Transport properties and electroanalytical response characteristics of drotaverine ion-selective sensors

The construction and electroanalytical response characteristics of poly(vinyl chloride) matrix ion-selective sensors (ISSs) for drotaverine hydrochloride are described. The membranes incorporate ion-association complexes of drotaverine with tetraphenylborate, picrate, tetraiodomercurate, tetraiodobismuthate, Reinecke salt, and heteropolycompounds of Keggin structure—molybdophosphoric acid, tungstophosphoric acid, molybdosiliconic acid and tungstosiliconic acid as electroactive materials for ionometric sensor controls. These ISSs have a linear response to drotaverine hydrochloride over the range 8×10^–6 to 5×10^–2 mol L^–1 with cationic slopes from 51 to 58 mV per concentration decade. These ISSs have a fast response time (up to 1 min), a low determination limit (down to 4.3×10^–6 mol L^–1), good stability (3–5 weeks), and reasonable selectivity. Permeabilities and ion fluxes through a membrane were calculated for major and interfering ions. Dependences of the transport properties of the membranes on the concentrations of the ion exchanger and near-membrane solution and their electrochemical characteristics are presented. The ISSs were used for direct potentiometry and potentiometric titration (sodium tetraphenylborate) of drotaverine hydrochloride. Results with mean accuracy of 99.1±1.0% of nominal were obtained which corresponded well to data obtained by use of high-performance liquid chromatography.     

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.     

1H detection in MAS solid-state NMR spectroscopy of biomacromolecules employing pulsed field gradients for residual solvent suppression

In this communication, we demonstrate the feasibility of 1H detection in MAS solid-state NMR for a microcrystalline, uniformly 2H,15N-labeled sample of a SH3 domain of chicken alpha-spectrin, using pulsed field gradients for suppression of water magnetization. Today, B0 gradients are employed routinely in solution-state NMR for coherence order selection and solvent suppression. We suggest to use gradients to purge water magnetization which cannot be suppressed using conventional water suppression schemes. The achievable gain in sensitivity for 1H detection is in the order of 5 compared to the 15N detected version of the experiment (at a MAS rotation frequency of 13.5 kHz). We expect that this labeling concept which achieves high sensitivity due to 1H detection, in combination with the possibility to measure long range 1H-1H distances as we have shown previously, to be a useful tool for the determination of protein structures in the solid state.     

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.     

The key elements of traceability in chemical measurement: agreed or still under debate?

Talking about "traceability" means talking about a "property of the result of a measurement", about "the value of a standard", about "stated references" and about an "unbroken chain of comparisons". It describes by which comparison, and to which other value, the result of a measurement has been obtained, i.e. is "traceable to". It is about the underlying structure of the measurement process of the result of a measurement and therefore about the authority of the result. Since values carried by (certified) reference materials have also been obtained by measurement, the definition of traceability equally applies. Traceability in the context of reference materials is also about the authority of the values carried by the (certified) reference materials and is, therefore, of key importance for the authority of the reference materials themselves. Hence, values of results of measurements constitute part of the traceability chain and their uncertainties are an intrinsic accompanying phenomenon. Uncertainties need a traceability chain against which they can be evaluated, and a traceability chain is an a priori requirement for evaluating the uncertainty budget of a measurement result. An attempt has been made to exemplify "traceability" chains in some types of chemical measurement and to identify the degree of international agreement on the key elements of "traceability". It is concluded that there is less than universal agreement on this issue. The debate should continue in order to arrive at the international understanding and agreement needed, as "traceability" is now being incorporated in the International Organization for Standardization (ISO), the International Laboratory Accreditation Co-operation (ILAC) and in other "guiding" or regulatory documents. It is also the reason why the Institute for Reference Materials and Measurements (IRMM) has taken up the study of the concept in its core programme on Metrology in Chemistry, and why it sponsored the Workshop in Bratislava.     

Synthesis of tetrahydroimidazo[1,5-b]-β-carboline derivatives with complex basic substituents

Novel tetrahydroimidazo[1,5-b]-β-carbolines derivatives 6 bearing complex basic chains as substituents on the imidic nitrogen have been prepared in a one-pot reaction. This simple experimental procedure overcomes the direct handle of isocyanates which can be favorably generated “in situ” from carbonyldiimidazole (CDI) and different amines. The stereochemistry of the novel compounds was determined by nmr experiments.     

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.     

Thermodynamic Data for the Complex Formation of Alkylamines and Their Hydrochlorides with α-Cyclodextrin in Aqueous Solution

The formation of complexes between α-cyclodextrin and n-alkylamines and their hydrochlorides has been studied in aqueous solution using calorimetric titrations. All alkylamines form stronger complexes than the corresponding hydrochlorides. The values of the reaction enthalpies are smaller for the alkylamine hydrochlorides compared with the alkylamines. By increasing the number of methylene groups, these differences become smaller. In addition, the reaction enthalpies for protonation of the alkylamines and their complexes with α-cyclodextrin have been measured. The heat of protonation of these complexes is always smaller compared with the alkylamines. Due to the protonation and the formation of a strong solvation shell around the ammonium group the interactions with α-cyclodextrins are weakened. From a thermodynamic cycle using all measured reactions, it can be concluded that the aggregation of the alkylamines with long alkyl chains (heptyl-, octyl-, and nonylamine) has an influence on the values of the reaction enthalpies and entropies for the protonated form only.This revised version was published online in July 2005 with a corrected issue number.