Reaction rates for nucleophiles with cyanogen chloride: Comparison with two other digonal carbon compounds

The hydrolysis kinetics of CICN have been reinvestigated from pH 0.0–10.5 and from 18–40°C. In the pH range from 1–5, the hydrolysis rate is invariant and the activation parameters (ΔH? = 84 kJ mol^?1 and ΔS? = ?84 J mol^?1 K^?1) are consistent with water attack. In basic solution the rate is first order each in CICN and OH^? concentrations with parameters ΔH? and ΔS? equal to 82 kJ mol^?1 and + 54 J mol^?1 K^?1, respectively. The rate constants with 20 other donors have been measured. Nitrogen nucleophiles are more reactive than oxygen donors, and an alpha-effect is seen. The constants follow a pattern indicative of attack at carbon. Cyanate in its acid form reacts with nucleophiles. Further points on the cyanate rate–pH profile have been obtained. A chromate-catalyzed hydrolysis can contribute between pH 5–10. Some studies were made of the reaction of cyanate with hydrogen peroxide. Free energy correlations are presented.     

A miniature mass spectrometer for liquid chromatography applications

A miniature mass spectrometer capable of detecting analytes eluting from a high-performance liquid chromatography (HPLC) system is described and demonstrated for the first time. The entire instrument, including all pumps and the computer, is contained within a single enclosure that may be conveniently accommodated at the base of the HPLC stack. The microspray ion source, vacuum interface, ion guide, and quadrupole ion filter are all microengineered. These components are fabricated in batches using microelectromechanical systems (MEMS) techniques and considered to be consumables. When coupled to a standard HPLC system using an integrated passive split, the limit of detection for reserpine while scanning the full mass range is 5 ng on-column (1 pg of which is passed to the microspray). The mass range is m/z 100-800, and each spectrum is typically acquired at a rate of 1 scan per second.     

Vibrational Fano resonances in dipole-bound anions

This paper explores Fano resonances due to non-adiabatic coupling of vibrational modes and the electron continuum in dipole-bound anions. We adopt a simple one-electron model consisting of a point dipole and an auxiliary potential to represent the electron interaction with the neutral core. Nuclear motion is added by assuming that harmonic vibrations modulate the dipole moment. When the model is parameterized to simulate key features of the water tetramer anion, the resultant photodetachment lineshape closely resembles that observed experimentally and analyzed as a Fano resonance with a parameter q close to -1. Other parameterizations are explored for the model and it is found that large changes in the auxiliary potential are required to change the sign of q. This is consistent with the experimental finding that q is negative for all water cluster sizes studied.     

The structure, thermal properties and phase transformations of the cubic polymorph of magnesium tetrahydroborate

The structure of the cubic polymorph of magnesium tetrahydroborate (γ-Mg(BH(4))(2)) has been determined in space group Ia3[combining macron]d from a structural database of the isoelectronic compound SiO(2); this has been corroborated by DFT calculations. The structure is found to concur with that recently determined by Filinchuk et al. (Y. Filinchuk, B. Richter, T. R. Jensen, V. Dmitriev, D. Chernyshov and H. Hagemann, Angew. Chem. Int. Ed., 2011, DOI: 10.1002/anie.201100675). The phase transformations and subsequent decomposition of γ-Mg(BH(4))(2) on heating have been ascertained from variable-temperature synchrotron X-ray diffraction data combined with thermogravimetric and mass spectrometry measurements. At ～160 °C, conversion to a disordered variant of the β-Mg(BH(4))(2) phase (denoted as β') is observed along with a further unidentified polymorph. There is evidence of amorphous phases during decomposition but there is no direct crystallographic indication of the existence of Mg(B(12)H(12)) or other intermediate Mg-B-H compounds. MgH(2) and finally Mg are observed in the X-ray diffraction data after decomposition.     

Structural basis for efficient chromophore communication and energy transfer in a constructed didomain protein scaffold

The construction of useful functional biomolecular components not currently part of the natural repertoire is central to synthetic biology. A new light-capturing ultra-high-efficiency energy transfer protein scaffold has been constructed by coupling the chromophore centers of two normally unrelated proteins: the autofluorescent protein enhanced green fluorescent protein (EGFP) and the heme-binding electron transfer protein cytochrome b(562) (cyt b(562)). Using a combinatorial domain insertion strategy, a variant was isolated in which resonance energy transfer from the donor EGFP to the acceptor cyt b(562) was close to 100% as evident by virtually full fluorescence quenching on heme binding. The fluorescence signal of the variant was also sensitive to the reactive oxygen species H(2)O(2), with high signal gain observed due to the release of heme. The structure of oxidized holoprotein, determined to 2.75 ? resolution, revealed that the two domains were arranged side-by-side in a V-shape conformation, generating an interchromophore distance of ～17 ? (14 ? edge-to-edge). Critical to domain arrangement is the formation of a molecular pivot point between the two domains as a result of different linker sequence lengths at each domain junction and formation of a predominantly polar interdomain interaction surface. The retrospective structural analysis has provided an explanation for the basis of the observed highly efficient energy transfer through chromophore arrangement in the directly evolved protein scaffold and provides an insight into the molecular principles by which to design new proteins with coupled functions.     

Roots of solvable polynomials of prime degree

An explicit formula for the most general root of a solvable polynomial of prime degree is stated and proved. Such a root can be expressed rationally in terms of a single compound radical determined by the roots of a cyclic polynomial whose degree divides μ−1$\mu -1$, where μ$\mu$ is the prime. The study of such formulas was initiated by a formula of Abel for roots of quintic polynomials that are solvable, and was carried forward by Kronecker and a few others, but seems to have lain dormant since 1924. A formula equivalent to the one given here is contained in a paper of Anders Wiman in 1903, but it seems to have been forgotten.