Calixarenes as stationary phases in high performance. The calixarenes and resorcinarenes are macrocyclic phenolic molecules that can be modified a facon and a wide range of chemical modification strategies have been published over the last 30 years. Optically active calixarenes conduced by methylene substitution. This method would avoid the losses inherent in the. New boron material of high hardness created by plasma chemical vapor deposition. The name derives from the vaselike molecular structures. Calixarenes are versatile macromolecules in the field of supramolecules because of its synthetic feasibility and extensive analytical applications. Rather than emphasizing the molecular properties of calixarenes, it covers in depth their supramolecular functions, demonstrating the peculiar features of calixarenes as hosts and as platforms for the synthesis of more complex reactors and catalysts. Calixarenes in action world scientific publishing company. Selfassembly of amphiphilic calixarenes and resorcinarenes in. A green chemistry procedure was recently developed using solventfree conditions.
Calixarenes and resorcinarenes are families of macrocyclic species that have become a broad field of chemical research over the past few decades. A calixarene is a macrocycle or cyclic oligomer based on a hydroxyalkylation product of a phenol and an aldehyde the word calixarene is derived from calix or chalice because this type of molecule resembles a vase and from the word arene that refers to the aromatic building block. Calixarenes and resorcinarenes at interfaces springerlink. Calixarenes and resorcinarenes synthesis, properties and. There are some 3,000 publications reporting calixarenes, many of which can be obtained by searching.
The beginning born march 21, 1921 in oak park, il family. The various conformations of calixarenes are caused by the free rotation of sigma bonds at methylene, arcar, bridges. Their interaction with various substances of interest in pharmacy, engineering, and medicine is also described. A calixarene is a macrocycle or cyclic oligomer based on a hydroxyalkylation product of a phenol and an aldehyde. Curtis, institute of science and technology in medicine, keele university. The arsenal of structures based on calixarenes provides tools which are effective in numerous areas. Peptidebased tubular structures are based on mimicking natural protein secondary structures. Many chiral calixarenes including resorcinarenes and. Molecular modeling of calixarenes and their hostguest complexes f c j m van veggel.
Calixarenes was the first book to be published in the monographs in supramolecular chemistry series and is also the first complete survey available of this rapidly developing field. That is, at least half of the free hydroxyl groups present on the calix4resorcinarene molecule are protected with protecting groups that are removable with acid. Calixarenes by c david gutsche and a great selection of related books, art and collectibles available now at. In particular, the role of the calixnarenes in the detection. Information and translations of calixarenes in the most comprehensive dictionary definitions resource on the web. Selfassembly process between phenolic sectors and formaldehyde molecules under hightemperature conditions to afford oligomeric systems like resins 7, monoliths 8, and calixarenes 9, 10 have been the focus of interest over recent years. Wulff department of chemistry, michigan state university, east lansing, michigan 48824 received july 24, 2009. V arious analytical applications of calixarenes are discussed. As a result of their easy synthesis from phenols and aldehydes they are receiving increasingly wide attention. The properties and characteristics of calixnarenes are described, as well as their capacity to form amphiphilic assemblies by means of the design of synthetic macrocycles with a hydrophilic head and a hydrophobic tail. Important calixarene derivatives their synthesis and.
They are sparingly soluble and high melting solids. Usa home product directory chemical synthesis synthetic reagents chelationcomplexation compounds calixarenes chemistry products new chemistry products. Simple calixnarenes and calix4 resorcinarenes as drug solubilizing agents volume 2 issue 3 2015 clare hoskins and anthony dm curtis institute of science and technology in medicine, keele university, uk corresponding author. The large range of possible chemical modifications of the parent macrocycles allows finetuning the selfassembly properties of these macrocycles at interfaces. Calixarenes have hydrophobic cavities that can hold smaller. Operational calixarenebased fluorescent sensing systems. Ofarrell cm1, chudomel jm, collins jm, dignam cf, wenzel tj. The interest of calixarenes in analytical and separation chemistry has increased in recent years because of their ability to form reversible complexes with both neutral and charged molecules. Calixarenes and calix4resorcinarenes as chiral nmr. Optically active calixarenes conduced by methylene. It provides a fascinating and lively account of the history, development and applications of calixarenes, which are probably the worlds most readily available synthetic molecular baskets. This material is available free of charge via the internet. Contributions featuring the chemistry and applications of a family of macrocyclic compounds collectively known as calixarenes are presented in this edited volume.
The number n enclosed in brackets, which separates calix and arene, indicates the number of aromatic ring units in the macrocycle, for example, calix4arene, calix6arene and calix8arene. These basketshaped compounds possess the ability to hold metal ions, and molecules, in their interior. Calixarenes are probably the worlds most readily available synthetic molecular baskets. Dcu connectedconnectedwhat if you could work towards a worldclass online irish university degree on your own schedule, from the comfort of your own home, in your own town, in any place in the world. Besides classical calixarenes, also calixarenes containing modified meso bridges are known,22 they are calixradialenes,23 ketocalixarenes24 and homocalixarenes. Oct 25, 2009 porous materials are important in a wide range of applications including molecular separations and catalysis. A pastelike solid forms upon sitting for several minutes, which can be washed with water and crystallized to give the desired resorcinarene. Chemotherapy occupies a pivotal position in the treatment of cancer, and its significance in terms of cure and regression of various types of cancer should not be underestimated. For example, calix4resorcinarenes have four prochiral centers on carbon atoms at the methylene bridges, causing the compound to form four different diastereoisomers. The arsenal of structures based on calixarenes provides tools which are effective in numerous areas of supramolecular chemistry.
The latter notation was highly recommended for inherently chiral calixarenes by szumna because they are typical in concave molecules, including salphen complexes, cyclic amides, derivatives of sumanene, trioxatricornan or subphthalocyanine, cyclotriveratrylenes, homooxacalixarenes, resorcinarenes, phthalocyanines, corannulenes, and cavitands. The calixarenes are calix4resorcinarenes that are partially or wholly protected with acidlabile protecting groups. A calixarene is a macrocycle or cyclic oligomer based on a hydroxyalkylation product of a. Calixarenes we are interested in the application of multidentate aryloxide ligands to prepare reactive metal complexes that may emulate aspects of heterogeneous catalyst surfaces. Selfassembly of amphiphilic calixarenes and resorcinarenes in water. Calixarenessolubility of calixarenes physics forums. Applications of calixarenes in cancer chemotherapy. However, the class of calixarene compounds as known in the art includes calixn resorcinarenes, which comprise resorcinol moieties that are joined to each other, and typically possess phenoxy groups in a different arrangement around the ring. We demonstrate that covalently bonded organic cages can assemble into crystalline. The process has been found to be highly efficient, selective and versatile. Calixarenes as parent compounds are sparingly soluble and are high melting crystalline solids 3. Phenolic metacyclophanes derived from condensation of phenols and aldehydes. An introduction 2nd edition provides a concise overview of the field with particular attention to the historical development of calixarenes.
They have the ability to bind to a variety of ions and find applications as ion sensors. Facile synthesis of resorcinarenes functionalized magnetic nano solid acid. The word calixarene is derived from calix or chalice because this type of molecule resembles a vase and from the word arene that refers to the aromatic building block. Operational calixarenebased fluorescent sensing systems for. The various conformations of calixarenes are caused by the free rotation of sigma bonds at methylene, arcar, bridges 6. Aug, 2016 since the first synthesis of chiral calixarenes in 1979 by gutsche enormous progress has been made in preparation techniques and applications. Calixarenes are macrocyclic nanobaskets which belong to cavitands class of hostguest chemistry. A resorcinarene is a macrocycle, or a cyclic oligomer, based on the condensation of resorcinol 1,3dihydroxybenzene and an aldehyde. For example, calix4resorcinarenes have four prochiral centers on carbon atoms at the methylene bridges, causing the compound. Other macrocycles include cyclodextrin, resorcinarenes, calixarenes, pyrogalloarenes, cucurbiturils, and porphyrins 67. A study of the class of synthetic macrocycles, called calixarenes.
Calixarenes are macrocyclic oligomers, formed from phenolformaldehyde condensation. In our quest for the elaboration of supramolecular models of metalloenzyme active sites, we became interested in developing new methodologies for the selective functionalization of the large rim of calix6arenes. David gutsche macromolecular people aman imani macalester college, mn 2. Covalent or supramolecular combinations of resorcinarenes and. The nature of the substituent groups attached to the cavity permits the preparation of organic or watersoluble analogues. Because of their remarkable structural properties and their relative ease of chemical modification, they repres. Chiral calixarenes and resorcinarenes springerlink. In nmr applications, chirality of the cas or calix4resorcinarene. Synthesis and catalytic relevance of piii and p v functionalised calixarenes and resorcinarenes. The resulting structure can be compatible with the dimension of a bilayer. Green synthesis of oligomer calixarenes intechopen. Both the upper and lower rims can be tailor made to provide highly preorganized structures. The calixarenes and resorcinarenes are macrocyclic phenolic molecules that can be modified a facon and a wide range of chemical modification strategies. Apr 04, 2008 watersoluble calix 4resorcinarenes with hydroxyproline groups as chiral nmr solvating agents.
Selfassembly of amphiphilic calixarenes and resorcinarenes. There are some 3,000 publications reporting calixarenes, many of which can be obtained by searching databases under the term calix. A universal method to wrap 3d curved surfaces with nonstretchable materials. Acetylprotected thiols calixarenes coupling reagents disulfides dithiols for nanoparticle assembly fluorinated thiols and silanes functionalized thiols graphene derivatives ligands for iron oxide surfaces mofs photoswitchable thiols silanes thiolated carbohydrates mimicking glycans thiolated crown ethers thiols and disulfides for fluorescent. A read is counted each time someone views a publication summary such as the title, abstract, and list of authors, clicks on a figure, or views or downloads the fulltext. They are the marvelous hosts with distinct hydrophobic three dimensional cavities to entrap and encapsulate biologically active guest drugs. Facile synthesis of resorcinarenes functionalized magnetic. In addition, several books have been written on calixarenes, and metal complexes are described in all of them. Simple calixnarene and calix4resorcinarene as drug. The optical detector was based on a calix4arene to which a nitrophenylazophenol chromophore is attached. Calixarenes article about calixarenes by the free dictionary. In nmr applications, chirality of the cas or calix4resorcinarene is usually. C david gutsche this book gives a concise, comprehensive overview of the field with particular attention to the historical development of calixarenes and will be of immediate value to researchers, graduates and.
Simple calixnarene and calix4resorcinarene as drug solubilizing. Drawing on reports published since 2005, this book is the only one to cover the latest advances concerning the properties of calixarenes of various structures, while highlighting their future applications in science and new technologies. Clearly divided into three main topic areas, this monograph deals with the synthesis of new calixarenes and. Arbuzov institute of organic and physical chemistry, kazan. Calixarenes cas and calix4resorcinarenes are cavity compounds, chiral analogues of which have the potential to be used as reagents for the differentiation of enantiomers in nmr spectroscopy. In 2005, research produced a pyrogallol4arene by simply mixing a solvent free dispersion of isovaleraldehyde with pyrogallol and a catalytic amount of ptoluenesulfonic acid in a mortar and pestle 2. This area flourishes and is vibrant today as these molecules are studied in areas such as catalysis, molecular recognition, sensing, and devices. Other substances exist that have structures analogous to calixarenes, but which, for example include. The formylated resorcinarene reacts easily with primary aliphatic and aromatic. Calixarenes in action is a valuable reference book for researchers in organic, inorganic, analytical and environmental chemistry and can serve as a graduatelevel text for students of supramolecular science and technology. The shape of calixarenes is like a cup or a bucket with a defined upper and lower rim along with a central annulus. Calixarenes and resorcinarenes in molecular recognition and supramolecular devices, cheminform on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips. All of this has been possible due to the fact that these compounds are able to form a complex with molecules of biological interest such as antibiotics 1, proteins and nucleic.
The calixarene and the related resorcinarenes represent an actively. Kazemian fard department of chemistry, faculty of science, university of shahid chamran, ahvaz, iran email. Rather than emphasizing the molecular properties of calixarenes, it covers in depth their supramolecular functions, demonstrating the peculiar features of calixarenes as hosts and as platforms for the synthesis of. Calixarenes in action luigi mandolini, rocco ungaro. University of wisconsin 19471951 under william summer johnson warf postdoctoral fellow at u. The first method for the synthesis of optically active calix4arenes that are chiral as a result of substitution on the methylene bridges is described. Watersoluble calix4resorcinarenes with hydroxyproline. Request pdf on sep 14, 2009, jack harrowfield and others published calixarenes and resorcinarenes. Immobilized calixarenes and related compounds and process for. Calixarenes have been utilized in gas chromatography, solidphase extraction. Polyhydroxylated platforms such as calixarenes, resorcinarenes, or pyrogalloarenes. Calixarenes in action luigi mandolini, rocco ungaro download. A bracketed n indicates the number of aromatic rings. Calixnarenes and calix4resorcinarenes have found use in supramolecular chemistry, catalysis and separation science but they have attracted much interest for their potential use in drug design and delivery 410.
For example, calix4 resorcinarenes have four prochiral centers on carbon atoms at the methylene bridges, causing the compound to form four different diastereoisomers. Calixarenes and resorcinarenes as scaffolds for supramolecular metalloenzyme mimicry. Jul 25, 2000 the calixarenes are calix4resorcinarenes that are partially or wholly protected with acidlabile protecting groups. Online learning with dcu connected gives you remote access to all the resources of an established university. Calixarenes and resorcinarenes research and markets. Porous materials are important in a wide range of applications including molecular separations and catalysis. Important calixarene derivatives their synthesis and applications. A green chemistry procedure was recently developed using solvent free conditions. This book contains extensive references to recent literature, offering the reader a valid. Purification of c 60 and c 70 by selective complexation with. Calixarenes are a class of host molecules with threedimensional cavity capable of accepting guest molecules. Optically active calixarenes conduced by methylene substitution vijay gopalsamuthiram, alexander v.
An introduction monographs in supramolecular chemistry by c. This chapter summarizes the most recent developments in the fabrication and potential applications of calixarenes and resorcinarenes based thin films on liquid and solid surfaces. Calixarenes chelationcomplexation compounds sigmaaldrich. All structured data from the file and property namespaces is available under the creative commons cc0 license. Calixarenes have hydrophobic cavities that can hold smaller molecules or ions and belong to the class of. Molecular complexation of fullerenes in hostguest complexes has the potential to afford efficient largescale purification of fullerenes1. Files are available under licenses specified on their description page. The key step in the synthesis involves the reaction of a biscarbene complex with a diyne, which generates two of the benzene rings and the macrocyclic ring of the calix in a single transformation. Applications of calixarenes as extractants and sensors 2. Peptidebased tubular structures are based on mimicking natural protein. Electronrich anionic calixarenes and resorcinarenes are known receptors for trimethylammoniumcontaining neurotransmitters, but the development of practical sensor applications has been impeded by the lack of suitable supramolecular sensing ensembles as well as the low selectivity and sensitivity of the mac.
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