Theoretical study on complexes and reactions of boron isotopic exchange separation with fluorinated anisoles as novel donors

  • Fan Zhou
  • Jingshuang Zhang
  • Tianyi Fu
  • Peng Bai
  • Peng BaiEmail author
  • Xianghai GuoEmail author


Semi-empirical and ab initio density-functional theory (DFT) methods were evaluated for the description of isotope exchange reactions to produce enriched 10B species. We found that DFT calculations using M06-2X/6-311+G(3d,2p) functional and basis sets in combination with the SMD implicit solvation model were able to correctly predict the performance of various anisole-derived donor molecules. We confirmed that fluorination results in greatly increased separation factors, and successfully identified the o- and 2,4-difluorinated anisole as superior donors for chemical exchange distillation. These findings provide the basis for an efficient approach to rapidly screen and design new donor species.


Boron isotopes Separation Chemical exchange distillation Computational chemistry 



This work was supported by the National Natural Science Foundation of China under Grant [Number 21202116]; Independent Innovation Foundation of Tianjin University under Grant [Number 2016XZC-0071]; and Natural Science Foundation of Tianjin under Grant [Number 16JCYBJC20300].

Supplementary material

10967_2018_5824_MOESM1_ESM.docx (928 kb)
Supplementary material 1 (DOCX 927 kb)
10967_2018_5824_MOESM2_ESM.docx (14 kb)
Supplementary material 2 (DOCX 14 kb)


  1. 1.
    Potapov S (1962) Application of stable boron isotopes. Sov J At Energy 10:234–241CrossRefGoogle Scholar
  2. 2.
    Ivanov V, Katalnikov S (2001) Physico-chemical and engineering principles of boron isotopes separation by using BF3–anisole·BF3 system. Sep Sci Technol 36:1737–1768CrossRefGoogle Scholar
  3. 3.
    Semiokhin I (1996) Chemical methods of stable isotope separation. J Radioanal Nucl Chem 205:201–213CrossRefGoogle Scholar
  4. 4.
    Angelone M, Atzeni S, Rollet S (2002) Conceptual study of a compact accelerator-driven neutron source for radioisotope production, boron neutron capture therapy and fast neutron therapy. Nucl Instr Methods Phys Res A 487:585–594CrossRefGoogle Scholar
  5. 5.
    Ono K, Masunaga S, Suzuki M, Kinashi Y, Takagaki M, Akaboshi M (1999) The combined effect of boronophenylalanine and borocaptate in boron neutron capture therapy for SCCVII tumors in mice. Int J Radiat Oncol Biol Phys 43:431–436CrossRefGoogle Scholar
  6. 6.
    Verbeke J, Leung K, Vujic J (2000) Development of a sealed-accelerator-tube neutron generator. Appl Radiat Isot 53:801–809CrossRefGoogle Scholar
  7. 7.
    Palko A, Drury J (1969) Chemical fractionation of boron isotopes. Adv Chem 89:40–56CrossRefGoogle Scholar
  8. 8.
    Takeda K, Morita K (1996) Enrichment factor, height of separation unit, and separation efficiency by ion exchange with chemical reaction. Sep Sci Technol 31:2655–2670CrossRefGoogle Scholar
  9. 9.
    Sevryugova N, Uvarov O, Zhavoronkov N (1961) Separation of the stable isotopes of boron. Sov J At Energy 9:614–629CrossRefGoogle Scholar
  10. 10.
    Joseph M, Manoravi P (2003) Boron isotope enrichment in nanosecond pulsed laser-ablation plume. Appl Phys A 76:153–156CrossRefGoogle Scholar
  11. 11.
    Buchanov V, Kazaryan M, Kalugin M, Prokhorov A (2001) The possibilities of producing 10B boron isotopes with the method of selective photoionization. Laser Phys 11:1332–1335Google Scholar
  12. 12.
    Wei F, Zhang W, Han M, Han L, Zhang X, Zhang S (2008) Operational policy of the boron isotopes separation by chemical exchange reaction and distillation. Chem Eng Process 47:17–21CrossRefGoogle Scholar
  13. 13.
    Palko A, Healy R, Landau L (1958) Separation of boron isotopes. II. The BF3 anisole system. J Chem Phys. 28:214–217CrossRefGoogle Scholar
  14. 14.
    Liguo H, Weijiang Z, Jingyang Y (2006) The enrichment technology for the separation and production of boron isotopes. J Isot 19:48–52Google Scholar
  15. 15.
    Healy R, Palko A (1958) Separation of boron isotopes. I. Boron trihalide addition compounds. J Chem Phys 28:211–213CrossRefGoogle Scholar
  16. 16.
    Palko A (1959) Separation of boron isotopes in the bench-scale boron fluoride-anisole unit. Ind Eng Chem 51:121–124CrossRefGoogle Scholar
  17. 17.
    Jancsó G (1977) Interpretation of the vapor pressure isotope effect of BF3. Isot Environ Health Stud 13:118–120Google Scholar
  18. 18.
    Huang Y, Cheng S, Xu J, Zhang W (2011) Research on chemical exchange process of boron isotope separation. Procedia Eng 18:151–156CrossRefGoogle Scholar
  19. 19.
    Nakane R, Isomura S (1966) Separation of boron-10 by low temperature distillation of boron fluoride-methyl fluoride complex. J Nucl Sci Technol 3:267–274CrossRefGoogle Scholar
  20. 20.
    Jiang L, Han L, Zhang W, Zhang L (2007) Decomposition reaction in separation of boron isotopes by chemical exchange reaction and distillation. Chem Eng. (China) 35:26–29Google Scholar
  21. 21.
    Song S, Mu Y, Li X, Bai P (2010) Advances in boron-10 isotope separation by chemical exchange distillation. Ann Nucl Energy 37:1–4CrossRefGoogle Scholar
  22. 22.
    Katal’nikov S, Paramonov P, Nedzvetskii V (1967) Separation of boron isotopes using isotopic exchange between BF3 and a complex of BF3 with phenetole. Sov At Energy 22:372–377CrossRefGoogle Scholar
  23. 23.
    Palko A, Drury J (1967) Fractionation of boron isotopes between boron trifluoride and its molecular addition compounds. J Chem Phys 47:2561–2566CrossRefGoogle Scholar
  24. 24.
    McLaughlin D, Tamres M (1960) The boron trifluoride addition compounds of dimethyl ether and diethyl ether. J Am Chem Soc 82:5618–5621CrossRefGoogle Scholar
  25. 25.
    Palko A (1959) Separation of boron isotopes. III. The n-butyl sulfide-BF3 system. J Chem Phys 30:1187–1189CrossRefGoogle Scholar
  26. 26.
    Herbst R, McCandless F (1994) Improved donors for the separation of the boron isotopes by gas-liquid exchange reactions. Sep Sci Technol 29:1293–1310CrossRefGoogle Scholar
  27. 27.
    Ownby P (2004) The boron trifluoride nitromethane adduct. J Solid State Chem 177:466–470CrossRefGoogle Scholar
  28. 28.
    Kiss I, Opauszky I, Matush L (1961) Data on the separation of boron isotopes in the form of volatile compounds. Sov J At Energy 10:72–75CrossRefGoogle Scholar
  29. 29.
    Palko A (1978) The chemical separation of boron isotopes. Department of Energy, Oak Ridge National Laboratory, Oak RidgeCrossRefGoogle Scholar
  30. 30.
    Wu X, Bai P, Guo X, He N (2014) 2, 4-Difluoro anisole: a promising complexing agent for boron isotopes separation by chemical exchange reaction and distillation. J Radioanal Nucl Chem 300:897–902CrossRefGoogle Scholar
  31. 31.
    Lin T, Zhang W, Wang L (2009) Theoretical calculation of separation factors for boron isotopic exchange between BF3 and BF3·C6H5OCH3. J Phys Chem A 113:7267–7274CrossRefGoogle Scholar
  32. 32.
    Khaliullin R, Bell A, Head-Gordon M (2008) Analysis of charge transfer effects in molecular complexes based on absolutely localized molecular orbitals. J Chem Phys 128:184112CrossRefGoogle Scholar
  33. 33.
    Khaliullin R, Cobar E, Lochan R, Bell A, Head-Gordon M (2007) Unravelling the origin of intermolecular interactions using absolutely localized molecular orbitals. J Phys Chem A 111:8753–8765CrossRefGoogle Scholar
  34. 34.
    Reed A, Curtiss L, Weinhold F (1988) Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint. Chem Rev 88:899–926CrossRefGoogle Scholar
  35. 35.
    Stewart J (1990) MOPAC: a semiempirical molecular orbital program. J Comput Aided Mol Des 4:1–103CrossRefGoogle Scholar
  36. 36.
    Stewart J (2012) Mopac2012. Stewart computational chemistry, Colorado springsGoogle Scholar
  37. 37.
    Rozanska X, Stewart J, Ungerer P, Leblanc B, Freeman C, Saxe P, Wimmer E (2014) High-throughput calculations of molecular properties in the MedeA environment: accuracy of PM7 in predicting vibrational frequencies, ideal gas entropies, heat capacities, and Gibbs free energies of organic molecules. J Chem Eng Data 59:3136–3143CrossRefGoogle Scholar
  38. 38.
    Frisch M, Trucks G, Schlegel HB, Scuseria G, Robb M, Cheeseman J, Scalmani G, Barone V, Mennucci B, Ge Petersson (2009) Gaussian 09. Gaussian, Inc., WallingfordGoogle Scholar
  39. 39.
    Zhao Y, Truhlar D (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc 120:215–241CrossRefGoogle Scholar
  40. 40.
    Montgomery J, Frisch M, Ochterski J, Petersson G (1999) A complete basis set model chemistry. VI. Use of density functional geometries and frequencies. J Chem Phys 110:2822–2827CrossRefGoogle Scholar
  41. 41.
    Montgomery J, Frisch M, Ochterski J, Petersson G (2000) A complete basis set model chemistry. VII. Use of the minimum population localization method. J Chem Phys 112:6532–6542CrossRefGoogle Scholar
  42. 42.
    Lu T, Chen F (2012) Multiwfn: a multifunctional wavefunction analyzer. J Comput Chem 33:580–592CrossRefGoogle Scholar
  43. 43.
    Taillandier M, Liquier J, Taillandier E (1968) Complexes par transfert de charge en spectroscopie ir: esters-BF3, esters-BCl3. J Mol Struct 2:437–463CrossRefGoogle Scholar
  44. 44.
    Taillandier M, Taillandier E (1969) Complexes par transfert de charge en spectroscopie infrarouge pyridine-BF3. Spectrochim Acta A 25:1807–1814CrossRefGoogle Scholar
  45. 45.
    Glendening E, Weinhold F (1998) Natural resonance theory: I. General formalism. J Comput Chem 19:593–609CrossRefGoogle Scholar
  46. 46.
    Marenich A, Cramer C, Truhlar D (2009) Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem B 113:6378–6396CrossRefGoogle Scholar
  47. 47.
    Marenich A, Cramer C, Truhlar D (2009) Performance of SM6, SM8, and SMD on the SAMPL1 test set for the prediction of small-molecule solvation free energies. J Phys Chem B 113:4538–4543CrossRefGoogle Scholar
  48. 48.
    Ribeiro R, Marenich A, Cramer C, Truhlar D (2010) Prediction of SAMPL2 aqueous solvation free energies and tautomeric ratios using the SM8, SM8AD, and SMD solvation models. J Comput Aided Mol Des 24:317–333CrossRefGoogle Scholar
  49. 49.
    Calculation of the HETP at total reflux: generalization of the Fenske equation. Accessed 17 Mar 2018

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  1. 1.Department of Pharmaceutical Engineering, School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina
  2. 2.Key Laboratory of Systems Bioengineering (Ministry of Education)Tianjin UniversityTianjinChina
  3. 3.Department of Chemical Engineering and Materials ScienceUniversity of MinnesotaMinneapolisUSA

Personalised recommendations