metal–hydrogen systems

“Hybrid” hydrogen storage, where hydrogen is stored in both the solid material and as a high pressure gas in the void volume of the tank can improve overall system efficiency by up to 50% compared to either compressed hydrogen or solid materials alone. Thermodynamically, high equilibrium hydrogen pressures in metal–hydrogen systems correspond to low enthalpies of hydrogen absorption–desorption. This decreases the calorimetric effects of the hydride formation–decomposition processes which can assist in achieving high rates of heat exchange during hydrogen loading—removing the bottleneck in achieving low charging times and improving overall hydrogen storage efficiency of large hydrogen stores. Two systems with hydrogenation enthalpies close to −20 kJ/mol H2 were studied to investigate the hydrogenation mechanism and kinetics: CeNi5–D2 and ZrFe2−xAlx (x = 0.02; 0.04; 0.20)–D2. The structure of the intermetallics and their hydrides were studied by in situ neutron powder diffraction at pressures up to 1000 bar and complementary X-ray diffraction. The deuteration of the hexagonal CeNi5 intermetallic resulted in CeNi5D6.3 with a volume expansion of 30.1%. Deuterium absorption filled three different types of interstices, Ce2Ni2 and Ni4 tetrahedra, and Ce2Ni3 half-octahedra and was accompanied by a valence change for Ce. Significant hysteresis was observed between deuterium absorption and desorption which profoundly decreased on a second absorption cycle. For the Al-modified Laves-type C15 ZrFe2−xAlx intermetallics, deuteration showed very fast kinetics of H/D exchange and resulted in a volume increase of the FCC unit cells of 23.5% for ZrFe1.98Al0.02D2.9(1). Deuterium content, hysteresis of H/D uptake and release, unit cell expansion and stability of the hydrides systematically change with the amount of Al content. In the deuteride D atoms exclusively occupy the Zr2(Fe,Al)2 tetrahedra. Observed interatomic distances are Zr–D = 1.98–2.11; (Fe, Al)–D = 1.70–1.75A˚ . Hydrogenation slightly increases the magnetic moment of the Fe atoms in ZrFe1.98Al0.02 and ZrFe1.96Al0.04 from 1.9 �B at room temperature for the alloy to 2.2 �B for its deuteride.

Nanostructured metal hydrides for hydrogen storage studied by in situ synchrotron and neutron diffraction

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C. The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content. Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra. For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling. A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides. The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

Mechanochemical synthesis of aluminium nanoparticles and their deuterium sorption properties to 2 kbar

A mechanochemical synthesis process has been used to synthesise aluminium nanoparticles. The aluminium is synthesised via a solid state chemical reaction which is initiated inside a ball mill at room temperature between either lithium (Li) or sodium (Na) metal which act as reducing agents with unreduced aluminium chloride (AlCl3). The reaction product formed consists of aluminium nanoparticles embedded within a by-product salt phase (LiCl or NaCl, respectively). The LiCl is washed with a suitable solvent resulting in aluminium (Al) nanoparticles which are not oxidised and are separated from the byproduct phase. Synthesis and washing was confirmed using X-ray diffraction (XRD). Nanoparticles were found to be ∼25–100nm from transmission electron microscopy (TEM) and an average size of 55nm was determined fromsmall angle X-ray scattering (SAXS) measurements. As synthesised Al/NaCl composites, washed Al nanoparticles, and purchased Al nanoparticles were deuterium (D2) absorption tested up to 2 kbar at a variety of temperatures, with no absorption detected within system resolution.

Generation and characterization of ionic and neutral dihydroxy boron B(OH)(2)(+/0) in the gas phase

The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.