Synthesis of poly(benzyl glutamate‐b‐styrene) rod‐coil block copolymers by dual initiation in one pot

We have developed a metal free synthetic pathway to homopolypeptide rod‐coil block copolymers. The concept was proven for the synthesis of poly(benzyl‐L ‐glutamate‐b‐styrene). A dual initiator containing a primary amine and a nitroxide group was used in a macroinitiation approach with high initiation efficiency. Good control over the molecular weight in the ring opening polymerization of benzyl‐L ‐glutamate N‐carboxyanhydride was obtained in DMF at 0 °C yielding poly(benzyl‐L ‐glutamates) with low polydispersities around 1.1. The almost quantitative incorporation of the dual initiator was confirmed by MALDI‐ToF analysis. Macroinitiation of styrene by nitroxide‐mediated controlled radical polymerization yielded the block copolymer with high structural control. The diblock structure was confirmed by molecular weight increase upon macroinitiation by size exclusion chromatography and retention time comparison with homopolymers using gradient polymer elution chromatography. Both polymerizations were also successfully conducted in one pot without intermediate isolation owing to the high compatibility of both polymerization techniques. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3068–3077, 2008     

ChemInform Abstract: An ab initio Study of Possible Pathways in the Thermal Decomposition of NaAlH4

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

An ab initio study of possible pathways in the thermal decomposition of NaAlH4

Density functional theory (DFT) has been used to study the structural stability of possible intermediate alanate structures, Na₅Al₃H₁₄ and Na₂AlH₅, in the thermal decomposition of NaAlH₄. Na₅Al₃H₁₄ crystallizes in the space group P4/mnc with lattice constants , and c/a=1.52. It is shown that both Na₅Al₃H₁₄ and Na₂AlH₅ have the right thermodynamics and can fit in as an intermediate state during the thermal decomposition process of NaAlH₄. The heat of formation of Na₅Al₃H₁₄ is −60 kJ/mol H₂, which is intermediate between that of NaAlH₄ (−51 kJ/mol H₂) and Na₃AlH₆ (−69.7 kJ/mol H₂). An alternative decomposition pathway based on Na₂AlH₅ has also been discussed. Frequency analysis showed that the least energetic Na₂AlH₅ structure has imaginary frequencies, implying that it is unstable. The presence of soft phonon modes also shows that Na₅Al₃H₁₄ is mechanically metastable. These results are consistent with the notion that they are the intermediate states that lead to the formation of AlH₃. This facilitates the mass transport of aluminum atoms in the decomposition pathway of NaAlH₄.     

Donor-functionalized polydentate pyrylium salts and phosphinines: synthesis, structural characterization, and photophysical properties

A series of donor-functionalized pyrylium salts have been prepared by classical condensation reactions which were further converted into the corresponding thienyl- and pyridyl-substituted polydentate lambda(3)-phosphinines by reaction with P(SiMe(3))(3). Further chemical modification of these phosphorus heterocycles with Hg(OAc)(2) in the presence of methanol resulted in the formation of lambda(5)-phosphinines. The photophysical properties of a selected series of thienyl- and pyridyl-functionalized pyrylium salts, lambda(3)- and lambda(5)-phosphinines, were investigated and the results compared and supported by theoretical calculations on the DFT level. Significant fluorescence was observed for the pyrylium salts and lambda(5)-phosphinines. In contrast, the heteroaromatic substituted lambda(3)-phosphinines show very little emission which is consistent with the low oscillator strength predicted by DFT calculations for this pi-->pi* transition. Furthermore, all three classes of compounds show readily observable phosphorescence in solution, which was determined by time-gated detection at low temperature.     

Effect of Chain Length on the Adsorption Behavior of n-Alkanes in Ferrierite

¹³ C NMR spectroscopy and computer simulations have shown that the chain length of hydrocarbons has a surprising effect on where these molecules reside in the zeolite FER. Propane and butane can access the entire two-dimensional channel structure, while hexane only the one-dimensional substructure. This difference has important consequences for the catalytic activity and explains some of the experimental observations.     

Template-aluminosilicate structures at the early stages of zeolite ZSM-5 formation. A combined preparative, solid-state NMR, and computational study

Species at three stages in the self-assembly of zeolite ZSM-5 have been studied with one- and two-dimensional magic-angle-spinning 13C, 27Al, 29Si, and 1H NMR spectroscopy and compared with the earlier proposed structures: (1) precursor species containing 33-36 T sites around a tetrapropylammonium (TPA) cation, (2) nanoslabs consisting of a flat 4 x 3 array of such precursors, and (3) the final TPA-ZSM-5 zeolite. Synthesis was carried out in D2O to suppress the water and silanol protons. Under such conditions, the effective Si-H and Al-H distances measured with 29Si-{1H} and 27Al-{1H} rotational echo double resonance (REDOR) reflect the interactions between TPA cations and the surrounding aluminosilica. The 29Si-{1H} REDOR curves for Q4-type silicon atoms at the three mentioned stages are closely similar, as well as the observed 27Al-1H REDOR curve for the precursor species compared to that for the TPA-ZSM-5. This indicates that in addition to externally attached TPA, there is also internal TPA already incorporated at an early stage into the aluminosilicate in a similar way as in the final zeolite, in accordance with the earlier proposed MFI self-assembly pathway (Kirschhock et al. Angew. Chem. Int. Ed. 2001, 40, 2637). However, the effective distances extracted from the initial REDOR curvatures are significantly (10-15%) larger than those computed for the model. Since there is no temperature effect, we tentatively assign this difference to a reduction of the 29Si-1H and 27Al-1H interactions by multispin decoherence effects or self-decoupling caused by proton spin diffusion. By assuming the computed model distances and fitting Anderson-Weiss curves to the observed REDOR data, we obtain similar "decoherence times" in the order of 0.1 ms. The observed 29Si-{1H} REDOR dephasing for the Q3 sites in the precursors is significantly faster than that for the Q4 sites. This is tentatively ascribed to a partial deuteron-proton back exchange at the silanol positions.