Constructing Dual-State Emissive Fluorophores via Boc Protection and Discovering a High-Fidelity Imaging Probe for Lipid Droplets.

Dual-state emissive (DSE) materials exhibit fluorescence in both solid and solution states and have become an emerging material in the fields of materials science and sensing in recent years. However, due to the lack of effective and universal preparation methods, DSE materials, especially those with long emission wavelengths, are still scarce. Developing an effective method for constructing such DSE molecules is urgently needed. In this study, we constructed three DSE molecules (NRP-Boc, DCIP-Boc, and DCMP-Boc) with far-red to near-infrared fluorescence by simply modifying three traditional aggregation-caused quenching (ACQ) fluorophores with tert-butyloxycarbonyl (Boc) groups. Density functional theory (DFT) calculations and crystal data revealed the reasons for the bright fluorescence of these three molecules in solution and solid, demonstrating that this Boc protection method is a simple and effective strategy for constructing DSE molecules. We also found that these three DSE molecules have the potential to target and visualize lipid droplets (LDs). Among them, DCIP-Boc shows advantages of a large Stokes shift, long emission wavelength, low fluorescence background, and good photostability in cells, providing a powerful new molecular tool with DSE property for high-fidelity imaging of LDs.

Methanol as an anti-solvent to improve the low open-circuit voltage of CsPbBr3 perovskite solar cells prepared with water.

CsPbBr3 has received more and more attention in the field of optoelectronic devices due to its excellent stability. To address the cost and environmental concerns associated with the use of toxic methanol, water has been explored as a substitute solvent for CsBr in the preparation of CsPbBr3 perovskite solar cells (PSCs). In this study, we utilized methanol as an anti-solvent of the CsBr/H2O solution to regulate the detrimental effects of water on the CsPbBr3 film and control the crystallization process. From results of the experiment, it was found that methanol anti-solvent treatment greatly improved the crystallization of the CsPbBr3 film, increased the grain size, and reduced the defect density. After the introduction of methanol anti-solvent treatment, the power conversion efficiency (PCE) increased from 6.09% to 7.91%, while the open-circuit voltage (Voc) increased from 1.18 V to 1.39 V. Furthermore, we incorporated 2-hydroxyethylurea into the CsPbBr3 PSCs to improve the wettability of PbBr2 towards the CsBr/H2O solution and ensure the formation of pure-phase CsPbBr3 films. The introduction of 2-hydroxyethylurea resulted in an additional increase in Voc from 1.19 V to 1.42 V. The PCE further improved from 6.56% to 8.62% after methanol anti-solvent treatment. These results demonstrate that methanol treatment effectively addresses the low Voc issue observed in CsPbBr3 PSCs prepared with water as a solvent. Importantly, this approach significantly reduces the reliance on methanol compared to conventional fabrication methods for CsPbBr3 PSCs. Overall, this work presents a promising pathway for achieving high Voc and efficiency in CsPbBr3 PSCs by utilizing water as a solvent.

A Pd2+-Free Near-Infrared Fluorescent Probe Based on Allyl Ether Isomerization for Tracking CORM-3 with High Contrast Imaging in Living Systems.

As a CO donor, CORM-3 is widely used nowadays to study the role of CO as a gasotransmitter and potential drug in biological systems. Developing methods to detect CORM-3 in live systems will contribute to these studies. Herein, we developed a novel Pd2+-free near-infrared fluorescent probe CORM3-AE for detecting CORM-3 both in live cells and in vivo. We found that the allyl ether group in CORM3-AE could be cleaved by CORM-3 directly via an isomerization process to release the NIR fluorophore QCy7 and cause distinct NIR fluorescence changes. Importantly, CORM3-AE responds quickly and shows high sensitivity and selectivity for CORM-3 with NIR fluorescence turn-on changes at 743 nm (λex = 662 nm), and when the excitation wavelength is 450 nm, CORM3-AE can respond to CORM-3 with ratiometric fluorescence signals at 743/605 nm. Moreover, CORM3-AE can track CORM-3 in live cells and animals with excellent imaging performance. Thus, this work not only provides a powerful new tool for CORM-3 detection in live systems but also provides a new method to construct CORM-3 probes by allyl ether isomerization.

Two Water-Soluble and Wash-Free Fluorogenic Probes for Specific Lighting Up Cancer Cell Membranes and Tumors.

The construction of microenvironment-sensitive probes with good cell membrane-targetability can reveal the fundamental properties of cell membranes. Herein, two polarity-sensitive probes, termed MEMs were reported for the first time to specifically light up cancer cell membranes. Both probes were designed with tetrahydroquinoxaline coumarin amide as the fluorophore, and quaternary ammonium groups were appended to increase water solubility and target cell membranes. In vitro studies showed that the fluorescence of both probes displayed strong polarity dependence and had a wide linear range to polarity (Δf). MEMs also displayed excellent cell membrane targeting ability and could long-term light up cell membranes with red fluorescence and a wash-free process. More excitingly, MEMs could specifically light up cancer cell membranes, revealing that cancer cells might have lower cell membrane polarity than normal cells. In vivo studies showed that MEMs could also effectively distinguish tumors from normal tissues. Overall, this work has not only developed two polarity-sensitive probes with good cell membrane targetability, but also provided new insights and methods for an in-depth understanding of cancer cells and cancer diagnosis.