Skip to main content
SpringerLink
Log in

Novel highly emissive non-proteinogenic amino acids: synthesis of 1,3,4-thiadiazolyl asparagines and evaluation as fluorimetric chemosensors for biologically relevant transition metal cations

  • Original Article
  • Published:
Amino Acids Aims and scope Submit manuscript

Abstract

Highly emissive heterocyclic asparagine derivatives bearing a 1,3,4-thiadiazolyl unit at the side chain, functionalised with electron donor or acceptor groups, were synthesised and evaluated as amino acid-based fluorimetric chemosensors for metal cations, such as Cu2+, Zn2+, Co2+ and Ni2+. The results suggest that there is a strong interaction through the donor heteroatoms at the side chain of the various asparagine derivatives, with high sensitivity towards Cu2+ in a ligand–metal complex with 1:2 stoichiometry. Association constants and detection limits for Cu2+ were calculated. The photophysical and metal ion sensing properties of these asparagine derivatives confirm their potential as fluorimetric chemosensors and suggest that they can be suitable for incorporation into chemosensory peptidic frameworks.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Abo-Ghalia M, Amr A (2004) Synthesis and investigation of a new cyclo (N α-dipicolinoyl) pentapeptide of a breast and CNS cytotoxic activity and an ionophoric specificity. Amino Acids 26:283–289

    Article  PubMed  CAS  Google Scholar 

  • Azab HA, El-Korashy SA, Anwar ZM, Hussein BHM, Khairy GM (2010) Synthesis and fluorescence properties of Eu-anthracene-9-carboxylic acid towards N-acetyl amino acids and nucleotides in different solvents. Spectrochim Acta A 75:21–27

    Article  CAS  Google Scholar 

  • Batista RMF, Oliveira E, Costa SPG, Lodeiro C, Raposo MMM (2007) Synthesis and ion sensing properties of new colorimetric and fluorimetric chemosensors based on bithienyl-imidazo-anthraquinone chromophores. Org Lett 9:3201–3204

    Article  PubMed  CAS  Google Scholar 

  • Batista RMF, Oliveira E, Costa SPG, Lodeiro C, Raposo MMM (2008) Synthesis and evaluation of bipendant-armed (oligo)thiophene crown ether derivatives as new chemical sensors. Tetrahedron Lett 49:6575–6578

    Article  CAS  Google Scholar 

  • Batista RMF, Oliveira E, Nuñez C, Costa SPG, Lodeiro C, Raposo MMM (2009) Synthesis and evaluation of new thienyl and bithienyl-bis-indolylmethanes as colorimetric sensors for anions. J Phys Org Chem 22:362–366

    Article  CAS  Google Scholar 

  • Cheng RP, Fisher SL, Imperiali B (1996) Metallopeptide design: tuning the metal cation affinities with unnatural amino acids and peptide secondary structure. J Am Chem Soc 118:11349–11356

    Article  CAS  Google Scholar 

  • Costa SPG, Maia HLS, Pereira-Lima SMMA (2003) An improved approach for the synthesis of α,α-dialkyl glycine derivatives by the Ugi–Passerini reaction. Org Biomol Chem 1:1475–1479

    Article  PubMed  CAS  Google Scholar 

  • Costa SPG, Oliveira E, Lodeiro C, Raposo MMM (2007) Synthesis, characterization and metal ion detection of novel fluoroionophores based on heterocyclic substituted alanines. Sensors 7:2096–2114

    Article  CAS  Google Scholar 

  • Costa SPG, Oliveira E, Lodeiro C, Raposo MMM (2008a) Heteroaromatic alanine derivatives bearing (oligo)thiophene units: synthesis and photophysical properties. Tetrahedron Lett 49:5258–5261

    Article  CAS  Google Scholar 

  • Costa SPG, Batista RMF, Raposo MMM (2008b) Synthesis and photophysical characterization of new fluorescent bis-amino acids bearing a heterocyclic bridge containing benzoxazole and thiophene. Tetrahedron 64:9733–9737

    Article  CAS  Google Scholar 

  • Esteves CIC, Silva AMF, Raposo MMM, Costa SPG (2009) Unnatural benz-X-azolyl asparagine derivatives as novel fluorescent amino acids: synthesis and photophysical characterization. Tetrahedron 65:9373–9377

    Article  CAS  Google Scholar 

  • Fan L-J, Zhang Y, Murphy CB, Angell SE, Parker MFL, Flynn BR, Jones WE Jr (2009) Fluorescent conjugated polymer molecular wire chemosensors for transition metal ion recognition and signaling. Coord Chem Rev 253:410–422

    Article  CAS  Google Scholar 

  • Fedorova OA, Andryukhina EN, Yu V, Fedorov M, Panfilov A, Alfimov MV, Jonusauskas G, Grelard A, Dufourc E (2006) Supramolecular assemblies of crown-containing 2-styrylbenzothiazole with amino acids. Org Biomol Chem 4:1007–1013

    Article  PubMed  CAS  Google Scholar 

  • García-Raso A, Fiol JJ, Adrover B, Tauler P, Pons A, Mata I, Espinosa E, Molins E (2003) Reactivity of copper(II) peptide complexes with bioligands (benzimidazole and creatinine). Polyhedron 22:3255–3264

    Article  Google Scholar 

  • Gooding JJ, Hibbert DB, Yang W (2001) Electrochemical metal ion sensors exploiting amino acids and peptides as recognition elements. Sensors 1:75–90

    Article  CAS  Google Scholar 

  • Gupta VK, Goyal RN, Agarwal S, Kumar P, Bachheti (2007) Nickel(II)-selective sensor based on dibenzo-18-crown-6 in PVC matrix. Talanta 71:795–800

    Article  PubMed  CAS  Google Scholar 

  • Heinrich MR, Steglich W (2003) Effective syntheses of quinoline-7,8-diol, 5-amino-l-DOPA, and 3-(7,8-dihydroxyquinolin-5-yl)-l-alanine. Tetrahedron 59:9231–9237

    Article  CAS  Google Scholar 

  • Heinrichs G, Schellentrager M, Kubic S (2006) An enantioselective fluorescence sensor for glucose based on a cyclic tetrapeptide containing two boronic acid binding sites. Eur J Org Chem 18:4177–4186

    Article  Google Scholar 

  • Hodgson DRW, Sanderson JM (2004) The synthesis of peptides and proteins containing non-natural amino acids. Chem Soc Rev 33:422–430

    Article  PubMed  CAS  Google Scholar 

  • Holler MG, Campo LF, Brandelli A, Stefani V (2002) Synthesis and spectroscopic characterization of 2-(2′-hydroxyphenyl)benzazole isothiocyanates as new fluorescent probes for proteins. J Photochem Photobiol A Chem 149:217–225

    Article  CAS  Google Scholar 

  • Ishida H, Kyakuno M, Oishi S (2004) Molecular design of functional peptides by utilizing unnatural amino acids: towards artificial and photofunctional protein. Biopolymers (Pep Sci) 76:69–82

    Article  CAS  Google Scholar 

  • Joshi BP, Park J, Lee WI, Lee K-H (2009) Ratiometric and turn-on monitoring for heavy and transition metal ions in aqueous solution with a fluorescent peptide sensor. Talanta 78:903–909

    Article  PubMed  CAS  Google Scholar 

  • Kozlowski H, Bal W, Dyba M, Kowalik-Jankowska T (1999) Specific structure–stability relations in metallopeptides. Coord Chem Rev 184:319–346

    Article  CAS  Google Scholar 

  • Kumar P, Shim Y-B (2009) A novel cobalt (II)-selective potentiometric sensor based on p-(4-n-butylphenylazo)calyx[4]arene. Talanta 77:1057–1062

    Article  PubMed  CAS  Google Scholar 

  • Li H, Yan H (2009) Ratiometric fluorescent mercuric sensor based on thiourea-thiadiazole-pyridine linked organic nanoparticles. J Phys Chem B 113:7526–7530

    CAS  Google Scholar 

  • Lin J, Li Z-B, Zhang H-C, Pu L (2004) Highly enantioselective fluorescent recognition of α-amino acid derivatives. Tetrahedron Lett 45:103–106

    Article  CAS  Google Scholar 

  • Mandl CP, König B (2005) Luminescent crown ether amino acids-selective binding to N-terminal lysine in peptides. J Org Chem 70:670–674

    Article  PubMed  CAS  Google Scholar 

  • Martínez-Manêz R, Sancenón F (2006) Chemodosimeters and 3D inorganic functionalised hosts for the fluoro-chromogenic sensing of anions. Coord Chem Rev 250:3081–3093

    Article  Google Scholar 

  • Mathews JM, Loughlin FE, Mackay JP (2008) Designed metal-binding sites in biomolecular and bioinorganic interactions. Curr Opin Struct Biol 18:484–490

    Article  Google Scholar 

  • Miller JC (1993) Statistics for analytical chemistry, 3rd ed, Prentice Hall, New York

  • Morris JV, Mahaney MA, Huber JR (1976) Fluorescence quantum yield determinations. 9,10-Diphenylanthracene as a reference standard in different solvents. J Phys Chem 80:969–974

    Article  CAS  Google Scholar 

  • Nadler A, Hain C, Diederichsen U (2009) Histidine analog amino acids providing metal-binding sites derived from bioinorganic model systems. Eur J Org Chem 2009:4593–4599

  • Pfeffer FM, Lim KF, Sedgewick KJ (2007) Indole as a scaffold for anion recognition. Org Biomol Chem 5:1795–1799

    Article  PubMed  CAS  Google Scholar 

  • Qu F, Liu J, Yan H, Peng L, Li H (2008) Synthesis of organic nanoparticles of naphthalene–thiourea–thiadiazole-linked molecule as highly selective fluorescent and colorimetric sensor for Ag(I). Tetrahedron Lett 49:7438–7441

    Article  CAS  Google Scholar 

  • Schneider HJ, Strongin RM (2009) Supramolecular interactions in chemomechanical polymers. Acc Chem Res 42:1489–1500

    Article  PubMed  CAS  Google Scholar 

  • Shimazaki Y, Takani M, Yamauchi O (2009) Metal complexes of amino acids and amino acid side chain groups. Structure and properties. Dalton Trans 38:7854–7869

    Google Scholar 

  • Togrul M, Askin M, Hosgoren H (2005) Synthesis of chiral monoaza-15-crown-5 ethers from a chiral amino alcohol and enantiomeric recognition of potassium and sodium salts of amino acids. Tetrahedron Asym 16:2771–2777

    Article  CAS  Google Scholar 

  • Torrado A, Imperiali B (1996) New synthetic amino acids for the design and synthesis of peptide-based metal ion sensors. J Org Chem 61:8940–8948

    Article  PubMed  CAS  Google Scholar 

  • Voyer N, Côté S, Biron E, Beaumont M, Chaput M, Levac S (2001) Chiral recognition of carboxylic acids by biscrown ether peptides. J Supramol Chem 1:1–5

    Article  CAS  Google Scholar 

  • Wang H-H, Xue L, Fang Z-J, Li G-P, Jiang H (2010) A colorimetric and fluorescent chemosensor for copper ions in aqueous media and its application in living cells. New J Chem 34:1239–1242

    Google Scholar 

  • Wright AT, Anslyn EV (2004) Cooperative metal coordination and ion-pairing in tripeptide recognition. Org Lett 6:1341–1344

    Article  PubMed  CAS  Google Scholar 

  • Xu Z, Yoon J, Spring DR (2010) Fluorescent chemosensors for Zn2+. Chem Soc Rev 39:1996–2006

    Article  PubMed  CAS  Google Scholar 

  • Yang W, Jaramillo D, Gooding JJ, Hibbert DB, Zhang R, Willett GD, Fisher KJ (2001) Subppt detection limits for copper ions with Gly-Gly-His modified electrodes. Chem Comm 19:1982–1983

    Article  PubMed  Google Scholar 

  • Zhao J, Davidson MG, Mahon MF, Kociok-Köhn G, James TD (2004) An enantioselective fluorescent sensor for sugar acids. J Am Chem Soc 126:16179–16186

    Article  PubMed  CAS  Google Scholar 

  • Zheng Y, Cao X, Orbulescu J, Konka V, Andreopoulos FM, Pham SM, Leblanc RM (2003) Peptidyl fluorescent chemosensors for the detection of divalent copper. Anal Chem 75:1706–1712

    Article  PubMed  CAS  Google Scholar 

Download references

Acknowledgments

Thanks are due to the Fundação para a Ciência e Tecnologia (Portugal) for financial support through project PTDC/QUI/66250/2006 (FCOMP-01-0124-FEDER-007428) and a research grant to C. Esteves. The NMR spectrometer Bruker Avance III 400 is part of the National NMR Network and was purchased within the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT.

Author information

Authors and Affiliations

  1. Centro de Química, Universidade do Minho, Campus de Gualtar, 4710-057, Braga, Portugal

    Cátia I. C. Esteves, M. Manuela M. Raposo & Susana P. G. Costa

Authors
  1. Cátia I. C. Esteves
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Manuela M. Raposo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Susana P. G. Costa
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Susana P. G. Costa.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Esteves, C.I.C., Raposo, M.M.M. & Costa, S.P.G. Novel highly emissive non-proteinogenic amino acids: synthesis of 1,3,4-thiadiazolyl asparagines and evaluation as fluorimetric chemosensors for biologically relevant transition metal cations. Amino Acids 40, 1065–1075 (2011). https://doi.org/10.1007/s00726-010-0730-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00726-010-0730-0

Keywords

Search

Navigation