Pronounced stabilisation of the ferrocenium state of ferrocenecarboxylic acid by salt bridge formation with a benzamidine

Salt bridge formation between ferrocenecarboxylic acid and an excess of a N,N^′-diethylsubstituted benzamidine leads to a −0.27 V shift in the half-wave potential of the ferrocene moiety, corresponding to a 26 kJ mol⁻¹ stabilisation of the ferrocenium state.     

Completion problem with partial correlation vines

This paper extends the results in [D. Kurowicka, R.M. Cooke, A parametrization of positive definite matrices in terms of partial correlation vines, Linear Algebra Appl. 372 (2003) 225-251]. We show that a partial correlation vine represents a factorization of the determinant of the correlation matrix. We show that the graph of an incompletely specified correlation matrix is chordal if and only if it can be represented as an m-saturated incomplete vine, that is, an incomplete vine for which all edges corresponding to membership-descendents (m-descendents for short) of a specified edge are specified. This enables us to find the set of completions, and also the completion with maximal determinant for matrices corresponding to chordal graphs.     

Optoelectronic resonant cavity technology based on inversion channel devices

In this paper the implementation of the inversion channel technology in a vertical cavity configuration is demonstrated. It is shown that by using a universal processing sequence a bistable surface emitting laser, a resonant cavity detector and a hetero-structure field effect transistor (H FET) can all be realized from a single epitaxial growth. The surface emitting double heterostructure opto-electronic switch (DOES) laser exhibits a pulsed threshold current of 10 mA for a 14 m diameter device. The resonant cavity detector achieved a peak responsivity of 0.6 AW^–1 in the H FET mode and 19 AW^–1 when operated in phototransistor mode. The H FET had a peak transconductance of 40 mS mm^–1 and a peak source to drain current density of 120 mA mm^–1.     

Pure rotational spectra of LuF and LuCl

The pure rotational spectra of two isotopic species of LuF and three of LuCl have been measured in the frequency range 5-17 GHz using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laser ablation of Lu metal in the presence of SF(6) or Cl(2), and stabilized in supersonic jets of Ar. Spectra of molecules in states having v= 0, 1, and 2 have been measured, to produce rotational constants and centrifugal distortion constants, along with hyperfine constants for all the nuclei. Dunham-type fits for LuCl produced a Born-Oppenheimer breakdown parameter for Cl. Although a theoretical calculation showed that Lu in LuCl should have a significant field shift effect parameter, it could not be determined from the spectrum. Equilibrium internuclear distances, r(e), and dissociation energies have been evaluated for both molecules. The nuclear quadrupole coupling constants are discussed in terms of the molecular electronic structure.     

Prediction of migration behavior of oligonucleotides in capillary gel electrophoresis.

The influence of the primary structure (base composition) on the electrophoretic migration properties of single-stranded oligodeoxyribonucleotides in capillary polyacrylamide gel electrophoresis was investigated using homo- and heterooligomers under denaturing and non-denaturing conditions. Homooligodeoxyribonucleotides of equal chain lengths but of different base composition showed significant differences in mobility. In addition, the migration properties of heterooligomers were found to be highly dependent on their base composition. A simple equation is presented for predicting relative migration times using denaturing and non-denaturing polyacrylamide capillary gel electrophoresis. Orange-G was used as an internal standard and as the basis of the relative migration time calculations. Examples are presented using homo- and heterooligomers in the 10-20-mer range to show the correlation of the primary structure and their predicted and observed migration rates.     

The influence of nuclear volume and electronic structure on the rotational energy of platinum monoxide, PtO

The pure rotational spectra of seven isotopic species of platinum monoxide have been measured with a cavity pulsed jet Fourier-transform microwave spectrometer. The molecules were prepared by laser ablation of Pt foil in the presence of O2 and stabilized in a supersonic jet of argon. A multi-isotopomer Dunham-type analysis of the spectra produced values for Y01 and Y11, along with unusually large values for Born-Oppenheimer breakdown (BOB) parameters for both Pt and O atoms. The values of the BOB parameters have been rationalized in terms of the molecular electronic structure and finite nuclear size (field shift) effects. A large negative 195Pt effective nuclear spin-rotation constant has been rationalized in terms of the electron-nucleus dipole-dipole hyperfine constant. Precise internuclear separations have been evaluated.     

Double diffusion for the programmable spatiotemporal patterning of multi-domain supramolecular gels

To achieve spatial resolution of a multi-component gel, a double diffusion approach is used which enables the precise programming of self-assembled patterned domains with well-defined shapes and sizes. The low-molecular-weight gelators (LMWGs) used in this study are pH-responsive DBS-CO₂H and thermally-responsive DBS-CONHNH₂ (both based on 1,3:2,4-dibenzylidenesorbitol, DBS). A DBS-CONHNH₂ gel was initially assembled in a tray, and then loaded at carefully-selected positions with either basified DBS-CO₂H (i.e. DBS-carboxylate) or an acid. These soluble components subsequently diffuse through the pre-formed gel matrix, and in the domains when/where they mix, protonation of the DBS-carboxylate induces self-assembly of the DBS-CO₂H network, leading to a patterned gel-in-gel object with well-defined shape and dimensions. Using a strong acid achieves fast gelation kinetics, creating smaller, better-defined macroscale objects but with less nanoscale order. Using a weak acid source with slow kinetics, gives slightly larger objects, but on the nanoscale the DBS-CO₂H network formation is better controlled, giving more homogeneous nanoscale structures and stiffer objects. The patterned objects can be further reinforced by the presence of agarose polymer gelator. The shape of the patterning is programmed by both the shape of the central reservoir and the starting geometry in which the reservoirs are organised, with the balance between factors depending on assembly kinetics, as dictated by the choice of acid. This simple methodology therefore enables programming of patterned gels with spatiotemporal control and emergent patterning characteristics.

To achieve spatial resolution of a multi-component gel, a double diffusion approach is used which enables the precise programming of emergent self-assembled patterned domains with well-defined shapes and sizes.