Fluorescent carbon nanoparticles: A low-temperature trypsin-assisted preparation and Fe sensing

In recent years, extensive researches are focused on the fluorescent carbon nanoparticles (CNPs) due to their excellent photochemical, biocompatible and water-soluble properties. However, these synthesis methods are generally suffered from tedious processes. In this paper, fluorescent carbon nanoparticles are synthesized by a facile, one-pot, low-temperature method with trypsin and dopamine as precursors. The synthesis process avoids any heating operation and organic solvent, which provides a “green” and effective preparation route. The obtained CNPs exhibit excellent water-solubility, salt-tolerance and photostability. Based on the synergistic action of the inner filter effect and static quenching mechanism, the CNPs are exploited as a “turn-off” fluorescence sensor for sensitive and selective detection of Fe³⁺ ions. The probe shows a wide linear range from 0.1 to 500 μM, with a limit of detection of 30 nM. Furthermore, the as-fabricated fluorescent sensing system is successfully applied to the analysis of Fe³⁺ in biological samples such as human urine and serum samples with satisfactory recoveries (92.8–113.3%).     

Anthrone-spirolactam and quinoline hybrid based sensor for selective fluorescent detection of Fe3+ ions

The synthesis of a novel, and highly selective Fe³⁺ ion sensor based on anthrone-spirolactam and its quinoline hybrid ligand is reported. The designed ligand displayed selective detection of Fe³⁺ ions with enhanced fluorescence emission. The complexation of Fe³⁺ ion led to a red shift of 32 nm from 420 nm to 452 nm, and a several fold increase in intensity with fluorescent green emission. The complexation (detection) of Fe³⁺ ions with ligand resulted in chelation enhanced fluorescence and intramolecular charge transfer through the inhibition of C=N isomerization. This hybrid sensor shows high sensitivity and selectivity, spontaneous response, and works on a wide pH range a minimum detection limit of 6.83 × 10⁻⁸ M. Importantly, the sensor works through the fluorescence turn-on mechanism that overcomes the paramagnetic effect of Fe³⁺ ions. The binding mechanism between the ligand and the Fe³⁺ ions was established from the Job's plot method, optical studies, Fourier transfor infrared spectroscopy, NMR titration, fluorescence life-time studies, and density functional theory optimization. The sensor displayed excellent results in the quantification of Fe³⁺ ions from real water samples. Furthermore, due to its biocompatibility nature, fluorescent spotting of Fe³⁺ ions in live cells revealed its bioimaging applications.     

Colorimetric detection of iron ions (III) based on the highly sensitive plasmonic response of the N-acetyl-l-cysteine-stabilized silver nanoparticles

We report here a facile colorimetric sensor based on the N-acetyl-l-cysteine (NALC)-stabilized Ag nanoparticles (NALC–Ag NPs) for detection of Fe³⁺ ions in aqueous solution. The Ag NPs with an average diameter of 6.55 ± 1.0 nm are successfully synthesized through a simple method using sodium borohydride as reducing agent and N-acetyl-l-cysteine as protecting ligand. The synthesized silver nanoparticles show a strong surface plasmon resonance (SPR) around 400 nm and the SPR intensity decreases with the increasing of Fe³⁺ concentration in aqueous solution. Based on the linear relationship between SPR intensity and concentration of Fe³⁺ ions, the as-synthesized water-soluble silver nanoparticles can be used for the sensitive and selective detection of Fe³⁺ ions in water with a linear range from 80 nM to 80 μM and a detection limit of 80 nM. On the basis of the experimental results, a new detection mechanism of oxidation–reduction reaction between Ag NPs and Fe³⁺ ions is proposed, which is different from previously reported mechanisms. Moreover, the NALC–Ag NPs could be applied to the detection of Fe³⁺ ions in real environmental water samples.     

Green synthesis of fluorescent carbon dots from Kumquat (Fortunella margarita) for detection of Fe3+ ions in aqueous solution

In this study, kumquat was first time used for synthesizing carbon dot structures (CDs) with the hydrothermal method. These newly synthesized CDs was characterized structurally and optically. The ion sensor application of the new CDs was carried out using 20 different metal ions. It was observed that CDs have high selectivity only for Fe³⁺ ions among the metal ions studied. Detection limit for Fe³⁺ ions was calculated as 0.70 µM. The results showed that these new CDs are highly selective against Fe³⁺ ions and have a very short response time such as 0.5 min. The Fe³⁺ ions selectivity of CDs was tested on real (tap water) samples. The results exhibited that this new CDs, obtained with green synthesis from Kumquat fruit without using chemical agents in one-pot simple and economical process, can be used as fluorometric sensor for detection of Fe³⁺ ions with high selectivity and sensitivity, low detection limit and rapid response time.

     

A novel nano‐size lanthanum metal–organic framework based on 5‐amino‐isophthalic acid and phenylenediamine: Photoluminescence study and sensing applications

In this paper, a novel lanthanum metal–organic framework La‐MOF was prepared via hydrothermal and reflux methods. The La‐MOF was achieved through the reaction of a 5‐amino‐isophthalic acid with 1, 2‐phenylenediamine and lanthanum chloride. The prepared La‐MOF structure was confirmed by XRD, mass spectrometry, IR, UV–Vis and elemental analysis, whereas the size, and morphology was examined by FE‐SEM/EDX and HR‐TEM. The results indicated that the La‐MOF prepared via both methods have the same structure and composition. Meanwhile, the MOF yield, reaction time, morphology, physiochemical and sensing properties were highly depended on the used preparation method. The photoluminescence (PL) study was carried out for the La‐MOF, and the results showed that La‐MOF exhibits strong emission at 558 nm after excitation at 369 nm. Moreover, the PL data indicating that the La‐MOF has highly selective sensing properties for iron (III) competing with different metal ions. The Stern‐Völmer graph shows a linear calibration curve which achieved over a concentration range 1.0–500 μM of Fe³⁺ with a correlation coefficient, detection, and quantitation limits 0.998, 1.35 μM and 4.08 μM, respectively. According to the remarkable quenching of the PL intensity of La‐MOF using various concentrations of Fe³⁺, it was successfully used as a sensor for Fe³⁺detecting in different water resources (pure and waste) samples. The quenching mechanism was studied and it has a dynamic type and due to efficient energy transfer between the La‐MOF and Fe³⁺.     

A Cerium Hexacyanoferrate (III) Nanoparticle‐modified Carbon Paste Electrode: Voltammetric Characterization and Behavior in the Presence of Dopamine

This study describes a fast and simple methodology for the preparation of Cerium (III) Hexacyanoferrate (II) (CeHCF) nanoparticles (NPs). The NPs were characterized by fourier transform infrared (FTIR), x‐ray diffraction (XRD), scanning electron microscopy (SEM) and cyclic voltammetry (CV). The CeHCF cyclic voltammogram indicate a well‐defined redox pair assigned as Fe²⁺/Fe³⁺ in the presence of cerium (III), with a formal potential of E^θ′=0.29 V (v=100 mV s^?1, KNO₃; 1.0 mol/L, pH 7.0). The carbon paste electrode modified with CeHCF (CeHCF‐CPE) was applied to the catalytic electrooxidation of dopamine applying Differential Pulse Voltammetry (DPV). DPV showed linear response at two concentration ranges, from 9.0×10^?7 to 8.0×10^?6 and 9.0×10^?6 to 1.0×10^?4 mol/L, with an LOD of 1.9×10^?7 and 1.0×10^?5 mol/L, respectively. The CeHCF‐CPE exhibited selectivity against substances commonly found in biological samples, with redox potentials close to that of dopamine, such as urea and ascorbic acid (AA). Subsequently the CeHCF‐CPE was successfully applied to the detection of dopamine in simulated urine samples, with recovery percentages ranging between 99 and 103%.     

Development of Fluorescent Film Sensors Based on Electropolymerization for Iron(III) Ion Detection

Two electroactive materials, M1 and M2 , are synthesized and their fluorescent electropolymerized (EP) films are prepared and used to detect metal ions. From the tested metal ions, M1 and M2 are demonstrated to be sensitive and selective for Fe³⁺ ions. In particular, M2 exhibits higher sensitivity towards Fe³⁺ ions. The fluorescent detection ranges from 10^?5 M to 4×10^?4 M . The excellent performance of the EP fluorescent films is mainly due to the strong metal‐chelated properties of M2 and the intrinsic porous cross‐linked‐network microstructure of the EP films. This study, thus, provides a promising Fe³⁺ sensing candidate and a potential preparation method for fluorescent sensing films.     

In situ Electrochemical Synthesis of a Composite Film Containing Nickel Hexacyanoferrate and Bentonite Clay for the Sensitive Determination of Acetaminophen and Dopamine

A composite film of nickel hexacyanoferrate (NiHCF) and bentonite (Bt) clay (abbreviated as NiHCF?Bt) is synthesized by an in situ electrochemical method. For this synthesis, nickel ions are immobilized on Bt clay by an ion‐exchange process, equilibrating Bt clay with nickel nitrate. On a glassy carbon electrode (GCE), the nickel ion‐exchanged Bt clay (Ni²⁺?Bt) is coated to get the modified electrode which is represented as GCE/Ni²⁺?Bt. The NiHCF?Bt composite film is prepared on the GCE surface using the GCE/Ni²⁺?Bt and scanning the electrode potentials between ?0.10 to 1.00 V continuously in an aqueous solution containing potassium hexacyanoferrate and potassium chloride. This NiHCF?Bt modified GCE (GCE/NiHCF?Bt) exhibits redox peaks due to the oxidation and reduction of the central metal ion, Fe²⁺. The electro‐generated Fe³⁺ present in the GCE/NiHCF?Bt, electrocatalytically oxidizes a range of drugs like acetaminophen (AC), dopamine (DA), and tyrosine (TY) at decreased overpotentials with high current. This property is advantageously used for the precise quantification of AC, DA, and TY. Sensitivity, limit of detection, and linear calibration range for the determination of AC are found to be 0.20 μA μM^?1 cm^?2, 1.5 μM, and 25.0–1000.0 μM, respectively. Further, the amount of AC present in pharmaceutical products is satisfactorily quantified which demonstrated the use of the NiHCF?Bt composite film in electroanalysis.     

Selective recognition of Fe3+ and Cr3+ in aqueous medium via fluorescence quenching of graphene quantum dots

Graphene quantum dots (GQDs) have been prepared from graphene oxide (GO) and characterized by standard analytical techniques. The size of the prepared GQDs ranges from 2-10?nm. Aqueous dispersion of GQDs exhibited excitation-dependent emission behavior. Emission intensity of the aqueous dispersion found stable for the examined duration of about four months. GQDs exhibited selective recognition of Fe³⁺ and Cr³⁺ out of various common ions such as alkali, alkaline-earth and transition metal ions in aqueous medium through fluorescence quenching. The lower limit of detection of Fe³⁺ is 1?µM and that of Cr³⁺ is 4?µM.     

Environmentally sensitive hydrogel functionalized with electroactive and complexing‐iron(III) catechol groups

Thermoresponsive pNIPA (poly (N‐isopropylacrylamide)) gels modified with dopamine methacrylamide were synthesized using free‐radical polymerization. In this way, the catechol groups were introduced into the polymer network. The presence of dopamine in the gel led to a significant shift in the volume phase transition temperature (VPTT). It was found that hydrogels were electroactive and that oxidation of catechol groups also led to a strong shift in the VPTT. The temperature window, that is, the range of temperature where volume of the gel could be substantially changed by oxidation of the catechol groups, for the gel formed from the polymerization solution containing 5% of the dopamine derivative, was 30–40 °C. Additionally, the influence of Fe³⁺ ions, which form the most stable complexes with dopamine, on swelling behavior of the gels was investigated at various pH. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3236–3242     

Enhanced Performance of CNT‐doped Imine Based Receptors as Fe(III) Sensor Using Potentiometry and Voltammetry

A highly sensitive and selective potentiometric and voltammteric assay for the detection of Fe³⁺ using (E)‐3‐((2‐(2‐(2‐aminoethylamino) ethylamino) ethylimino)methyl)‐4H‐chromen‐4‐one (IFE(III)) ionophore was developed. To demonstrate the ion‐to‐electron transfer ability of MWCNT, these were incorporated in the ion‐selective membrane and response characteristics of Fe³⁺ electrode was compared with those of the traditional ion selective electrode. The electrode showed an improved Nernstian slope, lower detection limit, response time of less than 5 s and working in a pH range of 3.0 to 8.0. Differential pulse voltammetric studies were performed for IFE(III)‐Fe³⁺ complex in DMSO solvent medium at glassy carbon (GC) electrode. A linear relationship between the cathodic peak current and concentration of Fe³⁺ was observed in the range of 1.6×10^?5 to 4.4×10^?5 mol/L with a detection limit of 5.2×10^?8 mol/L. The electrode shows remarkable selectivity for Fe³⁺ ions over alkali, alkaline earth, transition and heavy metal ions. The optimized electrode was successfully applied for the determination of Fe³⁺ ion in different real‐life samples using potentiometric technique. Theoretical calculations were used to support the complexation behavior of Fe³⁺ with IFE(III).     

Electrochemical Determination of Dopamine Using a Graphene–Screen-Printed Carbon Electrode with Magnetic Solid-Phase Microextraction

A magnetically separable Fe₃O₄@Diaion HP-2MG composite was prepared using the coprecipitation method and the resulting magnetic Fe₃O₄@Diaion HP-2MG composites were used for the separation and preconcentration of trace amounts of dopamine. For the detection stage, square wave voltammetry on a disposable graphene–screen-printed carbon electrode was successfully used for the determination of dopamine. The graphene–screen-printed carbon electrode exhibited excellent electroanalytical performance for dopamine. The linear concentration range was from 0.8 to 80?µM and a detection limit of 50?nM for dopamine was obtained. In combination with the magnetic solid-phase extraction method, the sensor response was linearly proportional to the concentration of dopamine in the range of 0.01–6.0?µM with a correlation coefficient of approximately 0.9992. The detection limit of the sensor was found to be 5.0?nM by square wave voltammetry. The combined methodology was successfully applied to determine dopamine in urine samples with good recoveries ranging from 95 to 98%.     

Green Synthesized Gold Nanoparticles as a Probe for the Detection of Fe3+ Ions in Water

Pure water which is free of toxic chemicals is necessary for human health. So, detection and control of heavy metal ions in water is very important. Keeping this in mind, selective and sensitive optical sensor based on surface plasmon resonance for detection of various heavy metals in water using gold nanoparticles was explained in this present study. These AuNPs were prepared using Hibiscus cannabinus leaf extract as reducing agent with the average particle size of 22 nm. These gold nanoparticles are considerably selective and sensitive towards Fe³⁺ and it was used to detect the concentration of Fe³⁺ ions in water in the range 29.82–173.74 μM by tracking the absorbance changes of SPR band and the sensitivity of the system towards the Fe³⁺ concentration and it was found to be 0.0037 μM^?1. We hope that these gold nanoparticles can be used for detecting Fe³⁺ ions concentration, in the water purification processes.     

Combining field‐amplified sample stacking with moving reaction boundary electrophoresis on a paper chip for the preconcentration and separation of metal ions

A common drawback of paper‐based separation devices is their poor detection limit. In this study, we combined field‐amplified sample stacking with moving reaction boundary electrophoresis on a paper chip with six array channels for the parallel separation and concentration of multiple samples. With a new hyphenated technique, the brown I₂ from the Fe³⁺/I⁻ oxidation–reduction reaction emerged near the boundary between the dilute ethylene diamine tetraacetic acid and potassium iodide and highly concentrated KCl solutions. For the separation and concentration of three components, Cr³⁺, Cu²⁺, and Fe³⁺, the Fe³⁺ detection limit was improved at least 266‐fold by comparing the hyphenated technique with moving reaction boundary electrophoresis. The detection limit of Fe³⁺ was found to be as low as 0.34 ng (20 μM) on the paper chip. We also demonstrated the analysis of a real sample of four metal ions, with detection limits as follows: 0.16 μg Cr³⁺, 1.5 μg Ni²⁺, 0.64 μg Cu²⁺, and 1.5 μg Co²⁺. The synergy of field‐amplified sample stacking and moving reaction boundary electrophoresis in the micron paper‐based array channels dramatically improved the detection limit and throughput of paper‐based electrophoresis.     

Development of solution‐dispersible hyperbranched conjugated polymer nanoparticles for Fe3+ fluorescent detection and their application in logic gate

Solution‐dispersible hyperbranched conjugated polymer nanoparticles (FT‐HBCPNs) consist of an intrinsic crosslinked rigid skeleton structure of both 9,9‐dihexyl‐fluorene and triphenylamine repeating units, and are synthesized via the miniemulsion Suzuki polymerization, and FT‐HBCPNs for highly selective and sensitive Fe³⁺ fluorescent detection and their application in logic gate at molecular level are successfully developed. FT‐HBCPNs with an average particle size of 10.6 nm can disperse in common organic solvents. FT‐HBCPNs show high selectivity and sensitivity for Fe³⁺ over other commonly co‐existent metal ions in THF solution with a detection limit of 3.65 × 10^?8 mol L^?1. Furthermore, homogeneous transparent thin films of FT‐HBCPNs developed by a simple spin‐coating method can be reversibly quenched by Fe³⁺ with a detection limit of 3.09 × 10^?7 mol L^?1. Using Fe³⁺ and EDTA as chemical inputs and the fluorescence intensity signal as outputs, FT‐HBCPNs films can be utilized as a logic gate at molecular level. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3694–3700     

Zeolite Nanoparticle Modified Carbon Paste Electrode as a Biosensor for Simultaneous Determination of Dopamine and Tryptophan

A new chemically modified electrode is constructed based on an iron(III) doped zeolite modified carbon paste electrode (Fe³⁺Y/ZCME). The electrode was evaluated as a sensor for sub‐micromolar determination of tryptophan (Trp) and dopamine (DA). The measurements were carried out using the differential pulse voltammetry (DPV) method in a phosphate buffer solution with pH = 5. The prepared modified electrode shows voltametric responses with high sensitivity and stability for DA and Trp in optimal conditions. The analytical performance of this sensor has been evaluated for detection of DA and Trp in human serum.     

A highly selective fluorescent probe for nanomolar detection of ferric ions in the living cells and aqueous media

A dipodal fluorescent probe 3, with imine and hydroxyl moieties as binding sites, has been synthesized and characterized with spectroscopic methods, single-crystal X-ray techniques, and DFT. The synthesized probe 3 (φ = 0.0028) showed highly sensitive and highly specific fluorescent ‘turn-on’ effect (λ_em = 453 nm) for the 1:1 binding with Fe³⁺ ions to form probe 3.Fe³⁺ complex (φ = 0.203) in semi-aqueous medium (acetonitrile:water (50:50; v/v)) and live cells. The 1:1 binding stoichiometry of probe 3 and Fe³⁺ ions was proposed by DFT calculations and confirmed by the NMR spectroscopy, crystal structures of probe 3 and 3.Fe³⁺ complex, and mass spectrum of probe 3.Fe³⁺ complex. The stability of probe 3.Fe³⁺ complex in a wide pH range (pH 2–12) and reversibility for binding with Fe³⁺ ions in the presence of EDTA indicates that it can be an effective chemosensor for the detection of Fe³⁺ ions in various samples, including living cells. Importantly, with the LOD of 21.5 nM for the detection of Fe³⁺ ions, probe 3 did not show any interference from potentially competing ions even at a 1:3 ratio, indicates its biocompatibility. The nanomolar limit of detection (21.5 nM), cell permeability, and low cytotoxicity allows the probe 3 to be an excellent tool for the live-cell imaging and detection of ferric ions in live cells.     

A Sensitive Fluorescence Quenching Method for the Determination of Iron( Ⅱ） with 1,10-Phenanthroline

A sensitive and selective fluorescence quenching method for the determination of Fe²⁺ with 1,10‐phenanthroline was developed. The fluorescence intensity of 1,10‐phenanthroline at λ_ex of 266 run and λ_em of 365 nm was constant in the range of pH 4.0 to 10.0 and decreased linearly upon addition of Fe²⁺ to its solution. This decrease was mainly due to a static quenching effect caused by the formation of a non‐fluorescent complex of Fe²⁺ with 1, 10‐phenanthroline. The total amount of iron was determined by using hydroxylamine hydrochloride to reduce Fe³⁺ to Fe²⁺. The linear range was from 5.0 × 10–⁷ to 2.0 × 10–⁵ mol/L with a detection limit of 2.4 × 10–⁸ mol/L at 3s?. The quenching constant of Fe²⁺ to 1,10‐phenanthroline was calculated to be (5.70 × 0.05) × 10⁴ L/mol at 25 °C. Effects of foreign ions on the determination of Fe²⁺ were investigated. The results of the new method for the determination of iron in tap water and natural water samples were in good agreement with those obtained by graphite atomic absorption spectrometry.     

A Novel Polymeric Chemosensor: Dual Colorimetric Detection of Metal Ions Through Click Synthesis

A highly colored polystyrene derivative bearing side chain chromophores composed of dialkylanilino donor and cyano‐based acceptor groups, prepared by atom‐economic click postfunctionalization, displays the dual colorimetric detection behavior of several metal ions based on the specific interactions with different nitrogen atoms. Hard to borderline metal ions, such as Fe³⁺, Fe²⁺, and Sn²⁺, are always recognized by the dialkylanilino nitrogen atom, resulting in a decrease in the charge‐transfer (CT) band intensity of the donor–acceptor chromophores. On the other hand, the recognition site of a soft metal ion of Ag⁺ is the cyano nitrogen atom due to the readily formed multivalent coordination, which produces a bathochromic shift of the CT band.     

A Nanoscale Multiresponsive Luminescent Sensor Based on a Terbium(III) Metal–Organic Framework

A nanoscale terbium‐containing metal–organic framework ( nTbL ), with a layer‐like structure and [H₂NMe₂]⁺ cations located in the framework channels, was synthesized under hydrothermal conditions. The structure of the as‐prepared sample was systematically confirmed by powder XRD and elemental analysis; the morphology was characterized by field‐emission SEM and TEM. The photoluminescence studies revealed that rod‐like nTbL exhibited bright‐green emission, corresponding to ⁵D₄→⁷F_J (J=6–3) transitions of the Tb³⁺ ion under excitation. Further sensing measurements revealed that as‐prepared nTbL could be utilized as a multiresponsive luminescent sensor, which showed significant and exclusive detection ability for Fe³⁺ ions and phenylmethanol. These results highlight the practical applications of lanthanide‐containing metal–organic frameworks as fluorescent probes.