Dual Sulfide–Disulfide Crosslinked Networks with Rapid and Room Temperature Self‐Healability

Polymer‐based crosslinked networks with intrinsic self‐repairing ability have emerged due to their built‐in ability to repair physical damages. Here, novel dual sulfide–disulfide crosslinked networks (s‐ssPxNs) are reported exhibiting rapid and room temperature self‐healability within seconds to minutes, with no extra healing agents and no change under any environmental conditions. The method to synthesize these self‐healable networks utilizes a combination of well‐known crosslinking chemistry: photoinduced thiol‐ene click‐type radical addition, generating lightly sulfide‐crosslinked polysulfide‐based networks with excess thiols, and their oxidation, creating dynamic disulfide crosslinkages to yield the dual s‐ssPxNs. The resulting s‐ssPxN networks show rapid self‐healing within 30 s to 30 min at room temperature, as well as self‐healing elasticity with reversible viscoelastic properties. These results, combined with tunable self‐healing kinetics, demonstrate the versatility of the method as a new means to synthesize smart multifunctional polymeric materials.

     

Mono(cycloheptatrienyl) tantalum chemistry: synthesis and characterization of new tantalum halide, hydride, and alkyl species

The new tantalum(II) complex (eta (6)-C 7H 8)TaCl 2(PMe 3) 2 ( 1) was synthesized by the reduction of TaCl 5 with n-butyllithium in the presence of PMe 3 and cycloheptatriene. Compound 1 adopts a four-legged piano stool structure in which the tantalum center is bound to a eta (6)-cycloheptatriene ring in addition to two chlorides and two phosphine ligands in a transoid arrangement. Treatment of 1 with methyllithium results in a loss of the equivalents of HCl and formation of the eta (7)-cycloheptatrienyl complex (eta (7)-C 7H 7)TaCl(PMe 3) 2 ( 2), whereas treatment of 1 with sodium or sodium borohydride affords small amounts of the eta (5)-cycloheptadienyl complex (eta (5)-C 7H 9)TaCl 2(PMe 3) 2 ( 3). Compound 2 adopts a three-legged piano stool structure; the eta (7)-C 7H 7 ring is fully aromatic and planar. The molecular structure of 3 is similar to that of 1, except for the eta (5) binding mode of the seven-membered ring. Treatment of the previously described sandwich compound (C 5Me 5)Ta(C 7H 7) with allyl bromide affords the tantalum(V) product (C 5Me 5)Ta(C 7H 7)Br ( 4), which reacts with LiAlH 4 to give the tantalum(V) hydride (C 5Me 5)Ta(C 7H 7)H ( 5). Compound 4 also reacts with alkylating agents to generate the methyl, allyl, and cyclopropyl complexes (C 5Me 5)Ta(C 7H 7)Me ( 6), (C 5Me 5)Ta(C 7H 7)(eta (1)-CH 2CHCH 2) ( 7), and (C 5Me 5)Ta(C 7H 7)(c-C 3H 5) ( 8). Compounds 4- 8 all adopt bent sandwich structures in which the dihedral angle between the two carbocyclic rings is 34.9 degrees for the bromo compound 4, 26.6 degrees for the hydride 5, 33.1 degrees for the methyl compound 6, 34.2 degrees for the allyl compound 7, and 37.5 degrees for the cyclopropyl compound 8. (1)H and (13)C NMR data are reported for the diamagnetic compounds.     

2‐[(Diphenylphosphino)methyl]pyridine as ligand for iron‐based atom transfer radical polymerization

2‐[(Diphenylphosphino)methyl]pyridine (DPPMP) was successfully used as a bidentate ligand in the iron‐mediated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with various initiators and solvents. The effect of the catalytic system on ATRP was studied systematically. Most of the polymerizations with DPPMP ligand were well controlled with a linear increase in the number‐average molecular weights (M_n) versus conversion and relatively low molecular weight distributions (M_w/M_n = 1.10–1.3) being observed throughout the reactions, and the measured molecular weights matched the predicted values. Initially added iron(III) bromide improved the controllability of the polymerization reactions in terms of molecular weight control. The ratio of ligand to metal influenced the controllability of ATRP system, and the optimum ratio was found to be 2:1. It was shown that ATRP of MMA with FeX₂/DPPMP catalytic system (X = Cl, Br) initiated by 2‐bromopropionitrile (BPN) was controlled more effectively in toluene than in polar solvents. The rate of polymerization increased with increasing the polymerization temperature and the apparent activation energy was calculated to be 56.7 KJ mol^?1. In addition, reverse ATRP of MMA was able to be successfully carried out using AIBN in toluene at 80 °C. Polymerization of styrene (St) was found to be controlled well by using the PEBr/FeBr₂/DPPMP system in DMF at 110 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2922–2935, 2008     

Surface plasmon delocalization by short-range correlations in percolating metal systems

Theoretical and experimental studies of the electromagnetic response of semicontinuous metal films are presented. A scaling theory is developed by solving the surface plasmon eigenproblem. The short-range correlations in the governing Kirchhoff Hamiltonian result in delocalization of the surface plasmon eigenmodes. Although their relative weight in the spectrum becomes asymptotically small for large systems, the existence of these delocalized states modifies the critical indices for the high-order field moments. This modification is confirmed experimentally by the near-field measurement of high-order intensity moments for percolating silver films on glass substrates. PACS 68.37.Uv; 73.20.Mf; 42.25.Dd; 78.67.-n     

Bacterial formation of extracellular U(VI) nanowires

Shewanella oneidensis MR-1 rapidly accumulates long, extracellular, U(VI) nanowires composed of polycrystalline chains of discrete meta-schoepite (UO(3)·2H(2)O) nanocrystallites. The production of uranium(VI) nanowires could provide a novel strategy for remediation of uranium contamination in sediments and aquifers, as well as the recovery of uranium in manufacturing processes.     

Newtonian versus relativistic nonlinear cosmology

Both for the background world model and its linear perturbations Newtonian cosmology coincides with the zero-pressure limits of relativistic cosmology. However, such successes in Newtonian cosmology are not purely based on Newton's gravity, but are rather guided ones by previously known results in Einstein's theory. The action-at-a-distance nature of Newton's gravity requires further verification from Einstein's theory for its use in the large-scale nonlinear regimes. We study the domain of validity of the Newtonian cosmology by investigating weakly nonlinear regimes in relativistic cosmology assuming a zero-pressure and irrotational fluid. We show that, first, if we ignore the coupling with gravitational waves the Newtonian cosmology is exactly valid even to the second order in perturbation. Second, the pure relativistic correction terms start appearing from the third order. Third, the correction terms are independent of the horizon scale and are quite small in the large-scale near the horizon. These conclusions are based on our special (and proper) choice of variables and gauge conditions. In a complementary situation where the system is weakly relativistic but fully nonlinear (thus, far inside the horizon) we can employ the post-Newtonian approximation. We also show that in the large-scale structures the post-Newtonian effects are quite small. As a consequence, now we can rely on the Newtonian gravity in analyzing the evolution of nonlinear large-scale structures even near the horizon volume.     

Random field Ising model and community structure in complex networks

We propose a method to determine the community structure of a complex network. In this method the ground state problem of a ferromagnetic random field Ising model is considered on the network with the magnetic field B_s = +∞, B_t = -∞, and B_i≠s,t=0 for a node pair s and t. The ground state problem is equivalent to the so-called maximum flow problem, which can be solved exactly numerically with the help of a combinatorial optimization algorithm. The community structure is then identified from the ground state Ising spin domains for all pairs of s and t. Our method provides a criterion for the existence of the community structure, and is applicable equally well to unweighted and weighted networks. We demonstrate the performance of the method by applying it to the Barabási-Albert network, Zachary karate club network, the scientific collaboration network, and the stock price correlation network. (Ising, Potts, etc.)     

Synthesis of monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex

We successfully synthesized monodisperse chromium nanoparticles from the thermolysis of a Fischer carbene complex.     

Synthesis and characterization of Al-modified SBA-15 for Fischer–Tropsch synthesis (FTS) reaction

Research on Chemical Intermediates - In this work, we synthesized a Co-based catalyst supported on modified SBA-15 to obtain the uniform particle size of active metal and selective products with...