From Chemistry Towards Technology Step-By-Step From Chemistry Towards Technology Step-By-Step От химии к технологии шаг за шагом 2782-1900 81561 10.52957/27821900_2023_01_86 Научные статьи Scientific articles Научные статьи Effect of solvent H/D isotope substitution and temperature on some thermodynamic properties of tetramethylenediethylentetramine (pharmaceutical theotropin) in aqueous solutions Effect of solvent H/D isotope substitution and temperature on some thermodynamic properties of tetramethylenediethylentetramine (pharmaceutical theotropin) in aqueous solutions Иванов Евгений Викторович Ivanov Evgeny Viktorovich evi@isc-ras.ru

кандидат химических наук;

candidate of chemical sciences;

 Лебедева Елена Юрьевна Lebedeva Elena Yurievna eyl@isc-ras.ru

кандидат химических наук;

candidate of chemical sciences;

 Иванова Надежда Геннадьевна Ivanova Nadezhda Gennadievna nadezhda.ing@gmail.com

кандидат химических наук;

candidate of chemical sciences;

 Баранов Владимир Владимирович Baranov Vladimir Vladimirovich

кандидат химических наук;

candidate of chemical sciences;

 Кравченко Ангелина Николаевна Kravchenko Angelina Nikolaevna

доктор химических наук;

doctor of chemical sciences;

 Институт химии растворов им. Г.А. Крестова Российской академии наук Institute of Solution Chemistry of G.A. Krestov of the Russian Academy of Sciences Ивановский государственный энергетический университет Ivanovo Power Engineering Institute Институт органической химии им. Н.Д. Зелинского Российской академии наук Москва Россия N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences Moscow Russian Federation Институт органической химии им. Н.Д. Зелинского Российской академии наук Москва Россия N.D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences Moscow Russian Federation 23 03 2023 23 03 2023 4 1 86 100 13 02 2023 21 03 2023 https://chemintech.ru/en/nauka/article/81561/view

The paper considers the measurements of densities the pharmaceutical “teotro-pine” or tetramethylenediethylenetetramine (TMDETA) solutions in heavy water (D2O) with the solute molality from (0.01 to 0.12) mol∙(kg solvent) 1 at T = (278.15, 288.15, 298.15, 308.15, and 318.15) K and ambient pressure (p = 0.1 MPa). The uncertainty in density measured using the Anton Paar DMA 5000 M densimeter (equipped with oscillating U-tube) was 0.03 kg m-3 or lower. We obtain the standard (at infinite dilution) molar volumes and isobaric expansibilities of TMDETA as a solute in D2O, along with the corresponding solvent D2O–H2O isotope effects (IEs). We define the isotope effects using the previously ob-tained data on volumetric properties of the system (H2O + TMDETA). We also find that the insignificant IEs in the standard molar volume of TMDETA increase with increasing temperature. Based on the analysis of contributions to the standard molar volume of TMDETA in terms of the Scaled Particle Theory (SPT) we confirm that a bulkier molecule of this solute interacts with water (especially, in D2O) actively than it does with a molecule of hexamethylenetetramine (HMTA) or pharmaceutical “urotropine” being the related aminal (cage-like) compound. The colloborating discussion of volume- and enthalpy-isotope characteristics of TMDETA (and HMTA) hydration within the scope of SPT led us to the conclusion that the structure matrix of D2O is more efficient for incorporat-ing the bulkier TMDETA molecule into it

The paper considers the measurements of densities the pharmaceutical “teotro-pine” or tetramethylenediethylenetetramine (TMDETA) solutions in heavy water (D2O) with the solute molality from (0.01 to 0.12) mol∙(kg solvent) 1 at T = (278.15, 288.15, 298.15, 308.15, and 318.15) K and ambient pressure (p = 0.1 MPa). The uncertainty in density measured using the Anton Paar DMA 5000 M densimeter (equipped with oscillating U-tube) was 0.03 kg m-3 or lower. We obtain the standard (at infinite dilution) molar volumes and isobaric expansibilities of TMDETA as a solute in D2O, along with the corresponding solvent D2O–H2O isotope effects (IEs). We define the isotope effects using the previously ob-tained data on volumetric properties of the system (H2O + TMDETA). We also find that the insignificant IEs in the standard molar volume of TMDETA increase with increasing temperature. Based on the analysis of contributions to the standard molar volume of TMDETA in terms of the Scaled Particle Theory (SPT) we confirm that a bulkier molecule of this solute interacts with water (especially, in D2O) actively than it does with a molecule of hexamethylenetetramine (HMTA) or pharmaceutical “urotropine” being the related aminal (cage-like) compound. The colloborating discussion of volume- and enthalpy-isotope characteristics of TMDETA (and HMTA) hydration within the scope of SPT led us to the conclusion that the structure matrix of D2O is more efficient for incorporat-ing the bulkier TMDETA molecule into it

 teotropine standard volume and expansibility standard enthalpy of dissolution ordinary and heavy water solvent H/D isotope effect

Zwier, J.M., Brouwer, A.M., Buma, W.J., Troisi, A. & Zerbetto, F. (2002) Structure and photophysics of an old, new molecule: 1,3,6,8-tetraazatricyclo[4.4.1.1(3,8)]dodecane, J. Am. Chem. Soc., (124), pp. 149-158. DOI: 10.1021/ja016971b. Zwier, J.M., Brouwer, A.M., Buma, W.J., Troisi, A. & Zerbetto, F. (2002) Structure and photophysics of an old, new molecule: 1,3,6,8-tetraazatricyclo[4.4.1.1(3,8)]dodecane, J. Am. Chem. Soc., (124), pp. 149-158. DOI: 10.1021/ja016971b. Ivanov, E.V. (2018) Temperature-dependent standard volumetric properties of hexamethylenetetramine in ordinary and deuterated water: A study resolving debatable issues being commented in the [Journal of Molec-ular Liquids, 248 (2017) 48-52], J. Mol. Liq., (272), pp. 218-225. DOI: 10.1016/j.molliq.2018.09.046. Ivanov, E.V. (2018) Temperature-dependent standard volumetric properties of hexamethylenetetramine in ordinary and deuterated water: A study resolving debatable issues being commented in the [Journal of Molec-ular Liquids, 248 (2017) 48-52], J. Mol. Liq., (272), pp. 218-225. DOI: 10.1016/j.molliq.2018.09.046. Vasil’ev, D.A., Khairullin, I.N., Zolotukhin, S.N., Feoktistova, N.A. & Kuryanova, N.Kh. (2011) Study of the bactericidal and bacteriostatic action of teotropine on microorganisms of various morphological structures, Vestnik Ul’yanovskoi GSKhA, 1(13), pp. 75-78 (in Russian). Vasil’ev, D.A., Khairullin, I.N., Zolotukhin, S.N., Feoktistova, N.A. & Kuryanova, N.Kh. (2011) Study of the bactericidal and bacteriostatic action of teotropine on microorganisms of various morphological structures, Vestnik Ul’yanovskoi GSKhA, 1(13), pp. 75-78 (in Russian). Balysheva, V.I., Nesterov, E.A., Lunitsin, A.V., Zhivoderov, S.P., Gorshkova, T.F., Lapteva, O.G., Balyshev, V.M. & Kolbasov, D.V. (2013) Efficacy of a trivalent inactivated vaccine against bluetongue in both cattle and small ruminants, Doklady Ross. akad. selskokhoz. nauk, (39), pp. 516-518. DOI: 10.3103/S1068367413050030 (in Russian). Balysheva, V.I., Nesterov, E.A., Lunitsin, A.V., Zhivoderov, S.P., Gorshkova, T.F., Lapteva, O.G., Balyshev, V.M. & Kolbasov, D.V. (2013) Efficacy of a trivalent inactivated vaccine against bluetongue in both cattle and small ruminants, Doklady Ross. akad. selskokhoz. nauk, (39), pp. 516-518. DOI: 10.3103/S1068367413050030 (in Russian). Blanco, L.H. & Dávila, M.T. (2010) Osmotic and activity coefficients of two macrocyclic aminals in aqueous solution at 288.15, 293.15, 298.15 and 303.15 K, Fluid Phase Equil., (293), pp. 237-241. DOI: 10.1016/j.fluid.2010.03.012. Blanco, L.H. & Dávila, M.T. (2010) Osmotic and activity coefficients of two macrocyclic aminals in aqueous solution at 288.15, 293.15, 298.15 and 303.15 K, Fluid Phase Equil., (293), pp. 237-241. DOI: 10.1016/j.fluid.2010.03.012. Romero, C.M. & Mesa, H.J. (2017) Effect of temperature on the partial molar volumes and viscosities of two macrocyclic aminals in water and deuterium oxide, J. Mol. Liq., (242), pp. 244-248. DOI: 10.1016/j.molliq.2017.06.101. Romero, C.M. & Mesa, H.J. (2017) Effect of temperature on the partial molar volumes and viscosities of two macrocyclic aminals in water and deuterium oxide, J. Mol. Liq., (242), pp. 244-248. DOI: 10.1016/j.molliq.2017.06.101. Ivanov, E.V., Batov, D.V., Lebedeva, E.Yu. & Baranov, V.V. (2021) Some interaction-related thermodynamic properties of aqueous tetramethylenediethylenetetramine (drug teotropine) solutions: Effect of the solvent H/D isotope substitution and temperature, J. Mol. Liq., (326), pp. 115274/1-115274/8. DOI: 10.1016/j.molliq.2020.115274. Ivanov, E.V., Batov, D.V., Lebedeva, E.Yu. & Baranov, V.V. (2021) Some interaction-related thermodynamic properties of aqueous tetramethylenediethylenetetramine (drug teotropine) solutions: Effect of the solvent H/D isotope substitution and temperature, J. Mol. Liq., (326), pp. 115274/1-115274/8. DOI: 10.1016/j.molliq.2020.115274. Blanco, L.H. & Sanabria, N.R. (2007) Solubility of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (TATD) in water at temperatures between 275 K and 303 K, J. Chem. Eng. Data, (52), pp. 2288-2290. DOI: 10.1021/je700304z. Blanco, L.H. & Sanabria, N.R. (2007) Solubility of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (TATD) in water at temperatures between 275 K and 303 K, J. Chem. Eng. Data, (52), pp. 2288-2290. DOI: 10.1021/je700304z. Salamanca, Y.P., Blanco, L.H. & Vargas E.F. (2013) Enthalpies of solution of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane in aqueous solution as a function of concentration and temperature, J. Therm. Anal. Calorim., (114), pp. 451-455. DOI: 10.1007/s10973-012-2870-9. Salamanca, Y.P., Blanco, L.H. & Vargas E.F. (2013) Enthalpies of solution of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane in aqueous solution as a function of concentration and temperature, J. Therm. Anal. Calorim., (114), pp. 451-455. DOI: 10.1007/s10973-012-2870-9. Ivanov, E.V. & Batov, D.V. (2019) Unusual behavior of temperature-dependent solvent H/D isotope effects in the enthalpy and heat capacity of hexamethylenetetramine (urotropine) hydration, J. Mol. Liq., (285), pp. 508 514. DOI: 10.1016/j.molliq.2019.04.104. Ivanov, E.V. & Batov, D.V. (2019) Unusual behavior of temperature-dependent solvent H/D isotope effects in the enthalpy and heat capacity of hexamethylenetetramine (urotropine) hydration, J. Mol. Liq., (285), pp. 508 514. DOI: 10.1016/j.molliq.2019.04.104. Soper, A.K. & Benmore, C.J. (2008) Quantum differences between heavy and light water, Phys. Rev. Lett., (101), pp. 065502/1-065502/4. DOI: 10.1103/PhysRevLett.101.065502. Soper, A.K. & Benmore, C.J. (2008) Quantum differences between heavy and light water, Phys. Rev. Lett., (101), pp. 065502/1-065502/4. DOI: 10.1103/PhysRevLett.101.065502. Ivanov, E.V. (2017) Some comments on the paper “Effect of temperature on the partial molar volumes and viscosities of two macrocyclic aminals in water and deuterium oxide” by Carmen M. Romero and Holman J. Mesa [Journal of Molecular Liquids, 242 (2017) 244-248], J. Mol. Liq., (248), pp. 48-52. DOI: 10.1016/j.molliq.2017.09.125 Ivanov, E.V. (2017) Some comments on the paper “Effect of temperature on the partial molar volumes and viscosities of two macrocyclic aminals in water and deuterium oxide” by Carmen M. Romero and Holman J. Mesa [Journal of Molecular Liquids, 242 (2017) 244-248], J. Mol. Liq., (248), pp. 48-52. DOI: 10.1016/j.molliq.2017.09.125 Ivanov, E.V., Lebedeva, E.Y., Baranov, V.V. & Kravchenko, A.N. (2022) Volume properties of tetramethylenediethylenetetramine (pharmaceutical teotropine) in aqueous solutions between 278.15 and 318.15 K, J. Mol. Liq., (174), pp. 106-860/1-106860/6. DOI: 10.1016/j.jct.2022.106860. Ivanov, E.V., Lebedeva, E.Y., Baranov, V.V. & Kravchenko, A.N. (2022) Volume properties of tetramethylenediethylenetetramine (pharmaceutical teotropine) in aqueous solutions between 278.15 and 318.15 K, J. Mol. Liq., (174), pp. 106-860/1-106860/6. DOI: 10.1016/j.jct.2022.106860. Ansari, M.S. & Hafiz-ur-Rehman (2011) Aquamolality: a useful concentration unit, Phys. Chem. Liq.: Int. J., (49), pp. 743-745. DOI: 10.1080/00319104.2010.509723. Ansari, M.S. & Hafiz-ur-Rehman (2011) Aquamolality: a useful concentration unit, Phys. Chem. Liq.: Int. J., (49), pp. 743-745. DOI: 10.1080/00319104.2010.509723. Abrosimov, V.K. & Ivanov, E.V. (2011) Densimetry of solutions. Theoretical and Experimental Methods of Solution Chemistry, Moscow: Prospekt (in Russian). Abrosimov, V.K. & Ivanov, E.V. (2011) Densimetry of solutions. Theoretical and Experimental Methods of Solution Chemistry, Moscow: Prospekt (in Russian). Ivanov, E.V. (2021) The solvomolality concept as a step in developing the ideas of structure-thermodynamic characteristics of solutions: dedicated to the anniversaries of the birth of G.A. Krestov and the foundation of the institute of solution chemistry of RAS being named after him, Izv. Vuzov. Khimiya i Khim. Theknol., 64(10), pp. 6-15. DOI: 10.6060/ivkkt.20216410.6461 (in Russian). Ivanov, E.V. (2021) The solvomolality concept as a step in developing the ideas of structure-thermodynamic characteristics of solutions: dedicated to the anniversaries of the birth of G.A. Krestov and the foundation of the institute of solution chemistry of RAS being named after him, Izv. Vuzov. Khimiya i Khim. Theknol., 64(10), pp. 6-15. DOI: 10.6060/ivkkt.20216410.6461 (in Russian). Wüzburger, S., Sartorio, R., Guarino, G. & Nisi, M. (1988) Volumetric properties of aqueous solutions of polyols between 0.5 and 25°C, J. Chem. Soc., Faraday Trans., 1(84), pp. 2279-2287. DOI: 10.1039/F19888402279. Wüzburger, S., Sartorio, R., Guarino, G. & Nisi, M. (1988) Volumetric properties of aqueous solutions of polyols between 0.5 and 25°C, J. Chem. Soc., Faraday Trans., 1(84), pp. 2279-2287. DOI: 10.1039/F19888402279. Ivanov, E.V., Lebedeva, E.Yu., Petrovskaya, S.G., Baranov, V.V., Kravchenko, A.N. & Ivanova, N.G. (2017) Volume-related interaction parameters for dilute solutions of Mebicaret (2,4-dimethyl-6,8-diethylglycoluril) in normal and heavy water between 278.15 K and 318.15 K, J. Mol. Liq., (242), pp. 160-167. DOI: 10.1016/j.molliq.2017.07.003. Ivanov, E.V., Lebedeva, E.Yu., Petrovskaya, S.G., Baranov, V.V., Kravchenko, A.N. & Ivanova, N.G. (2017) Volume-related interaction parameters for dilute solutions of Mebicaret (2,4-dimethyl-6,8-diethylglycoluril) in normal and heavy water between 278.15 K and 318.15 K, J. Mol. Liq., (242), pp. 160-167. DOI: 10.1016/j.molliq.2017.07.003. Mak, T.C.W. (1965) Hexamethylenetetramine hexahydrate: a new type of clathrate hydrate, J. Chem. Phys., (43), pp. 2799-2805. DOI: 10.1063/1.1697212. Mak, T.C.W. (1965) Hexamethylenetetramine hexahydrate: a new type of clathrate hydrate, J. Chem. Phys., (43), pp. 2799-2805. DOI: 10.1063/1.1697212. Kell, G.S. (1977) Effect of isotopic composition, temperature, pressure, and dissolved gases on the density of liquid water, J. Phys. Chem. Ref. Data, (6), pp. 1109-1131. DOI: 10.1063/1.555561. Kell, G.S. (1977) Effect of isotopic composition, temperature, pressure, and dissolved gases on the density of liquid water, J. Phys. Chem. Ref. Data, (6), pp. 1109-1131. DOI: 10.1063/1.555561. Lepori, L. & Gianni, P. (2000) Partial molar volumes of ionic and nonionic organic solvents in water: a simple additivity scheme based on the intrinsic volume approach, J. Solution Chem., (29), pp. 405-447. DOI: 10.1023/A:1005150616038. Lepori, L. & Gianni, P. (2000) Partial molar volumes of ionic and nonionic organic solvents in water: a simple additivity scheme based on the intrinsic volume approach, J. Solution Chem., (29), pp. 405-447. DOI: 10.1023/A:1005150616038. Kuz’min, V.S. & Katser, S.B. (1992) Calculation of the Van der Waals volumes of organic molecules, Izv. RAN. Ser. khim., (41), pp. 720-729. DOI: 10.1007/BF01150899 (in Russian). Kuz’min, V.S. & Katser, S.B. (1992) Calculation of the Van der Waals volumes of organic molecules, Izv. RAN. Ser. khim., (41), pp. 720-729. DOI: 10.1007/BF01150899 (in Russian). Hepler, L.G. (1969) Thermal expansion and structure in water and aqueous solutions, Can. J. Chem., (47), pp. 4613-4617. DOI: 10.1139/v69-762. Hepler, L.G. (1969) Thermal expansion and structure in water and aqueous solutions, Can. J. Chem., (47), pp. 4613-4617. DOI: 10.1139/v69-762. Pierotti, R.A. (1976) A scaled particle theory of aqueous and nonaqueous solutions, Chem. Rev., (76), pp. 717 726. DOI: 10.1021/cr60304a002. Pierotti, R.A. (1976) A scaled particle theory of aqueous and nonaqueous solutions, Chem. Rev., (76), pp. 717 726. DOI: 10.1021/cr60304a002. Ivanov E.V. (2012) Thermodynamic interrelation between excess limiting partial molar characteristics of a liquid nonelectrolyte, J. Chem. Thermodyn., 47, pp. 437-440. DOI: 10.1016/j.jct.2011.11.018. Ivanov E.V. (2012) Thermodynamic interrelation between excess limiting partial molar characteristics of a liquid nonelectrolyte, J. Chem. Thermodyn., 47, pp. 437-440. DOI: 10.1016/j.jct.2011.11.018. Malenkov, G.G. & Toryanik, A.I. (1976) Molecular structure of aqueous solutions of hexamethylenetetramine, Zhurn. strukt. khimii, (17), pp. 46-49. DOI: 10.1007/BF00748391 (in Russian). Malenkov, G.G. & Toryanik, A.I. (1976) Molecular structure of aqueous solutions of hexamethylenetetramine, Zhurn. strukt. khimii, (17), pp. 46-49. DOI: 10.1007/BF00748391 (in Russian). Kuznetsov, A.I., Shukkur, A.H. & Kamara, K. (2008) Synthesis of 4,5-dihydro-1,6:3,8-dimethano-1,3,6,8-benzotetrazecine, Izv. RAN. Ser. khim., (57), pp. 1575-1577. DOI: 10.1007/s11172-008-0205-6 (in Russian). Kuznetsov, A.I., Shukkur, A.H. & Kamara, K. (2008) Synthesis of 4,5-dihydro-1,6:3,8-dimethano-1,3,6,8-benzotetrazecine, Izv. RAN. Ser. khim., (57), pp. 1575-1577. DOI: 10.1007/s11172-008-0205-6 (in Russian). Peori, M.B., Vaughan, K. & Hooper, D. (1998) Synthesis and characterization of novel bis-triazenes: 3,8-di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes and 1,3-di-2-[(4-methoxyphenyl)-1-diazenyl] imidazoli-dine. The reaction of diazonium ions with ethylenediamine/formaldehyde mixtures, J. Org. Chem., (63), pp. 7437-7444. DOI: 10.1021/jo981276g. Peori, M.B., Vaughan, K. & Hooper, D. (1998) Synthesis and characterization of novel bis-triazenes: 3,8-di[2-aryl-1-azenyl]-1,3,6,8-tetraazabicyclo[4.4.1]undecanes and 1,3-di-2-[(4-methoxyphenyl)-1-diazenyl] imidazoli-dine. The reaction of diazonium ions with ethylenediamine/formaldehyde mixtures, J. Org. Chem., (63), pp. 7437-7444. DOI: 10.1021/jo981276g. Clavijo, J.A. & Blanco, L.H. (2012) Effect of two macrocyclic aminals on the temperature of maximum density of water, J. Solution Chem., (41), pp. 680-689. DOI: 10.1007/s10953-011-9736-9. Clavijo, J.A. & Blanco, L.H. (2012) Effect of two macrocyclic aminals on the temperature of maximum density of water, J. Solution Chem., (41), pp. 680-689. DOI: 10.1007/s10953-011-9736-9. Wagner, Z., Bendová, M., Rotrekl, J., Sýkorová, A., Čanji, M. & Parmar, N. (2021) Density and sound velocity measurement by an Anton Paar DSA 5000 density meter: Precision and long-time stability, J. Mol. Liq., (329), pp. 155547/-155547/17. DOI: 10.1016/j.molliq.2021.115547. Wagner, Z., Bendová, M., Rotrekl, J., Sýkorová, A., Čanji, M. & Parmar, N. (2021) Density and sound velocity measurement by an Anton Paar DSA 5000 density meter: Precision and long-time stability, J. Mol. Liq., (329), pp. 155547/-155547/17. DOI: 10.1016/j.molliq.2021.115547.