{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,15]],"date-time":"2025-10-15T17:18:54Z","timestamp":1760548734076,"version":"build-2065373602"},"reference-count":115,"publisher":"Wiley","issue":"30","license":[{"start":{"date-parts":[[2008,8,29]],"date-time":"2008-08-29T00:00:00Z","timestamp":1219968000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2008,10,20]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The use of hydrogen\u2010bonding patterns in the same way as is known from DNA building blocks is a challenge for the construction of novel types of suitable chromophoric probes. This feature has been utilised for the construction of a novel type of UV\/Vis probe for detection of supramolecular AAD or DAD sequences (A=hydrogen bond acceptor, D=hydrogen bond donor). Here we report on the structure of the enolisable chromophore 1\u2010<jats:italic>n<\/jats:italic>\u2010butyl\u20105\u2010(4\u2010nitrophenyl)barbituric acid (<jats:bold>1<\/jats:bold>), which has an adjustable hydrogen\u2010bonding pattern. The position of the keto\u2013enol equilibrium of this dye is strongly influenced both by the solvent polarity and by the chemical environment. Furthermore, the recognition properties of the barbiturate were examined by the use of seven artificial receptors: the pyridine bases 2,6\u2010diaminopyridine (<jats:bold>DAP<\/jats:bold>), 2,6\u2010diacetamidopyridine (<jats:bold>DAC<\/jats:bold>) and 2,6\u2010bis(trifluoroacetamido)pyridine (<jats:bold>TFA<\/jats:bold>), as well as the nucleic acid bases 9\u2010ethyladenine (<jats:bold>EtAd<\/jats:bold>), 9\u2010ethylguanine (<jats:bold>EtGu<\/jats:bold>), 1\u2010<jats:italic>n<\/jats:italic>\u2010butylcytosine (<jats:bold>BuCy<\/jats:bold>) and 1\u2010<jats:italic>n<\/jats:italic>\u2010butylthymine (<jats:bold>BuTy<\/jats:bold>). It was found that <jats:bold>1<\/jats:bold> can interact with these bases either through acid\u2013base interaction or by hydrogen\u2010bonding complexation. The balance between the interactions is dependent both on the basicity strength and on the presence of a suitable recognition sequence in the base. The induced formation of the enol form of <jats:bold>1<\/jats:bold> thus causes a significant UV\/Vis shift as function of the nature of the base.<\/jats:p>","DOI":"10.1002\/chem.200800626","type":"journal-article","created":{"date-parts":[[2008,8,29]],"date-time":"2008-08-29T01:57:57Z","timestamp":1219975077000},"page":"9338-9346","source":"Crossref","is-referenced-by-count":16,"title":["An Enolisable Barbiturate with Adjustable Hydrogen\u2010Bonding Structure for UV\/Vis Detection of Nucleic Acid Bases and Related Compounds"],"prefix":"10.1002","volume":"14","author":[{"given":"Ina","family":"Bolz","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Stefan","family":"Spange","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2008,10,10]]},"reference":[{"key":"e_1_2_5_1_2","unstructured":"Standard works on biochemistry and bioanalytics:"},{"volume-title":"Fundamentals of Biochemistry","year":"2002","author":"Voet D.","key":"e_1_2_5_2_2"},{"volume-title":"Biochemistry","year":"2002","author":"Berg J. 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After a 1:1 stoichiometry had been attained no increase in the UV\/Vis absorption band of the enolate anion was observed so self\u2010aggregation of the enolate anion in the concentration range studied plays only a minor role (see Supporting Information)."},{"key":"e_1_2_5_90_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00156a004"},{"key":"e_1_2_5_91_2","unstructured":"In the1H\u2005NMR dilution titrations in [D6]DMSO performed on the salt of1and the proton sponge (see ref.\u2005[11\u2009c]) the self\u2010association of the enolate anion could be deduced from the downfield shift of the barbiturate NH proton with increasing concentration. The equilibrium constant (KA) was found to be 2.8\u00b11.8\u00d710\u22123\u2009M\u22121(see Supporting Information)."},{"key":"e_1_2_5_92_2","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-1395(199903)12:3<247::AID-POC122>3.0.CO;2-U"},{"key":"e_1_2_5_93_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01020a041"},{"key":"e_1_2_5_94_2","unstructured":"CD2Cl2does not compete with the donor and acceptor positions of hydrogen bonds because of its negligible hydrogen\u2010bonding acidity and basicity (see ref.\u2005[13\u2009b])."},{"key":"e_1_2_5_95_2","unstructured":"In this manner maximum excesses of 35\u2005equiv forBuCy 60 forEtAdand 3 forEtGuwere reached. The polarity of the solvent environment is somewhat raised by the low concentration of MeOH which leads to additional stabilisation of the enol form. The small amount of the enol form detectable at ca. 420\u2005nm is only solvatated by MeOH. At the same time MeOH competes with the receptor for the donor and acceptor positions of the hydrogen\u2010bonding sequence of1 so that only sufficiently strong complex formation with the receptor can lead to a change in the UV\/Vis absorption bands of1(see refs.\u2005[ 4\u2009d \u20096\u2009b])."},{"key":"e_1_2_5_96_2","unstructured":"Complex formation ofEtAdwith pyrimidine derivatives is known from the literature. The association constants for the formation of this doubly hydrogen\u2010bonded complex in CDCl3lie between 40 and 130\u2009M\u22121."},{"key":"e_1_2_5_97_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.57.2.250"},{"key":"e_1_2_5_98_2","doi-asserted-by":"publisher","DOI":"10.1038\/218069a0"},{"key":"e_1_2_5_99_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00771a057"},{"key":"e_1_2_5_100_2","doi-asserted-by":"publisher","DOI":"10.1039\/a910295g"},{"key":"e_1_2_5_101_2","unstructured":"Association constantsKA=104\u2013105\u2009M\u22121in CDCl3(KA=4\u2009M\u22121in [D6]DMSO) have been determined for the interaction between guanine and cytosine which is in the same order of magnitude as for other triply hydrogen\u2010bonded complexes. Complex formation between 5 5\u2010disubstituted barbiturates and guanine or cytosine derivatives has not been described."},{"key":"e_1_2_5_102_2","doi-asserted-by":"publisher","DOI":"10.1016\/0005-2787(69)90116-6"},{"key":"e_1_2_5_103_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja01020a041"},{"key":"e_1_2_5_104_2","doi-asserted-by":"publisher","DOI":"10.1021\/j150659a027"},{"key":"e_1_2_5_105_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00161a061"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.200800626","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.200800626","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T15:16:56Z","timestamp":1760282216000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.200800626"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,10,10]]},"references-count":115,"journal-issue":{"issue":"30","published-print":{"date-parts":[[2008,10,20]]}},"alternative-id":["10.1002\/chem.200800626"],"URL":"https:\/\/doi.org\/10.1002\/chem.200800626","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"type":"print","value":"0947-6539"},{"type":"electronic","value":"1521-3765"}],"subject":[],"published":{"date-parts":[[2008,10,10]]}}}