Determination of the refractive index and thickness of a hydroxide-catalysis bond between fused silica from reflectivity measurements.

Hydroxide-catalysis bonding is a high precision jointing technique producing strong, transparent and thin bonds, the use of which in the delicate fused silica mirror suspensions of aLIGO have been instrumental in the first detections of gravitational radiation. More sensitive future gravitational wave detectors will require more accurate (ideally in situ) measurements of properties such as bond thickness. Here a non-destructive technique is presented in which the thickness and refractive index of a bond are determined from measurements of optical reflectivity. The reflectivity of a bond made between two fused silica discs using sodium silicate solution is less than 1⋅10-3 after 3 months. The thickness decreases to a constant value of around 140 nm at its minimum and the refractive index increases from 1.36 to 1.45. This proves that as well as determination of bond thickness in situ this bonding technique is highly interesting for optical applications.

Spatiotemporal accuracy of real-time 3D echocardiography in the neonatal and pediatric setting--validation studies using small dynamic test objects.

UNLABELLED: The precision of real-time 3D-echocardiography (RT3DE) is not sufficiently validated for small, fast-moving structures such as the neonatal and pediatric heart. PURPOSE: To assess the spatiotemporal accuracy of RT3DE in small, moving test objects. MATERIALS AND METHODS: Small, calibrated test objects in the size of neonatal and pediatric heart chambers were made from polyurethane foam or metal wire mesh and moved in a water bath through a calibrated dynamic test system. Using matrix transducers (X7-2, ie33 and X4-1, Sonos 7500, Philips, Andover, USA), 2 D and live 3 D datasets under variation of the motion speed (0.033 - 0.133 m/s corresponding to 50 - 200 heart cycles/minute), the volume rate and transducer position were recorded and analyzed (QLab 7.0, Philips). RESULTS: 3 D datasets of the moving test objects showed relevant spatial distortion, which was obviously related to the sequential scanning technology of the matrix transducer. Different segments of a test object were not recorded simultaneously, but rather row-by-row, so that there was a time delay between the first and the last-recorded voxel of a single 3 D volume (mean±SD: 28.9 ±â€Š7.82 m/s or 80 ±â€Š7 % of the time duration of a 3 D volume). With increasing motion speed of the test object and reduced 3 D volume rate, the distortion artifacts increased significantly. CONCLUSION: 3 D acquisitions using matrix technology demonstrate relevant spatiotemporal inaccuracies. This may lead to misinterpretations during the evaluation of the synchronicity of valvular or ventricular motion and incorrect definition of volume estimations. In particular, at higher heart rates and higher rates of movement, these limitations have to be taken into account in clinical practice.

A decision tree to help determine the best timing and antiretroviral strategy in HIV-infected patients.

Optimal antiretroviral strategies for HIV-infected patients still need to be established. To this end a decision tree including different antiretroviral strategies that could be adopted for HIV-infected patients was built. A 10-year follow-up was simulated by using transitional probabilities estimated from a large cohort using a time-homogeneous Markov model. The desired outcome was for patients to maintain a CD4 cell count of >500 cells/mm3 without experiencing AIDS or death. For patients with a baseline HIV viral load ≥5 log10 copies/ml, boosted protease inhibitor-based immediate highly active antiretroviral therapy (HAART) allowed them to spend 12% more time with CD4 ≥500/mm3 than did delayed HAART (6·40 vs. 5·69 and 5·57 vs. 4·90 years for baseline CD4 ≥500 and 350-499/mm3, respectively). In patients with a baseline HIV viral load ≤3·5 log10 copies/ml, delayed HAART performed better than immediate HAART (6·43 vs. 6·26 and 5·95 vs. 5·18 for baseline CD4 ≥500 and 350-499/mm3, respectively). Immediate HAART is beneficial in patients with a baseline HIV viral load 5 log10 copies/ml, whereas deferred HAART appears to be the best option for patients with CD4 ≥350/mm3 and baseline HIV viral load <3·5 log10 copies/ml.

[Regional audit on fluoroquinolones usage in the hospital and the community: are these antibiotics over-used?]. / Audit régional de l'usage des fluoroquinolones à l'hôpital et en ville : y a-t-il une surconsommation de ces antibiotiques ?

AIM OF THE STUDY: The ecological impact of an over-use or a mis-use of fluoroquinolones (FQs) appears of great importance according to published data. With the objective to set up a regional antibiotic stewardship program, we conducted a regional audit on FQs usage. MATERIAL AND METHODS: [corrected] Ninety general practionners and 15 health care facilities participated to this prospective study. Overall, 511 prescriptions were evaluated (276 from hospital physicians and 235 [46%] from general practionners). The compliance of FQs prescription with national recommendations and with a regional referential was assessed. This regional referential was established in order to preserve FQs. RESULTS: Only 14,3% of the prescriptions complied with the regional referential, even if the choice of FQs were in accordance with national recommendations in 56,8% of the prescriptions. Urinary tract infections (mostly non-complicated) were the most common indication for FQs prescription. CONCLUSION: Analysis of FQs prescriptions shows that there is a significant potential for FQs preservation in Franche-Comté.

Laser beam directed at the lunar retro-reflector array: observations of the first returns.

On 1 August between 10:15 and 12:50 Universal Time, with the Lick Observatory 120-inch (304-cm) telescope and a laser operating at 6943 angstroms, return signals from an optical retro-reflector array placed on the moon by the Apollo 11 astronauts were successfully detected. After the return signal was first detected it continued to appear with the expected time delay for the remainder of the night. The observed range is in excellent agreement with the predicted ephemeris. Transmitting between 7 and 8 joules per pulse, we found that each return signal averaged more than one photoelectron. This is in good agreement with calculations of the expected signal strength.

Earth rotation measured by lunar laser ranging.

The estimated median accuracy of 194 single-day determinations of the earth's angular position in space is 0.7 millisecond (0.01 arc second). Comparison with classical astronomical results gives agreement to about the expected 2-millisecond uncertainty of the 5-day averages obtained by the Bureau International de l'Heure. Little evidence for very rapid variations in the earth's rotation is present in the data.

Lunar laser ranging: a continuing legacy of the apollo program.

On 21 July 1969, during the first manned lunar mission, Apollo 11, the first retroreflector array was placed on the moon, enabling highly accurate measurements of the Earthmoon separation by means of laser ranging. Lunar laser ranging (LLR) turns the Earthmoon system into a laboratory for a broad range of investigations, including astronomy, lunar science, gravitational physics, geodesy, and geodynamics. Contributions from LLR include the three-orders-of-magnitude improvement in accuracy in the lunar ephemeris, a several-orders-of-magnitude improvement in the measurement of the variations in the moon's rotation, and the verification of the principle of equivalence for massive bodies with unprecedented accuracy. Lunar laser ranging analysis has provided measurements of the Earth's precession, the moon's tidal acceleration, and lunar rotational dissipation. These scientific results, current technological developments, and prospects for the future are discussed here.

Laser ranging retro-reflector: continuing measurements and expected results.

After successful acquisition in August of reflected ruby laser pulses from the Apollo 11 laser ranging retro-reflector (LRRR) with the telescopes at the Lick and McDonald observatories, repeated measurements of the round-trip travel time of light have been made from the McDonald Observatory in September with an equivalent range precision of +/-2.5 meters. These acquisition period observations demonstrated the performance of the LRRR through lunar night and during sunlit conditions on the moon. Instrumentation activated at the McDonald Observatory in October has yielded a precision of +/-0.3 meter, and improvement to +/-0.15 meter is expected shortly. Continued monitoring of the changes in the earth-moon distance as measured by the round-trip travel time of light from suitably distributed earth stations is expected to contribute to our knowledge of the earth-moon system.

The Lunar Laser Ranging Experiment: Accurate ranges have given a large improvement in the lunar orbit and new selenophysical information.

The lunar ranging measurements now being made at the McDonald Observatory have an accuracy of 1 nsec in round-trip travel time. This corresponds to 15 cm in the one-way distance. The use of lasers with pulse-lengths of less than 1 nsec is expected to give an accuracy of 2 to 3 cm in the next few years. A new station is under construction in Hawaii, and additional stations in other countries are either in operation or under development. It is hoped that these stations will form the basis for a worldwide network to determine polar motion and earth rotation on a regular basis, and will assist in providing information about movement of the tectonic plates making up the earth's surface. Several mobile lunar ranging stations with telescopes having diameters of 1.0 m or less could, in the future, greatly extend the information obtainable about motions within and between the tectonic plates. The data obtained so far by the McDonald Observatory have been used to generate a new lunar ephemeris based on direct numerical integration of the equations of motion for the moon and planets. With this ephemeris, the range to the three Apollo retro-reflectors can be fit to an accuracy of 5 m by adjusting the differences in moments of inertia of the moon about its principal axes, the selenocentric coordinates of the reflectors, and the McDonald longitude. The accuracy of fitting the results is limited currently by errors of the order of an arc second in the angular orientation of the moon, as derived from the best available theory of how the moon rotates in response to the torques acting on it. Both a new calculation of the moon's orientation as a function of time based on direct numerical integration of the torque equations and a new analytic theory of the moon's orientation are expected to be available soon, and to improve considerably the accuracy of fitting the data. The accuracy already achieved routinely in lunar laser ranging represents a hundredfold improvement over any previously available knowledge of the distance to points on the lunar surface. Already, extremely complex structure has been observed in the lunar rotation and significant improvement has been achieved in our knowledge of lunar orbit. The selenocentric coordinates of the retroreflectors give improved reference points for use in lunar mapping, and new information on the lunar mass distribution has been obtained. Beyond the applications discussed in this article, however, the history of science shows many cases of previously unknown, phenomena discovered as a consequence of major improvements in the accuracy of measurements. It will be interesting to see whether this once again proves the case as we acquire an extended series of lunar distance observations with decimetric and then centimetric accuracy.

Manganese catalysts with molecular recognition functionality for selective alkene epoxidation.

Selective epoxidation of alkenes is possible with a new manganese porphyrin catalyst, C(PMR), that uses hydrogen bonding between the carboxylic acid on the substrate molecule and a Kemp's triacid unit. For two out of three olefin substrates employed, molecular recognition prevents the unselective oxidation of C-H bonds, and directs oxidation to the olefin moiety, giving only epoxide products. Weak diastereoselectivity is observed in the epoxide products, suggesting that molecular recognition affects the orientation of the catalyst-bound substrate. The previously reported manganese terpyridine complex C(TMR) is shown to be a superior epoxidation catalyst to the porphyrin catalyst C(PMR). Good conversion of 2-cyclopentene acetic acid (substrate S2) with C(PMR) is consistent with molecular modeling, which indicates a particularly good substrate/catalyst match. Evidence suggests that hydrogen bonding between the substrate and the catalyst is critical in this system.

Hyperuricemia in glycogen storage disease type I. Contributions by hypoglycemia and hyperglucagonemia to increased urate production.

Studies were performed to determine whether hypoglycemia or the glucagon response to hypoglycemia increases uric acid production in glycogen storage disease type I (glucose-6-phosphatase deficiency). Three adults with this disease had hyperuricemia (serum urate, 11.3-12.4 mg/dl) and reduced renal clearance of urate (renal urate clearance, 1.1-3.1 ml/min). These abnormalities were improved in one patient by intravenous glucose infusion for 1 mo, suggesting a role for hypoglycemia and its attendant effects on urate metabolism and excretion. A pharmacologic dose of glucagon caused a rise in serum urate from 11.4 to 13.0 mg/dl, a ninefold increase in urinary excretion of oxypurines, a 65% increase in urinary radioactivity derived from radioactively labeled adenine nucleotides, and a 90% increase in urinary uric acid excretion. These changes indicate that intravenous glucagon increases ATP breakdown to its degradation products and thereby stimulates uric acid production. To observe whether physiologic changes in serum glucagon modulate ATP degradation, uric acid production was compared during saline and somatostatin infusions. Serum urate, urinary oxypurine, radioactivity, and uric acid excretion increased during saline infusion as patients became hypoglycemic. Infusion of somatostatin suppressed these increases despite hypoglycemia and decreased the elevated plasma glucagon levels from a mean of 81.3 to 52.2 pg/ml. These data suggest that hypoglycemia can stimulate uric acid synthesis in glucose-6-phosphatase deficiency. Glucagon contributes to this response by activating ATP degradation to uric acid.

The chemical nature of osmium tetroxide fixation and staining of membranes by x-ray photoelectron spectroscopy.

X-ray photoelectron spectroscopy was used to determine the oxidation states of osmium compounds present in erythrocyte ghost preparations and related systems treated with osmium tetroxide. Osmium tetroxide and cholesterol, codeposited at -100 degrees C, began to react at -70 degrees C, and Os(VI) was formed. Similarly, Os(VI) was detected for the known cholesterol-osmate ester prepared and purified chemically. However, osmium tetroxide applied in phosphate buffer (pH 7.2) gave rise to large proportions of Os(IV) and Os(III) species in addition to Os(VI) compounds. Egg phosphatidylcholine likewise produced a mixture of Os(VI), Os(IV), and Os(III), but dipalmitoyl phosphatidylcholine failed to give significant amounts of osmium containing products under identical conditions. Glutaraldehyde gave a mixture of compounds with the same osmium oxidation states when allowed to react with aqueous osmium tetroxide. Unfixed and glutaraldehyde-fixed erythrocyte ghosts also produced mixtures of Ss(VI), Os(IV) and Os(III) under conditions identical to those of normal tissue processing. Additionally, the mixture of adducts initially formed by treatment with osmium tetroxide was further reduced by dehydration of the tissue with ethanol, rpesulting in a final mixture which was 50-60% Os(III). The results support a scheme for the reaction os osmium tetroxide with tissues in which the initial reaction site is the double bonds of unsaturated lipids to form Os(VI) derivatives. Subsequent hydrolysis and further reduction yield complexes of Os(IV) and Os(III). A mixture of these three states is present in membrane specimens during microscopic observation. Os(VI) and Os(IV) could be present as osmate esters and osmium dioxide, respectively; Os(III) could be present as an oxo- or amino complex(es). The photoelectron spectrum of intact erythrocyte ghosts can be synthesized from the spectra of phospholipid and cholesterol only, suggesting the predominance of the reaction with lipids in the fixation process.

Palladium/BINAP(S)-catalyzed asymmetric allylic amination.

The enantioselective allylic amination of acyclic allylic carbonates catalyzed by a palladium/(S)-BINAP(S) system was investigated. Amination of several substrates proceeded with high ee. Crotyl carbonates show an unusually high regioselectivity for the branched isomer. The use of (S)-TolBINAP(S) and (S)-3,5-xylyl-BINAP(S) as ligands was found to increase the enantioselectivity of the aminations. A P,S binding mode of the BINAP(S) ligand was found in an X-ray crystallographic study. [reaction: see text]

Respiratory changes in aortic blood velocity as an indicator of fluid responsiveness in ventilated patients with septic shock.

STUDY OBJECTIVE: To investigate whether the respiratory changes in peak velocity (Vpeak) of aortic blood flow could be related to the effects of volume expansion on cardiac index. DESIGN: Prospective clinical study. SETTING: Medical ICUs of a university hospital (20 beds) and of a nonuniversity hospital (15 beds). PATIENTS: Nineteen sedated septic shock patients who were receiving mechanical ventilation and who had preserved left ventricular (LV) systolic function. INTERVENTION: Volume expansion. MEASUREMENTS AND RESULTS: Analysis of aortic blood flow by transesophageal echocardiography allowed beat-to-beat measurement of Vpeak before and after volume expansion. Maximum values of Vpeak (Vpeakmax) and minimum values of Vpeak (Vpeakmin) were determined over one respiratory cycle. The respiratory changes in Vpeak (Delta Vpeak) were calculated as the difference between Vpeakmax and Vpeakmin divided by the mean of the two values and were expressed as a percentage. The indexed LV end-diastolic area (EDAI) and cardiac index were obtained at the end of the expiratory period. The volume expansion-induced increase in cardiac index was > or = 15% in 10 patients (responders) and < 15% in 9 patients (nonresponders). Before volume expansion, Delta Vpeak was higher in responders than in nonresponders (20 +/- 6% vs 10 +/- 3%; p < 0.01), while EDAI was not significantly different between the two groups (9.7 +/- 3.7 vs 9.7 +/- 2.4 cm(2)/m(2)). Before volume expansion, a Delta Vpeak threshold value of 12% allowed discrimination between responders and nonresponders with a sensitivity of 100% and a specificity of 89%. Volume expansion-induced changes in cardiac index closely correlated with the Delta Vpeak before volume expansion (r(2) = 0.83; p < 0.001). CONCLUSION: Analysis of respiratory changes in aortic blood velocity is an accurate method for predicting the hemodynamic effects of volume expansion in septic shock patients receiving mechanical ventilation who have preserved LV systolic function.

Enantioselective routes to both enantiomers of aryl alcohols with a single catalyst antipode: Ru and Os transfer hydrogenation catalysts.

[reaction--see text] The kinetic resolution of secondary aryl alcohols has been investigated. When (CyRuCl(2))(2), (1R,2S)-(+)-cis-1-amino-2-indanol, and KOH or (t)BuOK (catalyst 1) were combined in the presence of (+/-)-alcohols, ee's > 90% were generally observed. When applied to the kinetic resolution of (+/-)-indanol and (+/-)-tetralol, ee's = 99% (R) were observed. In addition, the asymmetric transfer hydrogenation of ketones was investigated with a catalyst, 2, generated in situ from (CyOsCl(2))(2), (1R,2S)-(+)-cis-1-amino-2-indanol, and (t)BuOK, yielding ee's of up to 98% (S).

Kinetic resolution and unusual regioselectivity in palladium-catalyzed allylic alkylations with a chiral P,S ligand.

Effective kinetic resolutions of acyclic allylic acetates and benzoates have been obtained using a palladium/(S)-BINAP(S) catalyst system. Unusually large preferences for the formation of branched alkylation products from 3-but-2-enyl and crotyl substrates have been observed. [reaction: see text]

Altered cell cycle distributions of cultured human lymphoblasts during cytotoxicity related to adenosine deaminase inhibition.

Serial-flow cytometric analysis of DNA content of T lymphoblasts (MOLT-4) and B lymphoblasts (MGL-8) was performed to correlate the cytotoxic properties of adenosine deaminase inhibition with alterations of DNA synthesis and disruptions of the cell cycle. The addition of deoxyadenosine up to 50 mumol/L potently decreased the growth of T lymphoblasts, and these changes were enhanced with the addition of 100 mumol/L homocysteine thiolactone. These conditions caused a virtual absence of cells from S and G2M phases after 24 hours. The DNA distribution was similar in cells cultured for 24 hours in 50 mumol/L deoxyguanosine or 2.5 mumol/L hydroxyurea. These observations suggested accumulation of cells in the G1 phase. T lymphoblasts cultured with up to 50 mumol/L adenosine had a substantial decrease in growth, which was not modified by the addition of homocysteine thiolactone. Cell cycle distributions of T lymphoblasts cultured for 24 to 48 hours under these conditions showed mild decreases in the G2M population. The addition of adenosine up to 50 mumol/L decreased the growth of B lymphoblasts, and these changes were enhanced by the addition of 100 mumol/L homocysteine thiolactone. These conditions induced mild decreases in the S-phase population in B lymphoblasts. The addition of deoxyadenosine, even with homocysteine thiolactone, did not modify growth in B lymphoblasts and the cell-cycle distributions were indistinguishable from distributions of control populations after 24 and 48 hours. The observations provide independent support for a reduction of DNA synthesis associated with cytotoxicity during adenosine-deaminase inhibition.(ABSTRACT TRUNCATED AT 250 WORDS)

Abnormal binding in a carbene complex formed from an imidazolium salt and a metal hydride complex.

2-Pyridylmethylimidazolium salts and IrH5(PPh3)2 give an [(N-C)IrH2(PPh3)2]+ species with the imidazole ring bound in the 'wrong way': at C-5, not at the expected C-2.

Effect of extrusion on isoflavone content and antiproliferative bioactivity of soy/corn mixtures.

The present studies were conducted to determine changes in the quantities of select isoflavones and in the bioactivity (ability to inhibit proliferation of human breast cancer cell lines) of extracts from blends of soy protein and cornmeal during extrusion processing. The extrusion of samples resulted in an average 24% decrease in the concentration of total isoflavones for all samples. Although the amounts of specific genistein-derived and daidzein-derived forms changed following extrusion, the content of the aglycones genistein and daidzein per g sample generally did not change. The extrusion of samples generally resulted in decreased antiproliferative action toward breast cancer cells, although antiproliferative activity was not eliminated. Therefore, extrusion of soy protein/cornmeal-containing foods are likely to retain a considerable portion of their isoflavone content and some of the health benefits associated with soy.