The novel thiophene-chalcone compound (2), phthalonitrile derivatives bearing thiophene-chalcone group (3 and 4) and their zinc (II) (ZnPcs) (3a and 4a) and magnesium (II) (MgPcs) (3b and 4b) phthalocyanine compounds were synthesized in this study. The structure of all these new compounds were elucidated by spectroscopic techniques like IR, 1 H NMR, 13 C NMR (for compounds 2, 3 and 4), MALDI–TOF mass and UV-Vis. The fluorescence quantum yields and lifetimes (photophysical properties), and the singlet oxygen and photodegradation quantum yields (photochemical properties) of thiophene bearing chalcone substituted ZnPcs (3a and 4a) and MgPcs (3b and 4b) were studied in DMSO (dimethylsulfoxide) to determine if they are convenient photosensitizers for photodynamic therapy (PDT) applications.
{"title":"Photophysical, photochemical properties of chalcone substituted Zinc(II) and Magnesium(II) metallophthalocyanines bearing thiophene units","authors":"Ayse Aktas Kamiloglu, Ipek Omeroglu, Halise Yalazan, Mahmut Durmus, Gonca Celik, Halit Kantekin","doi":"10.1007/s10847-022-01152-3","DOIUrl":"10.1007/s10847-022-01152-3","url":null,"abstract":"<div><p>The novel thiophene-chalcone compound (<b>2</b>), phthalonitrile derivatives bearing thiophene-chalcone group (<b>3</b> and <b>4</b>) and their zinc (II) (ZnPcs) (<b>3a</b> and <b>4a</b>) and magnesium (II) (MgPcs) (<b>3b</b> and <b>4b</b>) phthalocyanine compounds were synthesized in this study. The structure of all these new compounds were elucidated by spectroscopic techniques like IR, <sup>1</sup> H NMR, <sup>13</sup> C NMR (for compounds <b>2, 3</b> and <b>4)</b>, MALDI–TOF mass and UV-Vis. The fluorescence quantum yields and lifetimes (photophysical properties), and the singlet oxygen and photodegradation quantum yields (photochemical properties) of thiophene bearing chalcone substituted ZnPcs (<b>3a</b> and <b>4a</b>) and MgPcs (<b>3b</b> and <b>4b</b>) were studied in DMSO (dimethylsulfoxide) to determine if they are convenient photosensitizers for photodynamic therapy (PDT) applications.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2022-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"5047811","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 : 2022-06-15DOI: 10.1007/s10847-022-01151-4
S. P. Babailov
The temperature sensitivity of paramagnetic chemical shifts in 1H NMR spectra for the [Co(DTPA)]3− complex in 10% gelatin gel (as a model substrate of human or animal tissues) was studied in detail. The maximum temperature sensitivity of the chemical shifts d(δexp)/dT studied in the gelatin gel of the complex was found to be 0.73 ppm/K (which is about 7% higher than in the previously studied D2O solution of the compound). It turned out that the studied complex is characterized by the highest temperature sensitivity of chemical shifts in the NMR spectra among the complexes of paramagnetic d-elements. Moreover, this complex also shows the highest temperature sensitivity of chemical shifts taking into consideration the half-width of the signal itself (|CT|/W = 0.8 K−1). The [Co(DTPA)]3− complex can be considered as a promising compound for the design of temperature-sensitive NMR probes aimed at determining the local temperature in aqueous media and prospective MRI-assisted disease diagnosis.
{"title":"[Co(DTPA)]3− complex in gelatin gel as a highly sensitive shifting NMR/MRI temperature probe","authors":"S. P. Babailov","doi":"10.1007/s10847-022-01151-4","DOIUrl":"10.1007/s10847-022-01151-4","url":null,"abstract":"<div><p>The temperature sensitivity of paramagnetic chemical shifts in <sup>1</sup>H NMR spectra for the [Co(DTPA)]<sup>3−</sup> complex in 10% gelatin gel (as a model substrate of human or animal tissues) was studied in detail. The maximum temperature sensitivity of the chemical shifts <i>d(δ</i><sub><i>exp</i></sub><i>)/dT</i> studied in the gelatin gel of the complex was found to be 0.73 ppm/K (which is about 7% higher than in the previously studied D<sub>2</sub>O solution of the compound). It turned out that the studied complex is characterized by the highest temperature sensitivity of chemical shifts in the NMR spectra among the complexes of paramagnetic <i>d</i>-elements. Moreover, this complex also shows the highest temperature sensitivity of chemical shifts taking into consideration the half-width of the signal itself <i>(|CT|/W</i> = 0.8 K<sup>−1</sup>). The [Co(DTPA)]<sup>3−</sup> complex can be considered as a promising compound for the design of temperature-sensitive NMR probes aimed at determining the local temperature in aqueous media and prospective MRI-assisted disease diagnosis.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2022-06-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10847-022-01151-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4616631","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}
Pub Date : 2022-06-08DOI: 10.1007/s10847-022-01145-2
Ryosuke Miyake
Biological systems display a range of sophisticated functions that cannot be performed by artificial systems, through intricate cooperative structural changes involving multiple functional units. The designability and structural flexibility of peptides are demonstrated by biological systems that display cooperative structural changes; these properties also make them well-suited for the formation of artificial systems that display such changes. The problem with the use of peptide frameworks is that long peptide residues, which are not suitable for gram-scale use, are required for the formation of stable ordered structures. However, if ordered structures containing peptides could be constructed by coordinating them to metal ions, peptides could be widely used to develop sophisticated functional materials. Crystal packing can be used for the design of functional materials made from simple molecules because it provides a way to place the components relative to each other. Although crystalline systems have been reported in which the small size of the cavities has been attributed to the flexibility of the peptide, recently, large systems with giant cavities have been developed with flexible peptides. In this review, we summarize the formation of cooperative multicomponent systems in the crystalline state using metal complexes of simple peptides, along with recent advances in the construction of giant artificial systems using short peptides.
{"title":"Cooperative systems constructed using crystalline metal complexes of short flexible peptides","authors":"Ryosuke Miyake","doi":"10.1007/s10847-022-01145-2","DOIUrl":"10.1007/s10847-022-01145-2","url":null,"abstract":"<div><p>Biological systems display a range of sophisticated functions that cannot be performed by artificial systems, through intricate cooperative structural changes involving multiple functional units. The designability and structural flexibility of peptides are demonstrated by biological systems that display cooperative structural changes; these properties also make them well-suited for the formation of artificial systems that display such changes. The problem with the use of peptide frameworks is that long peptide residues, which are not suitable for gram-scale use, are required for the formation of stable ordered structures. However, if ordered structures containing peptides could be constructed by coordinating them to metal ions, peptides could be widely used to develop sophisticated functional materials. Crystal packing can be used for the design of functional materials made from simple molecules because it provides a way to place the components relative to each other. Although crystalline systems have been reported in which the small size of the cavities has been attributed to the flexibility of the peptide, recently, large systems with giant cavities have been developed with flexible peptides. In this review, we summarize the formation of cooperative multicomponent systems in the crystalline state using metal complexes of simple peptides, along with recent advances in the construction of giant artificial systems using short peptides.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2022-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10847-022-01145-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4343326","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}
Pub Date : 2022-06-06DOI: 10.1007/s10847-022-01148-z
Edison Matamala-Cea, Luciano Becerra-Pino, Walter A. Rabanal-León, Rodrigo Arancibia, Paulina I. Hidalgo, Claudio A. Jiménez, Néstor Novoa
The dissymmetrical and dipolar Y(III) complex 2 and its cationic precursor 1, containing the proligands 5,10,15,20-tetrakis(4-bromophenyl)porphyrin L1 and 1-anisyl-1,3-butanedione L2, were synthesized at fairly high yields, ranging from 40 to 78%, by conventional and microwave-assisted techniques, and were isolated as a microcrystalline compound. The products obtained in each case were characterized by 1H-NMR, mass spectrometry, elemental analysis, Med-IR and Far-IR. The IR information collected shows good agreement with respect to the density functional theory (DFT) calculations carried out, validating the molecular geometry in each case. This innovative one-pot microwave-based method contributes an efficient pathway for obtaining challenging molecular architectures based on monoporphyrinate complexes without Diglyme.
{"title":"Preparation of dipolar Y(III)-based monoporphyrinate complexes: conventional vs microwave-assisted reaction and theoretical IR study","authors":"Edison Matamala-Cea, Luciano Becerra-Pino, Walter A. Rabanal-León, Rodrigo Arancibia, Paulina I. Hidalgo, Claudio A. Jiménez, Néstor Novoa","doi":"10.1007/s10847-022-01148-z","DOIUrl":"10.1007/s10847-022-01148-z","url":null,"abstract":"<div><p>The dissymmetrical and dipolar Y(III) complex <b>2</b> and its cationic precursor <b>1</b>, containing the proligands 5,10,15,20-tetrakis(4-bromophenyl)porphyrin <b>L1</b> and 1-anisyl-1,3-butanedione <b>L2</b>, were synthesized at fairly high yields, ranging from 40 to 78%, by conventional and microwave-assisted techniques, and were isolated as a microcrystalline compound. The products obtained in each case were characterized by <sup>1</sup>H-NMR, mass spectrometry, elemental analysis, Med-IR and Far-IR. The IR information collected shows good agreement with respect to the density functional theory (DFT) calculations carried out, validating the molecular geometry in each case. This innovative one-pot microwave-based method contributes an efficient pathway for obtaining challenging molecular architectures based on monoporphyrinate complexes without Diglyme.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2022-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10847-022-01148-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4259036","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}
The designing of efficient macrocyclic complexes for the alteration in nucleic acids and understanding is still in debate. Herein, to study the deoxyribonucleic acid (DNA) interaction with MN5-complexes, two macrocyclic complexes, A (MnII) and B (FeII), have been synthesized and characterized using multiple analytical techniques. The electronic absorption, fluorescence, and electrochemical methods were utilized to examine the binding ability of both complexes with calf thymus-DNA (ct-DNA). The spectral results were found to be in good agreement with the interaction of both complexes with ct-DNA, as also supported by the remarkable decrease in both anodic peak current (ipa) and cathodic peak current (ipc) during cyclic voltammetric analysis in the presence of ct-DNA. The spectral investigations clearly indicated the higher binding affinity of complex A as compared to complex B towards ct-DNA. Additionally, both complexes were also found to be potential antibacterial agents.
{"title":"Ct-DNA binding and antimicrobial studies of MnII and FeII macrocyclic complexes","authors":"Anuj Kumar, Vinod Kumar Vashistha, Dipak Kumar Das, Ram K. Gupta, Ghulam Yasin","doi":"10.1007/s10847-022-01150-5","DOIUrl":"10.1007/s10847-022-01150-5","url":null,"abstract":"<div><p>The designing of efficient macrocyclic complexes for the alteration in nucleic acids and understanding is still in debate. Herein, to study the deoxyribonucleic acid (DNA) interaction with MN<sub>5</sub>-complexes, two macrocyclic complexes, A (Mn<sup>II</sup>) and B (Fe<sup>II</sup>), have been synthesized and characterized using multiple analytical techniques. The electronic absorption, fluorescence, and electrochemical methods were utilized to examine the binding ability of both complexes with calf thymus-DNA (ct-DNA). The spectral results were found to be in good agreement with the interaction of both complexes with ct-DNA, as also supported by the remarkable decrease in both anodic peak current (<i>i</i><sub>pa</sub>) and cathodic peak current (<i>i</i><sub>pc</sub>) during cyclic voltammetric analysis in the presence of ct-DNA. The spectral investigations clearly indicated the higher binding affinity of complex A as compared to complex B towards ct-DNA. Additionally, both complexes were also found to be potential antibacterial agents.</p></div>","PeriodicalId":54324,"journal":{"name":"Journal of Inclusion Phenomena and Macrocyclic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3,"publicationDate":"2022-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s10847-022-01150-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4130127","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}
Pub Date : 2022-06-02DOI: 10.1007/s10847-022-01149-y
Preeti Dali, Pravin Shende
Purpose
The anti-migraine drugs show first-pass metabolism, short half-life, and low bioavailability resulting in repeated dose or overdose effect. Polymeric, biodegradable and highly porous nanosponges emerge as a promising carrier for migraine treatment to improve aqueous solubility, stability and bioavailability.
Method
Ergotamine nanosponges prepared by interfacial polymerization method wherein hydroxypropyl beta-cyclodextrin inclusion complex was crosslinked using toluene diisocyanate. Caffeine used as a permeation enhancer for ergotamine by forming soluble molecular complex with cyclodextrin moiety of nanosponges. Further, nanosponges were characterized for particle size, zeta potential, entrapment efficiency, percentage drug release profile, antioxidant activity, photostability and instrumental analytical studies.
Results
Caffeine significantly improved the permeation of ergotamine nanosponges. The particle size for optimized nanosponges was 693.5 ± 11.7 nm, zeta potential of − 19.4 ± 5.69 mV with high colloidal stability and maximum entrapment efficiency of 98.88 ± 2.8%. In-vitro and ex-vivo studies exhibited controlled release profiles of ergotamine 81.6% ± 3.4% and 79% ± 4.2% for 24 h, respectively. Nanosponges demonstrated higher antioxidant activity 85.68% ± 1.23% whereas photostability data showed no significant decrease in drug content indicating good stability. Fourier transform infrared spectroscopy confirmed significant interaction of ergotamine with cyclodextrin-based nanosponges.
Conclusion
Nanosponges showed improvement in bioavailability of ergotamine and long-term stability offering inexpensive, productive and safe alternative for migraine.