Iron pentacarbonyl: are the axial or the equatorial iron-carbon bonds longer in the gaseous molecule?

The structure of iron pentacarbonyl, Fe(CO)(5), was reinvestigated by gas-phase electron diffraction using an experimental rotational constant available from the literature as a constraint on the structural parameters. The study utilized a B3LYP/6-311+G(d) ab initio quadratic force field, scaled to fit observed infrared wavenumbers, from which were calculated corrections for the effects of vibrational averaging on distances and certain other quantities useful for the structural analysis. The results confirm that the equatorial Fe-C bonds are longer than the axial ones, an important difference with the structure in the crystal where the equatorial Fe-C bonds are the shorter. Some distance (r(g)/A) and vibrational amplitude (l(alpha)/A) parameter values with estimated 2sigma uncertainties based on assumption of D(3h) symmetry are [r(Fe-C)] = 1.829(2), r(Fe-C)(eq) - r(Fe-C)(ax) = 0.032(20), [r(C=O)] = 1.146(2), r(C=O)(eq) - r(C=O)(ax) = 0.006(27), r(Fe-C)(ax) = 1.810(16), r(Fe-C)(eq) = 1.842(11), r(C=O)(ax) = 1.142(23), r(C=O)(eq) = 1.149(16), l(Fe-C)(ax) = l(Fe-C)(eq) = 0.047(5), and l(C=O)(ax) = l(C=O)(eq) = 0.036(3).     

Alignment locking to suspended Fabry-Perot cavity

In this paper we report on the alignment locking of an in vacuum 77 m long suspended mirror Fabry-Perot cavity. Lock was achieved by mode-matching a 500 mW Nd:YAG NPRO onto a pre-mode cleaner, the output of which was then mode-matched to the suspended cavity. The longitudinal locking was achieved by feeding back to the laser frequency actuator to follow the cavity resonance. Subsequent implementation of a hybrid auto-alignment system enhanced the stability of the circulating power inside the cavity. Preliminary results are presented.     

Laser frequency noise immunity in multiplexed displacement sensing

Digitally enhanced interferometry (DI) can be used to distinguish between interferometric signals and simultaneously monitor in-line object displacements with subnanometer sensitivity. In contrast to conventional interferometry-where these signals interfere with each other and degrade performance-we experimentally show that by using DI, each of these signals can be isolated and measured at the same time. We present what we believe to be the first demonstration of DI's signal multiplexing capabilities, showing simultaneous length sensing of three sections of an optical fiber. The cross talk between length measurements was less than 2.6×10(-3) with a displacement noise floor of 200 pm/√Hz, which corresponds to a strain sensitivity of less than 80 picostrain(p?) in each sensor. We also enhance our system's displacement sensitivity at low frequencies by combining information from multiple lengths to suppress errors due to laser frequency noise.     

Compulsive checking behavior of quinpirole-sensitized rats as an animal model of Obsessive-Compulsive Disorder(OCD): form and control

Background

A previous report showed that the open field behavior of rats sensitized to the dopamine agonist quinpirole satisfies 5 performance criteria for compulsive checking behavior. In an effort to extend the parallel between the drug-induced phenomenon and human obsessive-compulsive disorder (OCD), the present study investigated whether the checking behavior of quinpirole rats is subject to interruption, which is an attribute characteristic of OCD compulsions. For this purpose, the rat's home-cage was placed into the open field at the beginning or the middle of a 2-hr test.

Results

Introduction of the home-cage reduced checking behavior, as rats stayed inside the cage. After 40 min, checking resurfaced, as quinpirole rats exited the home-cage often. An unfamiliar cage had no such effects on quinpirole rats or saline controls.

Conclusions

Checking behavior induced by quinpirole is not irrepressible but can be suspended. Results strengthen the quinpirole preparation as an animal model of OCD compulsive checking.     

Diels-alder reactions with 2-(Arylsulfinyl)-1,4-benzoquinones: effect of aryl substitution on reactivity, chemoselectivity, and pi-facial diastereoselectivity

Diels-Alder reactions of (SS)-2-(2'-methoxynaphthylsulfinyl)-1, 4-benzoquinone (1b), 2-(p-methoxyphenylsulfinyl)-1,4-benzoquinone (1c), and 2-(p-nitrophenylsulfinyl)-1,4-benzoquinone (1d) with cyclopentadiene are reported. These cycloadditions allowed the highly chemo- and stereoselective formation of both diastereoisomeric endo-adducts resulting from reaction on the unsubstituted double bond C(5)-C(6) of quinones working under thermal and Eu(fod)(3)- or BF(3).OEt(2)-catalyzed conditions. The synthesis of endo-adduct [4aS,5S,8R,8aR,SS]-9d resulting from cycloaddition on the substituted C(2)-C(3) double bond was achieved in a chemo- and diastereoselective way from quinone 1d in the presence of ZnBr(2). The reactivity and selectivity of the process proved to be dependent on the electron density of the arylsulfinyl group.