Anion sensing 'venus flytrap' hosts: a modular approach

A series of podands based on three hydrogen bonding 'arms' have been prepared and their affinities for simple inorganic anions measured.     

Large amplitude vibration in polyatomic molecules. I. A polar representation of orthogonal relative coordinates

A general expression for the rovib kinetic energy operator in a system of orthogonal internal coordinates is derived for arbitrary amplitudes of motion. Plots of the molecular potential in such coordinates serve to determine coordinate subsets in which the potential approaches separability. A revision of previous theory for the three-body problem is presented. A rovib hamiltonian for non-branched four-atom molecules (such as C₂H₂) is derived. Certain features of application to polyatomic (five-atom) molecules are considered.     

Evaluation of methods for determining the refraction correction for light-scattering photometers

Recent literature reports from three laboratories have treated the refraction correction for the Sofica and a noncommercial light scattering photometer. Our re-evaluation of the data contained in these reports, as well as our experiments, indicate that the usually cited n² refraction correction has not been unquestionably established for these instruments. In some cases, imprecise experimental techniques have been used to support this particular form of the correction. In addition, we find the optical system of the Sofica instrument results in the detector seeing vertically past the horizontal edge of the illuminated volume in violation of a basic assumption in the deduction of the n² correction. Our experiments, as well as our interpretation of recent literature data, support an exponent of less than 2.0 for the Sofica apparatus, which is consistent with an instrument whose detector views outside the illuminated volume. However, the experimental methods available to evaluate the exponent lack the desired precision.     

A comparison of T2*-weighted magnitude and phase imaging for measuring the arterial input function in the rat aorta following intravenous injection of gadolinium contrast agent

The arterial input function (AIF) is important for quantitative MR imaging perfusion experiments employing Gd contrast agents. This study compared the accuracy of T(2)*-weighted magnitude and phase imaging for noninvasive measurement of the AIF in the rat aorta. Twenty-eight in vivo experiments were performed involving simultaneous arterial blood sampling and MR imaging following Gd injection. In vitro experiments were also performed to confirm the in vivo results. At 1.89 T and TE=3 ms, the relationship between changes in 1/T(2)* in blood (estimated from MR signal magnitude) and Gd concentration ([Gd]) was measured to be approximately 19 s(-1) mM(-1), while that between phase and [Gd] was approximately 0.19 rad mM(-1). Both of these values are consistent with previously published results. The in vivo phase data had approximately half as much scatter with respect to [Gd] than the in vivo magnitude data (r(2)=.34 vs. r(2)=.17, respectively). This is likely due to the fact that the estimated change in 1/T(2)* is more sensitive than the phase to a variety of factors such as partial volume effects and T(1) weighting. Therefore, this study indicates that phase imaging may be a preferred method for measuring the AIF in the rat aorta compared to T(2)*-weighted magnitude imaging.     

An artificial siderophore for the detection of iron(III)

An artificial siderophore in the form of a squaraine dye (1) has been synthesized. The bidentate ligand chelates to Fe(III) between the deprotonated hydroxyl group on the ortho position of the ring adjacent to the carbonyl group of the cyclobutadiene ring. The optical response is due to a subtle geometry change of 1 on chelation to Fe(III). This artificial siderophore forms a 2 ratio 1 ligand ratio metal complex, as indicated by a sigmoidal isotherm (K(a)= 10(7) M(-1)). The optical response on the addition of Fe(III) is observed at low concentrations in comparison to other metal salts. The X-ray crystal structure and calculated structures of dye (1) are also included, and will be discussed.     

Radiation-driven hydrodynamics of high- hohlraums on the national ignition facility

The first hohlraum experiments on the National Ignition Facility (NIF) using the initial four laser beams tested radiation temperature limits imposed by plasma filling. For a variety of hohlraum sizes and pulse lengths, the measured x-ray flux shows signatures of filling that coincide with hard x-ray emission from plasma streaming out of the hohlraum. These observations agree with hydrodynamic simulations and with an analytical model that includes hydrodynamic and coronal radiative losses. The modeling predicts radiation temperature limits with full NIF (1.8 MJ), greater, and of longer duration than required for ignition hohlraums.     

Wavepacket propagation using time-sliced semiclassical initial value methods

A new semiclassical initial value representation (SC-IVR) propagator and a SC-IVR propagator originally introduced by Kay [J. Chem. Phys. 100, 4432 (1994)], are investigated for use in the split-operator method for solving the time-dependent Schrodinger equation. It is shown that the SC-IVR propagators can be derived from a procedure involving modified Filinov filtering of the Van Vleck expression for the semiclassical propagator. The two SC-IVR propagators have been selected for investigation because they avoid the need to perform a coherent state basis set expansion that is necessary in other time-slicing propagation schemes. An efficient scheme for solving the propagators is introduced and can be considered to be a semiclassical form of the effective propagators of Makri [Chem. Phys. Lett. 159, 489 (1989)]. Results from applications to a one-dimensional, two-dimensional, and three-dimensional Hamiltonian for a double-well potential are presented.