The iron-carbonyl geometries in carboxymyoglobin (MbCO) and carboxyhemoglobin (HbCO) in ambient temperature solution have been investigated using picosecond time-resolved infrared spectroscopy. Polarized infrared and visible beams were used to monitor the change in infrared absorbance of the bound CO stretch bands on photodissociation of the ligand. The ratio of the change in absorbance for perpendicular and parallel relative polarizations of the photolysis and infrared probe beams is directly related to the angle between the ligand bond axis and the normal to the heme plane. Ratios, and hence the angles, have been obtained for the configurations giving rise to the principal CO We have recently suggested a new method of determining IR spectra with ps time resolution (2). In this measurement the sample is first pumped by a ps pulse of visible or UV light and the IR spectrum of the sample consisting of both photoproducts and unphotolyzed material can be recorded at variable ps delay times. The experiment can be done with polarized IR and visible beams, so that the magnitude and decay of the orientational correlation function for photoproducts and unphotolyzed material can be evaluated. For heme proteins-where the overall molecular rotation is slow-the magnitude of the polarization anisotropy is directly related to the angle between the transition dipoles for the IR and visible absorptions. In this paper we present results from a significantly improved version of the original experimental design, applied to the photodissociation of carboxymyoglobin (MbCO) and carboxyhemoglobin (HbCO). The measurements are used to define the heme-CO geometry for these heme proteins in solution. The preliminary results (2) for MbCO involved an uncertainty in the polarization anisotropy of >50%. In this study the error is reduced to -10% and allows a sharp definition of the ligand geometry of this heme protein in solution.
MATERIALS AND METHODSSpectroscopic Method. The transient IR spectra were recorded using the same principles as previously described (2 The polarization experiment was carried out as follows. The upconversion signal intensity was measured both with the photolyzing beam blocked and with the photolyzing beam incident on the sample. The A/2 plate in the photolyzing beam was then rotated such that the polarization of that beam was rotated by 900, and the signal measurements were repeated.In this way, the change in IR absorbance could be measured for both parallel and perpendicular IR/photolysis laser polarizations. Measurements were taken using a time delay of 40 ps between the pump and probe lasers. A correction factor of ==5% was required to compensate for the difference in reflectance for the two polarizations of the dichroic beam Abbreviations: MbCO, carboxymyoglobin; HbCO, carboxyhemoglobin.
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During the Hubble Space Telescope (HST) second servicing mission (SM2), degradation of unsupported Teflon ® FEP (fluorinated ethylene propylene), used as the outer layer of the multilayer insulation (MLI) blankets, was evident as large cracks on the telescope light shield. A sample of the degraded outer layer was retrieved during the mission and returned to Earth for ground testing and evaluation. The results of the Teflon ® FEP sample evaluation and additional testing of pristine Teflon ® FEP led the investigative team to theorize that the HST damage was caused by thermal cycling with deep-layer damage from electron and proton radiation which allowed the propagation of cracks along stress concentrations, and that the damage increased with the combined total dose of electrons, protons, ultraviolet and x-ray radiation along with thermal cycling. This paper discusses the testing and evaluation of the retrieved Teflon ® FEP.
and final report, she: 'sets out recommendations that taken together, will help to reform the child protection system from being over bureaucratised and concerned with compliance to one that keeps a focus on children, checking whether they are being effectively helped, and adapting when problems are identified.' This article, which is a selective review of the final report, firstly cites the principles of an effective child protection system and then the principles to guide 'risk-sensible' decision-making as put forward in the report. It concludes with the 15 major recommendations of the Munro report and makes some comment and comparisons with recent Australian state-and territory-based reviews of child protection services. ■
This note is about the attempt by the Australian State and Territory child care and protection systems to do without residential programmes. It traces the process of moving to this position and the historical and policy imperatives that supported this service direction. It also outlines the consequences of the absence of 24 hours‐a‐day 7‐days‐a‐week residential education or treatment programmes for difficult and disturbed young people. It is both a cautionary and corrective note designed to underline the need for some specialised and highly selective residential programmes as part of any mature child care and protection system. This is something that Australia forgot.
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