A new multi analytical approach for the identification of synthetic and natural dyes mixtures. The case of orcein-mauveine mixture in a historical dress of a Sicilian noblewoman of nineteenth century

Abstract

In this paper, the application of a multi-analytical approach for the characterisation of synthetic and natural dyes in a historical textile is presented. The work is focused on a historical dress of a Sicilian noblewoman, dating from about 1865–1870. Firstly, SERS on fibre was performed, in order to individuate the classes of dyes employed. The SERS spectra suggested the presence of two main dyes: mauveine and orcein. In order to confirm these preliminary results, two different extraction protocols were applied. The extracts obtained were analysed by ESI-MS, MALDI-ToF and UHPCL-MS analyses, confirming the SERS results. In particular, the application of the ammonia mild extraction technique allowed to selectively extract the phenoxazonic dyes, separating them already in the extraction step from the synthetic ones. Thanks to this multi-analytical approach, this dress could be considered as one of the first examples of employment of synthetic dyes in association with natural ones.     

A novel bioassay for screening and quantification of taxanes

We report a novel method for screening and quantifying tubulin-binding antimitotic agents that promote microtubule formation. The method is based on the shift in the peak of the fluorescence emission difference spectrum of tubulin complexed to metal free tetrakis(4-carboxyphenyl)porphyrin (TCPP) in the presence of antimitotic agents. Taxol (paclitaxel), an anti-tumor drug approved for the treatment of a variety of cancers, caused the appearance of a new fluorescence peak at 645 nm at concentrations as low as 125 nM, the intensity of which was a function of the paclitaxel concentration. Cephalomannine caused the induction of a new fluorescence peak at 651 nm only above 1 muM. Baccatin did not induce the appearance of any new peak within detectable operating measurement conditions. These observations are in accordance with the biological activities/cytotoxicities of these compounds. Accordingly, it is proposed that the new method can be used for high throughput screening of antimitotic compounds.     

Application of Graphite-Epoxy Composite Electrodes in Differential Pulse Anodic Stripping Voltammetry of Heavy Metals

An analytical study on the use of graphite-epoxy composite (GEC) electrodes for differential pulse anodic stripping voltammetry (DPASV) of heavy metals is presented. This study is accompanied by microscopic observations of the electrode surface before and after the stripping step in comparison to glassy carbon electrode. GEC electrodes show much better accumulation properties and consequently acceptable behaviour which makes them suitable as working electrodes in the DPASV of heavy metals. Lead determination in real water samples in a batch system as well as some preliminary results in a flow-through system are presented. The detection limits in batch measurements were 100ppb for Cd, 10pb for lead and 50ppb for copper. The detection limit for lead in the flow-through system was similar to that in the batch. The results obtained show that these low cost and easy to prepare materials can be of interest in future research concerning stripping techniques of heavy metals and other analytes.     

Assessment of enzyme-linked immunosorbent assay for the determination of 2,4,5-TP in water and soil

A highly sensitive and specific indirect enzyme-linked immunosorbent assay is described for Silvex, 2-(2,4,5 trichlorophenoxy)propionic acid, (2,4,5-TP). One specific feature of the immunoassay is the use of simple chemical activation of chlorophenoxy acids to prepare both the immunizing and coating conjugates. The assay is based on the use of polyclonal antibodies raised against 2,4,5-TP, and a peroxidase-labeled secondary antibody for colorimetric detection. The effect of different chemical conditions (pH, and salt and detergent concentration) on immunoassay performance has been studied. Under the best conditions the least detectable dose and the sensitivity (IC(50)) for 2,4,5-TP were 0.05 micro g L(-1) and 0.80 micro g L(-1), respectively. The optimized immunoassay was also highly specific, showing little (6.9% for 2,4,5-T) or no cross-reactivity with other similar herbicides. The assay was used to determine 2,4,5-TP in water and soils. The excellent recoveries obtained (mean values ranging between 89% and 104%) make this immunoassay a suitable screening method for either environmental monitoring or laboratory quantification of 2,4,5-TP.     

Statistical mechanics of quantum-classical systems with holonomic constraints

The statistical mechanics of quantum-classical systems with holonomic constraints is formulated rigorously by unifying the classical Dirac bracket and the quantum-classical bracket in matrix form. The resulting Dirac quantum-classical theory, which conserves the holonomic constraints exactly, is then used to formulate time evolution and statistical mechanics. The correct momentum-jump approximation for constrained systems arises naturally from this formalism. Finally, in analogy with what was found in the classical case, it is shown that the rigorous linear-response function of constrained quantum-classical systems contains nontrivial additional terms which are absent in the response of unconstrained systems.     

Determination of the two major endocannabinoids in human plasma by μ-SPE followed by HPLC-MS/MS

Endocannabinoids (ECs) are endogenous compounds that interact with type-1 and type-2 cannabinoid receptors (CB₁ and CB₂), as well as non-cannabinoid receptors. The multitude of roles attributed to ECs makes them an emerging target of pharmacotherapy for a number of disparate diseases. Here a high-throughput bioanalytical method based on micro SPE (μ-SPE) followed by LC-MS/MS analysis for the simultaneous determination of the two major endocannabinoids 2-arachidonoylglycerol (2-AG) and N-arachidonoylethanolamine (anandamide, AEA) in human plasma is presented. The chromatographic conditions obtained with the fused-core column allowed a good separation in 10 min also of the AG isomers. A very simple and reliable extraction has been optimised by means of C18-modified tips: it requires only 100 μL of plasma and allows the use of minimal volumes of organic solvent. The present method allows a rapid and effective clean-up, which also minimises the isomerisation of 2-AG. The whole procedure has been validated following the FDA guidelines for bioanalytical methods validation: the satisfactory recovery values, the negligible matrix effect and the good values of accuracy and reproducibility make it a simple and high-throughput analytical tool for clinical and biochemical studies on endocannabinoid signaling in humans.

Amplified signal response in scale-free networks by collaborative signaling

Many natural and artificial two-states signaling devices are connected forming networks. The information-processing potential of these systems is usually related to the response to weak external signals. Here, using a network of overdamped bistable elements, we study the effect of a heterogeneous complex topology on the signal response. The analysis of the problem in random scale-free networks, reveals that heterogeneity plays a crucial role in amplifying external signals. We have contrasted numerical simulations with analytical calculations in simplified topologies.     

The X-Class and Almost-Increasing Permutations

In this paper we give a bijection between the class of permutations that can be drawn on an X-shape and a certain set of permutations that appears in Knuth [4] in connection to sorting algorithms. A natural generalization of this set leads us to the definition of almost-increasing permutations, which is a one-parameter family of permutations that can be characterized in terms of forbidden patterns. We find generating functions for almost-increasing permutations by using their cycle structure to map them to colored Motzkin paths. We also give refined enumerations with respect to the number of cycles, fixed points, excedances, and inversions.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.