The 'apparent' hydrolysis of alkyl esters during electrospray ionization

Electrospray ionization (ESI) mass spectrometry was employed to obtain both molecular weight confirmation and structural information for a series of novel alkenyldiarylmethane (ADAM) analogs. The mass spectral data were intended for use during the structure elucidation of ester hydrolysis products formed during an in vitro metabolism study of a series of novel ADAM analogs. The data on the precursor molecules show the presence of the molecular ion peak, [M+H](+), as well as a peak consistent with the hydrolysis product of the original ester ([MH-ROH+H(2)O](+)). However, chemical ionization mass spectrometry, elemental analysis and (1)H NMR data indicated the presence of only the intact diester compounds, suggesting that the formation of the hydrolysis product was an instrumental artifact, i.e., in-beam hydrolysis during ESI or a result of longer ion residence times of the ion trap mass analyzer.     

Modelling in the design of a flow-through ultrasonic separator

This paper describes the design and testing of a flow-through ultrasonic separation device that allows the concentration of particles within a fluid. The device operates without the use of an acoustically transparent element. Three models are used to examine the behaviour of the cell, dealing with acoustic-particle interaction, electro-acoustic characteristics, and fluid flow. The device is able to concentrate up to 84% of the 60 microns sand particles in the 'dirty' stream, 13% in the intermediate stream and 3% in the 'clean' stream. Flow rates of up to 20 lh-1 (equating to an inlet velocity of 10(-2) ms-1) have been used with an electrical power input of up to 50 W (10 kWm-1).     

Field-induced motion of ferrofluids through immiscible viscous media: Testbed for restorative treatment of retinal detachment

Biocompatible, hydrophobic ferrofluids comprised of magnetite nanoparticles dispersed in polydimethylsiloxane show promise as materials for the treatment of retinal detachment. This paper focuses on the motion of hydrophobic ferrofluid droplets traveling through viscous aqueous media, whereby the movement is induced by gradients in external fields generated by small permanent magnets. A numerical method was utilized to predict the force on a spherical droplet, and then the calculated force was used to estimate the time required for the droplet to reach the permanent magnet. The calculated forces and travel times were verified experimentally.     

Mushroom Polysaccharide-Assisted Anticarcinogenic Mycotherapy: Reviewing Its Clinical Trials

Of the biologically active components, polysaccharides play a crucial role of high medical and pharmaceutical significance. Mushrooms have existed for a long time, dating back to the time of the Ancient Egypt and continue to be well explored globally and experimented with in research as well as in national and international cuisines. Mushroom polysaccharides have slowly become valuable sources of nutraceuticals which have been able to treat various diseases and disorders in humans. The application of mushroom polysaccharides for anticancer mycotherapy is what is being reviewed herein. The widespread health benefits of mushroom polysaccharides have been highlighted and the significant inputs of mushroom-based polysaccharides in anticancer clinical trials have been presented. The challenges and limitation of mushroom polysaccharides into this application and the gaps in the current application areas that could be the future direction have been discussed.     

Adsorption of some toxic elements from water samples on modified activated carbon,activated carbon and red soil using neutron activation analysis

A simple and sensitive method for the determination of some metalloids and heavy metals in water samples is presented. The method is based on the preconcentration of the attachment of chelating functionalities with metalloids and toxic metals irreversibly and targeted towards toxic metals adsorbed on modified activated carbon, activated carbon and red soil particles at pH 3.0–9.0±0.2, followed by quantitative determination using instrumental neutron activation analysis (INAA), on the absorbers. Attachment results from attraction that may be physical, chemical, electrical, or a combination of all three. The efficient removal of metalloids and toxic metals, especially arsenic, chromium and mercury is anticipated. The adsorption capacity of the chemically modified activated carbon materials was evaluated for the above mentioned metalloid and toxic metal ions in the presence of iron ions and simulated water samples. Red soil particles containing iron was utilized in the control of oxidation-reduction reaction with metalloids and toxic metals. The preconcentration of the elements of interest on red soil particles, activated carbon and modified activated carbon at different depths, pH and oxidation states was investigated. The results obtained showed good agreement with certified values giving relative errors of less than 10%.     

Scanning a triple quadrupole mass spectrometer for doubly charged ions

Charge exchange reactions within a triple quadrupole mass spectrometer characterize doubly charged ions formed in the ion source. Two methods have been developed for identifying the singly charged ions formed from doubly charged ions by charge exchange in the collision quadrupole. The first is based on the characteristically high kinetic energy-to-charge ratios of the products of charge exchange; this property can be used to separate these ions from all other singly charged ions. This retarding potential method is analogous to procedures for recording doubly charged ion mass spectra using sector instruments. The second method is based on the fact that, although mass remains constant in the charge exchange reaction, the change in mass-to-charge ratio can be followed. A charge exchange linked scan, predicated on changes in charge rather than mass, but otherwise analogous to neutral loss/gain scans, is described. Information on the structure of doubly charged ions can be obtained by recording the fragmentation products of dissociative charge exchange. The utility of the charge exchange linked scan for the selective identification of polynuclear aromatic compounds in a complex mixture is described. The methods given can be generalized to cover other charge permutation reactions.     

The effect of water on the ion trap analysis of trimethylsilyl derivatives of long-chain fatty acids and alcohols

Gas chromatography/mass spectrometry (GC/MS), with an ion trap mass analyzer, was used to examine the very-long-chain cuticular acid and certain non-acid wax constituents on the leaf sheath surface of Sorghum bicolor before and during 36 hours of light exposure. The mass spectra of the trimethylsilylated acids and alcohols did not match any of those published in searchable mass spectral libraries. The observed differences can be related to the interaction between water and the trimethylsilylated acids and alcohols. Understanding the observed mass spectra of the very-long-chain plant waxes is critical for studies that employ GC/MS with the ion trap mass analyzer to elucidate cuticular wax compositions on plants.     

Quantitative determination of polyphosphate in sediments using Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy and partial least squares regression

Phosphorus (P) is a major cause of eutrophication and subsequent loss of water quality in freshwater ecosystems. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. Despite the broad relevance of polyphosphate (Poly-P) in bioremediation and P release processes in the environment, its quantification is not yet well developed for sediment samples. Current methods possess significant disadvantages because of the difficulties associated with using a single extractant to extract a specific P compound without altering others. A fast and reliable method to estimate the quantitative contribution of microorganisms to sediment P release processes is needed, especially when an excessive P accumulation in the form of polyphosphate (Poly-P) occurs. Development of novel approaches for application of emerging spectroscopic techniques to complex environmental matrices such as sediments significantly contributes to the speciation models of P mobilization, biogeochemical nutrient cycling and development of nutrient models. In this study, for the first time Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy in combination with partial least squares (PLS) was used to quantify Poly-P in sediments. To reduce the high absorption matrix components in sediments such as silica, a physical extraction method was developed to separate sediment biological materials from abiotic particles. The aim was to achieve optimal separation of the biological materials from sediment abiotic particles with minimum chemical change in the sample matrix prior to ATR-FTIR analysis. Using a calibration set of 60 samples for the PLS prediction models in the Poly-P concentration range of 0-1 mg g(-1) d.w. (dry weight of sediment) (R(2) = 0.984 and root mean square error of prediction RMSEP = 0.041 at Factor-1) Poly-P could be detected at less than 50 μg g(-l) d.w. Using this technique, there is no solvent extraction or chemical treatment required, sample preparation is minimal and simple, and the analysis time is greatly reduced. The results from this study demonstrated the potential of ATR FT-IR spectroscopy as an alternative method to study Poly-P in sediments.     

Individually addressable recessed gold microelectrode arrays with monolayers of thio-cyclodextrin nanocavities

Four, individually addressable 30 microm diameter, e-beam deposited, gold microelectrodes recessed by 6 microm were suitably spaced on a single substrate to avoid diffusional overlap between each microelectrode. The single substrate device was functionalised with thiolated alpha-, beta-, and gamma-cyclodextrin nanocavities without spacer groups to ensure close proximity of the cavities to the electrode surface. The microelectrodes were assessed in two stages. The e-beam deposited micron sized electrodes were characterized using models for recessed and inlaid microdisk electrodes. Subsequently, each individually addressable, atomically flat, micro-patterned gold electrode with thiolated CD ensembles was treated as a nanoporous electrode assembly. Theoretical and experimental results were compared using cyclic voltammetry. Atomic force microscopy was also used to characterise the modified microelectrodes. Comparisons were made with thiolated CDs deposited on macroelectrodes. This is the first report of the behaviour of immobilized CD nanocavities ensembles on atomically flat gold microelectrodes.     

Catalysts for convenient aerobic alcohol oxidations in air: systematic ligand studies in Pd/pyridine systems

We report highly convenient Pd catalysts for the aerobic oxidation of alcohols, which are generated in situ by combining commercially available catalyst precursors. Systematic optimizations of the L- and X-type ligand environment and the employed additive allow the use of air as the sole oxidant without formation of Pd black. The resulting novel protocol provides quantitative yields of a broad variety of ketones and aldehydes.