Imaging Molecular Motion: Femtosecond X-Ray Scattering of an Electrocyclic Chemical Reaction.

Structural rearrangements within single molecules occur on ultrafast time scales. Many aspects of molecular dynamics, such as the energy flow through excited states, have been studied using spectroscopic techniques, yet the goal to watch molecules evolve their geometrical structure in real time remains challenging. By mapping nuclear motions using femtosecond x-ray pulses, we have created real-space representations of the evolving dynamics during a well-known chemical reaction and show a series of time-sorted structural snapshots produced by ultrafast time-resolved hard x-ray scattering. A computational analysis optimally matches the series of scattering patterns produced by the x rays to a multitude of potential reaction paths. In so doing, we have made a critical step toward the goal of viewing chemical reactions on femtosecond time scales, opening a new direction in studies of ultrafast chemical reactions in the gas phase.

The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction.

The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subångström length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.

Detecting unsuspected thyroid dysfunction by the free thyroxine index.

The free thyroxine index (FTI) was used in 2,704 adults to detect unsuspected thyroid dysfunction. Among 2,581 adults found to be clinically euthyroid without thyroid medication, 2,571 had a truly normal FTI (121 to 360) and ten had a falsely abnormal FTI (seven less than 121, three greater than 360). Among 25 subjects with newly diagnosed thyroid dysfunction, there were eight hyperthyroid (prevalence, 0.31%) and 14 hypothyroid (prevalence, 0.50%) subjects. The sensitivity of the FTI was 1.0, and the specificity was 0.996. The predictive value of an abnormal FTI with a prevalence of 0.81% was 67%. The cost to find a new case averaged $127. The annual incidence of symptomatic hyperthyroidism was 0.05%; of hypothyroidism, about 0.08%. We conclude that the FTI is cost-effective for case finding in thyroid dysfunction.

Radioimmunoassay for herpes simplex virus.

Radioimmunoassay has been used for time in the detection of the Australia Antigen. In this experiment, radioimmunoassay with Iodine-125 (125I) permitted rapid detection of the presence of herpes simplex virus, type I, in vitro. This is a convenient technique for the detection of virus, which now requires laborious methods involving observation for the cytopathic effect of virus upon cultured cells.

A new 80-lens oscilloscope camera for routine dynamic organ scintigraphy.

A simple, reliable, and cost-effective 80-lens photographic camera records dynamically from the oscilloscope of a scintillation camera without degradation of spatial resolution or data loss. Most physiologic events can be recorded completely and without interruption on a single 9 X 12-cm negative film as 40 sequential time-frames, using one of six available exposures per frame. In addition, 40 simultaneous sequential time-frames of four times the chosen duration may bracket a transient event with increased data density. The 80-lens camera has been used routinely for perfusion scintigraphy of brain, heart, liver, kidneys,and lungs with excellent results.

Effect of pulse shape on the efficiency of multiphoton processes: implications for biological microscopy.

The effects of spectral shape on two photon fluorescence excitation are investigated experimentally using an acousto-optic pulse shaper to modify femtosecond pulses from a Ti:sapphire laser. By using different spectral window shapes, we find that the measured two photon efficiency can vary by a factor of 2 for differently shaped spectra with the same full width at half maximum. We find that these effects are described well by a simple model assuming transform-limited pulses. The fact that even small changes in the spectral wings can significantly affect the efficiency of nonlinear processes has implications for biological multiphoton imaging, where it may be desirable to minimize sample exposure to radiation and maximize fluorescence or harmonic efficiency. © 1999 Society of Photo-Optical Instrumentation Engineers.

Diagnosis of acute cholecystitis using hepatobiliary scan with technetium-99m PIPIDA.

Sixty patients were evaluated for acute abdominal pain using technetium-99m PIPIDA hepatobiliary imaging. The sensitivity of the test was 90.6 percent in all patients and the accuracy was 93.3 percent. In the evaluation of acutely ill patients with right upper quadrant pain, fever, nausea and vomiting, hepatobiliary imaging with PIPIDA is the preferred test for diagnosing acute cholecystitis. If the test is positive, disease of the gallbladder and probably acute cholecystitis are present. Early operation can proceed if desirable. If the test is negative and the bilirubin level is less than 5.0 mg/dl, acute cholecystitis is not present. In such cases conservative treatment is appropriate, and follow-up tests should be performed to evaluate the possibility of chronic cholecystitis. When the bilirubin level exceeds 5.0 mg/dl, the test is often indeterminate.

Confinement of lactating sows in crates for 4 days after farrowing reduces piglet mortality.

To reduce mortality among suckling piglets, lactating sows are traditionally housed in farrowing crates. Alternatively, lactating sows can be housed in farrowing pens where the sow is loose to ensure more behavioural freedom and consequently a better welfare for the sow, although under commercial conditions, farrowing pens have been associated with increased piglet mortality. Most suckling piglets that die do so within the first week of life, so potentially lactating sows do not have to be restrained during the entire lactation period. Therefore, the aim of the current study was to investigate whether confinement of the sow for a limited number of days after farrowing would affect piglet mortality. A total of 210 sows (Danish Landrace × Danish Yorkshire) were farrowed in specially designed swing-aside combination farrowing pens measuring 2.6 m × 1.8 m (combi-pen), where the sows could be kept loose or in a crate. The sows were either: (a) loose during the entire experimental period, (b) crated from days 0 to 4 postpartum, (c) crated from days 0 to 7 postpartum or (d) crated from introduction to the farrowing pen to day 7 postpartum. The sows and their subsequent litters were studied from introduction to the combi-pen ∼1 week before expected farrowing and until 10 days postpartum. Confinement period of the sow failed to affect the number of stillborn piglets; however, sows that were crated after farrowing had fewer live-born mortality deaths (P < 0.001) compared with the sows that were loose during the experimental period. The increased piglet mortality among the loose sows was because of higher mortality in the first 4 days after farrowing. In conclusion, the current study demonstrated that crating the sow for 4 days postpartum was sufficient to reduce piglet mortality.