Asymmetric conjugate addition of thioglycolate to a range of chalcones using tetrahydroisoquinoline (TIQ) N,N′-dioxide ligands

A series of novel TIQ based N,N′-oxide ligands were synthesised and screened for their catalytic activity in the enantioselective conjugate addition of thioglycolate to chalcones. Bulky groups on the side chain of the TIQ backbone provided the highest enantioselectivity of up to 88% with 10 mol % catalyst loading. It was also observed that these reactions proceeded optimally in the presence of dichloromethane as a solvent. Screening of various metals emphasized La(OTf)₃ as the ideal pre-catalyst for this particular reaction.     

Synthesis of tetrahydroisoquinoline (TIQ)–oxazoline ligands and their application in enantioselective Henry reactions

A novel family of eleven new tetrahydroisoquinoline (TIQ)–oxazoline intermediates and five corresponding copper(II) catalysts has been developed and applied to the catalytic asymmetric Henry reaction of various aldehydes with nitromethane to provide β-hydroxy nitroalkanes in high conversion (>99%). This paper describes the synthesis of the TIQ compounds from l-dihydroxyphenylalanine (l-DOPA) as the starting material. The chiral ligands were complexed in situ with various transition metals such as Cu, Sc, Co, Zn, Ni and Mn and tested as a chiral catalyst for the Henry reaction. The reaction was optimized in terms of the metal, counter ion, solvent, temperature and over a range of substrates. The corresponding catalyst with copper(II) acetate and 2-propanol as the solvent provides the best enantioselectivities (up to 77% ee) of the corresponding nitroalcohol for 4-chlorobenzaldehyde.     

Synthesis of tetrahydroisoquinoline-diamine ligands and their application in asymmetric transfer hydrogenation

The use of the tetrahydroisoquinoline scaffold is well documented in biologically active compounds. However, reports of the utilisation of tetrahydroisoquinoline compounds in asymmetric catalysis are limited. The synthesis of novel diamine ligands possessing the tetrahydroisoquinoline (tetrahydroisoquinoline) backbone and evaluation of their activity in the asymmetric transfer hydrogenation of acetophenone are presented. The diamine ligands in conjunction with i-PrOH as the hydrogen source and [RhCl₂(Cp1)]₂ as the metal precursor proved to be the most effective of the tetrahydroisoquinoline derivatives for this catalytic system. Water was found to have a profound influence on the enantioselectivity of the reaction. Optimisation of the amount water, i-PrOH and catalytic loading content rendered the best result of 70% enantioselectivity for the (S)-1-phenylethanol isomer product.     

Further search for selectivity of positron annihilation in the skin and cancerous systems

Positronium annihilation lifetime (PAL) spectroscopy and Doppler broadening energy spectra (DBES) have been used to search for selectivity and sensitivity for cancerous skin samples with and without cancer. This study is to further explore the melanoma cancerous system and other different types of skin samples. We found that the S parameter in melanoma skin samples cut at 0.39 mm depth from the same patient's skin is smaller than near the skin surface. However in 10 melanoma samples from different patients, the S parameters vary significantly. Similarly, among 10 normal skin samples without cancer, the S parameters also vary largely among different patients. To understand the sensitivity of PAS as a tool to detect cancer formation at the early stage, we propose a controlled and systematic study of in vivo experiments using UV-induced cancer skin from living animals.     

The MMCPP/GE/c Queue

We obtain the queue length probability distribution at equilibrium for a multi-server, single queue with generalised exponential (GE) service time distribution and a Markov modulated compound Poisson arrival process (MMCPP) – i.e., a Poisson point process with bulk arrivals having geometrically distributed batch size whose parameters are modulated by a Markovian arrival phase process. This arrival process has been considered appropriate in ATM networks and the GE service times provide greater flexibility than the more conventionally assumed exponential distribution. The result is exact and is derived, for both infinite and finite capacity queues, using the method of spectral expansion applied to the two dimensional (queue length by phase of the arrival process) Markov process that describes the dynamics of the system. The Laplace transform of the interdeparture time probability density function is then obtained. The analysis therefore could provide the basis of a building block for modelling networks of switching nodes in terms of their internal arrival processes, which may be both correlated and bursty.     

Polymeric membrane studied using slow positron beam

A radioisotope slow positron beam has been built at the Chung Yuan Christian University in Taiwan for the research and development in membrane science and technology. Doppler broadening energy spectra and positron annihilation lifetime have been measured as a function of positron energy up to 30 keV in a polyamide membrane prepared by the interfacial polymerization between triethylenetetraamine (TETA) and trimesoyl chloride (TMC) on modified porous polyacrylonitrile (PAN) asymmetric membrane. The multilayer structures and free-volume depth profile for this asymmetric membrane system are obtained. Positron annihilation spectroscopy coupled with a slow beam could provide new information about size selectivity of transporting molecules and guidance for molecular designs in polymeric membranes.     

Synthesis,Structure and Photophysical Properties of Ferrocenyl or Mixed Sandwich Cobaltocenyl Ester Linked meso‐Tetratolylporphyrin Dyads

We report here the design and synthesis of porphyrin–metallocene dyads consisting of a metallocene [either ferrocene or mixed sandwich η⁵‐[C₅H₄(COOH)]Co(η⁴‐C₄Ph₄) connected via an ester linkage at meso phenyl position of either free‐base or zinc porphyrin. All these dyad systems were characterized by various spectroscopic and electrochemical methods. A dimeric form of this molecule was observed in the X‐ray crystal structure of Zn‐TTPCo. The absorption spectra of all four dyads indicated the absence of electronic interactions between porphyrin macrocycle and metallocene in the ground state. However, interestingly, in all four dyads, fluorescence emission of the porphyrin was quenched (19–55%) as compared to their monomeric units. The quenching was more pronounced in ferrocene derivatives rather than cobaltocenyl derivatives. The emission quenching can be attributed to the excited‐state intramolecular photoinduced electron transfer from metallocene to singlet excited state of porphyrin and the electron‐transfer rates (k_ET) were established in the range 1.51 × 10⁸ to 1.11 × 10⁹ s^?1. They were found to be solvent dependent.     

Iridium-catalyzed asymmetric hydrogenation of olefins using TIQ phosphine–oxazoline ligands

A novel family of tetrahydroisoquinoline (TIQ) phosphine–oxazoline ligands and four corresponding iridium complexes have been developed and applied to the asymmetric hydrogenation of unfunctionalized olefins. The results showed that the best conversion rates were observed in up to 99% with an enantiomeric excess of 91%.     

Magnetic Properties and Antiferromagnetic Coupling in Inhomogeneous Zn1-xFexO Magnetic Semiconductor

Zn1-xFexO inhomogeneous oxide magnetic semiconductor films with high Fe concentration are prepared by sputtering, and fast annealing is carried out at different temperatures. It is found that magnetic properties are greatly modulated by controlling the composition inhomogeneity and subsequently fast annealing. Both ferromagnetic and paramagnetie components are found to coexist in the as-deposited Zn1-xFexO magnetic semiconductor. In particular, the antiferromagnetic coupling between the neighbouring local ferromagnetic regions is found in the as-deposited Zn0.23Fe0.77O film, and the antiferromagnetic coupling strength increases with increasing temperature from 110K to 300 K. We believe that this unusual antiferromagnetic coupling is mediated by thermally activated hopping carriers.