Polycondensation of mono- and difunctional derivatives of p-xylene

A new method for the production of polydimethylbenzylenes,$ \rlap{--} [{\rm C}_6 {\rm H}_4 ({\rm CH})_2 {\rm CH}_{\rm 2} \rlap{--} ]_n $, involves the polycondensation of the mono- and dichloromethyl and mono- and diacetoxymethyl derivatives of p-xylene via an acid-catalyzed reaction in anhydrous acetic acid. The reaction of the difunctional derivatives is slower than the reaction of the monofunctional ones, leading to linear, predominantly crystalline, high-melting polymers with molecular weights of 2000–3000. Polycondensation of both monomers under different feed ratios leads to polymers with the same structure, and the monofunctional monomers condense with themselves more favorably than with the difunctional ones. Thus a head-to-head structure is preferred, and crystalline polymers of high structural purity are obtained.     

Polymer microgels: reactors for semiconductor, metal, and magnetic nanoparticles

We report a strategy for the production of materials with structural hierarchy. The approach employs polymer microgels as templates for the synthesis of semiconductor, metal, or magnetic nanoparticles (NPs). We show that NPs with predetermined dimensions and size-dependent properties can be synthesized by using a very delicate balance between the reaction conditions, the composition and the structure of microgel templates, and the concentration of NPs in the microgel. Postheat treatment of microgels doped with semiconductor nanoparticles reduces NP polydispersity and allows control of their photoluminescence. Microgel templates are particularly beneficial in the synthesis of polymer microspheres heavily loaded with monodisperse superparamagnetic Fe(3)O(4) NPs. Hybrid submicrometer-size microgels have promising potential applications in photonics, catalysis, and separation technologies.     

Polyoxometalates as Inorganic Building Blocks of Multifunctional Molecular Materials

The use of polyoxometalates (pOM's) as inorganic component in the synthesis of new molecular hybrid materials is presented. Here we show that the combination of organic molecules of the tetrathiafulvalene (TTF) type or perylene (per) with POM's yields new radical salts with unprecedented structures that present interesting magnetic and/or electrical properties or coexistence of both. The first true metallic radical salt containing a POM has been prepared and characterized. We also describe the recent results obtained by combining magnetic POM's with the organometallic cation decamethylferrocene.     

Interdisciplinary study on pottery experimentally impregnated with wine

Experimentally developed ceramic pots, with two different sizes of grain, were half-filled with wine and subjected to thermal alteration at constant elevated temperature ((60 ± 2)°C) in darkness for 12 weeks. This work sought to characterise the samples thereby obtained from chemical and mineralogical perspectives using scanning electron microscopy and an energy-dispersive X-ray microanalysis system (SEM-EDX), Fourier transform infrared spectroscopy (FTIR) and capillary electrophoresis (CE) with UV detection as an alternative to chromatographic methods, due to its good resolution, automation, simplicity, high speed, low consumption of chemicals and short time required for sample preparation. The capillary electrophoresis method was used for the detection of five wine biomarkers: succinic acid, malic acid, tartaric acid, citric acid and lactic acid. In general, it was noted that the fine-grained ceramic assortment retained the organic material better than the coarser-grained ceramics. An interesting observation derived from this study was that not only could tartaric acid be considered as a biomarker for wine residues in archaeological pottery, but malic acid could also act similarly for white wine and lactic acid for red wine.     

Density Functional Theory Study of Hypoxanthine Tautomerism in Both the Isolated State and a Modeled-Ideal Aqueous Solution at Several Heterocyclic Protonation Levels

In order to advance the knowledge of prototropic tautomerism from the physicochemical point of view, the purine derivative hypoxanthine has been selected and studied. The overall purpose has been to explore thermodynamic aspects of the heterocycle tautomerism under the influence of both its protonation level and the surrounding dielectric constant. A Density Functional Theory study (at the B3LYP/6-31++G** level) was performed, in which the energetic and thermodynamic stabilities, the electric dipole moment values, the tautomeric equilibrium constants and the tautomeric populations were obtained for several hypoxanthine tautomers under systematically modified heterocyclic protonation levels, considering both isolated and ideal aqueous solution states. Among the interesting results obtained are changes in the tautomeric populations for several heterocyclic protonation states and with the increase of the dielectric constant. Several of the predictions made for an aqueous solution show good agreement with recently reported experimental conclusions. Also, the ionizable groups that contribute to the different hypoxanthine ionization steps in the main tautomers have been established. These and other related results are presented and discussed. Finally, the confidence developed in the predicted tautomeric populations in a modeled-ideal aqueous solution allows us to propose that the methodology applied here can be used for the study of prototropic tautomerism in heterocycles belonging to this class, particularly when the experimental work is challenging in both performance and physicochemical data analysis.     

Spectroscopy of Hafnium Monohalides

The modern intracavity laser method has been applied to study electronic spectra of the hafnium monohalides molecules. Results of new investigation of HfF and HfBr molecules are presented: the bands at 589.3, 590.6, and 593.1 nm observed in intracavity laser spectra of HfF₄ have been assigned to the bands of HfF or ionized HfF; new molecular constants of the HfBr molecule have been obtained. Spectroscopic studies of HfCl and Hfl molecules are discussed, and the most reliable molecular constants of HfCl, HfBr, and Hfl molecules are recommended.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.