Simultaneous determination of cobalt, nickel and palladium in micellar media using partial least square regression and direct orthogonal signal correction

A simple, novel and sensitive spectrophotometric method was described for the simultaneous determination of cobalt, nickel and palladium. The method is based on the complex formation of Co, Ni and Pd with 1-(2-pyridylazo)-2-naphtol (PAN) in Tween-80 micellar media. All factors affecting on the sensitivity were optimized and the linear dynamic range for determination of Co, Ni and Pd was found. The experimental calibration matrix was designed by measuring the absorbance over the range of 520-700 nm for 21 samples of 0.10-1.0, 0.050-0.50 and 0.050-4.0 microg ml(-1) of Co, Ni and Pd, respectively. The partial least square (PLS) modeling based on singular value decomposition (SVD) was used for the multivariate calibration of the spectrophotometric data. The direct orthogonal signal correction was used for pre-processing of data matrices and the prediction results of model, with and without using direct orthogonal signal correction, were statistically compared. The effects of various anions and cations on selectivity of the method were investigated. The proposed method was successfully applied to the determination of Co, Ni and Pd in water and alloy samples.     

Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111)

In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates.     

Relaxation processes in room temperature ionic liquids: the case of 1-butyl-3-methyl imidazolium hexafluorophosphate

A detailed investigation on the nature of the relaxation processes occurring in a typical room temperature ionic liquid (RTIL), namely, 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF(6)]), is reported. The study was conducted using both elastic and inelastic neutron scattering over a wide temperature range from 10 to 400 K, accessing the dynamic features of both the liquid and glassy amorphous states. In this study, the inelastic fixed energy scan technique has been applied for the first time to this class of materials. Using this technique, the existence of two relaxation processes below the glass transition and a further diffusive process occurring above the glass-liquid transition are observed. The low temperature processes are associated with methyl group rotation and butyl chain relaxation in the glassy state and have been modeled in terms of two Debye-like, Arrhenius activated processes. The high temperature process has been modeled in terms of a Kohlraush-Williams-Watts relaxation, with a distinct Vogel-Fulcher-Tamman temperature dependence. These results provide novel information that will be useful in rationalizing the observed structural and dynamical behavior of RTILs in the amorphous state.     

Kinetics of diffusion-limited catalytically activated reactions: an extension of the Wilemski-Fixman approach

We study the kinetics of diffusion-limited catalytically activated A+B-->B reactions taking place in three-dimensional systems, in which an annihilation of diffusive A particles by diffusive traps B may happen only if the encounter of an A with any of the Bs happens within a special catalytic subvolumen: these subvolumens being immobile and uniformly distributed within the reaction bath. Suitably extending the classical approach of Wilemski and Fixman [J. Chem. Phys. 58, 4009 (1973)] to such three-molecular diffusion-limited reactions, we calculate analytically an effective reaction constant and show that it comprises several terms associated with the residence and joint residence times of Brownian paths in finite domains. The effective reaction constant exhibits a nontrivial dependence on the reaction radii, the mean density of catalytic subvolumens, and particles' diffusion coefficients. Finally, we discuss the fluctuation-induced kinetic behavior in such systems.     

Nonlinear optical property calculations by the long-range-corrected coupled-perturbed Kohn-Sham method

The long-range correction (LC) scheme for the exchange functional of density-functional theory (DFT) was combined with the coupled-perturbed Kohn-Sham (CPKS) method to calculate nonlinear optical response properties. By using this LC-CPKS method, we calculated the hyperpolarizabilities of typical molecules and the dipole moments, polarizabilities, and hyperpolarizabilities of push-pull pi-conjugated systems: p-nitroaniline, 4-amino-4'-nitrostilbene, and alpha,omega-nitroaminopolyenes. It was found that the LC scheme clearly improved the calculation of these optical properties for all of these systems, which have been significantly overestimated by conventional DFTs. We therefore concluded that the long-range exchange interaction played an important role in calculating the optical properties using the DFT formalism.     

The Mechanism on Cyclization, Debenzylation and Oxidation of 1-[1-（Benzyloxy）-3-methylnaphthalen-4-yloxy]propan-2-one

Mansonone compounds represent a series of naturally occurring o-quinones mainly isolated from the heartwood of Mansonia Altissima1 and Ulmus Glabra2. Mansonone F contained oxaphenalene skeleton which was a relatively novel structure and rarely existed in …     

Synthesis, Characterization and Conductivity of α-Keggin-type Nanoparticles, Co(en)_3PMo_(12)O_(40)·8H_2O with Optical Activity

IntroductionChirality is ubiquitous in the nature.Chiralcompounds have many applications in the areas ofmedicine,catalysis and materials,etc. Polyox-ometallates are inorganic polymers,which have at-tracted much interest since they have electri-cal[1_ 3 ] ,magnetic[4] ,optical properties[5_ 7] ,andsome characters as liquid crystals[8,9] .In this workwe report theα- Keggin structural polyoxometallatenanoparticles with optical activities.The opticalactivities of the samples are [α]13 D =+ 1 7…     

Palladium-catalyzed amination of aryl bromides with hindered N-alkyl-substituted anilines using a palladium(I) tri-tert-butylphosphine bromide dimer

An efficient palladium-catalyzed amination of aromatic bromides with hindered N-alkyl-substituted anilines is described, either using the combination of Pd(OAc)(2) and P(t-Bu)(3) or a palladium(I) tri-tert-butylphosphine bromide dimer, [Pd(mu-Br)(t-Bu(3)P)](2), a new, commercially available, and easily handled catalyst.     

Characterization of CNS disorders and evaluation of therapy using structural and functional MRI

Modern drug development requires technologies that allow rapid translation from the preclinical to the clinical stage. It is obvious that non-invasive imaging modalities such as magnetic resonance imaging (MRI) will play a central role in this regard. This article reviews the use of structural and functional MRI readouts for characterization of central nervous system (CNS) disorders and evaluation of the efficacy of potential CNS drugs. Examples comprise dementia of Alzheimer's type, cerebral ischemia, and neuroinflammation covering both clinical and preclinical aspects. In these examples MRI has been used to obtain relevant structural information on brain atrophy, on the location and extent of ischemic brain areas, and on the number and distribution of demyelinated plaques. These structural data are complemented by readouts assessing the functional consequences associated with the pathomorphological changes. In the last decade, MRI has evolved into a standard tool for the development of CNS drugs. With regard to target-specific/molecular imaging applications MRI is limited by its inherently low sensitivity; complementary imaging modalities utilizing optical and radionuclear reporter systems will thus be required.     

Prenylated xanthones from Garcinia xanthochymus

A new prenylated xanthone, 1,3,5,6-tetrahydroxy-4,7,8-tri(3-methyl-2-butenyl)xanthone (1), was isolated from the wood of Garcinia xanthochymus together with a known xanthone, garciniaxanthone E (2). Their structures were determined by spectroscopic analysis. Compounds 1 (3 microM) and 2 (10 microM) elicited marked enhancement of nerve growth factor-mediated neurite outgrowth in PC12D cells.