Liquid chromatographic determination of trimethylamine in water

A method for the selective determination of trimethylamine (TMA) in aqueous matrices by liquid chromatography is reported. The proposed procedure is based on the derivatization of the analyte with 9-fluorenylmethyl chloroformate (FMOC) in a precolumn (Hypersil C18, 30 microm, 20 mm x 2.1 mm i.d.) connected on-line to the analytical column (LiChrosphere 100 RP18, 5 microm, 125 mm x 4 mm i.d.). Gradient elution was performed with a mixture of acetonitrile-water-0.05 M borate buffer (pH 9.0). The method has been applied to the direct determination of TMA in water within the 0.25-10.0 microg/ml concentration interval, and can also be adapted to the determination of TMA over the range 0.05-1.0 microg/ml by incorporating a preconcentration stage with C18 solid-phase extraction (SPE) cartridges. Good linearity, reproducibility and accuracy was achieved within the tested concentration intervals. The limits of detection at 262 nm were 50 and 5 ng/ml for the direct method and for the method involving preconcentration, respectively. The proposed conditions allowed the selective determination of TMA in the presence of other primary and secondary short-chain aliphatic amines. The utility of the described procedure has been tested by determining TMA in different water samples.     

FI automatic method for the determination of copper(II) based on coproporphyrin I-Cu(II)/TCPO/H(2)O(2) chemiluminescence reaction for the screening of waters

In this paper, an automatic method for the screening of water samples containing Cu(II) was proposed, based on peryoxalate chemiluminescence reaction using coproporphyrin I as fluorophor compound to provide selectivity and a simple flow injection (FI) chemiluminescence detector (CLD). FI system conditions were chosen in order to distinguish samples over or under legislation limit established (50 μg l⁻¹) with high reliability. The detection limit found was 9 μg l⁻¹ and the linear dynamic range was 15-125 μg l⁻¹ of Cu(II). Repeatibility and reproducibility studies gave good precision and accuracy with recovery near 100%. Under these conditions, the method resulted selective and only Fe(II), Fe(III) and Pb(II) could interfere, but at a concentration level higher than their normal concentration in waters. The proposed method was found to be highly reliable for screening purposes and it was successfully applied to the screening of a variety of real water samples.     

Immunochemical tools for mycotoxin detection in food

Abstract  

As a result of the deleterious effects of mycotoxins on human and animal health, and the consequently increasing stringency in the determination of food contamination levels, many researchers have focused their efforts on developing new devices for the detection of these compounds. Biosensors merit special mention due to their sensitivity, accuracy, cost-effectiveness and simplicity, not only of the construction, but also of the sample pre-treatment, if necessary, and the measurement step. Furthermore, biosensor arrays offer additional advantages, such as the possibility to measure multiple samples and provide multi-mycotoxin profiles in one assay. In this case, apart from shortening the analysis time, accuracy is improved by the assessment of matrix interferences and synergistic effects among mycotoxins. Biosensors and arrays for mycotoxins are thus promising biotechnological tools for mycotoxin detection in food.     

Design,synthesis and spectroscopic characterisation of a focused library based on the polyandrocarpamine natural product scaffold

A focused library based on the marine natural products polyandrocarpamines A ( 1 ) and B ( 2 ) has been designed and synthesised using parallel solution‐phase chemistry. In silico physicochemical property calculations were performed on synthetic candidates in order to optimise the library for drug discovery and chemical biology. A library of ten 2‐aminoimidazolone products ( 3–12 ) was prepared by coupling glycocyamidine and a variety of aldehydes using a one‐step stereoselective aldol condensation reaction under microwave conditions. All analogues were characterised by NMR, UV, IR and MS. The library was evaluated for cytotoxicity towards the prostate cancer cell lines, LNCaP, PC‐3 and 22Rv1. Copyright © 2013 John Wiley & Sons, Ltd.     

Merging structural biology with chemical biology: Structural Chemistry at Eskitis

This review introduces the Structural Chemistry Program at Griffith University’s Eskitis Institute, and provides a brief overview over its current and future research portfolio. Capitalising on the co-location with the Queensland Compound Library (QCL), Australia’s only small molecule repository, our laboratory investigates the structure and function of proteins with the aim of learning about their molecular mechanisms. Consequently, these studies also feed into drug discovery and design. The thematic focus of our Program is on proteins involved in infection, inflammation and neurological diseases, and this review highlights a few of our recent research efforts in this area.

     

Twisted mannitol crystals establish homologous growth mechanisms for high-polymer and small-molecule ring-banded spherulites

D-Mannitol belongs to a large and growing family of crystals with helical morphologies (Yu, L. J. Am. Chem. Soc.2003, 125, 6380). Two polymorphs of D-mannitol, α and δ, when grown in the presence of additives such as poly(vinylpyrrolidone) (PVP) or D-sorbitol, form ring-banded spherulites composed of handed helical fibrils, where the helix axes correspond to the radial growth directions. The two polymorphs form helices with opposite senses in the presence of PVP but the same sense in the presence of D-sorbitol. The characteristic dimensions of the fibrils, including thickness, aspect ratio, and pitch, were determined by scanning probe and electron microscopies. These values must form the basis of any theory that presupposes what forces give rise to crystal twisting, a problem that has been broached but unsettled in the literature of polymer crystallization. The interdependence of the rhythmic variations of both linear and circular birefringence, as determined by Mueller matrix microscopy, informs the cooperative organization of mannitol fibers. The microstructure of mannitol ring-banded spherulites compares favorably to that of high polymers and is evaluated within the context of current theories of crystal twisting.     

Theory and simulation of anisotropic pair correlations in ferrofluids in magnetic fields

Anisotropic pair correlations in ferrofluids exposed to magnetic fields are studied using a combination of statistical-mechanical theory and computer simulations. A simple dipolar hard-sphere model of the magnetic colloidal particles is studied in detail. A virial-expansion theory is constructed for the pair distribution function (PDF) which depends not only on the length of the pair separation vector, but also on its orientation with respect to the field. A detailed comparison is made between the theoretical predictions and accurate simulation data, and it is found that the theory works well for realistic values of the dipolar coupling constant (λ = 1), volume fraction (φ ≤ 0.1), and magnetic field strength. The structure factor is computed for wavevectors either parallel or perpendicular to the field. The comparison between theory and simulation is generally very good with realistic ferrofluid parameters. For both the PDF and the structure factor, there are some deviations between theory and simulation at uncommonly high dipolar coupling constants, and with very strong magnetic fields. In particular, the theory is less successful at predicting the behavior of the structure factors at very low wavevectors, and perpendicular Gaussian density fluctuations arising from strongly correlated pairs of magnetic particles. Overall, though, the theory provides reliable predictions for the nature and degree of pair correlations in ferrofluids in magnetic fields, and hence should be of use in the design of functional magnetic materials.