{"title":"Sequence-selective interaction between mercury(II) ions and the DNA dodecamer [d(GCCGATATCGGC)]2 studied by 1H NMR spectroscopy.","authors":"S Steinkopf, W Nerdal, A Kolstad, E Sletten","doi":"10.3891/acta.chem.scand.50-0775","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0775","url":null,"abstract":"<p><p>The palindromic dodecamer [d(GCCGATATCGGC)]2 has been titrated by Hg(ClO4)2 in order to study sequence dependent HgII ion interactions. The titration pattern as monitored by 1D and 2D 1H NMR is consistent with a transition to a new conformer of the dodecamer induced by HgII ions. At intermediate stages of the titration, the proton signals from the new conformer coexist with those of the original one, indicating slow exchange between the two forms on the NMR timescale. The data clearly show that there is no major alteration in the secondary structure, e.g. B-->Z-form or duplex-->hairpin transition. The intra- and inter-residue sequential walk is completed except for a break between T6 and A7. At a concentration level r = [HgII]/[nucleobase] < 0.20 all four central imino signals are present. This definitely excludes thymine N3 as a possible mercuration site. In the imino region of the spectra HgII ions induce a large upfield shift of the thymine imino resonance T8-N3H, while the other thymine resonance T6-N3H is unperturbed. The guanine imino signal G4-N1H shows a large downfield ring current shift caused by major conformational changes in the duplex. The complete titration experiment indicates that mercury, initially, binds selectively to the A5'-T8 base pair. A tentative model is proposed where mercury is cross-linking the two strands via thymine T8-O4 and the deprotonated amino group of the complementary adenine base A5'.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 9","pages":"775-82"},"PeriodicalIF":0.0,"publicationDate":"1996-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19785822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
E Keinan, S C Sinha, D Shabat, H Itzhaky, J L Reymond
{"title":"Asymmetric organic synthesis with catalytic antibodies.","authors":"E Keinan, S C Sinha, D Shabat, H Itzhaky, J L Reymond","doi":"10.3891/acta.chem.scand.50-0679","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0679","url":null,"abstract":"<p><p>The science of catalytic antibodies has undergone a rapid maturation process within its first nine years of existence. From initial 'proof of concept' and demonstration of fundamental, enzyme-like characteristics, antibodies have been shown to catalyze a remarkably broad scope of organic transformations, including difficult and unfavorable chemical reactions. Yet, the ultimate testing ground for new concepts in organic chemistry has always been the synthesis of natural products. Here we focus on several issues related to the applicability of antibody catalysis in organic synthesis. We show that (a) in the hydrophobic environment of the antibody active site, short-lived intermediates can be formed and reacted in a controlled way, thus allowing antibodies to catalyze reactions that are normally incompatible with aqueous media, (b) the intrinsic order of reactivity (chemoselectivity) in a series of structurally related enol ethers and ketals can be inverted from 1:10 in the uncatalyzed hydrolysis reaction to 1000:1 under antibody catalysis, and (c) an efficient total synthesis of alpha-multistriatin, an important, biologically active natural product can be achieved via antibody catalysis.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 8","pages":"679-87"},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19728276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
S F Betz, J W Bryson, M C Passador, R J Brown, K T O'Neil, W F DeGrado
{"title":"Expression of de novo designed alpha-helical bundles.","authors":"S F Betz, J W Bryson, M C Passador, R J Brown, K T O'Neil, W F DeGrado","doi":"10.3891/acta.chem.scand.50-0688","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0688","url":null,"abstract":"<p><p>The successful design of proteins requires careful consideration of the multiplicity of forces that stabilize their three-dimensional structures including hydrophobic interactions, hydrogen-bonding, electrostatics and weakly polar interactions. Early attempts to design proteins relied too heavily on hydrophobic interactions to provide stability, resulting in structures with dynamic properties. Addition of more specific interactions to these initial designs gives rise to proteins with more native-like properties. This manuscript describes the design of native-like three- and four-helix bundles, and their cloning and expression of these proteins.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 8","pages":"688-96"},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19728763","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Catalytic asymmetric aminohydroxylation provides a short taxol side-chain synthesis.","authors":"G Li, K B Sharpless","doi":"10.3891/acta.chem.scand.50-0649","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0649","url":null,"abstract":"<p><p>The p-toluenesulfonamide derivate of the C-13 side-chain of taxol was prepared on a one third mole scale in a single step from methyl cinnamate. The process employed is catalytic asymmetric aminohydroxylation (catalytic AA). In the present case, there is no work-up other than filtration of the pure product which is insoluble in the reaction mixture. The sulfonamide protecting group is removed by acidic hydrolysis.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 8","pages":"649-51"},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19728274","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Molecular recognition and assembly.","authors":"J Rebek","doi":"10.3891/acta.chem.scand.50-0707","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0707","url":null,"abstract":"<p><p>The synthesis and characterization of a series of self-assembling capsules is described. Assembly takes place as a result of the self-complementary hydrogen bonding patterns on the subunit pieces and dimerization occurs in such a manner that the concave surfaces of the two subunits are directed at one another. This feature gives rise to close-shelled capsules which are shown to encapsulate smaller guest species. Selectivity is shown for guests ranging in size from methane to adamantane derivatives. Shape selectivity is shown in special capsules capable of recognizing disc-like molecules such as benzene and cyclohexane. Disproportionation reactions are shown to exist between capsules of slightly different sizes, and these are shown to be controlled by the nature of the guest species. The use of these capsules as reaction chambers is proposed.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 8","pages":"707-16"},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19728764","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Using the process of reactive immunization to induce catalytic antibodies with complex mechanisms: aldolases.","authors":"R A Lerner, C F Barbas","doi":"10.3891/acta.chem.scand.50-0672","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0672","url":null,"abstract":"<p><p>The process of reactive immunization has been used to induce efficient aldolase catalytic antibodies that use the enamine mechanism of natural enzymes. Reactive immunogens are those that react chemically during induction of the immune response. This same reaction is used later in catalysis. In essence one immunizes with the equivalent of a mechanism-based inhibitor. The difference is that instead of inhibiting a mechanism, a mechanism is induced. This advance allows the experimenter to dictate the exact mechanism by which catalytic antibodies proceed. The hapten used in the present study is a 1,3-diketone that both traps the requisite lysine residue to initiate formation of the enamine and induces a binding pocket that overcomes the entropic barrier of this bimolecular reaction.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 8","pages":"672-8"},"PeriodicalIF":0.0,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19728275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Lithofibrin. A new remarkably stable substance found in renal stones.","authors":"S Ohman, L Larsson","doi":"10.3891/acta.chem.scand.50-0633","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0633","url":null,"abstract":"<p><p>Besides inorganic constituents, renal stones contain organic matter known as stone matrix. We have examined such matrix obtained from stones that had been crushed by extracorporeal shock-wave lithotripsy, in order to determine its chemical properties. Morphologically, the matrix was composed of fibers of different colors, most of them exhibiting autofluorescence. Proteins or any other well-known biochemical material were not present. It was remarkably stable against chemical degradation, and could not be dissolved in hot concentrated acids or bases or any common organic solvent. Elementary analysis revealed carbon (60.8%), oxygen (26.9%), nitrogen (7.6%), hydrogen (5.3%) and sulfur (0.77%) to be present. Furthermore, X-ray emission spectroscopy revealed the presence of titanium and chromium. Solid-phase 13C NMR spectroscopy revealed the presence of aromatic and aliphatic carbon as well as carbon bound to O and/or N. The material was paramagnetic. All findings indicated the matrix to be composed of a new class of organic compound, probably a polyaromatic heterocyclic organic material. We welcome suggestions on further methods that can ultimately elucidate the nature of lithofibrins.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 7","pages":"633-6"},"PeriodicalIF":0.0,"publicationDate":"1996-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19662273","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
K Hammer, J Hatlelid, M Grøtli, J Arukwe, J Klaveness, F Rise, K Undheim
{"title":"Ether, carbonate and urethane deoxynucleoside derivatives as prodrugs.","authors":"K Hammer, J Hatlelid, M Grøtli, J Arukwe, J Klaveness, F Rise, K Undheim","doi":"10.3891/acta.chem.scand.50-0609","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0609","url":null,"abstract":"<p><p>3'-Deoxythymidine and its 3'-azido derivative, 2',3'-dideoxycytidine, 2',3'-dideoxyinosine and 2',3'-dideoxyadenosine have been acylated to form carbonates and urethanes in chemoselective reactions. The nucleosides have been N- and/or O-alkylated by alpha-chloroethyl or chloromethyl alkyl carbonates to form alpha-alkyloxycarbonyloxyethyl or alkyloxycarbonyloxymethyl derivatives. The products are lipophilic in order to facilitate transport through biological membranes and are designed to be cleaved by esterases with liberation of the bioactive nucleoside. Initial esterase cleavage of the alkylated derivatives produces hemiacetals or -aminals which subsequently dissociate to the active nucleoside.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 7","pages":"609-22"},"PeriodicalIF":0.0,"publicationDate":"1996-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19662272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
V S Parmar, S Gupta, K S Bisht, S Mukherjee, P M Boll, W Errington
{"title":"Synthesis and X-ray structure of 2-(3-methyl-2-butenyl)-3,4,5-trimethoxyphenol: a potent anti-invasive agent against solid tumours.","authors":"V S Parmar, S Gupta, K S Bisht, S Mukherjee, P M Boll, W Errington","doi":"10.3891/acta.chem.scand.50-0558","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0558","url":null,"abstract":"","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 6","pages":"558-60"},"PeriodicalIF":0.0,"publicationDate":"1996-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19889930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
E Larsen, K Danel, G B Vaaben, A A el-Emam, E B Pedersen, C Nielsen
{"title":"Synthesis of an AZT-HEPT hybrid and homologous AzddU derivatives.","authors":"E Larsen, K Danel, G B Vaaben, A A el-Emam, E B Pedersen, C Nielsen","doi":"10.3891/acta.chem.scand.50-0417","DOIUrl":"https://doi.org/10.3891/acta.chem.scand.50-0417","url":null,"abstract":"<p><p>3'-Azido-2',3'-dideoxyuridines 6 and their corresponding alpha anomers 5 were synthesized by condensation of silylated 6-alkyl and 5,6-dialkyl substituted uracils 2 with methyl 3-azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-alpha, beta-D-erythro-pentofuranoside (4). Compounds 5 and 6 were treated with tetrabutylammonium fluoride to obtain the deprotected nucleosides 7 and 8, respectively.</p>","PeriodicalId":76966,"journal":{"name":"Acta chemica Scandinavica (Copenhagen, Denmark : 1989)","volume":"50 5","pages":"417-21"},"PeriodicalIF":0.0,"publicationDate":"1996-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"19612383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}