Fluorescent Chemosensors for Ion and Molecule Recognition PDF
Preview Fluorescent Chemosensors for Ion and Molecule Recognition
g or1 acs.w00 http://pubs.993-0538.f FluorescMenotl eCcuhleem Roseecnosgonristi ofonr Ion and 2010 | 1/bk-1 9, 02 21 y 0. n Juloi: 1 od LL 93 | O9 C1 H 0, UTer 2 Ob Mcto TO ARe: Dat by n D nloaded ublicatio wP o D In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. g or1 acs.w00 http://pubs.993-0538.f 2010 | 1/bk-1 9, 02 21 y 0. n Juloi: 1 od LL 93 | O9 C1 H 0, UTer 2 Ob Mcto TO ARe: Dat by n D nloaded ublicatio wP o D In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. ACS SYMPOSIUM SERIES 538 Fluorescent Chemosensors for Ion and Molecule Recognition g or1 acs.w00 http://pubs.993-0538.f AnthoOnhyi Wo S.ta Ctzea Urnniikve, rsiEtyDI TOR 2010 | 1/bk-1 9, 02 21 y 0. n Juloi: 1 od LL 93 | O9 C1 H 0, UTer 2 Ob Mcto Developed from a symposium sponsored TO ARe: by the Division of Organic Chemistry Dat by n D at the 204th National Meeting nloaded ublicatio of the AmWearsichainng tConhe, mDiCca, l Society, wP o D August 23-28, 1992 American Chemical Society, Washington, DC 1992 In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. Library of Congress Cataloging-in-Publication Data Fluorescent chemosensors for ion and molecule recognition / Anthony W. Czarnik, editor. p. cm —(ACS symposium series, ISSN 0097-6156; 538) "Developed from a symposium sponsored by the Division of Organic Chemistry of the American Chemical Society at the 204th Meeting of the American Chemical Society, Washington, DC, August 23-28, 1992." g or1 Includes bibliographical references and index. http://pubs.acs.993-0538.fw00 II1S.. BCBNzioa 0sre-nn8iks4o,1 rA2s—-n2tCh7o2onn8yg-r4 We ss.e sI.I . 2A. mFeluriocraensc Cenhceem—iCcaoln Sgorceisesteys.. Division of 2010 | 1/bk-1 O19r9g2a:n iWc Cashheimngitsotrny,. D .ICII..) AImVe. rSicearnie sC. hemical Society. Meeting (204th: 29, 102 R857.B54F58 1993 y 0. 681'.761—dc20 93-21067 n Juloi: 1 CIP od LL 93 | O9 C1 H 0, The paper used in this publication meets the minimum requirements of American National OUTber 2 SZt3a9n.d4a8r-1d9 f8o4r. Information Sciences—Permanence of Paper for Printed Library Materials, ANSI TMOcto Copyright © 1993 ARe: Dat American Chemical Society by n D nloaded ublicatio csAcphhleaal cppRittfeeiicgrr h cimtnlisea tnRyhti sesb.s eevrT ovmlheudiamsd. ceeoT infnhosdeerin c aatpp teiepsrse sg aotirnhvaaeennl c c eooo prno y fitrnh igtteheh rectn ooacnwold dnuiteesir oe'ans t o,c hrotho nfwesoe ernbv oettr thtt,hoe ta mhtpa ertore stfpho rnteoha gcelro apofpiirrhes ritic n p pctaeoarypgn ieteah sloe fous tfsea eatth ecohedf wP o per-copy fee through the Copyright Clearance Center, Inc., 27 Congress Street, Salem, MA D 01970, for copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Law. This consent does not extend to copying or transmission by any means—graphic or electronic—for any other purpose, such as for general distribution, for advertising or promotional purposes, for creating a new collective work, for resale, or for information storage and retrieval systems. The copying fee for each chapter is indicated in the code at the bottom of the first page of the chapter. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. 1993 Advisory Board ACS Symposium Series M. Joan Comstock, Series Editor V. Dean Adams Bonnie Lawlor University of Nevada— Institute for Scientific Information Reno Douglas R. Lloyd Robert J. Alaimo The University of Texas at Austin Procter & Gamble g or1 Pharmaceuticals, Inc. Robert McGorrin acs.w00 Kraft General Foods http://pubs.993-0538.f MUnaivrekr sAityr noof lIdow a JPulalniut sS cJie. nMceesn Inns titute, 2010 | 1/bk-1 DUnaivviedrs iBtya okfe Tre nnessee U.S. Department of Agriculture 29, 102 Vincent Pecoraro y 0. on Juldoi: 1 APfrizienrd Camen tBraol sRee search University of Michigan LL 93 | Marshall Phillips O9 C1 Robert F. Brady, Jr. Delmont Laboratories H 0, UTer 2 Naval Research Laboratory Ob George W. Roberts TMOcto Margaret A. Cavanaugh North Carolina State University ARe: National Science Foundation Dat by n D A. Truman Schwartz nloaded ublicatio LDeehnignhi sU nWiv.e rHsiteys s Macalaster College wP John R. Shapley o D Hiroshi Ito University of Illinois IBM Almaden Research Center at Urbana-Champaign Madeleine M. Joullie L. Somasundaram University of Pennsylvania DuPont Gretchen S. Kohl Peter Willett Dow-Corning Corporation University of Sheffield (England) In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. Foreword THE ACS SYMPOSIUM SERIES was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of this series is to publish comprehensive books developed from symposia, which are usually "snapshots org 1 in time" of the current research being done on a topic, plus acs.w00 some review material on the topic. For this reason, it is neces http://pubs.993-0538.f psarroyp toBhseaeftdo trhteae ba lp esa ypomefrp sco osbinuetm epn-ubtbsal siiseshd er bdevo aioeskw q eiusdi c pfkuoltry uaansp dpperoros pscirobinalettr.e ancets,s t htoe 2010 | 1/bk-1 tphaep etrosp iacr ea nedx cflourd ecdom aptr ethheins sipvoeninets,s aonfd thoteh ecrosl leacrtieo na.d dSeodm teo 9, 02 round out the scope of the volume. In addition, a draft of each 21 n July oi: 10. pTahpise ra niso npyemero-uresv ireewveiedw pprrioorc etsos fiisn asul paecrcveipsteadn cbey othr er eojregcatinoinz. od LL 93 | er^) of the symposium, who become the editor(s) of the book. CO19 The authors then revise their papers according to the recom OUTH ber 20, mcaemnedraat-iroenasd yo cf opbyo,t ha ntdh esu bremviietw theres fiannadl ptahpee resd tioto rths,e perdeiptoarrse, Mcto who check that all necessary revisions have been made. TO ARe: As a rule, only original research papers and original re Dat by n D view papers are included in the volumes. Verbatim reproduc nloaded ublicatio tions of previously published papers are not accepted. wP o M Joan Comstock D Series Editor In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. Preface IN THE FLUORESCENT CHEMOSENSOR FIELD, three conditions have impressed me in the past five years. First, this area represents an unusual opportunity for the organic chemistry community to make contributions to an important technological problem. Applications of real-time sensing methods are tremendously varied. Until the invention of fluorescent g or1 chemosensors for calcium, little research was done on intracellular cal ubs.acs.38.pr00 ccieullm b cioonlocgeinsttrsa taiosn sa. O"bnlaccek a tboooxl" b, eicta mwea sa vraailpaibdlley thaassti mcoilualtde db ei nutsoe dt hbey p5 p://3-0 biochemistry community; calcium sensing is now virtually a new field unto htt99 itself. There remain a great many biological analytes worth seeing in real 10 | bk-1 time, among them inorganic phosphate, magnesium, sodium, potassium, 9, 20021/ and glucose. A new functional fluorescent chemosensor for any one of y 20.1 these species would open up an entire new fieldo f investigation. L on Jul3 | doi: 1 wheTnh be losoamd eco hnoceldnstr tartuioen fso ro fr iemmpootert asennts ainngal yatpesp laicraet idoentse.r mIminaegdin neo ta idna ay L9 batch mode, but rather through the use of a fiber-optic bundle inserted O9 UTH Cer 20, 1 itnhtaot athne a rrteearly-t.i mEea ccho fnicbeenrtr iast ieoqnusi popfe dse wveirthal a d doizffeenr eannt aclyhteems oasreen sporro,v siudcehd MOctob on a monitor at the patient's bedside. Devices for real-time monitoring TO of blood pH, p0, and pC0 that are now available use fluorescent nloaded by DARublication Date: mcinhvoeenmTsitthomoesr eeinnnssetgosc .ro dsn.e dvi Tcfeaes2cc;ht ,n nisecovamel reitswhshuelaee2sts s, ,us ontmsheetet loipnfag yt,ho efisfm st hedeaamtu ntsht iwne goc,r oatmhw amtihtu enn eirtwiees sbe altorhcoahdt ow P need chemosensors and those that might synthesize them are largely D unaware of each other. Application-driven communities such as cell biol ogists, environmental scientists, electrical and electronic engineers, medi cal diagnosticians, and researchers in chemical warfare agent detection are virtually unaware that a branch of chemistry exists whose goal is to design and synthesize receptors for ions and molecules. Most of these communi ties are aware of progress in biosensor research because useful selectivi- ties already exist in biotic receptors such as antibodies. However, the argument can readily be made that chemosensors represent an important complement to biosensors. Compared to chemosensors, biosensors are likely to be expensive and unstable. Antibody binding tends to be irrever sible and yields dosimeters rather than sensors. Biosensors based on enzyme catalysis are reagent based and therefore of limited lifetime by ix In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. design. Finally, because high-affinity antibodies cannot be raised easily against small molecules or ions, biosensors for abiotic species (e.g., lead ion) are difficult to envision. The third puzzling fact is that funding organizations have shown interest in the production of working devices but virtually no interest in supporting the more basic research that is needed to learn how to make them. For example, calcium chemosensors are almost all based on chela tion by the EGTA ligand, whose affinity for Ca(H) has been documented for many years. Agencies have shown little tolerance for proposed research acknowledging that sensors for other analytes will not immedi ately demonstrate the same quality of binding. Thus, the chemist seeking to do chemosensor research is placed in the position of having to propose g or1 the construction of new sensors with properties that likely cannot be ubs.acs.38.pr00 raecqhuieivree da sin m thuceh t icmreea ftrivaimty ea osf t ah agtr annete dceydcl eto. sOovlverec tohmei nregs etharisc ho bissstaucelse. will p5 p://3-0 The purpose of this book is to provide a starting point that is greater htt99 than zero so that both chemists and potential end-users can begin the 10 | bk-1 adventure that lies ahead. 201/ 9, 02 21 y 0. ANTHONY W. CZARNIK L on Jul3 | doi: 1 PCaurrkreen-Dt aadvdisr ePssh:a rmaceutical Research OL99 2800 Plymouth Road UTH Cer 20, 1 Ann Arbor, MI 48105 MOctob June 14, 1993 TO nloaded by DARublication Date: wP o D χ In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. Chapter 1 Supramolecular Chemistry, Fluorescence, and Sensing Anthony W. Czarnik1 Department of Chemistry, Ohio State University, Columbus, OH 43210 g or1 cs.00 ubs.a38.ch Epoarcthe nndesw t haeb iflaitbyr itcoa tvioisnu aolfi znee wan asleyntseo rcso. ncPeontteranttiioanl sa pinp lriceaatli-otinms e p5 p://3-0 include fiber optic-based remoting sensing of solution species and htt99 the monitoring of concentrations within living cells. A fluorescent 2010 | 1/bk-1 cahneamlyotes ernesvoerr siisb lay c womithp ocuonndc oomf iatabniot tfilcu oorreigscine ntchea ts cigonmapl lexes to an 29, 102 transduction. Such chemosensors have been used for fluorimetric y 0. LL on Jul93 | doi: 1 medneegstiiagnlne i eoornifn cdghe ehtemarsmo siinenntarstooidoruns c wfeodirt hao vnmeeorw re1 s 0es0yl esycteetiamvrisat.ti iecsT ahapnepd ar odsiavgcenhna tl t oo f tlhieg and H CO0, 19 tursaenfsudl ucchtieomno sscehnesmoress .w iTll hset itmecuhlantoel oingviceaslt idgraitvioinng offo nrceew t oto apcichsie ivne UTer 2 molecule recognition, fluorescent signal transduction, and their Ob Mcto intersection. TO ARe: Dat by n D nloaded ublicatio A sensor is a device that interacts with matter or energy and yields a measurable ow P signal in response. Many scientists to date have considered sensors as macroscopic D devices, such as the pH electrode (an H* sensor) or the bimetallic strip (a temperature sensor). However, with the increasing recognition of nanotechnology there remains little reason not to view suitably engineered individual molecules as devices capable of performing useful work on other molecules. A catalyst is therefore a construction device able to fabricate new compounds. A transport protein is a transportation device able to move species through barriers. 1Current address: Parke-Davis Parmaceutical Research, 2800 Plymouth Road, Ann Arbor, MI 48105 NOTE: Portions of this chapter have been adapted from the Ph.D. theses of Michael Huston (1990) and Scott Van Annan (1990), Ohio State University. 0097-6156/93A)538-O001$06.00A) © 1993 American Chemical Society In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993. 2 FLUORESCENT CHEMOSENSORS FOR ION AND MOLECULE RECOGNITION Likewise, phenolphthalein is a sensing device able to signal the concentration of hydrogen ion. As such, phenolphthalein is an abiotic molecule that senses an abiotic analyte. Because living organinisms have provided such a rich array of both analytes worth sensing and receptors for many of them, biotic sensors have received considerable attention. As we begin a discussion of fluorescent chemosensors, a definition of terms is in order. Chemical sensor: a micro- or macroscopic device that interacts reversibly with a chemical analyte with signal transduction. Chemosensor: a molecule of abiotic origin that signals the presence of matter or energy. Biological sensor: a micro- or macroscopic device that interacts reversibly with a biological analyte with signal transduction. Biosensor: a molecule of biotic origin that signals the presence of matter or energy. Intrinsic fluorescence probe: a chemosensor in which the mechanism for signal transduction involves interaction of the analyte with a ligand that is part of the fluorophore π- g or1 system. Conjugate fluorescence probe: a chemosensor in which the mechanism for acs.h00 signal transduction involves interaction of the analyte with a ligand electronically- bs.8.c insulated from the fluorophore π-system. u3 p5 p://3-0 Thus, phenolphthalein is a chemosensor. In the presence of a sufficient htt99 concentration of OH", phenolphthalein is deprotonated with visible light signalling 2010 | 1/bk-1 awti t5h5 2an namlyt. e Syiigenladls tar amnesadsuucrtaibolne ifso trhme mofe ecnhearngisym, w bhyi cwh hmicahy arne siindtee rianc twioanv eolfe nsgenths or 9, 02 regimes characterized by various spectroscopies (e.g., UV, visible, NMR) or may 21 LL on July 93 | doi: 10. yfaunien lcedtn itoeilnree c otlfrit oetchrhaisteu msryei cmwaplh oroesssiuep mosnu swmeasm.s atroIyn sifusar cvbtee, yye oacncodhn ttmehmeo dpieno rteoanrfy ts iorgefn staehali rstcr ahcnh siandptutoec rtt.ih oenR saoytchncetuhrp,e isteihsse O9 of abiotic molecules that sense analyte concentrations with fluorescent signal H C0, 1 transduction: fluorescent chemosensors. UTer 2 Ob Mcto Statement Of The Research Topic TO ARe: Dat The requisite research issues essential to the creation of fluorescent chemosensors by n D are: (1) how can one bind a molecular entity with selectivity (preferably from nloaded ublicatio mwaectehra),n (i2sm) ws fhoar t bminodleincugl aarn dc hflaunogreessc erenscue lts iignn falul otrraenscsednucceti ocnh ainntgeerss,e catn d (3) what wP o D Binding a Molecular Entity with Selectivity. While much of organic chemistry focusses on the selective creation of covalent bonds, such irreversible associations of potential analytes yield chemodosimeters (designed for cumulative assay) in contrast to chemosensors (designed for real-time assay). Thus, sensing applications require the existence of receptors (hosts) that associate with analytes (guests) selectively and reversibly. One approach to the fabrication of such hosts is to utilize the many such receptors available from biological sources. Selective binding of species is demonstrated by enzymes for their substrates (and cofactors), by transport proteins for their transportées, and by antibodies for their antigens. In particular, because antibodies can be raised to many antigens, the biotic creation of hosts proves a powerful method for binding analytes with selectivity. Indeed, it is fair to say that In Fluorescent Chemosensors for Ion and Molecule Recognition; Czarnik, A.; ACS Symposium Series; American Chemical Society: Washington, DC, 1993.
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