A new concept of designing a photocontrollable supramolecular polymer nanocontainer through the electrostatic association between an azobenzene-containing surfactant (AzoC10) and a double-hydrophilic block ionomer, poly(ethylene glycol)-b-poly(acrylic acid) (PEG(43)-PAA(153)), is described. Such a block ionomer complex can self-assemble in aqueous solution and form vesicle-like aggregates, which are composed of a poly(ethylene glycol) corona and a poly(acrylic acid) shell associated with azobenzene-containing surfactant. The photoisomerization of azobenzene moieties in the block ionomer complex can reversibly tune the amphiphilicity of the surfactants, inducing the disassembly of the vesicles. Such block ionomer complex vesicles are further evaluated as nanocontainers capable to encapsulate and release guest solutes on demand controlled by light irradiation. For example, the vesicles encapsulating the fluorescein sodium display clear spherical images observed by fluorescence microscopy. However, such fluorescence-marked images disappear after releasing the solute from the vesicles triggered by the UV light. Such novel materials are of both basic and practical significance, especially as prospective nanocontainers for cargo delivery.
We have fabricated a polymeric superamphiphile based on the electrostatic interaction between the double hydrophilic block copolymer of poly(ethylene glycol)-b-acrylic acid (PEG-b-PAA) and a selenium-containing surfactant (SeQTA). The polymeric superamphiphiles are able to self-assemble to form micelles in solution. The micelles can be disassembled with the addition of 0.1% H(2)O(2) because SeQTA is very sensitive to oxidation. The selenide group in SeQTA is oxidized into selenoxide (SeQTA-Ox) by H(2)O(2), which makes the surfactant more hydrophilic, thus leading to the disassembly of the micelles. In addition, small guest molecules such as fluorescein sodium can be loaded into the micelles made from the polymeric superamphiphiles and released in a controlled way under mild oxidation conditions. This study represents a new way to fabricate stimuli-responsive superamphiphiles for controlled self-assembly and disassembly.
We showed here that red light can be used to tune the self-assembly of amphiphilic diselenide-containing block copolymers, via the production of singlet oxygen in the presence of chromophores such as porphyrin derivatives. Furthermore, red light can be used to trigger the release of encapsulated cargo in polymeric micelles.
A novel photocatalyst of Ta-doped ZnO nanoparticles was prepared by a modified Pechini-type method. The antimicrobial study of Ta-doped ZnO nanoparticles on several bacteria of Gram-positive Bacillus subtilis (B. subtilis) and Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) were performed using a standard microbial method. The Ta-doping concentration effect on the minimum inhibitory concentration (MIC) of various bacteria under dark ambient has been evaluated. The photocatalytical inactivation of Ta-doped ZnO nanoparticles under visible light irradiation was examined. The MIC results indicate that the incorporation of Ta5+ ions into ZnO significantly improve the bacteriostasis effect of ZnO nanoparticles on E. coli, S. aureus, and B. subtilis in the absence of light. Compared to MIC results without light irradiation, Ta-doped ZnO and pure ZnO nanoparticles show much stronger bactericidal efficacy on P. aeruginosa, E. coli, and S. aureus under visible light illumination. The possible antimicrobial mechanisms in Ta-doped ZnO systems under visible light and dark conditions were also proposed. Ta-doped ZnO nanoparticles exhibit more effective bactericidal efficacy than pure ZnO in dark ambient, which can be attributed to the synergistic effect of enhanced surface bioactivity and increased electrostatic force due to the incorporation of Ta5+ ions into ZnO. Based on the antibacterial tests, 5 % Ta-doped ZnO is a more effective antimicrobial agent than pure ZnO.
A nonperturbative electron transfer rate theory is developed on the basis of reduced density matrix dynamics, which can be evaluated readily for the Debye solvent model without further approximation. Not only does it recover for reaction rates the celebrated Marcus' inversion and Kramers' turnover behaviors, but the present theory also predicts reaction thermodynamics, such as equilibrium Gibbs free energy and entropy, some interesting solvent-dependent features that are calling for experimental verification. Moreover, a continued fraction Green's function formalism is also constructed, which can be used together with the Dyson equation technique for efficient evaluation of nonperturbative reduced density matrix dynamics.
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