Estimation of Multinomial Probabilities under a Model Constraint

In this paper estimation of the probabilities of a multinomial distribution has been studied. The five estimators considered are: unrestricted estimator (UE), restricted estimator (RE) (under model ), preliminary test estimator (PTE) based on a test of the model , shrinkage estimator (SE) and the positive-rule shrinkage estimator (PRSE). Asymptotic distributions of these estimators are given under Pitman alternatives and the asymptotic risk under a quadratic loss has been evaluated. The relative performance of the five estimators is then studied with respect to their asymptotic distributional risks (ADR). It is seen that neither of the preliminary test and shrinkage estimators dominates the other, though each fares well relative to the other estimators. However, the positive rule estimator is recommended for use for dimension 3 or more while the PTE is recommended for dimension less than 3.     

Charge separation versus recombination in dye-sensitized nanocrystalline solar cells: the minimization of kinetic redundancy

In this paper we focus upon the electron injection dynamics in complete dye-sensitized nanocrystalline metal oxide solar cells (DSSCs). Electron injection dynamics are studied by transient absorption and emission studies of DSSCs and correlated with device photovoltaic performance and charge recombination dynamics. We find that the electron injection dynamics are dependent upon the composition of the redox electrolyte employed in the device. In a device with an electrolyte composition yielding optimum photovoltaic device efficiency, electron injection kinetics exhibit a half time of 150 ps. This half time is 20 times slower than that for control dye-sensitized films covered in inert organic liquids. This retardation is shown to result from the influence of the electrolyte upon the conduction band energetics of the TiO2 electrode. We conclude that optimum DSSC device performance is obtained when the charge separation kinetics are just fast enough to compete successfully with the dye excited-state decay. These conditions allow a high injection yield while minimizing interfacial charge recombination losses, thereby minimizing "kinetic redundancy" in the device. We show furthermore that the nonexponential nature of the injection dynamics can be simulated by a simple inhomogeneous disorder model and discuss the relevance of our findings to the optimization of both dye-sensitized and polymer based photovoltaic devices.     

Chelating ion-exchangers containing n-substituted hydroxylamine functional groups: Part 6. Sorption and separation of gold and silver by a polyhydroxamic acid

The sorption and desorption characteristics of gold and silver on a polyhydroxamic acid chelating resin are described. Gold is quantitatively sorbed from 0.5 M nitric acid or neutral solutions, and readily eluted with 0.5% ($\text{w}\text{v}$) potassium cyanide solution. Silver is removed from 0.05 M nitric acid or neutral solutions, and can be eluted with the cyanide solution or with 0.5 M nitric acid. Gold can be quantitatively separated from copper, iron and silver; gold and silver are sorbed from dilute cyanide solutions. Tests with river water and other eluting systems are reported.     

Partial Molar Volumes and Partial Molar Adiabatic Compressibilities of Fe(III) Tetrafluoroborate Complexes with DMSO, Pyridine, and Pyridine Derivatives

The apparent and limiting apparent molar volumes of dilute aqueous solutions of KBF₄, and the complexes [Fe(DMSO)₆](BF₄)₃, [Fe(Py)₄(H₂O)₂](BF₄)₃, [Fe(4-Mepy)₂(H₂O)₂](BF₄)₃, and [Fe(4-Etpy)₂(H₂O)₂](BF₄)₃ were determined from density data measured at 5, 15, and 25°C. The apparent and limiting apparent molar adiabatic compressibilities of these complexes were determined from ultrasonic sound velocities measured at the same temperatures in dilute aqueous solutions. The volume change associated with complex formation is discussed in terms of the nature of the coordinate bond and also the role of the central metal atom and ligands in the solvation behavior of these complexes.     

Unexpected, drastic effect of triflic acid on oxidative diacetoxylation of iodoarenes by sodium perborate. A facile and efficient one-pot synthesis of (diacetoxyiodo)arenes

An easy, safe, and effective method for preparing (diacetoxyiodo)arenes from iodoarenes is presented. Addition of trifluoromethanesulfonic acid (triflic acid) as a promoter causes a drastic increase in the yield of (diacetoxyiodo)arenes in the reaction of iodoarenes with sodium perborate. The reaction of the iodoarenes with sodium perborate in acetic acid in the presence of triflic acid at 40-45 degrees C efficiently generates the corresponding (diacetoxyiodo)arenes in high yields within short time.     

Computer-assisted optimization of reversed-phase HPLC isocratic separation of neutral compounds

An appropriate optimization strategy should be used to find a desired resolution or selectivity with a minimum number of experiments in a limited time, which could assure the baseline separation of all target compounds. It was usually realized by means of a specialized computer program. In this paper, mapping optimization method and overlapping resolution mapping were compared for the optimization of a reversed-phase high-performance liquid chromatography (HPLC) isocratic separation of neutral compounds. The calculated resolutions and separation time of 7 to 10 experiments are fitted by different equations, which were used to build a contour plot with a minimum effective resolution and maximum retention time as a function of a mobile phase composition. The balance between resolution and analysis time could be easily realized by the overlapping of the final overlapping resolution mapping and analysis time mapping. The validity of the two methods was confirmed by some typical experiments. The models are simple, visual, and common without theoretical arithmetic.     

Synthesis, characterization and FET properties of novel dithiazolylbenzothiadiazole derivatives

Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility.     

De novo enantioselective syntheses of galacto-sugars and deoxy sugars via the iterative dihydroxylation of dienoate

An efficient route to various sugar lactones has been developed. Key to the overall transformation is the sequential osmium-catalyzed dihydroxylation of 2,4-dienoates. The simplest (one-step/racemic) example of this reaction occurs when the dihydroxylation is performed with aqueous NMO in MeOH. When the first dihydroxylation is performed using the AD-mix procedure, an enantioselective variant results. When a matched AD-mix procedure is used for the second dihydroxylation, an exceedingly diastereo- and enantioselective synthesis of galacto-1,4-lactone results. [Reaction: see text]     

Xanthine Sensors Based on Anodic and Cathodic Detection of Enzymatically Generated Hydrogen Peroxide

A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s^?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10^?6?1.0×10^?4 M and 5.0×10^?7 to 1.0×10^?4 M, respectively. The detection limits were determined to be of 1.0×10^?6 M and 9.0×10^?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples.     

CSE-MECC two-dimensional capillary electrophoresis analysis of proteins in the mouse tumor cell (AtT-20) homogenate

Two-dimensional capillary electrophoresis was used for the separation of proteins and biogenic amines from the mouse AtT-20 cell line. The first-dimension capillary contained a TRIS–CHES–SDS–dextran buffer to perform capillary sieving electrophoresis, which is based on molecular weight of proteins. The second-dimension capillary contained a TRIS–CHES–SDS buffer for micellar electrokinetic capillary chromatography. After a 61-s preliminary separation, fractions from the first-dimension capillary were successively transferred to the second-dimension capillary, where they further separated by MECC. The two-dimensional separation required 60 min.