Dual Sensing Performance of 1,2-Squaraine for the Colorimetric Detection of Fe3+ and Hg2+ Ions.
ABSTRACT: A simple 1,2-squaraine based chemosensor material (SQ) has been reported to show dual sensing performance for colorimetric detection of Fe3+ and Hg2+ ions. Compared to common instrumental analysis, this method could provide fast and direct detection though colorimetric changes by the naked eye. The sensor has shown excellent selectivity over the other metal ions by tuning different solvent environments. The detection limit for Fe3+ could reach to 0.538 ?M, which was lower than that in the environmental agency guideline (U.S. Environmental Protection Agency, U.S. EPA) in drinking water. And for Hg2+ detection, the limit was calculated as 1.689 ?M in our case. A 1:1 binding mode between SQ?Fe3+ and SQ?Hg2+ ion were evidenced by Job's plot measurement and IR analysis. The proposed different binding mechanisms were also supported by Density Function Theory (DFT) calculation. All these findings provide a unique material and a simple, facile, and low cost colorimetric method for dual metal ions analysis and have shown preliminary analytical applications in industrial water sample analysis.
Project description:Accurate recognition and speciation analysis of heavy-metal ions in complex hydrological environments is always a serious challenge. In this work, we proposed a small-molecule-based ultrasensitive colorimetric detection strategy and successfully applied it to the accurate detection of Fe2+, Fe3+, Co2+, and Hg2+ in groundwater through the specific recognition of multiple ligands of different metal ions. The detection limits for Hg2+, Co2+, Fe2+, and Fe3+ are calculated to be 6.51, 0.34, 0.49, and 1.01 ppb, respectively, which are far below the drinking water standards and superior to most of the reported colorimetric sensors. Remarkably, the speciation analysis of Fe2+/Fe3+ also has been successfully realized by a one-step method without complex pretreatment. The speciation and concentration of Fe2+ and Fe3+ in actual water samples can be accurately identified and monitored. In addition, as an attempt of visual onsite detection, we have developed a simple test strip, which has been applied to visual monitoring of four metal ions with the detection limit estimated by the naked eye to be as low as ppb level. This proposed colorimetric method realizes the rapid, sensitive, and portable multiple metal ions recognition and Fe2+/Fe3+ speciation analysis, displaying great potential for onsite rapid water quality analysis.
Project description:A highly selective and sensitive optical sensor was developed to colorimetric detect trace Fe3+ ions in aqueous solution. The sensor was the sulfasalazine (SSZ) functionalized microgels (SSZ-MGs), which were fabricated via in-situ quaternization reaction. The obtained SSZ-MGs had hydrodynamic radius of about 259 ± 24 nm with uniform size distribution at 25 °C. The SSZ-MG aqueous suspensions can selectively and sensitively response to Fe3+ ions in aqueous solution at 25 °C and pH of 5.6, which can be quantified by UV-visible spectroscopy and also easily distinguished by the naked eye. Job's plot indicated that the molar binding ratio of SSZ moiety in SSZ-MGs to Fe3+ was close to 1:1 with an apparent association constant of 1.72 × 104 M-1. A linear range of 0-12 μM with the detection limit of 0.110 μM (0.006 mg/L) was found. The obtained detection limit was much lower than the maximum allowance level of Fe3+ ions in drinking water (0.3 mg/L) regulated by the Environmental Protection Agency (EPA) of the United States. The existence of 19 other species of metal ions, namely, Ag+, Li+, Na+, K+, Ca2+, Ba2+, Cu2+, Ni2+, Mn2+, Pb2+, Zn2+, Cd2+, Co2+, Cr3+, Yb3+, La3+, Gd3+, Ce3+, and Bi3+, did not interfere with the detection of Fe3+ ions.
Project description:Two new spiroindolinonaphthoxazine derivatives with an electron-accepting styrylquinolizinium or styrylcoralyne unit, respectively, were synthesized, and the influence of such an arylvinyl substituent on the chemical and photochemical properties of the compounds was investigated. Specifically, these spirooxazines turned out to be resistant towards the photoinduced merocyanine formation, and the irradiation with light mainly led to photodegradation of the substrates. However, it was shown by colorimetric and fluorimetric screening assays as well as by detailed NMR spectroscopic and mass spectrometric studies that the addition of particular metal ions (Cu2+, Fe3+, and to a certain extent Hg2+) initially induced a ring-opening reaction that was irreversibly followed by a fast ring closure-deprotonation-oxidation sequence to give styryl-substituted naphthoxazole derivatives as the products quantitatively. For the quinolizinium-substituted spirooxazine derivative, the formation of the respective oxidation product caused the development of a broad absorption band between 425 nm and 500 nm and a new emission band at ?fl = 628 nm, so that it may be employed as a selective chemosensor or chemodosimeter for the colorimetric and fluorimetric detection of Cu2+ and Fe3+.
Project description:The fluorescence intensity of N, S co-doped graphene quantum dots (N, S-GQDs) can be quenched by Fe3+ and Hg2+. Density functional theory (DFT) simulation and experimental studies indicate that the fluorescence quenching mechanisms for Fe3+ and Hg2+ detection are mainly attributed to the inner filter effect (IFE) and dynamic quenching process, respectively. The electronegativity difference between C and doped atoms (N, S) in favor to introduce negative charge sites on the surface of N, S-GQDs leads to charge redistribution. Those negative charge sites facilitate the adsorption of cations on the N, S-GQDs' surface. Atomic population analysis results show that some charge transfer from Fe3+ and Hg2+ to N, S-GQDs, which relate to the fluorescent quenching of N, S-GQDs. In addition, negative adsorption energy indicates the adsorption of Hg2+ and Fe2+ is energetically favorable, which also contributes to the adsorption of quencher ions. Blue fluorescent N, S-GQDs were synthesized by a facile one-pot hydrothermal treatment. Fluorescent lifetime and UV-vis measurements further validate the fluorescent quenching mechanism is related to the electron transfer dynamic quenching and IFE quenching. The as-synthesized N, S-GQDs were applied as a fluorescent probe for Fe3+ and Hg2+ detection. Results indicate that N, S-GQDs have good sensitivity and selectivity on Fe3+ and Hg2+ with a detection limit as low as 2.88 and 0.27 nM, respectively.
Project description:A novel label-free fluorescence assay for detection of Hg2+ was developed based on the Hg2+-binding single-stranded DNA (ssDNA) and SYBR Green I (SG I). Differences from other assays, the designed rich-thymine (T) ssDNA probe without fluorescent labelling can be rapidly formed a T-Hg2+-T complex and folded into a stable hairpin structure in the presence of Hg2+ in environmental drinking water samples by facilitating fluorescence increase through intercalating with SG I in one-step. In the assay, the fluorescence signal can be directly obtained without additional incubation within 1?min. The dynamic quantitative working ranges was 5-1000?nM, the determination coefficients were satisfied by optimization of the reaction conditions. The lowest detection limit of Hg2+ was 3?nM which is well below the standard of U.S. Environmental Protection Agency. This method was highly specific for detecting of Hg2+ without being affected by other possible interfering ions from different background compositions of water samples. The recoveries of Hg2+ spiked in these samples were 95.05-103.51%. The proposed method is more viable, low-costing and simple for operation in field detection than the other methods with great potentials, such as emergency disposal, environmental monitoring, surveillance and supporting of ecological risk assessment and management.
Project description:A fluorescent optical fiber sensor for the detection of mercury (Hg2+) ions in aqueous solutions is presented in this work. The sensor was based on a fluorophore-labeled thymine (T)-rich oligodeoxyribonucleotide (ON) sequence that was directly immobilized onto the tip of a tapered optical fiber. In the presence of mercury ions, the formation of T-Hg2+-T mismatches quenches the fluorescence emission by the labeled fluorophore, which enables the measurement of Hg2+ ions in aqueous solutions. Thus, in contrast to commonly designed sensors, neither a fluorescence quencher nor a complementary ON sequence is required. The sensor presented a response time of 24.8 seconds toward 5 × 10-12 M Hg2+. It also showed both good reversibility (higher than the 95.8%) and selectivity: the I0/I variation was 10 times higher for Hg2+ ions than for Mn2+ ions. Other contaminants examined (Co2+, Ag+, Cd2+, Ni2+, Ca2+, Pb2+, Mn2+, Zn2+, Fe3+, and Cu2+) presented an even lower interference. The limit of detection of the sensor was 4.73 × 10-13 M Hg2+ in buffer solution and 9.03 × 10-13 M Hg2+ in ultrapure water, and was also able to detect 5 × 10-12 M Hg2+ in tap water.
Project description:A novel colorimetric assay employing oligonucleotide-conjugated gold nanoparticle (AuNP probes) and rolling circle amplification (RCA) was developed for simple detection of mercuric ions (Hg2+). The thymine-Hg2+-thymine (T-Hg2+-T) coordination chemistry makes our detection system selective for Hg2+. In the presence of Hg2+, the thymine 12-mer oligonucleotide is unable to act as a primer for RCA due to the formation of T-Hg2+-T before the RCA reaction. However, in the absence of Hg2+, DNA coils as RCA products are generated during the RCA reaction, and is further labeled with AuNP probes. Colorimetric signals that depend on the amount of DNA coil-AuNP probe complexes were generated by drop-drying the reaction solution on nitrocellulose-based paper. As the reaction solution spread radially because of capillary action, the complexes formed a concentric red spot on the paper. The colorimetric signals of the red spots were rapidly measured with a portable spectrophotometer and determined as the ?E value, which indicates the calculated color intensity. Our assay displays great linearity (detection limit: 22.4 nM), precision, and reproducibility, thus demonstrating its utility for Hg2+ quantification in real samples. We suggest that our simple, portable, and cost-effective method could be used for on-site Hg2+ detections.
Project description:Mercury ion (Hg2+) is recognized as one of the most toxic metal ions for the environment and for human health. Techniques utilized in the detection of Hg2+ are an important factor. Herein, a simple thymine was successfully employed as the surface enhanced Raman spectroscopy sensor for Hg2+ ion detection. The limit of detection (LOD) of the developed sensor is better than 0.1 nM (0.02 ppb). This sensor can also selectively distinguish Hg2+ ions over 7 types of alkali, heavy metal and transition-metal ions. Moreover, the LOD of the sensor can even achieve 1 ppb in practical application in the nature system, which is half the maximum allowable level (10 nM, 2 ppb) stipulated in the US Environmental Protection Agency standard. Further investigation of the thymine-Hg2+-thymine coordination mechanism provides a possible means of detecting other metal ions by replacing the metal ion-specific ligands. This work paves the way for the detection of toxic metal ions and environmental problems.
Project description:In the present study, we describe the facile synthesis of silver nanoparticles (AgNPs) and their nanostructures functionalized with 2-aminopyrimidine-4,6-diol (APD-AgNPs) for Hg2+ ion detection. The promising colorimetric response of APD-AgNPs to detect Hg2+ ions was visible with naked eyes and spectroscopic changes were examined by using a UV-Visible spectrophotometer. The aggregation of APD-AgNPs upon addition of Hg2+ ions was due to the chelation effect of the functionalized nanostructures and results in a color change from pale brown to deep yellow color. The probing sensitivity was observed within five minutes with a detection limit of about 0.35 µM/L. The TEM images of APD-AgNPs showed polydispersed morphologies with hexagonal, heptagonal and spherical nanostructures with an average size between 10 to 40 nm. Furthermore, the sensing behavior of APD-AgNPs towards Hg2+ ions detection was investigated using docking and interaction studies.
Project description:Rhodamine-based fluorescent chemosensors 1 and 2 exhibit selective fluorescence enhancement to Fe3+ and Hg2+ over other metal ions at 580 nm in CH(3)CN/H(2)O (3/1, v/v) solution. Bis(rhodamine) chemosensor 1, under optimized conditions (CH(3)CN/HEPES buffer (0.02 M, pH = 7.0) (95/5, v/v)), shows a high selectivity and sensitivity to Hg2+, with a linear working range of 0-50 ?M, a wide pH span of 4-10, and a detection limit of 0.4 ?M Hg2+.