Riboflavin (Vitamin B2) Assay by Adsorptive Cathodic Stripping Voltammetry (Adcsv) at the Hanging Mercury Drop Electrode (HMDE)

In this study the interactions of Riboflavin (Vitamin B2) with a mercury surface are investigated. Firstly, by using Cyclic Voltammetry, it is demonstrated that Riboflavin can be efficiently accumulated, by adsorption from buffered solutions containing an excess of NaClO4, onto the mercury drop of a HMDE. Secondly, it is shown that the adsorbed Riboflavin can be reduced through an electrochemical reaction whose stoichiometry is extricated by confronting simulated with experimental CV voltammograms acquired in a range of pH between about four and nine. Finally, the cathodic current, sustained by the surface reduction of Riboflavin, is exploited for assaying Riboflavin via Differential Pulse Adsorption Cathodic Stripping Voltammetry (DP AdCSV) within the frame of the standard additions calibration procedure. By applying the suggested DP AdCSV procedure with standard voltammetric equipment, typical DP settings and pre-electrolysis time of about 10 s, a linear response is maintained if Riboflavin concentration in the electrolysed solution does not exceed about 2 mg/l. On the other side, a limit of detection (expressed as the concentration of Riboflavin in the electrolysed solution) of 7 μg/l has been achieved with a pre-electrolysis time of 68 s

A Strategy for GC/MS Quantification of Polar Compounds via their Silylated Surrogates: Silylation and Quantification of Biological Amino Acids

Substitution of polar functionalized compounds with silylated (e.g., trimethylsilylated) surrogates prior to GC/ MS analysis is a widely used analytical strategy. Calibration is a most demanding step of this strategy. In fact, a calibration function is usually acquired by converting known amounts of the pure analyte to its silylated surrogate using the same conditions employed for processing unknown samples. The cumbersome need of acquiring a new calibration function prevents, to a large extend, the possibility of modifying silylation and instrumental settings on a sample by sample basis as would be appropriate in a number of cases. The modified standard additions calibration method, suggested in this paper, overcomes this difficulty by integrating in a single analytical procedure calibration and sample analysis. Furthermore, the suggested procedure compensates for matrix effects which may be a serious source of inaccuracy and is a tool that can be used during method development in order to find the most suitable silylation conditions for a given analyte. The implementation and benefits of the modified standard additions calibration method are explored in this paper on the basis of a symbolic but enlightening experiment dealing with the very representative GC/MS quantification of biological amino acids via their trimethylsilylated derivatives

pH and Acid-Base Equilibrium Calculations via a Matrix Representation of Solutions of Acids and/or Bases

In this article we implement the idea of representing an aqueous solution of acids and/or bases with a matrix from which the pH and equilibrium concentrations of all species in any described solution can be extracted. Given that this matrix can be readily generated using an ad hoc MS Excel sheet, whatever pH calculation is reduced to the problem of selecting a row from the matrix by using as a guide the proton balance equation in the solution. A special scheme is presented allowing the needed proton balance relation to be derived from the specified solution data in all cases. This preserves the fundamental unity of the topic without sacrificing chemical understanding and simplicity. By consequence, the presented calculation technique is eminently suitable to be used in introductory courses as a complement, an extension or a substitute whenever the usual way of dealing with the topic (which, in general, consists in developing a menu of special cases, formulas and/or algebraic procedures) is judged insufficient. A MS Excel file named , attached to the present paper as supporting material, allows the matrix representation of any given solution to be developed in a very short time