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      Colorimetric Sensor for Cr(VI) Ion Detection in Tap Water Using a Combination of AuNPs and AgNPs

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          Abstract

          Colorimetric sensors are a promising technique for the simple screening of water, food, and environmental samples contaminated with interferents, allowing for color changes to be observed with the naked eye or a spectrophotometer. In this study, a colorimetric sensor for the selective detection of hexavalent chromium ion (Cr(VI)) contamination in water was developed. A combination of sodium borohydride-coated gold and citrate-capped silver nanoparticles (Na-AuNPs/cit-AgNPs) was employed as a colorimetric probe. Upon the addition of Cr(VI)-contaminated tap water in the colorimetric probe solution, the color sequentially transitioned from its initial orange to dark reddish-purple, dark purplish-red, dark blue-violet, and gray. This colorimetric strategy relies on AgNP dissolution and AuNP aggregation in the presence of the Cr(VI) ions. The dissolution of AgNPs is evidenced by the reduction of the characteristic peak of AgNPs at 400 nm, while the aggregation of AuNPs leads to a red shift in the absorption band at 514 nm, accompanied by broad absorption in the 500–700 nm range. The limits of detections were found to be 22.9 and 50 ppb using a spectrometer and by visual observation, respectively. The synthesized AuNPs and AgNPs are very stable in the presence of media containing complicated ions. We further demonstrated the practical applicability of the developed system for detecting Cr(VI) in real samples, including natural water and artificial urine, highlighting its potential for addressing Cr(VI) contamination in practical scenarios.

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          Chromium in Drinking Water: Sources, Metabolism, and Cancer Risks

          Drinking water supplies in many geographic areas contain chromium in the +3 and +6 oxidation states. Public health concerns are centered on the presence of hexavalent Cr that is classified as a known human carcinogen via inhalation. Cr(VI) has high environmental mobility and can originate from anthropogenic and natural sources. Acidic environments with high organic content promote the reduction of Cr(VI) to nontoxic Cr(III). The opposite process of Cr(VI) formation from Cr(III) also occurs, particularly in the presence of common minerals containing Mn(IV) oxides. Limited epidemiological evidence for Cr(VI) ingestion is suggestive of elevated risks for stomach cancers. Exposure of animals to Cr(VI) in drinking water induced tumors in the alimentary tract, with linear and supralinear responses in the mouse small intestine. Chromate, the predominant form of Cr(VI) at neutral pH, is taken up by all cells through sulfate channels and is activated nonenzymatically by ubiquitously present ascorbate and small thiols. The most abundant form of DNA damage induced by Cr(VI) is Cr-DNA adducts, which cause mutations and chromosomal breaks. Emerging evidence points to two-way interactions between DNA damage and epigenetic changes that collectively determine the spectrum of genomic rearrangements and profiles of gene expression in tumors. Extensive formation of DNA adducts, clear positivity in genotoxicity assays with high predictive values for carcinogenicity, the shape of tumor–dose responses in mice, and a biological signature of mutagenic carcinogens (multispecies, multisite, and trans-sex tumorigenic potency) strongly support the importance of the DNA-reactive mutagenic mechanisms in carcinogenic effects of Cr(VI). Bioavailability results and kinetic considerations suggest that 10–20% of ingested low-dose Cr(VI) escapes human gastric inactivation. The directly mutagenic mode of action and the incompleteness of gastric detoxification argue against a threshold in low-dose extrapolation of cancer risk for ingested Cr(VI).
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            On-off-on fluorescent carbon dot nanosensor for recognition of chromium(VI) and ascorbic acid based on the inner filter effect.

            Chromium(VI) [Cr(VI)] is considered as a severe environmental pollutant, due to its highly toxic and carcinogenic properties. Therefore, low cost, highly sensitive sensors for the determination of Cr(VI) are highly demanded. It is well-known that highly luminescent carbon dots (CDs) have been successfully applied as fluorescent nanosensors for pH, ions, and molecular substances. In the present work, we have demonstrated an on-off fluorescent CD probe for detecting Cr(VI) based on the inner filter effect (IFE) because the absorption bands of Cr(IV) fully covered the emission and excitation bands of CDs. This CD-based nanosensor provides obvious advantages of simplicity, convenience, rapid response, high selectivity, and sensitivity, which have potential application for the detection of Cr(VI) in the environmental industry. In addition, because Cr(VI) can be reduced to low valent chromium species easily by reductant, resulting in the elimination of the IFE and recovery of CD fluorescence, the CD-Cr(VI) mixture could behave as an off-on type fluorescent probe for reductant. We employed ascorbic acid (AA) as an example molecule to demonstrate this off-on type fluorescent probe.
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              Effect of chloride on the dissolution rate of silver nanoparticles and toxicity to E. coli.

              Pristine silver nanoparticles (AgNPs) are not chemically stable in the environment and react strongly with inorganic ligands such as sulfide and chloride once the silver is oxidized. Understanding the environmental transformations of AgNPs in the presence of specific inorganic ligands is crucial to determining their fate and toxicity in the environment. Chloride (Cl(-)) is a ubiquitous ligand with a strong affinity for oxidized silver and is often present in natural waters and in bacterial growth media. Though chloride can strongly affect toxicity results for AgNPs, their interaction is rarely considered and is challenging to study because of the numerous soluble and solid Ag-Cl species that can form depending on the Cl/Ag ratio. Consequently, little is known about the stability and dissolution kinetics of AgNPs in the presence of chloride ions. Our study focuses on the dissolution behavior of AgNPs in chloride-containing systems and also investigates the effect of chloride on the growth inhibition of E.coli (ATCC strain 33876) caused by Ag toxicity. Our results suggest that the kinetics of dissolution are strongly dependent on the Cl/Ag ratio and can be interpreted using the thermodynamically expected speciation of Ag in the presence of chloride. We also show that the toxicity of AgNPs to E.coli at various Cl(-) concentrations is governed by the amount of dissolved AgCl(x)((x-1)-) species suggesting an ion effect rather than a nanoparticle effect.
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                Author and article information

                Journal
                ACS Omega
                ACS Omega
                ao
                acsodf
                ACS Omega
                American Chemical Society
                2470-1343
                06 June 2024
                18 June 2024
                : 9
                : 24
                : 26472-26483
                Affiliations
                []National Nanotechnology Center (NANOTEC), National Science and Technology Development Agency (NSTDA) , Klongluang 12120, Pathum Thani, Thailand
                []Faculty of Science, Center of Excellence for Innovation in Chemistry, Prince of Songkla University , Hat Yai 90110, Thailand
                Author notes
                Author information
                https://orcid.org/0000-0001-7912-5778
                Article
                10.1021/acsomega.4c02699
                11191111
                38911821
                e2a27d56-488b-4e88-8617-45236d87d700
                © 2024 The Authors. Published by American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 20 March 2024
                : 30 May 2024
                : 25 May 2024
                Funding
                Funded by: National Science and Technology Development Agency, doi 10.13039/501100004192;
                Award ID: P2351470
                Funded by: Ministry of Higher Education, Science, Research and Innovation, Thailand, doi 10.13039/501100016204;
                Award ID: 4709265
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                Article
                Custom metadata
                ao4c02699
                ao4c02699

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