An AIE-active bacterial inhibitor and photosensitizer for selective imaging, killing, and photodynamic inactivation of bacteria over mammalian cells.

Photodynamic therapy is becoming increasingly popular for combat of bacteria. In the clinical photodynamic combat of bacteria, one critical issue is to avoid the potential damage to the host since the reactive oxygen species produced by photosensitizers are also harmful to mammalian cells. In this work, we report an aggregation-induced-emission-active bacterial inhibitor and photosensitizer, OEO-TPE-MEM (OTM), for the imaging, killing, and light-enhanced inactivation of bacteria. OTM could efficiently bind to and kill Gram-positive bacteria, while its affinity to Gram-negative bacteria is lower, and a higher OTM concentration is required for killing Gram-negative bacteria. OTM is also an efficient photosensitizer and could efficiently sensitize the production of reactive oxygen species, which enhances its killing effect on both Gram-positive and Gram-negative bacteria. More interestingly, OTM is very biocompatible with normal mammalian cells both in the dark and under light irradiation. OTM in mice models with bacteria-infected wounds could promote the healing of infected wounds without affecting their organs and blood parameters, which makes it an excellent candidate for clinical applications.

Recent Advances in Metal Complexes for Antimicrobial Photodynamic Therapy.

Antimicrobial resistance (AMR) is a growing global problem with more than 1 million deaths due to AMR infection in 2019 alone. New and innovative therapeutics are required to overcome this challenge. Antimicrobial photodynamic therapy (aPDT) is a rapidly growing area of research poised to provide much needed help in the fight against AMR. aPDT works by administering a photosensitizer (PS) that is activated only when irradiated with light, allowing high spatiotemporal control and selectivity. The PS typically generates reactive oxygen species (ROS), which can damage a variety of key biological targets, potentially circumventing existing resistance mechanisms. Metal complexes are well known to display excellent optoelectronic properties, and recent focus has begun to shift towards their application in tackling microbial infections. Herein, we review the last five years of progress in the emerging field of small-molecule metal complex PSs for aPDT.

A dual organelle-targeting mechanosensitive probe.

Cells are responsive to the mechanical environment, but the methods to detect simultaneously how different organelles react in mechanobiological processes remain largely unexplored. We herein report a dual organelle-targeting fluorescent probe, (E)-1-[3-(diethoxyphosphoryl)propyl]-4-[4-(diethylamino)styryl]pyridin-1-ium bromide (ASP-PE), for mechanical mapping in live cells. ASP-PE is aggregation-induced emission active and is sensitive to the local mechanical environment. It targets the plasma membrane (PM) and intracellular mitochondria in cells by its phosphonate moiety and pyridinium. In this work, through ASP-PE staining, changes of membrane tension in the PM and mitochondria in response to varied osmotic pressure and substrate stiffness are visualized using fluorescence lifetime imaging microscopy. The mechanobiological importance of actin filaments and microtubules in the PM and mitochondria is also investigated using this probe. Computational simulations are applied to study the sensing mechanism of the probe. This study introduces a unique tool for mapping the membrane tension in the PM and mitochondria together, providing us great opportunities to study organelle's interactions in mechanobiology.

Development of Strong Visible-Light-Absorbing Cyclometalated Iridium(III) Complexes for Robust and Efficient Light-Driven Hydrogen Production.

Weak light absorption of common Ir(III) complexes (e. g., using phenylpyridine as the ligand) has hindered their applications in photocatalytic hydrogen generation from water as an efficient photosensitizer. To address this issue, a series of cyclometalated Ir(III) complexes (Ir1-Ir5), featuring different electron-donating substituents to enhance the absorptivity, have been synthesized and studied as photosensitizers (PSs) for light-driven hydrogen production from water. Ir6-Ir7 were prepared as fundamental systems for comparisons. Electron donors, including 9-phenylcarbazole, triphenylamine, 4,4'-dimethoxytriphenylamine, 4,4'-di(N-hexylcarbazole)triphenylamine moieties were introduced on 6-(thiophen-2-yl)phenanthridine-based cyclometalating (C^N) ligands to explore the donor effect on the hydrogen evolution performance of these cationic Ir(III) complexes. Remarkably, Ir4 with 4,4'-dimethoxytriphenylamine achieved the highest turn-over number (TON) of 12 300 and initial turnover frequency (TOFi ) of 394 h-1 , with initial activity (activityi ) of 547 000 µmol g-1 h-1 and initial apparent quantum yield (AQYi ) of 9.59 %, under the illumination of blue light-emitting diodes (LEDs) for 105 hours, which demonstrated a stable three-component photocatalytic system with high efficiency. The TON (based on n(H2 )/n(PSr)) in this study is the highest value reported to date among the similar photocatalytic systems using Ir(III) complexes with Pt nanoparticles as catalyst. The great potential of using triphenylamine-based Ir(III) PSs in boosting photocatalytic performance has also been shown.

Fluorescence Imaging and Photodynamic Inactivation of Bacteria Based on Cationic Cyclometalated Iridium(III) Complexes with Aggregation-Induced Emission Properties.

Antibacterial photodynamic therapy (PDT) is one of the emerging methods for curbing multidrug-resistant bacterial infections. Effective fluorescent photosensitizers with dual functions of bacteria imaging and PDT applications are highly desirable. In this study, three cationic and heteroleptic cyclometalated Ir(III) complexes with the formula of [Ir(CˆN)2 (NˆN)][PF6 ] are prepared and characterized. These Ir(III) complexes named Ir(ppy)2 bP, Ir(1-pq)2 bP, and Ir(2-pq)2 bP are comprised of three CˆN ligands (i.e., 2-phenylpyridine (ppy), 1-phenylisoquinoline (1-pq), and 2-phenylquinoline (2-pq)) and one NˆN bidentate co-ligand (bP). The photophysical characterizations demonstrate that these Ir(III) complexes are red-emitting, aggregation-induced emission active luminogens. The substitution of phenylpyridine with phenylquinoline isomers in the molecules greatly enhances their UV and visible-light absorbance as well as the photoinduced reactive oxygen species (ROS) generation ability. All three Ir(III) complexes can stain both Gram-positive and Gram-negative bacteria efficiently. Interestingly, even though Ir(1-pq)2 bP and Ir(2-pq)2 bP are constitutional isomers with very similar structures and similar ROS generation ability in buffer, the former eradicates bacteria much more effectively than the other through white light-irradiated photodynamic inactivation. This work will provide valuable information on the rational design of Ir(III) complexes for fluorescence imaging and efficient photodynamic inactivation of bacteria.

Panchromatic Sensitization with ZnII Porphyrin-Based Photosensitizers for Light-Driven Hydrogen Production.

Three molecular photosensitizers (PSs) with carboxylic acid anchors for attachment to platinized titanium dioxide nanoparticles were studied for light-driven hydrogen production from a fully aqueous medium with ascorbic acid (AA) as the sacrificial electron donor. Two zinc(II) porphyrin (ZnP)-based PSs were used to examine the effect of panchromatic sensitization on the photocatalytic H2 generation. A dyad molecular design was used to construct a difluoro boron-dipyrromethene (bodipy)-conjugated ZnP PS (ZnP-dyad), whereas the other one featured an electron-donating diarylamino moiety (YD2-o-C8). To probe the use of the ZnP scaffold in this particular energy conversion process, an organic PS without the ZnP moiety (Bodipy-dye) was also synthesized for comparison. Ultrafast transient absorption spectroscopy was adopted to map out the energy transfer processes occurring in the dyad and to establish the bodipy-based antenna effect. In particular, the systems with YD2-o-C8 and ZnP-dyad achieved a remarkable initial activity for the production of H2 with an initial turnover frequency (TOFi ) higher than 300 h-1 under white light irradiation. The use of ZnP PSs in dye-sensitized photocatalysis for the H2 evolution reaction in this study indicated the importance of the panchromatic sensitization capability for the development of light absorbing PSs.

Starburst Triarylamine Donor-Based Metal-Free Photosensitizers for Photocatalytic Hydrogen Production from Water.

Three metal-free molecular photosensitizers (S1-S3) featuring a starburst triarylamine donor moiety have been synthesized. They show attractive photocatalytic performance in visible light-driven H2 production from water in their platinized TiO2 composites. A remarkable H2 turnover number (TON) of 10 200 (48 h) was achieved in an S1-anchored system.

Bis(phenothiazyl-ethynylene)-Based Organic Dyes Containing Di-Anchoring Groups with Efficiency Comparable to N719 for Dye-Sensitized Solar Cells.

A new series of acetylene-bridged phenothiazine-based di-anchoring dyes have been synthesized, fully characterized, and used as the photoactive layer for the fabrication of conventional dye-sensitized solar cells (DSSCs). Tuning of their photophysical and electrochemical properties using different π-conjugated aromatic rings as the central bridges has been demonstrated. This molecular design strategy successfully inhibits the undesirable charge recombination and prolongs the electron lifetime significantly to improve the power conversion efficiency (η), which was proven by the detailed studies of electrochemical impedance spectroscopy (EIS) and open-circuit voltage decay (OCVD). Under a standard air mass (AM) 1.5 irradiation (100 mW cm-2 ), the DSSC based on the dye with phenyl bridging unit exhibits the highest η of 7.44 % with open-circuit photovoltage (Voc ) of 0.796 V, short-circuit photocurrent density (Jsc ) of 12.49 mA cm-2 and fill factor (ff) of 0.748. This η value is comparable to that of the benchmark N719 under the same conditions.

Chromophoric Dyads for the Light-Driven Generation of Hydrogen: Investigation of Factors in the Design of Multicomponent Photosensitizers for Proton Reduction.

Two new dyads have been synthesized and studied as photosensitizers for the light-driven generation of H2 from aqueous protons. One of the dyads, Dy-1, consists of a strongly absorbing Bodipy (dipyrromethene-BF2) dye and a platinum diimine benzenedithiolate (bdt) charge transfer (CT) chromophore, denoted as PtN2S2. The two components are connected through an amide linkage on the bdt side of the PtN2S2 complex. The second dyad, Dy-2, contains a diketopyrrolopyrrole dye that is linked directly to the acetylide ligands of a Pt diimine bis(arylacetylide) CT chromophore. The two dyads, as well as the Pt diimine bis(arylacetylide) CT chromophore, were attached to platinized TiO2 via phosphonate groups on the diimine through sonication of the corresponding esters, and each system was examined for photosensitizer effectiveness in photochemical generation of H2 from aqueous protons and electrons supplied by ascorbic acid. Of the three photosensitizers, Dy-1 is the most active under 530 nm radiation with an initial turnover frequency of 260 h(-1) and a total of 6770 turnovers over 60 h of irradiation. When a "white" LED light source is used, samples with Dy-2 and the Pt diimine bis(arylacetylide) chromophore, while not as effective as Dy-1, perform relatively better. A key conclusion is that the presence of a strongly absorbing organic dye increases dyad photosensitizer effectiveness only if the energy of the CT excited state lies below that of the organic dye's lowest excited state; if not, the organic dye does not improve the effectiveness of the CT chromophore for promoting electron transfer and the light-driven generation of H2. The nature of the spacer between the organic dye and the charge transfer chromophore also plays a role in the effectiveness of using dyads to improve light-driven energy-storing reactions.

Synthesis and Characterization of Phenothiazine-Based Platinum(II)-Acetylide Photosensitizers for Efficient Dye-Sensitized Solar Cells.

Three new unsymmetrical phenothiazine-based platinum(II) bis(acetylide) complexes PT1-PT3 with different electron-donating arylacetylide ligands were synthesized and characterized. Their photophysical, electrochemical, and photovoltaic properties have been fully investigated and the density functional theory (DFT) calculations have been carried out. Under AM 1.5 irradiation (100 mW cm(-2)), the PT1-based dye-sensitized solar cell (DSSC) device exhibited an attractive power conversion efficiency (η) up to 5.78 %, with a short-circuit photocurrent density (J(sc)) of 10.98 mA cm(-2), an open-circuit photovoltage (V(oc)) of 0.738 V, and a fill factor (ff) of 0.713. These findings provide strong evidence that platinum-acetylide complexes have great potential as promising photosensitizers in DSSC applications.