Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Ion-pair formation of a copper(II)-ammine complex with an anionic surfactant and the recovery of copper(II) from ammonia medium by the surfactant-gel extraction method.

The extraction and separation of copper(II), zinc(II), cobalt(II), and cadmium(II) were investigated. Both copper(II) and zinc(II) formed ammine-complexes, while cadmium(II) and cobalt(II) formed hydroxide precipitates in an ammonia medium. By the addition of sodium dodecylsulfate (SDS), a copper(II) complex formed an ion-pair (copper-ammine-DS), which was extracted into the SDS phase. However, a zinc(II) complex did not form an ion-pair, and was soluble in water. Copper(II) ion was recovered by stripping (back-extraction) after the addition of hydrochloric acid. This method was applied to the separation of copper(II) in a brass alloy.     

Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.     

New methods and reagents in organic synthesis. 56. Total syntheses of patellamides B and C,cytotoxic cyclic peptides from a tunicate 2. Their real structures have been determined by their syntheses.

The proposed structures of patellamides B and C, cytotoxic lipophilic cyclic peptides from a marine tunicate, have been revised on the basis of the spectral data of their partial hydrolysates, and their revised structures have been synthetically confirmed by the use of diphenyl phosphorazidate(DPPA) and diethyl phosphorocyanidate(DEPC).     

Total synthesis of cis-solamin

[structure: see text] A convergent total synthesis of cis-solamin and its diastereomer was accomplished using VO(acac)2-catalyzed diastereoselective epoxidation followed by cyclization of bis-homoallylic alcohol as the key step. By comparison of the optical rotation of two possible diastereomers, it is suggested that the absolute configuration of natural cis-solamin is 1a.     

Supramolecular Hybrids from Cyanometallate Complexes and Diblock Copolypeptide Amphiphiles in Water

The self-assembly of discrete cyanometallates has attracted significant interest due to the potential of these materials to undergo soft metallophilic interactions as well as their optical properties. Diblock copolypeptide amphiphiles have also been investigated concerning their capacity for self-assembly into morphologies such as nanostructures. The present work combined these two concepts by examining supramolecular hybrids comprising cyanometallates with diblock copolypeptide amphiphiles in aqueous solutions. Discrete cyanometallates such as [Au(CN)₂]⁻, [Ag(CN)₂]⁻, and [Pt(CN)₄]²⁻ dispersed at the molecular level in water cannot interact with each other at low concentrations. However, the results of this work demonstrate that the addition of diblock copolypeptide amphiphiles such as poly-(L-lysine)-block-(L-cysteine) (Lys_m-b-Cys_n) to solutions of these complexes induces the supramolecular assembly of the discrete cyanometallates, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Electron microscopy images confirmed the formation of nanostructures of several hundred nanometers in size that grew to form advanced nanoarchitectures, including those resembling the original nanostructures. This concept of combining diblock copolypeptide amphiphiles with discrete cyanometallates allows the design of flexible and functional supramolecular hybrid systems in water.     

Pseudo-Binary Phase Diagram of LiNH2-MH (M = Na,K) Eutectic Mixture

The hunt for a cleaner energy carrier leads us to consider a source that produces no toxic byproducts. One of the targeted alternatives in this approach is hydrogen energy, which, unfortunately, suffers from a lack of efficient storage media. Solid-state hydrogen absorption systems, such as lithium amide (LiNH₂) systems, may store up to 6.5 weight percent hydrogen. However, the temperature of hydrogenation and dehydrogenation is too high for practical use. Various molar ratios of LiNH₂ with sodium hydride (NaH) and potassium hydride (KH) have been explored in this paper. The temperature of hydrogenation for LiNH₂ combined with KH and NaH was found to be substantially lower than the temperature of individual LiNH₂. This lower temperature operation of both LiNH₂-NaH and LiNH₂-KH systems was investigated in depth, and the eutectic melting phenomenon was observed. Systematic thermal studies of this amide-hydride system in different compositions were carried out, which enabled the plotting of a pseudo-binary phase diagram. The occurrence of eutectic interaction increased atomic mobility, which resulted in the kinetic modification followed by an increase in the reactivity of two materials. For these eutectic compositions, i.e., 0.15LiNH₂-0.85NaH and 0.25LiNH₂-0.75KH, the lowest melting temperature was found to be 307 °C and 235 °C, respectively. Morphological studies were used to investigate and present the detailed mechanism linked with this phenomenon.     

Application of 28Mg to the kinetic study of Mg uptake by rice plants

The time course of Mg uptake and release using intact rice plants and ²⁸Mg as a tracer is presented. Since there is no conventional Mg tracer available, ²⁸Mg was produced via ²⁷Al(α, 3p)²⁸Mg reaction using a cyclotron. Using the purified ²⁸Mg tracer, it was found that the uptake amount of ²⁸Mg by the rice plants increased linearly during 30 min of application. After ²⁸Mg treatment for 90 min, the roots were sequentially washed with iced solution for 120 min. Within about 10 min, almost all of the ²⁸Mg, that was thought to be weakly bound to the apoplast, was washed away.     

Long wavelength InAs self-assembled quantum dots embedded in GaNAs strain-compensating layers

We investigated the effect of GaNAs strain-compensating layers (SCLs) on the properties of InAs self-assembled quantum dots (QDs) grown on GaAs (0 0 1) substrates. The GaNAs material can be used as SCL thereby minimizing the net strain, and thus is advantageous for multi-stacking of InAs QDs structures and achieving long wavelength emission. The emission wavelength of InAs QDs can be tuned by changing the nitrogen (N) composition in GaNAs SCLs due to both effects of strain compensation and lowering of potential barrier height. A photoluminescence emission at 77 K was clearly observed for sample with GaN_0.024As_0.976 SCL. Further, we observed an improvement of optical properties of InAs QDs by replacing the more popular GaAs embedding layers with GaNAs SCLs, which is a result of decreasing non-radiative defects owing to minimizing the total net strain.