Removal of major interference sources in aqueous near-infrared spectroscopy techniques

This work describes a hybrid procedure for eliminating major interference sources in aqueous near-infrared (NIR) spectra, that include aqueous influence, noise, and systemic variations irrelevant to concentration. The scheme consists of two parts: extension of wavelet prism (WPe) and orthogonal signal correction (OSC). First, WPe is employed to remove variations due to aqueous absorbance and noise; then OSC is applied to remove systemic spectral variations irrelevant to concentration. Although water possesses strong absorption bands that overshadow and overlap the absorption bands of analytes, along with noise and systematic interference, successful calibration models can be generated by employing the method proposed here. We show that the elimination of major interference sources from the aqueous NIR spectra results in a substantial improvement in the precision of prediction, and reduces the required number of PLS components in the model. In addition, the strategy proposed here can be applied to various analytical data for quantitative purposes as well.     

The role of acidic residues and of sodium ion adduction on the gas-phase H/D exchange of peptides and peptide dimers

Gas-phase H/D exchange is widely used for characterizing the structure of ions. However, many structural parameters that affect the rate of H/D exchange are poorly understood, which complicates the interpretation of experimental data. Here, the effects of sodium ion adduction on the rate of H/D exchange with D₂O for a series of peptides and peptide dimers with varying numbers of acidic residues are described. The maximum number of sodium ion adducts that can be accommodated by the peptides and peptide dimers in this study is N + 1, where N is the number of free carboxylic acid groups. The formation of methyl-esters at all carboxylic acid groups, or the replacement of all the acidic hydrogens with sodium ions, effectively shuts down H/D exchange with D₂O. In contrast, both the rate and the extent of H/D exchange with D₂O are increased for most of the peptides and peptide dimers by the adduction of an intermediate number of sodium ions. These results are consistent with the H/D exchange occurring via a salt-bridge mechanism and show that the presence of two carboxylic acid groups is much better than one. The results with peptide dimers also indicate that surface accessibility may not be a dominant factor in the extent of H/D exchange for these ions.     

Nucleophilic substitution of hydrogen in meso-nitroaryl-substituted porphyrins—unprotected at the NH-centers in the core ring

Unprotected 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and 5,10-bis(4-nitrophenyl)-15,20-diphenylporphyrin react in the presence of a base at low temperature with carbanions (which bear a leaving group X at the carbanionic center) affording vicarious nucleophilic substitution of hydrogen (VNS) products in good yields (50-89%). The reactivity is explained in terms of the predominance of the porphyrin N-anion resonance forms at this temperature.     

Synthesis of the Deuterium Labeled Isoflavone-<Emphasis Type="Italic">O</Emphasis>-glucoside 8,3′,5′-D<Subscript>3</Subscript>-Daidzin

The regio- and stereospecific glycosylation of 8,3′,5′-trideuterodaidzein 1 with α-acetobromoglucose to provide 8,3′,5′-trideuterodaidzein-7-O-β-glucopyranoside 2 is presented.     

Structural Characteristics of Xyloglucan – Congo Red Aggregates as Observed by Small Angle X-ray Scattering

Xyloglucan is a type of hemicellulose with a cellulose backbone containing (1→6)-α-xylose or (1→2)-β-galactoxylose as a side chain. It is soluble in water. Its aqueous solution forms a gel or gel-like precipitate by addition of Congo red. Xyloglucan gel structures with various concentrations of Congo red were observed by small angle X-ray scattering (SAXS) at the nano-level. SAXS results indicated that the xyloglucan chains interacted with Congo red, and that an increase of concentration of Congo red induced a characteristic cross-linking domain, which consisted of a flat structure containing stacked xyloglucan chain assemblies. The Congo red molecules are inserted between the xyloglucan chains.     

Additivity Factors in the Binding of the Diethyltin(IV) Cation by Ligands Containing Amino and Carboxylic Groups at Different Ionic Strengths

Complex formation constants were determined potentiometrically (by a ISE-H⁺, glass electrode) in the systems, M²⁺ – L^z – H⁺ [M²⁺ = (C₂H₅)₂Sn²⁺, L^z = malonate, glycinate and ethylenediamine] at t = 25 ^∘C and 0.1 mol-L⁻¹≤ I/ ≤ 1 mol-L⁻¹ in NaCl_aq (0.1 mol-L⁻¹ ≤ I ≤ 0.75 mol-L⁻¹ for the ethylenediamine system). Thermodynamic values of formation constants, at infinite dilution, are [± 95% confidence interval, ^Tβ_pqr refer to the equilibrium, pM²⁺ + qL^z + rH⁺ = M_pL_qH_r^(2+z+r)]: for malonate, log₁₀ ^Tβ₁₁₀ = (5.47 ± 0.10); for glycinate, log₁₀ ^Tβ₁₁₀ = (9.54 ± 0.08), log₁₀ ^Tβ₁₁₁ = (12.97 ± 0.10); and for ethylenediamine, log₁₀ ^Tβ₁₁₀ = (10.47 ± 0.10), log₁₀ ^Tβ₁₂₀ = (16.17 ± 0.12) and log₁₀ ^Tβ₁₁₁ = (15.46 ± 0.10). The dependence on ionic strength of the formation constants was modeled by a simple Debye–Hückel type equation and by the SIT approach. By analyzing the stability of the species in the three different systems we found a simple additivity rule that can be expressed by the relationship: log₁₀ K = 6.46 n_N + 3.96 n_O − 0.60 (n_N²+ n_O²), with a mean deviation, ε(log₁₀ K) = 0.15 (K = equilibrium constant for the interaction of the organometal cation with the unprotonated or protonated ligand, n_N = number of amino groups and n_O = number of carboxylic groups of the ligand(s) involved in the formation reaction of complex species).     

Inclusion and fractionated release of nucleic acids using microcapsules made from plant cells.

The encapsulation and fractionated release of nucleic acids on vesicular packing (VP) materials have been investigated. The earlier described dependence of the permeation of nucleic acid molecules through the vesicle membranes on the salt concentration is a necessary precondition for both encapsulation and fractionation. Encapsulation is achieved by applying a suitable sample onto a VP column that has been equilibrated with a high-salt buffer. In that buffer the sample molecules are permeable. Immediately after sample application, elution is started with a low-salt buffer, from which the sample molecules are excluded. At the front between the two buffers the permeability changes, and some of the sample molecules distributed inside the vesicles cannot pass through the membranes. These encapsulated molecules can be released by increasing the salt concentration in the eluent. If the encapsulated nucleic acid sample is polydisperse, a stepwise or linear increase in the salt concentration leads to a fractionated release. The fractions obtained differ in their molecular size composition.     

Simultaneous determination of chromium(III) and chromium(VI) in aqueous solutions by ion chromatography and chemiluminescence detection.

A method for the simultaneous determination of chromium(iii) and chromium(vi) in a flow system based on chemiluminescence was developed. A Dionex cation-exchange guard column was used to separate chromium(iii) from chromium(vi), and chromium(vi) was reduced by potassium sulfite, whereupon both species were detected by use of the luminol-hydrogen peroxide chemiluminescence system. Linear calibration for both species was established over the concentration range 1-1000 micrograms l-1. The precision at the 20 micrograms l-1 level was 3.5% for chromium(iii) and 3.3% for chromium(vi), respectively. The detection limit was 0.5 micrograms l-1 for both species. Data were in agreement with Zeeman-effect background corrected atomic absorption spectrometry measurements.     

Ferrocenecarbothioamide and N-ethoxycarbonylferrocenecarbothioamide: Synthesis, structure and application in synthesis of 2,4-diferrocenylthiazole

Ferrocenecarbothioamide (1) and its N-ethoxycarbonyl derivative (2) were synthesised by a Friedel-Crafts type reaction of ferrocene with potassium thiocyanate and ethoxycarbonyl isothiocyanate, respectively, in a strongly acidic medium. The X-ray structure of 1 was determined and shows conjugation between the ferrocene moiety and the thioamido group. Compound 1 reacts with chloroacetylferrocene affording 2,4-diferrocenylthiazole, whose structure was determined by X-ray diffraction and electronic properties studied by cyclic voltammetry.     

Ionene–surfactant complexes: temperature and humidity sensitive materials

Solid stoichiometric complexes of [3,12]-ionene and dodecyl sulfate form upon reaction of the bromide of the ionene and the silver salt of dodecyl sulfate in methanol. IR, DSC, and TG investigations indicated that the solid complexes are stable between 30 and 120 °C. TG and DSC also showed that the complexes easily take up water at ambient conditions. These samples are optically isotropic. When exposed to an increased humidity they exhibit optical anisotropy, i.e., birefringence, which is caused by the formation of a hexagonal mesogenic phase. Mesogenicity is necessarily accompanied by a further uptake of water (4–5 H₂O molecules per ionic unit), which is dependent on the relative humidity. The phase behavior as a function of temperature and controlled relative humidity was studied using birefringence measurements and polarizing microscopy.