An SPR biosensor for the detection of microcystins in drinking water

A surface plasmon resonance (SPR) biosensor for the detection of microcystins (MCs) in drinking water has been developed. Several assay formats have been evaluated. The selected format is based on a competitive inhibition assay, in which microcystin-LR (MCLR) has been covalently immobilized onto the surface of an SPR chip functionalized with a self-assembled monolayer. The influence of several factors affecting sensor performance, such as the nature and concentration of the antibody, the composition of the carrier buffer, and the blocking and regeneration solutions, has been evaluated. The optimized SPR biosensor provides an IC₅₀ 0.67 ± 0.09 μg L⁻¹, a detection limit of 73 ± 8 ng L⁻¹, and a dynamic range from 0.2 to 2.0 μg L⁻¹ for MCLR. Cross-reactivity to other related MCs, such as microcystin-RR (88%) and microcystin-YR (94%), has also been measured. The SPR biosensor can perform four simultaneous determinations in 60 min, and each SPR chip can be reused for at least 40 assay–regeneration cycles without significant binding capacity loss. The biosensor has been successfully applied to the direct analysis of MCLR in drinking water samples, below the provisional guideline value of 1 μg L⁻¹ established by the World Health Organization for drinking water.     

A molecularly imprinted polymer for the determination of neopterin

A molecularly imprinted polymer (MIP) for the specific retention of neopterin has been developed. A set of 6 polymers was prepared by radical polymerization under different experimental condition using methacrylic acid as functional monomer and ethylene glycol dimethacrylate as crosslinker, with the aim to understand their influence on the efficiency of the MIP. The performance of each MIP was tested in batch experiments via their binding capacity. The MIP prepared in the presence of nickel ions in dimethylsulfoxide-acetonitrile mixture (P4) exhibited the highest binding capacity for neopterin (260 μmol per gram of polymer). A selectivity study with two other pteridines demonstrated the polymer P4 also to possess the best selectivity.

Investigation on novel thermoplastic poly(urethane-thiourea-imide)s with enhanced chemical and heat resistance

A new generation of segmented thermoplastic poly(urethane-thiourea-imide)s (PUTIs) was synthesized via reaction of polyethylene glycol and thiourea-based prepolymer with dianhydride as chain extenders. NCO-terminated prepolymer was synthesized from a new diisocyanate, 3-(3-((4-isocyanatophenyl)carbamoyl)thioureido)phenyl-4-isocyanatophenylcarbamate (IPCT), as a hard segment and PEG forming soft segment. The starting materials and polymers were characterized by conventional methods and physical properties such as solubility, solution viscosity, molecular weight, thermal stability and thermal behavior were studied. PUTIs showed partially crystalline structures. Weight average molecular weights of PUTIs (GPC measurements) were in the range of 1,68,694-1,97,035. Moreover, thermogravimetric analysis indicated that poly(urethane-thiourea-imide)s were fairly stable above 500 °C having T₁₀ of 521-543 °C. Investigation of the results authenticated the approach of introducing thiourea (using IPCT) and imide structure in polyurethanes for the improvement of thermal stability. In comparison to typical polyurethanes, these polymers exhibited better heat resistance, chemical resistance as well as processability.     

THE INTERACTION OF THE EXCITED STATES OF SAFRANINE T WITH ALIPHATIC AMINES IN ORGANIC SOLVENTS

Abstract—
The reactions of the excited states of safranine T with aliphatic amines have been studied in methanol and acetonitrile. Quenching of the singlet and triplet states occurs by different mechanisms. Whereas the former excited state is quenched by a charge-transfer mechanism, the triplet state is quenched through proton transfer from the excited dye to the amine. This process leads to the unprotonated form of the dye in the triplet state, which is later quenched by amines to form the corresponding semireduced species. The monoprotonated triplet also undergoes self-quenching in both solvents (k = 1.2 × 10⁸ M ^-1 s^-1).     

Coelectroosmotic capillary electrophoresis of phenolic acids and derivatized amino acids using N,N-dimethylacrylamide-ethylpyrrolidine methacrylate physically coated capillaries

Two different families of compounds, i.e., phenolic and amino acids have been separated by capillary electrophoresis using a physically adsorbed polymer as capillary coating. The polymer used was N,N-dimethylacrylamide-ethylpyrrolidine methacrylate (DMA-EpyM) and it provided an stable coating by only flushing the capillary with a DMA-EpyM aqueous solution for 2 min between runs. The usefulness of this procedure has been demonstrated through the fast analysis of different families of solutes. Two different detection systems, diode-array detector and laser-induced fluorescence, have been used to determine phenolic acids and derivatized amino acids with fluorescein isothiocyanate, respectively. The main factors affecting reversal of electroosmotic flow (EOF) such as pH, type and concentration of buffer, and concentration and influence of organic solvents, as well as all the instrumental conditions were studied and optimized for both families of compounds.     

CW laser-induced photothermal conversion and shape transformation of gold nanodogbones in hydrated chitosan films

We investigate the photothermal conversion and transformation of gold nanoparticles with an initial dogbone shape after dispersion in hydrated chitosan films, which is a representative model of biological tissue, and excitation by a CW diode laser for 1 min. Gold nanodogbones are observed to undergo a distinct modification above a sharp threshold of ~11 W cm⁻² and 110 °C. Surprisingly, the very same modification is achieved up to at least 36 W cm⁻² and 250 °C. We use an analytical model derived from Gans theory to associate the change in color of the films with the change in shape statistics of these gold nanoparticles. This model proves both convenient and dependable. We interpret the photothermal transformation as a rearrangement of particles with a dogbone shape and an aspect ratio of 4.1 into rods with an aspect ratio of 2.5, where material from the end lobes of the dogbones may relocate to the waists of the rods. In turn, additional transitions to stable gold nanospheres may exhibit fairly slower kinetics.     

Parallel or classical kinetic resolution of a planar chiral ferrocenylketone through asymmetric reductions

Racemic 1-acetyl-2-methoxymethylferrocene, (±)-1 was subjected to asymmetric reduction with two different methodologies and complementary results were obtained. When the reduction of (±)-1 was carried out in the presence of CBS-oxazaborolidine catalyst and BH₃·Me₂S as the hydrogen source, both enantiomers of the substrate were converted with comparable reaction rates and selectivities. The corresponding diastereoisomeric ferrocenylalcohols 3a and 3b were obtained in a 1:1 ratio and >90% enantiomeric excess; this reaction profile being related with a parallel kinetic resolution with high ds₁ and ds₂ diastereofacial selectivities. On the contrary, the transfer hydrogenation of (±)-1 with HCOOH/triethylamine in the presence of (R,R)-Noyori’s catalyst proceeded via classical kinetic resolution, so that the formed (?)-3b or unreacted (+)-1 could be obtained in highly enantiopure form before or beyond 50% of the substrate conversion, respectively. Alcohol 3b with an (1R_p,S)- or (1S_p,R)-configuration is not easily accessible by the diastereoselective metallation/electrophilic quenching sequence routinely applied in the synthesis of planar chiral ferrocenes. As a result, the described procedures provide a valuable access to this useful starting material for the synthesis of homochiral related derivatives.     

Carbon composite electrodes: surface and electrochemical properties

Electrodes based on particulate carbon-epoxy or silicone composites have been formed and characterised using electrochemical methods, scanning electron microscopy and scanning electrochemical microscopy. These composites are rigid, exhibit high electrical conductivity and are stable in organic solvents for prolonged periods. The bulk resistance of the Araldite-M and Araldite-CW2215 based electrodes is low, 130+/-12 and 185+/-15 ohms, respectively. In contrast, the bulk resistance of the silicone based electrodes is 1480+/-112 ohms. The uncompensated resistance of electrochemical cells where the composites act as working electrodes is significantly larger than that expected on the basis of solution resistance alone, i.e., up to 7.5 kohms in the case of the silicone composites. These results are interpreted in terms of the presence of pores within the composite material. The response times of the composite electrodes to changes in the applied potential is between 3.1 and 7.2 ms which, although almost an order of magnitude longer than a comparable glassy carbon electrode, is sufficiently rapid to give useful voltammetric data for scan rates of several V s(-1). Close to ideal reversible cyclic voltammetry is observed for ferrocene under semi-infinite diffusion control for scan rates between 0.01 and 0.1 V s(-1) at the Araldite composites. In contrast, the large resistance associated with the silicone based materials causes quasi-reversible responses to be observed over this range of scan rate. Scan rate dependent cyclic voltammetry and time resolved chronoamperometry responses observed for ferrocene in solution are consistent with those expected for a random array of microelectrodes. Scanning electron microscopy and scanning electrochemical microscopy has been used to image the shape, size and electrochemical activity of the electroactive zones. In the case of Araldite-M, the quality of the electrode surface has been probed by comparing the rate of heterogeneous electron transfer at a composite microelectrode with that found for a carbon fibre electrode. The standard heterogeneous electron transfer rate constant, k degrees , is 6.0+/-0.1 x 10(-3) cm s(-1) for the composite compared to 1.5+/-0.1 x 10(-1) cm s(-1) for the carbon fibre electrode. While the smaller rate constant found for the composite suggests a less pristine surface, k degrees is sufficiently large to support reversible, electron transfer under typical electroanalytical conditions. These fundamental measurements will underpin the development of enzyme based biosensors for use in organic solvents.