3,3′-Diethylthiadicarbocyanine (DiSC 2 (5)) is a symmetrical cationic cyanine dye consisting of two N-ethylated benzothiazole groups linked by a pentamethine bridge. Spectroscopic analysis indicates dimerization of the dye in the presence of duplex DNA sequences consisting of alternating adenine/thymine (A/T) or inosine/ cytosine (I/C) residues, based on the following observations: (i) the absorption maximum shifts from 647 to 590 nm, (ii) exciton splitting is observed in the induced circular dichroism spectrum, and (iii) fluorescence from the dye is strongly quenched. Dimerization on I/C, but not G/C sequences indicates that the cyanine dimers insert into the minor groove, a conclusion that is supported by viscometric analysis. Spectroscopic studies with short synthetic oligonucleotide duplexes demonstrate that dimerization is highly cooperative: binding of one dimer greatly facilitates binding of a second dimer. For longer binding sites, this cooperativity leads to the formation of extended helical cyanine dye aggregates consisting of dimers aligned in an end-to-end fashion within the minor groove of the DNA. The DNA structure strictly controls the dimensions of the aggregate, permitting distinction between inter-and intradimer interactions.
UV−vis and CD spectroscopy reveal that a tricationic cyanine dye spontaneously assembles into a
helical J-aggregate in the presence of a double-helical DNA template. The stability of the J-aggregate is strongly
dependent on the dye concentration and DNA length in a manner that reflects a high degree of cooperativity
in formation of the aggregate. Slight changes in environmental conditions such as temperature and ionic strength
result in interconversion between J- and H-aggregates. The aggregate likely consists of dimeric units assembled
in an offset, face-to-face orientation within the minor groove of the DNA template, analogous to an earlier
report of H-aggregation on DNA by a related cyanine dye. A model is proposed that relates the two aggregate
structures by translation of one monomer from a given dimer along the floor of the minor groove. This translation
requires adjacent monomers to also translate, leading to the observed cooperativity.
Incorporation of a guanidine functional group into the PNA backbone facilitates cellular uptake of PNA into mammalian cells with efficiency comparable to that of the TAT transduction domain. The modified PNA recognizes and binds to the complementary DNA strand in accordance with Watson-Crick recognition rules. However, unlike polypyrimidine PNA which binds to DNA in 2:1 stoichiometry, the modified PNA binds to complementary DNA in a 1:1 ratio to form a highly stable duplex.
Quantum dots are a new class of fluorophores, whose more prominent characteristics include size-tunable, narrow, fluorescence emission bands and broad overlapping excitation spectra of multiple color dots. Here, we present an efficient, versatile, and gentle approach for intracellular delivery of quantum dots that is easily extended to multicolor optical coding of mammalian cells. In this method, a nine residue biotinylated L-arginine peptide is used to enhance delivery of streptavidin conjugated quantum dots into mammalian cells.
Inspired by natural columnar nacre, artificial montmorillonite/hydroxyethyl cellulose columnar nacre-like materials with a site-specific layered structure in the interior and a hierarchical columnar structure on the surface are prepared. The materials exhibit improved tensile strength, good chemical stability in seawater, superior resistance to sand-grain impingement, and robust underwater low-adhesive superoleophobicity.
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