ISMSC 2007 - Università degli Studi di Pavia

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New Amido-Based Multicyclic Hosts for Anions Sung Ok Kang, Victor W. Day, Kristin Bowman-James Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence KS 66045. Anions play very important roles in biochemical systems as well as in the environment. Since anion coordination chemistry has become an intense research area, hosts for anions with elegant architectures have developed rapidly over several decades.[1] Because anions have several different distinguishing aspects compared to cations, such as larger size, high solvation energy, various shapes (spherical, linear, trigonal planar, and tetrahedral), and sometimes pH dependence, designing anion receptors is even more challenging.[2] In order to achieve the goal of designing highly selective hosts for anions, both the choice of functional groups as a hydrogen bonding sites and their arrangements in host frameworks will be crucial. Even though multicycles have tended to bind anions strongly due to their increased dimensionality as well as their increased number of binding sites, only a few amido-based multicyclic hosts for anions have been published to date.[3] These reported hosts include a bicycle and tricycle based on the prototype 1 reported by our group.[4,5] Recently we modified the design strategy to obtain two new classes of bicyclic and tricyclic hosts, 2 and 3, the frameworks of which are also based on monocycle 1. H 3 C O N H N H N O O X N H A N CH3 H N X O - A- A- A- 1 X=CHorN Monocycle 2 Bicycles 3 Tricycles PSA 83 Each of the new multicyclic hosts displays its own unique structural and chemical binding properties in terms of anion binding. NMR and crystallographic studies of the new anion hosts will be described. [1] A. Bianchi, K. Bowman-James, E. García-España (Eds.), Supramolecular Chemistry of Anions, WILEY-VCH, New York, 1997. [2] P. D. Beer, P. A. Gale, Angew. Chem. Int. Ed. 2001, 40, 486-516. [3] S. O. Kang, M. A. Hossain, K. Bowman-James, Coord. Chem. Rev. 2006, 250, 3038-3052. [4] S. O. Kang, J. M. Llinares, D. Powell, D. VanderVelde, K. Bowman-James, J. Am. Chem. Soc. 2003, 125, 10152-10153. [5] S. O. Kang, D. Powell, V. W. Day, K. Bowman-James, Angew. Chem. Int. Ed. 2006, 45, 1921-1925. Prodigiosin Analogues and Related Polypyrrolic Anion Receptors; Thermodynamic and Kinetic Studies Jonathan L. Sessler † , Elizabeth T. Karnas † , Dustin E. Gross † , Leah R. Eller † , Won-Seob Cho † , Sergios Nicolaou † , Apolonio Aguilar † , Jeong Tae Lee † , Vincent M. Lynch † , Darren J. Magda, ‡ Kenneth A. Johnson † † Univeristy of Texas at Austin, 1 University Station A5300, Austin, TX 78712, USA ‡ Pharmacyclics, Inc. 995 East Arques Avenue Sunnyvale, California 94085, USA The prodigiosin alkaloid is a natural product consisting of a pyrrolylpyrromethene core and has been shown to have a broad range of biological activity 1 , including pH modulation, cell cycle inhibition, DNA cleavage, 2 and mitogen-activated protein kinase inhibition. 3 We are most interested in the role of prodigiosin as a pH modulator, which it accomplishes by H + /Cl - symport activity. 4,5 Our group has sought to provide chemical evidence for this binding/transport event by synthesizing a basic series consisting of a ‘natural’ prodigiosin 1, and simple prodigiosin analogues. 6 Binding constants were determined through isothermal titration calorimetry (ITC), transport efficiency was determined by efflux across a phospholipid membrane as a function of time and anticancer activity was tested in vitro with A549 human lung and PC3 human prostate cancer cells. These studies 6 revealed a correlation between transport efficiency and anticancer activity, while the binding constants (Ka), a thermodynamic parameter, was not found to be a predictor of biological activity. This leads us to suggest that kinetic effects, associated with anion complexation or decomplexation, play a dominant role. Ongoing detailed analyses, which will be the subject of this presentation, have served to underscore the fact that prodigiosin analogues 2, as well as several other oligopyrrolic systems, are characterized by complex thermodynamic and kinetic anion binding interactions that are a function of not only the structure itself, but also the counter-ion and solvent as well. N H X- N H H + OMe N 1 2 [1] Fürstner, A. Angew. Chem. Int. Ed. 2003, 42, 3582-3603. [2] Melvin, M.; Tomlinson, J.; Saluta, G.; Kucera, G.; Lindquist, N.; Manderviller, R. J. Am. Chem. Soc. 2000, 122, 6333-6334. [3] Tomas, R.; Montaner, B.; Llagostera, E.; Soto-Cerrato, V. Biochem. Pharmacol. 2003, 66, 1447-1452. [4] Sato, T.; Konno, H.; Tanaka, Y.; Kataoka, T.; Nagai, K.; Wasserman, H.; Okhuma, S. J. Bio. Chem. 1998, 273, 21455-21462. [5] Seganish, J.; Davis, J. Chem. Commun., 2005, 5781-5783 [6] Sessler, J.; Eller, L.; Cho, W.S.; Nicolau, S.; Aguilar, A.; Lee, J.T.; Lynch, V.; Magda, D. Angew. Chem. Int. Ed. 2005, 44, 5989-5992. N H N H H N + X- PSA 84
Binding of perrhenate and pertechnetate anions by bipyrrole based receptors Evgeny A. Katayev a , Patricia Melfi b , Nikolay V. Boev a , Grigory V. Kolesnikov a , Ivan G. Tananaev c and Jonathan L. Sessler b a A. N. Nesmeyanov Institute for Organoelement Compounds, Russian Academy of Sciences, Vavilova st. 28, 119991, Moscow, Russian Federation b Department of Chemistry & Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165 USA c Frumkin Institute of Physical Chemistry and Electrochemistry Russian Academy of Science, Leninskiy pr. 31, 119991, Moscow, Russian Federation Development of highly efficient systems capable of binding specific anions selectively is recognized as being a key predicate to solving a number of fundamental problems, including anion sensing, extraction, and separation. A number oxoanions are also recognized as toxic or undesirable in certain situations. Sulfate can interfere with the vitrification processes that have been proposed for long-term containment and storage of low activity wastes (LAW). Pertechnetate anion is the most common form of the long-lived isotope 99 (t1/2 = 2.13 x 10 5 years) that is formed from 235 U or 239 Pu. Our previous investigations showed the ability of oligopyrrolic macrocycles to bind tetrahedral oxoanions efficiently [1]. The aim of the work that will be summarized in this presentation is to examine the fundamental determinants of our macrocyclic molecules as applied to the areas of recognition, binding, and extraction. Towards this end, the anion-binding properties of a series of bipyrrole containing receptors were measured using UV-VIS titration methods. From this analysis, two bipyrrole-containing receptors, namely 1 and 2, were identified that proved effective for the ReO4 - anion (used as non-radioactive analogue of TcO4 - ). These receptors were studied as their tetrafluoroborate salts for extraction experiments and both were found to extract pertechnetate efficiently over a wide range of pH without the need for phase transfer agents. Follow-up competitive extraction studies revealed that receptor 1 effected a high level of pertechnetate extraction at neutral pH even in presence of the potentially competing anions, sulfate and perchlorate anions. NH NH NH N N HN HN HN Ph Ph O N H HN O NH HN n-Pr N N NH 1 2 [1] Evgeny A. Katayev, Nikolay V. Boev, Victor N. Khrustalev, Yuri A. Ustynyuk, I. G. Tananaev, and Jonathan L. Sessler, J. Org. Chem., 2007, 10.1021/jo0624849 HN n-Pr PSA 85 Host-Assisted Guest Protonation with Cucurbit[7]uril Apurba L. Koner a , Na'il Saleh b , Werner M. Nau* a a Jacobs University Bremen, Campus Ring 1, D-28759 Bremen, Germany b Yarmouk University, Department of Chemistry, 21163 Irbid, Jordan The tuning of molecular properties by supramolecular complexation is of prime interest in supramolecular chemistry. Recently, we explored the complexation-induced shift of the protonation equilibria of guest molecules, particularly fluorescent dyes and drugs, by macrocycles [1,2,3]. In this presentation, the potential of cucurbit[7]uril (CB7), a water-soluble macrocyclic host molecule comprised of seven methylene-bridged glycoluril units is being explored with respect to (i) its effect on the protonation equilibria of included guests, (ii) solubility enhancement, (iii) photostabilization, and (iv) fluorescence enhancement, compare Scheme below. H Dye Dye H N N CB7•DyeH + H N Benzimidazole Thiabendazole N N Solubility Enhancement Photostabilization Fluorescence Enhancement The hydrophobic cavity along with the cation receptor properties of the two portals of CB7 causes a considerable shift of protonation equilibrium of fluorescent dyes. This hostassisted guest protonation, along with its supramolecular confinement, results in novel and desirable photophysical properties. Solubility and fluorescence enhancement of poorly soluble benzimidazole-based fungicides (see above) are observed. A significant photostabilization for these guests is also observed due to the host-assisted guest protonation by CB7. The altered photophysical properties can be used for improved applications to create new sensors based on a protolytic displacement assay principle [3]. [1] H. Bakirci, A. L. Koner, T. Schwarzlose, and W. M. Nau, Chem. Eur. J., 2006, 12, 4799 - 4807. [2] J. Mohanty, A. C. Bhasikuttan, W. M. Nau, and H. Pal, J. Phys. Chem. B., 2006, 110, 5132 - 5138. [3] A. L. Koner and W. M. Nau, Supramol. Chem., 2007, 19, 53 - 65. S H N O N Fuberidazole PSA 86
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nd International Symposium on Macro
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Eric Anslyn University of Texas at
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1 Map of Salice Terme 7 5 6 3 9 2 8
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Symposium Program All sessions will
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11:40 - 12:00 Oral Presentation: V.
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PSA 22 Anion Receptors Based On The
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PSA 72 Molecular Tectonics: STM Stu
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PSB 11 Dual binding properties of p
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PSB 57 Removal Of Heavy Metal Ions
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40 years of polyazamacrocycles. A p
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PL 5 Anion-Templated Assembly of In
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Exercising Demons: Synthetic Molecu
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Synthetic Strategies and Structural
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Anion binding as a conformational a
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Supramolecular control of a metal c
Page 31 and 32: OP 3 Control of molecular architect
Page 33 and 34: Catalyst discovery using dynamic co
Page 35 and 36: Cucurbit[n]uril Molecular Container
Page 37 and 38: OP 15 From non-mesomorphic nature t
Page 39 and 40: OP 19 Pyrrolic Tripodal Receptors f
Page 41 and 42: PSA 1 Efficient synthesis of pseudo
Page 43 and 44: Tetra-Cationic phthalocyanines Yasi
Page 45 and 46: PSA 9 Cell penetrating borosilica n
Page 47 and 48: PSA 13 Halide anion interactions wi
Page 49 and 50: Sensing with cavitands: Moving from
Page 51 and 52: Lead(II) complexation by calix[4]-h
Page 53 and 54: Functional [2×2] Grids Xiao-Yu Cao
Page 55 and 56: Neutral supramolecular systems inco
Page 57 and 58: PSA 33 Ratiometric Ion Sensors by R
Page 59 and 60: A photocontrollable receptor for Cu
Page 61 and 62: New emitters for mass spectrometric
Page 63 and 64: PSA 45 A fast-moving electrochemica
Page 65 and 66: Macrocyclic Porphyrin-Bidentate Che
Page 67 and 68: PSA 53 Electronic spectroscopy of e
Page 69 and 70: PSA 57 Self-assembly of calixarene/
Page 71 and 72: PSA 61 Piperazine Containing Polyam
Page 73 and 74: PSA 65 Synthesis of Self-Assembly S
Page 75 and 76: PSA 69 Assembly of Metallomacrocycl
Page 77 and 78: Supra-Biomolecular Tandem Assays -
Page 79 and 80: PSA 77 Synthesis and molecular reco
Page 81: PSA 81 Reaction of phthalic aldehyd
Page 85 and 86: PSA 89 Supramolecular assemblies of
Page 87 and 88: Polytopic Ligands for the Recovery
Page 89 and 90: PSB 1 Rosette Nanotubes as Scaffold
Page 91 and 92: PSB 5 Towards the development of ne
Page 93 and 94: PSB 9 A Quantitative [2]Rotaxane Sy
Page 95 and 96: Metal Complexes of the Polyether Io
Page 97 and 98: PSB 17 Metal controlled anion inter
Page 99 and 100: Crown Ether-tert-Ammonium Salt Comp
Page 101 and 102: PSB 25 A Minimalist Design for Self
Page 103 and 104: PSB 29 Control of Translation of th
Page 105 and 106: PSB 33 Multinuclear NMR, ESI MS and
Page 107 and 108: PSB 37 New Anthracene-based cycloph
Page 109 and 110: PSB 41 1,3,5-Tris(2-aminophenyl)ben
Page 111 and 112: Simple Isophthalamide Derivatives A
Page 113 and 114: PSB 49 On Sokolov’s approach to a
Page 115 and 116: PSB 53 New chromogenic sensors usin
Page 117 and 118: PSB 57 Removal of heavy metal ions
Page 119 and 120: PSB 61 Molecular Recognition of Ele
Page 121 and 122: PSB 65 Switching of Self to non-Sel
Page 123 and 124: Investigation of -cyclodextrin bind
Page 125 and 126: Novel ditopic probes for different
Page 127 and 128: PSB 77 Synthesis, supramolecular ar
Page 129 and 130: PSB 81 Tripodal polyamines as anion
Page 131 and 132: PSB 85 Templated Synthesis of Large
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PSB 89 Direct C-C coupling of 1,2,4
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PSB 93 The study of cytotoxicity ef
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PSB 97 Development of innovative so
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Campbell B. PSA 39 Campbell F. PSB
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Jensen L.G. PSA 82 Jeppesen J.O. IL
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Peters A.J. PSB 39 Peters A.J. PSB
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Sponsors of ISMSC 2007 The contribu
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