Some causes of bending of analytical curves in atomic emission flame spectrometry

Factors affecting the shape of analytical curves in atomic emission flame spectrometry are discussed. Equations are presented by which the effect on the analytical curve of self-absorption, ionization, compound formation, variation in solution flow rate and atomization efficiency, entrance optics, and multiple spectral lines can be considered quantitatively. Theoretical and experimental curves are compared for Na introduced as aqueous NaCI solution into H₂/air, H₂/O₂, and C₂H₂/O₂ flames. The portion dealing with the effect of ionization, compound formation, and variation in solution flow rate and atomization efficiency on the atomic concentration in the flame applies as well to atomic absorption and atomic fluorescence flame spectrometry.     

Fundamental properties characterizing low-pressure microwave-induced plasmas as excitation sources for spectroanalytical chemistry

Experimental measurements of the spectroscopic temperature and the electron temperature in low-pressure rare gas plasmas sustained by a microwave generator operating at 2450 MHz have revealed divergent values. These measurements have been interpreted on the basis of a radiative recombination model originally proposed by Schlüter. The importance of Penning ionization by metastable rare gas atoms in the excitation of foreign atoms has been discussed in terms of this model.On the basis of the radiative recombination model for these plasmas, the parameters of analytical importance are the concentration and energy of electrons in a high energy electron group, the concentration and energy of electrons in a low energy electron group, and the concentration of metastable rare gas atoms. Measurements of the spectroscopic temperature of an argon plasma have revealed that the energy of electrons in the low energy electron group is not greatly affected by applied microwave power and pressure over the range from 1–25 torr. The energy of electrons in the high energy electron group is not greatly affected by pressure and applied microwave power over the range studied, but has been shown to depend on the ionization potential of the plasma gas. The total electron concentration is not greatly affected by gas pressure for low applied powers, but varies with applied power, particularly at low pressures. The concentration of metastable argon atoms has been shown to depend on both the applied power and pressure. Studies of the excitation of mercury by these plasmas have led to results which are consistent with the radiative recombination model.     

Solid-phase microextraction for the enantiomeric analysis of flavors in beverages

Solid-phase microextraction combined with gas chromatographic/mass spectrometric analysis and separation on a chiral cyclodextrin stationary phase was a rapid, reliable technique for profiling chiral aroma compounds in flavored alcoholic beverages. Several enantiomeric terpenes, esters, alcohols, norisoprenoids, and lactones were identified in berry-, peach-, strawberry-, and citrus-flavored wine and malt beverages (wine coolers). Using this technique, we were able to confirm the addition of synthetic flavoring to several beverages, consistent with label designations.     

Efficient light-driven carbon-free cobalt-based molecular catalyst for water oxidation

The abundant-metal-based polyoxometalate complex [Co(4)(H(2)O)(2)(PW(9)O(34))(2)](10-) is a hydrolytically and oxidatively stable, homogeneous, and efficient molecular catalyst for the visible-light-driven catalytic oxidation of water. Using a sacrificial electron acceptor and photosensitizer, it exhibits a high (30%) photon-to-O(2) yield and a large turnover number (>220, limited solely by depletion of the sacrificial electron acceptor) at pH 8. The photocatalytic performance of this catalyst is superior to that of the previously reported precious-metal-based polyoxometalate water oxidation catalyst [{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)](10-).     

Enthalpies of ionization for 2,3-diphosphoglyceric acid

A commercial titration calorimeter, modified to measure as little as 2 mcal in 2 mL, was used to perform thermometric titrations on 2,3-diphosphoglyceric acid with both tetraethylammonium hydroxide and sodium hydroxide. The enthalpies of ionization for each of the five ionizable protons on 2,3-diphosphoglyceric acid were derived from calorimetric data to be 0.0±0.3 kcal-mol^?1. Similar titrations with HCl on the penta-anion produced results that are consistent with the values derived from the titrations with base.     

An oxidatively-activated safety catch linker for solid phase synthesis

A N-benzyl-4-amino-2,2-dimethylbutanoic acid-based system has been developed as a new oxidatively activated safety catch linker for reaction monitoring and optimisation on solid support. The CAN promoted oxidative debenzylation of the tertiary N-benzylamine moiety, followed by concomitant cyclisation and release of alcohols and amines has been demonstrated both in solution phase model studies and on the solid phase. The linker system has been applied to the solid phase synthesis of a collection of phenol derivatives, and to the demonstration of the attachment and release of a chiral auxiliary from a solid support.     

Anion templated assembly of mechanically interlocked structures

This tutorial review describes the evolution of the field of chemical templation, in particular, emphasising the impact its application has made to the synthesis of mechanically interlocked structures. Recent advances in the use of negatively charged template species for the synthesis of interlocked structures are detailed, with the main focus of this review describing the development of a general anion templation strategy that combines anion recognition with ion-pairing. The versatility of this methodology is demonstrated by the chloride anion templated synthesis of a series of interpenetrated pseudorotaxane, rotaxane and catenane structures. Upon template removal, the mechanically interlocked rotaxanes and catenanes are shown to bind anions within their topologically unique anion binding clefts by virtue of electrostatic and hydrogen bonding interactions, exhibiting a strong selectivity for the chloride halide anion template. The incorporation of the photo-active rhenium(I) bipyridyl signalling group into the rotaxane structural framework highlights the potential of these interlocked systems in future chemical sensor design.     

Separation of two phenotypically similar cell types via a single common marker in microfluidic channels

To isolate clinically and biologically relevant cell types from a heterogeneous population, fluorescent or magnetic tagging together with knowledge of surface biomarker profiles represents the state of the art. To date, it remains exceedingly difficult to separate phenotypically and physically similar cell types from a mixed population. We report a microfluidic platform engineered to separate two highly similar cell types using a single antibody by taking advantage of subtle variations in surface receptor density and cell size. This platform utilizes antibody-conjugated surfaces in microfluidic channels together with precise modulation of fluid shear stresses to accomplish selective fractionation in a continuous flow process. Antibody conjugation density variation on the adhesive surfaces is achieved by covalently immobilizing an antibody in the presence of poly(ethylene glycol). This platform is used to demonstrate separation of two CD31 positive cell types, human umbilical vein endothelial cells and human micro vascular endothelial cells.     

Diophantinc approximation by linear forms on manifolds

The following Khintchine-type theorem is proved for manifoldsM embedded in ℝ ^k which satisfy some mild curvature conditions. The inequality |q·x| <Ψ(|q|) whereΨ(r) → 0 asr → ∞ has finitely or infinitely many solutionsqεℤ ^k for almost all (in induced measure) points x onM according as the sum Σ _r ^{= 1/∞} Ψ(r)r ^k−2 converges or diverges (the divergent case requires a slightly stronger curvature condition than the convergent case). Also, the Hausdorff dimension is obtained for the set (of induced measure 0) of point inM satisfying the inequality infinitely often whenψ(r) =r ^−t . τ >k − 1.