Electronic spectroscopy and photoisomerization of trans-urocanic acid in a supersonic jet.

trans-Urocanic acid (trans-UA), a component of the epidermal layer of skin, exhibits wavelength-dependent photochemistry. The quantum efficiency of isomerization to cis-UA is greatest when the molecule is excited on the long wavelength tail of its absorption profile in solution (300-320 nm). However, exciting the molecule where it absorbs UV light most efficiently (260-285 nm) causes almost no isomerization. We have used fluorescence excitation and dispersed emission methods in a supersonic jet to investigate the electronic states involved in this complex and interesting photochemistry. Three distinct regions are present in the excitation spectrum. Region I, which is below the isomerization barrier, contains sharp, well-resolved peaks that upon excitation emit from the S(1) state of trans-UA. Region II exhibits peaks that increase in broadness and decrease in intensity with increasing excitation energy. Upon excitation these peaks produce dual emission from the S(1) states of both trans- and cis-UA. The trans to cis isomerization barrier is estimated to be 1400 cm(-1). Region III exhibits excitation to the S(2) electronic state and has a broad structure that spans 3000 cm(-1) and occurs 4000 cm(-1) above S(1). S(2) excitation results in essentially no trans to cis isomerization.

Educational benefits and cost savings from an interactive multimedia "best practice".

BACKGROUND: Developing and deploying "clinical practice guidelines" and "best practices" is a major strategic goal of our organization. We developed and evaluated a novel way of educating our colleagues on the office management of shoulder pain, using an interactive multimedia computer program to allow rapid access to user-selected audiovisual educational materials through a simple point and click interface. METHODS: Pre- and post-testing of 30 practicing primary care providers was conducted to assess ability to evaluate and manage patients who present with shoulder pain, and a post-use survey was administered to assess clinician acceptance and confidence, ability to use as a just-in-time tool, and changes in utilization of medical resources. RESULTS: Pre- and post-testing demonstrated that clinicians used this tool to improve their scores in a wide variety of clinical areas including history, physical examination, diagnosis, and management of conditions causing painful shoulder above their scores using textbooks and other traditional educational materials alone. The post-use survey showed outstanding acceptance by clinicians and their reported increased confidence as well as the potential for their increased abilities to translate into significant cost savings through more focused use of radiographic studies, orthopedic consultations, and physical therapy treatments. CONCLUSIONS: It was concluded that "The Multimedia Reference for Office Management of Shoulder Pain" is an effective and valuable learning resource for practicing clinicians, and demonstrates the potential to use an interactive multimedia tool to augment clinical skills and promote cost effective management of patients with this common clinical problem.

Computer-facilitated collaboration: experiences building SNOMED-RT.

Collaborative development involving both individuals and groups is often less efficient than independent development because of communication overhead and integration costs. Despite the decreased development efficiency, collaborations promise more general-purpose products because of the opportunity for integration, with negotiation and reconciliation of diverse perspectives. Collaborations are also perhaps less costly when considered in contexts where there is significant duplication of effort. Computer-facilitated collaboration can reduce the communication and integration burden such that the increased effort required to manage a successful collaboration focuses primarily on the development of shared conceptual model among the developers by requiring that the work product be independently reproducible. This reproducibility requirement incorporates formal quality assurance processes into the development process. In this paper, we describe our initial experiences developing SNOMED-RT using such a computer-facilitated collaborative process. We quantify the extra costs incurred to achieve consistency in our efforts and reproducibility of our results.

The Hubble Space Telescope (HST) observing campaign on comet Shoemaker-Levy 9.

The Hubble Space Telescope made systematic observations of the split comet P/Shoemaker-Levy 9 (SL9) (P designates a periodic comet) starting in July 1993 and continuing through mid-July 1994 when the fragments plunged into Jupiter's atmosphere. Deconvolutions of Wide Field Planetary Camera images indicate that the diameters of some fragments may have been as large as approximately 2 to 4 kilometers, assuming a geometric albedo of 4 percent, but significantly smaller values (that is, < 1 kilometer) cannot be ruled out. Most of the fragments (or nuclei) were embedded in circularly symmetric inner comae from July 1993 until late June 1994, implying that there was continuous, but weak, cometary activity. At least a few nuclei fragmented into separate, condensed objects well after the breakup of the SL9 parent body, which argues against the hypothesis that the SL9 fragments were swarms of debris with no dominant, central bodies. Spectroscopic observations taken on 14 July 1994 showed an outburst in magnesium ion emission that was followed closely by a threefold increase in continuum emission, which may have been caused by the electrostatic charging and subsequent explosion of dust as the comet passed from interplanetary space into the jovian magnetosphere. No OH emission was detected, but the derived upper limit on the H2O production rate of approximately 10(27) molecules per second does not necessarily imply that the object was water-poor.

Hubble space telescope observations of comet p/shoemaker-levy 9 (1993e).

The Hubble Space Telescope observed the fragmented comet P/Shoemaker-Levy 9 (1993e) (P indicates that it is a periodic comet) on 1 July 1993. Approximately 20 individual nuclei and their comae were observed in images taken with the Planetary Camera. After subtraction of the comae light, the 11 brightest nuclei have magnitudes between approximately 23.7 and 24.8. Assuming that the geometric albedo is 0.04, these magnitudes imply that the nuclear diameters are in the range approximately 2.5 to 4.3 kilometers. If the density of each nucleus is 1 gram per cubic centimeter, the total energy deposited by the impact of these 11 nuclei into Jupiter's atmosphere next July will be approximately 4 x 10(30) ergs ( approximately 10(8) megatons of TNT). This latter number should be regarded as an upper limit because the nuclear magnitudes probably contain a small residual coma contribution. The Faint Object Spectrograph was used to search for fluorescence from OH, which is usually an excellent indicator of cometary activity. No OH emission was detected, and this can be translated into an upper limit on the water production rate of approximately 2 x 10(27) molecules per second.

The spectroscopy of very cold gases.

The technique of supersonic free jet spectroscopy can be used to study the structure and dynamics of molecules which have been cooled to far below their boiling points but which remain in the gas phase. Cooling of the internal degress of freedom, the molecular rotations and vibrations, produces a highly resolved and greatly simplified molecular spectrum. The principles of the technique are discussed and its utility is demonstrated by two examples. the spectroscopy of porphyrins in the gas phase and the photochemistry of van der Waals molecules.