The tropolone–isobutylamine complex: a hydrogen‐bonded troponoid without dominant π–π interactions

Tropolone long has served as a model system for unraveling the ubiquitous phenomena of proton transfer and hydrogen bonding. This molecule, which juxtaposes ketonic, hydroxylic, and aromatic functionalities in a framework of minimal complexity, also has provided a versatile platform for investigating the synergism among competing intermolecular forces, including those generated by hydrogen bonding and aryl coupling. Small members of the troponoid family typically produce crystals that are stabilized strongly by pervasive π–π, C—H…π, or ion–π interactions. The organic salt (TrOH·iBA) formed by a facile proton‐transfer reaction between tropolone (TrOH) and isobutylamine (iBA), namely isobutylammonium 7‐oxocyclohepta‐1,3,5‐trien‐1‐olate, C₄H₁₂N⁺·C₇H₅O₂⁻, has been investigated by X‐ray crystallography, with complementary quantum‐chemical and statistical‐database analyses serving to elucidate the nature of attendant intermolecular interactions and their synergistic effects upon lattice‐packing phenomena. The crystal structure deduced from low‐temperature diffraction measurements displays extensive hydrogen‐bonding networks, yet shows little evidence of the aryl forces (viz. π–π, C—H…π, and ion–π interactions) that typically dominate this class of compounds. Density functional calculations performed with and without the imposition of periodic boundary conditions (the latter entailing isolated subunits) documented the specificity and directionality of noncovalent interactions occurring between the proton‐donating and proton‐accepting sites of TrOH and iBA, as well as the absence of aromatic coupling mediated by the seven‐membered ring of TrOH. A statistical comparison of the structural parameters extracted for key hydrogen‐bond linkages to those reported for 44 previously known crystals that support similar binding motifs revealed TrOH·iBA to possess the shortest donor–acceptor distances of any troponoid‐based complex, combined with unambiguous signatures of enhanced proton‐delocalization processes that putatively stabilize the corresponding crystalline lattice and facilitate its surprisingly rapid formation under ambient conditions.     

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.     

NIR emitting ytterbium chelates for colourless luminescent solar concentrators

A new oxyiminopyrazole-based ytterbium chelate enables NIR emission upon UV excitation in colorless single layer luminescent solar concentrators for building integrated photovoltaics.     

Phase properties of squeezed states of light

Recently introduced unitary and hermitian phase operators are used to examine the phase properties of squeezed states of light with particular reference to the squeezed vacuum. The results differ markedly from previous calculations involving the Susskind and Glogower operators. The new formalism allows the construction of a phase probability density which, on a polar diagram, is a circle for the vacuum state, becomes elliptical with gentle squeezing and collapses to a line through the origin for full squeezing. This probability density together with the calculation of expectation values of various trigonometrical functions of phase show how squeezing impresses phase information onto the vacuum.     

Maximally robust unravelings of quantum master equations

The stationary state of an open quantum system has infinitely many representations as an ensemble of pure states. We argue that the most natural ensemble is the most robust physically realizable ensemble. Robustness is quantified by the survival probability. Physical realization requires monitoring the environment to “unravel” the dissipative evolution.     

Conformational effects on optical rotation. 3-substituted 1-butenes

A calculation of the optical rotation of (R)-(-)-3-chloro-1-butene found a remarkably large dependence on the C=C-C-C torsional angle. At tau = 0 degrees, [alpha](D) = +244 degrees, whereas at tau = 180 degrees, [alpha](D) = -526 degrees. The effect of conformation on the optical rotation was confirmed by a study of the temperature dependence of the rotation. An analysis of the data gave the difference in free energy between the low- and high-energy conformers as 1315 cal/mol and gave the optical rotation of the low-energy conformer and the average of the rotations of the higher energy forms. Although a large effect was found, the observed rotations are a factor of 2.6 smaller than the calculated values, independent of both conformation and wavelength from 589 to 365 nm. The effect of replacing Cl with F, CN, and CCH was examined theoretically. The effects of substituents are remarkably small despite large changes in the calculated electronic transition energies.     

Uncatalyzed and solvent-free multicomponent process for the synthesis of biphenyl-2-carbonitrile derivatives

An innovative route to prepare a number of variously substituted new biphenyl derivatives is presented here. The protocol avoids the use of a catalyst, an organic solvent, and dry conditions. [reaction: see text]     

Diffusion NMR spectroscopy for the characterization of the size and interactions of colloidal matter: the case of vesicles and nanoparticles

We report the application of the pulse gradient spin-echo (PGSE) NMR technique (PGSE NMR) to the analysis of large colloidal materials, specifically vesicles formed from macromolecular amphiphiles and nanoparticles. Measurements of size and size distribution were demonstrated to be comparable to those obtained through dynamic light scattering or hydrodynamic chromatography. In comparison to these more common analytical methods, the use of PGSE NMR is particularly advantageous in that, as a spectroscopic technique, it adds chemical selectivity to the study of physical dimensions. In this way, chemically different species contemporarily present in a sample may be individually studied. In addition, we demonstrate the use of PGSE NMR to probe the existence of equilibria between macroamphiphiles present in solution and those present in vesicles or on the surface of nanoparticles. This feature in particular opens exciting possibilities for the characterization of the phase behavior and of the surface adsorption phenomena of colloids.