Fast analysis of high-energy compounds and agricultural chemicals in water with desorption electrospray ionization mass spectrometry

Novel sampling and detection methods using desorption electrospray ionization (DESI) are examined in the detection of explosives (RDX, TNT, HMX, and TNB) and agricultural chemicals (atrazine, alachlor and acetochlor) from aqueous matrices and authentic contaminated groundwater samples. DESI allows analysis of solid and liquid compounds directly from surfaces of interest with little or no sample preparation. Significant savings in analysis time and sample preparation are realized. The methods investigated here include (i) immediate analysis of filter paper wetted with contaminated water samples without further sample preparation, (ii) rapid liquid-liquid extraction (LLE), and (iii) analyte extraction from contaminated groundwater samples on-site using solid-phase extraction (SPE) membranes, followed by direct DESI analysis of the membrane. The wetted filter paper experiment demonstrates the maximum sample throughput for DESI analysis of aqueous matrices but has inadequate sensitivity for some of these analytes. Both the LLE and the SPE methods have adequate sensitivity. The resulting SPE membranes and/or small volume solvent extracts produced in these experiments are readily transported to off-site facilities for direct analysis by DESI. This realizes a significant reduction in the costs of sample shipping compared with those for typical liter-sized samples of groundwater. Total analysis times for these preliminary DESI analyses are comparable with or shorter than those for GC/MS and limits of detection approach environmental action levels for these compounds while maintaining a modest relative standard deviation. Tandem mass spectrometric data is used to provide additional specificity as needed.     

Corrosion behavior of AA2024-T3 alloy treated with phosphonate-containing TEOS

Protection from corrosion of the aluminum alloy AA2024-T3 coated with a tetraethoxysilicate (TEOS)/aminotrimethyllenephosphonic acid (ATMP) film in a 0.05-mol L⁻¹ NaCl solution was evaluated using electrochemical impedance spectroscopy, scanning electron microscopy, energy disperse spectroscopy, and atomic force microscopy. The present work investigates the influence of different pretreatment procedures of the alloy surface and the ATMP concentration on the corrosion resistance of the coated samples. The undoped sol–gel coatings did not provide adequate corrosion protection. The best corrosion protection was achieved using acetic acid pretreatment and subsequent deposition of an ATMP-modified TEOS film with an optimal concentration of 5.00 × 10⁻⁴ mol L⁻¹ in the deposition bath. The acetic acid pretreatment promotes a decrease in galvanic corrosion and the surface enrichment of aluminum favoring the metalosiloxane and the metal–phosphonic bonds with increasing likely reaction sites, thus promoting the formation of a more homogeneous and compact coating with improved resistance.     

Preparation, microstructure characterization and catalytic performance of Cu/ZnO and ZnO/Cu composite nanoparticles for liquid phase methanol synthesis

Stearate@Cu/ZnO nanocomposite particles with molar ratios of ZnO?∶?Cu = 2 and 5 are synthesized by reduction of the metal-organic Cu precursor [Cu{(OCH(CH(3))CH(2)N(CH(3))(2))}(2)] in the presence of stearate@ZnO nanoparticles. In the case of ZnO?∶?Cu = 5, high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) combined with electron-energy-loss-spectroscopy (EELS) as well as attenuated total reflection Fourier transform infrared (ATR-IR) spectroscopy are used to localize the small amount of Cu deposited on the surface of 3-5 nm sized stearate@ZnO particles. For ZnO?∶?Cu = 2, the microstructure of the nanocomposites after catalytic activity testing is characterized by HAADF-STEM techniques. This reveals the construction of large Cu nanoparticles (20-50 nm) decorated by small ZnO nanoparticles (3-5 nm). The catalytic activity of both composites for the synthesis of methanol from syn gas is evaluated.     

Nanocarbon Paste Electrodes

The electrochemical behaviour of carbon paste electrodes prepared using nanocarbon and mineral oil was investigated and the results contrasted with different carbon and carbon pastes electrodes. The composition of carbon paste was studied by performing cyclic voltammetry performed in 0.1 M KCl solution in the presence of 4.0 mM Ru(NH₃)₆Cl₃, a well‐characterized redox system commonly used to test the electrode behaviour. After optimisation of the paste composition, the sensors chosen were tested for the analysis and characterization of three different systems: Ru(NH₃)₆^3+/2+, FcCH₂OH/FcCH₂OH⁺ and acetaminophen. The ability to obtain high quality voltammetry from the nanocarbon electrode was demonstrated and simulation of the voltammetry allowed the extraction of electrode kinetic parameters with high precision.     

Effect of dose of xylanase on bleachability of sugarcane bagasse ethanol/water pulps

Pulps obtained from the ethanol/water cooking of sugarcane bagasse were bleached with the xylanase enzyme obtained from the fungus Thermomyces lanuginosus IOC-4145 and with the commercial enzyme Cartazyme HS from Sandoz. By changing the enzyme dose from 4.3 to 36 IU/g of pulp, kappa number and viscosity were maintained when the xylanase from T. lanuginosus was used. On the other hand, by using Cartazyme HS, kappa number decreased by 17%, reaching 35.5. This pulp was further extracted with NaOH without a decrease in viscosity (10 cP), and pulp with a kappa number of 13 was obtained. Xylanases had no significant effect on the ethanol/water pulps.     

Chemical composition determination of complex organic-aqueous mixtures of alcohols, acetone, acetonitrile, hydrocarbons and water by near-infrared spectroscopy

Near-infrared spectroscopy (NIRS) combined with chemometric techniques has provided fast and precise methods for quality control in the petrochemical industry. In the present work, NIRS multivariate models were used to predict the chemical composition of an organic-aqueous solvent used in an isoprene production plant. The models were developed to predict the mass percent concentration of the components present in the solvent, namely water, acetonitrile, acetone, n-propanol, i-propanol, t-butanol, allyl alcohol and 1,3-dicyclopentadiene (DCPD) plus codimers. Each component concentration was estimated from FT-NIR spectra within the 7300-3900 cm⁻¹ region, using the whole range or only selected regions. Principal component analysis (PCA) was used for exploratory data analysis and partial least-squares models were employed for calibration based on at least 70 samples. The models’ accuracy, in terms of deviation from the primary method (gas chromatography) results, was also confirmed using external validation sets and expressed by the standard error of prediction (SEP) which ranged from 0.18 to 1.27% (w/w). Therefore, the feasibility of performing the chemical composition analysis required for process control of the isoprene unit solvent has been demonstrated. The simple and fast procedure, based on a single NIR spectrum, was able to differentiate between spectroscopic features of water, hydrocarbons, alcohols, ketones and nitrile compounds present in a complex organic-aqueous sample.     

Novel benzyl-substituted vanadocene anticancer drugs

From the reaction of 6-(p-methoxyphenyl) fulvene (1a), 6-(3,4-dimethoxyphenyl) fulvene (1b) and 6-(3,4,5-trimethoxyphenyl) fulvene (1c) with LiBEt₃H, lithiated cyclopentadienide intermediates (2a–c) were synthesised. These intermediates were then transmetallated to vanadium with VCl₄ to yield the benzyl-substituted vanadocenes bis-[(p-methoxybenzyl)cyclopentadienyl] vanadium(IV) dichloride (3a), bis-[(3,4-dimethoxybenzyl)cyclopentadienyl] vanadium(IV) dichloride (3b), and bis-[(3,4,5-trimethoxybenzyl)cyclopentadienyl] vanadium(IV) dichloride (3c). The two vanadocenes 3a and 3c were characterised by single crystal X-ray diffraction. All three vanadocenes had their cytotoxicity investigated through MTT based preliminary in vitro testing on the LLC-PK (pig kidney epithelial) cell line in order to determine their IC50 values and compare them with the corresponding titanocene dichloride derivatives. Vanadocenes 3b–c were found to have IC50 values of 9.1 and 8.3 μM, while 3a showed a superior value of 3.0 μM, respectively.     

Synthesis and Characterisation of Self‐Assembled and Self‐Adjuvanting Asymmetric Multi‐Epitope Lipopeptides of Ovalbumin

Designing a lipopeptide (LP) vaccine with a specific asymmetric arrangement of epitopes may result in an improved display of antigens, increasing host‐cell recognition and immunogenicity. This study aimed to synthesise and characterise the physicochemical properties of a library of asymmetric LP‐based vaccine candidates that contained multiple CD4⁺ and CD8⁺ T‐cell epitopes from the model protein antigen, ovalbumin. These fully synthetic vaccine candidates were prepared by microwave‐assisted solid phase peptide synthesis. The C12 or C16 lipoamino acids were coupled to the N or C terminus of the OVA CD4 peptide epitope. The OVA CD4 LPs and OVA CD8 peptide constructs were then conjugated using azide–alkyne Huisgen cycloaddition to give multivalent synthetic vaccines. Physiochemical characterisation of these vaccines showed a tendency to self‐assemble in aqueous media. Changes in lipid length and position induced self‐assembly with significant changes to their morphology and secondary structure as shown by transmission electron microscopy and circular dichroism.