A Raman spectroscopic study of the different vanadate-groups in solid-state compounds, model case : mineral phases vésigniéite, BaCu3(VO4)2(OH)2, and volborthite, Cu3V2O7(OH)2•2H2O

Raman spectroscopy has been used to study vanadates in the solid state. The molecular structure of the vanadate minerals vésigniéite [BaCu3(VO4)2(OH)2] and volborthite [Cu3V2O7(OH)2·2H2O] have been studied by Raman spectroscopy and infrared spectroscopy. The spectra are related to the structure of the two minerals. The Raman spectrum of vésigniéite is characterized by two intense bands at 821 and 856 cm−1 assigned to ν1 (VO4)3− symmetric stretching modes. A series of infrared bands at 755, 787 and 899 cm−1 are assigned to the ν3 (VO4)3− antisymmetric stretching vibrational mode. Raman bands at 307 and 332 cm−1 and at 466 and 511 cm−1 are assigned to the ν2 and ν4 (VO4)3− bending modes. The Raman spectrum of volborthite is characterized by the strong band at 888 cm−1, assigned to the ν1 (VO3) symmetric stretching vibrations. Raman bands at 858 and 749 cm−1 are assigned to the ν3 (VO3) antisymmetric stretching vibrations; those at 814 cm−1 to the ν3 (VOV) antisymmetric vibrations; that at 508 cm−1 to the ν1 (VOV) symmetric stretching vibration and those at 442 and 476 cm−1 and 347 and 308 cm−1 to the ν4 (VO3) and ν2 (VO3) bending vibrations, respectively. The spectra of vésigniéite and volborthite are similar, especially in the region of skeletal vibrations, even though their crystal structures differ.

Structural Systematics of the Anhydrous 1:1 Proton-Transfer Compounds of 3,5-Dinitrosalicylic Acid with Aniline and Monosubstituted Anilines

The crystal structures of the proton-transfer compounds of 3,5-dinitrosalicylic acid (DNSA) with a series of aniline-type Lewis bases [aniline, 2-hydroxyaniline, 2-methoxyaniline, 3-methoxyaniline, 4-fluoroaniline, 4-chloroaniline and 2-aminoaniline] have been determined and their hydrogen-bonding systems analysed. All are anhydrous 1:1 salts: [(C6H8N)+(C7H3N2O7)-], (1), [(C6H8NO)+(C7H3N2O7)-], (2), [(C7H10NO)+(C7H3N2O7)-], (3), [(C7H10NO)+(C7H3N2O7)-], (4), [(C6H7FN)+(C7H3N2O7)-], (5), [(C6H7ClN)+(C7H3N2O7)-], (6), and [(C6H9N2)+(C7H3N2O7)-], (7) respectively. Crystals of 1 and 6 are triclinic, space group P-1 while the remainder are monoclinic with space group either P21/n (2, 4, 5 and 7) or P21 (3). Unit cell dimensions and contents are: for 1, a = 7.2027(17), b = 7.5699(17), c = 12.9615(16) Å, α = 84.464(14), β = 86.387(15), γ = 75.580(14)o, Z = 2; for 2, a = 7.407(3), b = 6.987(3), c = 27.653(11) Å, β = 94.906(7)o, Z = 4; for 3, a = 8.2816(18), b = 23.151(6), c = 3.9338(10), β = 95.255(19)o, Z = 2; for 4, a = 11.209(2), b = 8.7858(19), c = 15.171(3) Å, β = 93.717(4)o, Z = 4; for 5, a = 26.377(3), b = 10.1602(12), c = 5.1384(10) Å, β = 91.996(13)o, Z = 4; for 6, a = 11.217(3), b = 14.156(5), c = 4.860(3) Å, α = 99.10(4), β = 96.99(4), γ = 76.35(2)o, Z = 2; for 7, a = 12.830(4), b = 8.145(3), c = 14.302(4) Å, β = 102.631(6)o, Z = 4. In all compounds at least one primary linear intermolecular N+-H…O(carboxyl) hydrogen-bonding interaction is present which, together with secondary hydrogen bonding results in the formation of mostly two-dimensional network structures, exceptions being with compounds 4 and 5 (one-dimensional) and compound 6 (three-dimensional). In only two cases [compounds 1 and 4], are weak cation-anion or cation-cation π-π interactions found while weak aromatic C-H…O interactions are insignificant. The study shows that all compounds fit the previously formulated classification scheme for primary and secondary interactive modes for proton-transfer compounds of 3,5-dinitrosalicylic acid but there are some unusual variants.

Effects of climate change on the wash-off of volatile organic compounds from urban roads

The predicted changes in rainfall characteristics due to climate change could adversely affect stormwater quality in highly urbanised coastal areas throughout the world. This in turn will exert a significant influence on the discharge of pollutants to estuarine and marine waters. Hence, an in-depth analysis of the effects of such changes on the wash-off of volatile organic compounds (VOCs) from urban roads in the Gold Coast region in Australia was undertaken. The rainfall characteristics were simulated using a rainfall simulator. Principal Component Analysis (PCA) and Multicriteria Decision tools such as PROMETHEE and GAIA were employed to understand the VOC wash-off under climate change. It was found that low, low to moderate and high rain events due to climate change will affect the wash-off of toluene, ethylbenzene, meta-xylene, para-xylene and ortho-xylene from urban roads in Gold Coast. Total organic carbon (TOC) was identified as predominant carrier of toluene, meta-xylene and para-xylene in <1µm to 150µm fractions and for ethylbenzene in 150µm to >300µm fractions under such dominant rain events due to climate change. However, ortho-xylene did not show such affinity towards either TOC or TSS (total suspended solids) under the simulated climatic conditions.

Hydrogen-bonding in the structures of the hydrated proton-transfer compounds of isonipecotamide with the isomeric indole-2 and indole-3-carboxylic acids

The structures of two hydrated proton-transfer compounds of 4-piperidinecarboxamide (isonipecotamide) with the isomeric heteroaromatic carboxylic acids indole-2-carboxylic acid and indole-3-carboxylic acid, namely 4-carbamoylpiperidinium indole-2-carboxylate dihydrate (1) and 4-carbamoylpiperidinium indole-3-carboxylate hemihydrate (2) have been determined at 200 K. Crystals of both 1 and 2 are monoclinic, space groups P21/c and P2/c respectively with Z = 4 in cells having dimensions a = 10.6811(4), b = 12.2017(4), c = 12.5456(5) Å, β = 96.000(4)o (1) and a = 15.5140(4), b = 10.2908(3), c = 9.7047(3) Å, β = 97.060(3)o (2). Hydrogen-bonding in 1 involves a primary cyclic interaction involving complementary cation amide N-H…O(carboxyl) anion and anion hetero N-H…O(amide) cation hydrogen bonds [graph set R22(9)]. Secondary associations involving also the water molecules of solvation give a two-dimensional network structure which includes weak water O-H…π interactions. In the three-dimensional hydrogen-bonded structure of 2, there are classic centrosymmetric cyclic head-to-head hydrogen-bonded amide-amide interactions [graph set R22(8)] as well as lateral cyclic amide-O linked amide-amide extensions [graph set R24(8)]. The anions and the water molecule, which lies on a twofold rotation axis, are involved in secondary extensions.

Prediction of the wash-off of traffic related semi- and non-volatile organic compounds from urban roads under climate change influenced rainfall characteristics

Traffic generated semi and non volatile organic compounds (SVOCs and NVOCs) pose a serious threat to human and ecosystem health when washed off into receiving water bodies by stormwater. Climate change influenced rainfall characteristics makes the estimation of these pollutants in stormwater quite complex. The research study discussed in the paper developed a prediction framework for such pollutants under the dynamic influence of climate change on rainfall characteristics. It was established through principal component analysis (PCA) that the intensity and durations of low to moderate rain events induced by climate change mainly affect the wash-off of SVOCs and NVOCs from urban roads. The study outcomes were able to overcome the limitations of stringent laboratory preparation of calibration matrices by extracting uncorrelated underlying factors in the data matrices through systematic application of PCA and factor analysis (FA). Based on the initial findings from PCA and FA, the framework incorporated orthogonal rotatable central composite experimental design to set up calibration matrices and partial least square regression to identify significant variables in predicting the target SVOCs and NVOCs in four particulate fractions ranging from >300-1 μm and one dissolved fraction of <1 μm. For the particulate fractions range >300-1 μm, similar distributions of predicted and observed concentrations of the target compounds from minimum to 75th percentile were achieved. The inter-event coefficient of variations for particulate fractions of >300-1 μm were 5% to 25%. The limited solubility of the target compounds in stormwater restricted the predictive capacity of the proposed method for the dissolved fraction of <1 μm.

Dynamic covalent chemistry on surfaces employing highly reactive cyclopentadienyl moieties

Silicon substrates coated with a bromide-terminated silane are transformed into highly reactive, cyclopentadiene covered analogues. These surfaces undergo rapid cycloaddition reactions with various dienophile-capped polymers. Mild heating of the substrates causes the retro-Diels-Alder reaction to occur, thus reforming the reactive cyclopentadiene surface, generating an efficiently switchable surface.

Atomistic investigations of single-crystal silicon with pre-existing defects

Molecular dynamics (MD) simulations have been employed to investigate the single-crystal Si properties with different pre-existing cavities under nanoindentation. Cavities with different radii and positions have been considered. It is found that pre-existing cavities in the Si substrate would obviously influence the mechanical properties of Si under nanoindentation. Furthermore, pre-existing cavities would absorb part of the strain energy during loading and then release during unloading. It would decrease plastic deformation to the substrate. Particularly, the larger of the cavity or the nearer of the cavity to the substrate’s top surface, the larger decrease of Young’s modulus and hardness is usually observed. Just as expected, the larger offset of the cavity in the lateral direction, the less influence is usually seen.

Hardness of silicon nitride thin films characterised by nanoindentation and nanoscratch deconvolution methods

Plasma enhanced chemical vapour deposition silicon nitride thin films are widely used in microelectromechanical system devices as structural materials because the mechanical properties of those films can be tailored by adjusting deposition conditions. However, accurate measurement of the mechanical properties, such as hardness, of films with thicknesses at nanometric scale is challenging. In the present study, the hardness of the silicon nitride films deposited on silicon substrate under different deposit conditions was characterised using nanoindentation and nanoscratch deconvolution methods. The hardness values obtained from the two methods were compared. The effect of substrate on the measured results was discussed.

Airborne concentration of Volatile Organic Compounds in school environment in Brisbane

Traffic emissions are considered as a major source of pollutants, particularly ultrafine particles, in the urban environment. There is an increased concern about airborne particles not only because of their environmental effects but also due to their potential adverse health effects on humans. There have been a number of studies related to the number concentration and size distribution of these particles but studies on the chemical composition of aerosols, especially in the school environment, are very limited. Mejia et. al (2011) reviewed studies on the exposure to and impact of air pollutants on school children and found that there were only a handful of studies on this topic. Therefore, the main focus of this research is on an analysis of the chemical composition of airborne particles, as well as source apportionment and the quantification of ambient concentrations of organic pollutants in the vicinity of schools, as a part of “Ultrafine Particles from Traffic Emissions on Children’s Health” (UPTECH) project. The aim of the present study was to find out the concentrations of different Volatile Organic Compounds (VOCs) in both outdoor and indoor locations from six different schools in Brisbane.

Advanced numerical characterization of silicon with defect by nanoindentation

Nano silicon is widely used as the essential element of complementary metal–oxide–semiconductor (CMOS) and solar cells. It is recognized that today, large portion of world economy is built on electronics products and related services. Due to the accessible fossil fuel running out quickly, there are increasing numbers of researches on the nano silicon solar cells. The further improvement of higher performance nano silicon components requires characterizing the material properties of nano silicon. Specially, when the manufacturing process scales down to the nano level, the advanced components become more and more sensitive to the various defects induced by the manufacturing process. It is known that defects in mono-crystalline silicon have significant influence on its properties under nanoindentation. However, the cost involved in the practical nanoindentation as well as the complexity of preparing the specimen with controlled defects slow down the further research on mechanical characterization of defected silicon by experiment. Therefore, in current study, the molecular dynamics (MD) simulations are employed to investigate the mono-crystalline silicon properties with different pre-existing defects, especially cavities, under nanoindentation. Parametric studies including specimen size and loading rate, are firstly conducted to optimize computational efficiency. The optimized testing parameters are utilized for all simulation in defects study. Based on the validated model, different pre-existing defects are introduced to the silicon substrate, and then a group of nanoindentation simulations of these defected substrates are carried out. The simulation results are carefully investigated and compared with the perfect Silicon substrate which used as benchmark. It is found that pre-existing cavities in the silicon substrate obviously influence the mechanical properties. Furthermore, pre-existing cavities can absorb part of the strain energy during loading, and then release during unloading, which possibly causes less plastic deformation to the substrate. However, when the pre-existing cavities is close enough to the deformation zone or big enough to exceed the bearable stress of the crystal structure around the spherical cavity, the larger plastic deformation occurs which leads the collapse of the structure. Meanwhile, the influence exerted on the mechanical properties of silicon substrate depends on the location and size of the cavity. Substrate with larger cavity size or closer cavity position to the top surface, usually exhibits larger reduction on Young’s modulus and hardness.

Structural characterisation and environmental application of organoclays for the removal of phenolic compounds

Modified montmorillonite was prepared at different surfactant (HDTMA) loadings through ion exchange. The conformational arrangement of the loaded surfactants within the interlayer space of MMT was obtained by computational modelling. The conformational change of surfactant molecules enhance the visual understanding of the results obtained from characterization methods such as XRD and surface analysis of the organoclays. Batch experiments were carried out for the adsorption of p-chlorophenol (PCP) and different conditions (pH and temperature) were used in order to determine the optimum sorption. For comparison purpose, the experiments were repeated under the same conditions for p-nitrophenol (PNP). Langmuir and Freundlich equations were applied to the adsorption isotherm of PCP and PNP. The Freundlich isotherm model was found to be the best fit for both of the phenolic compounds. This involved multilayer adsorptions in the adsorption process. In particular, the binding affinity value of PNP was higher than that of PCP and this is attributable to their hydrophobicities. The adsorption of the phenolic compounds by organoclays intercalated with highly loaded surfactants was markedly improved possibly due to the fact that the intercalated surfactant molecules within the interlayer space contribute to the partition phases, which result in greater adsorption of the organic pollutants.