Poly(selenoviologen)-Assembled Upconversion Nanoparticles for Low-Power Single-NIR Light-Triggered Synergistic Photodynamic and Photothermal Antibacterial Therapy.

The development of a highly effective photosensitizer (PS) that can be activated with a low-power single light is a pressing issue. Herein, we report a PS for synergistic photodynamic and photothermal therapy constructed through self-assembly of poly(selenoviologen) on the surface of core-shell NaYF4:Yb/Tm@NaYF4 upconversion nanoparticles. The hybrid UCNPs/PSeV PS showed strong ROS generation ability and high photothermal conversion efficiency (∼52.5%) under the mildest reported-to-date irradiation conditions (λ = 980 nm, 150 mW/cm2, 4 min), leading to a high efficiency in killing methicillin-resistant Staphylococcus aureus (MRSA) both in vitro and in vivo. Remarkably, after intravenous injection, the reported PS accumulated preferentially in deep MRSA-infected tissues and achieved an excellent therapeutic index. This PS design realizes a low-power single-NIR light-triggered synergistic phototherapy and provides a simple and versatile strategy to develop safe clinically translatable agents for efficient treatment of deep tissue bacterial inflammations.

Ligand-controlled rates of photoinduced electron transfer in hybrid CdSe nanocrystal/poly(viologen) films.

This paper describes a study of the rates of photoinduced electron transfer (PET) from CdSe quantum dots (QDs) to poly(viologen) within thin films, as a function of the length of the ligands passivating the QDs. Ultrafast (<10 ps), quantitative PET occurs from CdSe QDs coated with HS-(CH(2))(n)-COOH for n = 1, 2, 5, and 7 to viologen units. The observed decrease in the magnitude of the PET rate constant with n is weaker than that expected from the decay of the electron tunneling probability across extended all-trans mercaptocarboxylic acids but well-described by electron tunneling across a collapsed ligand shell. The PET rate constants for films with n = 10 and 15 are much slower than those expected based on the trend for n = 1-7; this deviation is ascribed to the formation of bundles of ligands on the surface of the QD that make the tunneling process prohibitively slow by limiting access of the viologen units to the surfaces of the QDs. This study highlights the importance of molecular-level morphology of donor and acceptor materials in determining the rate and yield of interfacial photoinduced electron transfer in thin films.

Antibacterial activity of polymeric substrate with surface grafted viologen moieties.

An asymmetric viologen, N-hexyl-N'-(4-vinylbenzyl)-4,4'-bipyridinium bromide chloride (HVV), was synthesized and graft copolymerized with commercial PET films. The surface graft concentration of HVV on the PET film is easily controlled by varying the monomer concentration used in the UV-induced graft copolymerization process. The HVV surface functionalized PET film functions as a smart window whose transmittance is reduced upon exposure to light. Concomitantly, the film possesses antibacterial activity, as shown by its bactericidal effect on Escherichia coli (E. coli). The antibacterial activity depends on the concentration of pyridinium groups on the surface and a surface concentration of 25 nmol/cm2 on PET has been shown to be highly effective in killing the bacteria.

Surface-grafted viologen for precipitation of silver nanoparticles and their combined bactericidal activities.

A viologen, N-hexyl-N'-(4-vinylbenzyl)-4,4'-bipyridinium dinitrate (HVVN), was synthesized and subsequently graft-copolymerized on poly(ethylene terephthalate) (PET) films. Silver nanoparticles can be deposited on the surface of the HVVN-PET film through photoinduced reduction of the silver ions in salt solution. The size and distribution of the silver nanoparticles can be varied by changing the reaction time. The pyridinium groups of the HVVN graft-copolymerized on the surface of the substrate possess bactericidal effects on Escherichia coli, and this antibacterial effect can be very significantly enhanced by the incorporation of silver nanoparticles on the HVVN-PET film. The dual functionalities of HVVN and silver remain stable after prolonged immersion in phosphate buffer solution and after aging in a weathering chamber.

Luminescence quenching by DNA-bound viologens: effect of reactant identity on efficiency and dynamics of electron transfer in DNA.

Photoinduced electron transfer from two intercalating photoactive donors, Ru(phen)2dppz2+ and ethidium, to intercalating viologen acceptors of the N,N'-dialkyl-6-(2'-pyridiniumyl)phenanthridinium family has been investigated through steady-state and time-resolved luminescence quenching measurements. Efficient quenching of the emission from these donors bound to DNA is observed at low concentrations of acceptor (1-10 eq.), and in time-resolved emission experiments it is determined that electron transfer occurs on the nanosecond time scale. Furthermore, transient absorption measurements confirm that the quenching is the result of a charge-transfer process; upon photoreaction of intercalated Ru(phen)2dppz2+ with a viologen acceptor, an intermediate with spectral properties resembling the expected charge-separated pair is observed. The quenching yields and kinetics obtained with this quencher are in marked contrast to those observed with these same donors paired with Rh(phi)2bpy3+ as an acceptor. The differing efficiencies of electron transfer for these donor/acceptor pairs bound to DNA as compared to others previously described are discussed qualitatively in terms of the structural and electronic properties of the different reactants.

Triplet radical ion pair state of the Zn-porphyrin-viologen dyad as a magnetic field sensitive probe of phase transitions in small unilamellar vesicles.

The magnetic field effect on the recombination kinetics of the triplet radical ion pair state (RIPS) of the Zn-porphyrin-viologen dyad (P-Ph-Vi2+) in the small unilamellar vesicles (SUV) of D,L-dipalmitoyl-alpha-phosphatidylcholine has been studied by the nanosecond laser flash photolysis technique at 5-60 degrees C. The increase in temperature from 25 to 40 degrees C enhances the rate constant (kr) of the RIPS recombination in zero magnetic field from 0.9 x 10(6) to 1.6 x 10(6) s-1, while kr is temperature insensitive at 5-25 and 40-60 degrees C. The typical break in the kr temperature dependence is observed in the temperature range of the phase transition of the SUV bilayers from the solid to the fluid state. The kr value in a strong magnetic field (B = 0.24 T) is equal to 2.7 x 10(5) s-1 and it is independent of temperature at 5-60 degrees C. The shape of the magnetic field dependence of kr is unaffected by the phase transition of the SUV bilayers and is characterized by the existence of an initial plateau of kr at B = 0 to 0.5 mT.