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Molecular Imprinting – Quantum Dots - Polyelectrolytes

Research group of Dr. Mikhail Beklemishev | e-mail

Current research

• Approaches to selective preconcentration of low-molecular-weight organic analytes based on self-organization (molecular imprinting)
o imprinting by polymerization in nanostructures (pores of track-etched membranes and nanoparticles)
o imprinting in polymers (polyelectrolyte multilayers) with subsequent cross-linking.

• Study of the regularities of the formation of optical analytical signal upon binding the analyte by quantum dots and molecularly imprinted structures; development of molecularly imprinted nanocomposite optical sensors. Search for approaches to visual imaging of small molecules in cells, tissues and organisms.

• Methods for the determination of water-soluble polymers based on their polymer nature.

Reseach Group Members

• Dr. Tatyana Samarina, Junior Research Scientist

• Darya Polyanina, Ph.D. student

• Undergraduate students

Current collaborations

Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia (Prof. P.Yu.Apel) – track-etched membranes
Division of Petroleum Chemistry and Organic Catalysis, Lomonosov Moscow State University (Dr. Aleksei Kudrinskii) – quartz crystal microbalance
Division of Inorganic Chemistry, Lomonosov Moscow State University (Dr. Sergei Dorofeev) – quantum dots

Some recent results

Molecular imprinting in polyelectrolyte multilayers

This is feasible for hydrogen-bonded layer-by-layer assemblies, preferably obtained from solutions of low water content (such as 91-96% ethanol), though imprinting from aqueous buffer solutions has also been demonstrated. The track-etched membranes were used as supports, and polyacrylic acid and polyallylamine as polyelectrolytes. Ionic liquid is useful in the deposition of the polymer multilayers, as it increases the ionic strength (impermeable membranes are obtained with from ionic strength solutions). The technique does not require cross-linking, though it might increase the quality of the impints. Polar compounds with ionizable groups (penicillins, Rhodamin B) can form the imprints, while less polar non-ionizable compounds (phytosterols) do not.

Imprinted membranes

• It was found that the molecularly imprinted membranes are conveniently prepared by photopolymerization of acrylic monomers on track-etched membrane in the presence of efficient photoinitiators. Introduction of transition metal salts (Cu(II) and Ni(II)) into the polymerization mixture improves the quality of imprints. The obtained membranes are highly permeable; they permit the separation of bioflavonoids not only from organic but also aqueous and aqueous-organic medium. The separation factor in pairs quercetin / rutin and quercetin / naringenin are 12–15, which is higher than in other systems.

Publications

Beklemishev M.K., Formanovskii A.A., Kuzmin N.M., Zolotov Yu.A. Nitrogen-containing derivatives of dibenzo-18-crown-6 as extractants. Zh. Neorg. Khim., 1986, vol. 31, No 10, p. 2617–2622.

Lischinsky V.L., Rahnyanskaya A.A., Pshezhetsky V.S., Beklemishev M.K., Formanovsky A.A. Features of binding transition metal salts by a nitrogen-containing polymeric ligand. Moscow Univ. Chem. Bull., 1987, vol. 28, No 6, p. 596–599.

Beklemishev M.K., Kuzmin N.M., Kardivarenko L.M. Extraction of silver complexes with aza-analogues of dibenzo-18-crown-6. Zh. Neorg. Khim., 1988, vol. 33, No 1, p. 185–189.

Morosanova E.I., Beklemishev M.K., Kardivarenko L.M. Silver dimeric complex extraction with a macrocyclic Schiff base and picrate ion. Zh. Neorg. Khim., 1988, 33(12), 3215–3217.

Beklemishev M.K., Kuzmin N.M., Zolotov Yu.A. Extraction and extraction kinetic determination of osmium using aza-analogues of dibenzo-18-crown-6. Zh. Analit. Khim., 1989, vol. 44, No 2, p. 356–362.

Beklemishev M.K., Panfilova S.E., Volynskii A.B., Kuzmin N.M., Zolotov Yu.A. Extraction-atomic-absorption determination of palladium using aza-analogues of dibenzo-18-crown-6. Moscow Univ. Chem. Bull., 1989, vol. 30, No 2, p. 168–171.

Beklemishev M.K., Gorodilova L.I., Shevtsov N.I., Kardivarenko L.M., Kuzmin N.M. Solvent extraction and extraction-X-ray fluorescence determination of thallium in single crystals of NaI(Tl) using aza-analogues of dibenzo-18-crown-6. Zh. Analit. Khim., 1989, vol. 44, No 6, p. 1058–1062.

Beklemishev M.K., Bazhenov D.V., Grishin Yu.K., Ustynyuk Yu.A. Study of mercury(II) chelation with aza-analogues of dibenzo-18-crown-6 by 1H and 13C NMR. Moscow Univ. Chem. Bull., 1989, vol. 30, No 4, p. 394–397.

Rodionova T.V., Beklemishev M.K. Continuous flow analysis. I. Determination of chromium(VI) with 1,5-diphenylcarbazide. Moscow Univ. Chem. Bull., 1990, vol. 31, No 6, p. 559–561.

Lishchinskii V.L., Nikolaeva L.S., Rahnyanskaya A.A., Beklemishev M.K., Kiryanov Yu.A., Evseev A.M., Pshezhetsky V.S. Mathematical modeling of extraction equilibria in the system polymeric azacrown ether – metal ion. Koord. Khim. 1991, vol. 17, No 8, p. 1025–1037.

Lishchinskii V.L., Nikolaeva L.S., Rahnyanskaya A.A., Beklemishev M.K., Mezhonova E.A., Kiryanov Yu.A., Evseev A.M., Pshezhetsky V.S. Mathematical modeling of extraction equilibria in the system polymeric azacrown ether – metal ion accounting on the polymer specificity of the ligand. Koord. Khim. 1991, vol. 17, No 8, p. 1314–1322.

Beklemishev M.K., Rodionova T.V., Chigvintseva E.V., Zolotov Yu.A. Continuous flow analysis. Determination of osmium by the catalytic reaction of p-phenylenediamine with hydrogen peroxide. Moscow Univ. Chem. Bull., 1992, vol. 33, No 5, p. 472–475.

Beklemishev M.K., Rodionova T.V., Dracheva L.V., Zolotov Yu.A. Continuous flow analysis. Determination of iron in technological solutions. Zh. Analit. Khim., 1992, vol. 47, No 7, p.1211–1217.

Shirinova A.G., Rodionova T.V., Beklemishev M.K., Ivanov V.M., Zolotov Yu.A. Continuous flow analysis. Photometric determination of nitrite ions. Zh. Analit. Khim., 1993, vol. 48, No 1, p.55–60.

Rodionova T.V., Kletskina E.V., Beklemishev M.K., Dracheva L.V., Zolotov Yu.A. Continuous flow analysis. Determination of copper in technological solutions. Zh. Analit. Khim., 1994, vol. 49, No 8, p. 813–816.

Beklemishev M.K., Elshani S., Wai C.M. Solvent Extraction of Radium with Crown Ether Carboxylic Acid. Analyt. Chem., 1994, vol. 66, No 20, p. 3521–3524.

Rodionova T.V., Benko M.A., Beklemishev M.K., Dracheva L.V. Sorption of manganese on oxidized activated carbon. Moscow Univ. Chem. Bull., 1995, vol. 36, No 6, p.551–555.

Beklemishev M.K., Stoyan T.A., Dolmanova I.F.. Sorption-Catalytic Determination of Manganese Directly on a Paper-Based Chelating Sorbent. Analyst, 1997, vol. 122, No 10, p. 1161–1165.

Efremova T.A., Beklemishev M.K., Shumsky A.N., Dolmanova I.F. Determination of manganese by a catalytic method using oxidation of 3,3',5,5'-tetramethylbenzidine with potassium periodate. Moscow Univ. Chem. Bull., 1998, vol. 39, No 4, p. 261–264.

Kapanadze A.L., Beklemishev M.K., Dolmanova I.F. Determination of organophosphorus pesticides by a catalytic method on TLC plates. Zh. Analit. Khim., 1999, vol. 54, No 11, p. 1182–1187.

Beklemishev M.K., Petrova Yu.Yu., Dolmanova I.F. Sorption-Catalytic Testing of Copper on a Paper-based Sorbent with Attached Alkylamino-groups. Analyst, 1999, vol. 124, No 10, p.1523–1527.

Beklemishev M.K., Kapanadze A.L., Bakhilina N.V., Dolmanova I.F. Accelerating Effect of Silica on the Indicator Reaction o-Dianisidine – H2O2. Talanta, 2000, vol. 51, no 2, p. 389–394.

Beklemishev M.K., Stoyan T.A., Dolmanova I.F. Sorption-catalytic determination of cadmium using bromobenzothiazo noncovalently bound to silica and paper. Fres. J. Anal. Chem., 2000, vol. 367, No 1, p. 17–23.

Petrova Yu.Yu., Beklemishev M.K., Bazhanova N.A., Druzhinin A.A., Dolmanova I.F. Determination of copper by its catalytic action in the oxidation reaction of hydrogen peroxide performed on carriers. Zh. Analit. Khim., 2000, vol. 55, No 3, p. 318–325.

Beklemishev M.K., Petrova Yu.Yu., Dolmanova I.F. Sorption-Catalytic Determination of Imazapyr on a Copper-Containing Sorbent. Mikrochim. Acta, 2001, vol. 136, No 1–2, p. 35–41.

Dolmanova I.F., Shekhovtsova T.N. Beklemishev M.K., Adsorption–Catalytic Test Methods. J. Analyt. Chem., 2002, vol. 57, No 10, p. 882–889.

Beklemishev M.K., Kozliak E.I. Bioremediation of Concrete Contaminated with nHexadecane and Naphtalene. Acta Biotechnol., 2003, vol. 23, pp. 197–210.

Beklemishev M.K., Petrova Yu.Yu., Abramova O.M., Dolmanova I.F. Sorption-catalytic method for the determination of nitrogen-containing organic compounds. Moscow Univ. Chem. Bull., 2003, vol. 44, No 2, p. 115–122.

Sofyina N.A., Beklemishev M.K., Kapanadze A.L., Dolmanova I.F.. Sorption-catalytic method for the determination of chromium. Moscow Univ. Chem. Bull., 2003, vol. 44, No 3, p. 193–198.

Shekhovtsova T.N., Dolmanova I.F., Beklemishev M.K. Novel Hybrid Sorption-Catalytic Method of Chemical Analysis. Egypt. J. Analyt. Chem., 2003, vol. 12, p. 9–13.

Popova I.E., Kiryushchenkov E.N., Filippova N.V., Beklemishev M.K. Determination of nickel(II) by its catalytic action in the oxidation of 3,3',5,5'-tetramethylbenzidine by periodate. Mendeleev Commun., 2004, vol. 14, No 5, p. 223–225.

Beklemishev M.K., Kiryushchenkov E.N., Stoyan T.A., Dolmanova I.F. A Catalytic Method for Determining Cadmium(II), Nickel(II), and Zinc(II) Inhibitor Metals. J. Analyt. Chem., 2005, vol. 60, No. 6, p. 589–595.

Popova I.E., Beklemishev M.K., Kozliak E.I. Bioremediation of Hydrocarbons from Contaminated Wood: A Proof-of-Concept Study. Engineering in Life Sciences, 2005, vol. 5, No 3, p. 223–233.

Beklemishev M.K., Kiryushchenkov E.N., Skosyrskaya E.K., Petrenko A.M., Periodate ion as an oxidant in the indicator reactions with aromatic amines in kinetic methods of analysis. J. Analyt. Chem., 2006, vol. 61, No. 11, p. 1067–1073.

Popova I.E., Beklemishev M.K., Frihart C.R., Seames W.S., Sundstrom T.J., Kozliak E.I. Penetration of naphthalene, n-hexadecane, and 2,4-dinitrotoluene into southern yellow pine under conditions modeling spills and floods. Forest Products J., 2006, vol. 56, Issue 6, p. 68–75.

Beklemishev M.K., Nikolaev I.V., Belyaeva L.Yu. Radical polymerization as indicator reaction for the determination of organic compounds. Moscow Univ. Chem. Bull., 2007, vol. 48, No 6, p. 407–417.

Kozel S.V., Skosyrskaya E.K., Beklemishev M.K. Kinetic Methods for Determining Water-Soluble Polymers. J. Analyt. Chem., 2008, vol. 63, No. 7, p. 693–699.

Belkova A.A., Sergeeva A.I., Apel P.Y., Beklemishev M.K. Diffusion of aniline through a polyethylene terephthalate track-etched membrane. J. Membr. Sci., 2009, vol. 330, No 1–2, p. 145–155.

Belyaeva L.Yu., Prokhorova A.F., Beklemishev M.K. Determination of Benzoate by Paper Chromatography with Visualization Due to Its Inhibitory Activity in the Reaction of the Photosensitized Autooxidation of Pyrogallol A. J. Analyt. Chem., 2010, vol. 65, No. 1, p. 64–70.

Belyaeva L.Yu., Beklemishev M.K. Determination of Glucose by a Kinetic Method on a Thin-Layer Chromatogram Using the Oxidation of 3,3',5,5'-Tetramethylbenzidine with Hydrogen Peroxide. J. Analyt. Chem., 2011, vol. 66, No. 4, p. 425–432.

Kryvshenko G.A., Beklemishev M.K. Determination of antioxidants by the reactions of oxidation of 3,3',5,5'-tetramethylbenzidine with persulfate and periodate. Khimiya Rastitel’nogo Syrya (Chemistry of Herbal Raw Materials), 2011, No 1, p. 123–128.

Kryvshenko G.A., Apel P.Yu., Abramchuk S.S., Beklemishev M.K. A highly permeable membrane for separation of quercetin obtained by nickel(II) ion-mediated molecular imprinting. Sep. Sci. Technol., 2012, vol. 47, No 12, p. 1715–1724.

Lohova L.O., Polyanina D.A., Beklemishev M.K. Molecular imprinting of penicillin V in polyelectrolyte layers deposited onto a track-etched membrane. Moscow Univ. Chem. Bull., 2014, vol. 55, No 1, p. 24–28.

Book chapters

Beklemishev M.K., Dmitrienko S.G., Isakova N.V. Extraction separation of elements and their subsequent determination. In the book. "Macrocyclic compounds in analytical chemistry", ed. Yu.A.Zolotov, N.M.Kuzmin. Moscow: "Nauka", 1993, 320 pp. P. 53–178 (in Russian).

Beklemishev M.K. and Wai C.M. Liquid Extraction, New Extraction Agents - Crown Ether Extractants. Chapter 3 in the book: "Separation Techniques in Nuclear Waste Management", T.E.Carleson, N.A.Chipman, C.M.Wai, editors. CRC Press, Boca Raton, FL. 1995, p. 47–67.

Beklemishev M.K., Dmitrienko S.G., and Isakova N.V. Solvent Extraction of Metals with Macrocyclic Reagents and its Analytical Applications. Chapter 3 in the book: Macrocyclic Compounds in Analytical Chemistry, ed. Yu.A.Zolotov. John Wiley & Sons, N.-Y., Chichester, ... , Toronto, 1997. P. 63–208.

Kinetic methods in environmental analysis. Chapter 10 in the book: Environmental samples and their analytical control. Book 2. Methods of environmental analysis. Ed. Shehovtsova T.N. Krasnodar, "Art Office", 2007. 380 pp. – P. 280–311 (in Russian).

Applied chemical analysis. A practical guide. (Barbalat Yu.A., Beklemishev M.K., Borzenko A.G. et al, ed. Shehovtsova T.N., Shpigun O.A.). Moscow University Publishing House, 2010. 456 pp. (in Russian).

Patents

Petrova Yu.Yu., Beklemishev M.K., Ginovker A.G. Pat. of Russia No 2225618. Method for the determination of copper(II) in serum. Priority of invention of June 18, 2001.

Kozliak E.I., Beklemishev M.K. Removal of toxic/hazardous chemicals absorbed in building materials. Pat. US 7144725 B2. 2003.

Kryvshenko G.A., Beklemishev M.K. Method of quercetin separation from aqueous solution. Patent application No 2011119249 of May 16, 2011. Pat. of Russia No 2458921 C1.