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161.
Replacement of adenine by 2,6-diaminopurine-two nucleobases to be considered equivalent from an etiological point of view-strongly enhances the stability of TNA/TNA, TNA/RNA, or TNA/DNA duplexes and efficiently accelerates template-directed ligation of TNA ligands. [reaction: see text] 相似文献
162.
In a follow-up of the earlier characterisation of botulinum toxins type A and B (BTxA and BTxB) by mass spectrometry (MS), types C, D, E, and F (BTxC, BTxD, BTxE, BTxF) were now investigated. Botulinum toxins are extremely neurotoxic bacterial toxins, likely to be used as biological warfare agent. Biologically active BTxC, BTxD, BTxE, and BTxF are comprised of a protein complex of the respective neurotoxins with non-toxic non-haemagglutinin (NTNH) and, sometimes, specific haemagglutinins (HA). These protein complexes were observed in mass spectrometric identification. The BTxC complex, from Clostridium botulinum strain 003-9, consisted of a 'type C1 and D mosaic' toxin similar to that of type C strain 6813, a non-toxic non-hemagglutinating and a 33 kDa hemagglutinating (HA-33) component similar to those of strain C-Stockholm, and an exoenzyme C3 of which the sequence was in full agreement with the known genetic sequence of strain 003-9. The BTxD complex, from C. botulinum strain CB-16, consisted of a neurotoxin with the observed sequence identical with that of type D strain BVD/-3 and of an NTNH with the observed sequence identical with that of type C strain C-Yoichi. Remarkably, the observed protein sequence of CB-16 NTNH differed by one amino acid from the known gene sequence: L859 instead of F859. The BTxE complex, from a C. botulinum isolated from herring sprats, consisted of the neurotoxin with an observed sequence identical with that from strain NCTC 11219 and an NTNH similar to that from type E strain Mashike (1 amino acid difference with observed sequence). BTxF, from C. botulinum strain Langeland (NCTC 10281), consisted of the neurotoxin and an NTNH; observed sequences from both proteins were in agreement with the gene sequence known from strain Langeland. As with BTxA and BTxB, matrix-assisted laser desorption/ionisation (MALDI) MS provided provisional identification from trypsin digest peptide maps and liquid chromatography-electrospray (tandem) mass spectrometry (LC-ES MS) afforded unequivocal identification from amino acid sequence information of digest peptides obtained in trypsin digestion. 相似文献
163.
The cob(I) alamin (1(I)) -catalyzed2 transformation of the aldehyde 2 has been studied (cf. Table 1). Kinetic examinations showed a rapid isomerization of 2 to 3 (cf. Fig. 1 and 2). From the transformations in glacial AcOH, the two cyclopropanols 5 and 7 were isolated as main products (cf. Tables 1–3 and Fig. 1 and 2). Using large amounts of 1(I) , the aldehyde 4 was very slowly transformed. Accepting the intermediate formation of 6 interconnected Co-complexes, i. e. A , B , C , D , E and F (cf. Scheme), the generation of all the products observed can be explained. 相似文献
164.
165.
Walter T. Smith John M. Patterson Albert C. Kovelesky 《Journal of heterocyclic chemistry》1990,27(3):549-550
Nitration of naphtho[2,3-c][1,2,5]thiadiazole gives the 5-nitro derivative in 61–66% yield. Chlorination of this product apparently gives an unstable addition product which loses hydrogen chloride on recrystallization to give 4-chloro-8-nitronaphtho[2,3-c][1,2,5]thiadiazole. Thus, naphtho[2,3-c][1,2,5]thiadiazole under nitrating conditions behaves as a 2-substituted naphthalene rather than as an anthracene analog. 相似文献
166.
Soran Loredana Coman Virginia Soran Albert Silvestru Cristian 《Central European Journal of Chemistry》2004,2(4):563-572
2-(Diethylaminomethyl)phenyl bromide and 1,3-bis(dimethylaminomethyl)-benzene, useful ligands for the synthesis of hypervalent
organometallic compounds, were prepared and characterized by NMR (1H, 13C, 2D experiments) spectroscopy. Their synthesis was monitored by the HPLC method. The compounds were eluted on a Nucleosil
120 Si column (5 μm, 25×0.4 cm) with n-hexane at room temperature using a 1.0 ml/min flow-rate. The maximum values of absorbance for the studied compounds, excepting
the diethylamine, were located in a narrow range around 212 nm, the wavelength used for their UV detection. The diethylamine
was detected at 190 nm. The calibration curves are straight lines with correlation factors r>0.995. The HPLC data are in good
agreement with those provided by NMR spectroscopy. 相似文献
167.
Chemistry of α-Aminonitriles. Formation of 2-Oxoethyl Phosphates (“Glycolaldehyde Phosphates”) from rac-Oxiranecarbonitrile and on (Formal) Constitutional Relationships between 2-Oxoethyl Phosphates and Oligo(hexo- and pentopyranosyl)nucleotide Backbones Oxiranecarbonitrile in basic acqueous solution at room temperature reacts regioselectively with inorganic phosphate to give the cyanohydrin of 2-oxoethyl phosphate (“glycolaldehyde phosphate”), a source of (the hydrate of) the free aldehyde, preferably in the presence of formaldehyde. In aqueous phosphate solution buffered to nearly neutral pH, oxiranecarbonitrile produces the phosphodiester of glycoladehyde as its bis-cyanohydrin in good yield. In contrast to mono- and dialkylation, trialkylation of phosphate with oxiranecarbonitrile is difficult, and the triester derivative is highly sensitive to hydrolysis. Glycolaldehyde phosphate per se is of prebiotic interest, since it had been shown [5] to aldomerize in basic aqueous solution regioselectively to rac-hexose 2, 4, 6-triphosphates and – in the presence of formaldehyde - mainly to rac-pentose 2, 4-diphosphates with, under appropriate conditions, rac-pentose 2, 4-diphosphates as the major reaction product. However, the question as to whether oxiranecarbonitrile itself has the potential of having been a prebiological natural constituent remains unanswered. Backbone structures of hexopyranosyl-oligonucleotides with phosphodiester linkages specifically between the positions 6′ → 4′, 6′ → 2′, or 4′ → 2′ of the sugar residues can formally be derived via the (hypothetical) aldomerization pathway, a combinatorial intermolecular aldomerization of glycoladehyde phosphate and bis(glycolaldehyde)-phosphodiester in a 1: 1 ratio. The constitutional relationships revealed by this synthetic analysis has played a decisive role as a selection criterion in the pursuit of our experimental studies toward a chemical etiology of the natural nucleic acids' structure. The Discussion in this paper delineates how the analysis contributed to the conception of the structure of p-RNA. The English Footnotes to Schemes 1–11 provide an extension of this summary. 相似文献
168.
Figuerola A Ribas J Llunell M Casanova D Maestro M Alvarez S Diaz C 《Inorganic chemistry》2005,44(20):6939-6948
The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions. 相似文献
169.
Efficient syntheses are reported for incorporating trimetal units of the type M(3)(dpa)(4)(2+) (M = Cr, Co, Ni, and dpa = 2,2'-dipyridylamide) into polyalkynyl assemblies to give the prototypical bis-phenylacetylide complexes M(3)(dpa)(4)(CCPh)(2). Reactions of M(3)(dpa)(4)Cl(2) with LiCCPh have led only to mixtures of products which cocrystallize forming materials of the composition M(3)(dpa)(4)(CCPh)(x)()Cl(2)(-)(x)(). Here we report that acetonitrile complexes [M(3)(dpa)(4)(NCCH(3))(2)](PF(6))(2) react cleanly with LiCCPh in MeCN to afford the desired target molecules in 40-60% yield and in excellent purity. Isolation of the mixed ligand complex [Co(3)(dpa)(4)(NCCH(3))(CCPh)]PF(6) has been accomplished, which suggests that these reactions are stepwise and that it will be possible to synthesize mixed acetylide complexes (i.e., M(3)(dpa)(4)(CCR)(CCR')) via this method. 相似文献
170.
A series of new C2-symmetric 2,2′-bipyridine-contaning crown macrocycles 1-4 has been developed for enantiomeric recognition of amino acid derivatives. These new macrocycles have been showed to be strong complexing agents for primary organic ammonium salts (with K up to 4.83×105 M−1 and −ΔG0 up to 32.4 kJ mol−1) and also useful chromophores for UV-vis titration studies. These macrocyclic hosts exhibited enantioselective binding towards the (S)-enantiomer of phenylglycine methyl ester hydrochloride (Am1) with K(S)/K(R) up to 2.10 (ΔΔG0=−1.84 kJ mol−1) in CH2Cl2 with 0.25% CH3OH. The structure-binding relationship studies showed that the aromatic subunit and the ester group of the ammonium guests are both important for good enantioselectivity. In addition, the host-guest complexes have been studied using various NMR experiments. 相似文献