Quantitative colorimetric sensing of heavy metal ions via analyte-promoted growth of Au nanoparticles with timer or smartphone readout.

This work describes two new colorimetric nanosensors for label-free, equipment-free quantitative detection of nanomolar copper (II) (Cu2+) and mercury (II) (Hg2+) ions. Both are based on the analyte-promoted growth of Au nanoparticles (AuNPs) from the reduction of chloroauric acid by 4-morpholineethanesulfonic acid. For the Cu2+ nanosensor, the analyte can accelerate such a redox system to rapidly form a red solution containing dispersed, uniform, spherical AuNPs that is related to these particles' surface plasmon resonance property. For the Hg2+ nanosensor, on the other hand, a blue mixture consisting of aggregated, ill-defined AuNPs with various sizes can be created, showing a significantly enhanced Tyndall effect (TE) signal (in comparison with that produced in the red solution of AuNPs). By using a timer and a smartphone to quantitatively measure the time of producing the red solution and the TE intensity (i.e., the average gray value of the corresponding image) of the blue mixture, respectively, the developed nanosensors are well demonstrated to achieve linear ranges of 6.4 nM to 100 µM and 6.1 nM to 1.56 µM for Cu2+ and Hg2+, respectively, with detection limits down to 3.5 and 0.1 nM, respectively. The acceptable recovery results obtained from the analysis of the two analytes in the complex real water samples including drinking water, tap water, and pond water ranged from 90.43 to 111.56%.

A bimetallic (Ni/Co) metal-organic framework with excellent oxidase-like activity for colorimetric sensing of ascorbic acid.

A novel nanozyme of bimetallic (Ni/Co) metal-organic framework (Ni/Co-MOF) was synthesized using a simultaneous precipitation and acid etching method with a zeolitic imidazolate framework ZIF-67 as the template. The as-synthesized Ni/Co-MOF catalyst presented a three-dimensional hollow nanocage structure and exhibited excellent intrinsic oxidase-like activity. It was demonstrated that Ni/Co-MOF could directly catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to produce a blue product (oxidized TMB, oxTMB) in the absence of H2O2. The mechanisms and kinetics of this nanozyme activity were investigated, and it was determined that the catalytic activity of Ni/Co-MOF was closely related to temperature and solution pH. Owing to its strong reducibility, ascorbic acid (AA) could reduce oxTMB, and the blue color of the reaction mixture faded over time. Therefore, a novel colorimetric platform was constructed to detect AA based on the oxidase-like activity of Ni/Co-MOF. Under optimal conditions, the absorbance of ox-TMB at 652 nm decreased linearly over the 0.015-50 µM AA range with a detection limit of 0.004 µM.

Tyndall-effect-based colorimetric assay with colloidal silver nanoparticles for quantitative point-of-care detection of creatinine using a laser pointer pen and a smartphone.

Herein, this paper initially reports a new colorimetric Tyndall effect-inspired assay (TEA) for simple, low-cost, sensitive, specific, and point-of-care detection of creatinine (an important small biomolecule) by making use of silver nanoparticles (AgNPs) as model colloidal nanoprobes for visual light scattering signaling. The naked-eye TEA method adopts negatively-charged citrate-capped AgNPs (Cit-AgNPs) prepared by sodium citrate reduction. In the presence of alkaline conditions, the creatinine analyte can form carbanion/oxoanion amino tautomers which in turn crosslink with carboxylate groups on the Cit-AgNPs via a hydrogen bonding network to mediate the aggregation of such colloidal nanoprobes showing a significantly-enhanced TE signal that was created and quantified by a hand-held laser pointer pen and a smartphone, respectively. The results demonstrate that the resulting equipment-free method with the TE readout could enable the portable quantification of creatinine with a detection limit of ∼55 nM, which was ∼90-2334 times lower than that obtained from AgNP-based colorimetric approaches with the most common localized surface plasma resonance signaling. Moreover, it shows a larger analytical sensitivity up to ∼580.8227 signal per nM, offering ∼2.4-232-fold improvement in comparison with many of the recent instrumental creatinine nanosensors. The accuracy and practicality of the developed nanosensing system was additionally confirmed with satisfactory recovery results ranging from ca. 98.52 to 100.36% when analyzing a set of real complex human urine samples.