Laboratory 1-7. Physical chemistry of solutions of macrocyclic compounds

Scientific direction: 
Chemistry and physical chemistry of solutions, theoretical foundations of chemical-engineering processes in liquid media

Research activities:


  The theme: «Investigation of solvation, coordination and photophysical properties of linear and macrocyclic oligomers: alkyl-substituted bis(dipyrrolyl methenes) with methylene  spacer, metal-complexes of tetraphenyl porphyn and water soluble phthalocyanines, glymes»


Basic problems, results and the current state of investigations:


  • The problem of cyclic form and molecules size influence on their condition in various media in comparison with their linear analogs is studied. On a vast data set on enthalpy of solvation and partial molar volumes of cyclic polyesters with various size of molecules (from 1,4-dioxan up to 18-crown-6) in various solvents is obtained. The approach to the analysis of thermodynamic characteristics of solvation on the basis of scale corpuscles theory of and an additive-group method is developed. The presence of the ring formation effect during solvation, most vividly manifested for minor cycles is shown. Abnormal features of ether rings in the processes of specific interact with various organic molecules (formation of H-bond and complexes of electrostatic nature) in comparison with linear ethers are detected. Regularity of these specific interactions modeling biochemical processes of selective linkage of molecules by pseudo-cyclic corpuscles are studied. (Research in charge is Barannikov V.P.). 
  • Processes of molecular complexation of porphyrins, phthalocyanines and their metallocomplexes with various ligands are studied. More than 300 systems with porphyrins have been investigated, as well as thermodynamic characteristics of molecular complexation processes of natural and synthetic metalloporphyrins with amines, amides, azoles, ketones, ethers, aldehydes, nitriles, alcohols. At a quantitative level it is shown, that thermodynamic stability of molecular complexes of metalloporphyrins with ligands, is mostly dew to polarization properties of ligands, and in a less extent depends on electron-donor ability and volume of coordinated molecules. Correlation dependence of thermodynamic stability of the formed ZnTPhP complexes with ligands on physical and chemical properties of coordinated polar molecules is established. The parameter of basic capacity (a scale of basic capacity) of polar molecules in the organic solvents, considering the polarization, electron-donor properties of polar molecules, solvation and steric effects is developed on the basis of complexation characteristics with metalloporphyrins. 
  • Affinity of sulfo- and carboxy-replaced metallophthalocyanines to dimerization in aqueous media is studied. The opportunity of the control  aggregative conditions of metallophthalocyanines by means of molecular complexation with proton- and electron-donor ligands is investigated. 
  • Effect of specific intermolecular interactions of metallophthalocyanines with solvent molecules on the formation of stable or metastable polymorphic modification of metallophthalocyanine at crystallization from matching solvent is studied. Theoretical bases of forecasting of the desired of polymorphic modification metallophthalocyanine under its crystallization from organic solvents are developed (Research in charge is Lebedeva N.Sh.) 
  • Fundamental problems of chemistry of natural tetrapyrrol compounds:
    • Molecular mechanisms of toxic act in of bile pigments on alive organisms; 
    • Creation of effective techniques of inactivation and quantitative analysis of bilirubinoids in physiological liquids and organic solvents. General regularities of structural and salvation factors effect on chromium, coordination and other physical and chemical properties of some alkyl substituted dipyrrolilmethene, biladiene and natural bile pigments (bilirubin, biliverdine etc.) are studied. The theoretical baseline for creation of effective techniques of the clinicobiochemical analysis of the bilirubinoids contents in bioliquids and non-aqueous medium, improvement of methods of porphyrins synthesis and effective chelating reagents search, including for utilization ions of toxic metals, are developed. (Research in charge is Antina E.V.) 


Achievements (awards, grants, patents and medals):


The State contract under the program of Presidium of the Russian Academy of Science: « the Directed synthesis of mineral substances with desired properties and creation of functional materials on their basis » the State Contract 10002-251/П-09/129-134/260603-894; Head Vjugin A.I. 


Grants of Russian Foundation of Basic Researches in a nomination « Candidates of sciences of the Russian Academy of Science » for 2004 gained Lebedeva N.Sh. 


Lebedeva N.Sh. in 2003 is awarded the Certificate of Honour of the Ministry of Education. 


Antina E.V. in 2001 is awarded breastplate of the Ministry of Education « For evolution of student's scientific work » (and in 1999). She is awarded with the certificate of Honour - gratitude of the Russian Academy of Science for long-term and effective work in Academy of Sciences. 


The Research team participates in the Program of Presidium of the Russian Academy of Science « the Directed synthesis of substances with desired properties and creation of functional materials on their basis », section П-8. Researches are supported by regional grants of the Russian Federal Property Fund: « Coordination properties of linear oligopyrroles as effective chelated ligands and extragents » 06-03-96341 and « Effect of acid-base equilibriums on electrostatic “ recognition ” molecules of amino acids and peptides in reactions with modelling receptors of coenzyme piridoxalphosphate in aqueous buffer systems » 06-03-96312. The Foundation of Assistance to Domestic Science supports work of the candidate of sciences Pavlycheva N.A. 


Laboratory facilities:     


 1. Equipment for spectroscopy.

Spectrophotometer UNICO 2800.


Wavelengths’ range is from 190 to 1100 nm and resolution comes to 0.1 nm with rate of scanning of 1000 nm/min.


2. Differential Automatic Calorimeter of Titration (DACT): 


The techniques implemented on DACT: 


Definitions of thermodynamic characteristics of processes molecular complexation (changes of an entropy, an enthalpy, thermodynamic stability of complexes of composition 1:1, 2:1, 1:2 (at simultaneous and consistent connection of molecular ligands)); 

Definitions of molar enthalpy of mixture of liquids; 

Definitions of integral and differential heats of adsorbtion. 


3. Equipment for thermal analysis:


Differential scanning calorimeter DSC 204 F1 Phoenix (Netzsch), 


the sensitivity is <0,1 mkW, the temperature range is from-180 up to 700°С; 


microthermobalance TG 209 F1 Iris (Netzsch), allowing to carry out thermogravimetric researches in inert gaze flow up to 1000°С, the weight resolution is 0,1 mkg.


The thermoanalytical apparatus including derivatograph 1000D (МОМ, Hungary) with the hardware-software complex intended for measurement, reinforcement and registration of output signals from sensing transducers of derivatograph, PC. 


The methods of thermal analysis used in the laboratory: 


  • Investigation a specific interaction between macrocyclic compounds and volatile organic substances by  original method developed in laboratory on basis of thermogravimetry data;
  • Determination of thermal stability of individual substances and their solvates; 
  • Determination of composition and energy characteristics of molecular complexes; 
  • Determination of enthalpy changes and temperatures of phase transitions; 
  • Determination of evaporation heats; 
  • Determination of activation energy in thermally activated processes, accompanied by removal of volatile component; 

Researches of desorption processes of solvents from a surface of adsorbates (definition of enthalpy of evaporation and temperature ranges for process stages, calculation of volume of pores of an adsorbate).

tical installation including derivatograph 1000D (МОМ, Hungary)


4.  Isoperibol calorimeters of dissolution.


 The uncertainty in heat effect is 0.01 J. 


The design of calorimeters allows to measure solution heats of solid and liquid substances in various organic solvents.

Leading researcher
Doctor of сhemical sciences
Head of the laboratory
Doctor of сhemical sciences
Senior Researcher
Leading researcher
Doctor of сhemical sciences
Phd in chemistry
Phd in chemistry
Старший научный сотрудник
Кандидат химических наук
Phd in chemistry
Leading researcher
Doctor of сhemical sciences
Head of the laboratory
Doctor of сhemical sciences