A Solvent-Mediated Excited-State Intermolecular Proton Transfer Fluorescent Probe for Fe3+ Sensing and Cell Imaging

Constructing excited-state intermolecular proton transfer (ESIPT-e) fluorophores represents significant challenges due to the harsh requirement of bearing a proton donor-acceptor (D-A) system and their matching proton donating-accepting ability in the same molecule. Herein, we synthesized a new-type ESIPT-e fluorophor (2-APC) using the “four-component one-pot” reaction. By the installing of a cyano-group on pyridine scaffold, the proton donating ability of -NH2 was greatly enhanced, enabling 2-APC to undergo ESIPT-e process. Surprisingly, 2-APC exhibited dual-emissions in protic solvents ethanol and normal fluorescence in aprotic solvents, which is vastly different from that of conventional ESIPT-a dyes. The ESIPT emission can be obviously suppressed by Fe3+ due to the coordination reaction of Fe3+ with the A-D system in 2-APC. From this basis, a highly sensitive and selective method was established using 2-APC as a fluorescent probe, which offers the sensitive detection of Fe3+ ranging from 0 to 13 μM with the detection limit of 7.5 nM. The recovery study of spiked Fe3+ measured by the probe showed satisfactory results (97.2103.4%) with the reasonable RSD ranging from 3.1 to 3.8%. Moreover, 2-APC can also exhibit aggregation-induced effect in poor solvent or solid-state, eliciting strong red fluorescence. 2-APC was also applied to cell-imaging, exhibiting good cell-permeability, biocompatibility and color rendering. This multi-mode emission of 2-APC is significant departure from that of conventional extended p-conjugated systems and ESIPT dyes based on a flat and rigid molecular design. The “one-pot synthesis” strategy for the construction of ESIPT molecules pioneered a new route to achieve tricolor-emissive fluorophores.

An Unexpected Dual-Emissive Luminogen: Tunable Aggregation-Induced Emission with Cyan-White-Red Colors, Stable Inherent Chirality, and Enhanced Chiroptical Property

Herein we report a novel chiral bismacrocycle with unexpected dual emission and tunable aggregation-induced emission colors. A facile four-step synthesis strategy is developed to construct this rigid bismacrocycle, (1,4)[8]cycloparaphenylenophane (SCPP[8]), which possesses a 1,2,4,5-tetraphenylbenzene core locked by two intersecting polyphenylene-based macrocycles. The luminescent behavior of SCPP[8] shows the unique characteristics of both aggregation-caused quenching effect and aggrega-tion-induced emission (AIE) effect, inducing remarkable redshift emission including near white-light emission. SCPP[8] is configurationally stable and possesses a novel shape-persistent bismacrocycle scaffold with a high strain energy (up to 127.83 kcal/mol). In addition, SCPP[8] displays enhanced circularly polarized luminescence properties due to AIE effect.

Novel CuBr-assisted graphdiyne synthesis strategy and application for efficient photocatalytic hydrogen evolution

As a new allotrope of carbon, graphdiyne (GDY) also shows great potential in photocatalysis based on the characteristics of narrow bandgap and high electron-hole mobility. This work synthesized the GDY-CuBr...

Bottom-up Synthesis Strategy of a Two-dimensional {Fe5} Cluster-Based Coordination Polymer: Stepwise Formation of {Fe5} Cluster and Its Dimension Augmentation

Sophisticated aggregation assembly is challenging in assembly chemistry. Monitoring the assembly process helps to understand the assembly mechanism and the create new building blocks. A two-dimensional (2D) cluster-based coordination polymer...

A Novel 3D Hierarchical Plasmonic Functional Cu@Co3O4@Ag Array as Intelligent SERS Sensing Platform with Trace Droplet Rapid Detection Ability for Pesticide Residue Detection on Fruits and Vegetables

Rapid and effective detection of pesticide residues from complex surfaces of fruits and vegetables has important significance. Herein, we report a novel three-dimensional (3D) hierarchical porous functional surface-enhanced Raman scattering (SERS) substrate, which is fabricated by successive two-step hydrothermal synthesis strategy of silver nanoparticles (Ag NPs) and cobalt oxide nanowires (Co3O4 NWs) on the 3D copper foam framework as Cu@Co3O4@Ag-H. The strategy offers a new avenue for localized plasmonic materials distribution and construction, which exhibits better morphology regulation ability and SERS activity (or hotspots engineering) than physical spurring obtained Cu@Co3O4@Ag-S. The developed Cu@Co3O4@Ag-H possesses large surface area and rich hotspots, which contributes to the excellent SERS performance, including homogeneity (RSD of 7.8%), sensitivity (enhancement factor, EF of 2.24 × 108) and stability. The Cu@Co3O4@Ag-H not only provides plenty of Electromagnetic enhancement (EM) hotspots but also the trace detection capability for droplet rapid sensing within 2 s. Cu@Co3O4@Ag-H substrate is further developed as an effective SERS sensing platform for pesticide residues detection on the surfaces of fruits and vegetables with excellent LOD of 0.1 ppm, which is lower than the most similar reported works. This work offers new potential for bioassay, disease POCT diagnosis, national security, wearable flexible devices, energy storage and other related fields.

Novel Metallochromic Hydrazone-Based Chemosensor Toward Colorimetric Paper Strip For Selective Detection Cu2+

A solid-state sensor was developed for the determination of copper ions (Cu2+) in aqueous media using tricyanofuranhydrazone as a spectroscopic probe and a paper sheet as the hosting strip. A new tricyanofuranhydrazone-based colorimetric chemosensor (TCFH) was synthesized for selective detection of Cu2+ in aqueous environments. The synthesis strategy of TCFH involved an azo-coupling process between the diazonium salt of 8-aminoquinoline and an active methyl-bearing tricyanofuran (TCF) heterocyclic moiety. The molecular structure of the prepared TCFH chemical sensor was verified with FT-IR, 1H and 13C NMR, as well as elemental analysis. Due to intramolecular charge transfer, TCFH chromophore demonstrated pronounced solvatochromism depending on the solvent polarity. Changes in both color and UV-vis absorption spectra demonstrated by the developed chemosensor proved that TCFH can be utilized to detect Cu2+ in the presence of other competing metallic cations and anions. The synthesized TCFH probe, which contains a hydrazone recognition moiety, demonstrates dramatic solvatochromic activity and high selectivity at the microlevel of copper ions with a color shift from yellow to purple. Mechanisms accounting for both metallochromic and solvatochromic activities were explored. Moreover, test strips of TCFH were successfully developed and applied for the detection of copper ions at different concentrations in aqueous media. The colorimetric properties of the prepared TCFH-immobilized paper strips were investigated by CIE Lab chromogenic parameters, colorimetric strength (K/S) and UV-Vis absorbance spectra. The metallochromic paper strip exhibited a detection limit at the ppm range. The best detection of Cu2+ was achieved in the pH range of 6.6-7.4 demonstrating an immediate color switch from yellow to purple relying on the total content of Cu2+. Scanning electron microscopy (SEM) was applied to characterize the deposition of tricyanofuranhydrazone onto the surface of the paper strip.