Measurement of energy landscape roughness of folded and unfolded proteins.

The dynamics of protein conformational changes, from protein folding to smaller changes, such as those involved in ligand binding, are governed by the properties of the conformational energy landscape. Different techniques have been used to follow the motion of a protein over this landscape and thus quantify its properties. However, these techniques often are limited to short timescales and low-energy conformations.

Comparison of the ATP binding sites of protein kinases using conformationally diverse bisindolylmaleimides.

The conformation of a bisindolylmaleimide may be controlled by the size of a macrocyclic ring in which it is constrained. A range of techniques were used to demonstrate that the tether controls both the ratio of the two limiting conformers (syn and anti) in solution and the extent of conjugation between the maleimide and indole rings. Screening the conformationally diverse bisindolylmaleimides against a panel of protein kinases allowed their ATP binding sites to be compared using a chemical approach which, like sequence alignment, does not require detailed structural information.

Synthesis and photochemistry of a new class of photocleavable protein cross-linking reagents.

A new series of photocleavable protein cross-linking reagents based on bis(maleimide) derivatives of diaryl disulfides have been synthesised. They have been functionalised with cysteine and transient absorption spectra for the photolysis reaction have been recorded by using the pump-probe technique with a time resolution of 100 femtoseconds. Photolysis of the disulfide bond yields the corresponding thiyl radicals in less than a picosecond.

Energy migration in novel pH-triggered self-assembled beta-sheet ribbons.

Energy migration between tryptophan residues has been experimentally demonstrated in self-assembled peptide tapes. Each peptide contains 11 amino acids with a Trp at position 6. The peptide self-assembly is pH-sensitive and forms amphiphilic tapes, which further stack in ribbons (double tapes) and fibrils in water depending on the concentration.

Accurate analysis of fluorescence decays from single molecules in photon counting experiments.

In time-resolved, single-photon counting experiments, the standard method of nonlinear least-squares curve fitting incorrectly estimates the fluorescence lifetimes. Even for single-exponential data, errors may be up to +/- 15%, and for more complex fits, may be even higher, although the fitted line appears to describe the data. The origin of this error is not a result of the Poisson distribution, as is often stated, but is entirely due to the weighting of the fit.

Excited state dynamics and rapid internal conversion in a stable dipole molecule.

The excited singlet state of an azomethine ylide or 'stable dipole' exhibits an ultrafast radiationless relaxation after femtosecond laser excitation. These transients are observed before the excited state decays in an almost activationless manner, the barrier is 440 cm-1, to the ground state with a 1.5 ps lifetime.

(eta2-tetracyanoethene)bis(triphenylphosphine-kappaP)palladium-dichloromethane (1/0.7).

The title compound, [Pd(C(6)N(4))(C(18)H(15)P)(2)].0.7CH(2)Cl(2), shows a planar coordination geometry around the metal atom that is an almost perfect isosceles triangle if the tetracyanoethene (tcne) ligand is deemed to occupy a single coordination site.

Femtosecond electron-transfer reactions in mono- and polynucleotides and in DNA.

Quenching of redox active, intercalating dyes by guanine bases in DNA can occur on a femtosecond time scale both in DNA and in nucleotide complexes. Notwithstanding the ultrafast rate coefficients, we find that a classical, nonadiabatic Marcus model for electron transfer explains the experimental observations, which allows us to estimate the electronic coupling (330 cm(-1)) and reorganization (8070 cm(-1)) energies involved for thionine-[poly(dG-dC)](2) complexes. Making the simplifying assumption that other charged, pi-stacked DNA intercalators also have approximately these same values, the electron-transfer rate coefficients as a function of the driving force, DeltaG, are derived for similar molecules.