A nanofluidic switching device

We present a nanofluidic switching function which allows directed transport in lipid bilayer nanotubes ( approximately 100 nm in diameter) between any two or several nanotube-connected vesicle containers (5-10 mum radius) in a large network. Liquid is transported in the form of small vesicular structures (10-15-10-18 L), and the transport direction is controlled by a two-point perturbation technique, where the surface membrane tension is decreased in one container while it is increased in another container. When reaching a target container, the transported vesicular structures could also inject their material into it.     

Silver nanoparticle formation in microemulsions acting both as template and reducing agent

A novel method of making silver nanoparticles in water-in-oil microemulsions using the surfactants as both the reducing agent and as the structure-directing agent is presented. Since no external strong reducing agent is used the kinetics of the formation is slow, which makes it possible to study the silver nanoparticle formation in situ. The microemulsions used were based on either the nonionic surfactant Brij30 (C12E4), which reduces the silver ion to metallic silver and is thereby partly oxidized, or mixtures of Brij30 and AOT (sodium bis(2-ethylhexyl) sulfosuccinate, where the latter does not reduce the silver ions. The influences of silver ion and nonionic surfactant concentrations on the formation kinetics of the nanoparticles were followed in situ using UV-vis spectroscopy, and both parameters were found to have a big influence. The microemulsion droplet's size, size distribution, and shape were examined by small-angle X-ray scattering (SAXS), and the formed silver nanoparticles were studied using both transmission electron microscopy and SAXS. The SAXS measurements showed that the presence of silver nitrate does not affect the microemulsion systems noticeably and that the droplet's size and shape are retained during the particle formation. It is shown that the size and morphology of the particles do not directly follow the shape and size of the microemulsion droplets even though there is a relation between the droplet size and the radii of the formed particles.     

Mechanistic study of the SmI2/H2O/amine-mediated reduction of alkyl halides: amine base strength (pKBH+) dependent rate

The kinetics of the SmI(2)/H(2)O/amine-mediated reduction of 1-chlorodecane has been studied in detail. The rate of reaction is first order in amine and 1-chlorodecane, second order in SmI(2), and zero order in H(2)O. Initial rate studies of more than 20 different amines show a correlation between the base strength (pK(BH+) of the amine and the logarithm of the observed initial rate, in agreement with Bronsted catalysis rate law. To obtain the activation parameters, the rate constant for the reduction was determined at different temperatures (0 to +40 degrees C, DeltaH++ = 32.4 +/- 0.8 kJ mol(-1), DeltaS++ = -148 +/- 1 J K(-1) mol(-1), and DeltaG++(298K) = 76.4 +/- 1.2 kJ mol(-1)). Additionally, the (13)C kinetic isotope effects (KIE) were determined for the reduction of 1-iododecane and 1-bromodecane. Primary (13)C KIEs (k(12)/k(13), 20 degrees C) of 1.037 +/- 0.007 and 1.062 +/- 0.015, respectively, were determined for these reductions. This shows that cleavage of the carbon-halide bond occurs in the rate-determining step. A mechanism of the SmI(2)/H(2)O/amine-mediated reduction of alkyl halides is proposed on the basis of these results.     

Coulometric Karl Fischer titration of trace water in diaphragm-free cells

Factors influencing the accuracy and precision for diaphragm-free Karl Fischer coulometric determinations of low μg-amounts of water have been studied using the Metrohm 756 (pulsed current) coulometer and eight different types of commercial coulometric reagents and some modifications of these. As in the case of diaphragm-free coulometric titration of large amounts of water, the positive errors, due to the formation of oxidizable reduction products (of sulfur dioxide) in the cathode reaction (besides hydrogen), were found to be minimized by the use of highest possible pulse current (in the range 100–400 mA) in combination with the fastest possible titration rate. Most accurate (102–103%) and precise results (typical relative standard deviation 1.8%) were obtained for reagents containing very large concentrations of imidazole in combination with the presence of modifiers like hexanol, chloroform and propylene glycol (i.e. the HYDRA-POINT reagents). Similar results were obtained when this type of reagent was mixed 60/40 with xylene according to the ASTM recommendation for water determinations in petroleum products like crude and lubricating oils. Addition of decanol to this type of reagent mixture was found to reduce the influence from the oxidative reduction products significantly. A reduction of the error from 3.6% relative to 1.6% was achieved by addition of 9% (v/v) of decanol to a 60/40 reagent mixture of HYDRA-POINT Coulometric Gen (containing hexanol as modifier) and xylene. For larger concentrations of decanol the pulse current had to be lowered to 100 mA and this might explain why no further improvement was observed. An additional attempt to minimize the interference by lowering the concentration of sulfur dioxide in the reagents gave no significant effect. However, by means of a home-built computer-controlled coulometric instrumentation based on continuous instead of pulsed current (including a large cathodic current density) it was possible to achieve recovery rates close to 100% for the best reagents investigated. The reason for this improvement is discussed.     

High-performance liquid chromatography–tandem mass spectrometry method for quantifying sulfonylurea herbicides in human urine: reconsidering the validation process

We have developed a method for measuring 17 sulfonylurea (SU) herbicides in human urine. Urine samples were extracted using solid phase extraction (SPE), preconcentrated, and analyzed by high-performance liquid chromatography–tandem mass spectrometry using turboionspray atmospheric pressure ionization. Carbon 13-labeled ethametsulfuron methyl was used as an internal standard. Chromatographic retention times were under 7 minutes. Total throughput was estimated as >100 samples per day. Because only one labeled internal standard was available for the analysis, we were forced to reconsider and restructure the validation process to include stringent stability tests and analyses of urine matrices of differing compositions. We describe our restructured validation process and the critical evaluation it provides for the method developed. The limits of detection (LOD) ranged from 0.05 μg/L to 0.10 μg/L with an average LOD of 0.06 μg/L. Average total relative standard deviations were 17%, 12% and 8% at 0.1 μg/L, 3.0 μg/L and 10 μg/L, respectively. Average extraction efficiencies of the SPE cartridges were 87% and 86% at 2.5 μg/L and 25 μg/L, respectively. Chemical degradation in acetonitrile and urine was monitored over 250 days. Estimated days for 10% and 50% degradation in urine and acetonitrile ranged from 0.7 days to >318 days. The influence of matrix effects on precision and accuracy was also explored. Electronic Supplementary Material Supplementary material is available for this article at For additional information, contact Anderson Olsson at     

Regioselective Heck couplings of alpha,beta-unsaturated tosylates and mesylates with electron-rich olefins

[chemical reaction: see text]. Highly regioselective Heck couplings of alpha,beta-unsaturated tosylate and mesylate derivatives with N-acyl N-vinylamines and vinyl ethers were achieved. Several 2-alkoxy-1,3-dienes and 2-acylamino-1,3-butadienes were synthesized in good yields using 1.5 mol % of Pd2(dba)3, 3 mol % of DPPF, and diisopropylethylamine in dioxane. When working with alpha,beta-unsaturated ketones and esters, this method provides a less costly alternative to similar couplings using a triflate electrophile.     

Modified phthalocyanines for efficient near-IR sensitization of nanostructured TiO(2) electrode

A zinc phthalocyanine with tyrosine substituents (ZnPcTyr), modified for efficient far-red/near-IR performance in dye-sensitized nanostructured TiO(2) solar cells, and its reference, glycine-substituted zinc phthalocyanine (ZnPcGly), were synthesized and characterized. The compounds were studied spectroscopically, electrochemically, and photoelectrochemically. Incorporating tyrosine groups into phthalocyanine makes the dye ethanol-soluble and reduces surface aggregation as a result of steric effects. The performance of a solar cell based on ZnPcTyr is much better than that based on ZnPcGly. Addition of 3alpha,7alpha-dihydroxy-5beta-cholic acid (cheno) and 4-tert-butylpyridine (TBP) to the dye solution when preparing a dye-sensitized TiO(2) electrode diminishes significantly the surface aggregation and, therefore, improves the performance of solar cells based on these phthalocyanines. The highest monochromatic incident photo-to-current conversion efficiency (IPCE) of approximately 24% at 690 nm and an overall conversion efficiency (eta) of 0.54% were achieved for a cell based on a ZnPcTyr-sensitized TiO(2) electrode. Addition of TBP in the electrolyte decreases the IPCE and eta considerably, although it increases the open-circuit photovoltage. Time-resolved transient absorption measurements of interfacial electron-transfer kinetics in a ZnPcTyr-sensitized nanostructured TiO(2) thin film show that electron injection from the excited state of the dye into the conduction band of TiO(2) is completed in approximately 500 fs and that more than half of the injected electrons recombines with the oxidized dye molecules in approximately 300 ps. In addition to surface aggregation, the very fast electron recombination is most likely responsible for the low performance of the solar cell based on ZnPcTyr.     

LONG WAVELENGTH UV RADIATION AFFECTS CHEMILUMINESCENCE OF HUMAN POLYMORPHONUCLEAR LEUCOCYTES

Abstract— Luminol-enhanced chemiluminescence in suspensions of human polymorphonuclear leucocytes stimulated with the chemotactic oligopeptide formyl-methionyl-leucyl-phenylalanine was increased by exposure of the cells to long wavelength UV radiation (mainly320–400 nm). Leucocytes treated with 0.3 × 10⁴ J m^-2 of UV responded with doubled peak values, and 4 × 10⁴ J m^-2 lead to a five-fold increase in peak chemiluminescence, as compared with non-exposed cells. Supernatants isolated from irradiated leucocytes contained increased amounts of both myeloperoxidase and lactate dehydrogenase and showed higher chemiluminescence values, when compared with supernatants from sham-irradiated cells. The results suggest that leucocyte degranulation contributes to the inflammatory properties of long wavelength UV.     

Gas chromatographic analysis of high-molecular-mass polycyclic aromatic hydrocarbons II. Polycyclic aromatic hydrocarbons with relative molecular masses exceeding 328

Three columns were used for the gas chromatographic analysis of polycyclic aromatic hydrocarbons (PAHs) with relative molecular masses (M_r) up to 450. Two of the columns were commercially available, coated with a 50% methyltrifluoropropyl-substituted polysiloxane a 5% diphenyl-substituted methylpolysiloxane. The third column was laboratory made, coated with a biphenyl-substituted silarylene-siloxane copolymer. All three columns were utilized for the analysis of high-M_r PAHs as regards both thermal stability of the stationary phases, i.e., low bleeding rate, and chromatographic efficiency. The column coated with a trifluoropropyl-substituted stationary phase showed, however, a low separation efficiency, possibly owing to low solute stationary phase compatibility. The biphenyl-substituted stationary phase, on the other hand, showed a very high separation efficiency, but the retention of the PAHs was significantly higher on this column compared with the other two, leading to the demand for higher oven temperatures. Different retention mechanisms were observed on these columns, as shown by differences in the retention indices of the PAHs measured in a system using PAHs as retention index markers. A comparatively faster elution of non-planar PAHs was observed on the columns coated with the trifluoropropyl-substituted stationary phase and the biphenyl-substituted stationary phase compared with the column coated with the 5% diphenyl-substituted polymer. The usefulness of the columns for separations of high-M_r PAHs is demonstrated by gas chromatograms of carbon black extracts and a coal tar extract standard reference material.     

Hard X-ray magnetochiral dichroism in a paramagnetic molecular 4f complex

Magnetochiral dichroism (MΧD) originates in the coupling of local electric fields and magnetic moments in systems where a simultaneous break of space parity and time-reversal symmetries occurs. This magnetoelectric coupling, displayed by chiral magnetic materials, can be exploited to manipulate the magnetic moment of molecular materials at the single molecule level. We demonstrate herein the first experimental observation of X-ray magnetochiral dichroism in enantiopure chiral trigonal single crystals of a chiral mononuclear paramagnetic lanthanide coordination complex, namely, holmium oxydiacetate, at the Ho L₃-edge. The observed magnetochiral effect is opposite for the two enantiomers and is rationalised on the basis of a multipolar expansion of the matter–radiation interaction. These results demonstrate that 4f–5d hybridization in chiral lanthanoid coordination complexes is at the origin of magnetochiral dichroism, an effect that could be exploited for addressing of their magnetic moment at the single molecule level.

Magnetochiral Dichroism of chiral mononuclear lanthanoid complexes is for the first time detected by X-ray absorption measurements on single crystals of Holmium oxydiacetate, at the Ho L₃-edge. The effect is of opposite sign for the two enantiomers.