Contact Ion Pairs on a Protonated Azamacrocycle: the Role of the Anion Basicity

A potassium-containing hexaazamacrocyclic dication, [M?H?K]²⁺, is able to add in the gas phase mono- and dicarboxylate anions as well as inorganic anions by forming the corresponding monocharged adducts, the structure of which markedly depends on the basicity of the anion. With anions, such as acetate or fluoride, the neutral hexaazamacrocycle M acts as an acceptor of monosolvated K⁺ ion. With less basic anions, such as trifluoroacetate or chloride, the protonated hexaazamacrocycle [M?H]⁺ performs the unusual functions of an acceptor of contact K⁺/anion pairs.

Open image in new window

Graphical Abstract ?

     

Structure and electrokinetic study of nickel electrodeposition

Electrodeposited layers of nickel show different growth characteristics depending on the composition of the electrolyte, namely the type of the anion, the presence or the absence of boric acid and the pH. These process parameters are examined in the present work in order to elucidate their influence upon the growth texture and the related surface morphology of the electrodeposits. The relationship between process and structure is investigated by studying the transient electrochemical behavior during deposition, in order to discriminate between different interface conditions corresponding to different growth modes. The observed preferred orientations can be in this way linked to different reactive species, which are assumed to be present at the surface, and to their stability. The correlation between kinetics and structure in nickel electrodeposition reported in the present work and the similar correlation found in cobalt electrodeposition suggest a rationalization of the growth modes of ECD inert metals, based on the correspondence between the transient Tafel parameter and the growth texture observed in defined conditions. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 6, pp. 771–783. The text was submitted by the authors in English.     

Simultaneous Measurement of Cortisol,Cortisone, Dexamethasone and Additional Exogenous Corticosteroids by Rapid and Sensitive LC–MS/MS Analysis

The simultaneous measurement of dexamethasone and cortisol has proven the ability to increase the diagnostic performance of the overnight dexamethasone-suppression test. Furthermore, the therapeutic drug monitoring of administered corticosteroid drugs could represent a crucial tool for investigating unexpected variations of steroid hormones’ circulating levels. In this work, an LC–MS/MS method for the quantification of cortisol, cortisone, dexamethasone and six additional exogenous corticosteroids in the serum/plasma matrix was developed and validated in compliance with the ISO/IEC requirements. To assess the efficiency of the validated method, serum samples of 75 patients undergoing the dexamethasone-suppression test and 21 plasma samples of patients under immunosuppressive treatment after kidney transplant were analyzed. In all dexamethasone-suppression test samples, it was possible to measure the circulating levels of cortisol, cortisone and dexamethasone. Concentrations of the latter were for all tested patients above the proposed cutoff for the dexamethasone-suppression test’s results, and the cortisol concentrations showed good correlation with the ones measured by routine immunometric analysis, therefore confirming the screening outcome for all enrolled patients. Prednisone was detected and quantified in all enrolled patients, confirming the use of such a corticosteroid for immunosuppressive therapy. Thanks to these two applications, we proved the overall performance of the developed LC–MS/MS method for four target analytes. The future implementation of such an analytical tool in the clinical biochemistry laboratory’s routine will guarantee a single and versatile tool for simultaneously monitoring dexamethasone-suppression-test results and corticosteroid drugs’ administration.     

Binding Motifs in the Naked Complexes of Target Amino Acids with an Excerpt of Antitumor Active Biomolecule: An Ion Vibrational Spectroscopy Assay

The structures of proton-bound complexes of 5,7-dimethoxy-4H-chromen-4-one ( 1 ) and basic amino acids (AAs), namely, histidine (His) and lysine (Lys), have been examined by means of mass spectrometry coupled with IR ion spectroscopy and quantum chemical calculations. This selection of systems is based on the fact that 1 represents a portion of glabrescione B, a natural small molecule of promising antitumor activity, while His and Lys are protein residues lining the cavity of the alleged receptor binding site. These species are thus a model of the bioactive adduct, although clearly the isolated state of the present study bears little resemblance to the complex biological environment. A common feature of [ 1 +AA+H]⁺ complexes is the presence of a protonated AA bound to neutral 1 , in spite of the fact that the gas-phase basicity of 1 is comparable to those of Lys and His. The carbonyl group of 1 acts as a powerful hydrogen-bond acceptor. Within [ 1 +AA+H]⁺ the side-chain substituents (imidazole group for His and terminal amino group for Lys) present comparable basic properties to those of the α-amino group, taking part to a cooperative hydrogen-bond network. Structural assignment, relying on the comparative analysis of the infrared multiple photon dissociation (IRMPD) spectrum and calculated IR spectra for the candidate geometries, derives from an examination over two frequency ranges: 900–1800 and 2900–3700 cm⁻¹. Information gained from the latter one proved especially valuable, for example, pointing to the contribution of species characterized by an unperturbed carboxylic OH or imidazole NH stretching mode.     

On–off intermittency and coherent bursting in stochastically-driven coupled maps

On–off intermittency is a phase space mechanism for bursting in dynamical systems. Here we recall how the simple example of a logistic map with a time-dependent control parameter, considered as a dynamical variable of the system, gives rise to bursting or on–off behavior. We show that, for a given realization of the driver, a stochastically driven logistic map in the on–off intermittent regime always converges to the same temporal dynamics, independently of initial conditions. In that sense, the map is not chaotic. We then explore the behavior of two coupled on–off logistic maps, each driven by a separate random process, and show that, for a wide range of coupling strengths, bursting becomes at least partially coherent. The bursting coherence has a smooth dependence on the coupling parameter and no sharp transition from coherence to incoherence is detected. In the system of two coupled on–off maps studied here, coherent bursting is rooted in the behavior during off phases when the mapped coordinates take on extremely small values.     

Valorization of raw materials from agricultural industry for astaxanthin and β-carotene production by Xanthophyllomyces dendrorhous

Waste deriving from food and agro-industries is a growing problem in our modern society. In order to reduce food waste and its associated impacts over the environment and public health, innovative strategies for the conversion of food wastes in added value products are studied. Whey is one of the prominent waste deriving from Sicilian diary industry. The growth and the carotenoid biosynthesis of the yeast Xanthophyllomyces dendrorhous by its cultivation in pre-treated whey were studied. The study showed the possibility of increasing the astaxanthin productivity from X. dendrorhous in a batch fermentative process under continuous illumination. Our work is focused on the importance of carotenogenesis by X. dendrorhous on whey for the economic and ecological aspect. The results obtained in the study provide useful information about the possible use of this waste material for carotenogenesis from X. dendrorhous.