An introduction monographs in supramolecular chemistry by c. Calixarenes are macrocyclic polyphenols with a wide range of structures and. Calixarenes are probably the worlds most readily available synthetic molecular baskets. The calixarenes are a class of cyclooligomers formed. As the third generation of supramolecules, after cyclodextrins and crown ethers, calixarenes have been extensively studied for hostguest chemistry and frequently used in separations, as sensors and catalysts, because of their unique cavityshaped architecture and preorganized binding sites. Gutsche this revised second edition is a must for advanced undergraduates and postgraduates studying bioorganic and supramolecular chemistry. Introduction calixarene, a third generation receptor easily synthesized by condensation of phenol and formaldehyde, provides a peerless three dimensional structure with several functional sites and gives flexibility to act as a specific receptor fig. Calixarenes acs publications american chemical society. 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. An introduction 2nd edition provides a concise overview of the field with particular attention to the historical development of calixarenes. These metrics are regularly updated to reflect usage leading up to the last few days. The calixarene and the related resorcinarenes represent an actively researched group of. Important calixarene derivatives their synthesis and.
Important calixarene derivativestheir synthesis and applications. Synthesis and reactivity of calixarenes functionalized at. 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. As it is the case for crown ethers, calixarenes with oxygen donor atoms turned out to be suitable for selectively binding alkali ions. Calixarenes chelationcomplexation compounds sigmaaldrich. Design and synthesis of calixarene y k agrawal j p pancholi and j m v yas institute of research and development, gujarat forensic sciences university, sector 18a, gandhinagar 382 007, india. As a result of their easy synthesis from phenols and aldehydes they are receiving increasingly wide attention.
Introduction to calixarenes ungaro, rocco 20010508 00. A thesis in chemistry submitted to the graduate faculty of texas tech university in partial fulfillment of the requirements for the degree of master of science approved richard bartsch chairperson of the committee david birney edward quitevis ralph ferguson. A calixarene is a macrocycle or cyclic oligomer based on a hydroxyalkylation product of a. Model reactions of calixarenes and their esterified. Calixarenes are good candidate for molecular ion recognition, drug recognition, metal recognition, diagnostics and drug delivery. Introduction the calixarenes are a class of cyclooligomers formed via a phenolformaldehyde condensation. As was discussed above, calixarenes are substances of easy access and of easy chemical modification, thus allowing one to obtain systems with the introduction of polar groups to the calixarenes, making it possible to design amphiphilic macrocycles with a hydrophilic head and a hydrophobic tail, which may selfassemble into micelles, vesicles. These basketshaped compounds possess the ability to hold metal ions, and molecules, in their interior. Calixarenes are cyclic oligomers obtained by condensation of suitable pfunctionalised phenols with formaldehyde, usually allowing for the synthesis. Some of the least studied calixarenes are those that consist of azulene rings bridged by ch 2 groups. Alkylation of calix4arenes with an excess of nah in dmf and 2. To access a cheminform abstract of an article which was published elsewhere, please select a full text option.
The addition of chirality to calixarenes is an exciting enhancement of their. Calixarene nomenclature is straightforward and involves counting. It provides a fascinating and lively account of the history, development and applications of calixarenes, which are probably the worlds most readily available. It is insoluble in aqueous phase while slightly soluble in organic solvents, melts at high. Lowerrim substituted calixarenes and their applications. Springer international publishing, switzerland, 2016. They exist in a cup like shape with a defined upper and lower rim and a central annulus see figure 1. 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. These compounds have other applications in ionselective membranes and electrodes 59, gas chromatography 10, capillary electrophoresis 1417 and solidphase. The earliest examples of lowerrimsubstituted calixarenes investigated for their complexation properties are the ethyleneoxy compounds 85, 86 which show only a modest degree of cation binding agency. Various analytical applications of calixarenes are discussed. Since lash and colbys discovery of a simple and convenient method for producing the parent allhydrocarbon calix4azulene, there have been two other allhydrocarbon calix4azulenes which have been synthesized in good yields by their method. Calixarenes we are interested in the application of multidentate aryloxide ligands to prepare reactive metal complexes that may emulate aspects of heterogeneous catalyst surfaces.
Roundhill, in comprehensive coordination chemistry ii, 2003. Calixarenes are versatile macromolecules in the field of supramolecules because of its synthetic feasibility and extensive analytical applications. Citations are the number of other articles citing this article, calculated by crossref and updated daily. This book contains extensive references to recent literature, offering the reader a valid. Calixarenes, crownethers, fullerenes, polymers introduction calixarene is a macrocycle or cyclic oligomer based on a hydroxyl alkylation product of phenols and aldehydes1. These basket shaped compounds possess the ability to hold metal ions, as well as molecules, in their interior and as a result of their extraordinarily easy synthesis from phenols and aldehyde. Notestein, enrique iglesia, and alexander katz department of chemical engineering, university of california at berkeley, berkeley, california 94720 received march 21, 2007. Article views are the countercompliant sum of full text article downloads since november 2008 both pdf and html across all institutions and individuals. Calixarene, ionselective electrode, sensor, synthesis, enatioselective, optodes. All the products 3 are obtained in the cone conformation and further alkylation does not take place.
Luminescent lanthanoid calixarene complexes and materials mdpi. Their rigid conformation enables calixarenes to act as host molecules as a result of their preformed cavities. Syntheses, structures and interactions of heterocalixarenes pdf. The driving forces of outersphere association of transition metal complexes with various macrocycles, dna and antibiotics 917 iii.
Calixarenes as a thirdgeneration of macrocyclic compounds were used as bonded highperformance liquid chromatography hplc phases in 1993 for the first time. Placido neri received his doctoral degree in chemistry in 1985 from the university of catania. Introduction calixarenes are interesting cage macrocycles, widely investigated due to their valuable properties, especially formation of inclusion complexes. The thermodynamics of outersphere association of watersoluble calixarenes with charged complexes and 920 organic ions in comparison with that of cyclodextrins and cucurbiturils iv. The synthesis and characterization of giant calixarenes.
Depending on the reaction conditions the products could be obtained in the cone or 1,3alternate conformation. Pdf design and synthesis of calixarene researchgate. Adsorption of myoglobin on calixarenes and biocatalysis in. General papers arkivoc 2012 i 173210 page 174 arkatusa, inc. The arsenal of structures based on calixarenes provides. Relates calixarenes to nanochemistry key information for industries engaged in the production of hightech materials. Calixarenes have been actively studied and utilized as the third generation of host compounds in addition to the wellknown cyclodextrins 1 10 and crown ethers 2 11, 12 first and second generation supramolecules, respectively.
Introduction and definitions syntheses of calixarenes one. Introduction the arsenal of structures based on calixarenes provides tools which are effective in numerous areas of supramolecular chemistry. Calixarenes cas are a class of macrocycle or cyclic oligomers formed by a condensation reaction between a phenol and an aldehyde. Introduction history structures of calixarenes chemical modification of calixarenes complexes with calixarenes bis and multicalixarenes oxacalixarenes.
Calixarenes are cyclic oligomers obtained by condensation reactions between paratbutyl phenol and formaldehyde. By judicious choice of base, reaction temperature, and reaction time, calixarenes having different ring sizes can be prepared in good yield. Introduction calixarene, a third generation receptor easily. Separation of amino acids by high performance liquid. A calixarene is a macrocycle or cyclic oligomer based on a hydroxyalkylation product of a phenol and an aldehyde. From 1984 to 1998 he worked at the istituto per lo studio delle sostanze naturali di interesse alimentare e chimicofarmaceutico issn of the italian national research council consiglio nazionale delle ricerche c.
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