Highly Enantioselective Hydrogenation of β‐Alkyl and β‐(ω‐Chloroalkyl) Substituted β‐Keto Esters

Highly enantioselective hydrogenation of β‐alkyl and β‐(ω‐chloroalkyl) substituted β‐keto esters was achieved with Ru catalysts based on chiral diphosphines in EtOH at 50°C under 50‐bar initial hydrogen pressure, affording the corresponding β‐hydroxy esters in >98% ee.     

Pristine and supported ZnO-based catalysts for phenazopyridine degradation with direct solar light

In search for safe techniques to manage waste pharmaceutical compounds drained in water, solar-driven degradation of phenazopyridine (a model drug) was investigated in aqueous media using different ZnO-based catalyst systems. Naked ZnO, CdS-sensitized ZnO (ZnO/CdS) and activated carbon-supported ZnO (AC/ZnO) have been studied. Both naked ZnO and AC/ZnO were highly efficient in mineralizing phenazopyridine, reaching complete removal in ～50 min, with AC/ZnO having the higher edge. The ZnO/CdS system showed lower efficiency, due to screening of light by CdS. Moreover, the tendency of CdS to leach out Cd²⁺ ions discouraged the use of CdS as sensitizer in this work. In both ZnO and AC/ZnO systems, the photo-degradation reaction was induced by the UV tail of the solar light. The visible region, with wavelength longer than 400 nm, failed to induce photo-degradation. The reaction was faster with higher catalyst loading, until a maximum efficiency was reached at a certain concentration. The rate of reaction increased with higher drug concentrations up to a certain limit. The effect of pH value was studied, and the catalysts showed highest efficiencies at pH close to 7. Stability of ZnO to degradation was studied. Both catalyst systems showed lowered efficiencies on recovery and reuse. The results suggest that complete mineralization of waste drugs, commonly dumped in sewage water, with direct solar light is a potentially feasible strategy using the AC/ZnO catalyst.     

Iridium-catalyzed alternative of the Meinwald rearrangement

A novel and easy to handle procedure for the regioselective rearrangement of epoxides has been developed, based on an iridium catalyst.     

Polynomial time approximation schemes and parameterized complexity

In this paper, we study the relationship between the approximability and the parameterized complexity of NP optimization problems. We introduce a notion of polynomial fixed-parameter tractability and prove that, under a very general constraint, an NP optimization problem has a fully polynomial time approximation scheme if and only if the problem is polynomial fixed-parameter tractable. By enforcing a constraint of planarity on the W-hierarchy studied in parameterized complexity theory, we obtain a class of NP optimization problems, the planar W-hierarchy, and prove that all problems in this class have efficient polynomial time approximation schemes (EPTAS). The planar W-hierarchy seems to contain most of the known EPTAS problems, and is significantly different from the class introduced by Khanna and Motwani in their efforts in characterizing optimization problems with polynomial time approximation schemes.     

Synthesis and vibrational circular dichroism of enantiopure chiral oxorhenium(V) complexes containing the hydrotris(1-pyrazolyl)borate ligand

The infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl)borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation (symmetry breaking due to the weak nuclear force). New chiral oxorhenium complexes have been synthesized, namely, [TpReO(eta2-O(CH3)CH2CH2O-O,O)] (4a and 4b) diastereomers and [TpReO(eta2-N(CH3)CH2CH2O-N,O)] (5) and [TpReO(eta2-N(tBu)CH2CH2O-N,O)] (6) enantiomers. All compounds could be obtained in enantiomerically pure form by using either column chromatography or HPLC over chiral columns. VCD spectroscopy of these compounds and of [TpReO(eta2-N(CH3)CH(CH3)CH(Ph)O-N,O)] (2) and [TpReO(eta2-N(CH2)3CHCO2-N,O)] (3) (with chiral bidentate ligands derived, respectively, from ephedrine and proline) were studied. This allowed the absolute configuration determination of all compounds together with their conformational analysis, by comparing calculated and experimental spectra. This is the first VCD study of rhenium complexes which further demonstrates the applicability of VCD spectroscopy in determining the chirality of inorganic complexes.     

Ultrafast laser assisted fabrication of ZnO nanorod arrays for photon detection applications

Orderly aligned ZnO nanorod arrays were grown by the ultrafast laser assisted ablation deposition method. These nanorod arrays were further used to make efficient p-n heterojunction photodetector arrays, which have the potential to have nanoscale spatial resolution for imaging, unique incident polarization discrimination capability, and much improved quantum efficiency as well as detection sensitivity. Both front- and back-illumination photodetection schemes were demonstrated by growing those ZnO nanorod arrays on p-type silicon and p-type Zn_0.9Mg_0.1O-coated Al₂O₃ (0 0 0 1) substrates, respectively. Typical diode rectification behavior and photosensitivity were observed in both designs through I-V and photocurrent measurements.     

A linear viscoelastic model for solid polyethylene

Stress relaxation tests have been carried out on a blue, pipe grade PE 80 medium density polyethylene (BP Chemicals), to provide thermo-viscoelastic rheology for use in calculating thermal stresses in pipe production. Stresses up to 4 MPa were used, with strains up to about 2%, in tests at temperatures from 23° to 90°C. Within this range a linear viscoelastic model was applicable, provided the initial ramp strain rate was less than 7×10^–5 s^–1. The stress relaxation data was fitted directly by a model incorporating an elastic response to volumetric strains, and a generalised linear solid model, consisting of two Maxwell elements and a purely elastic element in parallel, for deviatoric strains. Arrhenius type temperature dependence of relaxation times and shear moduli is found, and within experimental accuracy the temperature dependence of all these model parameters is the same. As a consequence, and provided that the duration of the strain ramp is sufficiently short relative to relaxation times, the model leads to time-temperature superposition of the relaxation moduli, using the same shift factor on both the response magnitude and time axes.     

Memetic techniques for examination timetabling

In this paper, we investigate the effectiveness of combining the main components of the memetic algorithms (MAs) on the quality of solutions produced for Uncapacitated Examination Timetabling Problem (UETP). These components are recombination, randomness, and neighbourhood structures. The Harmony Search Algorithm (HSA), which is a variation of MA, is used to perform different combinations of these components. It has three main components: Memory Consideration using the recombination, Random Consideration using the randomness and Pitch Adjustment using the neighbourhood structures (or local search). The combinations among MA components are evaluated using 17 different scenarios each of which reflects a combination of one, two or three components. The results show that the system that combines the three components (recombination, randomness, and neighbourhood structures) provides the best results. Furthermore, the best results obtained from the convergence scenarios were compared with 22 other methods that used a de facto dataset defined by Carter et al. (in Journal of the Operational Research Society 74:373–383, 1996) for UETP. The results exceed those produced by the previous methods in 2 out of 12 datasets.