Approximate D-optimal designs of experiments on the convex hull of a finite set of information matrices

In the paper we solve the problem of D _ℋ-optimal design on a discrete experimental domain, which is formally equivalent to maximizing determinant on the convex hull of a finite set of positive semidefinite matrices. The problem of D _ℋ-optimality covers many special design settings, e.g., the D-optimal experimental design for multivariate regression models. For D _ℋ-optimal designs we prove several theorems generalizing known properties of standard D-optimality. Moreover, we show that D _ℋ-optimal designs can be numerically computed using a multiplicative algorithm, for which we give a proof of convergence. We illustrate the results on the problem of D-optimal augmentation of independent regression trials for the quadratic model on a rectangular grid of points in the plane.     

Linear bound on extremal functions of some forbidden patterns in 0-1 matrices

In this note by saying that a 0-1 matrix A avoids a pattern P given as a 0-1 matrix we mean that no submatrix of A either equals P or can be transformed into P by replacing some 1 entries with 0 entries. We present a new method for estimating the maximal number of the 1 entries in a matrix that avoids a certain pattern. Applying this method we give a linear bound on the maximal number of the 1 entries in an n by n matrix avoiding pattern L₁ and thereby we answer the question that was asked by Gábor Tardos. Furthermore, we use our approach on patterns related to L₁.     

Determination of Copper in Human Urine by RP-LC After Pre-column Derivatization with Neocuproine and Use of Monolithic Column

A selective sensitive RP-LC–UV/VIS method with pre-column derivatization was developed for the determination of copper in human urine at a trace level. This method is based on the selective reaction of 2,9-dimethyl-1,10-phenanthroline (neocuproine) with copper(I) to produce a yellow-orange hydrophobic complex in a neutral or slightly acidic buffer solution (adjusted to pH 5.9). Copper(II) was reduced to copper(I) ions by ascorbic acid as a weak reducer, which was added both to urine sample and mobile phase, respectively. A hydrophobic copper(I)–neocuproine chelate was determined by RP-LC–UV/VIS using a monolithic column Chromolith Performance RP-8e (100 × 4 mm I.D.) at 30.0 ± 0.1 °C with a methanol: aqueous buffer (pH 5.9, ammonium acetate and ascorbic acid 2.8 mmol L^?1) mobile phase at flow rate of 2.00 mL min^?1. Sample injection volume was 20 μL and detection was done at 453 nm. The method was validated over a concentration range of 0.09–11.50 μmol L^?1. The LOD of copper in human urine was found to be 0.07 μmol L^?1 concentration level, suitable for clinical analysis. The precision of the results, reported as the RSD, was below 4.6 % for copper concentration within range 0.5–5.0 μmol L^?1 in the spiked human urine samples.     

Metalizing carbon nanotubes with Pd–Pt core–shell nanowires enhances electrocatalytic activity and stability in the oxygen reduction reaction

We describe an electrostatically induced self-assembly method to prepare ultrathin Pd nanowires (NWs) surrounding individual multiwalled carbon nanotubes, i.e., Pd_NW/MWNTs, that are noticeable for improving performance in the oxygen reduction reaction (ORR) of their supported Pt_ML electrocatalyst. The carbonaceous by-products in MWNTs, rather than the nanotubes themselves, are modified with the oxygenated terminals to allow the negatively charged and hydrophilic surface while retaining the intrinsic nature of the MWNTs. Encompassing the nanotubes' length are 2-nm-thick Pd NWs that are closely packed and homogeneously dispersed due to the unique processes for preparing Pd_NW/MWNTs and its components. Although the crystal lattice of the Pd NWs expands somewhat, which should cause an unfavorable interaction with supported Pt_ML, this adverse effect is counterweighed by the shape-determined features of Pd NWs, including their high specific surface area, excellent contiguousness, and low-energy atomic configuration. Consequently, these distinct chemical and physical properties substantially expedite the desorption of the intermediates to refresh the active centers during the reduction of oxygen with the Pt_ML electrocatalyst while ensuring a desirable electron transfer rate, so improving the overall ORR kinetics. Indeed, Pt_ML/Pd_NW/MWNTs exhibits the Pt mass and specific activities of 1.45 A/mg_Pt and 0.65 mA/cm² _Pt, respectively, each of which are several times those of the Pt/C and even higher than those of the Pt_ML supported on Pd nanoparticles. These high activities remained over a long-term stability test using the latest US Department of Energy-established protocol.     

Designing high performance Pt monolayer core–shell electrocatalysts for fuel cells

In proton exchange membrane fuel cells, platinum (Pt) has been the dominant choice for both the cathode and the anode catalysts. The high Pt content and high associated costs particularly at the cathode, and sluggish oxygen reduction reaction (ORR) kinetics and poor stability, remain a challenge. Pt monolayer (ML) catalysts offer a distinctively reduced Pt content while providing considerable possibilities for enhancing their catalytic activity and stability for the ORR. In this opinion, we first review the achievement in active and stable Pt ML on palladium (Pd) nanoparticle catalysts for the ORR. We then describe the mechanisms that rationalize their high activity and durability. Recently, we developed several novel nanostructured cores to further improve the ORR activity and stability by optimizing their surface orientation, composition, and morphology. The results from the Pt ML catalysts significantly impact the research of electrocatalysis and fuel-cell technology, as they demonstrate an exceptionally effective way of design and syntheses of catalysts.     

Simultaneous thermogravimetric and differential thermal analysis determination of products formed during hydration of blended Portland cement doped with zinc

Journal of Thermal Analysis and Calorimetry - With the increasing use of secondary raw materials and alternative fuels in the cement production industry, the amount of present trash...     

Enhanced electrocatalytic performance of processed, ultrathin, supported Pd-Pt core-shell nanowire catalysts for the oxygen reduction reaction

We report on the synthesis, characterization, and electrochemical performance of novel, ultrathin Pt monolayer shell-Pd nanowire core catalysts. Initially, ultrathin Pd nanowires with diameters of 2.0 ± 0.5 nm were generated, and a method has been developed to achieve highly uniform distributions of these catalysts onto the Vulcan XC-72 carbon support. As-prepared wires are activated by the use of two distinctive treatment protocols followed by selective CO adsorption in order to selectively remove undesirable organic residues. Subsequently, the desired nanowire core-Pt monolayer shell motif was reliably achieved by Cu underpotential deposition followed by galvanic displacement of the Cu adatoms. The surface area and mass activity of the acid and ozone-treated nanowires were assessed, and the ozone-treated nanowires were found to maintain outstanding area and mass specific activities of 0.77 mA/cm(2) and 1.83 A/mg(Pt), respectively, which were significantly enhanced as compared with conventional commercial Pt nanoparticles, core-shell nanoparticles, and acid-treated nanowires. The ozone-treated nanowires also maintained excellent electrochemical durability under accelerated half-cell testing, and it was found that the area-specific activity increased by ~1.5 fold after a simulated catalyst lifetime.