Developing Type‐I photosensitizers is considered as an efficient approach to overcome the deficiency of traditional photodynamic therapy (PDT) for hypoxic tumors. However, it remains a challenge to ...design photosensitizers for generating reactive oxygen species by the Type‐I process. Herein, we report a series of α,β‐linked BODIPY dimers and a trimer that exclusively generate superoxide radical (O2−.) by the Type‐I process upon light irradiation. The triplet formation originates from an effective excited‐state relaxation from the initially populated singlet (S1) to triplet (T1) states via an intermediate triplet (T2) state. The low reduction potential and ultralong lifetime of the T1 state facilitate the efficient generation of O2−. by inter‐molecular charge transfer to molecular oxygen. The energy gap of T1‐S0 is smaller than that between 3O2 and 1O2 thereby precluding the generation of singlet oxygen by the Type‐II process. The trimer exhibits superior PDT performance under the hypoxic environment.
Heavy‐atom‐free boron dipyrromethene (BODIPY)‐based photosensitizers generate ROS exclusively by the Type‐I process upon near‐infrared light illumination for tumor ablation.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The authors provide at a look at the biological applications of supramolecular assemblies that have been designed for excitation energy transfer. The topics discussed include biosensors and ...bioimaging.
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IJS, KILJ, NUK, PNG, UL, UM
To meet the requirements of potential applications, it is of great importance to explore new catalysts for formic acid oxidation that have both ultra-high mass activity and CO resistance. Here, we ...successfully synthesize atomically dispersed Rh on N-doped carbon (SA-Rh/CN) and discover that SA-Rh/CN exhibits promising electrocatalytic properties for formic acid oxidation. The mass activity shows 28- and 67-fold enhancements compared with state-of-the-art Pd/C and Pt/C, respectively, despite the low activity of Rh/C. Interestingly, SA-Rh/CN exhibits greatly enhanced tolerance to CO poisoning, and Rh atoms in SA-Rh/CN resist sintering after long-term testing, resulting in excellent catalytic stability. Density functional theory calculations suggest that the formate route is more favourable on SA-Rh/CN. According to calculations, the high barrier to produce CO, together with the relatively unfavourable binding with CO, contribute to its CO tolerance.
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FZAB, GEOZS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
It is a challenge to design photosensitizers to balance between the tumor‐targeting enrichment for precise treatment and efficient clearance within a reasonable timescale for reducing side effects. ...Herein, an ultra‐small nano‐photosensitizer 1a with excellent tumor‐specific accumulation and renal clearance is reported. It is formed from the self‐assembly of compound 1 bearing three triethylene glycol (TEG) arms and two pyridinium groups in water. The positively charged surface with neutral TEG coating enables 1a to efficiently target the tumor, with the signal‐to‐background ratio reaching as high as 11.5 after tail intravenous injection. The ultra‐small size of 1a with an average diameter of 5.6 nm allows its fast clearance through kidney. Self‐assembly also endows 1a with an 18.2‐fold enhancement of reactive oxygygen species generation rate compared to compound 1 in organic solution. Nano‐PS 1a manifests an excellent photodynamic therapy efficacy on tumor‐bearing mouse models. This work provides a promising design strategy of photosensitizers with renal clearable and tumor‐targeting ability.
Here, an ultra‐small nano photosensitizer is presented through a facile self‐assembly strategy that can target a disease state, boost reactive oxygen species (ROS) generation, as well as be cleared efficiently from the body in a reasonable amount of time.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
An organic crystal of 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl (pCBP) exhibits time‐dependent afterglow color from blue to orange over 1 s. Both experimental and computational data confirm that the color ...evolution results from well‐separated, long‐persistent thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP) with different but comparable decay rates. TADF is enabled by a small S1–T1 energy gap of 0.7 kcal mol−1. The good separation of TADF and RTP is due to a 11.8 kcal mol−1 difference in the S0 energies of the S1 and T1 structures, indicating that apart from the excited‐state properties, tuning the ground state is also important for luminescence properties. This afterglow color evolution of pCBP allows its applications in anticounterfeiting and data encryption with high security levels.
Organic sunset: A time‐dependent afterglow color in a single‐component organic molecular crystal was observed. It originates from well‐separated, long‐persistent thermally activated delayed fluorescence and room‐temperature phosphorescence with different but comparable decay rates.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Without external chiral intervention, it is a challenge to form homochirality from achiral molecules with conformational flexibility. We here report on a rational strategy that uses multivalent ...noncovalent interactions to clamp the molecular conformations of achiral D‐A molecules. These interactions overcome the otherwise dominant dipole‐dipole interactions and thus disfavor their symmetric antiparallel stacking. It in turn facilitates parallel packing, leading to spontaneous symmetry breaking during crystallization and thus the formation of homochiral conglomerates. When this emergent homochirality is coupled with optical gain characteristics of the molecules, the homochiral crystals are explored as excellent circularly polarized micro‐lasers with low lasing threshold (16.4 μJ cm−2) and high dissymmetry factor glum (0.9). This study therefore provides a facile design strategy for supramolecular chiral materials and active laser ones without the necessity of intrinsic chiral element.
We report on a rational strategy to clamp the molecular conformation and facilitate parallel packing of achiral D‐A molecules. This leads to spontaneous symmetry breaking during crystallization. When this emergent homochirality is coupled with the optical gain of the molecules, the homochiral crystals can be explored as excellent circularly polarized micro‐lasers with low lasing threshold (16.4 μJ cm−2) and high dissymmetry factor glum (0.9).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Simple thiol derivatives, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), play key roles in biological processes, and the fluorescent probes to detect such thiols
in vivo
...selectively with high sensitivity and fast response times are critical for understanding their numerous functions. However, the similar structures and reactivities of these thiols pose considerable challenges to the development of such probes. This review focuses on various strategies for the design of fluorescent probes for the selective detection of biothiols. We classify the fluorescent probes for discrimination among biothiols according to reaction types between the probes and thiols such as cyclization with aldehydes, conjugate addition-cyclization with acrylates, native chemical ligation, and aromatic substitution-rearrangement.
This review focuses on various strategies for the design of fluorescent probes for selective detection of biothiols, which are classified according to the unique reaction types between probes and thiols, such as cyclization with aldehydes, conjugate addition-cyclization with acrylates, native chemical ligation, and aromatic substitution-rearrangement.
The highly oxygen-dependent nature of photodynamic therapy (PDT) limits its therapeutic efficacy against hypoxic solid tumors in clinics, which is an urgent problem to be solved. Herein, we develop ...an oxygen-independent supramolecular photodynamic agent that produces hydroxyl radical (•OH) by oxidizing water in the presence of intracellularly abundant pyruvic acid under oxygen-free conditions. A fluorene-substituted BODIPY was designed as the electron donor and coassembled with perylene diimide as the electron acceptor to form the quadruple hydrogen-bonded supramolecular photodynamic agent. Detailed mechanism studies reveal that intermolecular electron transfer and charge separation upon light irradiation result in an efficient generation of radical ion pairs. Under oxygen-free conditions, the cationic radicals directly oxidize water to generate highly cytotoxic •OH, and the anionic radicals transfer electrons to pyruvic acid, realizing the catalytic cycle. Thus, this photodynamic agent exhibited superb photocytotoxicity even under severe hypoxic environments and excellent in vivo antitumor efficacy on HeLa-bearing mouse models. This work provides a strategy for constructing oxygen-independent photodynamic agents, which opens up an avenue for effective PDT against hypoxic tumors.
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Pure organic room temperature phosphorescence (RTP) is highly preferable because of its long lifetime and potential applications. However, these kinds of materials are still very scarce due to the ...weak spin–orbit coupling between singlet and triplet states and easily nonradiative decay of the excited states. Achieving room temperature phosphorescence under visible light excitation is particularly challenging in aqueous solution. Herein, a micelle‐assisted assembling strategy has been developed to realize pure organic RTP in water by using donor–acceptor molecules. A visible‐light responsive long‐lived RTP in water with a lifetime more than 3 ms is obtained by the prepared nanocrystals. However, the same molecules show no RTP as rigid bulk crystals. Spectroscopic studies, single‐crystal structure analysis, X‐ray diffraction patterns, and density functional theory calculations reveal that the intermolecular interactions, heavy atom effect, and the molecular packing way play critical role to the long‐lived RTP character for the assembled nanocrystals in water and thermally activated delayed fluorescence for crystals in solid.
A micelle‐assisted assembly strategy to realize long‐lived pure organic room temperature phosphorescence under visible light excitation in water is reported. The molecular packing plays a critical role to the room temperature phosphorescence character in the assembled nanocrystals and delayed fluorescence in the crystals.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Pure organic room temperature phosphorescence (RTP) has unique advantages and various potential applications. However, it is challengeable to achieve organic RTP under visible and near-infrared ...(NIR)-light excitation, especially in aqueous solution. Herein we assemble difluoroboron β-diketonate compounds to form organic nanoparticles (NPs) in water. The resulting NPs are able to show efficient RTP, effective uptake, and bright imaging of HeLa cells under both visible- and NIR-light excitation. More strikingly, spectroscopic study, single-crystal X-ray diffraction, and DFT calculation reveal that the efficient RTP in organic NPs is originated from dimers in their excited states. The multiple interactions and intermolecular charge transfer in the dimer structures are of significance in promoting the production of dimer triplet excited states and suppressing the nonradiative decays to boost the RTP under visible- and NIR-light irradiation in water.
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