SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE
Two thio-containing complexones – S,S'-ethylenedithiodialanin (EDAL) and S,S'-carboxy-ethylenedithiodialanin (СEDAL) – were synthesized by the alkylation reaction of L-cysteine with dibromoethane. The developed technique has a number of advantages compared to those described in the litera...
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| Дата: | 2022 |
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| Автори: | , , , , |
| Формат: | Стаття |
| Мова: | English |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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| Онлайн доступ: | https://ucj.org.ua/index.php/journal/article/view/494 |
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| Назва журналу: | Ukrainian Chemistry Journal |
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oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4942023-02-07T11:55:15Z SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE Trunova , Elena Artamonova, Ganna Rusakova, Mariya Vasin, Oleksei Glushakov, Vladimir synthesis, thio-containing complexones, complexes, cuprum, molybdenum, biological activity. Two thio-containing complexones – S,S'-ethylenedithiodialanin (EDAL) and S,S'-carboxy-ethylenedithiodialanin (СEDAL) – were synthesized by the alkylation reaction of L-cysteine with dibromoethane. The developed technique has a number of advantages compared to those described in the literature: the absence of ammonia and metallic sodium as synthesis reagents, a decrease in the synthesis temperature and time, an increase in the yield of the final product to ~95%. The physicochemical properties of complesones were investigated using (1H, 13C) NMR, pH-potentiometry, UV-VIS, IR-spectroscopy, DTA and non-quantitative mass spectrometry. The acid dissociation constants of EDAL (pКN1=9.79; pКN2=8.79; pКCOO1=3.25) and СEDAL (pКN1=9.81; pКN2=8.17; pКCOO1=2.82; pКCOO2=3.34) were calculated and the scheme of protonation of complexons depending on pH was proposed. On the basis of NMR spectroscopy data, it is shown that the complexons have a folded structure, mobile along the S-CN2СНСООН and N–CH–COOH axes, in which betaine nitrogen atoms form two intramolecular five-membered glycine cycles due to the rapid exchange of labile protons of СООН groups. In addition, there is an intermolecular cycle in the molecule, which includes an ethylenethioamine fragment. DTA data show the presence of adsorbed and crystallization water in molecules of thio-complexons, which is eliminated at 100–170 0С. Intraspherical water molecules are located between molecular layers and form a branched system of hydrogen bonds. The final temperature of the decomposition of compounds is ~4600C. Probably, the end products of EDAL and СEDAL decomposition are non-stoichiometric sulfates or sulfides. Complex formation of thio-complexons with Mo(VI) and Cu(II) at their equimolar ratio was investigated in aqueous solutions in a wide pH range (1÷10). The formation of complexes of the composition MoO3CEDAL and CuEDAL in the range of pH 4–9 is shown and the structure of the complexes is proposed. The biological activity of carboxy-ethylenedithiodialanin and its complexes with Cu(II) was studied. It has been proven that the compounds exhibit fungistatic properties against pathogenic bacteria Candida spp. (main causative agents of fungal infections). V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-12-23 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/494 10.33609/2708-129X.88.11.2022.11-38 Ukrainian Chemistry Journal; Vol. 88 No. 11 (2022): Ukrainian Chemistry Journal; 11-38 Украинский химический журнал; Том 88 № 11 (2022): Ukrainian Chemistry Journal; 11-38 Український хімічний журнал; Том 88 № 11 (2022): Український хімічний журнал; 11-38 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/494/254 |
| institution |
Ukrainian Chemistry Journal |
| baseUrl_str |
|
| datestamp_date |
2023-02-07T11:55:15Z |
| collection |
OJS |
| language |
English |
| topic_facet |
synthesis thio-containing complexones complexes cuprum molybdenum biological activity. |
| format |
Article |
| author |
Trunova , Elena Artamonova, Ganna Rusakova, Mariya Vasin, Oleksei Glushakov, Vladimir |
| spellingShingle |
Trunova , Elena Artamonova, Ganna Rusakova, Mariya Vasin, Oleksei Glushakov, Vladimir SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE |
| author_facet |
Trunova , Elena Artamonova, Ganna Rusakova, Mariya Vasin, Oleksei Glushakov, Vladimir |
| author_sort |
Trunova , Elena |
| title |
SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE |
| title_short |
SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE |
| title_full |
SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE |
| title_fullStr |
SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE |
| title_full_unstemmed |
SYNTHESIS AND COMPLEX-FORMING PROPERTIES OF THIO-CONTAINING COMPLEXONS: S,S'- ETHYLENEDITHIODIALANINE AND S,S'- CARBOXY- ETHYLENEDITHIODIALANINE |
| title_sort |
synthesis and complex-forming properties of thio-containing complexons: s,s'- ethylenedithiodialanine and s,s'- carboxy- ethylenedithiodialanine |
| description |
Two thio-containing complexones – S,S'-ethylenedithiodialanin (EDAL) and S,S'-carboxy-ethylenedithiodialanin (СEDAL) – were synthesized by the alkylation reaction of L-cysteine with dibromoethane. The developed technique has a number of advantages compared to those described in the literature: the absence of ammonia and metallic sodium as synthesis reagents, a decrease in the synthesis temperature and time, an increase in the yield of the final product to ~95%. The physicochemical properties of complesones were investigated using (1H, 13C) NMR, pH-potentiometry, UV-VIS, IR-spectroscopy, DTA and non-quantitative mass spectrometry. The acid dissociation constants of EDAL (pКN1=9.79; pКN2=8.79; pКCOO1=3.25) and СEDAL (pКN1=9.81; pКN2=8.17; pКCOO1=2.82; pКCOO2=3.34) were calculated and the scheme of protonation of complexons depending on pH was proposed. On the basis of NMR spectroscopy data, it is shown that the complexons have a folded structure, mobile along the S-CN2СНСООН and N–CH–COOH axes, in which betaine nitrogen atoms form two intramolecular five-membered glycine cycles due to the rapid exchange of labile protons of СООН groups. In addition, there is an intermolecular cycle in the molecule, which includes an ethylenethioamine fragment.
DTA data show the presence of adsorbed and crystallization water in molecules of thio-complexons, which is eliminated at 100–170 0С. Intraspherical water molecules are located between molecular layers and form a branched system of hydrogen bonds. The final temperature of the decomposition of compounds is ~4600C. Probably, the end products of EDAL and СEDAL decomposition are non-stoichiometric sulfates or sulfides.
Complex formation of thio-complexons with Mo(VI) and Cu(II) at their equimolar ratio was investigated in aqueous solutions in a wide pH range (1÷10). The formation of complexes of the composition MoO3CEDAL and CuEDAL in the range of pH 4–9 is shown and the structure of the complexes is proposed.
The biological activity of carboxy-ethylenedithiodialanin and its complexes with Cu(II) was studied. It has been proven that the compounds exhibit fungistatic properties against pathogenic bacteria Candida spp. (main causative agents of fungal infections). |
| publisher |
V.I.Vernadsky Institute of General and Inorganic Chemistry |
| publishDate |
2022 |
| url |
https://ucj.org.ua/index.php/journal/article/view/494 |
| work_keys_str_mv |
AT trunovaelena synthesisandcomplexformingpropertiesofthiocontainingcomplexonsssethylenedithiodialanineandsscarboxyethylenedithiodialanine AT artamonovaganna synthesisandcomplexformingpropertiesofthiocontainingcomplexonsssethylenedithiodialanineandsscarboxyethylenedithiodialanine AT rusakovamariya synthesisandcomplexformingpropertiesofthiocontainingcomplexonsssethylenedithiodialanineandsscarboxyethylenedithiodialanine AT vasinoleksei synthesisandcomplexformingpropertiesofthiocontainingcomplexonsssethylenedithiodialanineandsscarboxyethylenedithiodialanine AT glushakovvladimir synthesisandcomplexformingpropertiesofthiocontainingcomplexonsssethylenedithiodialanineandsscarboxyethylenedithiodialanine |
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2025-09-24T17:43:47Z |
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2025-09-24T17:43:47Z |
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