Platinum nanoparticles incorporated in silsesquioxane for use in LbL films for the simultaneous detection of dopamine and ascorbic acid

We describe the preparation of platinum nanoparticles (PtNPs) using the 3-n-propylpyridinium silsesquioxane chloride (SiPy+Cl-) as a nanoreactor and stabilizer. The formation of PtNPs was monitored by UV-Vis spectroscopy by measuring the decrease in the intensity of the band at 375 nm, which is attributed to the electronic absorption of PtCl62- ions. TEM images of Pt-SiPy+Cl- nanohybrid indicated an average size of 3-40 nm for PtNPs. The Pt-SiPy+Cl- was used as a polycation in the preparation of layer-by-layer films (LbL) on a glass substrate coated with fluorine-doped tin oxide (FTO) alternating with the polyanion poly(vinyl sulfonic acid) (PVS). The films were electrochemically tested in sulfuric acid to confirm the deposition of Pt-SiPy+Cl- onto the LbL films, observing the adsorption and desorption of hydrogen (E-pa = 0.1 V) and by the redox process of formation for PtO with E-pa = 1.3 V and E-pc = 0.65 V. FTIR and Raman spectra confirmed the presence of the PVS and Pt-SiPy+Cl- in the LbL films. A linear increase in the absorbance in the UV-Vis spectra of the Pt-SiPy+Cl- at 258 nm (pi -> pi* transition of the pyridine groups) with a number of Pt-SiPy+Cl-/PVS or PVS/SiPy+Cl- bilayers (R = 0.992) was observed. These LbL films were tested for the determination of dopamine (DA) in the presence of ascorbic acid (AA) with a detection limit (DL) on the order of 2.6 x 10(-6) mol L-1 and a quantification limit (QL) of 8.6 x 10(-6) mol L-1. The films exhibited a good repeatability and reproducibility, providing a potential difference of 550 mV for the oxidation of DA with AA interferent.

Platinum-Based Nanoalloys PtnTM55-n (TM=Co, Rh, Au): A Density Functional Theory Investigation

Structural and electronic properties of the PtnTM55-n (TM = Co, Rh, Au) nanoalloys are investigated using density functional theory within the generalized gradient approximation and employing the all-electron projected augmented wave method. For TM = Co and Rh, the excess energy, which measures the relative energy stability of the nanoalloys, is negative for all Pt compositions. We found that the excess energy has similar values for a wide range of Pt compositions, i.e., n = 20-42 and n = 28-42 for Co and Rh, respectively, with the core shell icosahedron-like configuration (n = 42) being slightly more stable for both Co and Rh systems because of the larger release of the strain energy due to the smaller atomic size of the Co and Rh atoms. For TM = Au, the excess energy is positive for all compositions, except for n = 13, which is energetically favorable due to the formation of the core-shell structure (Pt in the core and Au atoms at the surface). Thus, our calculations confirm that the formation of core-shell structures plays an important role to increase the stability of nanoalloys. The center of gravity of the occupied d-states changes almost linearly as a function of the Pt composition, and hence, based on the d-band model, the magnitude of the adsorption energy of an adsorbate can be tuned by changing the Pt composition. The magnetic moments of PtnCo55-n decrease almost linearly as a function of the Pt composition; however, the same does not hold for PtRh and PtAu. We found an enhancement of the magnetic moments of PtRh by a few times by increasing Pt composition, which we explain by the compression effects induced by the large size of the Pt atoms compared with the Rh atoms.

Angiographic Results in Intracranial Aneurysms Treated with Inert Platinum Coils

This study was designed in an attempt to identify the risk factors that could be significantly associated with angio graphic recurrences after selective endovascular treatment of aneurysms with inert platinum coils. A retrospective analysis of all patients with selective endovascular coil occlusion of intracranial aneurysms was prospectively collected from 1999 to 2003. There were 455 aneurysms treated with inert platinum coils and followed by digital subtraction angiography. Angio graphic results were classified according Roy and Raymond's classification. Recurrences were subjectively divided into minor and major. The most significant predictors for angio graphic recurrences were determined by ANOVAs logistic regression, Cochran-Mantel-Haenszel test, Fisher exact probability. Short-term (4.3 +/- 1.4 months) follow-up angiograms were available in 377 aneurysms, middle-term (14.1 +/- 4.0 months) in 327 and long-term (37.4 +/- 11.5 months) in 180. Recurrences were found in 26.8% of treated aneurysms with a mean of 21 +/- 15.7 months of follow-up. Major recurrences needing retreatment were present in 8.8% during a mean period follow-up of 17.9 +/- 12.29 months after the initial endovascular treatment. One patient (0.2%) experienced a bleed during the follow-up period. Recurrences after endovascular treatment of aneurysms with inert platinum coils are frequent, but hemorrhages are unusual. Single aneurysm, ruptured aneurysm, neck greater than 4 mm and time of follow-up were risk factors for recurrence after endovascular treatment. The retreatment of recurrent aneurysm decreases the risk of major recurrences 9.8 times. Long-term angiogram monitoring is necessary for the population with significant recurrence predictors.