排序方式: 共有13条查询结果,搜索用时 15 毫秒
1.
2.
Bichenkova EV Sardarian AR Wilton AN Bonnet P Bryce RA Douglas KT 《Organic & biomolecular chemistry》2006,4(2):367-378
Organic intramolecular exciplexes, N-(4-dimethylaminobenzyl)-N-(1-pyrenemethyl)amine (1) and N'-4-dimethylaminonaphthyl-N-(1-pyrenemethyl)amine (2), were used as model systems to reveal major factors affecting their exciplex fluorescence, and thus lay the basis for developing emissive target-assembled exciplexes for DNA-mounted systems in solution. These models with an aromatic pyrenyl hydrocarbon moiety as an electron acceptor appropriately connected to an aromatic dimethylamino electron donor component (N,N-dimethylaminophenyl or N,N-dimethylaminonaphthyl) showed strong intramolecular exciplex emission in both non-polar and highly polar solvents. The effect of dielectric constant on the maximum wavelength for exciplex emission was studied, and emission was observed for 1 and 2 over the full range of solvent from non-polar hydrocarbons up to N-methylformamide with a dielectric constant of 182. Quantum yields were determined for these intramolecular exciplexes in a range of solvents relative to that for Hoechst 33,258. Conformational analysis of 1 was performed both computationally and via qualitative 2D NMR using (1)H-NOESY experiments. The results obtained indicated the contribution of pre-folded conformation(s) to the ground state of 1 conducive to exciplex emission. This research provides the initial background for design of self-assembled, DNA-mounted exciplexes and underpins further development of exciplex-based hybridisation bioassays. 相似文献
3.
2-O-tert-Butyldimethylsilyl-4,6-bis-O-pyrenoyl-myo-inositol-1,3,5-orthoformate (6) and 2-O-tert-butyldimethylsilyl-4-O-[4-(dimethylamino)benzoyl]-6-O-pyrenoyl-myo-inositol-1,3,5-orthoacetate (10) adopt conformationally restricted unstable chairs with five axial substituents. In the symmetrical diester 6, the two pi-stacked pyrenoyl groups are electron acceptor-donor partners, giving a strong intramolecular excimer emission. In the mixed ester 10, the pyrenoyl group is the electron acceptor and the 4-(dimethylamino)benzoyl ester is the electron donor, giving a strong intramolecular exciplex emission. The conformation of the mixed ester 10 was assessed using 1H NMR spectroscopy (1H-NOESY) and computational studies. which showed the minimum inter-centroid distance between the two aromatic systems to be approximately 3.9 A. Upon addition of acid, the orthoformate/orthoacetate trigger in 6 and 10 was cleaved, which caused a switch of the conformation of the myo-inositol ring to the more stable penta-equatorial chair, leading to separation of the aromatic ester groups and loss of excimer and exciplex fluorescence, respectively. This study provides proof of principle for the development of novel fluorescent molecular probes. 相似文献
4.
Mansell D Rattray N Etchells LL Schwalbe CH Blake AJ Bichenkova EV Bryce RA Barker CJ Díaz A Kremer C Freeman S 《Chemical communications (Cambridge, England)》2008,(41):5161-5163
Natural myo-inositol phosphate antioxidants containing the 1,2,3-trisphosphate motif bind Fe(3+) in the unstable penta-axial conformation. 相似文献
5.
Bichenkova EV Yu X Bhadra P Heissigerova H Pope SJ Coe BJ Faulkner S Douglas KT 《Inorganic chemistry》2005,44(12):4112-4114
Octahedral tris-chelate complexes [M(II)(bpy)(3)](2+) (M = Ru or Os, bpy = 2,2'-bipyridyl), covalently attached to the 3'- and 5'-phosphates of two oligonucleotides, are juxtaposed when hybridized contiguously to a fully complementary DNA target. Visible metal-to-ligand charge-transfer (MLCT) excitation of the [Ru(II)(bpy)(3)](2+) unit leads to resonance energy transfer to the MLCT state of the [Os(II)(bpy)(3)](2+) moiety, with the energy transfer efficiency depending on the degree of hybridization. The extent of attenuation of the intense red luminescence from the Ru(II) chromophore hence allows highly sensitive structural probing of the assembly and constitutes a novel approach to DNA sensing which is capable of detecting mutations. 相似文献
6.
Subham Majumdar EV Sampathkumaran St Berger M Della Mea H Michor E Bauer M Brando J Hemberger A Loidl 《Pramana》2002,58(5-6):777-782
Recently, the solid solution Ce2Au1−
x
Co
xSi3 has been shown to exhibit many magnetic anomalies associated with the competition between magnetic ordering and the Kondo
effect. Here we report high pressure electrical resistivity of Ce2AuSi3, ac susceptibility (X) and magnetoresistance of various alloys of this solid solution in order to gain better knowledge of the magnetism of these
alloys. High pressure resistivity behavior is consistent with the proposal that Ce2AuSi3 lies at the left-hand side of the maximum in Doniach’s magnetic phase diagram. The ac X data reveal that there are in fact two magnetic transitions, one at 2 K and the other at 3 K for this compound, both of which
are spin-glass-like. However, as the Co concentration is increased, antiferromagnetism is stabilized for intermediate compositions
before attaining non-magnetism for the Co end member. 相似文献
7.
João Lavrado Alexandra Paulo Elena Bichenkova Kenneth T. Douglas Rui Moreira 《Magnetic resonance in chemistry : MRC》2012,50(3):216-220
Knowledge of protonable sites and acid dissociation constants of cryptolepine derivatives having C‐11 substituents containing two amino functionalities is of great importance to the understanding of the mechanism of their antimalarial action, which may contribute to their further development as drug candidates. In this work, we applied 1H NMR titration to investigate the acid–base characteristics of these polyprotic compounds in the pH range 3–13. We identified three acid–base equilibria with most acid dissociation constants (pKa*) being greater than 10.5, which prevented us from using the potentiometric method. Overall, 1H NMR titration was sensitive and suitable for the determination of pKa values for these drug leads. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
8.
Pope SJ Coe BJ Faulkner S Bichenkova EV Yu X Douglas KT 《Journal of the American Chemical Society》2004,126(31):9490-9491
Carboxylate-bearing d-transition metal bipyridyls form ternary complexes with seven-coordinate lanthanide centers. The neodymium,- ytterbium-, and erbium-containing complexes exhibit lanthanide-centered emissions sensitized by the MLCT states of the d-block components. 相似文献
9.
We have grown single crystals of the psuedo-one-dimensional compound Sr3CuIrO6, a K4CdCl6-derived monoclinic structure with Cu-Ir chains along the [101] direction. We present the ac and dc magnetization behavior
of the single crystals in comparison with that of the polycrystalline form reported earlier. There is a distinct evidence
for at least two magnetic transitions, at 5 K (T
1) and 19 K (T
2), with different relative magnitudes in the single and polycrystals. The low temperature magnetic relaxation behavior of
both the forms is found to be widely different, exhibiting unexpected time dependence. 相似文献
10.
Yaroslav Staroseletz Svetlana Gaponova Olga Patutina Elena Bichenkova Bahareh Amirloo Thomas Heyman Daria Chiglintseva Marina Zenkova 《Molecules (Basel, Switzerland)》2021,26(6)
RNA-targeting therapeutics require highly efficient sequence-specific devices capable of RNA irreversible degradation in vivo. The most developed methods of sequence-specific RNA cleavage, such as siRNA or antisense oligonucleotides (ASO), are currently based on recruitment of either intracellular multi-protein complexes or enzymes, leaving alternative approaches (e.g., ribozymes and DNAzymes) far behind. Recently, site-selective artificial ribonucleases combining the oligonucleotide recognition motifs (or their structural analogues) and catalytically active groups in a single molecular scaffold have been proven to be a great competitor to siRNA and ASO. Using the most efficient catalytic groups, utilising both metal ion-dependent (Cu(II)-2,9-dimethylphenanthroline) and metal ion-free (Tris(2-aminobenzimidazole)) on the one hand and PNA as an RNA recognising oligonucleotide on the other, allowed site-selective artificial RNases to be created with half-lives of 0.5–1 h. Artificial RNases based on the catalytic peptide [(ArgLeu)2Gly]2 were able to take progress a step further by demonstrating an ability to cleave miRNA-21 in tumour cells and provide a significant reduction of tumour growth in mice. 相似文献