Polymer Dots of Peryleneimide‐Functionalized Polyethyleneimine: Facile Synthesis and Effective Fluorescent Sensing of Iron (III) Ions

A simple and low‐cost method is reported here for synthesizing polymer dots (PDs) using branched polyethyleneimine and peryleneimide derivatives as precursors heated in dimethylacetamide. The as‐prepared PDs can be well‐dispersed in water and show excitation‐dependent fluorescence, stable fluorescence over a wide range (pH = 5.0 – 9.0), and high photostability. It is demonstrated that the prepared PDs can be used as a novel fluorescent sensing platform for sensitive and selective detection of Fe (III) ions. The fluorescent PDs may be applied to promising applications in chemical sensors for metal ions, as well as biological imaging or biological labeling for their excellent fluorescence properties.

     

Carbon Dots Prepared by Hydrothermal Treatment of Dopamine as an Effective Fluorescent Sensing Platform for the Label‐Free Detection of Iron(III) Ions and Dopamine

A facile, economic and green one‐step hydrothermal synthesis route using dopamine as source towards photoluminescent carbon nanoparticles (CNPs) is proposed. The as‐prepared CNPs have an average size about 3.8 nm. The emission spectra of the CNPs are broad, ranging from approximately 380 (purple) to approximately 525 nm (green), depending on the excitation wavelengths. Due to the favorable optical properties, the CNPs can readily enter into A549 cells and has been used for multicolor biolabeling and bioimaging. Most importantly, the as‐prepared CNPs contain distinctive catechol groups on their surfaces. Due to the special response of catechol groups to Fe³⁺ ions, we further demonstrate that such wholly new CNPs can serve as a very effective fluorescent sensing platform for label‐free sensitive and selective detection of Fe³⁺ ions and dopamine with a detection limit as low as 0.32 μM and 68 nM , respectively. The new “mix‐and‐detect” strategy is simple, green, and exhibits high sensitivity and selectivity. The present method was also applied to the determination of Fe³⁺ ions in real water samples and dopamine in human urine and serum samples successfully.     

基于银纳米粒子构建荧光传感平台用于核酸检测

报道了基于银纳米粒子构建的荧光传感平台,并用于核酸检测.此荧光传感平台对核酸检测基于以下策略:首先,荧光团标记的单链DNA探针被吸附到银纳米粒子的表面,荧光团与银纳米粒子近距离接触,发生荧光猝灭;加入与探针DNA序列互补的目标DNA,两者杂交形成双链DNA,并从银纳米粒子的表面脱离,荧光得到恢复.这种银纳米粒子构建的荧...     

A Water-Stable Lanthanide Coordination Polymer as Multicenter Platform for Ratiometric Luminescent Sensing Antibiotics

As a hot topic of global concern, the distinguishing and detecting of antibiotic pollution is crucial owing to its adverse effect on ecosystems and human health stemming from excessive use and poor management. Herein, a water-stable lanthanide coordination polymer sensor (Dy-TCPB) with multiple emitting centers is prepared. The versatile Dy-TCPB can conveniently differentiate various antibiotics, and displays a self-calibration luminescent response to nitrofurazone (NFZ) and furazolidone (FZD). Each antibiotic exhibits notable correlation to a unique combination of the two ligand-to-Dy ion emission intensity ratios, enabling two-dimensional fingerprint recognition. Furthermore, the novel self-calibration sensor demonstrates effective recognition of NFZ and FZD with excellent sensitivity and selectivity, and detection limits as low as 0.0476 and 0.0482 μm for NFZ and FZD, respectively. The synthetic approach for the fabrication of a singular coordination polymer exhibiting multiple emissions provides a promising strategy for the development of facile and effective ratiometric sensors.     

Toward Fluorescence‐Based High‐Throughput Screening for Enantiomeric Excess in Amines and Amino Acid Derivatives

A highly accurate and reliable screening method for enantiomeric excess of amine derivatives in the presence of water is reported. The fluorescence‐based screening system has been realized by self‐assembly of chiral diol‐type dyes (BINOL, VANOL and VAPOL), 2‐formylphenylboronic acid, and chiral amines forming iminoboronate esters. The structure and chirality of the amine analytes determine the stability of the diastereomeric iminoboronate esters, which in turn display differential fluorescence. The fluorescence signal reflects the enantiomeric purity of the chiral amines and was utilized in high‐throughput arrays. The arrays were able to recognize enantiomeric excess of amines, amino esters, and amino alcohols. In addition to qualitative analysis, quantitative experiments were successfully performed. Studies of the role of additives such as water or citrate were carried out to gain insight into the stability of the iminoboronate esters. It is shown that the above additives destabilize less stable esters while the stable esters remain unchanged. Thus, the presence of water and citrate leads to increased difference between the diastereomeric iminoboronates and contributes to the enantiodiscrimination of the chiral amines.     

Highly Luminescent N‐Doped Carbon Quantum Dots as an Effective Multifunctional Fluorescence Sensing Platform

The doping of carbon quantum dots with nitrogen provides a promising direction to improve fluorescence performance and broaden their applications in sensing systems. Herein we report a one‐pot solvothermal synthesis of N‐doped carbon quantum dots (NCQDs) and the synthesis of a series of NCQDs with different nitrogen contents. The as‐prepared NCQDs were compared with carbon quantum dots (CQDs); the introduction of nitrogen atoms largely increased the quantum yield of NCQDs and highest emission efficiency is up to 36.3 %. The fluorescence enhancement may originate from more polyaromatic structures induced by incorporated nitrogen atoms and protonation of nitrogen atoms on dots. It was found that NCQDs can act as a multifunctional fluorescence sensing platform because they can be used to detect pH values, Ag^I, and Fe^III in aqueous solution. The fluorescence intensity of NCQDs is inversely proportional to pH values across a broad range from 5.0 to 13.5, which indicates that NCQDs can be devised as an effective pH indicator. Selective detection of Ag^I and Fe^III was achieved based on their distinctive fluorescence influence because Ag^I can significantly enhance the fluorescence whereas Fe^III can greatly quench the fluorescence. The quantitative determination of Ag^I can be accomplished with NCQDs by using the linear relationship between fluorescence intensity of NCQDs and concentration of Ag^I. The sensitive detection of H₂O₂ was developed by taking advantage of the distinct quenching ability of Fe^III and Fe^II toward the fluorescence of NCQDs. Cellular toxicity test showed NCQDs still retain low toxicity to cells despite the introduction of a great deal of nitrogen atoms. Moreover, bioimaging experiments demonstrated that NCQDs have stronger resistance to photobleaching than CQDs and more excellent fluorescence labeling performance.     

Cobalt Ion‐Mediated Cysteine Detection With a Hyperbranched Conjugated Polyelectrolyte as a New Sensing Platform

A highly efficient colorimetric and fluorescence turn‐off probe for the sensitive and selective detection of the biologically important amino acid, cysteine (Cys), is demonstrated using a newly synthesized water‐soluble hyperbranched polymer (HP) containing sulfonic acid groups. The detection mechanism involves two steps: (i) the slight quenching of HP in the presence of Co²⁺ in advance; and (ii) the gradual quenching of the HP–Co²⁺ complex according to the concentration of Cys due to the absorption screening effect of the formation of the Cys‐Co²⁺ complex, which prevents HP from absorbing excitation energy.     

Nucleic Acid Driven DNA Machineries Synthesizing Mg2+‐Dependent DNAzymes: An Interplay between DNA Sensing and Logic‐Gate Operations

Polymerase/nicking enzymes and nucleic‐acid scaffolds are implemented as DNA machines for the development of amplified DNA‐detection schemes, and for the design of logic gates. The analyte nucleic acid target acts, also, as input for the logic gates. In the presence of two DNA targets, acting as inputs, and appropriate DNA scaffolds, the polymerase‐induced replication of the scaffolds, followed by the nicking of the replication products, are activated, leading to the autonomous synthesis of the Mg²⁺‐dependent DNAzyme or the Mg²⁺‐dependent DNAzyme subunits. These biocatalysts cleave a fluorophore/quencher‐functionalized nucleic‐acid substrate, thus providing fluorescence signals for the sensing events or outputs for the logic gates. The systems are used to develop OR, AND, and Controlled‐AND gates, and the DNA‐analyte targets represent two nucleic acid sequences of the smallpox viral genome.     

Fluorene‐based Lanthanide Coordination Polymer: Structure,Luminescence and Sensing of Picric Acid

Luminescent coordination polymers can be potential chemosensors and extensive efforts are being devoted to improve their selectivity and sensitivity. In this work, we report a new kind of fluorene‐based Tb‐CP, Tb₄L₆·7DMF·5H₂O ( Tb ₄ L ₆ , H₂L = 4,4′‐(9,9‐dimethyl‐9H‐fluorene‐2,7‐diyl)dibenzoic acid), showing 2D network and strong blue emission. Meanwhile, Tb ₄ L ₆ exhibits excellent selectivity and sensitivity for picric acid (PA). The quenching constant (K_sv) of Tb ₄ L ₆ is equal to 4.5 × 10⁴ L/mol during the concentration range of 0–30 μmol/L, which approaches the best reported CPs‐based on PA sensor up to now. Moreover, we went into depth on the possible mechanisms of luminescence quenching.     

A Water‐Soluble Conjugated Polymer for Protein Identification and Denaturation Detection

Rapid and sensitive methods to detect proteins and protein denaturation have become increasingly needful in the field of proteomics, medical diagnostics, and biology. In this paper, we have reported the synthesis of a new cationic water‐soluble conjugated polymer that contains fluorene and diene moieties in the backbone ( PFDE ) for protein identification by sensing an array of PFDE solutions in different ionic strengths using the linear discriminant analysis technique (LDA). The PFDE can form complexes with proteins by electrostatic and/or hydrophobic interactions and exhibits different fluorescence response. Three main factors contribute to the fluorescence response of PFDE , namely, the net charge density on the protein surface, the hydrophobic nature of the protein, and the metalloprotein characteristics. The denaturation of proteins can also be detected using PFDE as a fluorescent probe. The interactions between PFDE and proteins were also studied by dynamic light scattering (DLS) and isothermal titration microcalorimetry (ITC) techniques. In contrast to other methods based on conjugated polymers, the synthesis of a series of quencher or dye‐labeled acceptors or protein substrates has been avoided in our method, which significantly reduces the cost and the synthetic complexity. Our method provides promising applications on protein identification and denaturation detection in a simple, fast, and label‐free manner based on non‐specific interaction‐induced perturbation of PFDE fluorescence response.     

Harnessing Effective Molarity to Design an Electrochemical DNA‐based Platform for Clinically Relevant Antibody Detection

Easy‐to‐use platforms for rapid antibody detection are likely to improve molecular diagnostics and immunotherapy monitoring. However, current technologies require multi‐step, time‐consuming procedures that limit their applicability in these fields. Herein, we demonstrate effective molarity‐driven electrochemical DNA‐based detection of target antibodies. We show a highly selective, signal‐on DNA‐based sensor that takes advantage of antibody‐binding‐induced increase of local concentration to detect clinically relevant antibodies in blood serum. The sensing platform is modular, rapid, and versatile and allows the detection of both IgG and IgE antibodies. We also demonstrate the possible use of this strategy for the monitoring of therapeutic monoclonal antibodies in body fluids. Our approach highlights the potential of harnessing effective molarity for the design of electrochemical sensing strategies.     

Fabrication of Gold‐Directed Conducting Polymer Nanoarrays for High‐Performance Gas Sensor

Gold‐directed polypyrrole (PPy) nanoarrays are fabricated by hydrogel‐assisted nanotransfer edge printing (HnTEP) and electrochemical polymerization. Gold nanoarrays are fabricated through the HnTEP method, which involves metal deposition, hydrogel etching, and nanotransfer edge printing. By utilizing the well‐positioned gold nanostructures, PPy nanoarrays with smooth morphology and controllable dimensions are fabricated through in situ electrochemical polymerization, the results of which are characterized by scanning electron microscopy and atomic force microscopy. A gas sensor based on PPy nanoarrays results in excellent sensing capabilities towards NH₃ detection, especially the sensitivity and fast response. This method appears to be general and may aid in the future design and implementation of other active materials which can also be manipulated by the same procedure and serve as functional components for chemical sensing, optoelectronics, biodetection, and other applications.     

Dipyrenylcalix[4]arene—A Fluorescence‐Based Chemosensor for Trinitroaromatic Explosives

A new chemosensor‐based approach to the detection of nitroaromatics is described. It involves the analyte‐induced quenching of excimer emission of a dipyrenyl calix[4]arene ( L ). The chemical and photophysical properties of the complexes formed between L and mono‐, di‐, and trinitrobenzene, and di‐ and trinitrotoluene were studied in acetonitrile and chloroform by using ¹H NMR, UV/Vis, and fluorescence spectroscopy. Fluorescence spectroscopy revealed that the trinitroaromatics engendered the largest response among the various substrates tested, with the sensitivity for these analytes being correspondingly high. Quantitative analysis of the fluorescence titration profile generated from the titration of L with TNT provided evidence that this particular functionalized calix[4]arene receptor allows for the detection of TNT down to the low ppb level in CH₃CN. A single‐crystal X‐ray diffraction analysis revealed that in the solid state the complex L? TNT consists of a supramolecular crystalline polymeric structure, the formation of which appears to be driven by intermolecular π–π interactions between two pyrene units and a TNT molecule held at a distance of 3.2–3.6 Å, as well as by intra‐ and intermolecular hydrogen‐bonds among the amide linkages. Nevertheless, the changes in the ¹H NMR, UV/Vis, and fluorescence spectrum, including sharp color changes, are ascribed to a charge‐transfer interaction arising from complementary π–π overlap between the pyrene subunits and the bound trinitroaromatic substrates. A number of ab initio calculations were also carried out and, considered in concert, they provide further support for the proposed charge‐transfer interactions, particularly in the case of L? TNT.     

Complex‐Formation‐Enhanced Fluorescence Quenching Effect for Efficient Detection of Picric Acid

Amine‐functionalized α‐cyanostilbene derivatives (Z)‐2‐(4‐aminophenyl)‐3‐(4‐butoxyphenyl)acrylonitrile (ABA) and (Z)‐3‐(4‐butoxyphenyl)‐2‐[4‐(butylamino)phenyl]acrylonitrile (BBA) were designed for specific recognition of picric acid (PA), an environmental and biological pollutant. The 1:1 host–guest complexes formed between the chemosensors and PA enhanced fluorescence quenching, thus leading to sensitive and selective detection in aqueous media and the solid phase.     

Saccharide Sensing Based on Saccharide‐Induced Conformational Changes in Fluorescent Boronic Acid Polymers

Summary: A novel fluorometric saccharide detection strategy has been established by utilizing saccharide‐induced conformational changes in copolymers containing boronic acid and fluorescent units. The polymer chain changes its conformation due to an alteration of the charge state induced by binding with saccharides. The conformational changes are conveniently detected by monitoring excimer to monomer intensity ratio in the fluorescence spectra. Thus, the present strategy would be a promising way for the creation of highly selective and sensitive saccharide‐sensing systems.

Saccharide‐induced conformational change in copolymers containing boronic acid units.     

Bio‐Inspired Fabrication of Lotus Leaf Like Membranes as Fluorescent Sensing Materials

A fluorescent organic small molecule, hexaphenylsilole (HPS), has been used as a sensing material, while a HPS/polymethyl methacrylate composite film with a lotus leaf like structure is prepared by a simple electrospin method. The film shows high stability and excellent sensitivity for the metal ions Fe³⁺ and Hg²⁺, respectively. The special surface morphology containing micro‐/nanocomposite structure is attributed to the exhibition of these unusual properties.     

Fabrication and Visualization of Metal‐Ion Patterns on Glass by Dip‐Pen Nanolithography

Fluorescent self‐assembled monolayers (SAMs) are used as dip‐pen nanolithography (DPN) substrates for the fabrication of patterns of Ca²⁺ and Cu²⁺ ions. The driving force for the transfer of these ions from an atomic force microscopy (AFM) tip to the surface is their complexation to organic ligands on the monolayer. By means of fluorescent surfaces, the patterns can be visualized under a fluorescence microscope. We use a custom‐built atomic force fluorescence microscope (AFFM), a combination of atomic force and confocal fluorescence microscopes, to deposit the metal ions onto the sensing SAMs by DPN and to subsequently visualize modulations of fluorescence intensity in a sequential write–read mode.     

Benzothiazole‐Pyimidine‐Based BF2 Complex for Selective Detection of Cysteine

Due to the similar structure and reactivity of cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), the simultaneous discrimination of Cys over Hcy and GSH by a single fluorescent sensor is still a great challenge. In this work, a benzothiazole‐pyimidine‐based boron difluoride complex ( BPB ) was developed as a new fluorescent sensor for Cys. The sensor exhibits a highly selective “turn‐on” response to cysteine over Hcy, GSH and other amino acids in aqueous solution at physiological pH. The observed pseudo‐first‐order rate constant for the reaction of BPB with Cys was calculated to be about 0.062 min⁻¹. The detection limit of this sensor for Cys was determined to be 332 nm, and bioimaging of exogenous Cys by this sensor was successfully applied in living cells, thus indicating that this sensor holds great potential for biological applications.     

Combinatorial Energy Transfer between an End‐Capped Conjugated Polyelectrolyte and Chromophore‐Labeled PNA for Strand‐Specific DNA Detection

We report a macromolecular end‐capping approach to improve the detection sensitivity of cationic conjugated polymer (CCP) based DNA detection. A phenylethynyl anthracene (PEA) end‐capped cationic polyfluorene (PF) derivative ( P1 ) is synthesized via Suzuki coupling. Due to efficient fluorescence resonance energy transfer (FRET) from the polymer backbone to the end‐capper PEA units, the polymer ( P1 ) fluorescence is dominated by the emission from PEA even in dilute aqueous solution. P1 emission has a better spectral overlap with fluorescein (Fl) absorption compared to that for uncapped PF ( P2 ). In addition, the intra and intermolecular energy transfer for P1 is more efficient in the presence of DNA due to complexation‐induced polymer aggregation. These impart a combinatorial FRET between P1 and an Fl‐labeled probe which is more efficient than that between P2 and the same probe. P1 thus offers a better DNA detection sensitivity relative to P2 and opens up new opportunities to improve the performance of CCP based biosensors involving FRET.