Mössbauer study of some novel iron-bis-glyoxime and iron-tris-glyoxime complexes

Dioximes as ligands are used as analytical reagents and serve as models for biological systems as well as catalysts in chemical processes. A number of novel mixed complexes of the type [Fe(DioxH)2(amine)2] have been prepared and characterised by FTIR, 57Fe Mössbauer and mass spectroscopy by us. We have found strong Fe–N donor acceptor interactions and iron occurred in low-spin FeII state in all complexes. Later, we have also found that the incorporation of branching alkyl chains (isopropyl) in the complexes alters the Fe–N bond length and results in high-spin iron(II) state [1, 2]. The question arises: can the spin state of iron be manipulated generally by replacing the short alkyl chains with high volume demand ones in Fe-azomethine-amine complexes? To answer the question we have synthetized novel iron-bis-glioxime and iron-tris-gloxime complexes when long chain alkyl or aromatic ligands replaced the short alkyl ones and studied by 57Fe Mössbauer spectroscopy, MS, FTIR, UV-VIS, TG-DTA-DTG and XRD methods. Novel iron-bis-glyoxime and iron-tris-glyoxime type complexes, [Fe(Diethyl-Diox)3(BOH)2], [Fe(Diethyl-Diox)3(BOEt)2] and [Fe(phenyl-Me-Diox)3(BOEt)2], were synthesized similarly as described in [2]. The FTIR, UV-VIS, TG-DTA-DTG and MS measurements indicated that the expected novel complexes could be successfully synthesized.

Retention of Activity by Antibodies Immobilized on Gold Nanoparticles of Different Sizes: Fluorometric Method of Determination and Comparative Evaluation

Antibody–nanoparticle conjugates are widely used analytical reagents. An informative parameter reflecting the conjugates’ properties is the number of antibodies per nanoparticle that retain their antigen-binding ability. Estimation of this parameter is characterized by a lack of simple, reproducible methods. The proposed method is based on the registration of fluorescence of tryptophan residues contained in proteins and combines sequential measurements of first the immobilized antibody number and then the bound protein antigen number. Requirements for the measurement procedure have been determined to ensure reliable and accurate results. Using the developed technique, preparations of spherical gold nanoparticles obtained by the most common method of citrate reduction of gold salts (the Turkevich–Frens method) and varying in average diameter from 15 to 55 nm have been characterized. It was shown that the number of antibodies (immunoglobulins G) bound by one nanoparticle ranged from 30 to 194 during adsorptive unoriented monolayer immobilization. C-reactive protein was considered as the model antigen. The percentage of antibody valences that retained their antigen-binding properties in the conjugate increased from 17 to 34% with an increase in the diameter of gold nanoparticles. The proposed method and the results of the study provide tools to assess the capabilities of the preparations of gold nanoparticles and their conjugates as well as the expediency of seeking the best techniques for various practical purposes.

SORPTION OF BISMUTON (III) IONS FROM AQUEOUS SOLUTIONS BY SILICAS MODIFIED BY ORGANIC REAGENTS

In current paper, adsorbents based on silica L 40/100 modified with 4-(2-pyridylazo)resorcinol, 1-(2-pyrylazo)naphthol‑2, pyrocatechol violet and sodium N, N‑diethyldithiocarbamate were obtained. Adsorbents were modified by non-covalent immobilization of organic analytical reagents on the silica surface. It is noted that the preparation of such adsorbents is fast and easy to manufacture. The conditions of Bismuth (III) adsorption from dilute aqueous solutions by the proposed adsorbents are studied and optimized. The optimal values of the medium acidity for the effective Bismuth (III) preconcentration by the proposed adsorbents based on silica modified with organic analytical reagents have been established. It is shown that the use of modified silicas allows efficient (95–98%) removal of Bismuth (III) from dilute aqueous solutions. Under optimal adsorption conditions, the capacity of modified adsorbents is determined. It is established that the modification of silica leads to a significant (2–3 times) increase in the capacity of the obtained sorbents by Bismuth (III) in comparison with the unmodified silica, which is associated with the processes of complexation on the surface. The desorption of Bismuth (III) from the surface of unmodified and modified silicas by solutions of mineral acids has been studied. It is shown that Bi(III) is quantitatively desorbed from the surface of unmodified silicas by solutions of sulfuric and nitric acids, and in the case of modified silicas the degree of desorption is small and does not exceed 35%. The data obtained can then be used to develop a test system for determination of Bismuth (III) via corresponding colorimetric scales or for quantitative solid phase extraction and adsorption-spectroscopic quantification of Bismuth (III) in some real samples.