A Highly Sensitive and Selective Optical Sensor for the On-Line Detection of Cesium in Water.

In this study, we have undertaken the development of two fluorescent sensors based on calixarene compounds for the purpose of detecting cesium in water. By introducing the sulfonate functional groups, we have considerably improved the water solubility of sensors, enabling complete dissolution of products in aqueous media and direct analysis of polluted water samples. Through rigorous experiments, we have demonstrated that the complexation of Cs+ ions with sensors 1 and 2 in water leads to a remarkable enhancement of fluorescence. This fluorescence enhancement serves as a reliable indication of cesium presence and allows for sensitive detection. To further advance the practical application of our sensors, we have successfully integrated calixarene sensors 1 and 2 into a microfluidic sensor chip. This integration has enabled real-time, on-line measurements and has resulted in the development of a portable detection device capable of detecting cesium ions in water samples at parts per billion (ppb) levels. This device holds great promise for environmental monitoring and assessment, providing a convenient and efficient solution for cesium detection. Our work represents a significant advancement in the field of cesium detection, displaying the efficacy of calixarene-based fluorescent sensors and their integration into microfluidic systems. The enhanced water solubility, fluorescence response, and portability of our detection device offers tremendous potential for applications in environmental monitoring, water quality assessment, and emergency response scenarios where rapid and accurate cesium detection is crucial.

Archaeological Mortar Characterization Using Laser-Induced Breakdown Spectroscopy (LIBS) Imaging Microscopy.

Lime mortar is a complex mixture resulting from hardening of lime, water, and aggregates. Lime mortar was used from the time of the Roman Empire until the Industrial Revolution. The recipes used differ according to the period, geographical area of preparation, craftsman, or function. This is why the study of archaeological mortars is of such great importance in building archaeology. In this study, we used laser-induced breakdown spectroscopy (LIBS) to characterize the elemental composition of three lime mortar samples with a µ-LIBS instrument, allowing elemental image compilation. These samples originate from three different geographical locations: Angers (France), Dardilly (France), and Pompeii (Italy), and were taken from buildings that had different functions: cathedral, aqueduct, and house, respectively. Thanks to image processing and the creation of masks, it was possible to extract not only the lime signature and nature of the aggregate but also its granulometry and circularity. All this information is essential for cultural heritage research. This study shows the potential of the LIBS technique in archaeometric analysis of archaeological mortars.

Characterization of red blood cell microcirculatory parameters using a bioimpedance microfluidic device.

This paper describes the use of a microfluidic device comprising channels with dimensions mimicking those of the smallest capillaries found in the human microcirculation. The device structure, associated with a pair of microelectrodes, provides a tool to electrically measure the transit time of red blood cells through fine capillaries and thus generate an electrical signature for red blood cells in the context of human erythroid genetic disorders, such as sickle cell disease or hereditary spherocytosis, in which red cell elasticity is altered. Red blood cells from healthy individuals, heated or not, and red blood cells from patients with sickle cell disease or hereditary spherocytosis where characterized at a single cell level using our device. Transit time and blockade amplitude recordings were correlated with microscopic observations, and analyzed. The link between the electrical signature and the mechanical properties of the red blood cells is discussed in the paper, with greater transit time and modified blockade amplitude for heated and pathological red blood cells as compared to those from healthy individuals. Our single cell-based methodology offers a new and complementary approach to characterize red cell mechanical properties in human disorders under flow conditions mimicking the microcirculation.

[The role of caregivers in environmental health in hospital]. / Le rôle des soignants en matière de santé environnementale à l'hôpital.

Environmental health is part of the daily practice of caregivers in a health facility. It is particularly evident in the waste and water quality management systems. It is resulting in changes to roles and practices, particularly for nurse hygienists.

The invasive land planarian Platydemus manokwari (Platyhelminthes, Geoplanidae): records from six new localities, including the first in the USA.

The land planarian Platydemus manokwari de Beauchamp, 1963 or "New Guinea flatworm" is a highly invasive species, mainly in the Pacific area, and recently in Europe (France). We report specimens from six additional countries and territories: New Caledonia (including mainland and two of the Loyalty Islands, Lifou and Maré), Wallis and Futuna Islands, Singapore, Solomon Islands, Puerto Rico, and Florida, USA. We analysed the COI gene (barcoding) in these specimens with two sets of primers and obtained 909 bp long sequences. In addition, specimens collected in Townsville (Australia) were also sequenced. Two haplotypes of the COI sequence, differing by 3.7%, were detected: the "World haplotype" found in France, New Caledonia, French Polynesia, Singapore, Florida and Puerto Rico; and the "Australian haplotype" found in Australia. The only locality with both haplotypes was in the Solomon Islands. The country of origin of Platydemus manokwari is New Guinea, and Australia and the Solomon Islands are the countries closest to New Guinea from which we had specimens. These results suggest that two haplotypes exist in the area of origin of the species, but that only one of the two haplotypes (the "World haplotype") has, through human agency, been widely dispersed. However, since P. manokwari is now recorded from 22 countries in the world and we have genetic information from only 8 of these, with none from New Guinea, this analysis provides only partial knowledge of the genetic structure of the invasive species. Morphological analysis of specimens from both haplotypes has shown some differences in ratio of the genital structures but did not allow us to interpret the haplotypes as different species. The new reports from Florida and Puerto Rico are firsts for the USA, for the American continent, and the Caribbean. P. manokwari is a known threat for endemic terrestrial molluscs and its presence is a matter of concern. While most of the infected territories reported until now were islands, the newly reported presence of the species in mainland US in Florida should be considered a potential major threat to the whole US and even the Americas.

Mercury detection in a microfluidic device by using a molecular sensor soluble in organoaqueous solvent.

A series of fluorescent sensor molecules based on a phosphane sulfide derivative that is soluble in an organoaqueous solvent were designed and synthesized. The structure of the fluorophore has been optimized in order to have the best compromise in terms of solubility and photophysical properties. The obtained properties are in full agreement with quantum chemical calculations. A fluorescent molecular sensor containing one polyoxoethylene group has been synthesized and an efficient quenching upon mercury complexation has been observed. Finally, this sensing molecule has been introduced in a microfluidic chip in which fluorescence detection has been integrated. An efficient fluorescence response was observed upon mercury addition.

Thermodynamics and kinetics of the complexation reaction of lead by calix-DANS4.

The thermodynamics and kinetics of the complexation reaction between lead ions and the fluorescent sensor Calix-DANS4 are determined to optimize the geometry of the microreactor used for the flow-injection analysis of lead and to tune the working conditions of this microdevice. Under our experimental conditions (pH 3.2, low concentration of Calix-DANS4) the 1:1 Pb(2+)-Calix-DANS4 complex is predominantly formed with a high stability constant (log K(1:1)=6.82) and a slow second-order rate constant (k=9.4×10(4) L mol(-1) s(-1)). Due to this sluggish complexation reaction, the microchannel length must be longer than 130 mm and the flow rate lower than 0.25 mL h(-1) to have an almost complete reaction at the output of the microchannel and a high sensitivity for the heavy metal detection. After determination of the values of the reaction times in our different microdevices, it is possible to simulate the calibration curves for the fluorimetric detection of lead under different conditions. An original method is also presented to determine mixing times in microreactors.

Fluorimetric lead detection in a microfluidic device.

A microfabricated device has been developed for the selective detection of lead in water. It is based on the use of a selective and sensitive fluorescent molecular sensor for lead (Calix-DANS4) which contains a calix[4]arene bearing four dansyl groups. The microchip-based lead sensor contains a Y-shape microchannel equipped with a passive mixer and moulded on a glass substrate. An optimization of the microcircuit length has been performed in order to have a full complexation of the Calix-DANS4. The detection is performed by using a configuration in which the sensing molecules are excited by two optical fibres, each one connected to a 365 nm UV LED, and the light collection is made by another optical fibre with a photomultiplier. By using this configuration we have shown the possibility to detect lead with a detection limit of 5 ppb. The effect of interfering cations such as calcium has been evaluated. The obtained measurements have been validated by an alternative method (ASV).

Fluorescence lifetime standards for time and frequency domain fluorescence spectroscopy.

A series of fluorophores with single-exponential fluorescence decays in liquid solution at 20 degrees C were measured independently by nine laboratories using single-photon timing and multifrequency phase and modulation fluorometry instruments with lasers as excitation source. The dyes that can serve as fluorescence lifetime standards for time-domain and frequency-domain measurements are all commercially available, are photostable under the conditions of the measurements, and are soluble in solvents of spectroscopic quality (methanol, cyclohexane, water). These lifetime standards are anthracene, 9-cyanoanthracene, 9,10-diphenylanthracene, N-methylcarbazole, coumarin 153, erythrosin B, N-acetyl-l-tryptophanamide, 1,4-bis(5-phenyloxazol-2-yl)benzene, 2,5-diphenyloxazole, rhodamine B, rubrene, N-(3-sulfopropyl)acridinium, and 1,4-diphenylbenzene. At 20 degrees C, the fluorescence lifetimes vary from 89 ps to 31.2 ns, depending on fluorescent dye and solvent, which is a useful range for modern pico- and nanosecond time-domain or mega- to gigahertz frequency-domain instrumentation. The decay times are independent of the excitation and emission wavelengths. Dependent on the structure of the dye and the solvent, the excitation wavelengths used range from 284 to 575 nm, the emission from 330 to 630 nm. These lifetime standards may be used to either calibrate or test the resolution of time- and frequency-domain instrumentation or as reference compounds to eliminate the color effect in photomultiplier tubes. Statistical analyses by means of two-sample charts indicate that there is no laboratory bias in the lifetime determinations. Moreover, statistical tests show that there is an excellent correlation between the lifetimes estimated by the time-domain and frequency-domain fluorometries. Comprehensive tables compiling the results for 20 (fluorescence lifetime standard/solvent) combinations are given.

A novel microfluidic flow-injection analysis device with fluorescence detection for cation sensing. Application to potassium.

A microfabricated device has been developed for fluorimetric detection of potassium ions without previous separation. It is based on use of a fluorescent molecular sensor, calix-bodipy, specially designed to be sensitive to and selective for the target ion. The device is essentially made of a Y-shape microchannel moulded in PDMS fixed on a glass substrate. A passive mixer is used for mixing the reactant and the analyte. The optical detection arrangement uses two optical fibres, one for excitation by a light-emitting diode, the other for collection of the fluorescence. This system enabled the flow-injection analysis of the concentration of potassium ions in aqueous solutions with a detection limit of 0.5 mmol L(-1) and without interference with sodium ions. A calibration plot was constructed using potassium standard solutions in the range 0-16 mmol L(-1), and was used for the determination of the potassium content of a pharmaceutical pill. Figure Photography of the microfluidic channel showing the ridges in the PDMS substrate at the top of the channel.

Diastolic asynchrony is more frequent than systolic asynchrony in dilated cardiomyopathy and is less improved by cardiac resynchronization therapy.

OBJECTIVES: To compare the incidence of diastolic and systolic asynchrony, assessed by tissue Doppler imaging (TDI), in patients with congestive heart failure (CHF) and severe left ventricular (LV) dysfunction, and to assess TDI changes induced by cardiac resynchronization therapy (CRT). BACKGROUND: Thirty percent of CRT candidates are nonresponders. Besides QRS width, the presence of echographic systolic asynchrony has been used to identify future responders. Little is known about diastolic asynchrony and its change after CRT. METHODS: Tissue Doppler imaging was performed in 116 CHF patients (LV ejection fraction 26 +/- 8%). Systolic and diastolic asynchrony was calculated using TDI recordings of right ventricular and LV walls. RESULTS: The CHF group consisted of 116 patients. Diastolic asynchrony was more frequent than systolic, concerning both intraventricular (58% vs. 47%; p = 0.0004) and interventricular (72 vs. 45%; p < 0.0001) asynchrony. Systolic and diastolic asynchrony were both present in 41% patients, but one-third had isolated diastolic asynchrony. Although diastolic delays increased with QRS duration, 42% patients with narrow QRS presented with diastolic asynchrony. Conversely, 27% patients with large QRS had no diastolic asynchrony. Forty-two patients underwent CRT. Incidence of systolic intraventricular asynchrony decreased from 71% to 33% after CRT (p < 0.0001), but diastolic asynchrony decreased only from 81% to 55% (p < 0.0002). Cardiac resynchronization therapy induced new diastolic asynchrony in eight patients. CONCLUSIONS: Diastolic asynchrony is weakly correlated with QRS duration, is more frequent than systolic asynchrony, and may be observed alone. Diastolic asynchrony is less improved by CRT than systolic. Persistent diastolic asynchrony may explain some cases of lack of improvement after CRT despite good systolic resynchronization.

A single mutation in the activation site of bovine trypsinogen enhances its accumulation in the fermentation broth of the yeast Pichia pastoris.

We produced bovine trypsinogen in the yeast Pichia pastoris. Little or no trypsinogen was detected when the gene with its native leader sequence was expressed under the control of the strong aox1 promoter, suggesting that expression of the wild-type bovine trypsinogen was toxic to the cells. We altered the trypsinogen native propeptide sequence by replacing the lysine at position 6 with an aspartic acid, thus destroying the site in the propeptide cleaved by enterokinase and by trypsin. This mutant accumulated up to 10 mg of trypsinogen per liter in shake flask cultures and about 40 mg/liter in 6-liter fermentors. Trypsinogen could be activated in vitro with a dipeptidyl-aminopeptidase, which selectively removed the modified trypsinogen propeptide; the resulting trypsin was fully active and showed evidence of glycosylation. Thus, we have developed a novel protein production scheme that can be used for the expression of proteins, such as proteases, that are deleterious to the producing organism. This system relies on the expression of a zymogen that cannot be activated in vivo coupled with its in vitro purification and activation.

Effects of temperature on the dynamic behaviour of the HIV-1 nucleocapsid NCp7 and its DNA complex.

The nucleocapsid protein NCp7 of human immunodeficiency virus type 1 (HIV-1) contains two highly conserved CCHC zinc fingers and is involved in many crucial steps of the virus life-cycle. A large number of physiological rôles of NCp7 involve its binding to single-stranded nucleic acid chains. Several solution structures of NCp7 and its complex with single-stranded RNA or DNA have been reported. We have investigated the changes in the dynamic behaviour experienced by the (12-53)NCp7 peptide upon DNA binding using (15)N heteronuclear relaxation measurements at 293 K and 308 K, and fluorescence spectroscopy. The relaxation data were interpreted using the reduced spectral density approach, which allowed the high-frequency motion, overall tumbling rates and the conformational exchange contributions to be characterized for various states of the peptide without using a specific motional model. Analysis of the temperature-dependent correlation times derived from both NMR and fluorescence data indicated a co-operative change of the molecular shape of apo (12-53)NCp7 around 303 K, leading to an increased hydrodynamic radius at higher temperatures. The binding of (12-53)NCp7 to a single-stranded d(ACGCC) pentanucleotide DNA led to a reduction of the conformational flexibility that characterized the apo peptide. Translational diffusion experiments as well as rotational correlation times indicated that the (12-53)NCp7/d(ACGCC) complex tumbles as a rigid object. The amplitudes of high-frequency motions were restrained in the complex and the occurrence of conformational exchange was displaced from the second zinc finger to the linker residue Ala30.