Interface architecture determined electrocatalytic activity of Pt on vertically oriented TiO(2) nanotubes

The surface atomic structure and chemical state of Pt is consequential in a variety of surface-intensive devices. Herein we present the direct interrelationship between the growth scheme of Pt films, the resulting atomic and electronic structure of Pt species, and the consequent activity for methanol electro-oxidation in Pt/TiO(2) nanotube hybrid electrodes. X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) measurements were performed to relate the observed electrocatalytic activity to the oxidation state and the atomic structure of the deposited Pt species. The atomic structure as well as the oxidation state of the deposited Pt was found to depend on the pretreatment of the TiO(2) nanotube surfaces with electrodeposited Cu. Pt growth through Cu replacement increases Pt dispersion, and a separation of surface Pt atoms beyond a threshold distance from the TiO(2) substrate renders them metallic, rather than cationic. The increased dispersion and the metallic character of Pt results in strongly enhanced electrocatalytic activity toward methanol oxidation. This study points to a general phenomenon whereby the growth scheme and the substrate-to-surface-Pt distance dictates the chemical state of the surface Pt atoms, and thereby, the performance of Pt-based surface-intensive devices.     

Architecture-dependent surface chemistry for Pt monolayers on carbon-supported Au

Pt monolayers were grown by surface-limited redox replacement (SLRR) on two types of Au nanostructures. The Au nanostructures were fabricated electrochemically on carbon fiber paper (CFP) by either potentiostatic deposition (PSD) or potential square wave deposition (PSWD). The morphology of the Au/CFP heterostructures, examined using scanning electron microscopy (SEM), was found to depend on the type of Au growth method employed. The properties of the Pt deposit, as studied using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and cyclic voltammetry (CV), were found to depend strongly on the morphology of the support. Specifically, it was found that smaller Au morphologies led to a higher degree of cationicity in the resulting Pt deposit, with Pt(4+) and Pt(2+) species being identified using XPS and XAS. For fuel-cell catalysts, the resistance of ultrathin catalyst deposits to surface area loss through dissolution, poisoning, and agglomeration is critical. This study shows that an equivalent of two monolayers (ML) is the low-loading limit of Pt on Au. At 1 ML or below, the Pt film decreases in activity and durability very rapidly due to presence of cationic Pt.     

High-yield synthesis of well-crystalline alpha-Fe2O3 nanoparticles: structural, optical and photocatalytic properties

In this paper, the high-yield facile synthesis, detailed characterization and photocatalytic application of alpha-Fe2O3 nanoparticles are reported. The synthesis was done via simple hydrothermal process by using aqueous mixtures of iron chloride, hexamethylenediamine and NH3 x H2O at 110 degrees C. The morphologies of the synthesized products were examined by using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) which confirmed that the synthesized structures are almost spherical shaped nanoparticles with the average diameters of -35 +/- 5 nm, and are grown in high yield. The detailed structural characterizations and composition of the as-synthesized nanoparticles were investigated by using X-ray diffraction (XRD), high-resolution TEM (HRTEM), energy dispersive spectroscopy (EDS) attached with FESEM and Fourier transform infrared spectroscopy (FTIR) which substantiated that the as-synthesized nanoparticles are well crystalline and pure alpha-Fe2O3. The UV-Vis absorption spectrum of the synthesized nanoparticles demonstrated the existence of two optical band gaps which correspond to direct and indirect transitions, respectively. The as-synthesized alpha-Fe2O3 nanoparticles exhibit good photocatalytic properties on photocatalytic degradation of methylene blue.     

An LC-MS Method for Evaluating Photostability of Naloxone Hydrochloride I.V. Infusion

Naloxone is a well-known opioid antagonist indicated for the treatment of CNS （central nervous system） and respiratory depression induced by natural or synthetic opioid in adults and neonates whose mothers have received opioids. While it has been reported that an injection of 0.2 mg/mL of naloxone hydrochloride is physically and chemically stable, data on photostability on continuous i.v. infusion of 0.2 mg/mL of naloxone hydrochloride has not been reported. Therefore, a method was required for assessment of naloxone hydrochloride photostability. A high performance LC-MS （liquid chromatography/mass spectrometry） method was established to evaluate the photostability of naloxone hydrochloride. Injections of naloxone hydrochloride in 0.9% sodium chloride were exposed to artificial light and stored at room temperature （22 ~C） and 37 ~C. Naloxone losses up to 9.79% of its initial concentration when exposed to light at room temperature for 192 h, but the degradation increased up to 14.91% as the storage temperature increase. The disappearance of naloxone hydrochloride was correlated with the appearance of nor-oxymorphonedegradant. Naloxone hydrochloride is photosensitive and degradation increased at highly temperature and light intensity. Therefore, naloxone i.v. infusion solutions should either be protected from light and/or be frequently replaced when being administered to patients.     

Near Surface Phase Transition of Solute Derived Pt Monolayers

As the loadings of precious metals in surface-chemical systems continue to decrease for photo-and electro-catalysts for energy and environmental applications, the study of near-surface electronic and atomic structure in functional materials becomes critically important. Extremely small quantities of active elements, whether grown as clusters or ultrathin films, exhibit changes in catalytic activity that arise from both size effects and electron-transfer effects. These size and transfer effects can be related to increased propensity for oxidation of the metallic deposit, as well as to various changes in electrochemical performance such as durability or required overpotential for a given reaction. This work establishes a minimum threshold for Pt loading beyond which bulk-type electronic behavior may be expected. By iteratively growing atomic monolayers and multilayers using self-limited electrodeposition and studying these films using core-electron spectroscopy (X-ray absorption and X-ray photoelectron spectroscopy), electrochemical methods and DFT-based computations the fundamental interactions that govern oxidation state and electron transfer near the surface of a Pt–Au bimetallic system have been explored. It has been shown that the Pt–Au system exhibits increased tendency for the Pt layer to remain cationic below a minimum threshold film thickness of two monolayers. At monodispersed levels of submonolayer coverage Pt exhibits deviated electronic structure, reactivity, and metal stability compared to films in excess of this minimum threshold thickness. At three monolayers Pt is thick enough to avoid the preference for cationicity and the resulting higher rates of metal dissolution, but thin enough to benefit from electron transfers from Au that assist in lowering the overpotentials for CO oxidation. This study shows the efficacy of a concerted method for the investigation of near-surface phenomena in multicomponent systems. By combining electrochemical and vacuum studies of solute-derived samples with advanced computational techniques, a multifaceted understanding of these architectures has been achieved.     

Meta-learning for evolutionary parameter optimization of classifiers

The performance of most of the classification algorithms on a particular dataset is highly dependent on the learning parameters used for training them. Different approaches like grid search or genetic algorithms are frequently employed to find suitable parameter values for a given dataset. Grid search has the advantage of finding more accurate solutions in general at the cost of higher computation time. Genetic algorithms, on the other hand, are able to find good solutions in less time, but the accuracy of these solutions is usually lower than those of grid search.     

Molecular Characterization of α- and β-Thalassaemia among Malay Patients

Both α- and β-thalassaemia syndromes are public health problems in the multi-ethnic population of Malaysia. To molecularly characterise the α- and β-thalassaemia deletions and mutations among Malays from Penang, Gap-PCR and multiplexed amplification refractory mutation systems were used to study 13 α-thalassaemia determinants and 20 β-thalassaemia mutations in 28 and 40 unrelated Malays, respectively. Four α-thalassaemia deletions and mutations were demonstrated. −−^SEA deletion and α^CSα accounted for more than 70% of the α-thalassaemia alleles. Out of the 20 β-thalassaemia alleles studied, nine different β-thalassaemia mutations were identified of which β^E accounted for more than 40%. We concluded that the highest prevalence of (α- and β-thalassaemia alleles in the Malays from Penang are −−^SEA deletion and β^E mutation, respectively.     

Effect of various surface preparation techniques on the delamination properties of vacuum infused Carbon fiber reinforced aluminum laminates (CARALL): Experimentation and numerical simulation

Carbon fiber reinforced aluminum laminates (CARALL) are one of the aluminum based Fiber metal laminates (FMLs) which, due to their high strength to weight ratio and good impact resistance are greatly replacing aluminum alloys in aircraft structures. In this research work, interlaminate shear strength of Vacuum assisted resin transfer molding (VARTM) manufactured CARALL has been investigated. Numerical simulation model incorporated with real time material data has been developed to predict the delamination behavior of CARALL laminates. Standard CARALL specimens with different surface morphologies were prepared by electric discharge machining, mechanical, chemical and electrochemical surface treatments. T-peel tests were carried out according to standard ASTM D1876-08 to find out inter laminate shear strength. FMLs made out of mechanically, chemically and electrochemically cleaned metal sheets depicted high interlaminate shear strength. SEM micrographs of failed surfaces verify the high adhesive strength of epoxy. Developed numerical simulation model accurately predicts the delamination behavior of CARALL as observed during experimentation.