Laboratory of Langmuir-Blodgett technology

Research Institute of Macroheterocyclic compounds

Ivanovo State University of Chemistry and Technology

Head of the LaboratoryLarissa A. Maiorova, Doctor of Science (Phys. and Math.), leading researcher (a.k.a. Valkova L.A.)

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Research interests are development of experimental and theoretical bases of controlled self-assembling of complex organic compounds and construction of low-dimensional functional nanoarchitectures in confined space at nanolevel: at a gas-liquid interface, in films on solid substrates and in nanoengineered capsules.

The author of the concept of nanostructuring of organic compounds at the liquid-gas interface, according to which the structural units of the layer in the general case are not individual molecules (Langmuir approach), but their M-nanostructures formed as a result of self-assembling.  The main provisions are set forth in the works:

Maiorova L.A., Koifman O.I. The concept of nanostructuring of macroheterocyclic compounds at the liquid-gas interface and nanomaterials based on supermolecules formed on the surface of water, Chapter 18, pp. 701-740 in Monograph: «Functional materials based on tetrapyrrole macroheterocyclic compounds» ed by Koifman O.I. (in Russ.), M.: LENAND, 2019, 848 p.  ISBN 978-5-9710-6952-2

Maiorova L.A. Controlled Self-Assembling of Azaporphyrins in 2D- and 3D-Nanostructures in Langmuir Layers and Langmuir-Blodgett Films. Doctor of Science Dissertation (in Phys. and Math.), Russia, 2012, 328 P

Valkova (Maiorova) L.A., Zyablov S.V., Koifman O.I., Erokhin V.V. Nanoaggregates in floating layers of azaporphyrins Journal of Porphyrins and Phthalocyanines 2010, 14(6), 513-522

Valkova (Maiorova) L.A., Glibin A.S., Valli L. Quantitative analysis of compression isotherms of fullerene C60 Langmuir layers, Colloid Journal 2008, 70(1), 6-11

A fundamentally new result obtained using the basic principles of the concept is the possibility of the formation of a special type of nanostructures (supermolecules), the intermolecular interactions in which and the properties are radically different from the properties of the starting compounds (Figure 1). Presented in the article:

L.A. Maiorova, N. Kobayashi, S.V. Zyablov, V.A. Bykov, S.I. Nesterov, A.V. Kozlov, Ch.H. Devillers, A.V. Zavyalov, V.V. Alexandriysky, M. Orena, O.I. Koifman Magnesium porphine supermolecules and two-dimensional nanoaggregates formed using the Langmuir-Schaefer technique. ACS Langmuir 2018, 34(31), 9322-9329

The main directions of the research in the Laboratory

  • Nanoarchitectures of macroheterocyclic compounds formed in confined space at the nanolevel (at the gas-liquid interface, in thin films and in nanoengineered capsules);
  • Supermolecular porphyrin nanomaterials;
  • Reactions in two-dimensional layers at the gas-liquid interface (polymerization, complexation, etc.);
  • Layers and films with the active state of the functional component, thin-film sensors and catalysts;
  • Systems for targeted drug delivery (vitamin B12, chlorin e6, etc.);
  • Structure of floating layers, films and capsules according to X-ray reflectometry (XRR) and Grazing incidence X-ray diffraction (GIXD and GISAXS);
  • Theory of the condensed state. Generalized state equation of a nanostructured floating M-layer

The main scientific results

Theory

  • The concept of nanostructuring of complex organic compounds at the gas–liquid interface was proposed and developed [Doctor of Science Dissertation 2012Chapter 18 in Monograph 2019];
  • A model of a nanostructured layer on the surface of the liquid (M-monolayer) was built. The physical basis of model consists in representation of the monolayer as real two-dimensional gas whose structural units can be separate molecules (Langmuir layer) as well as their nanoaggregates (M-layer). Parameters of the model are quantitative characteristics of structure and properties of the layer [Colloid Journal 2008, Journal of Porphyrins and Phthalocyanines 2010];
  • A method for the quantitative analysis of compression isotherms and determination of the structure of the M-monolayer was developed, new characteristics of the structure and properties of the layer and methods for their presentation were introduced. The first M-isotherm and state diagram are determined [J. Porphyrins Phthalocyanines, 2018]. A passport of floating layers containing borders of existence regions and corresponding characteristic of layers of different structure is composed [BioNanoScience, 2017]. Foundations for creation of the knowledge base on floating layers of compounds are developed

Experiment

  • For the first time, stable 3D nanostructures of the same size of copper porphyrazine, which, when studied by X-ray scattering, manifest themselves as a whole were formed [ACS Langmuir 2008];
  • The first porphyrin supermolecules— unique nanostructures with strong non-covalent intermolecular interactions whose properties are radically different from the properties of the starting compound were discovered (ACS Langmuir, 2018);
  • The formation of vitamin B12 nanostructures in polymer capsules has been established [Colloids and surfaces B: Biointerfaces, 2019]

The significance of the tasks is determined by the fact that the processes of nanostructuring of biologically active compounds, in particular, chlorophyll a derivatives, the most important functions of which, in nature, are carried out precisely in ensembles are studied. Their properties are determined by the structure of the ensemble. Such compounds are actively used in catalysis and in medicine, where their aggregate behavior directly determines the properties of the material.

The results obtained make it possible to use the Langmuir-Blodgett technology as a tool for studying and forming 2D and 3D nanoarchitectures, including supermolecules of organic compounds, carrying out reactions in such layers and obtaining fundamentally new types of nanomaterials on their basis.

Areas of practical application of the results are as follows: (1) nano- and biotechnologies – new methods for obtaining of biomedical nanomaterials based on nanoarchitectures of biologically active compounds; (2) photonics – optical nanomaterials and photosensitizers; (3) ecology – water purification (decomposition of organic impurities); oxidative modification of natural compounds, including natural antioxidants; (4) pharmacology –  new drugs and their targeted delivery.


GRANTS and PROJECTS

- International Project Russia-Italy-France. Participants: Russia - Ivanovo State University of Chemistry and Technology and Kazan (Privolzhsky) Federal University; Italy - Institute of Materials for Electronics and Magnetism of the National Council for Scientific Research (Istituto dei materiali per l'elettronica ed il magnetismo - IMEM), Parma and the University of Genova (DIBRIS); France - Grenoble, ESRF.

Project № SC-4819 "X-ray reflectivity, GIXD and GISAXS study of unique nanostructures – magnesium porphine supermolecules at the air-water interface" of European Synchrotron Radiation Facility (ESRF), Grenoble, France, 2018;

- International Project (Russia-Italy). Participants: Russia - Ivanovo State University of Chemistry and Technology and Kazan (Privolzhsky) Federal University; Italy - Institute of Materials for Electronics and Magnetism of the National Council for Scientific Research (Istituto dei materiali per l'elettronica ed il magnetismo - IMEM), Parma and the University of Ancona (Department of Materials, Environmental Sciences and Urban Planning SIMAU). Project № SC-4673 "Identification and structural study of new unique nanostructures– magnesium porphine supermolecules at the air-water interface" of European Synchrotron Radiation Facility (ESRF), Grenoble, France, 2017;

Grant of the Polytechnic University of Marche (Italy) for a visiting scientist (Maiorova LA) at the Università Politecnica delle Marche, Department of Materials, Italy, May-June 2016;

Grant RFBR (2015-2017) № 15-42-03211-а Section: "Physics"; Title: "Nanostructures of amphyphilic calixarenes in Langmuir layers as a mean for control of structural organization in drugs";

- Grant of RFBR (2012-2014) Section: "Physics", № 12-02-00015-а, Title: "Nanostructured Langmuir-Blodgett films of porphyrins for thin-film photosensitive materials";

- Project of Ministry of Education and Science оf Russian Federation (2010-2012), Federal target program "Scientists and teachers of innovative Russia" in Scientific direction “Nanotechnologies and nanomaterials”, Project “Nanostructured monolayers and LB films based on porphyrins for thin-film materials”, State Contract 14.740.11.0268;

- Grant of RFBR № 08-02-00103-а (2008-2010), Section: "Physics"; Title: "A study of formation of nanoaggregates in floating layers and Langmuir-Blodgett films of fullerene C60";

- Grant of RFBR № 08-08-00644 Fundamentals of Engineering Sciences "Study of nanostructures in monomolecular layers and thin films of azaporphyrins"

The total amount of received grants is 20.6 million rubles.


Articles published in the Journals:

ACS: Langmuir (Q1, 2018, 2008), Colloids and surfaces B: Biointerfaces (Q1, 2019), Electrochimica Acta (Q1, 2014), BioNanoScience (2018), Journal of Porphyrins and Phthalocyanines (2018, 2011, 2010), Molecular Crystals and Liquid Crystals (2017), Macroheterocycles (2019, 2018, 2016, 2014, 2011), Russian Chemical Bulletin, (2013),  Protection of metals and physical chemistry of surfaces, 2015, Colloid Journal, 2008 and others.

The dissertation works

The dissertation works, studies on which in terms of studying the Langmuir layers and LB films were performed in the laboratory were defended:

  • Maiorova L.A. "Controlled self-organization of azaporphyrins in 2D and 3D nanostructures in Langmuir layers and Langmuir-Blodgett films", Doctor of Science in Phys. and Math. (2012).
  • Fokin Dm.S. "Physico-chemical properties and use of phenylbenzoate derivatives, azo- and azoxybenzenes with polar substituents," PhD (2011)
  • Wu Thi Thao (Vietnam) "Metalloporphyrinoids: stability in solution and solid phase, features of electrocatalysis and thin-film materials based on them", PhD (2016)

Main equipments

Langmuir-Blodgett troughs: "KSV NIMA" (commissioned in 2018) and "NT-MDT, Zelenograd, Russia"; high purity water preparation system


Young scientist’s research

In the Laboratory, PhD and master's dissertations, as far as scientific works of students in the direction "Nanostructures in Langmuir layers and Langmuir-Blodgett films of complex organic compounds" are carried out. For undergraduates of the 1st and 2nd year of study, a special course (lectures and practical exercises) "The scientific foundations of nanotechnological processes" was developed. The total number of prepared dissertations, works of specialists and bachelors is 21. Graduates are prepared for creative work at high-tech enterprises working in the field of nano- and biotechnologies, including those involved in the development of new effective personalized drugs

 

Prizes and diplomas

Vu Thi Thao (Vietnam)

  • First prize at the 9th competition for projects of young scientists at the International Exhibition of the Chemical Industry and Science "Chemistry - 2015" Expocentre, Moscow, for the oral presentation "Thin-film nanomaterials and electrocatalysts based on aromatic derivatives of vitamin B12 and their metal complexes", October 28-29, 2015;
  • A diploma for the best poster presentation "Obtaining of monomolecular layers of 5,10,15-triphenylcorrole" at the X All-Russian School-Conference of Young Scientists "Theoretical and Experimental Chemistry of Liquid-Phase Systems" (Krestovsky Readings), 2015, Ivanovo.

Kharitonova N.V.

  • In 2017-2018 and in the 2018-2019 academic years - an increased scholarship for success in research;
  • Winner of the contest "The best graduate of ISUCT 2017";
  • Diploma for active participation in the IX International Conference "Kinetics and the mechanism of crystallization. Crystallization and materials of the future", September 13-16, 2016;
  • A letter at the All-Russian Scientific Conference "Fundamental Sciences - to a specialist in the new century, DAYS OF SCIENCE AT ISUCT", April 16-18, 2018

Krygin Yu.Yu.

  • Second place for an oral report at the IX All-Russian Olympiad of young scientists and the international scientific conference "Nanostructured, fibrous and composite materials", St. Petersburg State University of Technology and Design, 2013

Scientific collaboration

Interdisciplinary scientific problems are solved in collaboration with experts in the field of Thin-film physics (Sorokin AV Ph.D. in Phys. and Math.); Mathematical modeling and programming (Zyablov SV); X-ray diffraction analysis (Dr O. Konovalov - ESRF,  France; Volkov VV Ph.D. in Phys. and Math., Yanusova LG Ph.D. in Phys. and Math., Astafiev SB Ph.D. in Phys. and Math. – Institute of Crystallography RAS, Moscow); Theoretical physics (Rutenberg ML Ph.D. in Phys. and Math. and Volkov AV Ph.D. in Tech.); Chemical synthesis and catalysis (ISUCT - Corresponding Member of RAS, Doctors of Chemical Sciences Koifman O.I., Doctors of Chemical Sciences: Kudrik EV, Berezin DB, Semeikin AS, Lyubimtsev AV; Ph.D. in Chem. - Ageeva TA, Salnikov DS and Romanenko YuV.; ISC RAS: Doctor of Chemical Sciences Mamardashvili NZh); Pharmacology (Gromova O.A. Doctor of Medical Sciences - Institute of Pharmacoinformatics, Federal Research Center “Computer Science and Control”, Russian Academy of Sciences, Moscow); Targeted drug delivery (Italy: Dr V. Erokhin and Dr S. Erokhina - Institute of Materials for Electronics and Magnetism of the National Council for Scientific Research, Parma; Dr M. Pisani, Prof. G. Barucca and Prof. M. Orena - Polytechnic University of Marche, Ancona); AFM and TEM microscopy (Doctor of Technical Science VA Bykov and SI Nesterov Ph.D. in Phys. and Math.- Research Institute of Physical Problems and NT-MDT, Zelenograd, Russia and Prof. M. Marcaccio, Italy)

International conferences and seminars

Reports and  lectures in Italy and China

- Lectures "Supermolecules of magnesium porphine", Istituto dei materiali per l'elettronica ed il magnetismo (IMEM), Parma, Italy, March 2017 and "Advances in low-dimensional nanoconstructing of new metal-organic species by using Langmuir-Blodgett technology", Shanxi Normal University, Xian, China, November 2016

- Series of lectures "Nanostructured thin-film organic materials. Formation, structure, properties" Università Politecnica delle Marche, Department of Materials, Environmental Sciences and Urban Planning SIMAU, Italy, May-Jun 2016:

  • Nanostructured Langmuir layers of the organic compounds. A state equation, model, structure and properties
  • Controlled self-organization of 2D and 3D nanostructures of organic compounds at the gas-liquid interface and in Langmuir-Blodgett films
  • Nanostructures of liquid crystal compounds in floating monolayers and Langmuir-Blodgett films
  • Self-organization of corroles and calixarenes in Langmuir layers
  • Supermolecular nanomaterials of tetrapyrrolic compounds. Formation and study.

Oral presentations at the International conferences

IX-th International conference on organized molecular films (LB-IX, Potsdam, Germany, 2000), VIII-th European conference on organized films (Otranto, Lecce, Italy, 2001), XI-th European conference on organized films ECOF-XI (Potsdam, Germany 2008), XI-th International conference on physical and coordination chemistry of porphyrins and their analogues (ICPC-11, Odessa, Ukraine, 2011), VII-th International conference on porphyrins and phthalocyanines (ICPP-7, Korea, 2012), VII-th International symposium "Design and Synthesis of Supramolecular Architectures" (Kazan, Russia, 2014), VIII International conference on porphyrins and phthalocyanines (ICPP-8, Istanbul, Turkey, 2014), 6th International conference "Nanoparticles, Nanostructured Coating and Microcontainers: Technology, Properties, Applications" (Saratov, Russia, 2015), IX International conference on porphyrins and phthalocyanines (ICPP-9, Nanjing, China, 2016), X International conference on porphyrins and phthalocyanines (ICPP-10, Munich, Germany, 2018), 8th International Workshop "Organic electronics of highly-correlated molecular systems" (Suzdal, Russia, 2018), XIII International Conference “Synthesis and Application of Porphyrins and Their Analogues ICPC- XIII“, Silver Ploys, Russia (plenary lecture) 2019.