Palladium and platinum organochalcogenolates and their transformation into metal chalcogenides

Platinum group metal chalcogenides find extensive applications in catalysis and in the electronic industry. To develop an efficient low temperature clean preparation of these materials, molecular routes have been explored. Thus the chemistry of mononuclear organochalcogenolates of the type [M(ER’)₂(PR₃)₂], binuclear benzylselenolates, [M₂Cl₂(μ-SeBz)₂(PR₃)₂], allylpalladium complexes [Pd₂(μ-ER)₂(η³-C₄H₇)₂] and palladium/platinum sulphido/selenido-bridged complexes, [M₂(μ-E)₂L₄] (M = Pd or Pt; E = S, Se or Te; L = tertiary phosphine ligand) has been investigated. All the complexes have been characterized by elemental analysis, NMR (¹H,³¹P,⁷⁷Se,¹⁹⁵Pt) spectroscopy and in some cases by X-ray diffraction. The thermal behaviour of these complexes has been studied by TGA. The pyrolysis of allylpalladium complexes in refluxing xylene yields Pd₄E as established by analysis and XRD patterns.     

Transitional intermittency detection by neural network

 A neural network has been used to predict the flow intermittency from velocity signals in the transition zone in a boundary layer. Unlike many of the available intermittency detection methods requiring a proper threshold choice in order to distinguish between the turbulent and non-turbulent parts of a signal, a trained neural network does not involve any threshold decision. The intermittency prediction based on the neural network has been found to be very satisfactory. Received: 15 December 1997/Accepted: 30 December 1998     

Characteristic Functions for Ergodic Tuples

Motivated by a result on weak Markov dilations, we define a notion of characteristic function for ergodic and coisometric row contractions with a one-dimensional invariant subspace for the adjoints. This extends a definition given by G. Popescu. We prove that our characteristic function is a complete unitary invariant for such tuples and show how it can be computed.     

Effect of Martensite Volume Fraction on Strain Partitioning Behavior of Dual Phase Steel

Monotonic deformation behavior of ferrite-martensite dual phase steels with martensite volume of 13-43% have been analyzed in the current investigation using micromechanics based finite element simulation on representative volume elements. The effects of martensite volume fraction on the strain partitioning behavior between soft ferrite matrix and hard martensite islands in dual phase steels during tensile deformation have been investigated. As a consequence of strain incompatibility between hard martensite and soft ferrite phases, inhomogeneous deformation and finally deformation localization occur during tensile deformation. Restricted local deformation in ferrite phase caused by the adjacent martensite islands triggers the local stress triaxiality development. As the martensite volume fraction increases, the local deformation restrictions in ferrite phase also increases and which results in higher stress triaxiality development. Similarly the strain partitioning behavior between ferrite matrix and martensite island is also influenced by the volume fraction of martensite. The strain partitioning coefficient increases with increasing martensite volume fraction.     

(1S*,2S*,4S*,5S*)‐Cyclo­hexa­ne‐1,2,4,5‐tetrol monohydrate

In the title compound, C₆H₁₂O₄·H₂O, 1,4/2,5‐cyclo­hexane­tetrol and water mol­ecules are seen to possess twofold symmetry. All four hydrox­yl groups of the tetrol participate in extensive inter­molecular O—H⋯O hydrogen bonding to form mol­ecular tapes propagating along the a axis. Translationally related tapes along the c axis are held together by four coordinated water mol­ecules.     

Contributions to cytochrome c inner- and outer-sphere reorganization energy

Cytochromes c are small water-soluble proteins that catalyze electron transfer in metabolism and energy conversion processes. Hydrogenobacter thermophilus cytochrome c₅₅₂ presents a curious case in displaying fluxionality of its heme axial methionine ligand; this behavior is altered by single point mutation of the Q64 residue to N64 or V64, which fixes the ligand in a single configuration. The reorganization energy (λ) of these cytochrome c₅₅₂ variants is experimentally determined using a combination of rotating disc electrochemistry, chronoamperometry and cyclic voltammetry. The differences between the λ determined from these complementary techniques helps to deconvolute the contribution of the active site and its immediate environment to the overall λ (λ_Total). The experimentally determined λ values in conjunction with DFT calculations indicate that the differences in λ among the protein variants are mainly due to the differences in contributions from the protein environment and not just inner-sphere λ. DFT calculations indicate that the position of residue 64, responsible for the orientation of the axial methionine, determines the geometric relaxation of the redox active molecular orbital (RAMO). The orientation of the RAMO with respect to the heme is key to determining electron transfer coupling (H_AB) which results in higher ET rates in the wild-type protein relative to the Q64V mutant despite a 150 mV higher λ_Total in the former.

Efficient delocalization of the redox-active molecular orbital (RAMO) in HtWT results in an increase in H_AB value which in turn accelerates the electron transfer (ET) rate in spite of the higher reorganization energy (λ) than the HtQ64V mutant.     

Defect detection and localization in orthotropic wood slabs by inversion of dynamic surface displacements

The nondestructive evaluation inversion and generalized force-mapping techniques developed and demonstrated for isotropic thin plates by Bucaro et al. [(2004). "Detection and localization of inclusions in plates using inversion of point actuated surface displacements," J. Acoust. Soc. Am. 115, 201-206] are extended to the case of orthotropic plates. The extended techniques are applied to a finite-element generated numerical database for point excited wooden slabs with and without an internal defect at 5 and 10 kHz. Operation of the original isotropic algorithms on the wood surface displacements is shown to fail in recovering the uniform elastic parameters or in detecting and locating the defect. The new algorithms based on the wave equation for a thin, orthotropic plate successfully convert the surface displacements on the uniform wooden slab to elastic parameter maps which serve to detect and localize the defect in the flawed plate. The results, particularly at the higher frequency, indicate that the onset of failure in the thin plate approximation impacts both the inversion and the generalized force-mapping accuracy. However, in this case use of the inversion algorithm to obtain modified wave equation coefficients followed by operation of the force-mapping algorithm with these new parameters inserted is shown to successfully mitigate this effect.     

Synthesis of multi-wall carbon nanotubes by simple pyrolysis

A new pyrolysis technique has been developed for the synthesis of multi-walled carbon nanotubes (MWCNTs). In this simple method diethyl ether and nickelocene is pyrolysized in a reaction quartz tube without using carrier gas. The samples are prepared at pyrolysis temperatures of 650 and 950 ^°C and the effect of temperature on the tube morphology investigated. Purification has been done following the standard oxidation and acid bath treatment. The as-synthesized and purified nanotubes have been characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and micro-Raman spectroscopy. The technique has great advantages such as low cost and easy operation for the production of CNTs.     

A perturbed angular correlation spectrometer for material science studies

A four-detector perturbed angular correlation (PAC) spectrometer has been developed with ultra-fast BaF₂ detectors to acquire four coincidence spectra simultaneously, two at 180° and two at 90°. This spectrometer has double efficiency compared to that of a three-detector set-up. Higher efficiency is desirable for PAC studies in solid state physics where large number of coincidences are required to obtain the PAC spectra with good statistics and is particularly useful when the half-lives of the parent probe nuclei used for PAC measurements are ∼2–3 days or less as in ¹¹¹In (2.8 d), ⁹⁹Mo (2.7 d) and ¹⁴⁰La (1.7 d). The performance of the spectrometer has been tested for the HfO₂ monoclinic crystal in the temperature range from 77 to 873 K and for the HfF₄·3H₂O crystal at room temperature. The polycrystalline HfO₂ has been synthesized from Hf metal by heating in air. The hydrated hafnium fluoride has been crystallized by dissolving Hf metal in 40% HF and drying slowly at room temperature.      

Lewis acid-mediated cross-coupling reaction of 7-azaindoles and aldehydes: Cytotoxic evaluation of C3-linked bis-7-azaindoles

The synthesis of 3,3′-bis-7-indolylmethane derivatives is important for their further development as pharmaceutical compounds and other synthetic purposes. Herein, we describe the zinc- or acid-mediated cross-coupling reaction of 7-azaindoles with aldehydes, such as paraformaldehyde, alkyl aldehydes, aryl aldehydes, enal, and α-ketoaldehyde, providing the corresponding C3-linked bis-7-azaindole derivatives, which are a crucial class towards the development of novel bioactive compounds. High levels of site selectivity and functional group tolerance were observed. Synthesized 3,3′-bis-7-azaindole derivatives were evaluated against human breast adenocarcinoma cells (MCF-7) and human ovarian carcinoma cells (SKOV-3), respectively. Notably, compounds 3s and 4e displayed promising anticancer properties competitive with anticancer doxorubicin as a positive control.