Skip to main content
SpringerLink
Log in

l-Leucinamide hydrogensquarate: spectroscopic and structural elucidation

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

Abstract

The hydrogensquarate [LeuNH2] (HSq) of l-leucinamide has been synthesized and its structure has been determined by single crystal X-ray diffraction. A three dimensional network is formed by hydrogen bonds with participation of the O=C–NH2 function, the hydrogensquarate ion and the N+H3 group [NH2⋯O=C(Sq) (2.840 and 2.749 Å), (Sq)OH⋯O=C(NH2) (2.618 Å), NH3 +⋯O=C(Sq) (3.246, 2.804 and 2.823 Å)], respectively. A theoretical approximation of the electronic structure was carried out by means of ab initio UMP2 and MP2 level of theory at the 6-311++G** basis set. The IR-spectroscopic assignment in the solid-phase was obtained by linear-polarized IR-spectroscopy of oriented samples as colloid suspensions in a nematic host and application of the reducing-difference procedure for the interpretation of polarized IR-spectra.

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
Scheme 2
Fig. 2
Scheme 3
Fig. 3
Fig. 4

Similar content being viewed by others

References

  • Chemla D, Zyss J (eds) (1987) Nonlinear optical properties of organic molecules and crystals, vol 1. Academic Press, New York, pp 23–187

  • Doi M, Asano A, Yamamoto D (2003) Hydrogen bond between water and the phenyl ring in the structure of a dipeptide H–Phe–Leu–NH2 at 90 K and the structure-based energy estimations. Chem Lett 32:1102–1003

    Article  CAS  Google Scholar 

  • Eipper BA, Mains RE (1988) Peptide alpha-amidation. Annu Rev Physiol 50:333–344. doi:10.1146/annurev.ph.50.030188.002001

    Article  PubMed  CAS  Google Scholar 

  • Head-Gordon H, Head-Gordon M, Frisch MJ, Brooks CIII, Pople J (1991) Theoretical study of blocked glycine and alanine peptide analogs. J Am Chem Soc 113:5989–5997. doi:10.1021/ja00016a010

    Article  CAS  Google Scholar 

  • Ichikawa T, Iitaka Y (1969) The crystal structure of dl-acetylleucine N-methylamide, C9H18O2N2. Acta Crystallogr 25B:1824–1833

    Google Scholar 

  • In Y, Fujii M, Sasada Y, Ishida Y (2001) Structural studies on C-amidated amino acids and peptides: structures of hydrochloride salts of C-amidated Ile, Val, Thr, Ser, Met, Trp, Gln and Arg, and comparison with their C-unamidated counterparts. Acta Crystallogr B 57:72–81. doi:10.1107/S0108768100013975

    Article  PubMed  CAS  Google Scholar 

  • Ivanova BB, Arnaudov MG, Bontchev PR (2004) IR/LD analysis of Cu(I) complex of homocysteine. Spectrochim Acta 60A:855

    CAS  Google Scholar 

  • Ivanova BB, Tsalev DL, Arnaudov MG (2006) Validation of reducing-difference procedure for the interpretation of non-polarized infrared spectra of n-component solid mixtures. Talanta 69:822–828. doi:10.1016/j.talanta.2005.11.026

    Article  PubMed  CAS  Google Scholar 

  • Ivanova BB, Simeonov V, Arnaudov M, Tsalev D (2007) Linear-dichroic infrared spectroscopy––validation and experimental design of the orientation technique as suspension in nematic liquid crystal. Spectrochim Acta [A] 67A:66–75. doi:10.1016/j.saa.2006.06.025

    Article  CAS  Google Scholar 

  • Kim CU, Misco PF (1992) A facile synthesis of 1-Hydroxy-2-phosphonocyclobutenedione. Tetrahedron Lett 33:3961–3962. doi:10.1016/0040-4039(92)88072-D

    Article  CAS  Google Scholar 

  • Kolev T, Petrova R, Spiteller M (2004) (R)-2-[(2-Ethoxy-3, 4-dioxocyclobut-1-en-1-yl)amino]-3-phenylpropanamide hemihydrate. Acta Crystallogr E 60:o634

    Article  CAS  Google Scholar 

  • Kolev T, Spiteller M, Sheldrick WS, Mayer-Figge H (2005) 1-(Aminocarbonyl)ethylammonium hydrogensquarate monohydrate. Acta Crystallogr E 61:o4292–o4293

    Article  CAS  Google Scholar 

  • Kolev T, Spiteller M, Sheldrick WS, Mayer-Figge H, Van Almsick T (2006a) l-Tyrosinamide hydrochloride monohydrate. Acta Crystallogr E 61:o3819

    Article  CAS  Google Scholar 

  • Kolev T, Cherneva E, Spiteller M, Sheldrick WS, Mayer-Figge H (2006b) l-Methioninamide ester amide of squaric acid diethyl ester. Acta Crystallogr E 62:o1390–o1392

    Article  CAS  Google Scholar 

  • Kolev T, Koleva BB, Cherneva E, Spiteller M, Sheldrick WS, Mayer-Figge H (2006c) Crystal structure, IR-LD spectroscopic, theoretical and vibrational analysis of valinamide ester amide of squaric acid diethyl ester. Struct Chem 17:491–499. doi:10.1007/s11224-006-9071-8

    Article  CAS  Google Scholar 

  • Kolev T, Yancheva D, Spiteller M, Sheldrick WS, Mayer-Figge H (2006d) l-Prolinamidium hydrogensquarate. Acta Crystallogr E 62:o463–o464

    CAS  Google Scholar 

  • Kolev T, Spiteller M, Sheldrick WS, Mayer-Figge H (2006e) l-Argininamidium bis(hydrogensquarate). Acta Crystallogr C 62:o299–o300. doi:10.1107/S0108270106012108

    Article  PubMed  CAS  Google Scholar 

  • Kolev T, Koleva BB, Spiteller M (2007a) Spectroscopic and theoretical characterization of hydrogensquarates of l-threonyl-l-serine and l-serine prediction of structures of the neutral and protonated forms of the dipeptide. Amino Acids 33:719–725. doi:10.1007/s00726-006-0391-1

    Article  PubMed  CAS  Google Scholar 

  • Kolev T, Koleva BB, Seidel RW, Mayer-Figge H, Spiteller M, Sheldrick WS (2007b) Tyrammonium 4-nitrophthalate dihydrate––structural and spectroscopic elucidation. Amino Acids. doi:10.1007/s00726-007-0021-6

  • Kolev TM, Koleva BB, Spiteller M, Sheldrick WS, Mayer-Figge H (2008a) Synthesis, spectroscopic and structural elucidation of tyrosinamide hydrogensquarate monohydrate. Amino Acids. doi:10.1007/s00726-008-0047-4

  • Kolev TM, Koleva BB, Spiteller M, Sheldrick WS, Mayer-Figge H (2008b) Synthesis, spectroscopic and structural elucidation of sympathomimetic amine, tyraminium dihydrogenphosphate. Amino Acids. doi:10.1007/s00726-008-0046-5

  • Koleva BB, Kolev TM, Simeonov V, Spassov T, Spiteller M (2008) Linear polarized IR-spectroscopy of partial oriented solids as a colloid suspension in nematic liquid crystal––new tool for structural elucidation of the chemical compounds. J Inclus Prenome. doi:10.1007/s10847-008-9425-5

  • Kulathila R, Merkler KA, Merkler DJ (1999) Enzymatic formation of C-terminal amides. Nat Prod Rep 16:145–155. doi:10.1039/a801346b

    Article  PubMed  CAS  Google Scholar 

  • Merkler D (1994) C-Terminal amidated peptides: production by the in vitro enzymatic amidation of glycine-extended peptides and the importance of the amide to bioactivity. J Enzyme Microb Technol 16:450–456. doi:10.1016/0141-0229(94)90014-0

    Article  CAS  Google Scholar 

  • Michl J, Thulstrup E (1986) Spectroscopy with polarized light. Solute alignment by photoselection, in liquid crystals, polymers, and membranes. VCH Publishers, New York

    Google Scholar 

  • Nalwa HS, Watanabe T, Miyata S (1997) In: Nalwa HS, Miyata S (eds) Nonlinear optics of organic molecules and polymers. CRC Press, Boca Raton, pp 89–29

    Google Scholar 

  • Gaussian 98: Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Zakrzewski VG, Montgomery Jr JA, Stratmann R, Burant C, Dapprich S, Millam M, Daniels A, Kudin K, Strain M, Farkas P, Tomasi J, Barone V, Cossi M, Cammi R, Mennucci B, Pomelli C, Adamo C, Clifford S, Ochterski J, Petersson GA, Ayala PY, Cui Q, Morokuma K, Salvador P, Dannenberg JJ, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Cioslowski J, Ortiz JV, Baboul AG, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komáromi I, Gomperts R, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Andres JL, Gonzalez C, Head-Gordon M, Replogle ES, Pople JP. Gaussian 98. Gaussian, Inc., Pittsburgh, 1998

  • Puliti R, Mattia CA, Giancola C, Barone G (2001) Crystal structure and conformational stability of N-acetyl-l-prolyl-l-leucinamide. Comparison between structural and thermophysical data. J Mol Struct 553:117–130. doi:10.1016/S0022-2860(00)00537-8

    Article  Google Scholar 

  • Ramachandran G, Sasisekharan V (1968) Conformation of polypeptides and proteins. Adv Protein Chem (Kyoto) 23:283–437

    Article  CAS  Google Scholar 

  • Sheldrick GM (1997a) SHELXS-97. Program for crystal structure solution. University of Cottingen, Germany

    Google Scholar 

  • Sheldrick GM (1997b) SHELXL-97. Program for crystal structure solution. University of Cottingen, Germany

    Google Scholar 

  • Suwan S, Isobe M, Yamashita O, Minakata H, Imai K (1994) Silkworm diapause hormone, structure–activity relationships indispensable role of C-terminal amide Ins Biochem. Mol Biol 24:1001–1007

    CAS  Google Scholar 

  • Sztaricskai F, Sum A, Roth E, Pelyvas I, Sandor S, Batta G, Herczegh P, Remenyi P, Miklan Z, Hudecz F (2005) A new class of semisynthetic anthracycline glycoside antibiotics incorporating a squaric acid moiety. J Antibiot 58:704–714

    Article  PubMed  CAS  Google Scholar 

  • Tevyashova A, Sztaricskai F, Batta G, Herczegh P, Jeney A (2004) Formation of squaric acid amides of anthracycline antibiotics synthesis and cytotoxic properties. Bioorg Med Chem Lett 14:4783–4789. doi:10.1016/j.bmcl.2004.06.072

    Article  PubMed  CAS  Google Scholar 

  • Vargas R, Garza J, Hay B, Dixon D (2002) Conformational study of the alanine dipeptide at the MP2 and DFT levels. J Phys Chem A 106:3213–3218. doi:10.1021/jp013952f

    Article  CAS  Google Scholar 

  • Wolff JJ, Wortmann R (1999) For a general introduction to non-linear optics of organic compounds. Adv Phys Org Chem 32:121–152. doi:10.1016/S0065-3160(08)60007-6

    Article  CAS  Google Scholar 

  • Xie J, Comeau AB, Seto CT (2004) Squaric Acids: a new motif for designing inhibitors of protein tyrosine phosphatases. Org Lett 6:83–86. doi:10.1021/ol036121w

    Article  PubMed  CAS  Google Scholar 

  • Zimmerman S, Pottle M, Nemethy G, Scheraga H (1977) Conformational analysis of the 20 naturally occurring amino acid residues using ECEPP. Macromolecules 10:1–9

    Article  PubMed  CAS  Google Scholar 

Download references

Acknowledgments

B. B. K. wishes to thank the Alexander von Humboldt Foundation for the Fellowship and T.K. the DAAD for a grant within the priority program “Stability Pact South-Eastern Europe” and the Alexander von Humboldt Foundation. Supporting information: Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC 693631 Copies of this information may be obtained from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (Fax: +44 1223 336 033; e-mail: deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).

Author information

Authors and Affiliations

  1. Institut für Umweltforschung, Universität Dortmund, Otto-Hahn-Strasse 6, 44221, Dortmund, Germany

    Tsonko Kolev & Michael Spiteller

  2. Faculty of Chemistry, University of Sofia “St. Kl. Ohridsky”, 1164, Sofia, Bulgaria

    Sonya Zareva

  3. Lehrstuhl für Analytische Chemie, Ruhr-Universität Bochum, Universitätsstraße 150, 44780, Bochum, Germany

    Heike Mayer-Figge, William S. Sheldrick & Bojidarka B. Koleva

Authors
  1. Tsonko Kolev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sonya Zareva
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Heike Mayer-Figge
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Michael Spiteller
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. William S. Sheldrick
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Bojidarka B. Koleva
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Bojidarka B. Koleva.

Electronic supplementary material

Below is the link to the electronic supplementary material.

SUPPORTING INFORMATION (DOC 40 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kolev, T., Zareva, S., Mayer-Figge, H. et al. l-Leucinamide hydrogensquarate: spectroscopic and structural elucidation. Amino Acids 37, 693–701 (2009). https://doi.org/10.1007/s00726-008-0189-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00726-008-0189-4

Keywords

Search

Navigation