INTAS project 94-2522

NOVEL BONDED OXIDES WITH COVALENTLY IMMOBILISED ORGANIC LIGANDS FOR CHEMICAL SENSORS DEVELOPMENT

03.96 – 09.98


CO:      J. Legrand (IFREMER, FR)

RDs: T. Iskanderov (Nukus, Uzbekistan),
        V.Skopenko (Kiev, Ukraine),
        Dr. J.M. Slater (London, UK)


Scientific Objectives

 The analysis of the environment has some specific features, the most important being that the toxicity of substances depends on their chemical form; from the point of view there is a basic difference between free ions and ions bound in complex. Most instrumental analytical methods are only capable of determining the overall concentration of substances, and thus sensors' utilisation, yielding the activity of  the free ion content, is of a great importance in the study of ion distribution among various chemical forms. Another characteristic feature in environmental analyses is that it is important to compare the actual amount of a pollutant with a certain critical value that is considered to be the toxicity limit in the biosphere and is usually specified by a standard of law, rather than to determine the absolute content of the substance. Sensors fitted very well for this.

Besides utilisation of sensors for environmental monitoring have good prospects because:

All these generally represent a major improvement over existing assays, and that is why sensors become increasingly important for monitoring of environment.

Metal oxides with ligands covalently bonded to their surface constitute a new class of 2 dimensional compounds. Metal oxides and particularly silicas with monolayer of bonded groups are near to ideal object for development of sensitive matrix for remote chemical sensors  thanks to

  1. high kinetic characteristics (it is an opportunity to use then in on-line analysis),

  2. large surface(it leads to effective analytical signal) and c)high chemical and mechanical stability (they can be implanted in to a polymer membrane).

It is important that in case of  it utilisation for optical sensoring analytical signal can be evaluated both from diffuse reflectance (for thick tablets) and transmission (for membranes) spectroscopy.


 

SUMMARY OF RESULTS

A sets of materials (around 100 compounds) based on silica with immobilised luminescent dyes have been obtained. The dyes was designed to be selective for important pH region (6 – 9) and for interaction with toxic metal ions in water. Different modified silicon oxide matrixes were used to improve stability, selectivity and sensitivity of the dyes. For developing of  optical sensors few configuration of membrane that incorporate optically active materials were tested: transparent films and bids, resistible slides and disks. Adsorption and fluorescent emission spectra were recorded from the most perspective materials. It was shown that fluorescent of some samples strongly depends form solution pH and contamination of water by heavy metals. Chelating nature of modified silica increase sensitivity of sensors. It can be used for increasing analytical signal in diluted solutions. As a prototype of metal-selective chemical sensor benzoilphenyl­hydroxyl­amine silica gel was used since  correlation between iron concentration in water and optical response of the sensor was found.   

New chemically modified silicas with covalently bonded chelating groups of N-benzoyl-N-phenylhydroxylamine (SiO2-BPHA) were obtained in a three-step surface reaction. A chemisorption of hydrogen and some metal ions contamination present in sea water (Fe(III), V(V), Cu(II), Mn(II), Co(II), Ni(II), Pb(II), Cd(II)) from aqueous media was investigated. From the results of a quantitative physicochemical analysis it was found that dissociation constant of bonded BPHA considerably rose in comparison with dissociation constants of analogue in solutions. Bonded complexes with all studied metals were less stable. Linear correlation between sta­bility of complexes in solution and on the surface was found as log b(surf.) = log b (sol.) – 3.07. Strong fixation of counter-ions near surface charged groups was concluded from ex­periment. SiO2-BPHA demonstrates high selectivity towards Fe(III) and V(V) with selectivity coefficient Fe/Cu = 150 and Fe/Cd = 105. Linear correlation was found between  concentration of sorbed Fe3+ and Kubelka-Munk function from SiO2-BPHA that has been used for iron optical sensoring.