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PREPARATION AND CHARACTERIZATION OF A NEW SILICA GEL -BASED PIRKLE -TYPE CHIRAL STATIONARY PHASE AS A NEW HPLC COLUMN PACKING MATERIAL

Yıl 2025, Cilt: 11 Sayı: 1, 23 - 31, 29.06.2025

Ramazan Altindağ , Murat Sunkur , Reşit Çakmak , Giray Topal

https://doi.org/10.51477/mejs.1679531

Öz

In this study, a new silica-based Pirkle-type chiral stationary phase was successfully prepared by using silica gel 60 as a matrix, 3-(chloropropyl)-trimethoxysilane as a spacer arm, and (S)-4-amino-N-(1-cyclohexylethyl)benzamide (II) a chiral selector; and loaded onto the high performance liquid chromatography column by using a mobile phase to prepare a new chiral high performance liquid chromatography column. The chiral selector was synthesized in two steps. In the first step, (S)-N-(1-cyclohexylethyl)-4-nitrobenzamide(I) was obtained, and then the aromatic amine derivative (II) of this compound was obtained with hydrazine hydrate and Pd/C catalyst. The prepared chiral selector (II) was then immobilized on 3-chloropropyl functionalized silica gel (III) prepared by condensation reaction of 3-(chloropropyl)-trimethoxy silane with silica gel 60. In the last step, the new chiral stationary phase derived from silica (IV) was loaded onto a commercial column with the aid of a column-packing apparatus using known methods. The structures of the synthesized chiral selector (II), the new chiral stationary phase (IV), and the characteristic features of the prepared column were investigated by spectroscopic techniques. As a result of the spectroscopic analysis, it was determined that the new chiral stationary phase was prepared successfully.

Anahtar Kelimeler

Chirality Chiral stationary phase HPLC Silica based chiral HPLC column

Etik Beyan

The author declares that this document does not require an ethics committee approval or any special permission. This study does not cause any harm to the environment.

Destekleyen Kurum

Dicle University Scientific Research Projects Coordination Unit

Proje Numarası

FBE.21.008.

Kaynakça

  • Yılmaz, H., Topal, G., Çakmak, R., Hosgoren, H., Resolution of (±)‐β‐methylphenylethylamine by a novel chiral stationary phase for Pirkle‐type column chromatography. Chirality: The Pharmacological, Biological, and Chemical Consequences of Molecular Asymmetry, 22(2), 252-257, 2010.
  • Basaran, E., Sogukomerogullari, H.G., Çakmak, R., Akkoc, S., Taskin-Tok, T., Köse, A., “Novel chiral Schiff base Palladium (II), Nickel (II), Copper (II) and Iron (II) complexes: Synthesis, characterization, anticancer activity and molecular docking studies”, Bioorganic Chemistry, 129, 106176, 2022. https://doi.org/10.1016/j.bioorg.2022.106176.
  • Başaran, E., Karaküçük‐Iyidoğan, A., Schols, D., Oruç‐Emre, E.E., “Synthesis of novel chiral sulfonamide‐bearing 1, 2, 4‐triazole‐3‐thione analogs derived from D‐and L‐phenylalanine esters as potential anti‐influenza agents”, Chirality, 28(6), 495-513, 2016. https://doi.org/10.1002/chir.22607.
  • Karaküçük-İyidoğan, A., Başaran, E., Tatar-Yılmaz, G., Oruç-Emre, E.E. “Development of new chiral 1, 2, 4-triazole-3-thiones and 1, 3, 4-thiadiazoles with promising in vivo anticonvulsant activity targeting GABAergic system and voltage-gated sodium channels (VGSCs)”, Bioorganic Chemistry, 151, 107662. 2024, https://doi.org/10.1016/j.bioorg.2024.107662.
  • Okamoto, Y., Ikai, T., “Chiral HPLC for efficient resolution of enantiomers”, Chemical Society Reviews, 37(12), 2593-2608, 2008. https://doi.org/10.1039/B808881K.
  • Lomenova, A., Hroboňová, K., “Comparison of HPLC separation of phenylalanine enantiomers on different types of chiral stationary phases”, Food Analytical Methods, 11, 3314-3323, 2018. https://doi.org/10.1007/s12161-018-1308-9.
  • Aral, H., Çelik, K.S., Altındağ, R., Aral, T., “Synthesis, characterization, and application of a novel multifunctional stationary phase for hydrophilic interaction/reversed phase mixed-mode chromatography”, Talanta, 174, 703-714, 2017. https://doi.org/10.1016/j.talanta.2017.07.014.
  • Lorenz, H., Seidel‐Morgenstern, A., “Processes to separate enantiomers”, Angewandte Chemie International Edition, 53(5), 1218-1250, 2014, https://doi.org/10.1002/anie.201302823.
  • Wang, Y., Chen, H., Xiao, Y., Ng, C.-H., Oh, T.S., Tan, T.T.Y., Ng, S.C., “Preparation of cyclodextrin chiral stationary phases by organic soluble catalytic'click'chemistry”, Nature protocols, 6(7), 935-942, 2011. https://doi.org/10.1038/nprot.2011.340.
  • Ali, I., Kumerer, K., Aboul-Enein, H.Y., “Mechanistic principles in chiral separations using liquid chromatography and capillary electrophoresis”, Chromatographia, 63, 295-307, 2006. https://doi.org/10.1365/s10337-006-0762-5.
  • Ward, T.J., “Chiral separations”, Analytical Chemistry, 72(18), 4521-4528, 2000. https://doi.org/10.1021/ac000841o.
  • Kuhn, R., Stoecklin, F., Erni, F., “Chiral separations by host-guest complexation with cyclodextrin and crown ether in capillary zone electrophoresis”, Chromatographia, 33, 32-36, 1992. https://doi.org/10.1007/BF02276847.
  • Wolf, C., Pirkle, W.H., “Synthesis and evaluation of a copolymeric chiral stationary phase”, Journal of Chromatography A, 799(1-2), 177-184, 1998. https://doi.org/10.1016/S0021-9673(97)01063-7.
  • Pirkle, W.H., Burke Iii, J.A., “Chiral stationary phase designed for β-blockers”, Journal of Chromatography A, 557, 173-185, 1991. https://doi.org/10.1016/S0021-9673(01)87131-4.
  • Pirkle, W.H., Sikkenga, D.L., “Resolution of optical isomers by liquid chromatography”, Journal of Chromatography A, 123(2), 400-404, 1976. https://doi.org/10.1016/S0021-9673(00)82210-4.
  • Vedovello, P., Costa, J.A.S., Fernandes, C., Tiritan, M. E., Paranhos, C.M., “Evaluation of chiral separation by Pirkle-type chiral selector based mixed matrix membranes”, Separation and Purification Technology, 289, 120722, 2022. https://doi.org/10.1016/j.seppur.2022.120722.
  • Çakmak, R., Ercan, S., Sunkur, M., Yilmaz, H., Topal, G., “Design, preparation and application of a Pirkle-type chiral stationary phase for enantioseparation of some racemic organic acids and molecular dynamics studies”, Organic Communications, 10(3), 216–227, 2017. http://doi.org/10.25135/acg.oc.25.17.07.0.
  • Pirkle, W.H., Pochapsky, T.C., “Considerations of chiral recognition relevant to the liquid chromatography separation of enantiomers”, Chemical Reviews, 89(2), 347-362, 1989. https://doi.org/10.1021/cr00092a006.
  • Zhao, Y., Zhu, X., Jiang, W., Liu, H., Wang, J., Sun, B., “Natural and artificial chiral-based systems for separation applications”, Critical Reviews in Analytical Chemistry, 53(1), 27-45, 2023. https://doi.org/10.1080/10408347.2021.1932408.
  • Peter, A., Lazar, L., Fülöp, F., Armstrong, D.W., “High-performance liquid chromatographic enantioseparation of β-amino acids,” Journal of Chromatography A, 926(2), 229-238, 2001. https://doi.org/10.1016/S0021-9673(01)01078-0.
  • Vargas‐Caporali, J., Juaristi, E., “Fundamental Developments of Chiral Phase Chromatography in Connection with Enantioselective Synthesis of β‐Amino Acids”, Israel Journal of Chemistry, 57(9), 896-912, 2017. https://doi.org/10.1002/ijch.201700011.
  • Simeonov, S.P., Simeonov, A.P., Todorov, A.R., Kurteva, V.B., “Enantioresolution of a series of chiral benzyl alcohols by HPLC on a dinitrobenzoylphenylglycine Stationary Phase after Achiral Pre-Column Derivatization”, American Journal of Analytical Chemistry, 1(1), 1-13, 2010. https://doi.org/10.4236/ajac.2010.11001.
  • Mane, S., “Racemic drug resolution: a comprehensive guide”, Analytical Methods, 8(42), 7567-7586, 2016. https://doi.org/10.1039/C6AY02015A.
  • Aral, H., Çelik, K.S., Aral, T., Topal, G., “Preparation of a novel ionic hybrid stationary phase by non-covalent functionalization of single-walled carbon nanotubes with amino-derivatized silica gel for fast HPLC separation of aromatic compounds”, Talanta, 149, 21-29, 2016. https://doi.org/10.1016/j.talanta.2015.11.029.
  • Ilisz, I., Aranyi, A., Péter, A., “Chiral derivatizations applied for the separation of unusual amino acid enantiomers by liquid chromatography and related techniques”, Journal of Chromatography A, 1296, 119-139, 2013. https://doi.org/10.1016/j.chroma.2013.03.034.
  • Colin, H., Guiochon, G., “Introduction to reversed-phase high-performance liquid chromatography”, Journal of Chromatography A, 141(3), 289-312, 1977. https://doi.org/10.1016/S0021-9673(00)93537-4.
  • Erdoğan, Ö., Topal, G., Çakmak, R., Sünkür, M., Canpolat, M., “The preparation of a new protein based HPLC column packing material and enantiomeric resolution of some pharmaceutical related compounds via this column”, Middle East Journal of Science, 2(1), 77-92, 2016. https://doi.org/10.23884/mejs/2016.2.1.07.
  • Engelhardt, H., Jungheim, M., “Comparison and characterization of reversed phases”, Chromatographia, 29, 59-68, 1990. https://doi.org/10.1007/BF02261141.
  • Kalili, K. M., de Villiers, A., “Recent developments in the HPLC separation of phenolic compounds”, Journal of Separation Science, 34(8), 854-876, 2011. https://doi.org/10.1002/jssc.201000811.

Yıl 2025, Cilt: 11 Sayı: 1, 23 - 31, 29.06.2025

Ramazan Altindağ , Murat Sunkur , Reşit Çakmak , Giray Topal

https://doi.org/10.51477/mejs.1679531

Öz

Proje Numarası

FBE.21.008.

Kaynakça

  • Yılmaz, H., Topal, G., Çakmak, R., Hosgoren, H., Resolution of (±)‐β‐methylphenylethylamine by a novel chiral stationary phase for Pirkle‐type column chromatography. Chirality: The Pharmacological, Biological, and Chemical Consequences of Molecular Asymmetry, 22(2), 252-257, 2010.
  • Basaran, E., Sogukomerogullari, H.G., Çakmak, R., Akkoc, S., Taskin-Tok, T., Köse, A., “Novel chiral Schiff base Palladium (II), Nickel (II), Copper (II) and Iron (II) complexes: Synthesis, characterization, anticancer activity and molecular docking studies”, Bioorganic Chemistry, 129, 106176, 2022. https://doi.org/10.1016/j.bioorg.2022.106176.
  • Başaran, E., Karaküçük‐Iyidoğan, A., Schols, D., Oruç‐Emre, E.E., “Synthesis of novel chiral sulfonamide‐bearing 1, 2, 4‐triazole‐3‐thione analogs derived from D‐and L‐phenylalanine esters as potential anti‐influenza agents”, Chirality, 28(6), 495-513, 2016. https://doi.org/10.1002/chir.22607.
  • Karaküçük-İyidoğan, A., Başaran, E., Tatar-Yılmaz, G., Oruç-Emre, E.E. “Development of new chiral 1, 2, 4-triazole-3-thiones and 1, 3, 4-thiadiazoles with promising in vivo anticonvulsant activity targeting GABAergic system and voltage-gated sodium channels (VGSCs)”, Bioorganic Chemistry, 151, 107662. 2024, https://doi.org/10.1016/j.bioorg.2024.107662.
  • Okamoto, Y., Ikai, T., “Chiral HPLC for efficient resolution of enantiomers”, Chemical Society Reviews, 37(12), 2593-2608, 2008. https://doi.org/10.1039/B808881K.
  • Lomenova, A., Hroboňová, K., “Comparison of HPLC separation of phenylalanine enantiomers on different types of chiral stationary phases”, Food Analytical Methods, 11, 3314-3323, 2018. https://doi.org/10.1007/s12161-018-1308-9.
  • Aral, H., Çelik, K.S., Altındağ, R., Aral, T., “Synthesis, characterization, and application of a novel multifunctional stationary phase for hydrophilic interaction/reversed phase mixed-mode chromatography”, Talanta, 174, 703-714, 2017. https://doi.org/10.1016/j.talanta.2017.07.014.
  • Lorenz, H., Seidel‐Morgenstern, A., “Processes to separate enantiomers”, Angewandte Chemie International Edition, 53(5), 1218-1250, 2014, https://doi.org/10.1002/anie.201302823.
  • Wang, Y., Chen, H., Xiao, Y., Ng, C.-H., Oh, T.S., Tan, T.T.Y., Ng, S.C., “Preparation of cyclodextrin chiral stationary phases by organic soluble catalytic'click'chemistry”, Nature protocols, 6(7), 935-942, 2011. https://doi.org/10.1038/nprot.2011.340.
  • Ali, I., Kumerer, K., Aboul-Enein, H.Y., “Mechanistic principles in chiral separations using liquid chromatography and capillary electrophoresis”, Chromatographia, 63, 295-307, 2006. https://doi.org/10.1365/s10337-006-0762-5.
  • Ward, T.J., “Chiral separations”, Analytical Chemistry, 72(18), 4521-4528, 2000. https://doi.org/10.1021/ac000841o.
  • Kuhn, R., Stoecklin, F., Erni, F., “Chiral separations by host-guest complexation with cyclodextrin and crown ether in capillary zone electrophoresis”, Chromatographia, 33, 32-36, 1992. https://doi.org/10.1007/BF02276847.
  • Wolf, C., Pirkle, W.H., “Synthesis and evaluation of a copolymeric chiral stationary phase”, Journal of Chromatography A, 799(1-2), 177-184, 1998. https://doi.org/10.1016/S0021-9673(97)01063-7.
  • Pirkle, W.H., Burke Iii, J.A., “Chiral stationary phase designed for β-blockers”, Journal of Chromatography A, 557, 173-185, 1991. https://doi.org/10.1016/S0021-9673(01)87131-4.
  • Pirkle, W.H., Sikkenga, D.L., “Resolution of optical isomers by liquid chromatography”, Journal of Chromatography A, 123(2), 400-404, 1976. https://doi.org/10.1016/S0021-9673(00)82210-4.
  • Vedovello, P., Costa, J.A.S., Fernandes, C., Tiritan, M. E., Paranhos, C.M., “Evaluation of chiral separation by Pirkle-type chiral selector based mixed matrix membranes”, Separation and Purification Technology, 289, 120722, 2022. https://doi.org/10.1016/j.seppur.2022.120722.
  • Çakmak, R., Ercan, S., Sunkur, M., Yilmaz, H., Topal, G., “Design, preparation and application of a Pirkle-type chiral stationary phase for enantioseparation of some racemic organic acids and molecular dynamics studies”, Organic Communications, 10(3), 216–227, 2017. http://doi.org/10.25135/acg.oc.25.17.07.0.
  • Pirkle, W.H., Pochapsky, T.C., “Considerations of chiral recognition relevant to the liquid chromatography separation of enantiomers”, Chemical Reviews, 89(2), 347-362, 1989. https://doi.org/10.1021/cr00092a006.
  • Zhao, Y., Zhu, X., Jiang, W., Liu, H., Wang, J., Sun, B., “Natural and artificial chiral-based systems for separation applications”, Critical Reviews in Analytical Chemistry, 53(1), 27-45, 2023. https://doi.org/10.1080/10408347.2021.1932408.
  • Peter, A., Lazar, L., Fülöp, F., Armstrong, D.W., “High-performance liquid chromatographic enantioseparation of β-amino acids,” Journal of Chromatography A, 926(2), 229-238, 2001. https://doi.org/10.1016/S0021-9673(01)01078-0.
  • Vargas‐Caporali, J., Juaristi, E., “Fundamental Developments of Chiral Phase Chromatography in Connection with Enantioselective Synthesis of β‐Amino Acids”, Israel Journal of Chemistry, 57(9), 896-912, 2017. https://doi.org/10.1002/ijch.201700011.
  • Simeonov, S.P., Simeonov, A.P., Todorov, A.R., Kurteva, V.B., “Enantioresolution of a series of chiral benzyl alcohols by HPLC on a dinitrobenzoylphenylglycine Stationary Phase after Achiral Pre-Column Derivatization”, American Journal of Analytical Chemistry, 1(1), 1-13, 2010. https://doi.org/10.4236/ajac.2010.11001.
  • Mane, S., “Racemic drug resolution: a comprehensive guide”, Analytical Methods, 8(42), 7567-7586, 2016. https://doi.org/10.1039/C6AY02015A.
  • Aral, H., Çelik, K.S., Aral, T., Topal, G., “Preparation of a novel ionic hybrid stationary phase by non-covalent functionalization of single-walled carbon nanotubes with amino-derivatized silica gel for fast HPLC separation of aromatic compounds”, Talanta, 149, 21-29, 2016. https://doi.org/10.1016/j.talanta.2015.11.029.
  • Ilisz, I., Aranyi, A., Péter, A., “Chiral derivatizations applied for the separation of unusual amino acid enantiomers by liquid chromatography and related techniques”, Journal of Chromatography A, 1296, 119-139, 2013. https://doi.org/10.1016/j.chroma.2013.03.034.
  • Colin, H., Guiochon, G., “Introduction to reversed-phase high-performance liquid chromatography”, Journal of Chromatography A, 141(3), 289-312, 1977. https://doi.org/10.1016/S0021-9673(00)93537-4.
  • Erdoğan, Ö., Topal, G., Çakmak, R., Sünkür, M., Canpolat, M., “The preparation of a new protein based HPLC column packing material and enantiomeric resolution of some pharmaceutical related compounds via this column”, Middle East Journal of Science, 2(1), 77-92, 2016. https://doi.org/10.23884/mejs/2016.2.1.07.
  • Engelhardt, H., Jungheim, M., “Comparison and characterization of reversed phases”, Chromatographia, 29, 59-68, 1990. https://doi.org/10.1007/BF02261141.
  • Kalili, K. M., de Villiers, A., “Recent developments in the HPLC separation of phenolic compounds”, Journal of Separation Science, 34(8), 854-876, 2011. https://doi.org/10.1002/jssc.201000811.
Toplam 29 adet kaynakça vardır.

Ayrıntılar

Birincil Dil İngilizce
Konular Organik Kimyasal Sentez
Bölüm Makale
Yazarlar

Ramazan Altindağ 0000-0003-2862-5312

Murat Sunkur 0000-0002-8513-7860

Reşit Çakmak 0000-0003-0401-7419

Giray Topal 0000-0002-7056-3912

Proje Numarası FBE.21.008.
Erken Görünüm Tarihi 26 Haziran 2025
Yayımlanma Tarihi 29 Haziran 2025
Gönderilme Tarihi 18 Nisan 2025
Kabul Tarihi 4 Haziran 2025
Yayımlandığı Sayı Yıl 2025 Cilt: 11 Sayı: 1

Kaynak Göster

IEEE R. Altindağ, M. Sunkur, R. Çakmak, ve G. Topal, “PREPARATION AND CHARACTERIZATION OF A NEW SILICA GEL -BASED PIRKLE -TYPE CHIRAL STATIONARY PHASE AS A NEW HPLC COLUMN PACKING MATERIAL”, MEJS, c. 11, sy. 1, ss. 23–31, 2025, doi: 10.51477/mejs.1679531.
 Kapak Resmi İndir

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