New methods for the direct determination of dissolved inorganic, organic and total carbon in natural waters by Reagent-Free Ion Chromatography and inductively coupled plasma atomic emission spectrometry

New methods have been developed and applied successfully for the determination of dissolved inorganic, organic and total carbon in water samples. The new methods utilize two instrumental setups, Reagent-Free™ Ion Chromatography (RF™-IC) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Dissolved inorganic carbon (DIC) was measured in untreated samples along with Cl⁻, F⁻ and SO₄²⁻ using RF™-IC and by in-line mixing with 0.1 M HNO₃ to enhance CO₂ removal in the nebulizer, followed by ICP-AES analysis. Total dissolved carbon (TDC) was measured by in-line mixing with 0.1 M NaOH following ICP-AES analysis. Dissolved organic carbon (DOC) was obtained as the difference between DIC and TDC. Only non-volatile organic carbon could be detected by the present method. The workable limits of detection obtained in the present study were 0.5 mM (RF™-IC) and 0.1 mM (ICP-AES) for dissolved inorganic and organic carbon, respectively. The power of the new methods lies in routine analysis of DIC and DOC in samples of natural waters of variable composition and salinity using analytical techniques and facilities available in most laboratories doing water sample analysis. The techniques are sensitive and precise, can be automated using gas-tight sample vials and auto-samplers, and are independent of most elemental interferences with the exception of chloride overload by saline samples when using RF™-IC. The new methods were successfully applied for analysis of DIC and DOC in selected samples of natural and synthetic waters.     

Continuous analysis of δ¹⁸O and δD values of water by diffusion sampling cavity ring-down spectrometry: a novel sampling device for unattended field monitoring of precipitation, ground and surface waters

A novel sampling device suitable for continuous, unattended field monitoring of rapid isotopic changes in environmental waters is described. The device utilises diffusion through porous PTFE tubing to deliver water vapour continuously from a liquid water source for analysis of δ1?O and δD values by Cavity Ring-Down Spectrometry (CRDS). Separation of the analysed water vapour from non-volatile dissolved and particulate contaminants in the liquid sample minimises spectral interferences associated with CRDS analyses of many aqueous samples. Comparison of isotopic data for a range of water samples analysed by Diffusion Sampling-CRDS (DS-CRDS) and Isotope Ratio Mass Spectrometry (IRMS) shows significant linear correlations between the two methods allowing for accurate standardisation of DS-CRDS data. The internal precision for an integration period of 3 min (standard deviation (SD) = 0.1‰ and 0.3‰ for δ1?O and δD values, respectively) is similar to analysis of water by CRDS using an autosampler to inject and evaporate discrete water samples. The isotopic effects of variable air temperature, water vapour concentration, water pumping rate and dissolved organic content were found to be either negligible or correctable by analysis of water standards. The DS-CRDS system was used to analyse the O and H isotope composition in short-lived rain events. Other applications where finely time resolved water isotope data may be of benefit include recharge/discharge in groundwater/river systems and infiltration-related changes in cave drip water.     

Injection molded nanofluidic chips: fabrication method and functional tests using single-molecule DNA experiments

We demonstrate that fabrication of well-defined nanofluidic systems can be greatly simplified by injection molding of thermoplastic polymers. Chips featuring nanochannel arrays, microchannels and integrated interconnects are produced in a single processing step by injection molding. The resulting open channel structures are subsequently sealed by facile plasma-enhanced thermal bonding of a polymer film. This fast, inexpensive and industry-compatible method thus provides a single-use all-polymer platform for nanofluidic lab-on-a-chip applications. Its applicability for nanofluidics is demonstrated by DNA stretching experiments performed on individual double-stranded DNA molecules confined in the injection molded nanochannels. The obtained results are consistent with measurements performed in costly state-of-the-art silica nanochannels, for both straight and tapered channel geometries.     

SCS-pincer palladium-catalyzed auto-tandem catalysis using dendritic catalysts in semi-permeable compartments

Novel monometallic and dendritic SCS-pincer palladium complexes 2, 3 and 4 have been synthesized in good yields (60-89%) and high purity (palladium loading >97%). These complexes were successfully used as catalysts in the stannylation of cinnamyl chloride with hexamethylditin and in the catalytic auto-tandem reaction consisting of this stannylation followed by an electrophilic addition with 4-nitrobenzaldehyde, showing similar reaction rates and selectivities for all complexes. Dendritic complex 4 has furthermore been used in the compartmentalized catalysis of single and auto-tandem reactions, allowing catalyst reuse for four consecutive runs.     

Phase diagrams of colloidal spheres with a constant zeta-potential

We study suspensions of colloidal spheres with a constant zeta-potential within Poisson-Boltzmann theory, quantifying the discharging of the spheres with increasing colloid density and decreasing salt concentration. We use the calculated renormalized charge of the colloids to determine their pairwise effective screened-Coulomb repulsions. Bulk phase diagrams in the colloid concentration-salt concentration representation follow, for various zeta-potentials, by a mapping onto published fits of phase boundaries of point-Yukawa systems. Although the resulting phase diagrams do feature face-centered cubic and body-centered cubic phases, they are dominated by the (re-entrant) fluid phase due to the colloidal discharging with increasing colloid concentration and decreasing salt concentration.     

Effects of ionic strength, temperature and conformation on affinity interactions of β₂-glycoprotein I monitored by capillary electrophoresis

We have used CE to evaluate the interaction between β?-glycoprotein I (β?gpI) and heparin. β?gpI is a human plasma protein involved in the blood coagulation cascade. It is of interest to functionally characterize the interactions of β?gpI because the exact function is not entirely known and because circulating autoantibodies against β?gpI are associated with an increased risk of thrombotic events. The effect of the ionic strength, temperature, and conformation of the protein on the interaction between β?gpI and heparin has been studied. The CE procedure for this study is simple, fast, and automatic. β?gpI and heparin were allowed to interact during electrophoresis at different ionic strength buffers and at different capillary temperatures. To mimic perturbation of the conformation of β?gpI, different denaturing agents (SDS, ACN, and urea) were added to the BGE. While simple 1:1 binding isotherms were obtained at 22 °C, the data strongly suggest that at physiological temperature the binding stoichiometry is not 1:1 and/or that cooperative interactions begin to play a role. We found that (i) the K(D)-values differed by a factor of 60 at the ionic strengths studied (ii) β?gpI was resistant to denaturation with SDS and ACN, but was partially denatured by urea, and (iii) the K(D) for the β?gpI-heparin interaction in the presence of urea was ten times higher than the K(D) determined at the same conditions without urea added. Therefore, we conclude that the interaction between β?gpI and heparin is dependent on electrostatic interactions and on the conformation of β?gpI.     

Columnar self-assembly and alignment of planar carbenium ions in Langmuir-Blodgett films

Structural and optical properties of multilayer Langmuir-Blodgett (LB) films of two amphiphilic carbenium salts 2-didecylamino-6,10-bis(dimethylamino)-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-1) and 2,6-bis(decylmethylamino)-10-dimethylamino-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-2) are described. The LB films were prepared on lipophilic glass by standard vertical dipping. Grazing incidence X-ray diffraction (GIXD) measurements show that the planar organic cores, in spite of their positive charge, form closely packed columns with a repeating distance of ～3.45 ?. Specular X-ray reflectivity (SXR) reveals the LB multilayers to consist of Y-type bilayers with thickness 31 ? for ATOTA-1 and 41 ? for ATOTA-2. This significant difference is ascribed to the different packing motifs of the alkyl chains in the two LB films. GIXD and polarized UV-vis absorption and emission spectroscopy show that the columnar aggregates in the LB films are oriented along the dipping direction. This alignment is attributed to shear effects during LB transfer. The main absorption band of the LB films is blue-shifted compared to that in solution, while the fluorescence is red-shifted by more than 100 nm. These findings suggest the presence of H-aggregates in agreement with the cofacial packing derived from the X-ray measurements. Polarized absorption spectroscopy with variable angle of incidence was used to resolve two perpendicular optical transitions in the visible range, one at 460 nm polarized perpendicular to the columnar direction, in the plane of the film, and one at 420 nm polarized along the film normal.     

Enhanced transduction of photonic crystal dye lasers for gas sensing via swelling polymer film

We present the enhanced transduction of a photonic crystal dye laser for gas sensing via deposition of an additional swelling polymer film. Device operation involves swelling of the polymer film during exposure to specific gases, leading to a change in total effective refractive index. Experimental results show an enhancement of 16.09 dB in sensing ethanol vapor after deposition of a polystyrene film. We verify different responses of the polystyrene film when exposed to either ethanol vapor or increased humidity, indicating selectivity. The concept is generic and, in principle, straightforward in its application to other intracavity-based detection schemes to enable gas sensing.     

Cascaded mode-locking of a spectrally controlled Yb:KYW laser

Self-starting and stable mode-locking of an Yb:KYW laser in the picoseconds pulse regime has been achieved by exploiting a positive cascaded Kerr lens in periodically poled KTP. The use of a volume Bragg grating (VBG), for locking the output spectrum of the laser, was essential to achieve a stable mode-locked operation in this wide gain bandwidth laser material. The laser emitted stable, nearly transform-limited pulses with a duration of 16 ps, at a repetition rate of 210 MHz, and with an energy of 3.2 nJ. The mode-locked spectrum was centred at 1,029.1 nm and featured a FWHM bandwidth of 85 pm, which was effectively determined by the VBG. Combination of a large cascaded Kerr nonlinearity with spectral limiting by a VBG represents so far the best opportunity for stable mode-locking of a broadband laser to produce near-transform-limited picosecond pulses.     

On the Use of a Supramolecular Coarse‐Grained Model for the Solvent in Simulations of the Folding Equilibrium of an Octa‐β‐peptide in MeOH and H2O

Molecular dynamics (MD) simulation can give a detailed picture of conformational equilibria of biomolecules, but it is only reliable if the force field used in the simulation is accurate, and the sampling of the conformational space accessible to the biomolecule shows many (un)folding transitions to allow for precise averages of observable quantities. Here, the use of coarse‐grained (CG) solvent MeOH and H₂O models to speed up the sampling of the conformational equilibria of an octa‐β‐peptide is investigated. This peptide is thought to predominantly adopt a 3₁₄‐helical fold when solvated in MeOH, and a hairpin fold when solvated in H₂O on the basis of the NMR data. Various factors such as the chirality of a residue, a force‐field modification for the solute, coarse‐graining of the solvent model, and an extension of the nonbonded interaction cut‐off radius are shown to influence the simulated conformational equilibria and the agreement with the experimental NMR data for the octa‐β‐peptide.