Synthesis and Characterization of Supramolecular Cucurbituril, Molybdenum 2,2'-Bipyridyl Complex
Total Page:16
File Type:pdf, Size:1020Kb
Load more
Recommended publications
-
Supramolecular Chemistry
Supramolecular Chemistry Rohit Kanagal Introduction Supramolecular Chemistry is one of the most rapidly growing areas of chemistry. This branch of chemistry emphasises on ‘chemistry beyond the molecule’ and ‘chemistry of molecular assemblies and the intermolecular bond’. Supramolecular Chemistry lends the idea of how molecules interact with one another. It aims to understand the structural and functional properties of systems that contain more than one molecular assembly. Phenomena such as molecular self-assembly, protein folding, molecular recognition, host-guest chemistry, mechanically-interlocked molecular architectures, and dynamic covalent chemistry are all integral parts of Supramolecular chemistry. These phenomena are controlled by certain non- covalent interactions between molecules such as ion-dipole, dipole-dipole interactions, van der Waals forces, hydrogen bonding, metal coordination, hydrophobic forces, pi-pi interactions, and various electrostatic effects. Over the last few decades, the ideas and studies of supramolecular chemistry have entered multiple fields such as chemical science, biological science, physical science, and material science. (Hasenknopf) An example of a supramolecular assembly Superamolecule A supramolecule or supramolecular assembly is a well-defined system of molecules that are held together with non-covalent intermolecular forces to form a bigger unit having its own organization, stability and tendency to associate or isolate. These are formed through the interactions between a molecule having convergent binding sites (such as hydrogen bond donor atoms and a large cavity) and another molecule having divergent binding sites (such as hydrogen bond acceptor atoms). The molecule having convergent binding sites is called host or receptor molecule while the molecule having divergent binding sites is called a guest or analyte molecule. -
Cucurbituril Assembly and Uses Thereof Cucurbiturilanordnung Und Seine Verwendungen Ensemble De Cucurbituril Et Ses Utilisations
(19) TZZ_Z__T (11) EP 1 668 015 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: C07D 487/22 (2006.01) C07D 519/00 (2006.01) of the grant of the patent: G01N 33/00 (2006.01) C08G 73/00 (2006.01) 21.08.2013 Bulletin 2013/34 (86) International application number: (21) Application number: 04770467.1 PCT/IL2004/000796 (22) Date of filing: 05.09.2004 (87) International publication number: WO 2005/023816 (17.03.2005 Gazette 2005/11) (54) CUCURBITURIL ASSEMBLY AND USES THEREOF CUCURBITURILANORDNUNG UND SEINE VERWENDUNGEN ENSEMBLE DE CUCURBITURIL ET SES UTILISATIONS (84) Designated Contracting States: (56) References cited: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR WO-A-00/68232 WO-A-03/004500 HU IE IT LI LU MC NL PL PT RO SE SI SK TR WO-A-03/055888 WO-A-03/055888 (30) Priority: 04.09.2003 US 499735 P • JON, SANG YONG ET AL: "Facile Synthesis of 13.01.2004 US 535829 P Cucurbit[n]uril Derivatives via Direct Functionalization: Expanding Utilization of (43) Date of publication of application: Cucurbit[n]uril" JOURNAL OF THE AMERICAN 14.06.2006 Bulletin 2006/24 CHEMICAL SOCIETY , 125(34), 10186-10187 CODEN: JACSAT; ISSN: 0002-7863, 8 June 2003 (73) Proprietor: TECHNION RESEARCH AND (2003-06-08), XP002316247 DEVELOPMENT FOUNDATION, LTD. • JON, SANG YONG ET AL: "Facile Synthesis of Haifa 32000 (IL) Cucurbit[n]uril Derivatives via Direct Functionalization: Expanding Utilization of (72) Inventor: KEINAN, Ehud Cucurbit[n]uril" JOURNAL OF THE AMERICAN 23 840 Timrat (IL) CHEMICAL SOCIETY , 125(34), 10186-10187 CODEN: JACSAT; ISSN: 0002-7863, 2003, (74) Representative: Dennemeyer & Associates S.A. -
Study on the Complexation of Macromolecule Cucurbituril with Metals and Acetamide
International Journal of Chemistry and Applications. ISSN 0974-3111 Volume 4, Number 3 (2012), pp. 219-226 © International Research Publication House http://www.irphouse.com Study on the Complexation of Macromolecule Cucurbituril with Metals and Acetamide T. Jaba Priya, Jasmine Rebecca and R. Wilfred Sugumar Department of Chemistry, Madras Christian College (Autonomous), Tambaram, Chennai-600059, India. E-mail: [email protected]; [email protected] Abstract Cucurbituril is a remarkably robust macro cyclic host molecule that has a rigid cavity capable of binding small guests under a variety of conditions. In the present study, macromolecule cucurbit[6]uril (CB[6]) and its complexes with metal ions lithium, cerium were synthesized. Mixed ligand complexes containing CB[6] and acetamide with central metal ions such as lithium were also prepared. The UV – visible spectrum of the complex of lithium with CB[6] shows a peak at 225nm. The mixed ligand complex of lithium with CB[6] and acetamide shows a sharp peak at 220nm which indicates the presence of amide functional group. The peak at 274nm indicates the presence of – NO2 group. UV-visible spectrum of the complex of cerium with CB[6] shows a peak at 213.17nm, which indicates the presence of – CONH2 group. The IR spectrum of Cucurbituril shows the following peaks 3436.96 cm-1 , 2931.16 to 2372.15 cm-1 and a sharp peak at 1726.39 cm-1 these frequencies indicate the presence of CO - N ,C-H and C=O stretching respectively. The IR spectra of the complex of Lithium with CB[6] and Cerium with CB[6] show significant variations especially around 3000 cm-1 and between 1700 to 1200 cm-1 indicating prevalence of enhanced hydrogen bonding. -
From Supramolecular Chemistry to Nanotechnology: Assembly of 3D Nanostructures*
Pure Appl. Chem.,Vol. 81, No. 12, pp. 2225–2233, 2009. doi:10.1351/PAC-CON-09-07-04 © 2009 IUPAC, Publication date (Web): 3 November 2009 From supramolecular chemistry to nanotechnology: Assembly of 3D nanostructures* Xing Yi Ling‡, David N. Reinhoudt, and Jurriaan Huskens Molecular Nanofabrication Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede, The Netherlands Abstract: Fabricating well-defined and stable nanoparticle crystals in a controlled fashion re- ceives growing attention in nanotechnology. The order and packing symmetry within a nanoparticle crystal is of utmost importance for the development of materials with unique op- tical and electronic properties. To generate stable and ordered 3D nanoparticle structures, nanotechnology is combined with supramolecular chemistry to control the self-assembly of 2D and 3D receptor-functionalized nanoparticles. This review focuses on the use of molecu- lar recognition chemistry to establish stable, ordered, and functional nanoparticle structures. The host–guest complexation of β-cyclodextrin (CD) and its guest molecules (e.g., adaman- tane and ferrocene) are applied to assist the nanoparticle assembly. Direct adsorption of supramolecular guest- and host-functionalized nanoparticles onto (patterned) CD self-as- sembled monolayers (SAMs) occurs via multivalent host–guest interactions and layer-by- layer (LbL) assembly. The reversibility and fine-tuning of the nanoparticle-surface binding strength in this supramolecular assembly scheme are the control parameters in the process. Furthermore, the supramolecular nanoparticle assembly has been integrated with top- down nanofabrication schemes to generate stable and ordered 3D nanoparticle structures, with con- trolled geometries and sizes, on surfaces, other interfaces, and as free-standing structures. Keywords: nanoparticles; nanoparticle arrays; self-assembly; self-assembled monolayer; supramolecular chemistry. -
Cucurbit[7]Uril Host-Viologen Guest Complexes
CUCURBIT[7]URIL HOST-VIOLOGEN GUEST COMPLEXES: ELECTROCHROMIC AND PHOTOCHEMICAL PROPERTIES by MARINA FREITAG A dissertation submitted to the Graduate School – Newark Rutgers, The State University of New Jersey in partial fulfillment of requirements for the degree of Doctor of Philosophy Graduate Program in Chemistry Written under the direction of Professor Elena Galoppini and approved by ________________________ ________________________ ________________________ ________________________ Newark, New Jersey October, 2011 ABSTRACT OF THE DISSERTATION Abstract Cucurbituril[7] Host - Viologen Guest Complexes: Electrochromic and Photochemical Properties By MARINA FREITAG Dissertation Director: Professor Elena Galoppini In this thesis, we demonstrated that a molecular host, cucurbit[7]uril, provides an alternative method of adsorbing molecules on semiconductors and shields the guest from the hetereogenous interface. These novel hybrid systems exhibited photophysical and electrochemical properties that differ from the properties of layers obtained by directly attaching the chromophore to the semiconductor through binding groups. This thesis describes the host-guest chemistry between cucurbit[7]uril (CB[7]) and various series of viologen guests. Methylviologen (1,1'-dimethyl-4,4'-bipyridinium dichloride, MV2+), 1-methyl-1'-p-tolyl-4,4'-bipyridinium dichloride (MTV2+), and 1,1'-di- p-tolyl-(4,4'-bipyridine)-1,1'-diium dichloride (DTV2+) were encapsulated in the macrocyclic host cucurbit[7]uril, CB[7]. The complexes MV2+@CB[7] and MTV2+@CB[7] were physisorbed to the surface of 1 TiO2 nanoparticle films. The complexation into CB[7] was monitored by H NMR. TiO2 films functionalized with the complexes were studied by FT-IR-ATR and UV-Vis ii absorption. The electrochemical and spectroelectrochemical properties of MV2+@CB[7] and MTV2+@CB[7] were studied in solution and in electrochromic windows (ECDs), where the complexes were bound to TiO2 films cast on FTO. -
Supramolecular Assembly of DNA-Phenanthrene Conjugates Into Vesicles with Light-Harvesting Properties Caroline D
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Bern Open Repository and Information System (BORIS) Supramolecular Assembly of DNA-Phenanthrene Conjugates into Vesicles with Light-Harvesting Properties Caroline D. Bösch, Jovana Jevric, Nutcha Bürki, Markus Probst, Simon M. Langenegger, and Robert Häner* Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland Supporting Information Placeholder ABSTRACT : Vesicle-shaped supramolecular polymers are formed by self-assembly of a DNA duplex containing phenanthrene overhangs at both ends. In presence of spermine, the phenanthrene overhangs act as sticky ends linking the DNA duplexes together. In aqueous solution, the assembly leads to vesicles in the range of 50 – 200 nm, as shown by electron microscopy and dynamic light scattering. Fluorescence measurements show that the assembled phenanthrene units act as light-harvesting antennae and transfer absorbed energy to an acceptor, such as pyrene or Cy3, which can either be directly added to the polymer or attached via a complementary DNA strand. The presence of DNA in the nanostructures allows the con- struction of light-harvesting vesicles that are amenable to functionalization with different chemical groups. DNA is used to create one-, two-, or three-dimensional assemblies phodiester groups. Hybridization leads to the formation of DNA du- due to its unique molecular recognition properties which opens oppor- plex 1*2 containing three phenanthrenes at each end. Oligonucleotides tunities to precisely organize functional groups within space.1-9 Func- 3 and 4 serve as unmodified control sequences. tional supramolecular assemblies of DNA object have a potential for biomedical, biomimetic and electronic applications.10-18 DNA Table 1. -
Formation of Functionalized Supramolecular Metallo-Organic Oligomers with Cucurbituril a Thesis Presented to the Faculty Of
Formation of Functionalized Supramolecular Metallo-organic Oligomers with Cucurbituril A thesis presented to the faculty of the College of Arts and Sciences of Ohio University In partial fulfillment of the requirements for the degree Master of Science Ian M. Del Valle December 2015 © 2015 Ian M. Del Valle. All Rights Reserved. 2 This thesis titled Formation of Functionalized Supramolecular Metallo-organic Oligomers with Cucurbituril by IAN M. DEL VALLE has been approved for the Department of Chemistry and Biochemistry and the College of Arts and Sciences by Eric Masson Associate Professor of Chemistry and Biochemistry Robert Frank Dean, College of Arts and Sciences 3 Abstract DEL VALLE, IAN M., M.S., December 2015, Chemistry Formation of Functionalized Supramolecular Metallo-organic Oligomers with Cucurbituril Director of Thesis: Eric Masson The goal of this project is to functionalize supramolecular oligomer chains with amino acids and nucleic acids in order to observe interactions with proteins and DNA. Chiral substituents are also desirable to induce helicality in the oligomer much like DNA. We explored different pathways to afford these oligomers. The first project involves forming metallo-organic oligomers using non-covalent bonds and then functionalizing them. We synthesize ligands and use alkyne-azide cycloadditions to functionalize them. These ligands can then be coordinated to various transition metals. The aromatic regions of these oligomers can then self-assemble into tube-like chains with the participation of cucurbit[8]uril. Second, we explore an alternate pathway to form functionalized chains. This second set of chains coupled amines with carboxylic acid groups attached to the ligands. This project hopes to avoid solubility problems experienced with the first project. -
Supramolecular Assemblies of Cucurbiturils with Photoactive, Π
Review 1 DOI: 10.1002/ijch.201700114 2 3 4 Supramolecular Assemblies of Cucurbiturils with 5 Photoactive, -conjugated Chromophores 6 p 7 [a] [a, b] 8 Ahmet Koc and Do¨nu¨s Tuncel* 9 10 11 Abstract: Supramolecular assemblies of cucurbituril (CBn) polymers. How supramolecular complexes of p-conjugated 12 homologues with p-conjugated chromophores will be over- chromophores including porphyrin derivatives, conjugated 13 viewed. Special emphasis will be given to the effect of CBn oligomers and polymers with CBn could be utilized in the 14 on the optical properties of conjugated oligomers and theranostic and photonic applications will also be discussed. 15 Keywords: Cucurbiturils · supramolecular assemblies · p-conjugated chromophores · porphyrins · conjugated polymers 16 17 18 1. Introduction 10 glycoluril units, respectively.[9] The new members of CB 19 family that shows remarkable differences in their cavity sizes, 20 In this review, we are going to discuss the supramolecular guest binding affinities, size selectivity and water-solubility 21 assemblies of cucurbituril (CBn) homologues with photo- attracted huge interest by the supramolecular chemists.[10] 22 active, conjugated chromophores. Photoactive, p-conjugated Among them, CB7, with good water solubility, appropriate 23 chromophores have many important applications in the areas guest size selectivity and binding affinity, have been the most 24 of sensing, catalysis, lasers, imaging, theranostics and pho- in demand up to now. 25 tonics.[1–6] However, there are some drawbacks that should be Compared to other well-known macrocyclic host mole- 26 overcome in order to utilize them in a wider context including cules such as cyclodextrins, calixarenes and crown ethers, CBs 27 stability (chemical, thermal, photo), solubility, poor optical not only exhibit the similar low-toxic nature, but they also 28 performance (low quantum yields, low lifetime) due to offer much higher chemical stability and far better guest 29 aggregation. -
Host-Guest Compounds Oligomeric Cucurbituril Complexes: from Peculiar Assemblies to Emerging Applications Xue Yang, Ruibing Wang, Anthony Kermagoret, David Bardelang
Host-Guest Compounds Oligomeric Cucurbituril Complexes: from Peculiar Assemblies to Emerging Applications Xue Yang, Ruibing Wang, Anthony Kermagoret, David Bardelang To cite this version: Xue Yang, Ruibing Wang, Anthony Kermagoret, David Bardelang. Host-Guest Compounds Oligomeric Cucurbituril Complexes: from Peculiar Assemblies to Emerging Applications. Ange- wandte Chemie International Edition, Wiley-VCH Verlag, 2020, pp.2-15. 10.1002/anie.202004622. hal-02972332 HAL Id: hal-02972332 https://hal-amu.archives-ouvertes.fr/hal-02972332 Submitted on 23 Oct 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Oligomeric Cucurbituril Complexes: from Peculiar Assemblies to Emerging Applications. Xue Yang,[a] Ruibing Wang,*[b] Anthony Kermagoret,*[a] and David Bardelang*[a] Abstract: Proteins are an endless source of inspiration. By carefully Xue Yang earned her Master’s degree from tuning the amino-acid sequence of proteins, nature made them evolve the University of Macau (China) in 2017. She from primary to quaternary structures, a property specific to protein is currently pursuing her PhD on the oligomers and often crucial to accomplish their function. On the other supramolecular chemistry of cucurbiturils at Aix- hand, the synthetic macrocycles cucurbiturils (CBs) have shown Marseille University. -
Nanoparticle As Supramolecular Platform for Delivery and Bioorthogonal Catalysis
University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations Dissertations and Theses November 2017 NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS Gulen Yesilbag Tonga University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_2 Part of the Materials Chemistry Commons, Medicinal-Pharmaceutical Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Yesilbag Tonga, Gulen, "NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS" (2017). Doctoral Dissertations. 1141. https://doi.org/10.7275/10521708.0 https://scholarworks.umass.edu/dissertations_2/1141 This Open Access Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS A Dissertation Presented by GULEN YESILBAG TONGA Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY September 2017 Department of Chemistry i © Copyright by Gulen Yesilbag Tonga 2017 All Rights Reserved ii NANOPARTICLE AS SUPRAMOLECULAR PLATFORM FOR DELIVERY AND BIOORTHOGONAL CATALYSIS A Dissertation Presented by GULEN YESILBAG -
Host-Guest Chemistry Between Cucurbit[7]Uril and Neutral and Cationic Guests
HOST-GUEST CHEMISTRY BETWEEN CUCURBIT[7]URIL AND NEUTRAL AND CATIONIC GUESTS by Ian William Wyman A thesis submitted to the Department of Chemistry In conformity with the requirements for the degree of Doctor of Philosophy. Queen’s University Kingston, Ontario, Canada (January, 2010) Copyright © Ian William Wyman, 2010 Dedicated in memory of my Grandfather, Norman Brannen, 1917-2009. ii Abstract This thesis describes the host-guest chemistry between cucurbit[7]uril (CB[7]) and various series of guests, including neutral polar organic solvents, bis(pyridinium)alkane dications, local anaesthetics, acetylcholine analogues, as well as succinylcholine and decamethonium analogues, in aqueous solution. A focus of this thesis is the effects of varying the chemical structures within different series of guests upon the nature of the host-guest chemistry, such as the relative position and orientation of the guest relative to the CB[7] cavity, and the strengths of the binding affinities. The binding affinities of polar organic solvents with CB[7] depend upon the hydrophobic effect and dipole-quadrupole interactions. The polar guests align themselves so that their dipole moment is perpendicular to the quadrupole moment of CB[7]. The binding strengths of acetone and acetophenone to CB[7] decrease in the presence of alkali metals. Discrete 1:1 and 2:1 host-guest complexes are formed between CB[7] and a series of α,ω -bis(pyridinium)alkane guests. In most cases the CB[7] initially occupies the aliphatic linker when the 1:1 complex is formed and migrates to the terminal regions as the second CB[7] is added. -
Cucurbiturils As Molecular Containers: the Mechanism Of
Cucurbiturils as Molecular Containers: The Mechanism of Complexation of Small Guests, the Effects of the Inclusion on their Photophysical Properties, and Potential Applications A thesis presented by César Augusto Márquez González to the School of Engineering and Science in fulfillment of the requirements for the degree of Doctor of Chemistry in the graduate program of Nanomolecular Sciences International University Bremen Bremen, 2003 Approved by the School of Engineering and Science by request of Prof. Dr. Hans-Jürgen Buschmann, Prof. Dr. Ulrich Kortz, Prof. Dr. Werner M. Nau, Prof. Dr. Thomas Nugent, and Prof. Dr. Ryan M. Richards Bremen, 17 December, 2003 Prof. Dr. Gerhard Haerendel Dean 2 Contents 1. Introduction 11 1.1. Supramolecular Chemistry 11 1.2. Cucurbiturils as Molecular Containers 16 1.3. Scope of Dissertation 22 2. Complexation Mechanism 26 2.1. Two Mechanisms of Slow Host-Guest Complexation between Cucurbit[6]uril and Cyclohexylmethylamine: pH-Responsive Supramolecular Kinetics 26 2.2. The Mechanism of Host-Guest Complexation by Cucurbit[6]uril 29 3. Fluorescent Host-Guest Systems 31 3.1. 2,3-Diazabicyclo[2.2.2]oct-2-ene in Supramolecular Chemistry 31 3.2. Polarizabilities Inside Molecular Containers 34 4. Potential Applications 37 4.1. Selective Fluorescence Quenching of 2,3-Diazabicyclo[2.2.2]oct-2-ene by Nucleotides 37 4.2. Cucurbiturils: Molecular Nanocapsules for Time-Resolved Fluorescence- based Assays 40 3 5. Ongoing Projects 44 5.1. The Cucurbit[7]uril•2,3-Diazabicyclo[2.2.2]oct-2-ene Host-Guest System. Influence of Associated Metal Ions on its Photophysical Properties 45 5.2.