Micellar enhanced photo-induced fluorescence and absorbance for the development of an on-site early warning water quality monitoring system for pesticides.

This paper describes two prototypes of an on-site Early Warning Water Quality Monitoring System (EWWQMS) for pesticide quantification in natural waters. As many pesticides are non-fluorescent, the EWWQMS setup uses UV photoconversion to form highly fluorescent photoproducts. To enhance sensitivity, the two prototypes use micellar-enhanced fluorescence with surfactant (cetyl trimethyl ammonium chloride) in aqueous solution. To improve specificity, four UV LEDs at different wavelengths then excite the fluorescent photoproducts. The EWWQMS prototypes also employ UV absorption for quantification of non-photosensitive pesticides. The first prototype detects the pesticides via a diode array spectrometer. The second system is developed with higher resolution spectrometer and an intensified CCD camera detection to improve the sensitivity of the method. These experimental set-ups are described, explained and tested. Analytical applications were carried out online in CTAC aqueous solution, for the determination of isoproturon, flufenoxuron and profenofos. The calibration curves obtained are linear over one order of magnitude, and the detection limits are in the ng mL-1 range. The analytical performances of these new methods are good compared with other published classical micellar enhanced photo-induced fluorescence methods for the determination of pesticides in aqueous solutions. Our results show that these EWWQMS prototypes can be used as a warning system to protect against pesticide contamination exceeding the threshold of treatment capabilities at industrial facilities using natural waters.

Combination of photoinduced fluorescence and GC-MS for elucidating the photodegradation mechanisms of diflubenzuron and fenuron pesticides.

Diflubenzuron (DFB) and fenuron (FEN) are benzoylurea and phenylurea pesticides, widely used in Senegal, that do not exhibit any natural fluorescence, but can be determined by means of photoinduced fluorescence (PIF) methods. Photodegradation of DFB and FEN yielded a number of fluorescent and non-fluorescent photoproducts. For both pesticides, at least 10 photoproducts were detected and identified by gas chromatography-mass spectrometry (GC/MS). To identify the formed fluorescent DFB and FEN photoproducts, their fluorescence spectra were compared with those of standard compounds, including phenol and p-hydroxyaniline.

Cell and Protein Fouling Properties of Polymeric Mixtures Containing Supramolecular Poly(ethylene glycol) Additives.

Fouling properties of new biomaterials are important for the performance of a material in a biological environment. Here, a set of three supramolecular polymeric additives consisting of ureidopyrimidinone (UPy)-functionalized poly(ethylene glycol) (UPyPEG) were formulated with UPy-modified polycaprolactone into thin supramolecular material films. The antifouling properties of these material films were determined by investigation of the relation of cell adhesion and protein adsorption on these materials films. The presence of the UPyPEG additives at the surface of the films was evident by an increased hydrophilicity. Adhesion of human epithelial and endothelial cells was strongly reduced for two of the UPyPEG-containing films. Analysis of adsorption of the first three proteins from the Vroman series, albumin, γ-globulin, and fibrinogen, using quartz crystal microbalance with dissipation in combination with viscoelastic modeling, revealed that the surfaces containing the UPyPEG additives had a limited effect on adsorption of these proteins. Despite a limited reduction of protein adsorption, UPyPEG-containing mixtures were non-cell-adhesive, which shows that non-cell-adhesive properties of supramolecular polymer surfaces are not always directly correlated to protein adsorption.

Bundle Formation in Biomimetic Hydrogels.

Bundling of single polymer chains is a crucial process in the formation of biopolymer network gels that make up the extracellular matrix and the cytoskeleton. This bundled architecture leads to gels with distinctive properties, including a large-pore-size gel formation at very low concentrations and mechanical responsiveness through nonlinear mechanics, properties that are rarely observed in synthetic hydrogels. Using small-angle X-ray scattering (SAXS), we study the bundle formation and hydrogelation process of polyisocyanide gels, a synthetic material that uniquely mimics the structure and mechanics of biogels. We show how the structure of the material changes at the (thermally induced) gelation point and how factors such as concentration and polymer length determine the architecture, and with that, the mechanical properties. The correlation of the gel mechanics and the structural parameters obtained from SAXS experiments is essential in the design of future (synthetic) mimics of biopolymer networks.

Mesoscale characterization of supramolecular transient networks using SAXS and rheology.

Hydrogels and, in particular, supramolecular hydrogels show promising properties for application in regenerative medicine because of their ability to adapt to the natural environment these materials are brought into. However, only few studies focus on the structure-property relationships in supramolecular hydrogels. Here, we study in detail both the structure and the mechanical properties of such a network, composed of poly(ethylene glycol), end-functionalized with ureido-pyrimidinone fourfold hydrogen bonding units. This network is responsive to triggers such as concentration, temperature and pH. To obtain more insight into the sol-gel transition of the system, both rheology and small-angle X-ray scattering (SAXS) are used. We show that the sol-gel transitions based on these three triggers, as measured by rheology, coincide with the appearance of a structural feature in SAXS. We attribute this feature to the presence of hydrophobic domains where cross-links are formed. These results provide more insight into the mechanism of network formation in these materials, which can be exploited for tailoring their behavior for biomedical applications, where one of the triggers discussed might be used.

[Impact of acute normovolemic hemodilution on primary hemostasis]. / Einfluss der akuten normovolämischen Hämodilution auf die primäre Hämostase.

BACKGROUND: Acute normovolemic hemodilution (ANH) is performed with the intention to reduce the requirement for allogeneic blood transfusions. After preoperative withdrawal of whole blood, corresponding amounts of crystalloids and/or colloids are infused to maintain normovolemia. The main benefit of ANH is the availability of whole blood containing red blood cells, clotting factors and platelets for reinfusion after removal during the dilution process. Until retransfusion whole blood components are stored at the patient's bedside in the operating theatre. AIM: It was the aim of the present investigation to analyze potential changes in ex vivo induced platelet aggregation in stored blood components. MATERIAL AND METHODS: After obtaining approval 15 patients undergoing complex cardiac surgery were enrolled into this prospective observational study. Acute normovolemic hemodilution (ANH) was routinely performed in this collective based on institutional standards. Besides analyses of pH and plasma concentrations of ionized calcium and hemoglobin, hematological analyses included aggregometric measurements using multiple electrode aggregometry (MEA, Multiplate®, Roche, Grenzach, Germany). Ex vivo platelet aggregation was induced using arachidonic acid (ASPI test), as well as thrombin receptor activating peptide (TRAP test) and adenosine diphosphate (ADP test). Laboratory analyses were performed before beginning ANH (baseline), as well as immediately (T1), 30 min (T2), 60 min (T3), 90 min (T4), 120 min (T5), 150 min (T6) and 180 min (T7) after beginning of storage. The areas under the aggregation curves (AUC) in the MEA were defined as primary (ASPI test) and secondary endpoints (ADP test, TRAP test). RESULTS: As compared to baseline, arachidonic acid induced platelet aggregation was significantly reduced at T1 [77 U (68/94 U) vs. 53 U (25/86 U), p = 0.003] and each consecutive measuring point. As compared to T1 (begin of storage), arachidonic acid induced platelet aggregation was significantly reduced at T4 [26 U (14/54 U); p = 0.002], T5 [30 U (21/36 U); p = 0.007], T6 [25 U (17/40 U); p = 0.004] and T7 [28 U (17/39 U); p < 0.001]. The extent of ex vivo induced platelet aggregation in the TRAP test and ADP test remained unchanged during the study period. The pH as well as the concentrations of ionized calcium and hemoglobin remained unchanged in the blood component during storage. CONCLUSION: The results of the present study indicate that disturbances of platelet aggregation may occur during storage of whole blood components prepared for the purpose of ANH. Further investigations are needed to analyze whether the observed phenomena are of hemostatic relevance.

Multiverse analysis and the Bradley-Terry model: A proposed approach for evaluating palatability and preference.

The palatability of feed for dairy cows is an important consideration but is difficult to measure, particularly when considering more than 2 feeds. We outline how a combination of multiverse analysis and Bradley-Terry modeling, 2 methodological tools that have rarely been applied in dairy science, can be adapted to address this problem. Specifically, we propose to apply multiverse analysis as a way to consider a range of thresholds for how much of a mixed grass-legume (MGL) silage had to be consumed (as a percent of the total DMI) to be designated as preferred. Each threshold gives rise to a separate dataset and a corresponding fitted Bradley-Terry model. Bradley-Terry models attribute to each feed what is commonly referred to as an "ability" in the context of sports or other competitions but can be interpreted as palatability when applied to feeds. This combined approach is a way of estimating palatabilities that appropriately reflect the degree of preference cows express through their feeding behavior. It has the advantages of being transparent and relatively easy to implement. A possible disadvantage is that this method is limited to a paired comparison approach and has difficulties with main-effects statistical inference. We demonstrate the use of this methodology on an example dataset comparing MGL silages under different ensiling conditions and exposed to oxygen for different durations.

Anterior dislocation of the shoulder associated with a diaphyseal fracture of the ipsilateral humerus: a case report.

Background: Anterior dislocation of the shoulder associated with a diaphyseal fracture of the ipsilateral humerus is a rare and controversial occurrence, with very few cases reported in the literature. Case presentation: We present a case of a 39-year-old right-handed driver who presented with an anterior dislocation of the shoulder associated with a diaphyseal fracture of the ipsilateral humerus following a road traffic accident. The lateral approach to the fracture allowed us to use two forceps to gain a good grip on the proximal fragment and perform the maneuver to reduce the dislocation. The fracture was reduced and fixed with a molded Lecestre-type plate. Conclusion: In this case, we employed the approach of initially reducing the shoulder dislocation with forceps, followed by osteosynthesis of the humeral fracture. The functional results were excellent after 6 months.

Mesoscale modulation of supramolecular ureidopyrimidinone-based poly(ethylene glycol) transient networks in water.

In natural systems, highly synergistic non-covalent interactions among biomolecular components exert mesoscopic control over hierarchical assemblies. We herein present a multicomponent self-assembly strategy to tune hierarchical supramolecular polymer architectures in water using highly affine and directional ureidopyrimidinone-poly(ethylene glycol)s (UPy-PEG). Using scattering methods and oscillatory rheology, we observe the structural and mechanical regulation of entangled monofunctional UPy-PEG fibrils by cross-linking bifunctional UPy-PEG fibrils. This supramolecular mixing approach opens the door to a range of subtly distinct materials for chemical and biological applications.

The limit of anemia tolerance during hyperoxic ventilation with pure oxygen in anesthetized domestic pigs.

BACKGROUND: During acellular replacement of an acute blood loss, hyperoxic ventilation (HV) increases the amount of O2 physically dissolved in the plasma and thereby improves O2 supply to the tissues. While this effect could be demonstrated for HV with inspiratory O2 fraction (FiO2) 0.6, it was unclear whether HV with pure oxygen (FiO2 1.0) would have an additional effect on the physiological limit of acute normovolemic anemia. METHODS: Seven anesthetized domestic pigs were ventilated with FiO2 1.0 and subjected to an isovolemic hemodilution protocol. Blood was drawn and replaced by a 6% hydroxyethyl starch (HES) solution (130/0.4) until a sudden decrease of total body O2 consumption (VO2) indicated the onset of O2 supply dependency (primary endpoint). The corresponding hemoglobin (Hb) concentration was defined as 'critical Hb' (Hbcrit). Secondary endpoints were parameters of myocardial function, central hemodynamics, O2 transport and tissue oxygenation. RESULTS: HV with FiO2 1.0 enabled a large blood-for-HES exchange (156 ± 28% of the circulating blood volume) until Hbcrit was met at 1.3 ± 0.3 g/dl. After termination of the hemodilution protocol, the contribution of O2 physically dissolved in the plasma to O2 delivery and VO2 had significantly increased from 11.7 ± 2 to 44.2 ± 9.7% and from 29.1 ± 4.2 to 66.2 ± 11.7%, respectively. However, at Hbcrit, cardiovascular performance was found to have severely deteriorated. CONCLUSION: HV with FiO2 1.0 maintains O2 supply to tissues during extensive blood-for-HES exchange. In acute situations, where profound anemia must be tolerated (e.g. bridging an acute blood loss until red blood cells become available for transfusion), O2 physically dissolved in the plasma becomes an essential source of oxygen. However, compromised cardiovascular performance might require additional treatment.

Analysis of non-native fluorescent pesticides by thermo-induced and photo-induced fluorescence, a comparative study.

This paper compares the performance of three analytical methods for the determination of pesticides in natural waters. As many pesticides are non-fluorescent, they are transformed into highly fluorescent by-products in two ways: elevated temperature in an alkaline medium (thermo-induced fluorescence - TIF); or UV irradiation in water (photo-induced fluorescence - PIF). The first method studied uses TIF, the second one uses PIF and the third one uses an automatic sampling and analysing PIF system. Analytical applications were carried out using the three methods for the determination of deltamethrin and cyhalothrin, pesticides widely used in Senegal. In both cases, the calibration curves obtained are linear without matrix effects, and the detection limits are good in the ng mL-1 range. It appears that the analytical performances of the automatic PIF method are better than the two others. The advantages and disadvantages of the three methods are then compared and discussed in term of analytical performance and usability.

High sensitivity on-site early warning system monitoring of pesticides by photo-induced fluorescence.

This paper describes the prototype of an on-site High Sensitivity Early Warning Monitoring System, using Photo-Induced Fluorescence, for pesticide monitoring in natural waters (HSEWPIF). To obtain a high sensitivity, the prototype was designed with four main features. Four UV LEDs are used to excite the photoproducts at different wavelengths and select the most efficient one. Two UV LEDs are used simultaneously at each wavelength to increase the excitation power and then the fluorescence emission of the photoproducts. High-pass filters are used to avoid the saturation of the spectrophotometer and to increase the signal-to-noise ratio. The HSEWPIF prototype also employs UV absorption to detect any occasional increase of suspended and dissolved organic matter, which could disrupt the fluorescence measurement. The conception of this new experimental set-up is explained and described, then analytical applications are carried out online for the determination of fipronil and monolinuron. We obtained a linear calibration range from 0 to 3 µg mL-1 with limits of detection of 1.24 ng mL-1 for fipronil and 0.32 ng mL-1 for monolinuron. A mean recovery of 99.2% for fipronil and 100.9% for monolinuron show that the method is accurate, moreover a standard deviation of 1.96% for fipronil and 2.49% for monolinuron show that the method is repeatable. Compared to other methods for the determination of pesticides by photo-induced fluorescence, the HSEWPIF prototype has good sensitivity with better limits of detection, and good analytical performances. These results show that HSEWPIF can be used for monitoring pesticide in natural waters to protect industrial facilities against accidental contamination.

Neuromuscular blockade with rocuronium bromide increases the tolerance of acute normovolemic anemia in anesthetized pigs.

BACKGROUND: The patient's individual anemia tolerance is pivotal when blood transfusions become necessary, but are not feasible for some reason. To date, the effects of neuromuscular blockade (NMB) on anemia tolerance have not been investigated. METHODS: 14 anesthetized and mechanically ventilated pigs were randomly assigned to the Roc group (3.78 mg/kg rocuronium bromide followed by continuous infusion of 1 mg/kg/min, n = 7) or to the Sal group (administration of the corresponding volume of normal saline, n = 7). Subsequently, acute normovolemic anemia was induced by simultaneous exchange of whole blood for a 6% hydroxyethyl starch solution (130/0.4) until a sudden decrease of total body O(2) consumption (VO(2)) indicated a critical limitation of O(2) transport capacity. The Hb concentration quantified at this time point (Hb(crit)) was the primary endpoint of the protocol. Secondary endpoints were parameters of hemodynamics, O(2) transport and tissue oxygenation. RESULTS: Hb(crit) was significantly lower in the Roc group (2.4 ± 0.5 vs. 3.2 ± 0.7 g/dl) reflecting increased anemia tolerance. NMB with rocuronium bromide reduced skeletal muscular VO(2) and total body O(2) extraction rate. As the cardiac index increased simultaneously, total body VO(2) only decreased marginally in the Roc group (change of VO(2) relative to baseline -1.7 ± 0.8 vs. 3.2 ± 1.9% in the Sal group, p < 0.05). CONCLUSION: Deep NMB with rocuronium bromide increases the tolerance of acute normovolemic anemia. The underlying mechanism most likely involves a reduction of skeletal muscular VO(2). During acellular treatment of an acute blood loss, NMB might play an adjuvant role in situations where profound stages of normovolemic anemia have to be tolerated (e.g. bridging an unexpected blood loss until blood products become available for transfusion).

Alternative to High Pressure Mercury Vapor Lamp for Photo Induced Fluorescence Analytical Methods; Application to the Determination of Pesticides in Water.

The photo-induced fluorescence method is often applied to determine non-native fluorescent compounds. It typically uses UV irradiation from a high pressure mercury vapor discharge lamp to create photo-induced fluorescent compounds, which are then quantified by fluorescence spectroscopy. However, these mercury lamps require a high-voltage power supply and may accidentally induce electric shocks and the release of mercury vapors. As an alternative, we have evaluated in this technical note new UV-C germicidal lamps. These lamps exhibit a higher power at 254 nm and allowed us to obtain a far greater amount of photo-induced compounds in a shorter time. For the first time, this new irradiation system has been applied for the determination of pesticides in water and has shown a significant increase in the method sensitivity. These good results allowed us to conclude that the new UV-C lamps are a relevant alternative to high pressure mercury vapor discharge lamps for use with photo induced fluorescent methods.

Long-distance remote comparison of ultrastable optical frequencies with 10(-15) instability in fractions of a second.

We demonstrate a fully optical, long-distance remote comparison of independent ultrastable optical frequencies reaching a short term stability that is superior to any reported remote comparison of optical frequencies. We use two ultrastable lasers, which are separated by a geographical distance of more than 50 km, and compare them via a 73 km long phase-stabilized fiber in a commercial telecommunication network. The remote characterization spans more than one optical octave and reaches a fractional frequency instability between the independent ultrastable laser systems of 3 x 10 (-15) in 0.1 s. The achieved performance at 100 ms represents an improvement by one order of magnitude to any previously reported remote comparison of optical frequencies and enables future remote dissemination of the stability of 100 mHz linewidth lasers within seconds.

Analysis of Oxadiazon Herbicide in Natural Water Samples by a Micellar-enhanced Photo-induced Fluorescence.

A micellar-enhanced photo-induced fluorescence (ME-PIF) method was developed to analyze, for the first time, oxadiazole herbicide (namely oxadiazon) in natural water samples. Photo-conversion under UV irradiation of the herbicide into strongly fluorescent photoproducts was performed in aqueous solution and in the presence of two surfactants, cetyltrimethylammonium chloride (CTAC) or Tween 20, at micellar concentrations. The ME-PIF parameters were optimized. The ME-PIF method gave very good results with satisfactory analytical performance for the determination of a selected pesticide with concentration linear dynamic ranges of over one to two orders of magnitude. It yielded good reproducibility (RSD values of between 3.6 and 9.6%) in tap, river and sea water spiked samples, and the limits of detection were in the ng mL-1 range.

Development of an on-site early warning water quality monitoring system for pesticide detection by absorption and photo-induced fluorescence.

This paper describes prototypes of an on-site early warning water quality monitoring system (EWWQMS) for pesticide quantification in natural waters by fluorescence and absorbance. As many pesticides are not naturally fluorescent, this EWWQMS uses UV irradiation to transform these compounds into highly fluorescent photoproducts and obtain sufficient sensitivity. To obtain a better specificity, the system uses four UV LEDs at different wavelengths to excite the fluorescent photoproducts. For pesticides that are not sensitive to photoconversion, the EWWQMS prototypes also use UV absorption for their quantification, thus offering a wider application range. A first system uses a diode array spectrometer for detection. A second system uses a higher resolution spectrometer and an intensified CCD camera detection to increase sensitivity. Analytical applications were conducted for the determination of fipronil, acetamipride, cyprodinil, trifluraline and pendimethaline in water using both the EWWQMS prototypes. The analytical performances of these new systems are good compared with other photo-induced fluorescence methods already published. Limits of detection without pre-concentration are in the range of 0.2 to 3 ng mL-1 and the recovery values range from 95 to 108%. These results show that the EWWQMS prototypes can be used as an alert system to protect industrial plants from pesticide contaminations that exceed the capabilities of their cleaning processes.

Effective scale-up: avoiding the same old traps.

Despite progress in developing more effective training methodologies, training initiatives for health workers continue to experience common pitfalls that have beset the overall success and cost-effectiveness of these programs for decades. These include lack of country-level coordination of health training, inequitable access to training, interrupted services, and failure to reinforce skills and knowledge training by addressing other performance factors. These pitfalls are now seen as aggravating the current crisis in human resources for health and impeding the effective scale-up of training and the potential impact of promising strategies such as task shifting to address health worker shortages. Drawing on IntraHealth International's lessons learned in designing reproductive health and HIV/AIDS training and performance improvement programmes, this commentary discusses promising practices for strengthening human resources for health through more efficient and effective training and learning programmes that avoid the same old traps. These promising practices include the following: Assessing performance gaps and opportunities before designing a training initiative; addressing performance factors other than skills and knowledge that health workers need to perform well; applying a "learning for performance" approach; standardizing curricula throughout a country; linking pre-service education, in-service training and professional associations; enhancing traditional education; strengthening human resources information systems to improve workforce planning, policies and management; applying technology to meet training needs.

Quantum mechanical scattering cross sections and permeability coefficients for ions crossing the human red cell and resting squid axon membranes.

Quantum mechanical calculations of elastic scattering cross sections for some permeant ions crossing the human red blood cell and resting axolemma squid axon membranes have been carried out using the three-dimensional spherically symmetric square potential well. Making the assumption that the permeability coefficient is inversely proportional to scattering cross section, we obtain the order of membrane selectivity for the ions as well as values for the permeability coefficients. Despite the relatively simple method used, good agreement between calculated permeability coefficients and data available in the literature is obtained. We suggest that elastic scattering cross section measurements for ions in various membranes would be valuable not only because they give a precise idea about the permeability ratios between ions but they also determine the form of the potential the ions are moving in.

Experimental characterization and Monte Carlo simulation of Si(Li) detector efficiency by radioactive sources and PIXE.

This work relates to the study and characterization of the response function of an X-ray spectrometry system. The intrinsic efficiency of a Si(Li) detector has been simulated with the Monte Carlo codes MCNP and GEANT4 in the photon energy range of 2.6-59.5keV. After finding it necessary to take a radiograph of the detector inside its cryostat to learn the correct dimensions, agreement within 10% between the simulations and experimental measurements with several point-like sources and PIXE results was obtained.