Sol-Gel synthesis, spectroscopic and thermal behavior study of SiO2/PEG composites containing different amount of chlorogenic acid

In this work, new phenol-based materials have been synthesized by the sol-gel method, in which different amounts of the phenolic antioxidant chlorogenic acid (CGA) (from 5 wt % to 20 wt %) were embedded in two different silica matrices: pure silica and silica-based hybrids materials, containing 50 wt % of polyethylene glycol (PEG). The incorporation of CGA in different sol-gel matrices might protect them from degradation, which could cause the loss of their properties. The two series of materials were chemically characterized by Fourier transform infrared (FTIR) spectroscopy. In addition, the thermal behavior of both series of materials containing CGA was studied by thermogravimetry under both air and inert N2flowing gas atmosphere. The bioactivity was evaluated by soaking the synthesized hybrids in a simulated body fluid, showing that the bioactivity of the silica matrix is not modified by the presence of PEG and CGA

Influence of the sebaceous gland density on the stratum corneum lipidome

The skin surface lipids (SSL) result from the blending of sebaceous and epidermal lipids, which derive from the sebaceous gland (SG) secretion and the permeability barrier of the stratum corneum (SC), respectively. In humans, the composition of the SSL is distinctive of the anatomical distribution of the SG. Thus, the abundance of sebum biomarkers is consistent with the density of the SG. Limited evidence on the influence that the SG exerts on the SC lipidome is available. We explored the differential amounts of sebaceous and epidermal lipids in areas at different SG density with lipidomics approaches. SC was sampled with adhesive patches from forearm, chest, and forehead of 10 healthy adults (8F, 2M) after mechanical removal of sebum with absorbing paper. Lipid extracts of SC were analysed by HPLC/(-)ESI-TOF-MS. In the untargeted approach, the naïve molecular features extraction algorithm was used to extract meaningful entities. Aligned and normalized data were evaluated by univariate and multivariate statistics. Quantitative analysis of free fatty acids (FFA) and cholesterol sulfate (CHS) was performed by targeted HPLC/(-)ESI-TOF-MS, whereas cholesterol and squalene were quantified by GC-MS. Untargeted approaches demonstrated that the relative abundance of numerous lipid species was distinctive of SC depending upon the different SG density. The discriminating species included FFA, CHS, and ceramides. Targeted analyses confirmed that sebaceous FFA and epidermal FFA were increased and decreased, respectively, in areas at high SG density. CHS and squalene, which are biomarkers of epidermal and sebaceous lipid matrices, respectively, were both significantly higher in areas at elevated SG density. Overall, results indicated that the SG secretion intervenes in shaping the lipid composition of the epidermal permeability barrier. © 2018, The Author(s)

Modeling solid state stability for speciation: a ten-year long study

Speciation studies are based on fundamental models that relate the properties of biomimetic coordination compounds to the stability of the complexes. In addition to the classic approach based on solution studies, solid state properties have been recently proposed as supporting tools to understand the bioavailability of the involved metal. A ten-year long systematic study of several different complexes of imidazole substituted ligands with transition metal ions led our group to the definition of a model based on experimental evidences. This model revealed to be a useful tool to predict the stability of such coordination complexes and is based on the induced behavior under thermal stress. Several different solid state complexes were characterized by Thermally Induced Evolved Gas Analysis by Mass Spectrometry (TI-EGA-MS). This hyphenated technique provides fundamental information to determine the solid state properties and to create a model that relates stability to coordination. In this research, the model resulting from our ten-year long systematic study of complexes of transition metal ions with imidazole substituted ligands is described. In view of a systematic addition of information, new complexes of Cu(II), Zn(II), or Cd(II) with 2-propyl-4,5-imidazoledicarboxylic acid were precipitated, characterized, and studied by means of Thermally Induced Evolved Gas Analysis performed by mass spectrometry (TI-EGA-MS). The hyphenated approach was applied to enrich the information related to thermally induced steps, to confirm the supposed decomposition mechanism, and to determine the thermal stability of the studied complexes. Results, again, allowed supporting the theory that only two main characteristic and common thermally induced decomposition behaviors join the imidazole substituted complexes studied by our group. These two behaviors could be considered as typical trends and the model allowed to predict coordination behavior and to provide speciation information

New frontiers in thermal analysis: A TG/Chemometrics approach for postmortem interval estimation in vitreous humor

The coupling of thermogravimetric analysis (TG) associated with chemometrics is proposed as an innovative approach in thanatochemistry in order to develop a new analytical tool using thermal analysis for the characterization of vitreous humor. Vitreous samples were selected from the medicolegal deaths which occurred in casualty and where the death interval is known. Only hospital deaths with no metabolic disorders were taken, and the precise time of death was certified by the treating physician. Samples were analyzed by TG7 thermobalance, and principal component analysis was used to evaluate the results. The TG/Chemometrics outcomes show a clearly distinct behavior according to the postmortem interval, concluding that TG and Chemometrics are capable of predicting the time since death using only a few microliters of vitreous, without any pretreatment and with an hour of analysis tim

Application of innovative TGA/chemometric approach for forensic purposes: the estimation of the time since death in contaminated specimens

Chronothanatology has always been a challenge in forensic sciences. Therefore, the importance of a multidisciplinary approach for the characterization of matrices (organs, tissues, or fluids) that respond linearly to the postmortem interval (PMI) is emerging increasingly. The vitreous humor is particularly suitable for studies aimed at assessing time-related modifications because it is topographically isolated and well-protected. In this work, a novel approach based on thermogravimetry and chemometrics was used to estimate the time since death in the vitreous humor and to collect a databank of samples derived from postmortem examinations after medico-legal evaluation. In this study, contaminated and uncontaminated specimens with tissue fragments were included in order to develop a classification model to predict time of death based on partial least squares discriminant analysis (PLS-DA) that was as robust as possible. Results demonstrate the possibility to correctly predict the PMI even in contaminated samples, with an accuracy not lower than 70%. In addition, the correlation coefficient of the measured versus predicted outcomes was found to be 0.9978, confirming the ability of the model to extend its feasibility even to such situations involving contaminated vitreous humor

Biophysical and biological contributions of polyamine-coated carbon nanotubes and bidimensional buckypapers in the delivery of miRNAs to human cells

Recent findings in nanomedicine have revealed that carbon nanotubes (CNTs) can be used as potential drug carriers, therapeutic agents and diagnostics tools. Moreover, due to their ability to cross cellular membranes, their nanosize dimension, high surface area and relatively good biocompatibility, CNTs have also been employed as a novel gene delivery vector system. In our previous work, we functionalized CNTs with two polyamine polymers, polyethyleneimine (PEI) and polyamidoamine dendrimer (PAMAM). These compounds have low cytotoxicity, ability to conjugate microRNAs (such as miR-503) and, at the same time, transfect efficiently endothelial cells. The parameters contributing to the good efficiency of transfection that we observed were not investigated in detail. In fact, the diameter and length of CNTs are important parameters to be taken into account when evaluating the effects on drug delivery efficiency. In order to investigate the biophysical and biological contributions of polymer-coated CNTs in delivery of miRNAs to human cells, we decided to investigate three different preparations, characterized by different dimensions and aspect ratios. In particular, we took into account very small CNTs, a suspension of CNTs starting from the commercial product and a 2D material based on CNTs (ie, buckypapers [BPs]) to examine the transfection efficiency of a rigid scaffold. In conclusion, we extensively investigated the biophysical and biological contributions of polyamine-coated CNTs and bidimensional BPs in the delivery of miRNAs to human cells, in order to optimize the transfection efficiency of these compounds to be employed as efficient drug delivery vectors in biomedical applications

Hemorheological profiles and chronic inflammation markers in transfusion-dependent and non-transfusion- dependent thalassemia

: The rheological properties of blood play an important role in regulating blood flow in micro and macro circulation. In thalassemia syndromes red blood cells exhibit altered hemodynamic properties that facilitate microcirculatory diseases: increased aggregation and reduced deformability, as well as a marked increase in adherence to the vascular endothelial cells. A personalized approach to treating thalassemia patients (transfusions, iron chelation, and splenectomy), has increased patients' life expectancy, however they generally present many complications and several studies have demonstrated the presence of high incidence of thromboembolic events. In this study the hemorheological profiles of thalassemia patients have been characterized to point out new indices of vascular impairment in thalassemia. Plasma viscosity, blood viscosities at low and high shear rates (η1 and η200, respectively), erythrocyte aggregation index (η1/η200), and the erythrocyte viscoelastic profile (elastic modulus G', and viscous modulus G") have been studied in transfusion-dependent and non-transfusion-dependent thalassemia patients. Moreover, the levels of inflammation biomarkers in thalassemia have been evaluated to investigate a relationship between the biomarkers, the disease severity and the rheological parameters. The biomarkers studied are the main components of the immune and endothelial systems or are related to vascular inflammation: cytokines (IL-2, IL-6, IL-10, IL-17A, TNF-alpha), chemokines (IL-8, MIP-1alpha), adipocytokines (leptin and adiponectin), growth factors (VEGF, angiopoietin-1), adhesion molecules (ICAM-1, VCAM-1, E-selectin, L-selectin), and a monocyte/macrophage activation marker (CD163). This study shows that transfusion-dependent thalassemia patients, both major and intermedia, have blood viscosities comparable to those of healthy subjects. Non-transfusion-dependent thalassemia intermedia patients show high blood viscosities at low shear rates (η1), corresponding to the flow conditions of the microcirculation, an increase in erythrocyte aggregation, and high values of the elastic G' and viscous G" modules that reflect a reduced erythrocyte deformability and an increase in blood viscosity. Levels of cytokines, chemokines and adhesion molecules are different in transfusion- and non-transfusion dependent patients and positive correlations between η1 or η1/η200 and the cytokines IL-6 and IL-10 have been observed. The evaluation of the hemorheological profiles in thalassemia can provide new indicators of vascular impairment and disease severity in thalassemia in order to prevent the onset of thromboembolic events

Evolved Gas Analysis by Mass Spectrometry

Periodic publications have been published that address advances in evolved gas analysis techniques, because the correct interpretation for the mechanism of a thermally induced reaction, involving the formation of gaseous species, is strongly dependent on the characterization of the evolved products.When the nature of volatile products released by a substance subjected to a controlled-temperature program are online determined, the results allow one to prove a supposed reaction, either under isothermal or under heating conditions.Very recent analytical applications of evolved gas analysis performed by mass spectrometry, selected among those published in 2012 and 2013, are collected in this review

Mass spectrometry for evolved gas analysis: an update

Advances in evolved gas analysis (EGA) techniques are periodically reported by our group to provide useful examples of their applications in many different fields. It is actually recognized that anytime is requested a correct interpretation of the thermally induced reaction mechanism, involving the formation of gaseous species, it is strongly recommended the characterization of the evolved products. In this review, recent applications of mass spectrometry for EGA (EGA–MS), selected among those published in 2016 and 2017, are reported to show how the characterization of the nature of volatile products released by a substance subjected to a controlled temperature program allows to prove a supposed reaction, either under isothermal or under heating conditions. © 2018, © 2018 Taylor & Francis Group, LLC