WORKSHOP “ETICA E CHIMICA” A PISA

Resoconto del workshop nazionale promosso dalla Società Chimica Italiana su “Etica e sperimentazioni scientifiche” il 22 e 23 gennaio scorsi. Tra gli argomenti trattati: la sperimentazione dei farmaci, l’etica della pubblicazione scientifica e i risvolti della chimica su società e ambiente

Genipin diffusion and reaction into a gelatin matrix for tissue engineering applications

Genipin is a natural low-toxic cross-linker for molecules with primary amino groups, and its use with collagen and gelatin has shown a great potential in tissue engineering applications. The fabrication of scaffolds with a well-organized micro and macro topology using additive manufacturing systems requires an accurate control of working parameters, such as reaction rate, gelling time, and diffusion constant. A polymeric system of 5% w/v gelatin in PBS with 2 mg/mL collagen solutions in a 1:1 weight ratio was used as template to perform measurements varying genipin concentration in a range of 0.1-1.5% w/w with respect to gelatin. In the first part of this work, the reaction rate of the polymeric system was estimated using a new colorimetric analysis of the reaction. Then its workability time, closely related to the gelling time, was evaluated thanks to rheological analysis: finally, the quantification of static and dynamic diffusion constants of genipin across nonreacting and reacting membranes, made respectively by agarose and gelatin, was performed. It was shown that the colorimetric analysis is a good indicator of the reaction progress. The gelling time depends on the genipin concentration, but a workability window of 40 min guaranteed up to 0.5% w/w genipin. The dynamic diffusion constant of genipin in the proposed polymeric system is in the order of magnitude of 10(-7) . The obtained results indicated the possibility to use the genipin, gelatin, and collagen, in the proposed concentrations, to build well-defined hydrogel scaffolds with both extrusion-based and 3D ink-jet system. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2015

Thermal degradation chemistry of archaeological pine pitch containing beeswax as an additive

Thermo analytical techniques and gas chromatography/mass spectrometry (GC/MS) were used to evaluate the presence of chemical-physical interactions between pine pitch and beeswax used as additive The mixtures found in several archaeological objects demonstrate that by modifying the physical and chemical properties of pitch and tar, our ancestors were able to add a variety of organic materials, such as waxes or animal fats.Westudied pine pitch replicas from Pinus sylvestris prepared following a test from the field of experimental archaeology. Varying proportions of beeswax were added and then the resulting pitches were studied by a multi-analytical approach comprising the use of thermo analytical techniques (DSC, TG and TG-FTIR) and GC/MS, which provides molecular information. The same approach was also used to study a mixture of pitch from Pinus sylvestris L. and beeswax ("Zopissa"), whose relative proportions were unknown, and two archaeological adhesives collected from glass opus sectile fragments found in the northern necropolis of Antinoopolis (Egypt, 4th-5th century AD). Our thermo-analytical techniques managed to determine the relative proportion of pine pitch and additives, such as beeswax, in unknown archeological mixtures, and to evaluate the presence of interactions between pitch and additive

Thermal behavior study of pristine and modified halloysite nanotubes: A modern kinetic study

Pristine halloysite nanotubes (HNTs) were studied by thermogravimetry (TG) up to 800 C. Etching of alumina from inside the tube (causing a significant increase in tube lumen) was realized by treating the material with an acidic H2SO4 solution at 50 C. Both materials were characterized by TG-FTIR techniques and their thermal behaviors were compared with that of kaolinite. The coupling of TG with FTIR enables to detect the gases evolved during the TG experiments, thus confirming that only pristine HNTs undergo dehydration with the loss of interlayer water molecules at around 245 C, while dehydroxylation occurs in all these materials in close temperature ranges around 500 C. TG runs at five different heating rates (2, 5, 10, 15 and 20 C min-1), was carried out in the same experimental conditions used for the thermal analysis study with the aim to investigate dehydration and dehydroxylation kinetics using some isoconversional methods recommended by the ICTAC kinetic committee, and thermogravimetric data under a modulated rising temperature program. Finally, the results of the kinetic analysis were discussed and explained in terms of the strengths of the hydrogen bonds broken during these processes

Interactions between inorganic pigments and rabbit skin glue in reference paint reconstructions

The thermal degradation of rabbit skin glue, a collagen-based proteinaceous material used as a paint binder in paintings, was investigated in this paper. Paint reconstructions of the glue on its own or mixed with azurite (Cu3(CO3)2(OH)2), calcium carbonate (CaCO3), hematite (Fe2O3nH2O) and red lead (Pb3O4) were analysed using a thermoanalytical approach. This method enabled us to investigate the interactions between the glue and pigments before and after artificial indoor light ageing. The study was carried out using differential scanning calorimetry, thermogravimetry and thermogravimetry/FTIR analysis already successfully employed to characterize the paint binders. The results highlighted that all the inorganic pigments interact with rabbit skin glue, thus decreasing the thermal stability of the binder. Light ageing further decreased the thermal stability of pigmented paint replicas, suggesting a moderate increase in the rate of the degradation

Loading of halloysite nanotubes with BSA, α-Lac and β-Lg: A Fourier transform infrared spectroscopic and thermogravimetric study

Halloysite nanotubes (HNTs) are considered as ideal materials for biotechnological and medical applications. An important feature of halloysite is that it has a different surface chemistry on the inner and outer sides of the tubes. This property means that negatively-charged molecules can be selectively loaded inside the halloysite nanoscale its lumen. Loaded HNTs can be used for the controlled or sustained release of proteins, drugs, bioactive molecules and other agents. We studied the interaction between HNTs and bovine serum albumin, α lactalbumin and β -lactoglobulin loaded into HTNs using Fourier transform infrared spectroscopy and thermogravimetry. These techniques enabled us to study the protein conformation and thermal stability, respectively, and to estimate the amount of protein loaded into the HNTs. TEM images confirmed the loading of proteins into HTNs

Intercalation of Zn(II) and Cu(II) complexes of the cyclic polyamine Neotrien into DNA: equilibria and kinetics

The equilibria and kinetics of the interaction of the Zn(II) and Cu(II) complexes of the macrocyclic polyamine 2,5,8,11-tetraaza[12]-[12](2,9)[1,10]-phenanthrolinophane (Neotrien) with calf thymus DNA have been investigated at pH = 7.0 and T = 25 degreesC by spectrophotometry, spectrofluorimetry and stopped-flow method. At low dye/polymer ratios both complexes bind to DNA according to the excluded site model. At high dye/polymer ratios the binding displays cooperative features. The logarithm of the binding constant depends linearly on - log[NaCl]. The kinetic results suggest the D + S reversible arrow D, S reversible arrow DS mechanism where the metal complexes (D) react with the DNA sites (S) leading to fast formation of an externally bound form (D, S) which, in turn, is converted into internally bound complex (DS) by intercalation. The binding constants, evaluated as ratios of rate constants, agree with those obtained from equilibrium binding experiments, thus confirming the validity of the proposed model. Fluorescence titrations, where the metal-Neotrien complexes were added to DNA previously saturated with ethidium bromide (EB), show that both complexes displace EB from the DNA cavities. The reverse process, i.e. the addition of excess ethidium to the DNA/metal Neotrien systems, leads to fluorescence recovery for DNA/ZnNeotrien but not for DNA/CuNeotrien. This observation suggests that the binding of CuNeotrien induces deep alterations in the DNA structure. Experiments with Poly(dA-dT) . Poly(dA-dT) and Poly(dG-dC) . Poly(dG-dC) reveal that CuNeotrien mainly affects the structure of the latter polynucleotide. (C) 2004 Elsevier Inc. All rights reserved

Fourier transform infrared spectroscopic study of rabbit glue/inorganic pigments mixtures in fresh and aged reference paint reconstructions

We studied the interactions of rabbit glue, a collagen-based proteinaceous binder, with azurite (Cu3(CO3)2(OH)2), calcium carbonate (CaCO3), hematite (Fe2O3·nH2O), red lead (Pb3O4) and cinnabar (HgS) by Fourier transform infrared spectroscopy (FT-IR). The research was carried out on a set of paint reconstructions, which were analysed before and after artificial light ageing. A deconvolution of the amide I FT-IR absorption peak was performed with a written-in-house LabVIEW program to study the secondary structure of the glue.The changes in the glue conformation highlighted that all the inorganic pigments interact with the proteinaceous binder. The conformational changes were correlated with a loss of stability of the collagen structure, especially after ageing, likely due to the interlayer coordination of metals salts and oxide with protein functional groups. These results were correlated with the lower thermal stability of the glue/pigment mixtures with respect to the pure glue, evidenced by thermogravimetry (TG) and differential scanning calorimetry (DSC) analyses performed in a previous step of this work

Modeling of the acute toxicity of benzene derivatives by complementary QSAR methods

A data set containing acute toxicity values (96-h LC50) of 69 substituted benzenes for fathead minnow (Pimephales promelas) was investigated with two Quantitative Structure- Activity Relationship (QSAR) models, either using or not using molecular descriptors, respectively. Recursive Neural Networks (RNN) derive a QSAR by direct treatment of the molecular structure, described through an appropriate graphical tool (variable-size labeled rooted ordered trees) by defining suitable representation rules. The input trees are encoded by an adaptive process able to learn, by tuning its free parameters, from a given set of structureactivity training examples. Owing to the use of a flexible encoding approach, the model is target invariant and does not need a priori definition of molecular descriptors. The results obtained in this study were analyzed together with those of a model based on molecular descriptors, i.e. a Multiple Linear Regression (MLR) model using CROatian MultiRegression selection of descriptors (CROMRsel). The comparison revealed interesting similarities that could lead to the development of a combined approach, exploiting the complementary characteristics of the two approaches

Temporal and spatial analysis of the 2014-2015 Ebola virus outbreak in West Africa

West Africa is currently witnessing the most extensive Ebola virus (EBOV) outbreak so far recorded. Until now, there have been 27,013 reported cases and 11,134 deaths. The origin of the virus is thought to have been a zoonotic transmission from a bat to a two-year-old boy in December 2013 (ref. 2). From this index case the virus was spread by human-to-human contact throughout Guinea, Sierra Leone and Liberia. However, the origin of the particular virus in each country and time of transmission is not known and currently relies on epidemiological analysis, which may be unreliable owing to the difficulties of obtaining patient information. Here we trace the genetic evolution of EBOV in the current outbreak that has resulted in multiple lineages. Deep sequencing of 179 patient samples processed by the European Mobile Laboratory, the first diagnostics unit to be deployed to the epicentre of the outbreak in Guinea, reveals an epidemiological and evolutionary history of the epidemic from March 2014 to January 2015. Analysis of EBOV genome evolution has also benefited from a similar sequencing effort of patient samples from Sierra Leone. Our results confirm that the EBOV from Guinea moved into Sierra Leone, most likely in April or early May. The viruses of the Guinea/Sierra Leone lineage mixed around June/July 2014. Viral sequences covering August, September and October 2014 indicate that this lineage evolved independently within Guinea. These data can be used in conjunction with epidemiological information to test retrospectively the effectiveness of control measures, and provides an unprecedented window into the evolution of an ongoing viral haemorrhagic fever outbreak.status: publishe