Kosmotrope character of maltose in water mixtures

It is well known that water plays a fundamental role for living beings, because the nature of water transformations provides for the ability to preserve biostructures. Solute can be classified as “kosmotropes” or “chaotropes” depending on the interaction strength with water. In the case of solutes destroying the natural hydrogen bonded network of water, called “kosmotropes” or “structure-makers”, the denaturation processes can be inhibited.

The aim of this work is to investigate the vibrational behaviour of maltose/H₂O mixtures in order to characterise the changes induced by the sugar on the H₂O hydrogen-bonded network. The obtained findings point out that maltose has a destructuring effect on the water tetrahedral network and emphasise its kosmotrope character.     

Neutron Compton scattering investigation of sodium hydride: from bulk material to encapsulated nanoparticulates in amorphous silica gel

In this study we utilize neutron Compton scattering (NCS) to determine differences in nuclear momentum distributions in NaH, both as bulk material and encapsulated as nanoscale particles (from 20 to 50 nm in diameter) within an amorphous silica-gel matrix (SiGNaH). In addition, elemental Na dispersed in such a matrix is also studied (SiGNa). Data treatment and fitting of experimental spectra yields comparison of the nuclear Compton profiles and radial momentum distributions for the proton in both bulk NaH and nanoscale SiGNaH, with resultant proton kinetic energies being in agreement with previous inelastic neutron studies of bulk NaH. Slight differences in proton radial momentum distributions for bulk and nanoscale systems are witnessed and discussed. The technique of stoichiometric-fixing is applied to the backscattering spectra of each system in order to examine changes in the Na profile width, and NCS is shown to be sensitive to the chemical environment change of this heavier nucleus. Examination of the Si and O profile widths in the gel samples also supports this method.     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

Inelastic incoherent neutron scattering measurements of intact cells and tissues and detection of interfacial water

We have previously used inelastic incoherent neutron scattering spectroscopy to investigate the properties of aqueous suspensions of biomolecules as a function of hydration. These experiments led to the identification of signals corresponding to interfacial (hydration) water at low water content. A prediction from these studies was that in the crowded environment inside living cells, a significant proportion of the water would be interfacial, with profound implications for biological function. Here we describe the first inelastic incoherent neutron scattering spectroscopy studies of living cells and tissues. We find that the interfacial water signal is similar to that observed for water interacting with purified biomolecules and other solutes, i.e., it is strongly perturbed in the librational and translational intermolecular optical regions of the spectrum at 20-150 meV. The ratio of interfacial water compared to total water in cells (approximately 30%) is in line with previous experimental data for hydration water and calculations based on simple assumptions.     

Spectroscopic Studies of the Magnetic Excitation and Spin-Phonon Couplings in a Single-Molecule Magnet

Large separations between ground and excited magnetic states in single-molecule magnets (SMMs) are desirable to reduce the likelihood of spin reversal in the molecules. Spin-phonon coupling is a process leading to magnetic relaxation. Both the reversal and coupling, making SMMs lose magnetic moments, are undesirable. However, direct determination of large magnetic states separations (>45 cm⁻¹) is challenging, and few detailed investigations of the spin-phonon coupling have been conducted. The magnetic separation in [Co(12-crown-4)₂](I₃)₂(12-crown-4) ( 1 ) is determined and its spin-phonon coupling is probed by inelastic neutron scattering (INS) and far-IR spectroscopy. INS, using oriented single crystals, shows a magnetic transition at 49.4(1.0) cm⁻¹. Far-IR reveals that the magnetic transition and nearby phonons are coupled, a rarely observed phenomenon, with spin-phonon coupling constants of 1.7–2.5 cm⁻¹. The current work spectroscopically determines the ground–excited magnetic states separation in an SMM and quantifies its spin-phonon coupling, shedding light on the process causing magnetic relaxation.     

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal-Organic Framework Materials

We report the modulation of reactivity of nitrogen dioxide (NO₂) in a charged metal–organic framework (MOF) material, MFM-305-CH₃ in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl⁻ ions in the pores. Uptake of NO₂ into MFM-305-CH₃ leads to reaction between NO₂ and Cl⁻ to give nitrosyl chloride (NOCl) and NO₃⁻ anions. A high dynamic uptake of 6.58 mmol g⁻¹ at 298 K is observed for MFM-305-CH₃ as measured using a flow of 500 ppm NO₂ in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g⁻¹. The binding domains and reactivity of adsorbed NO₂ molecules within MFM-305-CH₃ and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.