RESUMEN

In the present study, supramolecular polyelectrolyte complexes (SPEC) based on a cyclodextrin-grafted chitosan derivative and carrageenan were prepared and evaluated for controlled drug release. Samples were characterized by FTIR, SEM, and ζ-potential measurements, which confirmed the formation of the polymeric complex. The phenolphthalein test confirmed the presence and availability of inclusion sites from the attached ßCD. Silver sulfadiazine was used as the model drug and the association with the SPEC was studied by FTIR and computational molecular modeling, using a semi-empirical method. DRS and TEM analyses have shown that Ag+ ions from the drug were reduced to form metallic silver nanostructures. In vitro tests have shown a clear bacterial activity toward Gram-positive bacteria Staphylococcus aureus and Enterococcus durans/hirae and Gram-negative bacteria Klebsiella pneumoniae and Escherichia coli. Finally, this work shows that ßCD-chitosan/carrageenan supramolecular polyelectrolyte complexes hold an expressive potential to be applied as a polymer-based system for controlled drug release.

Asunto(s)

RESUMEN

This work reports the preparation of HZSM-5/SBA-15 micro-mesoporous materials with composite structure by mechanosynthesis and their use as templates to micro-mesoporous carbons, with palm oil cooking waste as carbon source. HZSM-5/SBA-15 composites were prepared in different mass proportions (25:75, 50:50 and 75:25) by a mechanosynthetic strategy. The palm oil waste was infiltrated into the template pores by a two-step procedure involving grinding followed by stirring the suspension in an oil solution and carbonization under inert atmosphere. SEM images showed the efficiency of mechanosynthesis for all mass proportions, while textural properties were strongly influenced by the presence of SBA-15. A comparison of 50% HZSM-5/SBA-15 mixture with pristine SBA-15 and uncalcined SBA-15 as carbon templates evidenced that the 50% HZSM-5/SBA-15 mixture lead to the carbon with the highest surface area and pore volume. The resulting carbon material was studied as adsorbent to different dye molecules, including molecules with different charges and sizes. Results revealed that the carbon has a significantly higher affinity for cationic dyes, that the mesopore structure favors high diffusion rates and that the surface groups have a very high affinity for cationic dye molecules.

Asunto(s)

RESUMEN

Crosslinking and functionalizing agents play crucial roles in the properties/applications of cyclodextrin polymers. Here we report the synthesis of water-insoluble cyclodextrin polymers containing l-glutamic acid. In a first route, ß-cyclodextrin was crosslinked with citric acid and subsequently functionalized with l-glutamic acid, while a second route involved esterification of ß-cyclodextrin with l-glutamic acid, catalyzed by tin octoate. Combined evaluation by FTIR, 13C CP/MAS NMR and elemental analysis indicated that the sample from the first route had the largest fraction of glutamic acid. Sorption tests with methyl orange showed that the cyclodextrin cavities were slightly more available in the polymer obtained through the second route. Samples were employed as reductant and stabilizer for fast and easy synthesis of silver nanoparticles at room temperature. Brief UV irradiation was sufficient for samples produced by the first route.

RESUMEN

Synthesis of ternary polyurethanes (PUs) from hexamethylenediisocyanate, ß-cyclodextrin and ß-glycerophosphate (acid and calcium salt) was studies varying synthesis parameters such as monomer proportion, heating method (reflux and microwave), and catalyst amount. Favorable conditions were provided by microwave irradiation and use of ß-glycerophosphoric acid although the results suggest that it is possible to obtain ternary PUs with the calcium salt. FTIR data indicated the existence of secondary urea linkages. After characterization of ternary PUs by FTIR spectroscopy, XRD and thermal analysis, as well as evidences that the cyclodextrin cavities remained active toward inclusion of guest molecules, the possibility of inclusion of the antibiotic ciprofloxacin was evaluated. Absence of ciprofloxacin melting peak in DSC curves indicated that it is molecularly dispersed within the polymer, possibly included in the cyclodextrin. In vitro release experiments suggested additional non-inclusion interactions, showing also that the use of dialysis membranes may mask the actual release profile.

Asunto(s)

RESUMEN

Here we report the use of ß-cyclodextrin polyurethane nanosponges cross-linked with 1,6-hexamethylene diisocyanate as a template for the preparation of Aun quantum clusters, by the core-etching of glutathione-capped Au nanoparticles. The study of temporal evolution of the core-etching process using different Au concentrations indicated that formation of Aun clusters embedded in the nanosponge is favored by the use of lower Au concentrations, since it began at shorter times and lead to higher cluster loading. An estimation of the number of Au atoms based on the maximum photoluminescence wavelength suggested that, depending on the Au concentration and the core etching time, clusters with 11-15 atoms were formed. After excluding the possibility of an inclusion complex formation, evaluation of the catalytic activity of nanosponge-loaded Aun clusters toward the reduction of 4-nitrophenol has shown that the reaction is catalyzed by the Aun clusters with no induction time, following the Langmuir-Hinshelwood kinetic model.

Asunto(s)

RESUMEN

Here we report the use of a thiol-functionalized silica-gel to prepare supported CdS nanocrystals by a facile one-step procedure. Upon changing the relative proportion of the matrix we obtained nanocrystals with different average sizes and size distributions, as evidenced by spectroscopic measurements as well as TEM images. Photoluminescence spectra also indicated that the main effect of the matrix is related to the size control since the spectral profiles were found to be strongly dependent on the excitation wavelength. The performance of the material in the photocatalytic degradation of two commercial dyes (methylene blue and rhodamine 6G) has been tested under sunlight radiation, showing promising results. Almost complete decolorization has been observed after 80 min of exposure, with no adsorption on the silica surface.

Asunto(s)

RESUMEN

Here we report the preparation of a trimethoprim/2-hydroxypropyl-γ-cyclodextrin inclusion complex along with a physicochemical study, structural characterization, and molecular modeling of the complex. As main results, we observed from phase-solubility studies at two temperatures (20 °C and 35 °C) that the association constants decrease with increasing temperature. Values for K(1:1) constant were of the same magnitude order of those found for the parent γ-CD. The inclusion orientation as evidenced by ROESY measurements involves the inclusion of the 3,4,5-trimethoxybenzyl ring in the CD cavity from the larger rim. This is in agreement with semiempirical molecular modeling calculation.

Asunto(s)

RESUMEN

Here we report the structural characterization, physicochemical study and molecular modeling of the inclusion complex of trimethoprim in randomly methylated beta-cyclodextrin. The phase-solubility diagram obtained at pH 7.0 exhibited a linear behavior for the RAMEB concentrations studied suggesting a 1:1 stoichiometry and absence of aggregation in solution. From stoichiometric determination by the continuous variation method we confirmed a 1:1 stoichiometry. To make a detailed characterization of the inclusion mode, spectroscopic measurements by infrared and 1D and 2D (1)H NMR spectroscopy provided evidence that the inclusion mode is characterized by inclusion of the trimethoxyphenyl ring in the cavity; interactions with methyl groups located in the border of the cavity were also detected. The structure proposed was also confirmed by semiempirical molecular modeling.

Asunto(s)

RESUMEN

Oily sludge samples formed in water-oil separation tanks from a petroleum industry were collected, characterized and heat-treated at different temperatures, in order to yield carbon-clay composites. EDX microanalysis, XRD and FTIR data revealed that before carbonization the oily sludge was formed mainly by a mixture of quartz, montmorillonite, calcite, barite and oil residues. After carbonization, mineral phases present were mainly quartz, anorthite and gehlenite, in addition to graphitic and disordered carbon domains, according to XRD, Raman and TEM measurements. A preliminary evaluation of the electrical conductivity performed by Impedance Spectroscopy revealed that the composites formed are conductive, exhibiting conductivity values typical of semiconductors, in contrast to the precursor material.

Asunto(s)

RESUMEN

An inclusion complex between the dihydrofolate reductase inhibitor pyrimethamine (PYR) and alpha-cyclodextrin (alpha-CD) was prepared and characterized. From the phase-solubility diagram, a linear increase of PYR solubility was verified as a function of alpha-CD concentration, suggesting the formation of a soluble complex. A 1:1 host-guest stoichiometry can be proposed according to the Job's plot, obtained from the difference of PYR fluorescence intensity in the presence and absence of alpha-CD. Differential scanning calorimetry (DSC) measurements provided additional evidences of complexation such as the absence of the endothermic peak assigned to the melting of the drug. The inclusion mode characterized by two-dimensional (1)H NMR spectroscopy (ROESY) involves penetration of the p-chlorophenyl ring into the alpha-CD cavity, in agreement to the orientation optimized by molecular modeling methods.

Asunto(s)

RESUMEN

Thermal behavior of the complexes Pd2(dppm)2Cl2, Pd2(dppm)2(SnCl3)Cl and Pd2(dppm)2(SnCl3)2 (dppm=bis[diphenylphosphino(methane)], ((C6H5)2PCH2P(C6H5)2) in the solid state and immobilized onto porous Vycor glass was studied. Similar decomposition mechanisms were observed for the solid and immobilized complexes, with a small thermal stabilization upon immobilization. The decomposition products were characterized by X-ray diffractometry, Raman and diffuse reflectance infrared spectroscopy, which indicated the presence of a mixture of metallic palladium and oxidized species such as PdO,condensed phosphates, SnO2 and SnP2O7. According to X-ray diffractometry, the decomposition products of the immobilized complexes presented higher amounts of PdO than the solid-state residues, probably as an effect of interactions with silanol groups present in the glass surface.

RESUMEN

In this work we prepared and characterized an inclusion complex of the dihydropteroate synthase inhibitor sulfadiazine (SDZ) in 2-hydroxypropyl-beta-cyclodextrin (HPBCD). From the phase-solubility diagram we observed an increase in the water solubility of the drug, calculating a binding constant of 1879M(-1). The inclusion mode involves a NH(2)-in orientation of the drug in the HPBCD cavity, according to the 2D NMR (ROESY) data and confirmed by molecular modeling using the semiempirical PM6 and RM1 methods.

Asunto(s)

RESUMEN

The inclusion complexation of pyrimethamine in 2-hydroxypropyl-beta-cyclodextrin has been investigated by 2D (1)H NMR, FTIR and UV/visible spectroscopy and also by molecular modelling methods (AM1, PM3, MM3). From the phase-solubility diagram a linear increase was observed in pyrimethamine aqueous solubility in the presence of 2-hydroxypropyl-beta-cyclodextrin, evidencing the formation of a soluble inclusion complex. According to the continuous variation method (Job's plot) applied to fluorescence measurements, a 1:1 stoichiometry has been proposed for the complex. Concerning the structure of the complex, a Cl-in orientation of pyrimethamine in the 2-hydroxypropyl-beta-cyclodextrin cavity has been proposed from the theoretical calculations, being confirmed by two-dimensional (1)H NMR spectroscopy (ROESY). The thermal behaviour has also been studied, providing complementary evidences of complex formation.

Asunto(s)

RESUMEN

Principal component analysis was applied to XRD data from a series of Mg(OH)2 samples prepared under different hydrothermal conditions from bischofite (MgCl2.6H2O) and carnallite (KCl.MgCl2.6H2O), owing to differences in full width at half-maximum (fwhm) as well as in the intensity ratio I001/I101 of the respective diffraction peaks. According to the PCA results, the four principal components are able to explain 93% of the total variance and the samples can be classified into four main groups. For instance, the principal component PC1 can be interpreted as the crystallite size along the 101 direction since it is related to the fwhm of this peak. On the other hand, PC3 is related to orientation effects along 001 and 101 directions as it is dominated by the relative intensities of the two peaks. Finally, a comparison of the scanning electron microscopy images of the samples classified in each group revealed that in most of the cases a distinct morphology predominates within each group, which can be explained on the basis of the brucite growth mechanism.

Asunto(s)

RESUMEN

In this work silica gels have been prepared by a sol-gel method using tetraethylorthosilicate as gel precursor. The tetraruthenated porphyrins H2(3-TRPyP), Co(3-TRPyP), and H2(4-TRPyP) were incorporated into the systems during gel formation without problems commonly found in the process, such as aggregation. Spectroscopic studies of the resulting silica gels revealed the presence of absorption bands in the range 200-400 nm associated with the transitions of the groups ruthenium-bipyridine, along with the Soret band at the same wavelengths observed in solution. The porphyrins were found to preserve fluorescence emission properties in the range 650-700 nm even after the aging period. Study of the thermal behavior and decomposition kinetics evidenced that the porphyrin H2(4-TRPyP) is the least stable of the group and that all compounds decompose according to first-order kinetics.

Asunto(s)

RESUMEN

A method for the determination of free and total sulfur dioxide in wines, based on the use of an optical sensor that employs a dichlorobis(diphenylphosphino)methane dipalladium I complex [Pd(2)(dppm)(2)Cl(2)] immobilized in a PVC membrane plasticized with o-nitrophenyloctylether (o-NPOE) is described. A sensing membrane [4.2% Pd(2)(dppm)(2)Cl(2), 20.8% PVC, and 75% o-NPOE] was adapted to the tip of a bifurcated optical fiber bundle to perform reflectance measurements at 550 nm. The detection system consisted of two cells (40 mL), which hold the sample solution (plus reagents) and the optical sensor, respectively. For the determination of free SO(2), a wine sample was mixed with H(2)SO(4) solution in the sample cell, into which N(2) was bubbled, providing mixing of the solutions and conducting the SO(2) formed toward the detection cell. For determination of total SO(2), a KOH solution was mixed with the wine in the sample cell. Afterward, an H(2)SO(4) solution was added to the cell, and then N(2) was bubbled to conclude the measurement. Linear responses up to 50 and 150 mg L(-1) were obtained for free and total SO(2), with detection limits of 0.37 and 0.70 mg L(-1), respectively. The repeatability of the method was evaluated by carrying out 10 measurements using a single wine sample, providing relative standard deviation values of 2.2 and 2.5% for free and total SO(2), respectively. The sensing membrane prepared from 10 muL of the cocktail solution lasted for 80 measurements, whereas those prepared from 200 muL can be used for 250 measurements. The method was applied to free and total SO(2) determination in wines, and the results did not show significant difference from those obtained with the Ripper reference method at a confidence level of 95%.

Asunto(s)