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At least 433 records · Page 24Linked to original sources

Biomimetic surface modifications based on the cyanobacterial iron chelator anachelin.

Siderophores are natural iron chelators that have been evolutionarily selected to bind to Fe ions with very high binding constants. We utilize these unique properties to bind to metal oxide surfaces using a fragment of the cyanobacterial siderophore anachelin. The resulting poly(ethylene glycol) conjugate forms stable adlayers on TiO2 as has been shown by variable angle spectroscopic ellipsometry and X-ray photoelectron spectroscopy. Moreover, these coated surfaces are highly protein-resistant against the adsorption of full human serum.

Biomimetic Materials↗

Approaches to short-acting neuromuscular blocking agents: nonsymmetrical bis-tetrahydroisoquinolinium mono- and diesters.

Nonsymmetrical bisquaternary mono- and diesters combining the potency-enhancing properties of the (1R)-laudanosinium group with a second unhindered quaternary ammonium moiety have been studied as a means of promoting short action with high-potency neuromuscular block. Atracurium-related nonsymmetrical diesters showed high potency, freedom from vagal blockade at neuromuscular blocking doses, and short action. Nonsymmetrical monoesters were short acting but showed varying degrees of vagal block.

Animals↗

Photooxidation of dibenzothiophene and 4,6-dimethyldibenzothiophene sensitized by N-methylquinolinium tetrafluoborate: mechanism and intermediates investigation.

Photooxidation of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) sensitized by N-methylquinolinium tetrafluoborate (NMQ(+)BF4-) has been investigated in O2-saturated acetonitrile solutions. Nearly 100% oxidation of DBT and DMDBT was observed, and the oxidized products are predominantly composed of sulfoxides and sulfones, which are formed via photoinduced electron transfer (ET). Such ET processes were studied with fluorescence quenching of NMQ+, time-resolved transient absorption measurement, and ESR experiments. The fluorescence of NMQ+ is efficiently quenched by DBT and DMDBT via diffusion-controlled processes, with bimolecular quenching constants of 1.6 x 10(10) M(-1) s(-1) for DBT and 2.3 x 10(10) M(-1) s(-1) for DMDBT. The electron-transfer nature of the quenching is evidenced by the transient absorption measurement of the neutral radical NMQ*, which is formed by electron transfer from the substrates (DBT or DMDBT) to the excited singlet state of NMQ+. The ESR spectra of the superoxide radical anion (O2*-) trapped by 5,5-dimethyl-1-pyrroline N-oxide (DMPO) in the photooxygenation of DBT and DMDBT as well as their sulfoxides manifest that O2 traps an electron from NMQ* to form O2*-. The fact that the formation of sulfoxides and sulfones is greatly suppressed in the presence of benzoquinone (BQ), an efficient electron trap for NMQ* and O2*-, further indicates an ET process in the photooxidation of DBT and DMDBT. As inferred from the control experiments, the role of singlet oxygen (1O2) in the photooxidation is negligible. The intermediates responsible for the formation of sulfoxides and sulfones have been examined in detail.

Borates↗

Quantum chemical characterization of the structures, thermochemical properties, and singlet-triplet splittings of didehydroquinolinium and didehydroisoquinolinium ions.

Structural and energetic properties are predicted for the 21 didehydroquinolinium ion isomers and 21 didehydroisoquinolinium ion isomers in their lowest-energy singlet and triplet states by using density functional and multireference second-order perturbation theories. Singlet-triplet splittings and biradical stabilization energies are examined to gain insight into the degree of interaction between the biradical centers, with comparison being made to analogous didehydronaphthalenes and didehydropyridines.

Free Radicals↗

Quantum chemical characterization of the vertical electron affinities of didehydroquinolinium and didehydroisoquinolinium cations.

Vertical electron affinities (EA) are predicted for the lowest energy singlet states of the 21 didehydroquinolinium cation isomers and the 21 didehydroisoquinolinium cation isomers, as well as the doublet states of the seven dehydroquinolinium cation isomers, the seven dehydroisoquinolinium cation isomers, the seven N-methyldehydroquinolinium cations, and the seven N-methyldehydroisoquinolinium cations, by using density functional theory. For the monoradicals, the calculated EA of the radical site depends only on the distance from the (formally charged) nitrogen atom, and is reduced by 0.14-0.24 eV when the NH+ group is replaced with an NCH3+ group. Nearly all of the calculated EAs for the ortho biradicals are lower (by 0.04-0.72 eV) than those for either of the corresponding monoradicals. For the meta biradicals, the calculated EAs lie either between the EAs of the corresponding monoradicals or higher (by 0.07-0.58 eV), and they are extremely sensitive to the separation (distance) between the two dehydrocarbon atoms. For the biradicals that do not have either an ortho or meta relationship the calculated EAs are all higher (by 0.02-1.93 eV) than those for either of the corresponding monoradicals. The EAs are examined to gain insight into the nature of inductive/field and resonance effects that influence the electrophilicity of the radical site(s), which is a major factor controlling the reactivity of these types of (bi)radicals.

Cations↗

Degree of micelle ionization and micellar growth for gemini surfactants detected by 6-methoxy-N-(3-sulfopropyl)quinolinium fluorescence quenching.

The degree of micelle ionization of gemini surfactants has been investigated by using halide-sensitive fluorescence probes (e.g., 6-methoxy-N-(3-sulfopropyl)quinolinium (SPQ)). The fluorescence is quenched by the free bromide ions dissociated from surfactants. The degree of micelle ionization increased with increasing spacer chain length, but it decreased with increasing surfactant concentration. The Stern-Volmer plot gave two inflection points (i.e., not only at the cmc but also far above the cmc). The second inflection point suggested spherocylindrical micellar growth with decreases in the degree of micelle ionization. The spherocylindrical micellar growth was depressed with increasing spacer chain length, whereas it was enhanced with increasing tail chain length. The degree of micelle ionization of spherocylindrical micelles depended on the concentration and chain length of gemini surfactants. The change in SPQ fluorescence spectra upon hydrogenation was utilized to evaluate the solubilization site in micelle solutions. The dissolved SPQ in water was instantly reduced by the addition of NaBH4, resulting in abrupt changes in fluorescence intensity and spectral shift. All of the SPQ in micelle solution was also instantly reduced by NaBH4, indicating the existence of SPQ in the water bulk phase, but its fluorescence intensity increased upon the solubilization of hydrogenated SPQ into micelles.

Borohydrides↗

Nanocopying of individual DNA strands and formation of the corresponding surface pattern of titania nanotube.

Titania nanotube was prepared by nanocopying of the individual DNA double strand as template. DNA was first spread on a solid substrate, and its molecular surface was coated with an ultrathin titania layer by 3 cycles of the surface sol-gel process. Fluorescence microscopic images before and after titania coating of the DNA/YOYO-1 complex were essentially identical, showing that the titania coating did not change the chemical properties of the complex. Titania coating effectively prohibited chemical degradation of titania-coated DNA with DNase I and physically separated the DNA strand from the surrounding environment with an ultrathin titania barrier. The morphology of the DNA strand was preserved, as confirmed by microscopic and spectroscopic observations. The presence of the hollow (tubular) structure was confirmed by a silver staining experiment coupled with scanning transmission electron microscopy-energy-dispersive X-ray spectroscopy (STEM-EDX) analysis. The present finding shows the effectiveness of nanocopying of the individual DNA strand.

Benzoxazoles↗

Single molecule adsorption at compositionally patterned self-assembled monolayers on gold: role of domain boundaries.

This paper examines the single-molecule adsorption of YOYO-I-labeled lambda-DNA at compositionally patterned self-assembled monolayers (SAMs). The interactions of fluorescently labeled lambda-DNA molecule with the patterned SAMs, which are comprised of different functional groups (i.e., amine-, alcohol-, and acid-terminated thiolates), were monitored at optically transparent gold films using total internal reflection fluorescence microscopy. The role of solution pH, lambda-DNA concentration, and domain size was investigated. In addition to delineation of the relative adsorption strength as a function of terminal group identity (NH2 > COOH > OH), the potential importance of structural defects was also revealed. The latter result, found both at the disordered boundaries between domains and at adlayers in which structural order was affected by the length of the alkyl chain, points to the subtle but preferential adsorption of the "sticky ends" of lambda-DNA. These experiments also detected an intriguing dependence of adsorption with respect to domain size.

Adsorption↗