Abstract

A novel method of measuring the electrically induced dichroism of macromolecular solutions is described. Transient changes in the solution absorption are recorded when the solute molecules are aligned by pulsed electric fields that are applied along the incident path. Previous methods have applied fields transverse to the optical beam which has had to be variably polarized. The present longitudinal arrangement needs no polarizer, is simpler, can yield the required information in a single suitable measurement, and has other distinct advantages over the former transverse arrangements. The theory for the effect is derived, and the interrelation of these novel longitudinal measurements with the conventional transverse data is verified by measurements on an aqueous solution of the amylose triiodide complex.

© 1972 Optical Society of America

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References

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  1. L. F. Cavalieri, R. H. Rosenberg, M. Rosoff, J. Am. Chem. Soc. 78, 5235 (1956).
    [CrossRef]
  2. R. Morgan, Biophysical J. 3, 253 (1963).
    [CrossRef]
  3. K. Yoshioka, H. Watanabe, in Physical Principles and Techniques of Protein Chemistry, S. Leach, Ed. (Academic, New York, 1969), Part A.
  4. J. Milstien, E. Charney, Biopolymers 9, 991 (1970).
    [CrossRef]
  5. E. Charney, J. Milsteien, K. Yamaoka, J. Am. Chem. Soc. 92, 2657 (1970).
    [CrossRef] [PubMed]
  6. D. Zucker, J. F. Foster, G. H. Miller, J. Phys. Chem. 56, 170 (1952).
    [CrossRef]
  7. G. Bird, E. Blout, J. Chem. Phys. 25, 798 (1956).
    [CrossRef]
  8. G. Spach, Compt. Rend. 246, 667 (1959).
  9. G. A. Dvorkin, Dokl. Akad. Nauk. SSSR 135, 739 (1960) [Sov. Phys. Dokl. 5, 1375 (1960)].
  10. G. Houssier, Ind. Chem. Belg. 30, 235 (1965).
  11. C. M. Paulson, C. T. O’Konski, Polymer Preprints7, 1175 (1966).
  12. F. S. Allen, K. E. Van Holde, Rev. Sci. Instrum. 41, 211 (1970).
    [CrossRef]
  13. E. J. Ambrose, A. E. Elliott, Proc. Roy. Soc. (London) A205, 47 (1951).
  14. W. Gratzer, G. Holzwarth, P. Doty, Proc. Nat. Acad. Sci. 47, 1785 (1961).
    [CrossRef]
  15. G. Holzwarth, P. Doty, J. Am. Chem. Soc. 87, 218 (1965).
    [CrossRef]
  16. P. Callis, N. Davidson, Biopolymers 7, 335 (1969).
    [CrossRef]
  17. T. Miyazawa, in Poly-α-Amino Acids, G. Fasman, Ed. (E. Arnold, London, 1967), Chap. 2, p. 96.
  18. W. Kuhn, H. Duhrkop, H. Martin, Z. Phys. Chem. Abteilung B45, 121 (1940).
  19. D. N. Holcomb, I. Tinoco, J. Phys. Chem. 67, 2691 (1963).
    [CrossRef]
  20. C. T. O’Konski, in Encyclopedia of Polymer Science and Technology (Interscience, New York, 1966), Vol. 9.
  21. S. Zaromb, J. Y. Chang, J. Electrochem. Soc. 109, 1034 (1962).
    [CrossRef]

1970 (3)

J. Milstien, E. Charney, Biopolymers 9, 991 (1970).
[CrossRef]

E. Charney, J. Milsteien, K. Yamaoka, J. Am. Chem. Soc. 92, 2657 (1970).
[CrossRef] [PubMed]

F. S. Allen, K. E. Van Holde, Rev. Sci. Instrum. 41, 211 (1970).
[CrossRef]

1969 (1)

P. Callis, N. Davidson, Biopolymers 7, 335 (1969).
[CrossRef]

1965 (2)

G. Holzwarth, P. Doty, J. Am. Chem. Soc. 87, 218 (1965).
[CrossRef]

G. Houssier, Ind. Chem. Belg. 30, 235 (1965).

1963 (2)

R. Morgan, Biophysical J. 3, 253 (1963).
[CrossRef]

D. N. Holcomb, I. Tinoco, J. Phys. Chem. 67, 2691 (1963).
[CrossRef]

1962 (1)

S. Zaromb, J. Y. Chang, J. Electrochem. Soc. 109, 1034 (1962).
[CrossRef]

1961 (1)

W. Gratzer, G. Holzwarth, P. Doty, Proc. Nat. Acad. Sci. 47, 1785 (1961).
[CrossRef]

1960 (1)

G. A. Dvorkin, Dokl. Akad. Nauk. SSSR 135, 739 (1960) [Sov. Phys. Dokl. 5, 1375 (1960)].

1959 (1)

G. Spach, Compt. Rend. 246, 667 (1959).

1956 (2)

G. Bird, E. Blout, J. Chem. Phys. 25, 798 (1956).
[CrossRef]

L. F. Cavalieri, R. H. Rosenberg, M. Rosoff, J. Am. Chem. Soc. 78, 5235 (1956).
[CrossRef]

1952 (1)

D. Zucker, J. F. Foster, G. H. Miller, J. Phys. Chem. 56, 170 (1952).
[CrossRef]

1951 (1)

E. J. Ambrose, A. E. Elliott, Proc. Roy. Soc. (London) A205, 47 (1951).

1940 (1)

W. Kuhn, H. Duhrkop, H. Martin, Z. Phys. Chem. Abteilung B45, 121 (1940).

Allen, F. S.

F. S. Allen, K. E. Van Holde, Rev. Sci. Instrum. 41, 211 (1970).
[CrossRef]

Ambrose, E. J.

E. J. Ambrose, A. E. Elliott, Proc. Roy. Soc. (London) A205, 47 (1951).

Bird, G.

G. Bird, E. Blout, J. Chem. Phys. 25, 798 (1956).
[CrossRef]

Blout, E.

G. Bird, E. Blout, J. Chem. Phys. 25, 798 (1956).
[CrossRef]

Callis, P.

P. Callis, N. Davidson, Biopolymers 7, 335 (1969).
[CrossRef]

Cavalieri, L. F.

L. F. Cavalieri, R. H. Rosenberg, M. Rosoff, J. Am. Chem. Soc. 78, 5235 (1956).
[CrossRef]

Chang, J. Y.

S. Zaromb, J. Y. Chang, J. Electrochem. Soc. 109, 1034 (1962).
[CrossRef]

Charney, E.

J. Milstien, E. Charney, Biopolymers 9, 991 (1970).
[CrossRef]

E. Charney, J. Milsteien, K. Yamaoka, J. Am. Chem. Soc. 92, 2657 (1970).
[CrossRef] [PubMed]

Davidson, N.

P. Callis, N. Davidson, Biopolymers 7, 335 (1969).
[CrossRef]

Doty, P.

G. Holzwarth, P. Doty, J. Am. Chem. Soc. 87, 218 (1965).
[CrossRef]

W. Gratzer, G. Holzwarth, P. Doty, Proc. Nat. Acad. Sci. 47, 1785 (1961).
[CrossRef]

Duhrkop, H.

W. Kuhn, H. Duhrkop, H. Martin, Z. Phys. Chem. Abteilung B45, 121 (1940).

Dvorkin, G. A.

G. A. Dvorkin, Dokl. Akad. Nauk. SSSR 135, 739 (1960) [Sov. Phys. Dokl. 5, 1375 (1960)].

Elliott, A. E.

E. J. Ambrose, A. E. Elliott, Proc. Roy. Soc. (London) A205, 47 (1951).

Foster, J. F.

D. Zucker, J. F. Foster, G. H. Miller, J. Phys. Chem. 56, 170 (1952).
[CrossRef]

Gratzer, W.

W. Gratzer, G. Holzwarth, P. Doty, Proc. Nat. Acad. Sci. 47, 1785 (1961).
[CrossRef]

Holcomb, D. N.

D. N. Holcomb, I. Tinoco, J. Phys. Chem. 67, 2691 (1963).
[CrossRef]

Holzwarth, G.

G. Holzwarth, P. Doty, J. Am. Chem. Soc. 87, 218 (1965).
[CrossRef]

W. Gratzer, G. Holzwarth, P. Doty, Proc. Nat. Acad. Sci. 47, 1785 (1961).
[CrossRef]

Houssier, G.

G. Houssier, Ind. Chem. Belg. 30, 235 (1965).

Kuhn, W.

W. Kuhn, H. Duhrkop, H. Martin, Z. Phys. Chem. Abteilung B45, 121 (1940).

Martin, H.

W. Kuhn, H. Duhrkop, H. Martin, Z. Phys. Chem. Abteilung B45, 121 (1940).

Miller, G. H.

D. Zucker, J. F. Foster, G. H. Miller, J. Phys. Chem. 56, 170 (1952).
[CrossRef]

Milsteien, J.

E. Charney, J. Milsteien, K. Yamaoka, J. Am. Chem. Soc. 92, 2657 (1970).
[CrossRef] [PubMed]

Milstien, J.

J. Milstien, E. Charney, Biopolymers 9, 991 (1970).
[CrossRef]

Miyazawa, T.

T. Miyazawa, in Poly-α-Amino Acids, G. Fasman, Ed. (E. Arnold, London, 1967), Chap. 2, p. 96.

Morgan, R.

R. Morgan, Biophysical J. 3, 253 (1963).
[CrossRef]

O’Konski, C. T.

C. M. Paulson, C. T. O’Konski, Polymer Preprints7, 1175 (1966).

C. T. O’Konski, in Encyclopedia of Polymer Science and Technology (Interscience, New York, 1966), Vol. 9.

Paulson, C. M.

C. M. Paulson, C. T. O’Konski, Polymer Preprints7, 1175 (1966).

Rosenberg, R. H.

L. F. Cavalieri, R. H. Rosenberg, M. Rosoff, J. Am. Chem. Soc. 78, 5235 (1956).
[CrossRef]

Rosoff, M.

L. F. Cavalieri, R. H. Rosenberg, M. Rosoff, J. Am. Chem. Soc. 78, 5235 (1956).
[CrossRef]

Spach, G.

G. Spach, Compt. Rend. 246, 667 (1959).

Tinoco, I.

D. N. Holcomb, I. Tinoco, J. Phys. Chem. 67, 2691 (1963).
[CrossRef]

Van Holde, K. E.

F. S. Allen, K. E. Van Holde, Rev. Sci. Instrum. 41, 211 (1970).
[CrossRef]

Watanabe, H.

K. Yoshioka, H. Watanabe, in Physical Principles and Techniques of Protein Chemistry, S. Leach, Ed. (Academic, New York, 1969), Part A.

Yamaoka, K.

E. Charney, J. Milsteien, K. Yamaoka, J. Am. Chem. Soc. 92, 2657 (1970).
[CrossRef] [PubMed]

Yoshioka, K.

K. Yoshioka, H. Watanabe, in Physical Principles and Techniques of Protein Chemistry, S. Leach, Ed. (Academic, New York, 1969), Part A.

Zaromb, S.

S. Zaromb, J. Y. Chang, J. Electrochem. Soc. 109, 1034 (1962).
[CrossRef]

Zucker, D.

D. Zucker, J. F. Foster, G. H. Miller, J. Phys. Chem. 56, 170 (1952).
[CrossRef]

Biophysical J. (1)

R. Morgan, Biophysical J. 3, 253 (1963).
[CrossRef]

Biopolymers (2)

J. Milstien, E. Charney, Biopolymers 9, 991 (1970).
[CrossRef]

P. Callis, N. Davidson, Biopolymers 7, 335 (1969).
[CrossRef]

Compt. Rend. (1)

G. Spach, Compt. Rend. 246, 667 (1959).

Dokl. Akad. Nauk. SSSR (1)

G. A. Dvorkin, Dokl. Akad. Nauk. SSSR 135, 739 (1960) [Sov. Phys. Dokl. 5, 1375 (1960)].

Ind. Chem. Belg. (1)

G. Houssier, Ind. Chem. Belg. 30, 235 (1965).

J. Am. Chem. Soc. (3)

E. Charney, J. Milsteien, K. Yamaoka, J. Am. Chem. Soc. 92, 2657 (1970).
[CrossRef] [PubMed]

G. Holzwarth, P. Doty, J. Am. Chem. Soc. 87, 218 (1965).
[CrossRef]

L. F. Cavalieri, R. H. Rosenberg, M. Rosoff, J. Am. Chem. Soc. 78, 5235 (1956).
[CrossRef]

J. Chem. Phys. (1)

G. Bird, E. Blout, J. Chem. Phys. 25, 798 (1956).
[CrossRef]

J. Electrochem. Soc. (1)

S. Zaromb, J. Y. Chang, J. Electrochem. Soc. 109, 1034 (1962).
[CrossRef]

J. Phys. Chem. (2)

D. N. Holcomb, I. Tinoco, J. Phys. Chem. 67, 2691 (1963).
[CrossRef]

D. Zucker, J. F. Foster, G. H. Miller, J. Phys. Chem. 56, 170 (1952).
[CrossRef]

Proc. Nat. Acad. Sci. (1)

W. Gratzer, G. Holzwarth, P. Doty, Proc. Nat. Acad. Sci. 47, 1785 (1961).
[CrossRef]

Proc. Roy. Soc. (London) (1)

E. J. Ambrose, A. E. Elliott, Proc. Roy. Soc. (London) A205, 47 (1951).

Rev. Sci. Instrum. (1)

F. S. Allen, K. E. Van Holde, Rev. Sci. Instrum. 41, 211 (1970).
[CrossRef]

Z. Phys. Chem. Abteilung (1)

W. Kuhn, H. Duhrkop, H. Martin, Z. Phys. Chem. Abteilung B45, 121 (1940).

Other (4)

C. T. O’Konski, in Encyclopedia of Polymer Science and Technology (Interscience, New York, 1966), Vol. 9.

T. Miyazawa, in Poly-α-Amino Acids, G. Fasman, Ed. (E. Arnold, London, 1967), Chap. 2, p. 96.

K. Yoshioka, H. Watanabe, in Physical Principles and Techniques of Protein Chemistry, S. Leach, Ed. (Academic, New York, 1969), Part A.

C. M. Paulson, C. T. O’Konski, Polymer Preprints7, 1175 (1966).

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Figures (5)

Fig. 1
Fig. 1

Interrelation of coordinate systems, x, y, z define the laboratory set, with the electric field along the y axis. The a, b, c set refers to the molecular geometry.

Fig. 2
Fig. 2

Schematic diagram of the apparatus. The electrical components are identified as follows: PM, photomultiplier; PG, pulse generator; PA, pulse amplifier; L, load; AT, attenuator; O, oscilloscope; and C, camera. E designates the cell electrodes.

Fig. 3
Fig. 3

Cells; for longitudinal measurements. (A) and (B) indicate a single and a multiple cell assembly, respectively. Each body is of ptfe; the windows are of quartz, coated on the inner sides with a conducting stannic oxide film.

Fig. 4
Fig. 4

Test cells: (A) is a Kerr cell, used in conjunction with suitably polarized light for transverse field measurements; (B) is suitable for both longitudinal and transverse measurements. Windows W1 and W2 are coated with stannic oxide.

Fig. 5
Fig. 5

Transient dichroism measurements on amylose triiodide solutions. The top and bottom traces of (A) are the longitudinal and perpendicular transverse cases, respectively. They are of the same sign and amplitude. The top and bottom traces of (B) are the longitudinal and parallel transverse cases, respectively. They are of opposite sign and differ in magnitude by a factor of two.

Equations (16)

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

I = I * exp ( 0 c l ) ,
P = 22 cos 2 ϕ + 11 sin 2 ϕ .
S = 22 sin 2 ϕ cos 2 θ + 11 cos 2 ϕ cos 2 θ + 11 sin 2 θ = ( 22 11 ) sin 2 ϕ cos 2 θ + 11 .
L x = 22 sin 2 ϕ cos 2 θ + 11 cos 2 ϕ cos 2 θ + 11 sin 2 θ = ( 22 11 ) sin 2 ϕ cos 2 θ + 11 ,
L z = 11 cos 2 ϕ sin 2 θ + 22 sin 2 ϕ sin 2 θ + 11 cos 2 θ = ( 22 11 ) sin 2 ϕ sin 2 θ + 11 .
sin 2 θ = cos 2 θ = 1 2 ,
P = ( 22 + 2 11 3 ) + 1 3 ( 22 11 ) ( 3 cos 2 ϕ 1 ) .
S = ( 22 + 2 11 3 ) 1 6 ( 22 11 ) ( 3 cos 2 ϕ 1 ) ,
L = ( 22 + 2 11 3 ) 1 6 ( 22 11 ) ( 3 cos 2 ϕ 1 ) .
0 = [ ( 22 + 2 11 ) / 3 ] ,
i = 0 + Δ i , where i refers to P , S , or L .
Δ P = + 1 3 ( 22 11 ) . f . = P 0 , Δ S = 1 6 ( 22 11 ) . f . = S 0 ,
Δ L = 1 6 ( 22 11 ) . f . = L 0 ,
f = 3 cos 2 ϕ 1 .
Δ L sat = 1 3 ( 22 11 ) ,
0 = 1 3 ( 22 + 2 11 ) ,

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