Synthesis, characterization and heterogeneous catalytic application of copper integrated mesoporous matrices.

Ordered copper integrated mesoporous silicate catalysts (CuMSC) have been synthesized by the utilization of the amphiphilic tri-block copolymer pluronic F127 as a structure directing agent (SDA) under acidic aqueous conditions. The mesophase of the materials was investigated using small-angle powder X-ray diffraction and transmission electron microscopic (TEM) image analysis. N2 adsorption-desorption studies show that the BET surface area of CuMSC (214-407 m(2) g(-1)) is lower than that of pure silica (611 m(2) g(-1)) and has smaller average pore dimensions (4.0-5.0 nm), both prepared following the same synthetic route. The reduction of pore size and surface area points to incorporation of copper within the silicate network. FEG-SEM results suggest that the materials have a plate-like morphology and are composed of very tiny nanoparticles. EDS surface chemical analysis was utilized for the detection of the distribution of Si, O and Cu in the matrix. The FT IR spectral study suggests the complete removal of the surfactants from the calcined materials and the presence of Si-O-Cu bonds for high nominal contents. X-ray photoelectron spectroscopy (XPS) and UV-vis reflectance spectra show the oxidation state of copper and coordination mode, respectively. These mesoporous materials display a good catalytic activity in the oxidation of cyclohexane to cyclohexanone and cyclohexanol in the presence of the green oxidant hydrogen peroxide. The maximum yield (cyclohexanone and cyclohexanol) was ca. 29% and the TON (turnover number) was 276 under optimal reaction conditions. The good catalytic activity could be attributed to the large surface area and the presence of a high number of active sites located at the surface of the material, as well as to its stability. The catalysts showed negligible loss of activity after five cycles.

Reactivity of the antitumor complex (H2trz)[trans-RuCl4(N2-Htrz)2] in the presence of DNA purines within a fluorinated silica matrix.

The stability of the antitumor Ru(III) complex (H(2)trz)[trans-RuCl(4)(N(2)-Htrz)(2)] within a tailored sol-gel silica matrix was studied, combining the information from UV-vis and infrared spectroscopies. The matrix was synthesized by a one-step sol-gel process catalyzed by hydrofluoric acid, resulting extremely light, hydrophobic and fluorinated. It is shown that upon encapsulation, the complex undergoes a series of processes, starting with the increase in charge density on the metal center, followed by hydrolysis reactions. The modified complex interacts with the matrix through hydrogen bonds between the aquo/hydroxo ligands and the fluorine atoms. Its interactions with DNA purines (guanine and adenine) were probed within the confined medium defined by the same silica matrix. It is found that coencapsulated guanine does not interfere with the complex aquation processes, while coencapsulated adenine has a delaying effect. No covalent bonding between the complex and the purines is detected, but interactions between the triazole ligands and the imidazole ring of guanine and the imidazole and pyrimidine rings of adenine are observed. Hydrogen bonding is established between the carbonyl and the ammine groups of guanine and the aquo/hydroxo ligands of the complex. For adenine, those interactions involve mostly the N9H of the purine and the NH groups of the triazole ligands, in addition to π-π interactions.

Interactions between DNA purines and ruthenium ammine complexes within nanostructured sol-gel silica matrixes.

The interactions between DNA purines (guanine and adenine) and three ruthenium ammine complexes (hexaammineruthenium(III) chloride, hexaammineruthenium(II) chloride, and ruthenium-red) were studied in a confined environment, within sol-gel silica matrixes. Two encapsulation methods were rehearsed (differing in temperature and condensation pH), in order to analyze the effects of the sol-gel processes on the purines and on the Ru complexes separately. The extent of decomposition of the Ru complexes, as well as the interactions established with the purine bases, proved to be determined by the coencapsulation method. Combined results by diffuse reflectance UV-vis and infrared spectroscopies showed that, when coencapsulation is carried out at 60 degrees C, specific H bonding interactions are established between the amine group of Ade and the ammine groups of the Ru complex or the hydroxo group of an early decomposition product. These are responsible for the important role of the purine in inhibiting the oxidation reactions of the Ru(II) and Ru(III) complexes. In contrast, Gua establishes preferential H bonds with the matrix (mainly due to the carbonyl group), leading to higher yields in the final oxidation products of the Ru complexes, namely, trimers and dimers. Direct covalent bonding of either purine to the metal was not observed.

Encapsulation of ruthenium nitrosylnitrate and DNA purines in nanostructured sol-gel silica matrices.

The interactions between DNA purines (guanine and adenine) and the ruthenium complex Ru(NO)(NO(3))(3) were studied within nanostructured silica matrices prepared by a two-step sol-gel process. By infrared analysis in diffuse reflectance mode, it was proved that encapsulation induces a profound modification on the complex, whereas guanine and adenine preserve their structural integrity. The complex undergoes nitrate ligand exchange and co-condenses with the silica oligomers, but the nitrosyl groups remain stable, which is an unusual behavior in Ru nitrosyl complexes. In turn, the doping molecules affect the sol-gel reactions and eventually the silica structure as it forms: the complex yields a microporous structure, and the purine bases are responsible for the creation of macropores due to hydrogen bonding with the silanol groups of the matrix. In a confined environment, the interactions are much stronger for the coencapsulated pair guanine complex. While adenine only establishes hydrogen bonds or van der Waals interactions with the complex, guanine bonds covalently to Ru by one N atom of the imidazole ring, which becomes strongly perturbed, resulting in a deformation of the complex geometry.

A case-control study on risk factors for early-onset respiratory tract infection in patients admitted in ICU.

BACKGROUND: Respiratory tract infections are common in intensive care units (ICU), with incidences reported from 10 to 65%, and case fatality rates over 20% in pneumonia. This study was designed to identify risk factors for the development of an early onset respiratory tract infection (ERI) and to review the microbiological profile and the effectiveness of first intention antibiotic therapy. METHODS: Case-control, retrospective clinical study of the patients admitted to the Intensive Care Unit (ICU) of our hospital, a teaching and tertiary care facility, from January to September 2000 who had a respiratory tract infection diagnosed in the first 5 days of hospital stay. RESULTS: Of the 385 patients admitted to our unit: 129 (33,5%) had a diagnosis of ERI and 86 patients were admitted to the control group. Documented aspiration (adjusted OR = 5,265; 95% CI = 1,155 - 24,007) and fractured ribs (adjusted OR = 12,150; 95% CI = 1,571 - 93,941) were found to be independent risk factors for the development of ERI (multiple logistic regression model performed with the diagnostic group as dependent variable and adjusted for age, sex, SAPS II, documented aspiration, non-elective oro-tracheal intubation (OTI), fractured ribs, pneumothorax and pleural effusion).A total of 78 organisms were isolated in 61 patients (47%). The normal flora of the upper airway (Streptococcus pneumoniae, Staphylococcus aureus, Haemophilus influenza and Moraxella catharralis) accounted for 72% of all isolations achieved, polimicrobian infections were responsible for 25% of all microbiological documented infections. First intention treatment was, in 62% of the patients, the association amoxacillin+clavulanate, being effective in 75% of the patients to whom it was administered. The patients with ERI needed more days of OTI (6 vs 2, p < 0,001) and mechanical ventilation (6 vs 2, p < 0,001) and had a longer ICU (7 vs 2, p < 0,001) and hospital length of stay (17 vs 11, p = 0,018), when compared with controls. CONCLUSION: In this study documented tracheobronchial aspiration and fractured ribs were identified as independent risk factors for ERI. Microbiological profile was dominated by sensitive micro-organisms. The choice amoxacilin+clavulanate revealed to be a good option with an effectiveness rate of 77% in the patients in whom it was used.

Massive lower gastrointestinal bleeding from idiopathic ileocolonic varix: report of a case.

Idiopathic varices of the entire colon are very rare. We report on a 64-year-old patient with massive lower gastrointestinal hemorrhage from an extensive ileocolonic varix. Diagnosis was established by colonoscopy. The patient underwent an emergency ileocolectomy with satisfactory results. This rare case shows the importance of colonoscopy in the evaluation of patients with lower gastrointestinal hemorrhage and reminds us that sometimes the diagnosis is not what we expect. Recognition of this abnormality is important because varices may be the cause of massive lower gastrointestinal hemorrhage.