Photophysical Details and O2-Sensing Analysis of a Eu(III) Complex in Polymer Composite Nanofibers Prepared by Electrospinning

An as-synthesized Eu(III) complex, denoted as Eu(N-DPNQ)(TTD)3, was prepared and characterized, and the antenna mechanism between these ligands and central metal emitter was studied. Here DPNQ means 10-ethyl-10H-indolo [2′,3':5,6]pyrazino[2,3-f][1,10]phenanthroline and TTD is 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione. We find that Eu(N-DPNQ)(TTD)3 emission intensity dependents on oxygen concentration, and O2-sensing skill of Eu(N-DPNQ)(TTD)3 in polymer composite nanofibers of poly (vinylpyrrolidone) (PVP) prepared by electrospinning is investigated. Results reveal that the emission quenching of Eu(N-DPNQ)(TTD)3 is caused by the ground state (triplet) oxygen quenching on antenna ligands triplet state. The Eu(N-DPNQ)(TTD)3 doped composite nanofiber with a loading level of 6 wt% exhibits the best result with sensitivity of 2.43 and response time of 10 s, along with linear response.

Cyclometalated Iridium-Coumarin Ratiometric Oxygen Sensors: Improved Signal Resolution and Tunable Dynamic Ranges

In this work we introduce a new series of ratiometric oxygen sensors for hypoxic environments based on phosphorescent cyclometalated iridium centers partnered with organic coumarin fluorophores. Three different cyclometalating ligands and two different pyridyl-containing coumarin types were used to prepare six target complexes with tunable excited-state energies. Some of the complexes exhibit only phosphorescence originating from the cyclometalated Ir moiety, as a result of excited-state energy transfer from the coumarin to the Ir-centered excited states. Three of the complexes display dual emission, with fluorescence arising from the coumarin ligands and phosphorescence from the cyclometalated iridium synthons, and hence function as ratiometric oxygen sensors. Oxygen quenching experiments with these complexes demonstrate that the iridium centered phosphorescence is quenched under O₂ while fluorescence is unaffected. These sensors have good signal resolution, and the sensitivity and dynamic range, measured with Stern-Volmer analysis, span two orders of magnitude. This work demonstrates that this simple, modular approach for conjoining fluorescent and phosphorescent molecules can produce effective oxygen sensors with a wide range of attributes.

Cyclometalated Iridium-Coumarin Ratiometric Oxygen Sensors: Improved Signal Resolution and Tunable Dynamic Ranges

In this work we introduce a new series of ratiometric oxygen sensors for hypoxic environments based on phosphorescent cyclometalated iridium centers partnered with organic coumarin fluorophores. Three different cyclometalating ligands and two different pyridyl-containing coumarin types were used to prepare six target complexes with tunable excited-state energies. Some of the complexes exhibit only phosphorescence originating from the cyclometalated Ir moiety, as a result of excited-state energy transfer from the coumarin to the Ir-centered excited states. Three of the complexes display dual emission, with fluorescence arising from the coumarin ligands and phosphorescence from the cyclometalated iridium synthons, and hence function as ratiometric oxygen sensors. Oxygen quenching experiments on these complexes demonstrate that the iridium centered phosphorescence is quenched under O₂ while fluorescence is unaffected. These sensors have good signal resolution, and the sensitivity and dynamic range, measured with Stern-Volmer analysis, span two orders of magnitude. This work demonstrates that this simple, modular approach for conjoining fluorescent and phosphorescent molecules can produce effective oxygen sensors with a wide range of attributes.

One-photon red light-triggered disassembly of small-molecule nanoparticles for drug delivery

Background Photoresponsive drug delivery can achieve spatiotemporal control of drug accumulation at desired sites. Long-wavelength light is preferable owing to its deep tissue penetration and low toxicity. One-photon upconversion-like photolysis via triplet–triplet energy transfer (TTET) between photosensitizer and photoresponsive group enables the use of long-wavelength light to activate short-wavelength light-responsive groups. However, such process requires oxygen-free environment to achieve efficient photolysis due to the oxygen quenching of triplet excited states. Results Herein, we report a strategy that uses red light to trigger disassembly of small-molecule nanoparticles by one-photon upconversion-like photolysis for cancer therapy. A photocleavable trigonal molecule, BTAEA, self-assembled into nanoparticles and enclosed photosensitizer, PtTPBP. Such nanoparticles protected TTET-based photolysis from oxygen quenching in normoxia aqueous solutions, resulting in efficient red light-triggered BTAEA cleavage, dissociation of nanoparticles and subsequent cargo release. With paclitaxel as the model drug, the red light-triggered drug release system demonstrated promising anti-tumor efficacy both in vitro and in vivo. Conclusions This study provides a practical reference for constructing photoresponsive nanocarriers based on the one-photon upconversion-like photolysis. Graphical Abstract

Heterologous production of novel and rare C30-carotenoids using Planococcus carotenoid biosynthesis genes

Background Members of the genus Planococcus have been revealed to utilize and degrade solvents such as aromatic hydrocarbons and alkanes, and likely to acquire tolerance to solvents. A yellow marine bacterium Planococcus maritimus strain iso-3 was isolated from an intertidal sediment that looked industrially polluted, from the Clyde estuary in the UK. This bacterium was found to produce a yellow acyclic carotenoid with a basic carbon 30 (C30) structure, which was determined to be methyl 5-glucosyl-5,6-dihydro-4,4′-diapolycopenoate. In the present study, we tried to isolate and identify genes involved in carotenoid biosynthesis from this marine bacterium, and to produce novel or rare C30-carotenoids with anti-oxidative activity in Escherichia coli by combinations of the isolated genes. Results A carotenoid biosynthesis gene cluster was found out through sequence analysis of the P. maritimus genomic DNA. This cluster consisted of seven carotenoid biosynthesis candidate genes (orf1–7). Then, we isolated the individual genes and analyzed the functions of these genes by expressing them in E. coli. The results indicated that orf2 and orf1 encoded 4,4′-diapophytoene synthase (CrtM) and 4,4′-diapophytoene desaturase (CrtNa), respectively. Furthermore, orf4 and orf5 were revealed to code for hydroxydiaponeurosporene desaturase (CrtNb) and glucosyltransferase (GT), respectively. By utilizing these carotenoid biosynthesis genes, we produced five intermediate C30-carotenoids. Their structural determination showed that two of them were novel compounds, 5-hydroxy-5,6-dihydro-4,4′-diaponeurosporene and 5-glucosyl-5,6-dihydro-4,4′-diapolycopene, and that one rare carotenoid 5-hydroxy-5,6-dihydro-4,4′-diapolycopene is included there. Moderate singlet oxygen-quenching activities were observed in the five C30-carotenoids including the two novel and one rare compounds. Conclusions The carotenoid biosynthesis genes from P. maritimus strain iso-3, were isolated and functionally identified. Furthermore, we were able to produce two novel and one rare C30-carotenoids in E. coli, followed by positive evaluations of their singlet oxygen-quenching activities.

Comparison of Antioxidant Properties of Dehydrolutein with Lutein and Zeaxanthin, and their Effects on Cultured Retinal Pigment Epithelial Cells

Dehydrolutein accumulates in substantial concentrations in the retina. The aim of this study was to compare antioxidant properties of dehydrolutein with other retinal carotenoids, lutein, and zeaxanthin, and their effects on ARPE-19 cells. The time-resolved detection of characteristic singlet oxygen phosphorescence was used to compare the singlet oxygen quenching rate constants of dehydrolutein, lutein, and zeaxanthin. The effects of these carotenoids on photosensitized oxidation were tested in liposomes, where photo-oxidation was induced by light in the presence of photosensitizers, and monitored by oximetry. To compare the uptake of dehydrolutein, lutein, and zeaxanthin, ARPE-19 cells were incubated with carotenoids for up to 19 days, and carotenoid contents were determined by spectrophotometry in cell extracts. To investigate the effects of carotenoids on photocytotoxicity, cells were exposed to light in the presence of rose bengal or all-trans-retinal. The results demonstrate that the rate constants for singlet oxygen quenching are 0.77 × 1010, 0.55 × 1010, and 1.23 × 1010 M−1s−1 for dehydrolutein, lutein, and zeaxanthin, respectively. Overall, dehydrolutein is similar to lutein or zeaxanthin in the protection of lipids against photosensitized oxidation. ARPE-19 cells accumulate substantial amounts of both zeaxanthin and lutein, but no detectable amounts of dehydrolutein. Cells pre-incubated with carotenoids are equally susceptible to photosensitized damage as cells without carotenoids. Carotenoids provided to cells together with the extracellular photosensitizers offer partial protection against photodamage. In conclusion, the antioxidant properties of dehydrolutein are similar to lutein and zeaxanthin. The mechanism responsible for its lack of accumulation in ARPE-19 cells deserves further investigation.

Comparison of Antioxidant Properties of Dehydrolutein with Lutein and Zeaxanthin, and their Effects on Retinal Pigment Epithelial Cells

Dehydrolutein accumulates in substantial concentrations in the retina. The aim of this study was to compare antioxidant properties of dehydrolutein with other retinal carotenoids, lutein and zeaxanthin, and their effects on ARPE-19 cells. The time-resolved detection of characteristic singlet oxygen phosphorescence was used to compare the singlet oxygen quenching rate constants of dehydrolutein, lutein, and zeaxanthin. The effects of these carotenoids on photosensitized oxidation were tested in liposomes, where photooxidation was induced by light in the presence of photosensitizers, and monitored by oximetry. To compare the uptake of dehydrolutein, lutein, and zeaxanthin, ARPE-19 cells were incubated with carotenoids for up to 19 days, and carotenoid contents were determined by spectrophotometry in cell extracts. To investigate the effects of carotenoids on phototocytotoxicity, cells were exposed to light in the presence of rose bengal or all-trans-retinal. The results demonstrate that the rate constants for singlet oxygen quenching are 0.77x1010, 0.55x1010, and 1.23x1010 M-1s-1 for dehydrolutein, lutein and zeaxanthin, respectively. Overall, dehydrolutein is similar to lutein or zeaxanthin in protection of lipids against photosensitized oxidation. ARPE-19 cells accumulate substantial amounts of both zeaxanthin and lutein but no detectable amounts of dehydrolutein. Cells pre-incubated with carotenoids are equally susceptible to photosensitized damage as cells without carotenoids. Carotenoids provided to cells together with the extracellular photosensitizers offer partial protection against photodamage. In conclusion, the antioxidant properties of dehydrolutein are similar to lutein and zeaxanthin. The mechanism responsible for its lack of accumulation in ARPE-19 cells deserves further investigation.