Relevant bibliographies by topics / Calixareni

Academic literature on the topic 'Calixareni'

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Published: 10 March 2023

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Journal articles on the topic "Calixareni"

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Jose, Princy, and Shobana Menon. "Lower-Rim Substituted Calixarenes and Their Applications." Bioinorganic Chemistry and Applications 2007 (2007): 1–16. http://dx.doi.org/10.1155/2007/65815.

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This review discusses in detail “calixarenes” since their discovery as by-products of the phenol formaldehyde bakelites till the present scenario wherein calixarene has assumed a new dimension in the field of supramolecular chemistry. Extensive literature exists for calixarenes; but herein we have tried to concentrate on the different lower-rim modified calixarenes with their potential applications. An attempt has also been made to critically evaluate the synthesis procedures for different lower-rim substituted calixarenes.
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Mironova, Diana, Vladimir Burilov, Farida Galieva, Mohamed Ali Mohamed Khalifa, Sofia Kleshnina, Alsu Gazalieva, Ramil Nugmanov, Svetlana Solovieva, and Igor Antipin. "Azocalix[4]arene-Rhodamine Supramolecular Hypoxia-Sensitive Systems: A Search for the Best Calixarene Hosts and Rhodamine Guests." Molecules 26, no. 18 (September 7, 2021): 5451. http://dx.doi.org/10.3390/molecules26185451.

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A potential hypoxia-sensitive system host-guest complex of three calixarenes (including two with four anionic carboxyl and sulphonate azo fragments on the upper rim and a newly synthesized bis-azo adduct of calixarene in the cone configuration with azo fragments on the lower rim with the most widespread cationic and zwitterionic rhodamine dyes (123, 6G and B)) was studied using UV-VIS spectrometry and fluorescence as well as 1D and 2D NMR techniques. It was found that all three calixarenes form a complex with rhodamine dyes with a 1:1 composition. The association constants of calixarene-dye complexes with sulfonate calixarenes, especially in the case of tetra-anionic calixarene, turned out to be higher compared with carboxyl calixarene due to the more intense electrostatic interactions. For the first time using an HRESI MS technique, it was shown that the treatment of rhodamine 6G and 123 with sodium dithionite (SDT) produces a non-fluorescent leuco form of the dye, and only rhodamine B can be used with SDT without the occurrence of a side reduction. Moreover, it was identified that in addition to the reduction in the azo groups, SDT causes partial cleavage of the aryl ether bonds. The found features of SDT should be taken into account when SDT is used as an azoreductase mimic.
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Basilotta, Rossella, Deborah Mannino, Alessia Filippone, Giovanna Casili, Angela Prestifilippo, Lorenzo Colarossi, Gabriele Raciti, Emanuela Esposito, and Michela Campolo. "Role of Calixarene in Chemotherapy Delivery Strategies." Molecules 26, no. 13 (June 29, 2021): 3963. http://dx.doi.org/10.3390/molecules26133963.

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Since cancer is a multifactorial disease with a high mortality rate, the study of new therapeutic strategies is one of the main objectives in modern research. Numerous chemotherapeutic agents, although widely used, have the disadvantage of being not very soluble in water or selective towards cancerous cells, with consequent side effects. Therefore, in recent years, a greater interest has emerged in innovative drug delivery systems (DDSs) such as calixarene, a third-generation supramolecular compound. Calixarene and its water-soluble derivatives show good biocompatibility and have low cytotoxicity. Thanks to their chemical–physical characteristics, calixarenes can be easily functionalized, and by itself can encapsulate host molecules forming nanostructures capable of releasing drugs in a controlled way. The encapsulation of anticancer drugs in a calixarene derivate improves their bioavailability and efficacy. Thus, the use of calixarenes as carriers of anticancer drugs could reduce their side effects and increase their affinity towards the target. This review summarizes the numerous research advances regarding the development of calixarene nanoparticles capable of encapsulating various anticancer drugs.
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Lazar, Adina N., Oksana Danylyuk, Kinga Suwinska, and Anthony W. Coleman. "The Structure of the Tetra-Potassium Salt of Calix[4]Arene Dihydroxyphosphonic Acid." Chemistry Journal of Moldova 2, no. 1 (December 2007): 98–101. http://dx.doi.org/10.19261/cjm.2007.02(1).07.

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The solid-state structure of the tri-potassium calix[4]arene dihydroxyphosphonate salt is presented. In this structure, two potassium cations bridge between layers of dimeric calixarene diphosphonate units and two other potassium cations bridge along the face of the layers. The ubiquitous dimeric association of the calixarenes shows the highest interdigitation value so far observed. As expected, the cations are solvated and are complexed exo with respect to calixarene crown. The octahedral coordination sphere of the potassium cations is formed by two phosphonate groups of the calixarenes and four water molecules. Electrostatic forces represent the major element of interaction in the solid-state system.
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Lebrón, José Antonio, Manuel López-López, Clara B. García-Calderón, Ivan V. Rosado, Fernando R. Balestra, Pablo Huertas, Roman V. Rodik, et al. "Multivalent Calixarene-Based Liposomes as Platforms for Gene and Drug Delivery." Pharmaceutics 13, no. 8 (August 12, 2021): 1250. http://dx.doi.org/10.3390/pharmaceutics13081250.

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The formation of calixarene-based liposomes was investigated, and the characterization of these nanostructures was carried out using several techniques. Four amphiphilic calixarenes were used. The length of the hydrophobic chains attached to the lower rim as well as the nature of the polar group present in the upper rim of the calixarenes were varied. The lipid bilayer was formed with one calixarene and with the phospholipid 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine, DOPE. The cytotoxicity of the liposomes for various cell lines was also studied. From the results obtained, the liposomes formed with the least cytotoxic calixarene, (TEAC12)4, were used as nanocarriers of both nucleic acids and the antineoplastic drug doxorubicin, DOX. Results showed that (TEAC12)4/DOPE/p-EGFP-C1 lipoplexes, of a given composition, can transfect the genetic material, although the transfection efficiency substantially increases in the presence of an additional amount of DOPE as coadjuvant. On the other hand, the (TEAC12)4/DOPE liposomes present a high doxorubicin encapsulation efficiency, and a slow controlled release, which could diminish the side effects of the drug.
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Cohen, Yoram, and Sarit Slovak. "Diffusion NMR for the characterization, in solution, of supramolecular systems based on calixarenes, resorcinarenes, and other macrocyclic arenes." Organic Chemistry Frontiers 6, no. 10 (2019): 1705–18. http://dx.doi.org/10.1039/c9qo00329k.

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The use of diffusion NMR in studying calixarenes and other arene-based supramolecular systems is described, emphasizing the pivotal role played by the calixarene community in transforming the methods into a routine tool used in supramolecular chemistry.
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Schatz, Jürgen. "Recent Application of ab initio Calculations on Calixarenes and Calixarene Complexes. A Review." Collection of Czechoslovak Chemical Communications 69, no. 6 (2004): 1169–94. http://dx.doi.org/10.1135/cccc20041169.

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In this short review the application of ab initio quantum chemical calculations on calixarenes and calixarene complexes is highlighted. The main focus lies on results obtained mainly during the last 2-3 years. A review with 92 references.
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Kalchenko, Vitaly I. "Calixarene receptors of environmentally hazardous and biorelevant molecules and ions." Pure and Applied Chemistry 80, no. 7 (January 1, 2008): 1449–58. http://dx.doi.org/10.1351/pac200880071449.

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In the paper, a report on the rational design of the calixarene receptors bearing ligating, H-donor, H-acceptor fragments at the wide and/or narrow rim of the macrocycle is presented. The calixarenes form supramolecular complexes with various cations, anions, organic molecules, and biomolecules in solution, in the crystalline state and even in the gas phase. The calixarenes or their complexes can be used as materials for radionuclide extraction, construction of chemosensors, and drug design.
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Allen, Hillary F., Kevin D. Daze, Takashi Shimbo, Anne Lai, Catherine A. Musselman, Jennifer K. Sims, Paul A. Wade, Fraser Hof, and Tatiana G. Kutateladze. "Inhibition of histone binding by supramolecular hosts." Biochemical Journal 459, no. 3 (April 11, 2014): 505–12. http://dx.doi.org/10.1042/bj20140145.

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We report a new set of calixarene-based host compounds and show their applicability in characterizing functions of methyllysine-recognizing epigenetic readers. Calixarenes disrupt the association of the PHD finger of CHD4 with a trimethylated, but not an unmodified, histone tail.
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Ling, Irene, Alexandre N. Sobolev, and Colin L. Raston. "Controlling the organization of phosphonium cations relative to p-sulfonatocalix[4]arene anions." CrystEngComm 17, no. 7 (2015): 1526–30. http://dx.doi.org/10.1039/c4ce02086c.

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A composite material containing supermolecules of 1,4-bis(triethylammoniomethyl)benzene and p-sulfonated calix[4]arene involves preferential binding of the ammonium moieties in the cavities of two geometrically opposed calixarenes with mono-phosphonium cations arranged in the endo-orientation with respect to the calixarene bilayers, as a multi-layered structure.
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Dissertations / Theses on the topic "Calixareni"

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Talotta, Carmen. "Congegni Supramolecolari basati sul Threading di Calixareni." Doctoral thesis, Universita degli studi di Salerno, 2013. http://hdl.handle.net/10556/1475.

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2011 - 2012
Recently, Neri et al have introduced an efficient method to obtain endo-cavity complexation and through-the-annulus threading of large calixarenes exploiting the inducing effect of a weakly coordinating anion, tetrakis [3,5-bis (trifluoromethyl) phenyl]borate (TFPB-). In this PhD thesis this approach has been used for the synthesis of [2]rotaxanes, which showed an unprecedented inversion of the wheel orientation. Subsequently, it was extended to the synthesis of pseudo[3]rotaxane systems in which two calix[6]arene macrocycles are threaded by a bis(benzylalkylammonium) axle. Because of the three-dimensional nonsymmetrical nature of the calix[6]arene wheels, in these instances three sequence stereoisomers could be obtained, which were termed as headto- head (H,H), head-to-tail (H,T) and tail-to-tail (T,T). Taking advantage of these systems, it was possible to obtain the stereoprogrammed synthesis of the first examples of calixarene-based [3]rotaxane architectures. The base/acid treatment demonstrated that these systems act as molecular shuttles, which move on a nanometer scale level. The directionality of the threading and the observed high stereoselection have enabled the synthesis of directional calix[6]arene-based catenane. All these aspects represent interesting peculiar features of calixarene threading, which could be exploited for designing molecular machines with new properties or functions
XI n.s.
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Ciao, Roberta. "New chemical topologies based on calixarene threading." Doctoral thesis, Universita degli studi di Salerno, 2014. http://hdl.handle.net/10556/1428.

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2012 - 2013
Recently, Neri et al. have introduced an efficient method to obtain endo-cavity complexation and through-the-annulus threading of large calixarenes by exploiting the inducing effect of the weakly coordinating tetrakis[3,5-bis-trifluoromethyl)phenyl]borate (TFPB-) anion. The corresponding calix[6]-arene/dialkylammonium pair can be considered a versatile recognition motif, which can be used for the construction of a large variety of calixarene-threaded architectures. This Ph. D. thesis deals with the exploration of the stereochemical features of the threading of hosts containing multiple cavities. Therefore, the synthesis of double- and triple-calixarenes is reported, which is followed by the subsequent study of their threading abilities with dialkylammonium axles.The results confirmed the now well-known endo-alkyl rule of calix[6]arenes that give the inclusion of alkyl chains inside the calix-cavity. On this basis, we were then able to build new attractive chemical topologies. In particular, doubly-threaded pseudo[3]rotaxane structures have been obtained by the threading of double-calixarene hosts with mono-ammonium axles. The subsequent extention to triple-calixarene hosts, in which three macrocycles are covalently linked to one another by means of an appropriate spacer, gave triply-threaded pseudo[4]rotaxane structures. Because of the three-dimensional nonsymmetrical nature of the calix[6]arene wheels, by threading double-calixarene hosts with bis-ammonium axles three examples of beautiful stereoisomeric calixarene-based handcuff rotaxanes were obtained, which could be termed as head-to-head (H,H), head-to-tail (H,T), and tail-to-tail (T,T). On the basis of these results, it is conceivable that the extension of this approach could lead to novel mechanically interlocked architectures with high-order topologies. [edited by author]
XII n.s.
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Tommasone, Stefano. "Synthesis of calixarene derivatives active towards proteic targets involved in tumor pathologies." Doctoral thesis, Universita degli studi di Salerno, 2016. http://hdl.handle.net/10556/2213.

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2014 - 2015
Over the last 30 years a growing interest has been direct toward the biomolecular recognition of calixarene derivatives and more in particular to the interaction with druggable target(s).1,2 The aim of this PhD thesis was the synthesis and the study of calixarenes that were able to interact with biomolecules involved in tumor pathologies. One of the main topic of this work was the synthesis of calix[4]arene conjugates bearing pyrenylisoxazolidine moieties at the exo rim which could act as potential DNA intercalators. The in vitro cytotoxic activity against different human tumor cell lines was also tested. Moreover, the biomolecular recognition abilities of designed calixarenes was studied through a chemical proteomics approach. As calix[n]arene scaffolds are particularly suitable for the synthesis of multivalent ligands,3 the attention was also focused on the synthesis of multivalent iminosugar-calix[8]arene conjugates for the inhibition of glycosidases. The synthesis, characterization and all the biomolecular recognition studies were herein described. [edited by author]
XIV n.s.
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Ferreira, Paula Anastácia. "Modulação de vias de sinalização para indução de morte de células leucêmicas." [s.n.], 2010. http://repositorio.unicamp.br/jspui/handle/REPOSIP/314038.

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Orientador: Carmen Veríssima Ferreira
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia
Made available in DSpace on 2018-08-16T13:47:52Z (GMT). No. of bitstreams: 1 Ferreira_PaulaAnastacia_D.pdf: 2451128 bytes, checksum: a13caa2510a3ac1dca624878d50fafab (MD5) Previous issue date: 2010
Resumo: A eficiência do tratamento da leucemia sob vários aspectos, mesmo com os avanços farmacotecnológicos, ainda permanece como desafio para a medicina. Diante desse fator, maiores informações sobre a base molecular da leucemia e o desenvolvimento de agentes que atuem de forma alvo-específico, apresentem poucos efeitos colaterais e possam impedir o escape das células tumorais à indução de morte são extremamente desejáveis. No presente trabalho, foram abordados 2 aspectos: indução de morte das células leucêmicas por calix[6]areno, flavonóides e diterpeno lactona e contribuição da proteína tirosina fosfatase de baixo massa molecular (LMWPTP) para a resistência de células leucêmicas. As linhagens K562, Lucena-1 (resistente) e HL60 foram utilizadas como modelos no estudo. Calix[6]areno apresentou o mesmo nível de toxicidade para as duas linhagens celulares, mostrando valores de IC50 na faixa de 1-5 µM para K562 e 5-10 µM para Lucena-1. Calix[6]areno induziu vias apoptóticas como demonstrado pelo aumento da razão Bax/Bcl-2 e clivagem de PARP. A proteína tirosina fosfatase PTEN foi ativada pelo Calix[6]areno, fato relacionado com a diminuição da sobrevivência e proliferação. O Calix[6]areno aumentou a expressão de algumas enzimas antioxidantes e não afetou a atividade da proteína associada com o fenótipo de resistência, P-Glicoproteína. As células Lucena-1, que apresentam alta expressão da P-Glicoproteína, também apresentam altos níveis da LMWPTP. Observamos que quando esta enzima foi silenciada, a resposta frente a quimioterápicos das células leucêmicas se tornou mais eficiente. Por outro lado, o aumento da expressão da LMWPTP em células não resistentes provocou insensibilidade das mesmas à vincristina. Nossos dados sugerem que a LMWPTP contribui com o fenótipo resistente através da ativação das quinases Src e BCR-ABL. Outro aspecto investigado neste trabalho foi a indução da diferenciação e apoptose por compostos naturais. Quercetina e a apigenina apresentaram os dois efeitos desejados a um agente quimioterápico, ou seja, expressiva indução da diferenciação das células e também apoptose. Estes efeitos foram dependentes do tempo e modulação do estado redox celular.
Abstract: Leukemia therapy efficiency, under several aspects, even with the progress of pharmacotechnology, remains as a challenge in medicine. According to this, new information about the molecular basis of leukemia and development of agents that act on specific target, present low side-effects and prevent cancer cells escaping from death induction, are extremely desirable. In this work 2 aspects were evaluated: death induction of leukemia cells by calix[6]arene, flavonoids and diterpene lactone and the contribution of the low molecular weight protein tyrosine phosphatase (LMWPTP) for leukemia cells resistance. K562, Lucena-1 and HL60 cells were used as models in this study. Calix[6]arene presented the same level of toxicity on K562 and Lucena-1 cells, displaying an IC50 value ranging 1-5 µM to K562 cells and 5-10 µM to Lucena-1 cells. Calix[6]arene induce apoptosis signaling on both K562 and Lucena cells as molecularly demonstrated by the increased Bax/Bcl-2 ratio and PARP cleavage. Protein tyrosine phosphatase PTEN from leukemia cells became more active in the presence of calix[6]arene, which is related to a decrease of survival and proliferation. Calix[6]arene enhanced the expression of antioxidant enzymes and did not affect P-Glycoprotein activity. Lucena cells, which present high expression of P-Glycoprotein also contain high level of LMWPTP. Interestingly, when this phosphatase was silenced the leukemia cells response appeared to be more efficient towards chemotherapics. On the other hand, overexpression of this enzyme in K562 (non resistant cells) provoked insensitivity to vincristine. Our findings suggest that LMWPTP contributes with the resistance phenotype by supporting the activation status of Src and BCR-ABL kinases. Another aspect examined in this study was the induction of differentiation and apoptosis by natural compounds. Quercetin and apigenin displayed both desired effects of chemotherapics: induction of differentiation and apoptosis. These effects were time- and cellular redox status dependent.
Doutorado
Bioquimica
Doutor em Biologia Funcional e Molecular
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Lavendomme, Roy. "Development of strategies for the highly selective functionalization of calixarenes and study of host–guest properties of calixarene-based molecular boxes." Doctoral thesis, Universite Libre de Bruxelles, 2016. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/241320.

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Ce travail s’inscrit dans le cadre de l’étude de plateformes polyphénoliques et, plus spécifiquement, des calixarènes. Des macrocycles oligomériques tels que les calixarènes, cyclodextrines, cyclotrivératrylènes, pillararènes, etc. sont fortement utilisés dans de nombreuses applications telles que la reconnaissance moléculaire, la détection, la séparation, le greffage sur surface, etc. Le développement de telles applications requiert toutefois modification sélective de ces macrocycles pour leur conférer des propriétés utiles aux applications visées (e.g. affinité envers certaines espèces chimiques, hydrosolubilité, activité photoluminescente). La modification sélective de tels macrocycles oligomériques est cependant loin d’être triviale car, en plus de requérir un contrôle des chimio- régio- et stéréosélectivités classiques, la réaction d’un nombre défini de fonctions identiques est une problématique clé qui doit être résolue. En effet, la fonctionnalisation des oligomères cycliques tels que les calixarènes passe par la formation de produits mono-, di-, tri-fonctionnalisés, et ainsi de suite de manière itérative. Par analogie avec des processus itératifs, nous avons proposé le terme « itérosélectivité » pour décrire la sélectivité qui gouverne le nombre de transformations chimiques répétées. Dans ce contexte, nous avons proposé des stratégies rationnelles et hautement sélectives pour la fonctionnalisation de calixarènes. Ces stratégies exploitent principalement des réactions de carbamatation pour introduire sélectivement des groupements tert-butylaminocarbonyle (Bac) sur les positions phénoliques des calixarènes. Citons notamment la carbamatation « all-but-one » qui permet d’introduire itérosélectivement des groupements Bac sur tous les phénols sauf un pour une grande variété de calixarènes. De plus, l’utilisation de ces groupements Bac comme groupe protecteur nous a permis de synthétiser de nombreux dérivés calixaréniques jusqu’alors inaccessibles suivant les voies de fonctionnalisation connues. Certains de ces composés présentent notamment une chiralité inhérente. En dehors de nos travaux, aucune voie de fonctionnalisation sélective de calixarènes décrite à ce jour n’est aussi générale et efficace. Nous avons également présenté une nouvelle voie d’oxydation de calixarènes en calixquinones. Cette voie présente moins de risques pour la santé et l’environnement que la méthode la plus couramment utilisée à ce jour employant un sel de thallium, métal extrêmement toxique. Les différents aspects synthétiques développés ont permis de synthétiser des boites moléculaires originales dérivées de calixarènes qui ont été étudiées pour leurs propriétés intéressantes dans le cadre de la reconnaissance sélective de petites molécules dont l’eau et le DMSO, ainsi que le piégeage de gaz à l’état solide dont l’hexafluorure de soufre qui est le gaz à effet de serre le plus puissant répertorié à ce jour. Pour finir, la caractérisation poussée d’une bibliothèque de dérivés calixaréniques par spectroscopie de résonance magnétique nucléaire a permis de décrire une méthode générale pour la caractérisation structurale et conformationnelle des calixarènes.
This work concerns the study of polyphenolic platforms, and more particularly, of calixarenes. Oligomeric macrocycles such as calixarenes, cyclodextrins, cyclotriveratrylenes, pillararenes, etc. are widely used as molecular platforms in supramolecular chemistry and in particular for the design of sensors, catalysts, multivalent systems, biomimetic receptors, etc. In general, the synthesis of such supramolecular systems requires the controlled introduction of functional groups on the precursor platform. However, the development of efficient methods for selective modification of macrocyclic oligomers remains extremely challenging. Indeed, in addition to the control of the classical chemo-, regio-, and stereoselectivities, the reaction of a defined number of identical functional groups is a key issue that must be solved. Indeed, the functionalization of oligomeric macrocycles such as calixarenes goes through the formation of mono-, di, tri-functionalized products and so on, iteratively. By analogy with iterative processes, we proposed to name “iteroselectivity” the kind of selectivity that governs the number of repeating chemical transformations. In this context, we proposed rational and highly selective strategies for the functionalization of calixarenes. These strategies are mainly based on the carbamatation of calixarene phenolic functions to introduce tert-butylaminocarbonyl groups (i.e. Bac groups). Our leading example is the “all-but-one” carbamatation which can be used to introduce Bac groups on all but one phenol of a large variety of calixarenes. Moreover, using Bac groups as protecting groups led to the synthesis of numerous calixarene derivatives which were, until now, not accessible through conventional means. It is noteworthy that some of these compounds are inherently chiral. No other selective functionalization method described for calixarenes is as general and efficient than this “all-but-one” carbamatation. Besides, we also described a new oxidation method to synthesize calixquinone starting from calixarenes. This method is less risky and more environment-friendly than the most commonly used method which rely on thallium salts, an extremely toxic metal. Through the various synthetic methods developed herein, we also developed calixarene-based molecular boxes. The host–guest properties of these molecular boxes were studied revealing their ability to include small molecules such as water or DMSO. We also developed a method to sequester gases in the solid state relying on an original concept involving calix[6]arene-based molecular boxes. This was exemplified with the sequestration of SF6, known as the most potent greenhouse gas. At last, the extensive characterization of a library of calixarene derivatives by nuclear magnetic resonance spectroscopy led to the development of a general method for the structural and conformational characterization of calixarenes.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished
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Dougherty, Gary. "Electrochemically switchable calixarene ionophores." Thesis, University of Liverpool, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240418.

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The synthesis of a series of p-tert-butylcalixI4Iarcne based, electrochemically switchable, ionophores (1), (2), (3), (4) and (5) is described. Their electrochemical properties were investigated in the presence of added Croup I metal perchloratcs. Both compounds (1) and (2) displayed no enhancement of binding for metal ions, due to electrostatic interactions, upon electrochemical reduction. This behaviour is explained on steric grounds, as deduced by molecular modelling. Compounds (3), (4) and (5) all display significant enhancements of metal ion binding upon electrochemical reduction. Compounds (4) and (5) appear to display a high selectivity for sodium ions over other Croup I metal ions. Compound (3) displayed the highest binding enhancements yet recorded for both sodium (3.138 x loS) and potassium (1.398 x 103) ions. Compound (6) (from which (3), (4) and (5) were malic) could be converted to m,my other compounds in which the side arms bear difierent functional groups in an eiiort to control selectivity. For example thio esters or thin arnides for silver, ethyl groups tor potassium.
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De, Simone Nicola Alessandro. "Calixarene based catalytic systems." Doctoral thesis, Universita degli studi di Salerno, 2018. http://hdl.handle.net/10556/3187.

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2016 - 2017
Catalysis is the essence of chemistry as it provides useful tools to make and brake chemical bonds. As nature has been a guide to many scientists, it’s no surprise that in the field of catalysis enzymes were a source of inspiration. Harnessing non covalent interactions, as enzymes do, is a fascinating perspective, and, since supramolecular chemistry became more and more involved in catalysis, a new discipline was born, named supramolecular catalysis. Since supramolecular hosts such as calix[n]arenes have been fruitfully employed in the synthesis of catalysts, in these work we report the design, characterization and applications of new calixarene based catalytic systems. In details chiral calix[4]arene amides 1-7 were employed as phase-transfer catalysts thanks to their cation complexing properties, while the calix[4]arene functionalized with a chiral primary amine-thiourea moiety 8 acted as bifunctional catalyst in several asymmetric conjugate addiction reactions. Finally dinuclear Zirconium-calix[8]arene complex 9 proved to be active in the ring opening polymerization of cyclic esters... [edited by author]
XVI n.s.
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Taylor, Stephanie Merac. "Calixarene supported transition metal clusters." Thesis, University of Edinburgh, 2013. http://hdl.handle.net/1842/7770.

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This thesis describes a series of calix[n]arene polynuclear transition metal and lanthanide complexes. Calix[4]arenes possess lower-rim polyphenolic pockets that are ideal for the complexation of various transition metal and lanthanide centres. Surprisingly however, with only a few exceptions, the coordination chemistry of p-tBucalix[ 4]arene (TBC[4]), p-tBu-calix[8]arene (TBC[8]) and p-tBuhomotrioxacalix[ 3]arene (TBOC[3]) with paramagnetic transition metal ions for the purpose of making and studying magnetically interesting molecules is unknown. Chapter two describes the reaction of TBC[4] with manganese salts in the presence of an appropriate base (and in some cases co-ligand) resulting in the formation of a family of calixarene-supported [MnIII 2MnII 2] clusters (1-7) that behave as Single-Molecule Magnets (SMMs). These are: [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)6]·2MeOH (1), [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)4(H2O)2]·4MeOH·2DMF (2), [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)6]·2.8MeOH (3), [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)4(EtOH)(H2O)] (4), [MnIII 2MnII 2(OH)2(TBC[4])2(DMSO)6]·2MeOH·2DMSO (5) , [MnIII 2MnII 2(OH)2(TBC[4])2(DMSO)6] (6) and [MnIII 2MnII 2(OH)2(C[4])2(MeOH)6]·4MeOH (7). Variation in the alkyl groups present at the upper-rim of the cone allows for the expression of a degree of control over the self-assembly of these SMM building blocks, whilst retaining the general magnetic properties. The presence of various different ligands around the periphery of the magnetic core has some effect over the extended self-assembly of these SMMs. Chapter three describes how the combination of complementary cluster ligands; sodium phenylphosphinate and the N,O-chelate 2-(hydroxy-methyl)pyridine (hmpH) with TBC[4] results in the formation of two new calixarene-supported clusters. This being an unusual [MnIIIMnII]2 dimer of dimers [MnIIIMnII(O2P(H)Ph)(DMF)2(MeOH)2]2 (8) and a ferromagnetic [Mn5] cage that displays the characteristic bonding modes of each support [MnIII 3MnII 2(OH)2(TBC[4])2(hmp)2(DMF)6](TBC[4]-H)·xDMF ·xH2O (9). Chapter four details how using oxacalix[3]arenes can tune the nature of the metal binding site, by introduction of ≥ 1 ethereal bridge. This results in Mn(II) rather than Mn(III) bonding in the phenolic pocket, and that these components self-assemble with additional Mn(II) and Mn(III) ions to form a [Mn10] supertetrahedron with an unusual oxidation state distribution, [MnII 6MnIII 4O4(TBOC[3])4(Cl)4(DMF)3]∙3.3H2O ∙ 1.5DMF (10). Chapter five introduces a family of lanthanide complexes formed using TBC[8]. Variation in the experimental conditions employed in the reaction of TBC[8] with lanthanide salts (LnX3) provides access to Ln1, Ln2, Ln4, Ln5, Ln6, Ln7 and Ln8 complexes, [Gd(TBC[8]-2H)Cl(DMSO)4]·MeCN·H2O·(DMSO)2·hex (11), [CeIV 4(TBC[8]-6H)2(μ3- O)2(DMF)4]·(DMF)5·hex·MeCN (12), [TbIII 5(TBC[8]-5H)(μ4-O)(μ3- OH)4Cl(DMSO)8(H2O)3]Cl3·(DMSO)2(hex)2 (13), [CeIV 6(TBC[8]-6H)2(μ4-O)2(μ2-OMe)4(μ2- O)2(DMF)4]·(DMF)6·hex (14), [Dy7(TBC[8]-7H)(TBC[8]-6H)(μ4-O)2(μ3-OH)2(μ2- OH)2(DMF)9]·(DMF)3 (15) and [Gd8(TBC[8]-7H)2(μ4-CO3)2(μ5-CO3)2(μ2-HCO2)2(DMF)8] (16), with all polymetallic clusters containing the common bi-nuclear lanthanide fragment. Closer inspection of the structures of the polymetallic clusters reveals that all but one (Ln8) are in fact based on metal octahedra or the building blocks of octahedra.
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Khan, Latif Ullah. "Nanomateriais ópticos e magnéticos contendo matrizes de Fe3O4 e SiO2 funcionalizadas com calixareno e complexos de terras raras." Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-20072015-151110/.

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Neste trabalho são investigados o designer e a fabricação nanomateriais magnéticos e luminescentes sofisticados bifuncionais baseados em Fe3O4 e complexos de RE3+. Portanto, novos nanomateriais Fe3O4@calix-Eu(TTA) e Fe3O4@calix-Tb(ACAC) emissores vermelho e verde superparamagnéticos foram preparados pelo método one-pot. Neste caso, o ligante calixareno quimicamente modicado como surfactantes para estabilizar as nanopartículas de Fe3O4. O ligante calixareno proporciona uma superfície quimicamente modificada e estabilidade coloidal das nanopartículas magnetitas. Consequentemente, as nanopartículas funcionalizadas (Fe3O4@calix) foram coordenadas aos íons TR3+ por meio da síntese one-pot, usando ligantes TTA e ACAC como sensibilizadores (efeito antena) para produzir nanofósforos altamente luminescentes. Além do mais, nanocompósitos bifuncionais óptico e magnético Fe3O4@SiO2-TTA-Eu(L), L: TTA, TC, AB e AMB bem como Fe3O4@SiO2-TTA-Tb(AB ou AMB) foram também preparados por meio de um protocolo de múltiplas etapas, utilizando as nanopartículas Fe3O4 como precursoras. Elas foram modificas com camadas de sílica, usando o método Stöber modificado e ligados com complexos de TR3+ para produzir nanocompósitos luminescentes e magnéticos. As técnicas de difração de raios X pelo método do pó (XPD), Espalhamento de Raios-X a baixo ângulo (SAXS), microscopia eletrônica de transmissão (TEM) e microscopia de eletrônica de varredura (MEV) foram utilizas para determinar as estruturas, morfologias, distribuições de tamanhos e monodispersividade dos materiais sintetizados. Estes novos nanomateriais bifuncionais Fe3O4@calix-Eu(TTA), Fe3O4@calix-Tb(ACAC), Fe3O4@SiO2-TTA-Eu(L) e Fe3O4@SiO2-TTA-Tb(AB ou AMB) apresentam propriedades fotônicas e superparamagnéticas muito interessantes. As propriedades magnéticas (ZFC/FC e M-H) obtidas nas temperaturas de 2, 5 e 300 K foram investigadas a fim de obter informações sobre o efeito da cristalinidade na magnetização de saturação e das temperaturas de bloqueios. Também foram estudadas a influência dos íons TR3+ sobre a magnetização dos nanomateriais. Apesar da magnetita atuar como um forte supressor de luminescência, as camadas do ligante calixareno modificado e da sílica sobre as nanopartículas de Fe3O4 compensam esta desvantagem. Do mesmo modo foi considerada a discussão sobre a transferência de energia intramolecular do estado tripleto T1 dos ligantes TTA e ACAC para os níveis excitados dos íons Eu3+ e Tb3+ nos nanomateriais Fe3O4@calix-Eu(TTA) e Fe3O4@calix-Tb(ACAC). As eficiências quânticas de emissão (η) dos compostos Fe3O4@calix-Eu(TTA) e Fe3O4@SiO2-TTA-Eu(L) foram calculadas e discutidas, bem como suas características estruturais baseadas nos níveis de energia e parâmetros de intensidades experimentais dos sistemas contendo o íon Eu3+. Estes novos nanomateriais podem atuar como camadas emissores vermelha e verde para dispositivos moleculares conversores de luz e magnéticos (MLCMDs).
The design and fabrication of sophisticated bifunctional luminescent and magnetic nanomaterials based on Fe3O4 and RE3+ complexes are sought for. Accordingly, novel red-green emitting superparamagnetic Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) nanomaterials were prepared through on-pot method. In this regard, the chemically modified calixarene ligand was used as a surfactant to stabilize the Fe3O4 nanoparticles. The calixarene ligand provides colloidal stability and chemically modifiable surface to the magnetite nanoparticles. Thus, this ligand functionalized Fe3O4@calix nanoparticles were further coordinated to the RE3+ ions via one-pot synthesis, using TTA and ACAC ligands as sensitizers (antenna effect) to produce highly luminescent nanophosphors. In addition, bifunctional optical and magnetic Fe3O4@SiO2-TTA-Eu(L), L: TTA, TC, AB and AMB as well as Fe3O4@SiO2-TTA-Tb(AB or AMB) nanocomposites were also synthesized through multistep synthetic protocol, utilizing Fe3O4 nanoparticles as precursors. They were modified with silica shell, using modified Stöber method and further grafted with RE3+ complexes to produce the luminescent and magnetic nanocomposites. The X-ray powder diffraction (XPD), small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques were used to determine the structures, morphologies, size distribution and monodispersity of the synthesized materials. These novel Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) as well as Fe3O4@SiO2-TTA-Eu(L) and Fe3O4@SiO2-TTA-Tb(AB or AMB) magnetic luminescent nanomaterials show interesting superparamagnetic and photonic properties. The magnetic properties (M-H and ZFC/FC measurements) at temperatures of 2, 5 and 300 K were explored in order to investigate the extent of coating and crystalinity effect on the saturation magnetization and blocking temperatures. The influence of the RE3+ ions on the magnetization of the optical and magnetic nanomaterials was also studied. Even though magnetite is a strong luminescence quencher, the coating of the Fe3O4 nanoparticles with synthetically modified calixarene ligand (calix) and silica shell have overcome this difficulty. Moreover, the intramolecular energy transfer from the T1 excited triplet states of TTA and ACAC ligands to the emitting levels of Eu3+ and Tb3+ in the Fe3O4@calix-Eu(TTA) and Fe3O4@calix-Tb(ACAC) nanomaterials are discussed. The emission quantum efficiencies (η) for the Fe3O4@calix-Eu(TTA) and Fe3O4@SiO2-TTA-Eu(L) nanomaterials are also calculated and discussed, as well as the structural features based on the energy levels and experimental intensity parameters, in the case of the Eu3+ ion. These novel nanomaterials may act as the emitting layer for the red and green light for magnetic and light converting molecular devices (MLCMDs).
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Jensen, Svend Borup. "Schiff base calixarenes." Thesis, University of the West of Scotland, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.246345.

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Four different synthetic routes to the sub-target, the p-tert-butylcalix[4lethylamine (6a) from thep-tert-butylcalix[4]arene (1a) have been examined. The best one was a 5-step synthesis, which gave an overall yield of65%. p-tert-Butylcalix[6]ethylamine (6b) and p-tert-butylcalix[8]ethylamine (6c) were synthesised from their respective p-tertbutylcalixarenes by the same route as the p-tert-butylcalix[4]ethylamine (6a). The three different amines (compound (6a), (6b) and (6c)) were used in 14 different Schiff -base type reactions which resulted in six Schiff-base compounds which were fully characterised by NMR, IR, FAB-ms and UV-vis. Insertion studies of the Schiff-base compounds along with template synthesis of the Schiff-base compounds were also attempted. The uptake of solid metal salt by the Schiff-base compounds in solution was examined by UV-vis spectroscopy. One of the Schiff -base compounds synthesised was the ferrocenecarboxaldehyde Schiff-base calix[4]arene (22a). An electrochemical analysis of this compound was undertaken to assess whether if it could be used as a sensor for metal ions. Molecular modelling of the Schiff-base compound and a crystal structure ofp-tert-butylcalix[4]ethylnitrile (8) are also presented in the thesis
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Books on the topic "Calixareni"

1

Gutsche, C. David. Calixarenes. Cambridge: Royal Society of Chemistry, 1992.

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Asfari, Zouhair, Volker Böhmer, Jack Harrowfield, Jacques Vicens, and Mohamed Saadioui, eds. Calixarenes 2001. Dordrecht: Kluwer Academic Publishers, 2002. http://dx.doi.org/10.1007/0-306-47522-7.

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Calixarenes revisited. Cambridge: Royal Society of Chemistry, 1998.

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Z, Asfari, ed. Calixarenes 2001. Dordrecht: Kluwer Academic Publishers, 2001.

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Z, Asfari, ed. Calixarenes 2001. Dordrecht: Kluwer Academic Publishers, 2001.

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Surov, O. V. Calixarene complexes with solvent molecules. New York: Nova Science Publishers, 2010.

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Neri, Placido, Jonathan L. Sessler, and Mei-Xiang Wang, eds. Calixarenes and Beyond. Cham: Springer International Publishing, 2016. http://dx.doi.org/10.1007/978-3-319-31867-7.

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Lumetta, Gregg J., Robin D. Rogers, and Aravamudan S. Gopalan, eds. Calixarenes for Separations. Washington, DC: American Chemical Society, 2000. http://dx.doi.org/10.1021/bk-2000-0757.

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Luigi, Mandolini, and Ungaro Rocco, eds. Calixarenes in action. London: Imperial College Press, 2000.

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Royal Society of Chemistry (Great Britain), ed. Calixarenes: An introduction. 2nd ed. Cambridge: RSC Pub., 2008.

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Book chapters on the topic "Calixareni"

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Kumar, Rajesh, Yujin Jung, and Jong Seung Kim. "Fluorescent Calixarene Hosts." In Calixarenes and Beyond, 743–60. Cham: Springer International Publishing, 2016. http://dx.doi.org/10.1007/978-3-319-31867-7_28.

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Gutsche, C. David. "The Calixarenes." In Host Guest Complex Chemistry / Macrocycles, 375–421. Berlin, Heidelberg: Springer Berlin Heidelberg, 1985. http://dx.doi.org/10.1007/978-3-642-70108-5_9.

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Talotta, Carmen, Carmine Gaeta, Annunziata Soriente, Margherita De Rosa, Corrada Geraci, and Placido Neri. "Large Calixarenes." In Calixarenes and Beyond, 141–73. Cham: Springer International Publishing, 2016. http://dx.doi.org/10.1007/978-3-319-31867-7_7.

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Marson, Angelica, Piet W. N. M. van Leeuwen, and Paul C. J. Kamer. "Calixarene-Based Phosphorus Ligands." In Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis, 405–26. Chichester, UK: John Wiley & Sons, Ltd, 2012. http://dx.doi.org/10.1002/9781118299715.ch14.

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Diamond, Dermot. "Calixarene-Based Sensing Agents." In Calixarenes 50th Anniversary: Commemorative Issue, 149–66. Dordrecht: Springer Netherlands, 1994. http://dx.doi.org/10.1007/978-94-011-0267-4_10.

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Gutsche, C. David, Iftikhar Alam, Muzaffar Iqbal, Thomas Mangiafico, Kye Chun Nam, Janet Rogers, and Keat Aun See. "Topics in Calixarene Chemistry." In United States-Japan Seminar on Host-Guest Chemistry, 61–72. Dordrecht: Springer Netherlands, 1989. http://dx.doi.org/10.1007/978-94-009-0969-4_8.

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Davis, Frank, Seamus P. J. Higson, Osvaldo N. Oliveira, and Flavio M. Shimizu. "Calixarene-Based Gas Sensors." In Materials Horizons: From Nature to Nanomaterials, 433–62. Singapore: Springer Singapore, 2020. http://dx.doi.org/10.1007/978-981-15-4810-9_17.

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Ohnishi, Yoshitake, Naoko Wamme, and Jun-ichi Fujita. "Calixarene Resists for Nanolithography." In ACS Symposium Series, 249–61. Washington, DC: American Chemical Society, 1998. http://dx.doi.org/10.1021/bk-1998-0706.ch019.

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Cherenok, Sergey, and Vitaly Kalchenko. "Phosphorus-Containing Calixarenes." In Topics in Heterocyclic Chemistry, 229–73. Berlin, Heidelberg: Springer Berlin Heidelberg, 2009. http://dx.doi.org/10.1007/7081_2008_12.

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Böhmer, Volker, Dagmar Kraft, and Moniralsadat Tabatabai. "Inherently Chiral Calixarenes." In Calixarenes 50th Anniversary: Commemorative Issue, 17–39. Dordrecht: Springer Netherlands, 1994. http://dx.doi.org/10.1007/978-94-011-0267-4_2.

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Conference papers on the topic "Calixareni"

1

Kim, Taeho, Kyoji Komatsu, Okihiro Sugihara, Toshikuni Kaino, Hiroto Kudo, and Tadatomi Nishikubo. "Optical properties of calixarene polymers." In Integrated Optoelectronic Devices 2008, edited by Robert L. Nelson, Francois Kajzar, and Toshikuni Kaino. SPIE, 2008. http://dx.doi.org/10.1117/12.763211.

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Serban, B., M. Bercu, S. Voicu, M. Mihaila, Gh Nechifor, and C. Cobianu. "Calixarene-Doped Polyaniline for Applications in Sensing." In 2006 International Semiconductor Conference. IEEE, 2006. http://dx.doi.org/10.1109/smicnd.2006.283991.

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Yamagishi, Yoko, Toshikuni Kaino, Atsushi Kameyama, and Tadatomi Nishikubo. "Polymers of photoreactive calixarene derivatives for optical applications." In Integrated Optoelectronics Devices, edited by James G. Grote and Toshikuni Kaino. SPIE, 2003. http://dx.doi.org/10.1117/12.475422.

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Ali, S. S., N. Sen, F. Durmaz, F. Ozcan, S. Ertul, and F. Ozcan. "The use of calixarene nanofibers as an HPLC column filler." In 2017 IEEE 7th International Conference "Nanomaterials: Application & Properties" (NAP). IEEE, 2017. http://dx.doi.org/10.1109/nap.2017.8190220.

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Ozcan, F., F. Ozcan, and S. Ertul. "Use of polymer-free calixarene nanofibers in heavy metal extractions." In 2017 IEEE 7th International Conference "Nanomaterials: Application & Properties" (NAP). IEEE, 2017. http://dx.doi.org/10.1109/nap.2017.8190225.

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Arpaci, P. Uyar, P. Uyar Arpaci, F. Ozcan, M. Agac, F. Ozcan, and S. Ertul. "Calixarene nanofiber design for human colon cancer 3D-cell culture." In 2017 IEEE 7th International Conference "Nanomaterials: Application & Properties" (NAP). IEEE, 2017. http://dx.doi.org/10.1109/nap.2017.8190336.

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Echigo, Masatoshi, Hiromi Hayashi, Hiroaki Oizumi, Kazuyuki Matsumaro, and Toshiro Itani. "Development of molecular resists based on Phenyl[4]calixarene derivatives." In SPIE Advanced Lithography, edited by Robert D. Allen. SPIE, 2010. http://dx.doi.org/10.1117/12.846475.

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Takasuka, Masaaki, Yu Okada, Hiromi Hayashi, and Masatoshi Echigo. "Development of molecular resists based on Phenyl[4]calixarene for EBL." In SPIE Advanced Lithography, edited by Robert D. Allen and Mark H. Somervell. SPIE, 2011. http://dx.doi.org/10.1117/12.879122.

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Simões, Juliana B., Ângelo de Fátima, Luiz Claudio A. Barbosa, and Sergio A. Fernandes. "Calixarene Catalyze Cascade Povarov−Hydrogen-Transfer Reaction in Synthesis of Quinolines." In 15th Brazilian Meeting on Organic Synthesis. São Paulo: Editora Edgard Blücher, 2013. http://dx.doi.org/10.5151/chempro-15bmos-bmos2013_2013915211651.

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Kaestner, M., and I. W. Rangelow. "Multi-step Scanning Probe Lithography (SPL) on calixarene with overlay alignment." In SPIE Advanced Lithography, edited by William M. Tong. SPIE, 2012. http://dx.doi.org/10.1117/12.916263.

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Reports on the topic "Calixareni"

1

Peterson, R. A. Radiation Stability of Calixarene Based Solvent System. Office of Scientific and Technical Information (OSTI), January 1999. http://dx.doi.org/10.2172/4851.

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Jeffery Davis. Calix 2007:9th International Conference on Calixarene Chemistry. Office of Scientific and Technical Information (OSTI), September 2011. http://dx.doi.org/10.2172/1024123.

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Bartsch, Richard A. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations. Office of Scientific and Technical Information (OSTI), June 2012. http://dx.doi.org/10.2172/1041406.

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Wai, Chien M., and Clem Yonker. Solution Effects on Cesium Complexation with Calixarene - Crown Ethers from Liquid to Supercritical Fluids. Office of Scientific and Technical Information (OSTI), June 1999. http://dx.doi.org/10.2172/833192.

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Bonnesen, P. V., L. H. Delmau, T. J. Haverlock, and B. A. Moyer. Alkaline-Side Extraction of Cesium from Savannah River Tank Waste Using a Calixarene-Crown Ether Extractant. Office of Scientific and Technical Information (OSTI), December 1998. http://dx.doi.org/10.2172/3296.

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