Skip to main content
SpringerLink
Log in

Studies of decarboxylation in photolysis of α-carboxy-2-nitrobenzyl (CNB) caged compounds

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

Photolysis of α-carboxy-2-nitrobenzyl (CNB) caged compounds, studied here by time-resolved IR and UV spectroscopy, involves at least two pathways. In one, a conventional 2-nitrobenzyl type rearrangement takes place to release the photoprotected species via rapid decay of an aci- nitro intermediate. The α-carboxylate moiety of the CNB group is retained and the final by-product from this pathway is 2-nitrosophenylglyoxylate. Direct measurements of product formation confirmed that release via this pathway is faster for CNB-caged compounds than for related caged compounds without an a-carboxylate substituent and a rationale for the faster release rate is proposed. In a second pathway, photodecarboxylation of the starting material occurs: this pathway leads only to a slow, minor release of the photoprotected species. The extent to which the latter pathway contributes is affected by the nature of buffer salts in the irradiated solution. It was more prominent in an amine-based buffer (MOPS) than in phosphate buffer.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. J. E. T. Corrie, 2-Nitrobenzyl and 7-nitroindoline derivatives, in Dynamic Studies in Biology: Phototriggers, Photoswitches and Caged Biomolecules, ed. M. Goeldner and R. Givens, Wiley VCH, Weinheim, ch. 1.1, 2005.

    Google Scholar 

  2. S. R. Adams, R. Y. Tsien, Controlling cell chemistry with caged compounds, Annu. Rev. Physiol., 1993, 55, 755–784.

    Article  CAS  PubMed  Google Scholar 

  3. J. H. Kaplan, Photochemical manipulation of divalent cation levels, Annu. Rev. Physiol., 1990, 52, 897–914.

    Article  CAS  PubMed  Google Scholar 

  4. Caged Compounds, Methods in Enzymology, ed. G. Marriott, Academic Press, New York, 1998, vol. 291

  5. A. Pelliccioli, J. Wirz, Photochemical protecting groups: reaction mechanisms and applications, Photochem. Photobiol. Sci., 2002, 1, 441–458.

    Article  PubMed  Google Scholar 

  6. J. H. Kaplan, B. Forbush, J. F. Hoffman, Rapid photorelease of adenosine 5’-triphosphate from a protected analogue: utilization by the Na:K pump of human red blood cell ghosts, Biochemistry, 1978, 17, 1929–1935.

    Article  CAS  PubMed  Google Scholar 

  7. J. W. Walker, J. A. McCray, G. P. Hess, Photolabile protecting groups for an acetylcholine-receptor ligand-synthesis and photochemistry of a new class of ortho-nitrobenzyl derivatives and their effects on receptor function, Biochemistry, 1986, 25, 1799–1805.

    Article  CAS  PubMed  Google Scholar 

  8. T. Milburn, N. Matsubara, A. P. Billington, J. B. Udgaonkar, J. W. Walker, B. K. Carpenter, W. W. Webb, J. Marque, W. Denk, J. A. McCray, G. P. Hess, Synthesis, photochemistry, and biological activity of a caged photolabile acetylcholine receptor ligand, Biochemistry, 1989, 28, 49–55.

    Article  CAS  PubMed  Google Scholar 

  9. C. Y. Chang, B. Niblack, B. Walker, H. Bayley, A photogenerated pore-forming protein, Chem. Biol., 1995, 2, 391–400.

    Article  CAS  PubMed  Google Scholar 

  10. P. Pan, H. Bayley, Caged cysteine and thiophosphoryl peptides, FEBS Lett., 1997, 405, 81–85.

    Article  CAS  PubMed  Google Scholar 

  11. R. Wieboldt, K. R. Gee, L. Niu, D. Ramesh, B. K. Carpenter, G. P. Hess, Photolabile precursors of glutamate: synthesis, photochemical properties, and activation of glutamate receptors on a microsecond time scale, Proc. Natl. Acad. Sci. USA, 1994, 91, 8752–8756.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. A. P. Billington, K. M. Walstrom, D. Ramesh, A. P. Guzikowski, B. K. Carpenter, G. P. Hess, Synthesis and photochemistry of photolabile N-glycine derivatives and effects of one on the glycine receptor, Biochemistry, 1992, 31, 5500–5507.

    Article  CAS  PubMed  Google Scholar 

  13. D. Ramesh, R. Wieboldt, A. P. Billington, B. K. Carpenter, G. P. Hess, Photolabile precursors of biological amides: synthesis and characterization of caged o-nitrobenzyl derivatives of glutamine, asparagines, glycinamide and g-aminobutyrate, J. Org. Chem., 1993, 58, 4599–4605.

    Article  CAS  Google Scholar 

  14. K. R. Gee, L. Niu, K. Schaper, G. P. Hess, Caged bioactive carboxylates. Synthesis, photolysis studies, and biological characterization of a new caged N-methyl-d-aspartic acid, J. Org. Chem., 1995, 60, 4260–4263.

    Article  CAS  Google Scholar 

  15. R. Wieboldt, D. Ramesh, B. K. Carpenter, G. P. Hess, Synthesis and photochemistry of photolabile derivatives of g-aminobutyric acid for chemical kinetic investigations of the g-aminobutyric acid receptor in the millisecond time region, Biochemistry, 1994, 33, 1526–1533.

    Article  CAS  PubMed  Google Scholar 

  16. F. M. Rossi, M. Margulis, C. M. Tang, J. P. Y. Kao, N-Nmoc-l-glutamate, a new caged glutamate with high chemical stability and low pre-photolysis activity, J. Biol. Chem., 1997, 272, 32933–32939.

    Article  CAS  PubMed  Google Scholar 

  17. F. M. Rossi, J. P. Y. Kao, N-Nmoc-DBHQ, a new caged molecule for modulating sarcoplasmic/endoplasmic reticulum Ca2+ ATPase activity with light flashes, J. Biol. Chem., 1997, 272, 3266–3271.

    Article  CAS  PubMed  Google Scholar 

  18. J. W. Walker, H. Martin, F. R. Schmidt, R. J. Barsotti, Rapid release of an a-adrenergic receptor ligand from photolabile analogues, Biochemistry, 1993, 32, 1338–1345.

    Article  CAS  PubMed  Google Scholar 

  19. J. W. Walker, Z. Lu, R. L. Moss, Effects of Ca2+ on the kinetics of phosphate release in skeletal muscle, J. Biol. Chem., 1992, 267, 2459–2466.

    Article  CAS  PubMed  Google Scholar 

  20. C. Grewer, J. Jäger, B. K. Carpenter, G. P. Hess, A new photolabile precursor of glycine with improved properties: a tool for chemical kinetic investigations of the glycine receptor, Biochemistry, 2000, 39, 2063–2070.

    Article  CAS  PubMed  Google Scholar 

  21. K. Schaper, S. A. M. Mobarekeh, C. Grewer, Synthesis and photophysical characterization of a new, highly hydrophilic caging group, Eur. J. Org. Chem., 2002, 1037–1046.

    Google Scholar 

  22. Q. Cheng, M. G. Steinmetz, V. Jayaraman, Photolysis of λ-(a-carboxy-2-nitrobenzyl)-l-glutamic acid investigated in the microsecond time scale by time-resolved FTIR, J. Am. Chem. Soc., 2002, 124, 7676–7677.

    Article  CAS  PubMed  Google Scholar 

  23. M. Schwörer, J. Wirz, Photochemical reaction mechanisms of 2-nitrobenzyl compounds in solution. I. 2-Nitrotoluene: thermodynamic and kinetic parameters of the aci-nitro tautomer, Helv. Chim. Acta, 2001, 84, 1441–1457.

    Article  Google Scholar 

  24. Y. V. Il’ichev, J. Wirz, Rearrangements of 2-nitrobenzyl compounds. I. Potential, energy surface of 2-nitrotoluene and its isomers explored with ab initio and density functional theory methods, J. Phys. Chem. A, 2000, 104, 7856–7870.

    Article  CAS  Google Scholar 

  25. J. D. Margerum, C. T. Petrusis, The photodecarboxylation of nitrophenylacetate ions, J. Am. Chem. Soc., 1969, 91, 2467–2472.

    Article  CAS  Google Scholar 

  26. J. W. Walker, G. P. Reid, J. A. McCray, D. R. Trentham, Photolabile 1-(2-nitrophenyl)ethyl phosphate esters of adenine nucleotide analogues. Synthesis and mechanism of photolysis, J. Am. Chem. Soc., 1988, 110, 7170–7177.

    Article  CAS  Google Scholar 

  27. J. E. T. Corrie, A. de Santis, Y. Katayama, K. Khodakhah, J. B. Messenger, D. C. Ogden, D. R. Trentham, Post-synaptic activation at the squid giant synapse by flash photolytic release of glutamate from a “caged” l-glutamate, J. Physiol., 1993, 465, 1–8.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  28. F. S. Parker, Applications of Infrared Spectroscopy in Biochemistry, Biology and Medicine, Plenum, New York, 1971, p. 365.

    Book  Google Scholar 

  29. V. Jayaraman, S. Thiran, D. R. Madden, Fourier transform infrared spectroscopic characterization of a photolabile precursor of glutamate, FEBS Lett., 2000, 475, 278–282.

    Article  CAS  PubMed  Google Scholar 

  30. H. Brintzinger, G. G. Hammes, Inner- and outer-sphere complex formation in aqueous solutions of nickel(ii)-methyl phosphate, Inorg. Chem., 1966, 5, 1286–1287.

    Article  CAS  Google Scholar 

  31. J. E. T. Corrie, M. J. Gradwell, G. Papageorgiou, Non-photochemical rearrangements of o-nitrobenzyl compounds, J. Chem. Soc., Perkin Trans. 1, 1999, 2977–2982.

    Google Scholar 

  32. H. Tomioka, N. Ichikawa, K. Komatsu, Photochemistry of (2-nitrophenyl)diazomethane studied by the matrix isolation technique. (Nitrophenyl)carbene to (carboxypheny)carbene rearrangement by successive reduction of the nitro group with the carbonic center, J. Am. Chem. Soc., 1992, 114, 8045–8053.

    Article  CAS  Google Scholar 

  33. R. Sreekumar, Y. Q. Ping, X. P. Huang, J. W. Walker, Stereospecific protein kinase C activation by photolabile diglycerides, Bioorg. Med. Chem. Lett., 1997, 7, 341–346.

    Article  CAS  Google Scholar 

  34. A. Barth, S. R. Martin, J. E. T. Corrie, Decarboxylation is a significant reaction pathway for photolabile calcium chelators and related compounds, Photochem. Photobiol. Sci., 2006, 5, 107–115.

    Article  CAS  PubMed  Google Scholar 

  35. C. Ho, J. M. Sturtevant, The kinetics of hydration of carbon dioxide at 25°, J. Biol. Chem., 1963, 238, 3499–3501.

    Article  CAS  PubMed  Google Scholar 

  36. J. E. T. Corrie, Y. Katayama, G. P. Reid, M. Anson, D. R. Trentham, The development and application of photosensitive caged compounds to aid time-resolved structure determination of macromolecules, Philos. Trans. R. Soc. London, Ser. A, 1992, 340, 233–244.

    Article  CAS  Google Scholar 

  37. A. Barth, K. Hauser, W. Mäntele, J. E. T. Corrie, D. R. Trentham, The photochemical release of ATP from “caged ATP” studied by time-resolved infrared spectroscopy, J. Am. Chem. Soc., 1995, 117, 10311–10316.

    Article  CAS  Google Scholar 

  38. A. Barth, J. E. T. Corrie, M. J. Gradwell, Y. Maeda, W. Mäntele, T. Meier, D. R. Trentham, Time-resolved infrared spectroscopy of intermediates and products from photolysis of 1-(2-nitrophenyl)ethyl phosphates: reaction of the 2-nitrosoacetophenone by-product with thiols, J. Am. Chem. Soc., 1997, 119, 4149–4159.

    Article  CAS  Google Scholar 

  39. G. Papageorgiou, A. Barth, J. E. T. Corrie, Flash photolytic release of alcohols from photolabile carbamates or carbonates is rate-limited by decarboxylation of the photoproduct, Photochem. Photobiol. Sci., 2005, 4, 216–220.

    Article  CAS  PubMed  Google Scholar 

  40. E. Campaigne, G. Skwronski, R. B. Rogers, Synthesis of ß-dimethylaminoethyl and a-hydroxy-ß-dimethylaminoethyl derivatives from organolithium reagents and tetramethoxamide, Synth. Commun., 1973, 3, 325–332.

    Article  CAS  Google Scholar 

  41. T. Kolasa, M. J. Miller, Reactions of a-hydroxy carbonyl compounds with azodicarboxylates and triphenylphosphine: synthesis of a- N-hydroxy amino acid derivatives, J. Org. Chem., 1987, 52, 4978–4984.

    Article  CAS  Google Scholar 

  42. J. Chen, R. F. Cunico, Synthesis of a-ketoamides from a carbamoylsilane and acid chlorides, J. Org. Chem., 2004, 69, 5509–5511.

    Article  CAS  PubMed  Google Scholar 

  43. H. Bredereck, G. Simchen, G. Kapaun, R. Wahl, Über die Umsetzung von p-Tolyl-und Anisaldehyd mit einem Aminal-tert-butyl ester zu [1.2-Bis-dimethylamino-vinyl]-arylketonen, Chem. Ber., 1970, 103, 2980–2983.

    Article  CAS  Google Scholar 

  44. Y. Pocker, J. E. Meany, B. J. Nist, C. Zadorojny, The reversible hydration of pyruvic acid. I. Equilibrium, studies, J. Phys. Chem., 1969, 73, 2979–2882.

    Google Scholar 

  45. S. Pinchas and I. Laulicht, Infrared Spectra of Labelled Compounds, Academic Press, London, 1971, p. 212.

    Google Scholar 

  46. P. Wan, S. Muralidharan, Structure and mechanism in the photo-retro-aldol type reactions of nitrobenzyl derivatives. Photochemical heterolytic cleavage of C-C bonds, J. Am. Chem. Soc., 1988, 110, 4336–4365.

    Article  CAS  Google Scholar 

  47. W. P. Jencks, J. Carriuolo, Structure of pyruvate in aqueous solution, Nature, 1958, 182, 598–599.

    Article  CAS  PubMed  Google Scholar 

  48. M. Kakihana, M. Okamoto, Vibrational analysis of pyruvate ion molecules and estimation of equilibrium constants for their hydrogen isotopic exchange reactions, J. Phys. Chem., 1984, 88, 1797–1804.

    Article  CAS  Google Scholar 

  49. A. Barth and J. E. T. Corrie, unpublished data

  50. M. Aresta, A. Dibenedetto, E. Quaranta, Reaction of alkali-metal tetraphenylborates with amines in the presence of CO2; a new easy way to aliphatic and aromatic alkali-metal carbamates, J. Chem. Soc., Dalton Trans., 1995, 3359–3363.

    Google Scholar 

  51. J. Chouteau, Sur certaines anomalies du spectre infrarouge des acylglycines, C. R. Hebd. Seances Acad. Sci., 1953, 237, 891–893.

    CAS  Google Scholar 

  52. W. W. Wright, J. M. Vanderkooi, Use of IR absorption of the carbonyl group of amino acids and their metabolites to determine pKs, to study proteins and to monitor enzyme activity, Biospectroscopy, 1997, 3, 457–467.

    Article  CAS  Google Scholar 

  53. G. Papageorgiou, D. C. Ogden, A. Barth, J. E. T. Corrie, Photorelease of carboxylic acids from 1-acyl-7-nitroindolines in aqueous solution: rapid and efficient photorelease ofl-glutamate, J. Am. Chem. Soc., 1999, 121, 6503–6504.

    Article  CAS  Google Scholar 

  54. G. Papageorgiou, J. E. T. Corrie, Effects of aromatic substitution on the photocleavage of 1-acyl-7-nitroindolines, Tetrahedron, 2000, 56, 8197–8205.

    Article  CAS  Google Scholar 

  55. J. A. Dantzig, Y. E. Goldman, N. C. Millar, J. Lacktis, E. Homsher, Reversal of the cross-bridge force-generating transition by photogeneration of phosphate in rabbit psoas muscle fibres, J. Physiol., 1992, 451, 247–278.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  56. D. R. Trentham and J. E. T. Corrie, unpublished result

  57. G. Wettermark, E. Black, L. Dogliotti, Reactions of photochemically formed transients from 2-nitrotoluene, Photochem. Photobiol., 1965, 4, 229–239.

    Article  CAS  Google Scholar 

  58. G. Kortüm, W. Vogel and K. Andrusson, Dissociation Constants of Organic Acids in Aqueous Solution, Butterworths, London, 1961, p. 267.

    Google Scholar 

  59. E. P. Sergeant and B. Dempsey, Ionisation Constants of Organic Acids in Aqueous Solution, Pergamon, Oxford, 1979, p. 75.

    Google Scholar 

  60. J. E. T. Corrie and D. R. Trentham, in Biological Applications of Photochemical Switches, ed. H. Morrison, Wiley, New York, 1993, pp. 267–271.

  61. G. Papageorgiou, J. E. T. Corrie, Synthesis and properties of carbamoyl derivatives of photolabile benzoins, Tetrahedron, 1997, 53, 3917–3932.

    Article  CAS  Google Scholar 

  62. M. Caplow, Kinetics of carbamate formation and breakdown, J. Am. Chem. Soc., 1968, 90, 6795–6803.

    Article  CAS  Google Scholar 

  63. S. P. Ewing, D. Lockshon, W. P. Jencks, Mechanism of cleavage of carbamate anions, J. Am. Chem. Soc., 1980, 102, 3072–3084.

    Article  CAS  Google Scholar 

  64. J. Morrison, P. Wan, J. E. T. Corrie, V. R. N. Munasinghe, Chemistry of photogenerated a-hydroxy- p-nitrobenzyl carbanions in aqueous solution: protonation vs. disproportionation, Can. J. Chem., 2003, 81, 586–597.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. MRC National Institute for Medical Research, The Ridgeway, Mill Hill, London, UK, NW7 1AA.

    John E. T. Corrie, V. Ranjit N. Munasinghe & David R. Trentham

  2. Department of Biochemistry and Biophysics, Arrhenius Laboratories for Natural Sciences, Stockholm University, SE-106 91, Stockholm, Sweden

    Andreas Barth

Authors
  1. John E. T. Corrie
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. Ranjit N. Munasinghe
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. David R. Trentham
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Andreas Barth
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to John E. T. Corrie.

Additional information

Electronic supplementary information (ESI) available: Photolysis spectra of NPE-caged monomethyl phosphate (Fig. S1) and of 2-nitrobenzyl monomethyl phosphate (Fig. S2); isotope effect spectra for photolysis of the two isotopomers of 7 (Fig. S3); details of the synthesis of the precursor compounds for synthesis of 9 together with the method used for quantitative measurement of CO2 formation in the IR spectroscopic cells. See DOI: 10.1039/b711398f

Rights and permissions

Reprints and permissions

About this article

Cite this article

Corrie, J.E.T., Munasinghe, V.R.N., Trentham, D.R. et al. Studies of decarboxylation in photolysis of α-carboxy-2-nitrobenzyl (CNB) caged compounds. Photochem Photobiol Sci 7, 84–97 (2008). https://doi.org/10.1039/b711398f

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/b711398f

Search

Navigation