A highly selective turn-on fluorescence probe with large Stokes shift for detection of palladium and its applications in environment water and living cells.

Nowadays, palladium has been widely used in many fields, which facilitates all aspects of our life. However, it may cause water and soil pollution and bring irreversible damage to the environment and organisms. Developing a fluorescence probe for rapid, highly sensitive and selective detection of palladium is still a poser. In this work, we designed and synthesized a novel fluorescence probe (RHS) for specific detection of palladium. Based on Pd0-mediated Tsuji-Trost reaction, the fluorescence probe was constructed by a rhodol derivative as thefluorophore and an allyl carbonate moiety as the specific palladium reactive site. The probe displayed excellent properties for detecting palladium, such as high selectivity and sensitivity, rapid response (20 min) and large Stokes shift (155 nm). The detection limit was determined to be as low as 0.140 µM with a linear range from 20 to 80 µM. After addition of palladium in RHS solution, the color of the solution turned from yellow to blue, indicating palladium could be monitored by the naked eyes. Moreover, probe RHS was successfully applied to palladium detection in environmental water samples. Importantly, with low cytotoxicity and good biocompatibility, the probe could monitor palladium in living cells.

A near-infrared fluorescence turn-on probe based on Michael addition-intramolecular cyclization for specific detection of cysteine and its applications in environmental water and milk samples and living cells.

Owing to its important biological functions in many physiological and pathological processes, it is necessary to develop efficient and appropriate detection methods for monitoring the levels of Cys in biological systems. Based on this, a novel rhodol-isophorone derivative (RHI) was designed and synthesized as a reaction-based fluorescence probe for specific detection of Cys with high sensitivity and large Stokes shift (155 nm). This probe was composed of an acrylate moiety (recognition group) and a rhodol-isophorone derivative (fluorophore). Probe RHI could react with Cys rapidly (15 min) with a 100-fold fluorescence enhancement. The limit of detection value was calculated to be 0.168 µM. When Cys was added, the color of the probe RHI solution turned from yellow to blue, indicating that Cys could be monitored by the naked eye. In addition, probe RHI was successfully utilized for detecting Cys in environmental water and milk samples. More importantly, the probe could be applied to imaging Cys in living cells with low cytotoxicity and good biocompatibility.

Electrochemiluminescence-Repurposed Abiological Catalysts in Full Protein Tag for Ultrasensitive Immunoassay.

Being announced as one of the "2019 Top Ten Emerging Technologies in Chemistry" by IUPAC, the directed evolution of artificial metalloenzymes has led to a broad scope of abiotic processes. Here, inspired by those key proteins in bioluminescence, a rudimentary expression of bio-electrochemiluminescent (ECL) macromolecules was achieved via the complexation of zinc proto-porphyrin IX (ZnPPIX) within apo-hemoglobin (apo-Hb). A high-yield monochromic irradiation at 644 nm could be provoked potentiostatically from the reconstituted holo-HbZnPPIX in solutions. Its secondary structure integrity was elucidated by UV and circular dichroism spectrometry, while voltammetry-hyphenated surface plasmon resonance authenticated its ligation conservativeness in electrical fields. Further conjugation with streptavidin rendered a homogeneous Janus fusion of both receptor and reporter domains, enabling a new abiological catalyst-linked ECL bioassay. On the other hand, singular ZnPPIX inside each tetrameric subunit of Hb accomplished an overall signal amplification without the bother of luminogenic heterojunctions. This pH-tolerant and non-photobleaching optics was essentialized to be the unique configuration interaction between Zn and O2, by which the direct electrochemistry of proteins catalyzed the transient progression of O2 → O2·- → O2* + hυ selectively. Such principle was implemented as a signal-on strategy for the determination of a characteristic cancer biomarker, the vascular endothelial growth factor, resulting in competent performance at a low detection limit of 0.6 pg·mL-1 and a wide calibration range along with good stability and reliability in real practices. This simple mutation repurposed the O2-transport Hb in the erythrocytes of almost all vertebrates into a cluster of oxidoreductases with intrinsic ECL activity, which would enrich the chromophore library. More importantly, its genetically engineered variants may come in handy in biomedical diagnosis and visual electrophysiology.