Multivariate calibration analysis of colorimetric mercury sensing using a molecular probe

Selectivity is one of the main challenges of sensors, particularly those based on chemical interactions. Multivariate analytical models can determine the concentration of analytes even in the presence of other potential interferences. In this work, we have determined the presence of mercury ions in aqueous solutions in the ppm range (0-2 mg L⁻¹) using a ruthenium bis-thiocyanate complex as a chemical probe. Moreover, we have analyzed the mercury-containing solutions with the co-existence of higher concentrations (19.5 mg L⁻¹) of other potential competitors such as Cd²⁺, Pb²⁺, Cu²⁺ and Zn²⁺ ions. Our experimental model is based on partial least squares (PLS) method and other techniques as genetic algorithm and statistical feature selection (SFS) that have been used to refine, beforehand, the analytical data. In summary, we have demonstrated that the root mean square error of prediction without pre-treatment and with statistical feature selection can be reduced from 10.22% to 6.27%.     

A series of simple curcumin-derived colorimetric and fluorescent probes for ratiometric-pH sensing and cell imaging

Colorimetric and fluorescent probes have emerged as a potent tool for pH sensing due to easy operation and high sensitivity. However, most of the existing bimodal probes require complicated synthesis,which greatly limits their wide applications. Herein, a simple fluorescent dye（called BFCUR） featuring a D-π-A-π-D conjugated system was developed from the natural polyphenol curcumin（CUR）. BFCUR exhibited significant red-shift in UV absorption and fluorescence emission as pH increased because of th...     

Simple and sensitive aptamer-based colorimetric sensing of protein using unmodified gold nanoparticle probes

We describe herein simple and sensitive aptamer-based colorimetric sensing of protein (alpha-thrombin in this work) using unmodified gold nanoparticle probes.     

A colorimetric sensing ensemble for heparin

A receptor possessing ammoniums and a novel amino acid with a boronic acid side chain was designed and synthesized. The receptor shows good affinity and selectivity for heparin over similar polysaccharides possessing lower anionic charge density. The affinity for heparin is similar to that for a heparin disaccharide, indicating that disaccharidic units are the likely sites for binding to the receptor. The receptor has a potential use for creating a colorimetric assay for heparin.     

A highly selective colorimetric aqueous sensor for mercury

A new colorimetric mercury sensor is reported based on binding to terpyridine derivatives. It is able to selectively detect Hg II ions over a number of environmentally relevant ions including Ca II, Pb II, Zn II, Cd II, Ni II, Cu II, and others. The response time upon exposure to Hg II is instantaneous. By the "naked eye," the detection limit of Hg II is 2 ppm (25 microM) in solution. With a spectrometer, this detection limit is increased down to 2 ppb (25 nM), which is the current EPA standard for drinking water. The significant problem of mercury poisoning requires new methods of detection that are sensitive and selective. Here we report a new simple system that takes advantage of the unique optical properties generated by terpyiridine-Hg complexes.     

Parameters for selective colorimetric sensing of mercury(II) in aqueous solutions using mercaptopropionic acid-modified gold nanoparticles

We unveil a new homogeneous assay-using mercaptopropionic acid-modified Au nanoparticles in the presence of 2,6-pyridinedicarboxylic acid for the highly selective and sensitive detection of Hg(2+) ions.     

Use of surface-modified CdTe quantum dots as fluorescent probes in sensing mercury (II)

Thioglycolic acid (TGA)-capped CdTe quantum dots (QDs) were synthesized in aqueous medium, and their interaction with metal cations was studied with UV-vis absorption, steady-state and time-resolved fluorescence spectra. The results demonstrated that Hg(II), Cu(II) and Ag(I) could effectively quench the QD emission based on different action mechanisms: Cu(II) and Ag(I) quenched CdTe QDs because they bound onto particle surface and facilitated non-radiative electron/hole recombination annihilation of QDs; electron transfer process between the capping ligands and Hg(II) was mainly responsible for the remarkable quenching effect of Hg(II). To prevent the approach of metal cations to QD core, the original TGA-capped CdTe QDs were further coated by denatured bovine serum albumin (dBSA). It was found that the dBSA-coated CdTe QDs could be quenched effectively by Hg(II), but Cu(II) and Ag(I) could hardly quench the QDs even at fairly higher concentration levels because the dBSA shell layer effectively prevented the binding of metal cations onto the QD core. On the basis of this fact, a simple, rapid and specific method for Hg(II) determination was proposed. Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of Hg(II) ranging from 0.012 x 10(-6) to 1.5 x 10(-6) mol L(-1). The limit of detection for Hg(II) was 4.0 x 10(-9) mol L(-1). The developed method was successfully applied to the detection of trace Hg(II) in real samples.     

Fluorescent probes for sensing processes in polymers

Fluorescence spectroscopy is an important analytical technique that has been widely used in a variety of applications, such as biomedicine, biology, and science of materials, because it presents some properties which makes it unique, that is, extraordinary sensitivity and selectivity, short delay time (<10(-9) s), and it is neither invasive nor destructive, so it can be used for in situ measurements. Generally, intrinsic fluorescence of many materials, like polymers, is unspecific so it is not useful to analyse their properties or to be correlated to changes in their microenvironment. The incorporation of additives with fluorescent groups would be necessary. When the fluorescence emission of these molecules is sensitive to changes of properties, such as polarity, fluidity, order, molecular mobility, pH, or electric potential, they can be used for detecting such changes in their microenvironment, and they are called fluorescent probes. As long as these probes can follow processes of practical interest, they can be employed as sensors, if the information given by the measure of fluorescence adequately reflects the changes in the system. In addition, a sensor must fulfil some other requirements in order to make them of practical use, the most important being that the material support in which the sensor molecule is inserted. This support should permit a rapid detection of the process and should allow easy processing in a variety of forms. Polymers are well-known systems in which estimation of local parameters are possible by means of fluorimetric techniques. It allows the study of dynamic processes of interest, such as polymerization kinetics and mechanisms, thermal transitions, photodegradation, swelling morphology changes, and so forth.     

Reversible fluorescent probes for chemical and biological redox process

In this review, we discuss the recent progress of reversible fl uorescent probes for chemical and biological redox process according to different active centers.     

Stimuli-responsive disassembly of nanoparticle aggregates for light-up colorimetric sensing

Controlled assembly of nanomaterials has been the focus of much research. In contrast, controlled disassembly has not received much attention, even though both processes have been shown to be important in biology. By using a Pb2+-dependent RNA-cleaving DNAzyme, we demonstrate here control of the disassembly of gold nanoparticle aggregates in response to Pb2+. In the process, we show that nanoparticle alignment plays an important role in the disassembly process, with the tail-to-tail configuration being the most optimal, probably because of the large steric hindrance of other configurations. The rate of disassembly is significantly accelerated by using small pieces of DNA to invade the cleaved substrate of the DNAzyme. Investigation of such a controlled disassembly process allows the transformation of previously designed "light-down" colorimetric Pb2+ sensors into "light-up" sensors.     

Coumarin-based symmetrical bisamide as fluorescent and colorimetric probes for copper ions

Coumarin-based new symmetrical bisamide 1 has been designed and synthesised. The bisamide 1 fluorometrically recognises Cu²⁺ in CH₃CN containing 0.06% DMSO by exhibiting an increase in emission upon complexation. In comparison, the isomeric structure 2 also reports the selectivity for Cu²⁺ under identical condition by showing an opposite mode of emission. In addition, Cu²⁺ gives rise to a change in colour of the solution of 1, which is clearly visible to the naked eye.     

Chromogenic silica nanoparticles for the colorimetric sensing of long-chain carboxylates

Silica nanoparticles functionalized with chromogenic spirobenzopyran and thiourea subunits show selective colour changes in the presence of certain long-chain carboxylates.     

Amide-nitrophenyl based colorimetric receptors for selective sensing of fluoride ions

New chromogenic receptors containing 2-nitrophenyl or 3,5-dinitrophenyl groups appended to the amide or in secondary amine positions have been synthesized and characterized. Upon addition of fluoride to two of the receptors in acetonitrile, the solution acquired a yellow colour. The third receptor showed an intense purple colour with fluoride in acetonitrile and the appearance of the purple colour can be detected by the naked eye at parts per million level. The addition of chloride, bromide and iodide to the receptors did not induce any colour. Thus the receptors can act as fluoride ion sensors even in the presence of other halide ions.     

A gold nanoparticle-based colorimetric sensing ensemble for the colorimetric detection of cyanide ions in aqueous solution

A colorimetric sensing ensemble was prepared by mixing readily prepared adenosine triphosphate (ATP)-stabilized AuNPs with Cu²⁺-phenanthroline complexes. The sensing mechanism of the ensemble was examined by UV-vis spectrometry and transmission electron microscopy. The studies showed that the Cu²⁺-phenanthroline complex was converted to free phenanthroline when exposed to cyanide anions and the free phenanthroline caused the ATP-stabilized AuNPs to aggregate, which in turn, resulted in a visible color change in the AuNP solution. The ensemble could detect cyanide ions in aqueous solution at physiological pH, either spectrophotometrically or visually, with high selectivity toward cyanide anions over a range of mono- and di-anions commonly found in biological and environmental systems. This sensing ensemble also allows a quantitative assay of the analyte in a neutral aqueous solution, down to a concentration of 10⁻⁵ M.     

DDTC-Na-based colorimetric chemosensor for the sensing of cyanide in water

Sodium diethyldithiocarbamate (DDTC-Na) was demonstrated to be a new colorimetric cyanide chemosensor by utilizing an indirect trick. First, some copper ions were added to the colorless aqueous solution of DDTC-Na. Then, the resultant brown solution was studied upon the addition of different anions, including Cl⁻, I⁻, IO₃⁻, SO₄²⁻, NO₂⁻, Br⁻, H₂PO₄⁻, F⁻, SCN⁻, HSO₄⁻, ClO₄⁻ and CN⁻. It was observed by naked eyes that the brown solution changed to colorless immediately after the addition of the trace cyanide, but there were no changes towards other anions, making DDTC-Na a good selective cyanide chemosensor in pure water. Supported by the National Natural Science Foundation of China (Grant Nos. 20674059 & 20402011)     

Label-free colorimetric sensing of ascorbic acid based on Fenton reaction with unmodified gold nanoparticle probes and multiple molecular logic gates

A label-free strategy based on Fenton reaction with unmodified gold nanoparticles (AuNPs) as probe is demonstrated for ascorbic acid (AA) sensing. AuNPs is stable in the presence of single stranded DNA (ssDNA) which prevents salt-induced aggregation of AuNPs in solution. The hydroxyl free radicals generated by Fenton reaction lead to ssDNA cleavage into different sequence fragments which induce aggregation of AuNPs to produce a red-to-blue color change. As an efficient biological antioxidant, AA could effectively scavenge free radicals to avoid the cleavage of ssDNA, so that it prevents color change of the AuNPs solution. Thus, the color change of AuNPs in the presence and absence of AA provides a new approach for the detection of AA. The absorbance ratio at two wavelengths, A₆₇₀/A₅₂₀, decreases linearly with AA content within 1–15 μM, giving rise to a detection limit of 0.3 μM and a RSD of 2.8% (10 μM). The color display of AuNPs solution makes it feasible for the estimation of AA content by naked eye visualization. Moreover, based on Fenton reaction and unmodified gold nanoparticles, a multiple logic gate system includes two logic operations, i.e., INHIBIT and NOR, has been designed with small molecules (AA, l-cysteine, glutathione) as inputs and the colorimetric changes of AuNPs solution as outputs.     

A ditopic colorimetric sensor for fluoride ion based on thiourea mercury complex

A novel ditopic chromogenic receptor, N-5-(8-hydroxy)quinoline-N'-4'-nitro-phenyl thiourea (1), was synthesized. The metal complex 1-Hg(2+) showed sensitive and highly selective responses to F(-) over other anions such as CH(3)CO(2)(-), H(2)PO(4)(-), HSO(4)(-) and Cl(-). 1-Hg(2+)-F(-) complex formed, which promoted the intramolecular charge transfer and led to a dramatic spectral change. The color of 1-Hg(2+) solution changed from colorless to red upon addition of F(-). Thus, a colorimetric assay of F(-) was developed in acetonitrile by naked-eye detection. F(-) behaved linearly in the 8.0 x 10(-6) to 2.0 x 10(-5) mol L(-1) concentration range with LOD as 1.4 x 10(-6) mol L(-1).     

Azobenzene-based colorimetric chemosensors for rapid naked-eye detection of mercury(II)

Two new highly selective colorimetric chemosensors for Hg²⁺, based on azobenzene and highly selective Hg²⁺‐promoted deprotection of a dithioacetal have been designed and synthesized. In the presence of as little as 20 μM Hg²⁺, the sensors change their color from light yellow to deep red, which can easily be observed by the naked eye. The underlying signaling mechanism is intramolecular charge transfer (ICT). The sensors have good selectivity for Hg²⁺ with respect to several common alkali, alkaline earth, and transition metal ions. Furthermore, they can be used for in‐the‐field measurements by virtue of a dipstick approach without any additional equipment.     

A colorimetric and fluorometric dual-model assay for mercury ion by a molecule

The synthesis and sensing characteristics of a new class of colorimetric and fluorometric dual-modal probe for mercury ion are outlined. Judicious placement of two dithia-dioxa-aza macrocycles on the BODIPY chromophore generates this interesting molecule. A highly Hg2+-selective fluorescence enhancing property (>7-fold) in conjunction with a visible colorimetric change from purple to red-pink can be observed, leading to potential fabrication of both "naked-eye" and ratiometric fluorescent detection of Hg2+.