The interaction of the newly approved pharmacon esketamine with HSA (human serum albumin) has been investigated by various spectrographic methods. The fluorescence quenching results of HSA by esketamine revealed that the 1:1 ground state complex has formed. The results of binding parameters lead to the conclusion that the reaction was exothermic. In the presence of esketamine, HSA was found to undergo partial unfolding, and thermodynamic parameters (ΔG° = − 2.08 × 104 J·mol−1, ΔS° = 35.7 J·mol−1·K−1, and ΔH° = − 1.20 × 104 J·mol−1 at 298 K) revealed that electrostatic forces dominated the stabilization of the complex. The qualitative and quantitative analyses of conformational changes of HSA were conducted using circular dichroism, three-dimensional, and synchronous fluorescence spectroscopy, revealing the loosening of skeleton structure and adaptive modifications of secondary structures. Fe3+ and Mg2+ may help prolong the storage time and improve the drug efficacy.
{"title":"Binding of esketamine to human serum albumin for clinical implications","authors":"Yan Li, Fengqiang Sun, Jingui Yu, Lingzhi Yu, Wei Shao, Yulin Zhu","doi":"10.1007/s10847-021-01090-6","DOIUrl":"10.1007/s10847-021-01090-6","url":null,"abstract":"<div><p>The interaction of the newly approved pharmacon esketamine with HSA (human serum albumin) has been investigated by various spectrographic methods. The fluorescence quenching results of HSA by esketamine revealed that the 1:1 ground state complex has formed. The results of binding parameters lead to the conclusion that the reaction was exothermic. In the presence of esketamine, HSA was found to undergo partial unfolding, and thermodynamic parameters (Δ<i>G°</i> = − 2.08 × 10<sup>4</sup> J·mol<sup>−1</sup>, Δ<i>S°</i> = 35.7 J·mol<sup>−1</sup>·K<sup>−1</sup>, and Δ<i>H°</i> = − 1.20 × 10<sup>4</sup> J·mol<sup>−1</sup> at 298 K) revealed that electrostatic forces dominated the stabilization of the complex. The qualitative and quantitative analyses of conformational changes of HSA were conducted using circular dichroism, three-dimensional, and synchronous fluorescence spectroscopy, revealing the loosening of skeleton structure and adaptive modifications of secondary structures. Fe<sup>3+</sup> and Mg<sup>2+</sup> may help prolong the storage time and improve the drug efficacy.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2021-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10847-021-01090-6","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4940461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-05DOI: 10.1007/s10847-021-01087-1
Numan Yuksel, Ahmet Köse, M. Ferdi Fellah
While the world is in search of a vaccine that can cure COVID-19 disease, favipiravir is the most commonly used antiviral drug in the treatment of patients during the pandemic process. In this study, we investigated the host–guest interaction between the popular supramolecule calix[4]arene derivatives and the favipiravir drug by using the DFT (Density Functional Theory) method. The B3LYP hybrid method and 6-31G (d,p) basis set were utilized to determine the optimized structures of the host and guest molecules and their complexes. The negative adsorption energy (∆E) and adsorption enthalpy (∆H) calculated for the complexes formed between calix[4]arene compounds and favipiravir drug molecule mentioned that adsorption of favipiravir molecule was an exothermic process on calix[4]arene structures. On the other hand, among the calixarene derivatives in the study, Gibbs free energy change (∆G) value for the adsorption was only negative on calix[4]arene4 molecule. The infrared spectroscopy (IR) calculations were performed by examining the C=O, O–H and NH2 vibrational frequencies to see the adsorption behavior in the favipiravir-calix[4]arene complex. After adsorption of the favipiravir molecule, HOMO–LUMO gap values decreased significantly for the structures and therefore electrical conductivity increased proportionally. In addition, sensor response factors, Fermi energy levels and workfunction changes of calix[4]arene derivatives were calculated and examined. Charge transfer between the four calix[4]arene compounds and the favipiravir molecule has occurred after adsorption. This attributes that calix[4]arene derivatives can be used as a well-suited favipiravir sensor (electronic and workfunction) and adsorbent at room temperature. Based on the calculations made to see the solvent effect on the adsorption of favipiravir it was determined that it did not affect the interaction between the drug molecule and the calix[4]arene compound too much and the adsorption energy turned into a slightly less negative value.
{"title":"The supramolecularly complexes of calix[4]arene derivatives toward favipiravir antiviral drug (used to treatment of COVID-19): a DFT study on the geometry optimization, electronic structure and infrared spectroscopy of adsorption and sensing","authors":"Numan Yuksel, Ahmet Köse, M. Ferdi Fellah","doi":"10.1007/s10847-021-01087-1","DOIUrl":"10.1007/s10847-021-01087-1","url":null,"abstract":"<div><p>While the world is in search of a vaccine that can cure COVID-19 disease, favipiravir is the most commonly used antiviral drug in the treatment of patients during the pandemic process. In this study, we investigated the host–guest interaction between the popular supramolecule calix[4]arene derivatives and the favipiravir drug by using the DFT (Density Functional Theory) method. The B3LYP hybrid method and 6-31G (d,p) basis set were utilized to determine the optimized structures of the host and guest molecules and their complexes. The negative adsorption energy (∆E) and adsorption enthalpy (∆H) calculated for the complexes formed between calix[4]arene compounds and favipiravir drug molecule mentioned that adsorption of favipiravir molecule was an exothermic process on calix[4]arene structures. On the other hand, among the calixarene derivatives in the study, Gibbs free energy change (∆G) value for the adsorption was only negative on calix[4]arene4 molecule. The infrared spectroscopy (IR) calculations were performed by examining the C=O, O–H and NH<sub>2</sub> vibrational frequencies to see the adsorption behavior in the favipiravir-calix[4]arene complex. After adsorption of the favipiravir molecule, HOMO–LUMO gap values decreased significantly for the structures and therefore electrical conductivity increased proportionally. In addition, sensor response factors, Fermi energy levels and workfunction changes of calix[4]arene derivatives were calculated and examined. Charge transfer between the four calix[4]arene compounds and the favipiravir molecule has occurred after adsorption. This attributes that calix[4]arene derivatives can be used as a well-suited favipiravir sensor (electronic and workfunction) and adsorbent at room temperature. Based on the calculations made to see the solvent effect on the adsorption of favipiravir it was determined that it did not affect the interaction between the drug molecule and the calix[4]arene compound too much and the adsorption energy turned into a slightly less negative value.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2021-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10847-021-01087-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4550702","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-06-04DOI: 10.1007/s10847-021-01085-3
Jusung An, Paramesh Jangili, Sungsu Lim, Yun Kyung Kim, Peter Verwilst, Jong Seung Kim
The pathological origin of Alzheimer’s disease (AD) remains uncharted terrain, despite intensive investigation. Discriminating aberrant proteinaceous deposits, such as β-amyloid (Aβ) and (hyperphosphorylated) tau protein by imaging methods, is a vital tool to support investigations towards the network of interacting features that results in AD pathology. In this context, multispectral fluorescence imaging (MSFI) has drawn much attention enabling the distinction of several analytes with merely a single fluorophore emitting a multichromatic fluorescent signal. Herein, we developed three kinds of benzimidazole-derived fluorescent dyes, BZ1–BZ3. The photophysical properties and intramolecular charge transfer (ICT) characteristics of the probes were evaluated in various solvents. Furthermore, a benzimidazole-associated polar-sensitivity displayed multichromatic behavior and enabled the visualization of minute differences in microenvironmental polarity between Aβ and tau aggregates, resulting in different maximal fluorescent emission wavelengths. Indeed, BZ2 demonstrated an approximately 30 nm bathochromic shift in maximal fluorescent emission. All these observations offer a potential for the development of a future generation of benzimidazole-derived ICT-based fluorescent probes.
{"title":"Multichromatic fluorescence towards aberrant proteinaceous aggregates utilizing benzimidazole-based ICT fluorophores","authors":"Jusung An, Paramesh Jangili, Sungsu Lim, Yun Kyung Kim, Peter Verwilst, Jong Seung Kim","doi":"10.1007/s10847-021-01085-3","DOIUrl":"10.1007/s10847-021-01085-3","url":null,"abstract":"<div><p>The pathological origin of Alzheimer’s disease (AD) remains uncharted terrain, despite intensive investigation. Discriminating aberrant proteinaceous deposits, such as β-amyloid (Aβ) and (hyperphosphorylated) tau protein by imaging methods, is a vital tool to support investigations towards the network of interacting features that results in AD pathology. In this context, multispectral fluorescence imaging (MSFI) has drawn much attention enabling the distinction of several analytes with merely a single fluorophore emitting a multichromatic fluorescent signal. Herein, we developed three kinds of benzimidazole-derived fluorescent dyes, <b>BZ1</b>–<b>BZ3</b>. The photophysical properties and intramolecular charge transfer (ICT) characteristics of the probes were evaluated in various solvents. Furthermore, a benzimidazole-associated polar-sensitivity displayed multichromatic behavior and enabled the visualization of minute differences in microenvironmental polarity between Aβ and tau aggregates, resulting in different maximal fluorescent emission wavelengths. Indeed, <b>BZ2</b> demonstrated an approximately 30 nm bathochromic shift in maximal fluorescent emission. All these observations offer a potential for the development of a future generation of benzimidazole-derived ICT-based fluorescent probes.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2021-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10847-021-01085-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4168898","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A methylene crosslinked calix[4]arene tetracarboxylic acid resin that exhibits high precious metal adsorption properties was prepared. The maximum loading capacity of this resin was compared with that of an unmodified methylene crosslinked calix[4]arene resin to verify its applicability for platinum and palladium adsorption. The introduction of multiple acetic acid groups improved the adsorption capacity for divalent palladium, while that for tetravalent platinum was slightly suppressed. The newly obtained capacity of palladium was 1.17 mmol/g, while that of platinum was 0.23 mmol/g. The stoichiometry of Pd(II) to the calix[4]arene tetracarboxylic acid monomer in the methylene crosslinked tetracarboxylic acid calix[4]arene resin was found to be 1:2, while that of Pt(IV) to the same monomer was 9:1. Linear and non-linear methods were applied to evaluate the fitting of the Langmuir and Freundlich models for the studied adsorption isotherm. The results showed that the adsorption isotherm was consistently fitted by the Langmuir model. Further, the non-linear method was found to be more suitable for obtaining the isotherm parameters.
{"title":"Improved precious metal adsorption by introduction of carboxylic acid groups on methylene crosslinked calix[4]arene resin matrix","authors":"Yoga Priastomo, Shintaro Morisada, Hidetaka Kawakita, Keisuke Ohto, Jumina Jumina","doi":"10.1007/s10847-021-01079-1","DOIUrl":"10.1007/s10847-021-01079-1","url":null,"abstract":"<div><p>A methylene crosslinked calix[4]arene tetracarboxylic acid resin that exhibits high precious metal adsorption properties was prepared. The maximum loading capacity of this resin was compared with that of an unmodified methylene crosslinked calix[4]arene resin to verify its applicability for platinum and palladium adsorption. The introduction of multiple acetic acid groups improved the adsorption capacity for divalent palladium, while that for tetravalent platinum was slightly suppressed. The newly obtained capacity of palladium was 1.17 mmol/g, while that of platinum was 0.23 mmol/g. The stoichiometry of Pd(II) to the calix[4]arene tetracarboxylic acid monomer in the methylene crosslinked tetracarboxylic acid calix[4]arene resin was found to be 1:2, while that of Pt(IV) to the same monomer was 9:1. Linear and non-linear methods were applied to evaluate the fitting of the Langmuir and Freundlich models for the studied adsorption isotherm. The results showed that the adsorption isotherm was consistently fitted by the Langmuir model. Further, the non-linear method was found to be more suitable for obtaining the isotherm parameters.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2021-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10847-021-01079-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4037689","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-24DOI: 10.1007/s10847-021-01081-7
Quentin Vicens, Yang Kim, Jack Harrowfield
{"title":"Jacques Vicens: his life in research","authors":"Quentin Vicens, Yang Kim, Jack Harrowfield","doi":"10.1007/s10847-021-01081-7","DOIUrl":"10.1007/s10847-021-01081-7","url":null,"abstract":"","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2021-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10847-021-01081-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4948925","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-21DOI: 10.1007/s10847-021-01076-4
Yan-Mei Jin, Dao-Fa Jiang, Ye Meng, Jie Gao, Jun Zheng, Pei-Hua Ma
The host and guest supramolecular interactions between symmetric dicyclohexanocucurbit[6]uril (CyH2Q[6]) and 1H-benzotriazole (BTA) were investigated using nuclear magnetic resonance spectroscopy, isothermal titration calorimetry (ITC), MALDI-TOF mass spectrometry and single-crystal X-ray diffraction analysis. From the experimental results, it was concluded that there was a 1:1 mode of inclusion in BTA@CyH2Q[6]. In addition, the benzene ring of the BTA molecule entered the cavity of CyH2Q[6], while the triazole part was at the port of the CyH2Q[6], forming a supramolecular framework. According to ITC, the complexation process for BTA with CyH2Q[6] is exothermic and mainly driven by enthalpy.
{"title":"Crystal structure of self-assembled inclusion complex of symmetric dicyclohexanocucurbit[6]uril with 1H-benzotriazole","authors":"Yan-Mei Jin, Dao-Fa Jiang, Ye Meng, Jie Gao, Jun Zheng, Pei-Hua Ma","doi":"10.1007/s10847-021-01076-4","DOIUrl":"10.1007/s10847-021-01076-4","url":null,"abstract":"<div><p>The host and guest supramolecular interactions between symmetric dicyclohexanocucurbit[6]uril (CyH<sub>2</sub>Q[6]) and 1<i>H</i>-benzotriazole (BTA) were investigated using nuclear magnetic resonance spectroscopy, isothermal titration calorimetry (ITC), MALDI-TOF mass spectrometry and single-crystal X-ray diffraction analysis. From the experimental results, it was concluded that there was a 1:1 mode of inclusion in BTA@CyH<sub>2</sub>Q[6]. In addition, the benzene ring of the BTA molecule entered the cavity of CyH<sub>2</sub>Q[6], while the triazole part was at the port of the CyH<sub>2</sub>Q[6], forming a supramolecular framework. According to ITC, the complexation process for BTA with CyH<sub>2</sub>Q[6] is exothermic and mainly driven by enthalpy.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2021-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s10847-021-01076-4","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5133390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2021-05-15DOI: 10.1007/s10847-021-01078-2
N. S. Venkataramanan, A. Suvitha, R. Sahara, Y. Kawazoe
The binding properties of 1,ω-bisbenzimidazolyl derivatives with cucurbit[6]uril (Q[6]) and cyclohexanocucurbit[6]uril (Cy6Q[6]) host, for 1:1 stoichiometry, have been studied using density functional theory. The distance between the two benimidazole acidic hydrogen’s along with the flexible butyl spacer group play a vital role in the complexation with host. The energetic analysis exhibits strong complexation ability of guests with Q[6] than Cy6Q[6] host. The computed enthalpy and free energy change were negative indicating the encapsulation process to be spontaneous and thermodynamically favorable and enthalpy driven. The global reactivity descriptors based charge transfer calculations show that charge transfer occurs from the guest to host molecule which was supported by the electron density difference map. The main factors for the higher stability of stable complex was the presence of C–H····O=C hydrogen bonding interactions in addition to the weak C···O, C···N, N···O, C···H, H···N type of interactions. AIM topological parameters and NCI analysis reveals the existence of weak interaction, mainly of electrostatic in nature and more number of hydrogen bonds are present in stable complexes. EDA analysis demonstrates the presence of noncovalent and electrostatic interaction with partial covalent character in the encapsulated complexes. The lower stability of Cy6Q[6] complexes compare to Q[6] are due to the presence of positive Vs,max values of cyclohexanone methylene hydrogen’s on Cy6Q[6] host.