SUPERCRITICAL AND SUB-CRITICAL FLUID SOLVENT EFFECTS ON A DIELS-ALDER REACTION

The effect of pressure on the measured bimolecular rate constant of the Diels-Alder reaction between maleic anhydride and isoprene was investigated in supercritical CO₂ and sub-critical propane. The reaction was carried out at 35°C in CO₂ and 80°C in propane. Measured bimolecular rate constants are also compared to predictions from the thermodynamic pressure effect using transilion state theory and the Peng-Robinson equation of state. The rate constants in supercritical C0₂ agreed closely with the thermodynamic pressure effect predictions over the entire pressure range. Furthermore, the mole fraction based rate constants were found to vary linearly with the density of the solution. The rate constants in the sub-critical propane solvent significantly diverged from the thermodynamic pressure effect predictions and were found to deviate from this linear density dependence at the lower pressures studied. The results are interpreted in the context of local reactant concentrations about the reacting maleic anhydride and solvent-solute and cosolvent-solute interactions.     

Low temperature swelling and densification properties of LWR fuels

Analysis of recent data reported in the literature on low temperature swelling and densification behavior of light water reactor (LWR) fuel suggests that, at low irradiation temperatures, the extent of irradiation induced densification shows a simple exponential dependence on burnup with a rate constant that is insensitive to temperature and flux level. These data are also consistent with the view that the total porosity controls the kinetics of irradiation-induced densification process. In the same temperature range the rate of swelling was found to be constant to a burnup near 50 GWD/MTU, with a value of approximately 1% per 10 GWD/MTU. The significance of these results is discussed in terms of current theories.     

Correlation of functional magnetic source imaging with intraoperative cortical stimulation in neurosurgical patients

This study compared noninvasive preoperative functional imaging by using magnetoencephalography (MEG) with intraoperative direct cortical stimulation in ten patients undergoing neurosurgery. The goal was to assess the accuracy and reliability of MEG-based functional imaging in these patients as a possible replacement or adjunct for direct cortical stimulation with electrocorticography. Objective comparison of intraoperative mapping with preoperative MEG procedures was achieved by intraoperative recording of mapped cortical locations for motor responses using an interactive image-guided surgical device, the ISG viewing wand, with which mapping points could be marked on a previously acquired (MRI) set. In all ten patients, at least one stimulation site elicited a response during both MEG and intraoperative mapping. The central sulcus ipsilateral to the lesion was only directly visible on high-resolution MRIs in 3/10 cases and equivocally in 2/10. Coregistered with MRI to form magnetic source images (MSIs), MEG predictions of the postcentral gyrus were possible in all 10 cases. In all 10 cases, these were in agreement with intraoperative estimation of the precentral gyrus. Functional mapping of somatosensory cortex was achieved noninvasively in surgical patients by using MSI. The accuracy, compared with cortical stimulation, was always sufficient to define motor and somatosensory strips.     

Distribution of abnormal karyotypes among malformed fetuses detected by ultrasound throughout gestation

The participation of sarcoplasmic reticulum Ca2+ release channels in the activation of Ca(2+)-sensitive K+ currents (IK(Ca)) by cyclic dibutyryl GMP was investigated in smooth muscle cells from the circular layer of guinea-pig gastric fundus. All experiments were performed in the presence of 3 microM nicardipine into the bath and low Ca2+ buffering capacity of the pipette-filling solution (pCa 7.4). Ruthenium red (10 microM) as well as its combination with 10 microM heparin abolished the cyclic GMP-induced activation of IK(Ca), while 10 microM heparin remained ineffective. Ryanodine (10 microM) and the subsequently added 1 microM thapsigargin induced a relatively small increase in IK(Ca) amplitudes. The addition of 10 microM ryanodine to 1 microM thapsigargin-containing bath solution caused a vast increase in IK(Ca). It is hypothesyzed that protein kinase G-induced vectorial Ca2+ flux from the cell bulk and sarcoplasmic reticulum Ca2+ stores toward the plasma membrane is realized by a spontaneous Ca(2+)-induced Ca2+ release from a superficially situated Ca2+ store.     

Comparison of factor VIII-related antigen and erythrocyte sedimentation rate in outpatient management of vasculitis

Electroimmunodiffusion (Laurell rocket) determinations of factor VIII-related antigen in plasma were ordered to determine the cost/benefit ratio for factor VIII-related antigen as a putative test for endothelial damage in suspected vasculitis. Twenty-seven consecutive patients referred for vasculitis or suspected vasculitis were identified and followed up for an average of 9.1 +/- months (range: one to thirty-three months) in a prospective, unblinded study performed in a clinic, associated with a 1054-bed inner-city university hospital. There was no difference in Westergren erythrocyte sedimentation rate (WESR) in patients with final diagnosis of systemic vasculitis (SV) (38 +/- 12 mm/hour) compared to those without vasculitis (NV) (27 +/- 7) as the final diagnosis. The mean plasma concentration of factor VIII-related antigen was significantly elevated in SV (344 +/- 100%) when compared with NV (147 +/- 39%) (P < 0.016). The factor VIII-related antigen test in this study was 2.56 times more likely (crude odds ratio) than the WESR to contribute to a change in diagnosis or therapy (P = 0.016). Positive and negative predictive values (PPV and NPV) for factor VIII-related antigen (abnormal at greater than 220% of the normal value) were both 70%. PPV and NPV for WESR were 56% and 86%, respectively. The factor VIII-related test was less cost-effective than the WESR in the follow-up period unless it was important to define complete remission or differentiate vasculitis flare from infection. The authors conclude that factor VIII-related antigen is a useful test in the initial diagnosis of vasculitis.     

Mechanism of Rab geranylgeranylation: formation of the catalytic ternary complex

Rab proteins are geranylgeranylated on one or two C-terminal cysteines by Rab geranylgeranyl transferase (RabGGTase). The reaction is dependent on a Rab-binding protein, termed Rab escort protein (REP). Here, we studied the role of REP in the geranylgeranylation reaction. We first characterized the interaction between REP and ungeranylgeranylated Rab using analytical ultracentrifugation and a fluorescence-based assay. We measured an equilibrium dissociation constant of 0.2 microM for the formation of a 1:1 REP-Rab complex and showed that this interaction relies mostly on ionic bonds and does not involve the two C-terminal cysteine residues. Second, we show that REP is required for recognition of Rab by RabGGTase and therefore that the REP-Rab complex is the true substrate for RabGGTase. Third, we show that free REP inhibits the geranylgeranylation reaction, suggesting that the complex is recognized by RabGGTase primarily via a REP-binding site. Our data suggest a model whereby REP behaves kinetically as an essential activator of the reaction.     

Prognostic value of S-phase fraction in lymph-node-negative breast cancer by image and flow cytometric analysis

A two-year multicentre prospective study was performed from 1992 to 1995 in order to evaluate the real value of various kinds of coral blocks as bone substitute in maxillofacial surgery. This study was supported by the French National Agency for Research Valorization (GBM/TEP procedure). Ten Maxillofacial Surgery Units were included. During this time, 28 coral blocks (23 patients) of two different shapes were used as malar implants for correction of congenital or acquired zygomatic hypoplasia. The mean follow-up was 1.8 year (min: 1.5; max: 2). The tolerance was perfect for 89% of cases. The radiologic opacity never decreased more than 30% and the volume augmentation was always stable at the end of the follow-up period. Three implants were removed because of septic complications. Rigid fixation between the implant and the zygomatic bone appears to be the most important factor of success. On the other hand, the surgical approach (endo- or exo-buccal) does not seem to influence the success rate. The aesthetic improvement was always evaluated as satisfactory and stable by the patients and the surgeons. The authors discuss the real value of the various kinds of biomaterials and especially coral, comparing their personal data with those of the literature. Coral blocks clearly constitute a safe and reliable bone substitute, but further investigations are required to determine its long-term behavior.