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.

Prototype of an auto-calibrating, context-aware, hybrid brain-computer interface.

We present the prototype of a context-aware framework that allows users to control smart home devices and to access internet services via a Hybrid BCI system of an auto-calibrating sensorimotor rhythm (SMR) based BCI and another assistive device (Integra Mouse mouth joystick). While there is extensive literature that describes the merit of Hybrid BCIs, auto-calibrating and co-adaptive ERD BCI training paradigms, specialized BCI user interfaces, context-awareness and smart home control, there is up to now, no system that includes all these concepts in one integrated easy-to-use framework that can truly benefit individuals with severe functional disabilities by increasing independence and social inclusion. Here we integrate all these technologies in a prototype framework that does not require expert knowledge or excess time for calibration. In a first pilot-study, 3 healthy volunteers successfully operated the system using input signals from an ERD BCI and an Integra Mouse and reached average positive predictive values (PPV) of 72 and 98% respectively. Based on what we learned here we are planning to improve the system for a test with a larger number of healthy volunteers so we can soon bring the system to benefit individuals with severe functional disability.

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.

[Spontaneous hepatic rupture during an uncomplicated twin pregnancy]. / Rupture hépatique spontanée au cours d'une grossesse gémellaire non compliquée.

Liver subcapsular haematoma and its consequence, spontaneous hepatic rupture, are very rare complications of pregnancy. They are mainly associated with pre-eclampsia. The diagnosis is difficult and the maternal and fetal mortality rates are high. We report the case of a spontaneous hepatic rupture on a normal liver during an uncomplicated twin pregnancy with a favorable outcome for both the mother and the newborns.

[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.

[Impact of regional guidelines on the management of urinary tract infections with antibiotics]. / Impact d'un guide régional pour la prise en charge des infections urinaires sur les pratiques d'antibiothérapies.

AIM AND METHOD: We assessed the impact of a committed guideline at the end of the first quarter 2008 on the management of urinary tract infection (UTI) with antibiotic prescription (fluoroquinolone, fosfomycin, and nitrofurantoin), by analysing reimbursement data for ambulatory care provided by the regional health insurance agency. RESULTS: During the survey, we observed a 13.2% decrease of norfloxacin prescriptions between the first quarter 2008 and the first quarter 2009. The (fosfomycin+nitrofurantoin)/norfloxacin ratio increased between the third quarter 2007 and the first quarter 2009 from 0.55 to 0.72 and from 0.82 to 1.13 for general practitioners and hospital physicians respectively. The global number of patients treated with these antibiotics remained stable during the period. The number of fluoroquinolone prescription was stable between the first quarter 2008 and the first quarter 2009 with 28,427 DDD and 28,363 DDD, respectively; while the number of single dose rise in the same time from 151 DDD to 427.5 DDD, respectively. DISCUSSION: The three messages which seem to be essential for an optimal use of fluoroquinolones in UTIs are: no treatment for bacterial colonisation (asymptomatic bacteriuria) except for specific cases, no indication for fluoroquinolones in non-complicated acute cystitis and for elderly women, UTI is complicated only if it occurs in women with co-morbidities regardless of age. CONCLUSION: Our indicators suggest that our guideline had an impact on the prescription of fluoroquinolones for uncomplicated acute cystitis.

Markov modelling of HIV infection evolution in the HAART era.

The aim was to investigate the impact of the main prognostic factors on HIV evolution. A multi-state Markov model was applied in a cohort of 2126 patients to estimate impact of these factors on patients' clinical and immunological evolutions. Clinical progression and immunological deterioration shared most of their prognostic factors: male gender, intravenous drug use, weight loss, low haemoglobin level (<110 g/l), CD8 cell count (<500/mm(3)) and HIV viral load (>5 log(10) copies/ml). Highly active retroviral therapy reduced the risks of clinical progression and immune deterioration whatever patients' CD4 cell count. Risk reductions were 41-60% for protease inhibitor-based and 27-68% for non-nucleoside reverse transcriptase inhibitor-based regimens. Three-year transition probabilities showed that only patients with a CD4 cell count >or=350 CD4/mm(3) could in most cases maintain their immunity. This model provides 'real life' transition probabilities from one immunological stage to another, allowing decision analyses that could help determine the beneficial therapeutic strategies for HIV-infected patients.

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.

New linear high-valent tetranuclear manganese-oxo cluster relevant to the oxygen-evolving complex of photosystem II with oxo, hydroxo, and aqua coordinated to a single Mn(IV).

An unprecedented atom connectivity, MnIV(mu-O)MnIV(mu-O)2MnIV(mu-O)MnIV, is found in the complex [MnIV4O4(EtO-terpy)4(OH)2(OH2)2](ClO4)(6).8H2O (EtO-terpy=4'-ethoxyl-2,2':6',2' '-terpyridine), which has been characterized by X-ray crystallography, X-ray powder diffraction, EPR spectroscopy, and magnetic studies. This complex is the first example of a compound where a MnIV ion is coordinated by all three types of water-derived ligands: oxo, hydroxo, and aqua. Bond distances and angles for this complex are consistent with a MnIV4 oxidation state assignment. The di-mu-oxo- and mono-mu-oxo-bridged Mn-Mn distances are 2.80 and 3.51 A, respectively. The variable-temperature magnetic susceptibility data for this complex, in the range of 10-300 K, are consistent with an S=0 ground state and were fit using the spin Hamiltonian HHDvV=-J1S2S1-J2S1S1A-J1S1AS2A (S1=S1A=S2=S2A=3/2) with J1=-432 cm-1 and J2=-164 cm-1 (where J1 and J2 are exchange constants through the mono-mu-oxo and the di-mu-oxo bridges, respectively). The first excited spin state of this tetramer is a spin triplet state at 279 cm-1 above the diamagnetic ground state. The next spin states are the S=1 and S=2 levels at about 700 and 820 cm-1 above the S=0 ground state, respectively. These large energy gaps are consistent with the absence of an EPR signal for this complex, even at high temperature.

General synthesis of di-mu-oxo dimanganese complexes as functional models for the oxygen evolving complex of photosystem II.

A series of complexes with the formula [Mn(III/IV)2(mu-O)2(L)2(X)2]3+ have been prepared in situ from Mn(II)LCl2 precursors by a general preparative method (L = terpy, Cl-terpy, Br-terpy, Ph-terpy, tolyl-terpy, mesityl-terpy, t Bu3-terpy, EtO-terpy, py-phen, dpya, Me2N-terpy, or HO-terpy, and X = a labile ligand such as water, chloride, or sulfate). The parent complex, where L = terpy and X = water, is a functional model for the oxygen-evolving complex of photosystem II (Limburg, et al. J. Am. Chem. Soc. 2001, 123, 423-430). Crystals of Mn(II)(dpya)Cl2, Mn(II)(Ph-terpy)Cl2, Mn(II)(mesityl-terpy)Cl2, and an organic-soluble di-mu-oxo di-aqua dimanganese complex, [Mn(III/)(IV)2(mu-O)2(mesityl-terpy)2(OH2)2](NO3)3, were obtained and characterized by X-ray crystallography. Solutions of the in situ-formed di-mu-oxo dimanganese complexes were characterized by electrospray mass spectrometry, EPR spectroscopy, and UV-visible spectroscopy, and the rates of catalytic oxygen-evolving activity were assayed. The use of Mn(II)LCl2 precursors leads to higher product purity of the Mn dimers while achieving the 1:1 ligand to Mn stoichiometry appropriate for catalytic activity assay. These methods can be used to screen the catalytic activity of other di-mu-oxo dimanganese complexes generated by using a ligand library.

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]

[Risk factors for Abacavir-induced hypersensibility syndrome in the "real world"]. / Facteurs de risque de syndrome d'hypersensibilité à l'Abacavir en pratique clinique de routine.

UNLABELLED: Abacavir (ABC) is a generally well-tolerated NRTI. However, up to 5% of patients may develop hypersensitivity syndrome (HSS) within the first weeks of treatment. The objectives of this study were to describe the side effects of ABC, to evaluate the incidence of the ABC-HSS, and to identify the risk factors of HSS after first exposure to ABC in a cohort of patients followed up in a university HIV clinic. METHODS: The charts of all HIV-infected patients who started ABC between February 1998 and May 2002 were reviewed. HSS was defined as the onset, within 8 weeks of ABC initiation, of either a skin rash associated with at least one of the following symptoms (fever, gastrointestinal symptoms, respiratory symptoms, myalgia, malaise) or at least three of the above symptoms in the absence of rash. A multivariate logistic regression analysis was performed to identify risk factors of HSS. RESULTS: Of the 191 patients studied (134 M, 57 F, mean age 39 years), 53 (27.8%) presented with manifestations that were regarded as potential side-effects of ABC. Ten (5.2%) developed HSS, none of whom died. Two factors were independently associated with an increased risk of HSS: history of allergy to nevirapine (OR 8.1, 95% CI 1.6-40.5, p = 0.02), and being naïve to ART (OR 5.8, 95% CI 1.2-28.5, p = 0.04). CONCLUSION: This study "in the real world" confirms that the incidence of ABC-induced HSS is of about 5%. It also confirms that HSS occurs more frequently in patients with a history of allergy to nevirapine and in ART-naïve patients.

Dimer-of-dimers model for the oxygen-evolving complex of photosystem II. Synthesis and properties of [MnIV4O5(terpy)4(H2O)2](ClO4)6.

A dimer-of-dimers model compound for the oxygen-evolving complex of photosystem II, [[(H(2)O)(terpy)Mn(IV)(micro-O)(2)Mn(IV)(terpy)](2)(micro-O)](ClO(4))(6) (terpy = 2,2':6',2' '-terpyridine), has been prepared and characterized by X-ray crystallography and ESI-MS. Low pH was found to promote the disproportionation of [Mn(III/IV)(2)O(2)(terpy)(2)(OH(2))(2)](3+) to Mn(2+) and a Mn(IV/IV)(2)O(2)(terpy)(2) species; the latter complex slowly dimerizes to form the title complex. Protonation of a micro-oxo bridge is proposed to initiate the disproportionation, based on analogy with the [Mn(III/)(IV)(2)O(2)(bpy)(4)](3+) system.

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]

A cis-IrL(CO) group responds to increasing steric bulk of L by M-L stretching, not M-C-O tilting or bending.

The crystal structures of [Ir(2-R-bq)(PPh(3))(2)(H)(CO)](+) (bq = benzoquinolinato; R = H, i-Pr, t-Bu) show that steric interference caused by contact between the bulky pendant R groups of the bq and the C of the cis-CO is relieved by Ir-N bond stretching in the Irbq system and bending of the trans-Ph(3)P-Ir-PPh(3) groups, rather than by tilting or bending of the CO. Ir-CO is therefore more rigid than the Ir-N and Ir-P bonds. The Ir-N stretching is aided by the presence of a high trans effect H trans to N.

[Medicamentous kidney protection in type 2 diabetic patients--is cheaper also more economical? A model calculation for Swiss health care]. / Medikamentöse Nephroprotektion bei Typ 2-Diabetikern--ist billiger auch ökonomischer? Eine Modellrechnung für Schweizer Verhältnisse.

Impaired renal function occurs in about 50% of patients suffering from type 2 diabetes, and diabetic nephropathy has become the leading cause of endstage renal disease. Reduction of blood pressure to levels around 120/80 mmHg is one of the most effective way to slow progression of diabetic nephropathy. Recent meta-analyses, however, have emphasized on the fact that ACE inhibitors (ACEI) and non-dihydropyridine calcium channel blockers (NDHP-CCB) exert nephro-protective effects which go beyond the effect of blood pressure reduction. This has lately been confirmed by a prospective trial in comparison to the betablocker atenolol. Based on these data, demographics of the Swiss population, literature data on mortality rates of type 2 diabetics with impaired renal function and studies on true costs of antihypertensives, we calculated the costs of a longterm intervention (20 years) with antihypertensives in 3536 middle-aged Swiss patients with type 2 diabetes and macro-albuminuria whose antihypertensive regimen was based either on the ACEI lisinopril, or the ND-HP-CCB verapamil, or the betablocker atenolol. Under atenolol, acquisition costs were lowest, whereas faster loss of renal function over time increased mortality rate and thus reduced the number of patients to be treated. Nevertheless, due to the fact that patients reached uremia and had to be dialyzed, 20 years of atenolol-based regimen with costs of 316 millions of Swiss francs turned out to be much more expensive than the lisinopril- or the verapamil-based regimen with 121 and 38 millions of Swiss francs, respectively. Thus, low acquisition cost is not necessarily the only important determinant of overall costs of drug therapy.