Cetyltrimethylammonium hydroxide (CTAOH) as a general, ecofriendly catalyst for the formation of carbon-carbon bond through nitroalkanes

Nitroalkanes have been found to give good yields in Michael and nitroaldol (Henry) reactions by the use of a catalytic amount (10 mol%) of CTAOH, at room temperature and under solvent free conditions and in very short reaction times. The methods do not need a large excess of the nitroalkanes and show good chemoselectivity toward further functionalities.     

New data on the ternary fission of 252Cf from the Gammasphere facility

Ternary fission of ²⁵²Cf was studied at Gammasphere using eight ΔE×E particle telescopes. Helium, beryllium, boron, and carbon light charged particles (LCPs) emitted with kinetic energy more than 9, 21, 26, and 32 MeV, respectively, were identified. The 3368-keV γ transition from the first 2⁺ excited state in ¹⁰Be was found and the population probability ratio N(2⁺)/N(0⁺) = 0.160 ± 0.025 was estimated. No evidence was found for 3368-keV γ rays emitted from a triple molecular state. For the first time, charge distributions are obtained for ternary fission fragments emitted with helium, beryllium, and carbon LCPs.     

In situ transmission electron microscopy study of the nucleation and grain growth of Ge2Sb2Te5 thin films

The nucleation and grain growth of the Ge₂Sb₂Te₅ (GST) thin films were studied using high voltage electron microscope operated at 1250 kV. As a result, we have found that 2 nm-sized nucleus forms as a cluster which atoms are arranged regularly at the stage of nucleation prior to the formation of grains having crystal structure. The high-resolution transmission electron microscopy study and fast-Fourier transformations revealed that coexistence of face-centered-cubic (FCC) and hexagonal structure occurs, and formation of twin defect is found in the hexagonal structure during the grain growth as the annealing temperature is increased. GST grain having the hexagonal structure grow from the surface, and the growth proceeded perpendicular to the [0 0 0 1], namely the path parallel to the (0 0 0 1) plane. Consequently, grain growth to a large-scale result in a lengthened shape.     

Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

Large-time behavior of perturbed diffusion markov processes with applications to the second eigenvalue problem for fokker-planck operators and simulated annealing

We study the large-time behavior and rate of convergence to the invariant measures of the processes dX (t)=b(X) (t)) dt + (X (t)) dB(t). A crucial constant appears naturally in our study. Heuristically, when the time is of the order exp( – )/² , the transition density has a good lower bound and when the process has run for about exp( – )/², it is very close to the invariant measure. LetL =(²/2) – U · be a second-order differential operator on ^d. Under suitable conditions,L ^z has the discrete spectrum