{"title":"利用简单的 Cu(II)-dppy 复合物瞬时检测 l-半胱氨酸和 l-组氨酸的实验和理论研究","authors":"Dipankar Das, Devu Prakash, Parnashabari Sarkar, Sourav Sutradhar, Shanti Gopal Patra, Biswa Nath Ghosh","doi":"10.1016/j.ica.2024.122346","DOIUrl":null,"url":null,"abstract":"<div><p>Developing simple and effective receptors for instantaneous detection of <span>l</span>-amino acids is vital for the recognition of life-threatening diseases in their early stage. Here, we report the synthesis and characterization of 2,6-di(pyrazin-2-yl)pyridine (dppy) based ligand <strong>L (L =</strong> 2,2′-(4-(3,4-diethoxyphenyl)pyridine-2,6-diyl)dipyrazine) and its copper (II) complex, <strong>[Cu(NO<sub>3</sub>)<sub>2</sub>L]</strong>. The in-situ prepared <strong>[Cu(H<sub>2</sub>O)<sub>2</sub>L](NO<sub>3</sub>)<sub>2</sub></strong> receptor in aqueous acetonitrile (4:1 <em>v</em>/<em>v,</em> 10 mM HEPES buffer, pH 7.4) medium displayed instantaneous response<del>s</del> towards biologically important bio-thiol <span>l</span>-Cysteine (Cys) and essential amino acid <span>l</span>-Histidine (His) over other <span>l</span>-amino acids through UV–Visible absorption spectral studies. Additionally, the competitive experiments confirmed that <em>in-situ</em> prepared <strong>[Cu(H<sub>2</sub>O)<sub>2</sub>L](NO<sub>3</sub>)<sub>2</sub></strong> receptor selectively detects Cys (1 equivalent) in the presence of other <span>l</span>-amino acids. The detection limits of Cys and His were calculated to be 8.23 × 10<sup>−7</sup> M and 2.55 × 10<sup>−6</sup> M, respectively. The density functional theory (DFT) calculation shows that selectivity of <strong>[Cu(H<sub>2</sub>O)<sub>2</sub>L](NO<sub>3</sub>)<sub>2</sub></strong> towards Cys is due to the reduction of Cu(II) to Cu(I) in the presence of Cys, while Cys is oxidized to cystine (Cys-Cys). For His, selectivity observed due to the formation of [Cu(His)<sub>2</sub>] moiety between Cu(II) ion with one His <em>via N</em>,<em>O</em> coordination mode and another His via <em>N,N,O</em>-coordination mode.</p></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"573 ","pages":"Article 122346"},"PeriodicalIF":2.7000,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Experimental and theoretical studies for instantaneous detection of l-cysteine and l-histidine using a simple Cu(II)-dppy complex\",\"authors\":\"Dipankar Das, Devu Prakash, Parnashabari Sarkar, Sourav Sutradhar, Shanti Gopal Patra, Biswa Nath Ghosh\",\"doi\":\"10.1016/j.ica.2024.122346\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Developing simple and effective receptors for instantaneous detection of <span>l</span>-amino acids is vital for the recognition of life-threatening diseases in their early stage. Here, we report the synthesis and characterization of 2,6-di(pyrazin-2-yl)pyridine (dppy) based ligand <strong>L (L =</strong> 2,2′-(4-(3,4-diethoxyphenyl)pyridine-2,6-diyl)dipyrazine) and its copper (II) complex, <strong>[Cu(NO<sub>3</sub>)<sub>2</sub>L]</strong>. The in-situ prepared <strong>[Cu(H<sub>2</sub>O)<sub>2</sub>L](NO<sub>3</sub>)<sub>2</sub></strong> receptor in aqueous acetonitrile (4:1 <em>v</em>/<em>v,</em> 10 mM HEPES buffer, pH 7.4) medium displayed instantaneous response<del>s</del> towards biologically important bio-thiol <span>l</span>-Cysteine (Cys) and essential amino acid <span>l</span>-Histidine (His) over other <span>l</span>-amino acids through UV–Visible absorption spectral studies. Additionally, the competitive experiments confirmed that <em>in-situ</em> prepared <strong>[Cu(H<sub>2</sub>O)<sub>2</sub>L](NO<sub>3</sub>)<sub>2</sub></strong> receptor selectively detects Cys (1 equivalent) in the presence of other <span>l</span>-amino acids. The detection limits of Cys and His were calculated to be 8.23 × 10<sup>−7</sup> M and 2.55 × 10<sup>−6</sup> M, respectively. The density functional theory (DFT) calculation shows that selectivity of <strong>[Cu(H<sub>2</sub>O)<sub>2</sub>L](NO<sub>3</sub>)<sub>2</sub></strong> towards Cys is due to the reduction of Cu(II) to Cu(I) in the presence of Cys, while Cys is oxidized to cystine (Cys-Cys). For His, selectivity observed due to the formation of [Cu(His)<sub>2</sub>] moiety between Cu(II) ion with one His <em>via N</em>,<em>O</em> coordination mode and another His via <em>N,N,O</em>-coordination mode.</p></div>\",\"PeriodicalId\":13599,\"journal\":{\"name\":\"Inorganica Chimica Acta\",\"volume\":\"573 \",\"pages\":\"Article 122346\"},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-08-29\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganica Chimica Acta\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0020169324004377\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganica Chimica Acta","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0020169324004377","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Experimental and theoretical studies for instantaneous detection of l-cysteine and l-histidine using a simple Cu(II)-dppy complex
Developing simple and effective receptors for instantaneous detection of l-amino acids is vital for the recognition of life-threatening diseases in their early stage. Here, we report the synthesis and characterization of 2,6-di(pyrazin-2-yl)pyridine (dppy) based ligand L (L = 2,2′-(4-(3,4-diethoxyphenyl)pyridine-2,6-diyl)dipyrazine) and its copper (II) complex, [Cu(NO3)2L]. The in-situ prepared [Cu(H2O)2L](NO3)2 receptor in aqueous acetonitrile (4:1 v/v, 10 mM HEPES buffer, pH 7.4) medium displayed instantaneous responses towards biologically important bio-thiol l-Cysteine (Cys) and essential amino acid l-Histidine (His) over other l-amino acids through UV–Visible absorption spectral studies. Additionally, the competitive experiments confirmed that in-situ prepared [Cu(H2O)2L](NO3)2 receptor selectively detects Cys (1 equivalent) in the presence of other l-amino acids. The detection limits of Cys and His were calculated to be 8.23 × 10−7 M and 2.55 × 10−6 M, respectively. The density functional theory (DFT) calculation shows that selectivity of [Cu(H2O)2L](NO3)2 towards Cys is due to the reduction of Cu(II) to Cu(I) in the presence of Cys, while Cys is oxidized to cystine (Cys-Cys). For His, selectivity observed due to the formation of [Cu(His)2] moiety between Cu(II) ion with one His via N,O coordination mode and another His via N,N,O-coordination mode.
期刊介绍:
Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews.
Topics covered include:
• chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies;
• synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs);
• reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models;
• applications of inorganic compounds, metallodrugs and molecule-based materials.
Papers composed primarily of structural reports will typically not be considered for publication.