Amine oxidase amperometric biosensor coupled to liquid chromatography for biogenic amines determination

A selective and sensitive method is presented for biogenic amines (BA) determination. The novelty consists in coupling a highly selective electrochemical biosensor to a weak acid cation-exchange column for online detection of amines. A bienzyme design, based on a recently isolated amine oxidase from grass pea and commercial horseradish peroxidase, was used for the biosensor construction. The enzymes were co-immobilized on the surface of a graphite electrode together with the electrochemical mediator (Os-redox polymer). The electrochemical detection was performed at a low applied potential (?50 mV vs. Ag/AgCl, KCl_0.1 M), where biases from interferences are minimal. The separation and determination of six BA, with relevance in food analysis (tyramine, putrescine, cadaverine, histamine, agmatine and spermidine), were investigated. Irrespective of the BA nature, the amine oxidase-based biosensor showed a linear response up to 5 mM, and its sensitivity decreases in the following order: cadaverine, putrescine, spermidine, agmatine, histamine and tyramine. The approach was used to estimate the BA content in fish samples, after their extraction with methanesulfonic acid.     

DNA-based phosphane ligands

In order to expand the repertoire of DNA sequences specifically interacting with transition metals, we report here the first examples of DNA sequences carrying mono- and bidentate phosphane ligands as well as P,N-ligands. Aminoalkyl-modified oligonucleotides have been reacted at predetermined internal sites with carboxylate derivatives of pyrphos, BINAP and phosphinooxazoline (PHOX) 2 b-d. Carbodiimide coupling in the presence of N-hydroxysuccinimide provided the DNA-ligand conjugates in 38-78 % yield. Phosphane-containing oligonucleotides and their phosphane sulfide analogues were characterized by mass spectrometry (MALDI-TOF and FT-ICR-ESI) and their stability after purification and isolation was systematically investigated. While DNA-appended pyrphos ligand was quickly oxidized, BINAP and PHOX conjugates showed high stabilities, making them useful precursors for incorporation of transition metals into DNA.     

Efficient synthesis of substituted 1‐dimethylamino or 1‐methylthio but‐3‐enylidene‐bis‐phosphonates,via the [2,3]‐sigmatropic rearrangement of related transient ammonium or sulfonium ylides

New variously substituted 1‐dimethylamino or 1‐methylthio but‐3‐enylidene‐bis‐phosphonates have been prepared from readily availableα‐dimethylamino or α‐methylthio methylene‐bis‐phosphonates by postulated [2,3]‐Wittig rearrangements of the corresponding N‐ or S‐allylic intermediate ylides. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 281–289, 1999     

Synthesis of trifunctional somatostatin based derivatives for improved cellular and subcellular uptake

It is now well established that the biological effects of Auger-emitting radionuclides are critically dependent on their subcellular location. Therefore, for their use in molecular imaging and targeted radionuclide therapy, attempts should be made to increase the nuclear specificity of the carriers. In the present paper the synthesis of novel trifunctional somatostatin derivatives containing a nuclear localization motif is described. These derivatives of [DOTA⁰, Tyr³]-octreotide (DOTATOC, DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) were obtained in high yields using Fmoc peptide synthesis in solid and in solution phase.     

Antiproliferative and Antimicrobial Effects of Rosmarinus officinalis L. Loaded Liposomes

Rosmarinus officinalis L. is a species that is widely known for its culinary and medicinal uses. The purpose of the present study consisted of the evaluation of the antiproliferative and antimicrobial effects of R. officinalis-loaded liposomes (L-R). Characterization of the liposomes was performed by establishing specific parameters. The load of the obtained liposomes was analyzed using an LC-MS method, and antiproliferative assays evaluated the cell viability on a liver adenocarcinoma cell line and on a human hepatic stellate cell line. Antimicrobial assays were performed by agar–well diffusion and by broth microdilution assays. The obtained liposomes showed high encapsulation efficiency, suitable particle size, and good stability. High amounts of caffeic (81.07 ± 0.76), chlorogenic (14.10 ± 0.12), carnosic (20.03 ± 0.16), rosmarinic (39.81 ± 0.35), and ellagic (880.02 ± 0.14) acids were found in their composition, together with other polyphenols. Viability and apoptosis assays showed an intense effect on the cancerous cell line and a totally different pattern on the normal cells, indicating a selective toxicity towards the cancerous ones and an anti-proliferative mechanism. Antimicrobial potential was noticed against all tested bacteria, with a better efficacy towards Gram-positive species. These results further confirm the biological activities of R. officinalis leaf extract, and proposes and characterizes novel delivery systems for their encapsulation, enhancing the biological activities of polyphenols, and overcoming their limitations.     

Electrochemical Behaviour and Rapid Determination of L‐Dopa at Electrochemically Pretreated Screen Printed Carbon Electrode

A simple and rapid voltammetric method based on a disposable electrochemically pretreated screen‐printed carbon electrode is proposed for the determination of L ‐dopa. Under optimum differential pulse voltammetry conditions a limit of detection of 3.6×10^?7 M for L ‐dopa was obtained. The method was successfully applied to the determination of L ‐dopa in a commercial pharmaceutical formulation.     

Set-valued average value at risk and its computation

New versions of the set-valued average value at risk for multivariate risks are introduced by generalizing the well-known certainty equivalent representation to the set-valued case. The first ’regulator’ version is independent from any market model whereas the second version, called the market extension, takes trading opportunities into account. Essential properties of both versions are proven and an algorithmic approach is provided which admits to compute the values of both versions over finite probability spaces. Several examples illustrate various features of the theoretical constructions.     

Information structuring—a new way of perceiving the content of learning

Dominating information by formation seems to be the only realistic solution to overcome the crisis generated by the higher and higher accumulation of information in each domain. The paper is proposing a model of building structured knowledge able to generate in the child's mind strategies for efficient processing of information.