Conjugate addition of pyrroles to α,β-unsaturated ketones using copper bromide as a catalyst

Copper bromide was used as a catalyst for the addition of pyrroles to enones. When both the reactants were used in equimolar amounts, mono and dialkylated products were obtained. However, the use of excess enone furnished only dialkylated products. Thus, copper bromide was shown to be an efficient catalyst for the dialkylation of pyrroles.     

Phonon density of states of ann-component alloy

We have generalized the coherent potential approximation (CPA) of Tripathi and Behera to the case of ann-component alloy. It is seen that then-component CPA density of states reproduces the binary, ternary quartenary alloys etc when the appropriate limits are adopted.     

Synthesis and characterization of novel thermoresponsive‐co‐biodegradable hydrogels composed of N‐isopropylacrylamide,poly(L‐lactic acid), and dextran

A series of novel multifunctional hydrogels that combined the merits of both thermoresponsive and biodegradable polymeric materials were designed, synthesized, and characterized. The hydrogels were copolymeric networks composed of N‐isopropylacrylamide (NIPAAM) as a thermoresponsive component, poly(L‐lactic acid) (PLLA) as a hydrolytically degradable and hydrophobic component, and dextran as an enzymatically degradable and hydrophilic component. The chemical structures of the hydrogels were characterized by an attenuated total reflection–Fourier transform infrared spectroscopy (ATR–FTIR) technique. The hydrogels were thermoresponsive, showing a lower critical solution temperature (LCST) at approximately 32 °C, and their swelling properties strongly depended on temperature changes, the balance of the hydrophilic/hydrophobic components, and the degradation of the PLLA component. The degradation of the hydrogels caused by hydrolytic cleavage of ester bonds in the PLLA component was faster at 25 °C below the LCST than at 37 °C above the LCST, determined by the ATR–FTIR technique. Due to their multifunctional properties, the designed hydrogels show great potential for biomedical applications, including drug delivery and tissue engineering. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5054–5066, 2004     

Kinetics and mechanism of the reactions of hexaaqua rhodium (III) with sulphur (IV) in aqueous medium

An O-bonded sulphito complex, Rh(OH₂)₅(OSO₂H)²⁺, is reversibly formed in the stoppedflow time scale when Rh(OH₂) ₆ ³⁺ and SO₂/HSO ₃ ⁻ buffer (1 <pH< 3) are allowed to react. For Rh(OH₂)₅OH₂₊+ SO₂ □ Rh(OH₂)₅(OSO₂H)²⁺ (k₁/k_-1), k₁ = (2.2 ±0.2) × 10³ dm³ mol⁻¹ s⁻¹, k₋1 = 0.58 ±0.16 s⁻¹ (25°C,I = 0.5 mol dm⁻³). The protonated O-sulphito complex is a moderate acid (K _d = 3 × 10⁻⁴ mol dm⁻³, 25°C, I= 0.5 mol dm⁻³). This complex undergoes (O, O) chelation by the bound bisulphite withk= 1.4 × 10⁻³ s⁻¹ (31°C) to Rh(OH₂)₄(O₂SO)⁺ and the chelated sulphito complex takes up another HSO ₃ ⁻ in a fast equilibrium step to yield Rh(OH₂)₃(O₂SO)(OSO₂H) which further undergoes intramolecular ligand isomerisation to the S-bonded sulphito complex: Rh(OH₂)₃(O₂SO)(OSO₂)^- → Rh(OH₂)₃(O₂SO)(SO₃)⁻ (k _iso = 3 × 10⁻⁴ s⁻¹, 31°C). A dinuclear (μ-O, O) sulphite-bridged complex, Na₄[Rh₂(μ-OH)₂(OH)₂(μ-OS(O)O)(O₂SO)(SO₃) (OH₂)]5H₂O with (O, O) chelated and S-bonded sulphites has been isolated and characterized. This complex is sparingly soluble in water and most organic solvents and very stable to acid-catalysed decomposition     

Photoinduced dissociative electron transfer (DET) interactions in methoxycalixarene–chloroalkane systems

Fluorescence quenching of methoxycalixarenes (MOCX) by chloroalkanes (CA) has been investigated in acetonitrile solutions. Observed quenching is attributed to photoinduced dissociative electron transfer (DET) interaction, which is supported by the characterization of the Cl⁻ ions and by the radical scavenging experiments. Comparing the Cl⁻ yields with different DET systems, it is inferred that both concerted and stepwise DET mechanisms operate simultaneously in MOCX–CA systems. A correlation of the quenching constants with the free-energy changes following a suitable DET theory supports the above inference.     

Working group report: Neutrino and astroparticle physics

This is the report of neutrino and astroparticle physics working group at WHEPP-7. Discussions and work on CP violation in long baseline neutrino experiments, ultra high energy neutrinos, supernova neutrinos and water Cerenkov detectors are discussed.     

Baseline studies of radon/thoron concentration levels in and around the Lambapur and Peddagattu areas in Nalgonda district, Andhra Pradesh, India

Studies conducted by Atomic Minerals Directorate of Exploration and Research (AMD) of Hyderabad, India had established the presence of higher concentrations of uranium in Lambapur and Peddagattu areas of Nalgonda district, AP, India and it was estimated that it could be a viable source for commercial extraction. The envisaged extraction process involves dispersion of radioactive particulate matter into atmosphere. Environmental radioactive studies in and around proposed mining areas at this point of time will be extremely useful for establishing base line data before a large scale uranium extraction process comes into existence. To this end, Solid State Nuclear Track Detectors were installed to evaluate indoor radon and thoron concentration levels in the dwellings of the area. The geometric means of radon and thoron concentration levels were found to be (7.1±0.2)×10¹ and (6.7±0.3)×10¹ Bq/m³, respectively. Simultaneously, natural background radiation measurements were also made and these levels are found to vary from 770 to 3995 μGy/y in the spatial distribution.     

Particle multiplicities in the fission-like reactions of 340 MeV Si on Th

Pre-scission and post-scission multiplicities of neutrons and alpha particles have been simultaneously measured for the fission-like reactions of 340 MeV ²⁸Si on ²³²Th. Dynamical model calculations using HICOL code predict that about 90% of the observed events are of quasi-fission type while the remaining 10% are from compound nucleus fission decay. Moving source fits were carried out to the observed neutron and alpha particle spectra, measured at different angles with respect to the fragment directions. The pre-scission and post-scission neutron multiplicities are deduced to be 8.7±2.0 and 9.4±2.0, respectively. The corresponding multiplicity values for alpha particles are found to be 0.22±0.08 and 0.1±0.03. From the measured post-scission neutron multiplicity, it is inferred that about 65±20 MeV of the initial excitation energy remains at scission. This may be compared to the value of 85±30 MeV estimated from PACE2 statistical model calculations, adjusted to reproduce the measured pre-scission neutron multiplicity. From a comparison of the Statistical Model predictions with the measured pre-scission neutron multiplicity, the fission delay is estimated to be of 5⁺⁷₋₃×10⁻²⁰ s which overlaps with the average duration of fission-like process from the contact to the scission point (2×10⁻²⁰ s) as determined from HICOL-based dynamical calculations. For the delay time deduced as above, the pre-scission alpha particle multiplicity calculated by the PACE2 code is about a factor two larger than the experimental one, demonstrating the difficulties in modelling the alpha particle emission from highly elongated shapes that characterize the fissioning system from the contact point to scission.