Antimicrobial Photosensitizing Material Based on Conjugated Zn(II) Porphyrins

The widespread use of antibiotics has led to a considerable increase in the resistance of microorganisms to these agents. Consequently, it is imminent to establish new strategies to combat pathogens. An alternative involves the development of photoactive polymers that represent an interesting strategy to kill microbes and maintain aseptic surfaces. In this sense, a conjugated polymer (PZnTEP) based on Zn(II) 5,10,15,20-tetrakis-[4-(ethynyl)phenyl]porphyrin (ZnTEP) was obtained by the homocoupling reaction of terminal alkyne groups. PZnTEP exhibits a microporous structure with high surface areas allowing better interaction with bacteria. The UV-visible absorption spectra show the Soret and Q bands of PZnTEP red-shifted by about 18 nm compared to those of the monomer. Also, the conjugate presents the two red emission bands, characteristic of porphyrins. This polymer was able to produce singlet molecular oxygen and superoxide radical anion in the presence of NADH. Photocytotoxic activity sensitized by PZnTEP was investigated in bacterial suspensions. No viable Staphylococcus aureus cells were detected using 0.5 µM PZnTEP and 15 min irradiation. Under these conditions, complete photoinactivation of Escherichia coli was observed in the presence of 100 mM KI. Likewise, no survival was detected for E. coli incubated with 1.0 µM PZnTEP after 30 min irradiation. Furthermore, polylactic acid surfaces coated with PZnTEP were able to kill efficiently these bacteria. This surface can be reused for at least three photoinactivation cycles. Therefore, this conjugated photodynamic polymer is an interesting antimicrobial photoactive material for designing and developing self-sterilizing surfaces.

Production and loss of O2(1Δg) at atmospheric pressure using microwave-driven microplasmas

We have used arrays of microwave-generated microplasmas operating at atmospheric pressure to generate high concentrations of singlet molecular oxygen, O2(1Δg), which is of interest for biomedical applications. The discharge is sustained by a pair of microstrip-based microwave resonator arrays which force helium/oxygen gas mixtures through a narrow plasma channel. We have demonstrated the efficacy of both NO and less-hazardous N2O additives for suppression of ozone and associated enhancement of the O2(1Δg) yield. Quenching of O2(1Δg) by ozone is sufficiently suppressed such that quenching by ground state molecular oxygen becomes the dominant loss mechanism in the post-discharge outflow. We verified the absence of other significant gas-phase quenching mechanisms by measuring the O2(1Δg) decay along a quartz flow tube. These measurements indicated a first-order rate constant of (1.2 ± 0.3) × 10-24 m3 s−1, slightly slower than but consistent with prior measurements of singlet oxygen quenching on ground state oxygen. The discharge-initiated reaction mechanisms and data analysis are discussed in terms of a chemical kinetics model of the system.

Bypassing the Multi-reference Character of Singlet Molecular Oxygen. Part 2: Ene-reaction

Theoretical calculations involving singlet molecular oxygen (O2(1g)) are challeng- ing due to their inherent multi-reference character. We have tested the quality of re- stricted and unrestricted DFT geometries obtained for the reaction between singlet oxy- gen and a series of alkenes (propene, 2-methylpropene, trans-butene, 2-methylbutene and 2,3-dimethylbutene) which are able to follow the ene-reaction. The electronic en- ergy of the obtained geometries are rened using 3 dierent methods which account for the multi-reference character of singlet oxygen. The results show that the mechanism for the ene-reaction is qualitatively dierent when either one or two allylic-hydrogen groups are available for the reaction. When one allylic-hydrogen group is available the UDFT calculations predict a stepwise addition forming a biradical intermediate, while, the RDFT calculations predict a concerted reaction where both hydrogen abstrac- tion and oxygen addition occur simultaneously. When two allylic-hydrogen groups are available for the reaction then UDFT and RDFT predict the same reaction mechanism, namely that the reaction occurs as a stepwise addition without a stable intermediate between the two transition states. The calculated rate constants are in reasonable agreement with experimental data, except for trans-butene where the calculated rate constant is three orders of magnitude lower than the experimental one. In conclusion we nd that the simple bypassing scheme tested in this paper is a robust approach for calculations of reaction involving singlet oxygen in the limit that the transition state processes low multi-reference character. 2

The removal efficiencies and mechanism of aniline degradation by peroxydisulfate activated with magnetic Fe-Mn oxides composite

The Fe-Mn oxides composite prepared by a chemical co-precipitation method was used as a heterogenous peroxydisulfate catalyst for the decomposition of aniline. This study investigated the mechanism of aniline degradation by PDS activated with catalyst. Reactive species resulting in the degradation of aniline was investigated via radical quenching experiments with different scavengers, including methanol, tert-butyl alcohol, EDTA and sodium azide. Based on the experiments made here, it is speculated that the predominant reactive species responsible for the degradation of aniline may be holes and singlet molecular oxygen rather than SO4·− and ·OH radicals. The degradation of compounds in catalyst/peroxydisulfate system was put forward. The three possible intermediates were speculated by high performance liquid chromatography-mass spectrometry, and two possible degradation pathways were proposed.