Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization

The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (M_n) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to M_n = 160,000 g mol^?1 for PBA (based on a linear PBA calibration) and up to M_n = 70,000 g mol^?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Practical algorithms for transposition-invariant string-matching

We consider the problems of (1) longest common subsequence (LCS) of two given strings in the case where the first may be shifted by some constant (that is, transposed) to match the second, and (2) transposition-invariant text searching using indel distance. These problems have applications in music comparison and retrieval. We introduce two novel techniques to solve these problems efficiently. The first is based on the branch and bound method, the second on bit-parallelism. Our branch and bound algorithm computes the longest common transposition-invariant subsequence (LCTS) in time O((m²+loglogσ)logσ) in the best case and O((m²+logσ)σ) in the worst case, where m and σ, respectively, are the length of the strings and the size of the alphabet. On the other hand, we show that the same problem can be solved by using bit-parallelism and thus obtain a speedup of O(w/logm) over the classical algorithms, where the computer word has w bits. The advantage of this latter algorithm over the present bit-parallel ones is that it allows the use of more complex distances, including general integer weights. Since our branch and bound method is very flexible, it can be further improved by combining it with other efficient algorithms such as our novel bit-parallel algorithm. We experiment on several combination possibilities and discuss which are the best settings for each of those combinations. Our algorithms are easily extended to other musically relevant cases, such as δ-matching and polyphony (where there are several parallel texts to be considered). We also show how our bit-parallel algorithm is adapted to text searching and illustrate its effectiveness in complex cases where the only known competing method is the use of brute force.     

Some Further Properties of the Accelerated Kerr-Schild Metrics

We extend the previously found accelerated Kerr-Schild metrics for Einstein-Maxwell-null dust and Einstein-Born-Infeld-null dust equations to the cases including the cosmological constant. This way we obtain the generalization of the charged de Sitter metrics in static space-times. We also give a generalization of the zero acceleration limit of our previous Einstein-Maxwell and Einstein-Born-Infeld solutions.     

Asymmetric hydrogenation of tri-substituted alkenes with Ir-NHC-thiazole complexes

An efficient chiral N-heterocyclic carbene ligand for the Ir-catalyzed asymmetric hydrogenation of largely unfunctionalized tri-substituted olefins has been developed. The Ir-NHC-thiazole catalyst is able to reduce a large variety of substrates with excellent conversions and good enantioselectivities with ee’s ranging from 34% to 90%, depending on the geometry around the double bond of the substrates.