The instability of the signal intensity of fluorescent biosensors and the false signals have been significant factors affecting the performance of biosensors. Herein, a novel signaling system is devised through the application of reversible addition-fragmentation chain transfer (RAFT) polymerization with monomers containing the tetraphenylethylene (TPE) groups. TPE exhibits an aggregation-induced emission (AIE) phenomenon in certain solvents, mainly due to the blockage of the rotation of its four benzene rings, which also exist in the aggregated state.
View Article and Find Full Text PDFBackground: Thrombin, a coagulation system protease, is a key enzyme involved in the coagulation cascade and has been developed as a marker for coagulation disorders. However, the methods developed in recent years have the disadvantages of complex operation, long reaction time, low specificity and sensitivity. Meanwhile, thrombin is at a lower level in the pre-disease period.
View Article and Find Full Text PDFDesigning and synthesizing well-defined crystalline catalysts for the photocatalytic oxidative coupling of amines to imines remains a great challenge. In this work, a crystalline dumbbell-shaped titanium oxo cluster, [TiO(Thdc)(Dmg)(PrO)] (Ti10, Thdc = 2,5-thiophenedicarboxylic acid, Dmg = dimethylglyoxime, PrOH = isopropanol), was constructed through a facile one-pot solvothermal strategy and treated as a catalyst for the photocatalytic oxidative coupling of amines. In this structure, Thdc serves as the horizontal bar, while the {TiDmg} layers on each side act as the weight plates.
View Article and Find Full Text PDFThe development of a convenient and efficient assay using miRNA-21 as a lung cancer marker is of great importance for the early prevention of cancer. Herein, an electrochemical biosensor for the detection of miRNA-21 was successfully fabricated under blue light excitation using click chemistry and photocatalytic atom transfer radical polymerization (photo-ATRP). By using hairpin DNA as a recognition probe, the electrochemical sensor deposits numerous electroactive monomers (ferrocenylmethyl methacrylate) on the electrode surface under the reaction of photocatalyst (fluorescein) and pentamethyldiethylenetriamine, thereby achieving signal amplification.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
December 2023
A solvent-directed, new Schiff base multiple correspondence fluorescent probe, (E)-2-(2-hydroxybenzylidene) hydrazine-1-carboxamid (L), was synthesized for selective sensing of Cu and Mg ions. L showed excellent selectivity and high sensitivity toward Cu in "turn off" mode with a detection limit of 40.5 nM in 10 mM, pH = 7.
View Article and Find Full Text PDFA green electrochemical biosensor was developed based on metal-organic framework (MOF)-catalyzed atom transfer radical polymerization (ATRP) for quantifying miRNA-21, used as the proof-of-concept analyte. Unlike conventional ATRP, Mn-PCN-222 (PCN, porous coordination network) could be used as an alternative for green catalyst to substitute traditional catalysts. First, poly (diallyldimethylammonium chloride) (PDDA) was fixed on the surface of the indium tin oxide (ITO) electrode, and then the Mn-PCN-222 was linked to ITO electrode via electrostatic binding with PDDA.
View Article and Find Full Text PDFCobalt-mediated radical polymerization is noted for its great level of control over the polymerization of acrylic and vinyl esters monomers, even at high molar mass. Vitamin B, a natural bionic enzyme cobalt complex, involves the conversion of organic halides to olefins through chain-growth polymerization. In this work, the notion of R-Co(III) free radical persistent free radical effect and vitamin B circulation were first reported for the perception of ultralow abundance of microRNA-21, a lung cancer biomarker.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
May 2023
It is of great significance to sensitively and selectively detect uranyl ion (UO) in environmental and biological samples due to the high risks of UO to human health. However, such suitable sensors are still scarce. A novel fluorescence sensor based on a dansyl-modified peptide, Dansyl-Glu-Glu-Pro-Glu-Trp-COOH (D-P5), was efficiently synthesized by Fmoc solid phase peptide synthesis.
View Article and Find Full Text PDFAccurate quantitative detection of tracing nucleic acids remains a great challenge in cancer genetic testing. It is crucial to propose a low-cost and highly sensitive direct gene detection method for cancer prevention and treatment. Herein, this work reports an ultrasensitive biosensor via a ferritin-enhanced atom-transfer radical polymerization (Ft-ATRP) process.
View Article and Find Full Text PDFArsenic is a toxic non-metallic element that is widely found in nature. In addition, arsenic and arsenic compounds are included in the list of Group I carcinogens and toxic water pollutants. Therefore, rapid and efficient methods for detecting arsenic are necessary.
View Article and Find Full Text PDFA double mutant of human H64M/V71C neuroglobin (Ngb) was engineered, which formed a single thioether bond as that in atypical cytochrome c, whereas the heme distal Met64 was oxidized to both sulfoxide (SO-Met) and sulfone (SO -Met). By contrast, no Cys-heme cross-link was formed in V71C Ngb with His64/His96 coordination, as shown by the X-ray crystal structure, which indicates that an open distal site facilitates the activation of heme iron for structural modifications.
View Article and Find Full Text PDFThe use of hemoglobin (Hb) to drive atom transfer radical polymerization (ATRP) process (Hb-ATRP) for detection of lung cancer related nucleic acid is firstly reported. Hb does not need to be treated prior to using indicating the potential for synthetic engineering in complex biological microenvironments without the need for in vitro techniques. Here, we report a new signal amplification strategy using Hb-mediated graft of nitronyl niroxide monoradical polymers as a signal-on electrochemical biosensor for ultralow level DNA highly selective detection.
View Article and Find Full Text PDFHuman cytochrome (Cyt ) is a crucial heme protein and plays an indispensable role in energy conversion and intrinsic apoptosis pathways. The sequence and structure of Cyt were evolutionarily conserved and only a few naturally occurring mutants were detected in humans. Among those variable sites, position 81 was proposed to act as a peroxidase switch in the initiation stages of apoptosis.
View Article and Find Full Text PDFHuman neuroglobin (Ngb) contains a heme group and three Cys residues (Cys46, Cys55, and Cys120) in the polypeptide chain. By introducing an additional Cys at position 15, the X-ray structure of A15C Ngb mutant was solved at a high resolution of 1.35 Å, which reveals the formation of both the native (C46C55) and the engineered (C15C120) disulfide bonds, likely playing a functional and structural role, respectively, according to the geometry analysis.
View Article and Find Full Text PDFUltrasensitive detection of biomarkers at an early stage is generally limited by external influence factors such as high reaction temperature, complex operations, and sophisticated instruments. Here, we circumvent these problems by using nicotinamide adenine dinucleotide (NAD) to control electroinitiated reversible addition fragmentation chain transfer (electro-RAFT) polymerization for biosensing that enables the detection of a few molecules of target DNA. In this coenzyme-catalyzed electro-RAFT polymerization, numerous ferrocenylmethyl methacrylate (FCMMA) as monomer with electrochemistry signal were linked to the biomarker on Au electrode.
View Article and Find Full Text PDFThe detection of trace tumor-related serum miRNA biomarkers is in great demand for the early diagnosis of cancer. Herein, for the first time, an electrochemical sensing platform based on atom transfer radical polymerization (ATRP) signal amplification strategy for ultrasensitive determination of the breast and prostate cancer marker miRNA-141 has been developed. The hairpin DNAs were immobilized on the benzoic acid modified electrode to capture the target miRNA-141, the recognition of miRNA-141 released thiol groups on the end of probes, followed by the association of ATRP initiators modified gold nanoparticles with thiol groups, and then triggered the polymerization on electrode surface, causing a great number of ferrocene (Fc) signal molecules grafted on the sensor interface.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
November 2021
Developing new chemosensors for detection of Zn has attracted great attentions because of the important roles of Zn in biological systems, and it will produce toxic effects with an excessive intake of zinc ion. Metalloproteins are often used as an effective template for the design and development of peptide-based fluorescent sensors. In this study, we designed a new and simple ratiometric fluorescent sensor for Zn, which was based on a zinc finger-like peptide and labeled with a dansyl group, i.
View Article and Find Full Text PDFProtein design has received much attention in the last decades. With an additional disulfide bond to enhance the protein stability, human A15C neuroglobin (Ngb) is an ideal protein scaffold for heme enzyme design. In this study, we rationally converted A15C Ngb into a multifunctional peroxidase by replacing the heme axial His64 with an Asp residue, where Asp64 and the native Lys67 at the heme distal site were proposed to act as an acid-base catalytic couple for HO activation.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
April 2021
Mercury is an environmental contaminant, which is highly toxic even at extremely low concentrations. Long-term accumulation of mercury in human body will damage the central nervous system or digestive tract system. Here, a new fluorescent chemical sensor Dansyl-His-Pro-Gly-Asp-NH (D-P4) was synthesized for the determination of Hg.
View Article and Find Full Text PDFA fluorescence ratio sensor based on dansyl-peptide, Dansyl-Glu-Cys-Glu-Glu-Trp-NH (D-P5), was efficiently synthesized by Fmoc solid phase peptide synthesis. The sensor exhibits high selectivity and sensitivity for Ag over 16 metal ions in 100 mM sodium perchlorate and 50 mM 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid buffer solution by fluorescence resonance energy transfer. The 1:1 binding stoichiometry of the sensor and Ag is measured by fluorescence ratio response and the job's plot.
View Article and Find Full Text PDFBioinorg Chem Appl
September 2020
Three hexacoordinated octahedral nickel (II) complexes, [Ni (Trp-sal) (phen) (CHOH)] (1), [Ni (Trp--van) (phen) (CHOH)]•2CHOH (2), and [Ni (Trp-naph) (phen) (CHOH)] (3) (where Trp-sal = Schiff base derived from tryptophan and salicylaldehyde, Trp--van = Schiff base derived from tryptophan and -vanillin, Trp-naph = Schiff base derived from tryptophan and 2-hydroxy-1-naphthaldehyde, phen = 1, 10-phenanthroline), have been synthesized and characterized as potential anticancer agents. Details of structural study of these complexes using single-crystal X-ray crystallography showed that distorted octahedral environment around nickel (II) ion has been satisfied by three nitrogen atoms and three oxygen atoms. All these complexes displayed moderate cytotoxicity toward esophageal cancer cell line Eca-109 with the IC values of 23.
View Article and Find Full Text PDFA mononuclear nickel(II) complex, [Ni(-van-tris)]·2HO (-van-tris = Schiff base derived from -vanillin and tris(hydroxymethyl)aminomethane), has been synthesized and structurally characterized. The single crystal structure shows a distorted octahedron geometry coordinated with Ni(II) atom, and 2 D plane structure has formed by O-H···O hydrogen bond interactions. An analysis to ascertain intermolecular interactions of the complex was performed based on the Hirshfeld surfaces and their associated two-dimensional fingerprint plots.
View Article and Find Full Text PDFMultidrug resistance (MDR) is a major obstacle for successful cancer chemotherapy, and the main cause of MDR has been attributed to overexpression of P-glycoprotein (P-gp). In this present study, four P-gp modulators (,)-4,6-bis(styryl)-2-(substituted amino)-pyrimidines were evaluated for their activity in a breast cancer cell line overexpressing P-gp (LCC6MDR). The four modulators displayed significantly better P-gp modulating activity compared with the positive control verapamil (RF = 5.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
April 2020
Dibutyl phthalate has been illegally used in beverages and directly affects the human health. Herein, the interaction occurred between dibutyl phthalate and bovine serum albumin was studied. The experimental results demonstrated that dibutyl phthalate could bind to bovine serum albumin and statically quench the intrinsic fluorescence of this protein.
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