Pub Date : 2021-08-03DOI: 10.1080/10610278.2022.2035386
Qiao Li, Jing Chang, Haixiong Shi, Teng Niu, Hongru Dong, H. Mu
ABSTRACT A highly selective red-emitting fluorescent and colorimetric double-channel probe incorporating a conjugated benzopyran–benzothiazole system is proposed for the detection of cyanide (CN−) in water samples. Under the presence of CN−, the probe displays red fluorescence disappearance, having an immediate (<30 s) visible colour variation from red to colourless. Due to a blocking process where an intramolecular charge transfer occurs, the benzothiazole C = N bond of the probe is attacked by the CN− nucleophile; 1H NMR titration and DFT calculations for this occurrence varied. Results from this investigation enable feasible and simple test strips to be produced for detecting CN− in water samples. Graphical Abstract
{"title":"Cyanide detection using a highly selective fluorescent and colorimetrical double channel probe incorporating hybrid naphthopyran–benzothiazole in an aqueous solution","authors":"Qiao Li, Jing Chang, Haixiong Shi, Teng Niu, Hongru Dong, H. Mu","doi":"10.1080/10610278.2022.2035386","DOIUrl":"https://doi.org/10.1080/10610278.2022.2035386","url":null,"abstract":"ABSTRACT A highly selective red-emitting fluorescent and colorimetric double-channel probe incorporating a conjugated benzopyran–benzothiazole system is proposed for the detection of cyanide (CN−) in water samples. Under the presence of CN−, the probe displays red fluorescence disappearance, having an immediate (<30 s) visible colour variation from red to colourless. Due to a blocking process where an intramolecular charge transfer occurs, the benzothiazole C = N bond of the probe is attacked by the CN− nucleophile; 1H NMR titration and DFT calculations for this occurrence varied. Results from this investigation enable feasible and simple test strips to be produced for detecting CN− in water samples. Graphical Abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"30 6 1","pages":"401 - 407"},"PeriodicalIF":3.3,"publicationDate":"2021-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90668960","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 : 2021-08-03DOI: 10.1080/10610278.2022.2039653
Yang Chao, A. C. Sue
ABSTRACT Herein we report the successful synthesis and isolation of tiara[6]arene, a constitutional isomer of calix[6]arene consisting of six phenol units linked by para-substituted methylene bridges, from an isomeric mixture of asymmetrically substituted pillar[6]arene intermediates. Similar to its pentameric analogue, tiara[6]arene displays high conformational freedom in solution and rich polymorphism in the solid state. The establishment of the tiara[n]arene family (n = 5 and 6) further expands the scope of macrocyclic chemistry. Graphical Abstract
{"title":"Tiara[6]arenes","authors":"Yang Chao, A. C. Sue","doi":"10.1080/10610278.2022.2039653","DOIUrl":"https://doi.org/10.1080/10610278.2022.2039653","url":null,"abstract":"ABSTRACT Herein we report the successful synthesis and isolation of tiara[6]arene, a constitutional isomer of calix[6]arene consisting of six phenol units linked by para-substituted methylene bridges, from an isomeric mixture of asymmetrically substituted pillar[6]arene intermediates. Similar to its pentameric analogue, tiara[6]arene displays high conformational freedom in solution and rich polymorphism in the solid state. The establishment of the tiara[n]arene family (n = 5 and 6) further expands the scope of macrocyclic chemistry. Graphical Abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"1 1","pages":"442 - 449"},"PeriodicalIF":3.3,"publicationDate":"2021-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72652441","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 : 2021-07-03DOI: 10.1080/10610278.2021.1999956
Alexander M Gilchrist, Patrick Wang, Israel Carreira-Barral, Daniel Alonso-Carrillo, Xin Wu, R. Quesada, Philip A. Gale
ABSTRACT The liposomal membrane transport assay, which uses 8-hydroxypyrene-1,3,6-trisulfonic acid to monitor the internal pH of the vesicles (the HPTS assay), is a widely used technique for analysing the activity of anionophore-facilitated transport across a phospholipid membrane. This paper describes the stepwise technique to conduct this transport assay, detailing both the perks and pitfalls of using this method to determine the activity of an anionophore and the transport mechanism. GRAPHICAL ABSTRACT
{"title":"Supramolecular methods: the 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS) transport assay","authors":"Alexander M Gilchrist, Patrick Wang, Israel Carreira-Barral, Daniel Alonso-Carrillo, Xin Wu, R. Quesada, Philip A. Gale","doi":"10.1080/10610278.2021.1999956","DOIUrl":"https://doi.org/10.1080/10610278.2021.1999956","url":null,"abstract":"ABSTRACT The liposomal membrane transport assay, which uses 8-hydroxypyrene-1,3,6-trisulfonic acid to monitor the internal pH of the vesicles (the HPTS assay), is a widely used technique for analysing the activity of anionophore-facilitated transport across a phospholipid membrane. This paper describes the stepwise technique to conduct this transport assay, detailing both the perks and pitfalls of using this method to determine the activity of an anionophore and the transport mechanism. GRAPHICAL ABSTRACT","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"60 1","pages":"325 - 344"},"PeriodicalIF":3.3,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76682424","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 : 2021-07-03DOI: 10.1080/10610278.2021.2025241
J. Kiruthika, Muniyappan Boominathan, S. Srividhya, V. Ajitha, M. Arunachalam
ABSTRACT Formation of pseudo[3]rotaxane assemblies by P4Q1 and H with bis-imidazolium and bis-pyridinium guests was established by NMR spectral analyses and high-resolution mass spectrometric analyses. Cooperativity in the formation of pseudo[3]rotaxane assemblies was thoroughly investigated from the binding constant values derived from 1H NMR titration experiments. The results indicated the preferential 1:1 host-guest binding of pillar[4]arene[1]quinone and 2:1 host-guest binding by functionalized pillar[4]arene[1]quinone via positive cooperativity. The presence of hydrogen bonding functional groups attached to the quinone motif of pillar[4]arene[1]quinone facilitated the inclusion formation, which resulted in the formation of pseudo[3]rotaxanes. Graphical abstract
{"title":"Pillar[4]arene[1]quinone-based pseudo[3]rotaxanes by cooperative Host-Guest binding","authors":"J. Kiruthika, Muniyappan Boominathan, S. Srividhya, V. Ajitha, M. Arunachalam","doi":"10.1080/10610278.2021.2025241","DOIUrl":"https://doi.org/10.1080/10610278.2021.2025241","url":null,"abstract":"ABSTRACT Formation of pseudo[3]rotaxane assemblies by P4Q1 and H with bis-imidazolium and bis-pyridinium guests was established by NMR spectral analyses and high-resolution mass spectrometric analyses. Cooperativity in the formation of pseudo[3]rotaxane assemblies was thoroughly investigated from the binding constant values derived from 1H NMR titration experiments. The results indicated the preferential 1:1 host-guest binding of pillar[4]arene[1]quinone and 2:1 host-guest binding by functionalized pillar[4]arene[1]quinone via positive cooperativity. The presence of hydrogen bonding functional groups attached to the quinone motif of pillar[4]arene[1]quinone facilitated the inclusion formation, which resulted in the formation of pseudo[3]rotaxanes. Graphical abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"184 1","pages":"390 - 399"},"PeriodicalIF":3.3,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85686349","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 : 2021-07-03DOI: 10.1080/10610278.2021.2011890
G. De Leener, D. Over, O. Reinaud, I. Jabin
ABSTRACT This study explores the impact of a small structural modification on a biomimetic receptor. The hosting structure is a calix[6]arene capped by a tetraaza core. Two receptors are compared: one (1) presents three anisole units while the other (2) has three phenols. The latter was obtained with an excellent yield by selective demethylation thanks to a supramolecular strategy. Complexation studies showed that [2.H]+ displays strong affinities for Cl−, NO3 −, HSO4 −, whereas [1.H]+ is non-responsive. The anions are embedded at the level of the small rim, hydrogen-bonded to the protonated cap and the phenol groups. Ternary complexes are obtained in the presence of ammoniums. Finally, [2.H]+ shows high affinity for small zwitterions presenting a carboxylate and an ammonium groups separated by one or two carbon atom(s), not three, due to multi-point recognition. These results open routes to the design of new receptors for a variety of anionic and zwitterionic guests.
{"title":"Turning on anion and betaine hosting by a small structural change of a biomimetic cavity: a case study","authors":"G. De Leener, D. Over, O. Reinaud, I. Jabin","doi":"10.1080/10610278.2021.2011890","DOIUrl":"https://doi.org/10.1080/10610278.2021.2011890","url":null,"abstract":"ABSTRACT This study explores the impact of a small structural modification on a biomimetic receptor. The hosting structure is a calix[6]arene capped by a tetraaza core. Two receptors are compared: one (1) presents three anisole units while the other (2) has three phenols. The latter was obtained with an excellent yield by selective demethylation thanks to a supramolecular strategy. Complexation studies showed that [2.H]+ displays strong affinities for Cl−, NO3 −, HSO4 −, whereas [1.H]+ is non-responsive. The anions are embedded at the level of the small rim, hydrogen-bonded to the protonated cap and the phenol groups. Ternary complexes are obtained in the presence of ammoniums. Finally, [2.H]+ shows high affinity for small zwitterions presenting a carboxylate and an ammonium groups separated by one or two carbon atom(s), not three, due to multi-point recognition. These results open routes to the design of new receptors for a variety of anionic and zwitterionic guests.","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"11 1","pages":"370 - 379"},"PeriodicalIF":3.3,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82417365","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 : 2021-07-03DOI: 10.1080/10610278.2021.2025240
Yu-ting Wang, Peng-Yu Xu, Zongshou Yu, Zikun Wang, Hua-Yu Wu, Shi Wang, Yonghua Li
ABSTRACT This paper reports the syntheses, crystal structures, magnetics and spectroscopic properties of high-spin (HS) salts of formula [Mn(salk-N-1,5,8,12)]Y·S (Y = AsF6 for 1, Y = BF4, S = CH3OH for 2, Y = PF6, S = CH3OH for 3), where (salk-N-1,5,8,12)2− (2,2ʹ-((2E,14E)-3,7,10,14-tetraazahexadeca-2,14-diene-2,15-diyl)diphenolate) is a hexadentate Schiff-base ligand. Crystal structural analysis indicates that the extensive hydrogen bonds play a primary role in stabilisation of their HS states. As an aid to understanding this behaviour, the crystal structure of the known spin crossover compound [Mn(sal-N-1,5,8,12)]AsF6 (4) has been re-examined. To understand the impact of intermolecular forces to the different magnetic behaviours of salts 1 and 4, we evaluate of their supramolecular structures and confirm that intermolecular interactions can significantly affect the cooperativity. Furthermore, electrochemical studies on 1 and 4 shows that the choice of spin state is controlled by the solid-state lattice effects, i.e. cooperativity rather than molecular electronic effect. Graphical abstract
摘要本文报道了式[Mn(salk- n -1,5,8,12)]Y·S (Y = AsF6为1,Y = BF4, S = CH3OH为2,Y = PF6, S = CH3OH为3)的高自旋(HS)盐的合成、晶体结构、磁性和光谱性质，其中(salk- n -1,5,8,12)2−(2,2′′-(2E,14E)-3,7,10,14-四氮杂十六烷基-2,14-二烯-2,15-二基)二酚酸盐为六齿状希夫碱配体。晶体结构分析表明，广泛的氢键对其HS态的稳定起主要作用。为了帮助理解这种行为，我们重新研究了已知的自旋交叉化合物[Mn(sal- n -1,5,8,12)]AsF6(4)的晶体结构。为了了解分子间作用力对盐1和盐4不同磁性行为的影响，我们评估了它们的超分子结构，并证实分子间相互作用可以显著影响协同性。此外，对1和4的电化学研究表明，自旋态的选择是由固态晶格效应即协同性控制的，而不是由分子电子效应控制的。图形抽象
{"title":"Solid-state lattice effects on high-spin Mn(III) complexes with hexadentate Schiff-base ligand","authors":"Yu-ting Wang, Peng-Yu Xu, Zongshou Yu, Zikun Wang, Hua-Yu Wu, Shi Wang, Yonghua Li","doi":"10.1080/10610278.2021.2025240","DOIUrl":"https://doi.org/10.1080/10610278.2021.2025240","url":null,"abstract":"ABSTRACT This paper reports the syntheses, crystal structures, magnetics and spectroscopic properties of high-spin (HS) salts of formula [Mn(salk-N-1,5,8,12)]Y·S (Y = AsF6 for 1, Y = BF4, S = CH3OH for 2, Y = PF6, S = CH3OH for 3), where (salk-N-1,5,8,12)2− (2,2ʹ-((2E,14E)-3,7,10,14-tetraazahexadeca-2,14-diene-2,15-diyl)diphenolate) is a hexadentate Schiff-base ligand. Crystal structural analysis indicates that the extensive hydrogen bonds play a primary role in stabilisation of their HS states. As an aid to understanding this behaviour, the crystal structure of the known spin crossover compound [Mn(sal-N-1,5,8,12)]AsF6 (4) has been re-examined. To understand the impact of intermolecular forces to the different magnetic behaviours of salts 1 and 4, we evaluate of their supramolecular structures and confirm that intermolecular interactions can significantly affect the cooperativity. Furthermore, electrochemical studies on 1 and 4 shows that the choice of spin state is controlled by the solid-state lattice effects, i.e. cooperativity rather than molecular electronic effect. Graphical abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"14 39 1","pages":"380 - 389"},"PeriodicalIF":3.3,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79461507","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 : 2021-07-03DOI: 10.1080/10610278.2021.2011283
D. Quaglio, Francesca Polli, Cristina Del Plato, Gabriele Cianfoni, C. Tortora, F. Mazzei, B. Botta, A. Calcaterra, F. Ghirga
ABSTRACT Calix[n]arenes, as the ‘third-generation’ host molecules, are cyclic oligomer, featuring a unique three-dimensional structure with a hydrophobic cavity, allowing the interaction with many size-matched guest molecules, and a surface which can be functionalised at both the upper and lower rims with several functional groups to tailor the recognition properties towards a specific class of analytes for various applications. In the last two decades, due to their configuration, unique molecule recognition function and aggregation properties, calixarenes and their derivatives have attracted considerable attention as a new versatile scaffold for highly sensitive detection and site-oriented immobilisation in biosensor development. In this review, the development of sensors featuring calixarene-based transducers tuned for binding many analytes, ranging from simple (i.e., amino acids and neurotransmitters) to complex (i.e., enzymes and antibodies) organic molecules, was described. The rational design, the synthetic strategies fine-tuned to prepare these complex structures and their grafting in surface modification were included. GRAPHICAL ABSTRACT
{"title":"Calixarene: a versatile scaffold for the development of highly sensitive biosensors","authors":"D. Quaglio, Francesca Polli, Cristina Del Plato, Gabriele Cianfoni, C. Tortora, F. Mazzei, B. Botta, A. Calcaterra, F. Ghirga","doi":"10.1080/10610278.2021.2011283","DOIUrl":"https://doi.org/10.1080/10610278.2021.2011283","url":null,"abstract":"ABSTRACT Calix[n]arenes, as the ‘third-generation’ host molecules, are cyclic oligomer, featuring a unique three-dimensional structure with a hydrophobic cavity, allowing the interaction with many size-matched guest molecules, and a surface which can be functionalised at both the upper and lower rims with several functional groups to tailor the recognition properties towards a specific class of analytes for various applications. In the last two decades, due to their configuration, unique molecule recognition function and aggregation properties, calixarenes and their derivatives have attracted considerable attention as a new versatile scaffold for highly sensitive detection and site-oriented immobilisation in biosensor development. In this review, the development of sensors featuring calixarene-based transducers tuned for binding many analytes, ranging from simple (i.e., amino acids and neurotransmitters) to complex (i.e., enzymes and antibodies) organic molecules, was described. The rational design, the synthetic strategies fine-tuned to prepare these complex structures and their grafting in surface modification were included. GRAPHICAL ABSTRACT","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"25 1","pages":"345 - 369"},"PeriodicalIF":3.3,"publicationDate":"2021-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85671154","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}
ABSTRACT The biological channels with chiral features are capable of intelligently regulating substance transport through cell membrane, which plays a pivotal role in maintaining normal functions for living organisms. However, the high complexity and variability of biological nanochannels are the major constraints on practical studies. At present, artificial solid-state channels have been developed to simulate the functionality of biological channels. The functional groups are often introduced into nanochannels to achieve selective sensing and transport molecules. In particular, the fast-paced progress has been made in developing artificial chiral nanochannels. This review highlights the recent advancement of artificial chiral nanochannels as constructed using various strategies, including chiral macrocyclic hosts, amino acids, and label-free methods, which are expected to support the researchers working in fields such as supramolecular chemistry, chiral chemistry, and drug development. Graphical Abstract
{"title":"Artificial chiral nanochannels","authors":"Q. He, Mingjie Tao, Wajahat Ali, Xuehong Min, Yanxi Zhao","doi":"10.1080/10610278.2021.1991924","DOIUrl":"https://doi.org/10.1080/10610278.2021.1991924","url":null,"abstract":"ABSTRACT The biological channels with chiral features are capable of intelligently regulating substance transport through cell membrane, which plays a pivotal role in maintaining normal functions for living organisms. However, the high complexity and variability of biological nanochannels are the major constraints on practical studies. At present, artificial solid-state channels have been developed to simulate the functionality of biological channels. The functional groups are often introduced into nanochannels to achieve selective sensing and transport molecules. In particular, the fast-paced progress has been made in developing artificial chiral nanochannels. This review highlights the recent advancement of artificial chiral nanochannels as constructed using various strategies, including chiral macrocyclic hosts, amino acids, and label-free methods, which are expected to support the researchers working in fields such as supramolecular chemistry, chiral chemistry, and drug development. Graphical Abstract","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"8 Suppl 2 1","pages":"283 - 294"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84265101","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 : 2021-06-03DOI: 10.1080/10610278.2021.1959035
A. S. Ferreira, J. Ascenso, P. M. Marcos, R. Schurhammer, N. Hickey, S. Geremia
ABSTRACT The conformational changes of the homooxa adamantyl ketones 1 and 2, as well as of the calix[4]arene analogue derivative 3, all in the cone conformation, upon Pb2+ complexation were investigated by 1H, 13C, 207Pb NMR and proton spin-lattice relaxation times (T 1) experiments. The X-ray crystal structures of ketones 1 and 3 were determined. The inclusion of an acetonitrile molecule in the hydrophobic cavity of the ligands was observed in the solid state. In solution, inclusion was observed only in the case of Pb2+ ⊂ ketone 3 complex. DFT calculations were also performed to complement the NMR conformational analysis and to bring further insights to the cation complexation. The data confirmed the formation of 1:1 complexes between Pb2+ and the ligands, and that the cation is located inside the cavity defined by the phenoxy and carbonyl oxygen atoms. In general, the ligand conformations became closer to a regular cone upon complexation, with the binding models found for the three ketones through the NMR studies corroborated by the DFT calculations.
{"title":"Calixarene-Based lead receptors: an NMR, DFT and X-Ray synergetic approach","authors":"A. S. Ferreira, J. Ascenso, P. M. Marcos, R. Schurhammer, N. Hickey, S. Geremia","doi":"10.1080/10610278.2021.1959035","DOIUrl":"https://doi.org/10.1080/10610278.2021.1959035","url":null,"abstract":"ABSTRACT The conformational changes of the homooxa adamantyl ketones 1 and 2, as well as of the calix[4]arene analogue derivative 3, all in the cone conformation, upon Pb2+ complexation were investigated by 1H, 13C, 207Pb NMR and proton spin-lattice relaxation times (T 1) experiments. The X-ray crystal structures of ketones 1 and 3 were determined. The inclusion of an acetonitrile molecule in the hydrophobic cavity of the ligands was observed in the solid state. In solution, inclusion was observed only in the case of Pb2+ ⊂ ketone 3 complex. DFT calculations were also performed to complement the NMR conformational analysis and to bring further insights to the cation complexation. The data confirmed the formation of 1:1 complexes between Pb2+ and the ligands, and that the cation is located inside the cavity defined by the phenoxy and carbonyl oxygen atoms. In general, the ligand conformations became closer to a regular cone upon complexation, with the binding models found for the three ketones through the NMR studies corroborated by the DFT calculations.","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"89 1","pages":"231 - 244"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90658001","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 : 2021-06-03DOI: 10.1080/10610278.2021.1999450
Rebecca J. Ellaby, Dominique F. Chu, Antigoni Pépés, Ewan R. Clark, J. Hiscock
ABSTRACT Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing global threat, through either purposeful environmental release or the need to dispose of historic stockpiles. This presents a need for the development of novel decontamination technologies. Due to the toxic nature and legal limitations placed on OP CWAs, the use of appropriate OP simulants that mimic the reactivity but not the toxicity of the agents themselves is vital to decontamination studies. Herein, we show that association constants derived from non-specific hydrogen bonded complexation events may be used as parameters within models to predict simulant reactivity. We also discuss the limitations that should be placed on such data. GRAPHICAL ABSTRACT
{"title":"Predicting the hydrolytic breakdown rates of organophosphorus chemical warfare agent simulants using association constants derived from hydrogen bonded complex formation events","authors":"Rebecca J. Ellaby, Dominique F. Chu, Antigoni Pépés, Ewan R. Clark, J. Hiscock","doi":"10.1080/10610278.2021.1999450","DOIUrl":"https://doi.org/10.1080/10610278.2021.1999450","url":null,"abstract":"ABSTRACT Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing global threat, through either purposeful environmental release or the need to dispose of historic stockpiles. This presents a need for the development of novel decontamination technologies. Due to the toxic nature and legal limitations placed on OP CWAs, the use of appropriate OP simulants that mimic the reactivity but not the toxicity of the agents themselves is vital to decontamination studies. Herein, we show that association constants derived from non-specific hydrogen bonded complexation events may be used as parameters within models to predict simulant reactivity. We also discuss the limitations that should be placed on such data. GRAPHICAL ABSTRACT","PeriodicalId":22084,"journal":{"name":"Supramolecular Chemistry","volume":"59 1","pages":"309 - 317"},"PeriodicalIF":3.3,"publicationDate":"2021-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73313935","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}
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