Abstract

No abstract available.

Full Article  |  PDF Article

References

  • View by:
  • |
  • |
  • |

  1. A. C. Hardy, J. Opt. Soc. Am. 25, 305 (1935).
    [Crossref]
  2. G. R. Harrison, Proceedings of the Sixth Spectroscopy Conference (John Wiley, New York, 1939); G. R. Harrison and E. P. Bentley, J. Opt. Soc. Am. 30, 290 (1940).
    [Crossref]
  3. K. Weber, Zeits. f. physik. Chemie B15, 18 (1931).
  4. E. Rabinowitch, J. Chem. Phys. 8, 551 (1940).
    [Crossref]
  5. E. Rabinowitch, J. Chem. Phys. 8, 560 (1940).
    [Crossref]
  6. W. M. Clark, H. D. Gibbs, and B. Cohen, Public Health Reports, 40, 1131 (1935).
  7. (a)Earlier papers on thionine and its spectrum are: J. H. Stebbins, J. Am. Chem. Soc. 6, 304 (1884); (b)A. Bernthsen, Ann. 230, 111, 209 (1885); (c)M. Althausse and G. Kruss, Ber. 22, 2066 (1889); (d) Formanék and E. Grandmougin, Untersuchung und Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1908), Part 1, pp. 143, 150; Untersuchung nd Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1911), Part 2, p. 124. (e)F. Eckert and R. Pummerer, Zeits. f. physik. Chemie 87, 613 (1914); (f)F. Eckert, R. Pummerer, and S. Gassner, Ber. 47, 1495 (1914); (g)F. Kehrman, E. Havas, and E. Grandmougin, Ber. 46, 2131 (1913); Ber. 47, 1881 (1914); (h)F. Kehrman, Ber. 49, 1018 (1916); (i)F. Kehrman and P. Zybs, Ber. 52, 130 (1919); (j)L. Michaelis, M. P. Schubert, and S. Granick, J. Am. Chem. Soc. 62, 204, 1802 (1940).
    [Crossref]
  8. The possibility of an orthoquinoid structure, with the heterocyclic sulfur forming a sulfonium base (as was hypothesized in the older literature7) cannot be entirely dismissed, although the evidence seems to be against it.7(i)
  9. L. Michaelis and M. P. Schubert, Chem. Rev. 22, 437 (1938).
    [Crossref]
  10. L. Pauling and co-workers, J. Chem. Phys. 1, 362, 606, 679 (1933); cf. also The Nature of the Chemical Bond, 2nd edition (Cornell University Press, Ithaca, New York, 1940).
    [Crossref]
  11. C. R. Bury, J. Am. Chem. Soc. 57, 2115 (1935); A. L. Sklar, J. Chem. Phys. 5, 669 (1937); L. Pauling, in H. Gilman, Organic Chemistry (John Wiley, 1938), II, p. 1888; L. Pauling, Proc. Nat. Acad. Sci. 25, 577 (1939); G. N. Lewis and M. Calvin, Chem. Rev. 25, 273 (1939); R. S. Mulliken, J. Chem. Phys. 7, 14, 20, 121, 339, 353, 356, 364, 570 (1939).
    [Crossref]
  12. (a)W. C. Holmes, Ind. Eng. Chem. 16, 35 (1924), Am. Dyestuff Rep. 16, 429 (1927), J. Am. Chem. Soc. 50, 1923 (1928); (b)G. Körtum, Zeits. f. physik. Chemie B30, 317 (1935), Zeits. f. physik. Chemie 31, 137 (1935), Zeits. f. physik. Chemie 31, 1, 243 (1936), Zeits. f. physik. Chemie 34, 255 (1936); (c)W. E. Speas, Phys. Rev. 31, 539 (1928); (d)G. Scheibe, Kolloid, Zeits. 82, 1 (1938); G. Scheibe and L. Kandler, Naturwiss. 26, 412 (1938); G. Scheibe, A. Schöntag, J. Kopske, and K. Meule, Zeits. f. wiss. Phot. 38, 1 (1939); G. Scheibe, A. Schöntag, and E. Katheder, Naturwiss. 27, 499 (1939); (e)V. L. Lewshin, Acta Physicochimica, U. R. S. S. 1, 685 (1935), Acta Physicochimica, U. R. S. S. 4, 221 (1936).
    [Crossref]
  13. Made by Mr. Henry Wayringer, to whom we wish to express our thanks.
  14. E. Rabinowitch and L. F. Epstein, “The polymerization of dye-stuffs in solution. Thionine and methylene blue.” Presented at the Symposium on Structure of Molecules and Aggregates of Molecules, Division of Physical and Inorganic Chemistry, American Chemical Society, Columbia University, New York, New York, December 30, 1940 to January 1, 1941. J. Am. Chem. Soc., paper in press.
  15. A. Thiel, A. Dassler, and F. Wülfken, Fortschritte Chemie, Physik, u. physik. Chemie 18, 4.3 (1924); E. B. R. Prideaux, Chem. Industry,  45, 664, 678 (1936); cf. W. M. Clark, Determination of Hydrogen Ions (Baltimore, 1928), p. 206.
  16. Cf. reference 14, Fig. 3.
  17. E. Q. Adams and L. Rosenstein, J. Am. Chem. Soc. 36, 1452 (1914).
    [Crossref]
  18. Adams and Rosenstein (cf. reference 17) also observed irreversible bleaching in acid solution of crystal violet, and studied the kinetics of the bleaching process. In this case the bleaching in acid solutions seemed to be independent of the anion.
  19. Beilstein reports that alkaline solutions of thionine are slowly transformed intoBoth of these reaction products are, however, strongly colored.
  20. We are indebted to Professor L. J. Gillespie and Dr. S. D. Stookey of this laboratory for the special Pd used in these experiments.

1940 (2)

E. Rabinowitch, J. Chem. Phys. 8, 551 (1940).
[Crossref]

E. Rabinowitch, J. Chem. Phys. 8, 560 (1940).
[Crossref]

1938 (1)

L. Michaelis and M. P. Schubert, Chem. Rev. 22, 437 (1938).
[Crossref]

1935 (2)

A. C. Hardy, J. Opt. Soc. Am. 25, 305 (1935).
[Crossref]

C. R. Bury, J. Am. Chem. Soc. 57, 2115 (1935); A. L. Sklar, J. Chem. Phys. 5, 669 (1937); L. Pauling, in H. Gilman, Organic Chemistry (John Wiley, 1938), II, p. 1888; L. Pauling, Proc. Nat. Acad. Sci. 25, 577 (1939); G. N. Lewis and M. Calvin, Chem. Rev. 25, 273 (1939); R. S. Mulliken, J. Chem. Phys. 7, 14, 20, 121, 339, 353, 356, 364, 570 (1939).
[Crossref]

1933 (1)

L. Pauling and co-workers, J. Chem. Phys. 1, 362, 606, 679 (1933); cf. also The Nature of the Chemical Bond, 2nd edition (Cornell University Press, Ithaca, New York, 1940).
[Crossref]

1931 (1)

K. Weber, Zeits. f. physik. Chemie B15, 18 (1931).

1924 (2)

(a)W. C. Holmes, Ind. Eng. Chem. 16, 35 (1924), Am. Dyestuff Rep. 16, 429 (1927), J. Am. Chem. Soc. 50, 1923 (1928); (b)G. Körtum, Zeits. f. physik. Chemie B30, 317 (1935), Zeits. f. physik. Chemie 31, 137 (1935), Zeits. f. physik. Chemie 31, 1, 243 (1936), Zeits. f. physik. Chemie 34, 255 (1936); (c)W. E. Speas, Phys. Rev. 31, 539 (1928); (d)G. Scheibe, Kolloid, Zeits. 82, 1 (1938); G. Scheibe and L. Kandler, Naturwiss. 26, 412 (1938); G. Scheibe, A. Schöntag, J. Kopske, and K. Meule, Zeits. f. wiss. Phot. 38, 1 (1939); G. Scheibe, A. Schöntag, and E. Katheder, Naturwiss. 27, 499 (1939); (e)V. L. Lewshin, Acta Physicochimica, U. R. S. S. 1, 685 (1935), Acta Physicochimica, U. R. S. S. 4, 221 (1936).
[Crossref]

A. Thiel, A. Dassler, and F. Wülfken, Fortschritte Chemie, Physik, u. physik. Chemie 18, 4.3 (1924); E. B. R. Prideaux, Chem. Industry,  45, 664, 678 (1936); cf. W. M. Clark, Determination of Hydrogen Ions (Baltimore, 1928), p. 206.

1914 (1)

E. Q. Adams and L. Rosenstein, J. Am. Chem. Soc. 36, 1452 (1914).
[Crossref]

1884 (1)

(a)Earlier papers on thionine and its spectrum are: J. H. Stebbins, J. Am. Chem. Soc. 6, 304 (1884); (b)A. Bernthsen, Ann. 230, 111, 209 (1885); (c)M. Althausse and G. Kruss, Ber. 22, 2066 (1889); (d) Formanék and E. Grandmougin, Untersuchung und Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1908), Part 1, pp. 143, 150; Untersuchung nd Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1911), Part 2, p. 124. (e)F. Eckert and R. Pummerer, Zeits. f. physik. Chemie 87, 613 (1914); (f)F. Eckert, R. Pummerer, and S. Gassner, Ber. 47, 1495 (1914); (g)F. Kehrman, E. Havas, and E. Grandmougin, Ber. 46, 2131 (1913); Ber. 47, 1881 (1914); (h)F. Kehrman, Ber. 49, 1018 (1916); (i)F. Kehrman and P. Zybs, Ber. 52, 130 (1919); (j)L. Michaelis, M. P. Schubert, and S. Granick, J. Am. Chem. Soc. 62, 204, 1802 (1940).
[Crossref]

Adams,

Adams and Rosenstein (cf. reference 17) also observed irreversible bleaching in acid solution of crystal violet, and studied the kinetics of the bleaching process. In this case the bleaching in acid solutions seemed to be independent of the anion.

Adams, E. Q.

E. Q. Adams and L. Rosenstein, J. Am. Chem. Soc. 36, 1452 (1914).
[Crossref]

Bury, C. R.

C. R. Bury, J. Am. Chem. Soc. 57, 2115 (1935); A. L. Sklar, J. Chem. Phys. 5, 669 (1937); L. Pauling, in H. Gilman, Organic Chemistry (John Wiley, 1938), II, p. 1888; L. Pauling, Proc. Nat. Acad. Sci. 25, 577 (1939); G. N. Lewis and M. Calvin, Chem. Rev. 25, 273 (1939); R. S. Mulliken, J. Chem. Phys. 7, 14, 20, 121, 339, 353, 356, 364, 570 (1939).
[Crossref]

Clark, W. M.

W. M. Clark, H. D. Gibbs, and B. Cohen, Public Health Reports, 40, 1131 (1935).

Cohen, B.

W. M. Clark, H. D. Gibbs, and B. Cohen, Public Health Reports, 40, 1131 (1935).

Dassler, A.

A. Thiel, A. Dassler, and F. Wülfken, Fortschritte Chemie, Physik, u. physik. Chemie 18, 4.3 (1924); E. B. R. Prideaux, Chem. Industry,  45, 664, 678 (1936); cf. W. M. Clark, Determination of Hydrogen Ions (Baltimore, 1928), p. 206.

Epstein, L. F.

E. Rabinowitch and L. F. Epstein, “The polymerization of dye-stuffs in solution. Thionine and methylene blue.” Presented at the Symposium on Structure of Molecules and Aggregates of Molecules, Division of Physical and Inorganic Chemistry, American Chemical Society, Columbia University, New York, New York, December 30, 1940 to January 1, 1941. J. Am. Chem. Soc., paper in press.

Gibbs, H. D.

W. M. Clark, H. D. Gibbs, and B. Cohen, Public Health Reports, 40, 1131 (1935).

Hardy, A. C.

Harrison, G. R.

G. R. Harrison, Proceedings of the Sixth Spectroscopy Conference (John Wiley, New York, 1939); G. R. Harrison and E. P. Bentley, J. Opt. Soc. Am. 30, 290 (1940).
[Crossref]

Holmes, W. C.

(a)W. C. Holmes, Ind. Eng. Chem. 16, 35 (1924), Am. Dyestuff Rep. 16, 429 (1927), J. Am. Chem. Soc. 50, 1923 (1928); (b)G. Körtum, Zeits. f. physik. Chemie B30, 317 (1935), Zeits. f. physik. Chemie 31, 137 (1935), Zeits. f. physik. Chemie 31, 1, 243 (1936), Zeits. f. physik. Chemie 34, 255 (1936); (c)W. E. Speas, Phys. Rev. 31, 539 (1928); (d)G. Scheibe, Kolloid, Zeits. 82, 1 (1938); G. Scheibe and L. Kandler, Naturwiss. 26, 412 (1938); G. Scheibe, A. Schöntag, J. Kopske, and K. Meule, Zeits. f. wiss. Phot. 38, 1 (1939); G. Scheibe, A. Schöntag, and E. Katheder, Naturwiss. 27, 499 (1939); (e)V. L. Lewshin, Acta Physicochimica, U. R. S. S. 1, 685 (1935), Acta Physicochimica, U. R. S. S. 4, 221 (1936).
[Crossref]

Michaelis, L.

L. Michaelis and M. P. Schubert, Chem. Rev. 22, 437 (1938).
[Crossref]

Pauling, L.

L. Pauling and co-workers, J. Chem. Phys. 1, 362, 606, 679 (1933); cf. also The Nature of the Chemical Bond, 2nd edition (Cornell University Press, Ithaca, New York, 1940).
[Crossref]

Rabinowitch, E.

E. Rabinowitch, J. Chem. Phys. 8, 551 (1940).
[Crossref]

E. Rabinowitch, J. Chem. Phys. 8, 560 (1940).
[Crossref]

E. Rabinowitch and L. F. Epstein, “The polymerization of dye-stuffs in solution. Thionine and methylene blue.” Presented at the Symposium on Structure of Molecules and Aggregates of Molecules, Division of Physical and Inorganic Chemistry, American Chemical Society, Columbia University, New York, New York, December 30, 1940 to January 1, 1941. J. Am. Chem. Soc., paper in press.

Rosenstein,

Adams and Rosenstein (cf. reference 17) also observed irreversible bleaching in acid solution of crystal violet, and studied the kinetics of the bleaching process. In this case the bleaching in acid solutions seemed to be independent of the anion.

Rosenstein, L.

E. Q. Adams and L. Rosenstein, J. Am. Chem. Soc. 36, 1452 (1914).
[Crossref]

Schubert, M. P.

L. Michaelis and M. P. Schubert, Chem. Rev. 22, 437 (1938).
[Crossref]

Stebbins, J. H.

(a)Earlier papers on thionine and its spectrum are: J. H. Stebbins, J. Am. Chem. Soc. 6, 304 (1884); (b)A. Bernthsen, Ann. 230, 111, 209 (1885); (c)M. Althausse and G. Kruss, Ber. 22, 2066 (1889); (d) Formanék and E. Grandmougin, Untersuchung und Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1908), Part 1, pp. 143, 150; Untersuchung nd Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1911), Part 2, p. 124. (e)F. Eckert and R. Pummerer, Zeits. f. physik. Chemie 87, 613 (1914); (f)F. Eckert, R. Pummerer, and S. Gassner, Ber. 47, 1495 (1914); (g)F. Kehrman, E. Havas, and E. Grandmougin, Ber. 46, 2131 (1913); Ber. 47, 1881 (1914); (h)F. Kehrman, Ber. 49, 1018 (1916); (i)F. Kehrman and P. Zybs, Ber. 52, 130 (1919); (j)L. Michaelis, M. P. Schubert, and S. Granick, J. Am. Chem. Soc. 62, 204, 1802 (1940).
[Crossref]

Thiel, A.

A. Thiel, A. Dassler, and F. Wülfken, Fortschritte Chemie, Physik, u. physik. Chemie 18, 4.3 (1924); E. B. R. Prideaux, Chem. Industry,  45, 664, 678 (1936); cf. W. M. Clark, Determination of Hydrogen Ions (Baltimore, 1928), p. 206.

Weber, K.

K. Weber, Zeits. f. physik. Chemie B15, 18 (1931).

Wülfken, F.

A. Thiel, A. Dassler, and F. Wülfken, Fortschritte Chemie, Physik, u. physik. Chemie 18, 4.3 (1924); E. B. R. Prideaux, Chem. Industry,  45, 664, 678 (1936); cf. W. M. Clark, Determination of Hydrogen Ions (Baltimore, 1928), p. 206.

Chem. Rev. (1)

L. Michaelis and M. P. Schubert, Chem. Rev. 22, 437 (1938).
[Crossref]

Fortschritte Chemie, Physik, u. physik. Chemie (1)

A. Thiel, A. Dassler, and F. Wülfken, Fortschritte Chemie, Physik, u. physik. Chemie 18, 4.3 (1924); E. B. R. Prideaux, Chem. Industry,  45, 664, 678 (1936); cf. W. M. Clark, Determination of Hydrogen Ions (Baltimore, 1928), p. 206.

Ind. Eng. Chem. (1)

(a)W. C. Holmes, Ind. Eng. Chem. 16, 35 (1924), Am. Dyestuff Rep. 16, 429 (1927), J. Am. Chem. Soc. 50, 1923 (1928); (b)G. Körtum, Zeits. f. physik. Chemie B30, 317 (1935), Zeits. f. physik. Chemie 31, 137 (1935), Zeits. f. physik. Chemie 31, 1, 243 (1936), Zeits. f. physik. Chemie 34, 255 (1936); (c)W. E. Speas, Phys. Rev. 31, 539 (1928); (d)G. Scheibe, Kolloid, Zeits. 82, 1 (1938); G. Scheibe and L. Kandler, Naturwiss. 26, 412 (1938); G. Scheibe, A. Schöntag, J. Kopske, and K. Meule, Zeits. f. wiss. Phot. 38, 1 (1939); G. Scheibe, A. Schöntag, and E. Katheder, Naturwiss. 27, 499 (1939); (e)V. L. Lewshin, Acta Physicochimica, U. R. S. S. 1, 685 (1935), Acta Physicochimica, U. R. S. S. 4, 221 (1936).
[Crossref]

J. Am. Chem. Soc. (3)

C. R. Bury, J. Am. Chem. Soc. 57, 2115 (1935); A. L. Sklar, J. Chem. Phys. 5, 669 (1937); L. Pauling, in H. Gilman, Organic Chemistry (John Wiley, 1938), II, p. 1888; L. Pauling, Proc. Nat. Acad. Sci. 25, 577 (1939); G. N. Lewis and M. Calvin, Chem. Rev. 25, 273 (1939); R. S. Mulliken, J. Chem. Phys. 7, 14, 20, 121, 339, 353, 356, 364, 570 (1939).
[Crossref]

E. Q. Adams and L. Rosenstein, J. Am. Chem. Soc. 36, 1452 (1914).
[Crossref]

(a)Earlier papers on thionine and its spectrum are: J. H. Stebbins, J. Am. Chem. Soc. 6, 304 (1884); (b)A. Bernthsen, Ann. 230, 111, 209 (1885); (c)M. Althausse and G. Kruss, Ber. 22, 2066 (1889); (d) Formanék and E. Grandmougin, Untersuchung und Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1908), Part 1, pp. 143, 150; Untersuchung nd Nachweis organischer Farbstoffe auf spektroskopischem Wege (Berlin, 1911), Part 2, p. 124. (e)F. Eckert and R. Pummerer, Zeits. f. physik. Chemie 87, 613 (1914); (f)F. Eckert, R. Pummerer, and S. Gassner, Ber. 47, 1495 (1914); (g)F. Kehrman, E. Havas, and E. Grandmougin, Ber. 46, 2131 (1913); Ber. 47, 1881 (1914); (h)F. Kehrman, Ber. 49, 1018 (1916); (i)F. Kehrman and P. Zybs, Ber. 52, 130 (1919); (j)L. Michaelis, M. P. Schubert, and S. Granick, J. Am. Chem. Soc. 62, 204, 1802 (1940).
[Crossref]

J. Chem. Phys. (3)

L. Pauling and co-workers, J. Chem. Phys. 1, 362, 606, 679 (1933); cf. also The Nature of the Chemical Bond, 2nd edition (Cornell University Press, Ithaca, New York, 1940).
[Crossref]

E. Rabinowitch, J. Chem. Phys. 8, 551 (1940).
[Crossref]

E. Rabinowitch, J. Chem. Phys. 8, 560 (1940).
[Crossref]

J. Opt. Soc. Am. (1)

Zeits. f. physik. Chemie (1)

K. Weber, Zeits. f. physik. Chemie B15, 18 (1931).

Other (9)

Made by Mr. Henry Wayringer, to whom we wish to express our thanks.

E. Rabinowitch and L. F. Epstein, “The polymerization of dye-stuffs in solution. Thionine and methylene blue.” Presented at the Symposium on Structure of Molecules and Aggregates of Molecules, Division of Physical and Inorganic Chemistry, American Chemical Society, Columbia University, New York, New York, December 30, 1940 to January 1, 1941. J. Am. Chem. Soc., paper in press.

Adams and Rosenstein (cf. reference 17) also observed irreversible bleaching in acid solution of crystal violet, and studied the kinetics of the bleaching process. In this case the bleaching in acid solutions seemed to be independent of the anion.

Beilstein reports that alkaline solutions of thionine are slowly transformed intoBoth of these reaction products are, however, strongly colored.

We are indebted to Professor L. J. Gillespie and Dr. S. D. Stookey of this laboratory for the special Pd used in these experiments.

G. R. Harrison, Proceedings of the Sixth Spectroscopy Conference (John Wiley, New York, 1939); G. R. Harrison and E. P. Bentley, J. Opt. Soc. Am. 30, 290 (1940).
[Crossref]

W. M. Clark, H. D. Gibbs, and B. Cohen, Public Health Reports, 40, 1131 (1935).

The possibility of an orthoquinoid structure, with the heterocyclic sulfur forming a sulfonium base (as was hypothesized in the older literature7) cannot be entirely dismissed, although the evidence seems to be against it.7(i)

Cf. reference 14, Fig. 3.

Cited By

OSA participates in Crossref's Cited-By Linking service. Citing articles from OSA journals and other participating publishers are listed here.

Alert me when this article is cited.


Figures (8)

Fig. 1
Fig. 1

Absorption spectrum of thionine solution in soft glass bottles, as function of time.

Fig. 2
Fig. 2

Thin cells.

Fig. 3
Fig. 3

The spectrum of thionine (2.5×10−5 m) in HCl solution (acid concentrations in moles/l).

Fig. 4
Fig. 4

The spectrum of thionine (2.5×10−5 m) in strong H2SO4 solution (acid concentrations in moles/l).

Fig. 5
Fig. 5

The spectrum of thionine (2.5×10−5 m) in alkaline solution.

Fig. 6
Fig. 6

Extinction curves of thionine solutions (2.5×10−5 m).

Fig. 7
Fig. 7

Extinction curve of methylene blue (2.0×10−5 m, pH 3.5).

Fig. 8
Fig. 8

Ultraviolet absorption spectra of leucothionine.

Tables (1)

Tables Icon

Table III Principal absorption maxima () of thionine (2.5×10−5 m).

Equations (5)

Equations on this page are rendered with MathJax. Learn more.

= ( 1 / d c ) log 10 I 0 / I
ThioH + + Thio + + H + K 1 = ( Thio + ) ( H + ) / ( ThioH + + ) .
ThioH + + + H + ThioH 2 + + +
R = NH 2 + + OH - R = NH 2 OH R = NH + H 2 O Thio + Thio hydroxide Thio base .
2 Semithionine Thionine + Leucothionine