Robust fuzzy principal component analysis (FPCA). A comparative study concerning interaction of carbon-hydrogen bonds with molybdenum-oxo bonds

Principal component analysis (PCA) is a favorite tool in chemometrics for data compression and information extraction. PCA finds linear combinations of the original measurement variables that describe the significant variations in the data. However, it is well-known that PCA, as with any other multivariate statistical method, is sensitive to outliers, missing data, and poor linear correlation between variables due to poorly distributed variables. As a result data transformations have a large impact upon PCA. In this regard one of the most powerful approaches to improve PCA appears to be the fuzzification of the matrix data, thus diminishing the influence of outliers. In this paper we discuss a robust fuzzy PCA algorithm (FPCA). The new algorithm is illustrated on a data set concerning interaction of carbon-hydrogen bonds with transition metal-oxo bonds in molybdenum complexes. Considering, for example, a two component model, FPCA accounts for 97.20% of the total variance and PCA accounts only for 69.75%.     

Spectrophotometric determination of cobalt with mucic acid

A procedure for the spectrophotometric determination of cobalt with mucic acid is proposed. The absorption spectra, pH, amount of reagent, temperature, and time are studied. Beer's law is obeyed in the range 2.3 and 28.3 μg Co(III)/ml, the Ringbom optimal interval falls between about 9.5 and 25.0 μg Co(III)/ml. The molar absorptivity is 1.4 × 10³ liter/ mol · cm. The stoichiometry of the reaction takes place in the metal-to-ligand ratio of 1:1. The stability constants of the complex are calculated. At the same time, the interferences produced by the commonest ions are studied. The method has been successfully applied to the determination of cobalt in vitamin B₁₂.     

Nuclear magnetic resonance of intermetallic compounds Gd2Ni17−xAlx

²⁷Al Knight shifts vs temperature and magnetic susceptibility for the intermetallic compounds Gd₂Ni_17?xAl_x (x = 17; 16.2; 16; 15) are presented. The results are discussed in terms of the uniform polarization model fo the conduction electrons by the 4f and 3d spins localized on the Gd and Ni ions. The phenomenological exchange constants J_sf and J_sd range between ?1.80×10^?3 and 1.19×10^?3 eV and ?0.63×10^?3 and ?0.52×10^?3 eV, respectively.     

High resolution NMR spectroscopy of heteroaromatic cations. II—pyrylium,thiapyrylium and seleninium cations

The barriers to internal rotation about the C? N bond in several thiopiperidides have been determined by the NMR technique. It was found that the barrier height (ΔG^?) increases in the series cinnamoylthiopiperidide<thiobenzoylpiperidide<phenylthioacetylpiperidide. This trend was discussed in terms of the electronic structure, using HMO calculations. For m-and p-substituted cinnamoylthiopiperidides the barriers were shown to increase with the electron withdrawing character of the substituent in the aromatic ring.     

Negative differential conductance and hot phonons in suspended nanotube molecular wires

Freely suspended metallic single-walled carbon nanotubes (SWNTs) exhibit reduced current carrying ability compared to those lying on substrates, and striking negative differential conductance at low electric fields. Theoretical analysis reveals significant self-heating effects including electron scattering by hot nonequilibrium optical phonons. Electron transport characteristics under strong self-heating are exploited for the first time to probe the thermal conductivity of individual SWNTs (approximately 3600 W m-1 K-1 at T=300 K) up to approximately 700 K, and reveal a 1/T dependence expected for umklapp phonon scattering at high temperatures.     

Asymptotic and numerical transient analysis of the free convection cooling of a vertical plate embedded in a porous medium

This paper analyzes the cooling process of a vertical thin plate originated by a fluid-saturated porous medium, taking into account the effects of both longitudinal and transversal heat conduction in the plate. Due to the finite thermal conductivity of the plate, a longitudinal temperature gradient arises within it, which prevents any similarity solution in the boundary layer, changing the mathematical character of the problem from parabolic to elliptic, for large values of the suitable Rayleigh number. The energy balance equations are reduced to a system of two differential equations with two parameters: the nondimensional plate thermal conductivity and the aspect ratio of the plate . In order to obtain the evolution of the temperature of the plate as a function of time and position, the coupled balance equations are integrated numerically for several values of the parameters, including the cases of very good and poor conducting plates. The results obtained, are compared with an asymptotic analysis based on the multiple scales technique carried out for the case of a very good conducting plate. There is at the beginning a fast transient in nondimensional time scale of order followed by a slow nondimensional time scale of order unity, which gives the evolution of the cooling process. Good agreement is achieved even for values of the conduction parameter of order unity. The asymptotic solution allows us to give closed form analytical solution for the plate temperature evolution in time and space. The overall thermal energy of the plate decreases faster for smaller values of .     

Synthesis and protection of aryl sulfates using the 2,2,2-trichloroethyl moiety

[reaction: see text] The 2,2,2-trichloroethyl (TCE) group was utilized as the first protecting group for aryl sulfates. Aryl sulfates, protected with the TCE group, were prepared in high yield by reacting phenols with chlorosulfuric acid TCE ester. Deprotection was accomplished using Pd/C-ammonium formate or with Zn-ammonium formate to give aryl sulfate monoesters in high yield. This approach to aryl sulfate synthesis was successfully applied to the construction of estrone sulfate derivatives, which could not be prepared by previous methodologies.     

Using micelles for a new approach to fluorescent sensors for metal cations

A new approach based on self-assembly inside micelles has been individuated to prepare a system behaving as a water-operating selective fluorescent sensor for Cu2+ and Ni2+.     

Bicyclic units of

We prove that the group generated by the bicyclic units of has torsion for . This answers a question of Sehgal (1993).

     

ForceFit: A code to fit classical force fields to quantum mechanical potential energy surfaces

The ForceFit program package has been developed for fitting classical force field parameters based upon a force matching algorithm to quantum mechanical gradients of configurations that span the potential energy surface of the system. The program, which runs under UNIX and is written in C++, is an easy‐to‐use, nonproprietary platform that enables gradient fitting of a wide variety of functional force field forms to quantum mechanical information obtained from an array of common electronic structure codes. All aspects of the fitting process are run from a graphical user interface, from the parsing of quantum mechanical data, assembling of a potential energy surface database, setting the force field, and variables to be optimized, choosing a molecular mechanics code for comparison to the reference data, and finally, the initiation of a least squares minimization algorithm. Furthermore, the code is based on a modular templated code design that enables the facile addition of new functionality to the program. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010