Spectroscopic investigation of Rose Bengal/cyclodextrin interactions in aqueous solution: the case of the hydroxypropyl-cyclodextrins

The interaction of Rose Bengal (RB) with hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD) and hydroxypropyl-γ-cyclodextrin (HP-γ-CD) has been studied in water and in acetate buffer at pH 4.5 by UV–Vis absorption, fluorescence spectroscopy and Induced Circular Dichroism at 298 K. Evidence of the complex formation between the RB and all HP-CDs have been obtained both in water and in buffer. Binding constants and stoichiometry of RB/HP-CD complexes in water have been determined by applying the modified Benesi-Hildebrand equation to the fluorescence measurements.     

Organic acid solutions in the chromatography of inorganic ions VIII. Cation-exchange of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media

Summary The cation-exchange behaviour of Mn(II), Cd(II), Co(II), Ni(II), Zn(II), Cu(II), Fe(III), Sc(III), Y(III), Eu(III), Dy(III), Ho(III), Yb(III), Ti(IV) and Nb(V) in malate media at various concentrations and pH, was studied with Dowex 50 WX8 resin (200–400 mesh) in the ammonium form. Separation of Fe(III)/Cu(II), Fe(III)/Cu(II)/Zn(II), Fe(III)/Co(II)/Mn(II), Cu(II)/Ni(II)/Mn(II), Fe(III)/Cu(II)/Co(II)/Mn(II), Fe(III)/Cu(II)/Ni(II)/Cd(II), Yb(III)/Eu(III), Sc(III)/Y(III),Sc(III)/Yb(III)/Dy(III) and Nb(V)/Yb(III)/Ho(III) has been achieved, among others.This work was supported by C.N.R. of Italy.     

The effects of increasing NaCl concentration on the stability of inclusion complexes in aqueous solution

Equilibrium constants and standard molar enthalpies of reaction were determined by titration calorimetry for the reaction of 1-butanol with 2-hydroxypropyl-b-cyclodextrin (HP-b-CD) in aqueous solution at different concentrations of NaCl (0-1.9 M). The standard molar free energy and entropy changes associated to the complexation were calculated from the corresponding equilibrium constants, K, and standard enthalpies determined experimentally. In NaCl solutions the inclusion complexes ButOH/HP-b-CD are more stable than in water and their stability increases at increasing NaCl concentration; otherwise, the standard molar enthalpy associated to the formation of the complexes does not change with the increasing of salt concentration. The dependence of K on NaCl concentration were used to evaluate the number of water molecules displaced from the hydration shells of HP-b-CD and ButOH in forming complexes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Identification of Ros Produced by Photodynamic Activity of Chlorophyll/Cyclodextrin Inclusion Complexes

Photodynamic therapy (PDT) is a way of treating malignant tumors and hyperproliferative diseases. It is based on the use of photosensitizer, herein the chlorophyll a (chl a), and a light of an appropriate wavelength. The interaction of the photosensitizer (PS) with the light produces reactive oxygen species (ROS), powerful oxidizing agents, which cause critical damage to the tissue. To solubilize chl a in aqueous solution and to obtain it as monomer, we have used cyclodextrins, carriers which are able to interact with the pigment and form the inclusion complex. The aim of this study is to examine which types of ROS are formed by Chl a/cyclodextrin complexes in phosphate buffered solution and cell culture medium, using specific molecules, called primary acceptors, which react selectively with the reactive species. In fact the changes of the absorption and the emission spectra of these molecules after the illumination of the PS provide information on the specific ROS formation. The ¹O₂ formation has been tested using chemical methods based on the use of Uric Acid (UA), 9,10‐diphenilanthracene (DPA) and Singlet oxygen sensor green (SOSG) and by direct detection of Singlet Oxygen (¹O₂) luminescence decay at 1270 nm. Moreover, 2,7‐dichlorofluorescin and ferricytochrome c (Cyt Fe³⁺) have been used to detect the formation of hydrogen peroxide and superoxide radical anion, which reduces Fe³⁺ of the ferricytochrome to Fe²⁺, respectively.     

Colloidal nanocrystal ZnO- and TiO<Subscript>2</Subscript>-modified electrodes sensitized with chlorophyll a and carotenoids: a photoelectrochemical study

Heterostructures formed of films of organic-capped ZnO and TiO₂ nanocrystals (both with the size of ca. 6 nm) and photosynthetic pigments were prepared and characterized. The surface of optically transparent electrodes (Indium Tin Oxide) was modified with nanocrystals and prepared by colloidal synthetic routes. The nanostructured electrodes were sensitized by a mixture of chlorophyll a and carotenoids. The characterization of the hybrid structures, carried out by means of steady-state optical measurements, demonstrated such class of dyes able to extend the photoresponse of the large band-gap semiconductors. The charge-transfer processes between the components of the heterojunction were investigated, and photoelectrochemical measurements taken on the sensitized ZnO and TiO₂ nanocrystals electrodes elucidated the photoactivity of the heterojunctions as a function of the dyes and of the red–ox mediator used in solution. The effect of methyl viologen as different red–ox mediator was also evaluated in order to show its effect on the heterojunction photoactivity. The overall results contributed to describe the photoelectrochemical potential of the investigated heterojunctions, highlighting a higher response of the dye-sensitized ZnO nanocrystals, and then provided the TiO₂-modified counterparts.     

Algorithm for preliminary evaluation of the correlation time of local dynamics in some polymeric materials

A method for preliminary evaluation of the correlation time of local dynamics of the polymeric chains, using the experimental nuclear magnetic resonance spin-lattice relaxation data, is proposed. The algorithm is based on the model of the passage of a particle over a potential energy barrier. This method was utilized for some molten polymers and concentrated polymeric solutions.     

Study on the aggregation and electrochemical properties of Rose Bengal in aqueous solution of cyclodextrins

The interactions of Rose Bengal (RB) with alpha-cyclodextrin (alpha-CD), hydroxypropyl-beta-cyclodextrin (HP-beta-CD), hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD), heptakis(2,3,6-tri-O-methyll)-beta-cyclodextrin (TM-beta-CD) were studied in aqueous solutions of 0.1 M KClO(4) and 0.1 M LiClO(4) by vis absorption, fluorescence spectroscopy as well as electrochemical measurements at 298 K. The spectrophometric results indicate that RB is included in all beta- and gamma-CDs forming complexes with a stoichiometry 1:1 whose stability is slightly higher in KClO(4) than in LiClO(4) solutions. The complex stability constants determined for salt-containing CD solutions are lower than those for water solutions. The complexation of RB with beta- and gamma-CD and the differences between the complexes obtained in the presence of the two salts were confirmed by an electrochemical study.     

A passive radon dosimeter based on the combination of a track etch detector and activated charcoal

The aim of this work is to test a combination of a Makrofol track detector with a new type of charcoal (Carboxen-564) to design a personal radon dosimeter. The intention is to use this dosimeter as a personal radon dosimeter to measure the monthly radon exposure in workplaces, especially when the occupancy is not ecactly known. The proposed combination was exposed to low and high concentrations of radon in a large range of relative humidity (RH). For the optimal layer thickness, a charcoal bed of 2.2 mm, a specific track density of 5.1 tracks cm⁻²/kBq h m⁻³ was obtained. For a monthly working exposure (170 h) at an average radon concentration of 100 Bq/m³, this means 87 tracks/cm² or 10 times the background of the Makrofol detector, with a statistical uncertainty of 15%.     

Studies on radon adsorption characteristics of different charcoals used as amplifiers for the track detectors

Ten sorts of charcoals were studied regarding their use as amplifier in the design of a personal dosimeter. It consists of a combination of a Makrofol detector and activated charcoal. The calibration factor for the Makrofol using the charcoals as an amplifier is about ten times higher comparing with an exposure without charcoal. The best results were obtained with Carboxen 563. The background radioactivity of charcoals must also be considered in the dosimeter's design.