Remarkably reactive dihydroindoloindoles via palladium-catalysed dearomatisation

Palladium-catalysed dearomatisation reactions allow access to a previously unknown class of indoloindole heterocycle: 5,10b-dihydroindolo[2,3-b]indoles. The highly reactive nature of these compounds is demonstrated by their facile reactions with water and with hydride, alkyl, aryl and allyl-based organometallic nucleophiles.     

A novel matrix-assisted laser desorption/ionisation mass spectrometry imaging based methodology for the identification of sexual assault suspects

An increase in the use of condoms by sexual offenders has been observed. This is likely to be due both to the risk of sexually transmitted diseases and to prevent the transfer of DNA evidence. In this scenario the detection of condom lubricants at a crime scene could aid in proving corpus delicti. Here we show a novel application of Matrix-Assisted Laser Desorption/Ionisation Mass Spectrometry Imaging (MALDI MSI) for mapping the fingermark ridge pattern simultaneously to the detection of the condom lubricant within the fingermark itself. Two condom brands have been investigated to prove the concept. Condoms were handled producing lubricant-contaminated fingermarks. Images of the ridge pattern were obtained simultaneously to the detection of two lubricants, even several weeks after the fingermark deposition. The results therefore show the potential of MALDI MSI to link the suspect (identification through fingermark ridge pattern) to the crime (detection of condom lubricant) in one analysis. This would enable forensic scientists to provide evidence with stronger support in alleged cases of sexual assault.     

Dynamical phase transition in a model for evolution with migration

We study a simple quasispecies model for evolution in two different habitats, with different fitness landscapes, coupled through one-way migration. Our key finding is a dynamical phase transition at a critical value of the migration rate, at which the time to reach the steady state diverges. The genetic composition of the population is qualitatively different above and below the transition. Using results from localization theory, we show that the critical migration rate may be very small-demonstrating that evolutionary outcomes can be very sensitive to even a small amount of migration.     

X‐ray crystal structure,NMR parameters,and conformational study of α‐aminopropanephosphonic acid

X‐ray structural data for α‐aminopropanephosphonic acid (APPA), together with ¹H NMR spectroscopy including PANIC and WIN‐DAISY spectral simulation, and theoretical calculations using the programs VAMP 4.4 (PM3) and GAUSSIAN 92 (3–21G**), confirm an antistaggered relationship between the methyl and phosphonic acid groups in this zwitterionic compound, both in the solid state and in aqueous solution. ³¹P{¹H} and ¹³C{¹H}‐NMR controlled titrations provide information on pK_a values, proton exchange, ion‐specific chemical shifts, and coupling constants in solution. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:314–325, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20609     

Trajectory reweighting for non-equilibrium steady states

Modern methods for sampling rugged landscapes in state space mainly rely on knowledge of the relative probabilities of microstates, which is given by the Boltzmann factor for equilibrium systems. In principle, trajectory reweighting provides an elegant way to extend these algorithms to non-equilibrium systems, by numerically calculating the relative weights that can be directly substituted for the Boltzmann factor. We show that trajectory reweighting has many commonalities with Rosenbluth sampling for chain macromolecules, including practical problems which stem from the fact that both are iterated importance sampling schemes: for long trajectories the distribution of trajectory weights becomes very broad and trajectories carrying high weights are infrequently sampled, yet long trajectories are unavoidable in rugged landscapes. For probing the probability landscapes of genetic switches and similar systems, these issues preclude the straightforward use of trajectory reweighting. The analogy to Rosenbluth sampling suggests though that path-ensemble methods such as PERM (pruned-enriched Rosenbluth method) could provide a way forward.     

Synthesis of some trifluoroethyl-substituted derivatives of aniline

A new procedure is presented for the preparation of N-trifluoroethylanilines by reaction of the appropriate aniline with ethyl trifluoroacetate or trifluoroacetic anhydride, followed by reduction with diborane in tetrahydrofuran. Yields are high unless the aniline carriers a carboyxl, carbonyl, olefin, or o-nitro substituent. several new N-substituted trifluoroacetamides and trifluoroethylanilines are reported.     

A mechanistic design principle for protein tyrosine kinase sensors: application to a validated cancer target

A new mechanistic principle for reporting the phosphorylation of tyrosine is described, which should prove applicable to even the most fastidious of protein tyrosine kinases, as demonstrated by the acquisition of a fluorescent sensor for the extraordinarily demanding anaplastic lymphoma kinase.