Ti3C2 MXene quantum dots as an efficient fluorescent probe for bioflavonoid quercetin quantification in food samples.

BACKGROUND: Quercetin (QC) is known as a typical antioxidant as a bioflavonoid, and its quick, sensitive, and specific detection is crucial for assessing food products. In this study, for the purpose of luminescence-based sensing of QC, bright bluish-green emissive quantum dots of N-doped MXene-based titanium carbide (Ti3C2) were fabricated. Recently, MXene quantum dots (MX-QDs), the rapidly emerging zero-dimensional nanomaterials made from two-dimensional transition metal carbides, have attracted much interest due to their unique physical and chemical features. These include the extremely large surface-to-volume ratio, biocompatibility, luminescence tunability, and hybridization capability while retaining properties of their two-dimensional counterpart including good conductivity and charge transferability. RESULTS: The fabricated Ti3C2 MX-QDs had a quantum yield of 8.13 % at the emission wavelength of λem = 465 nm and displayed excellent photostability with great colloidal stability. It was found that introducing QC to near Ti3C2 MX-QDs reduced their fluorescence signals due to quenching effects. These quenching effects that occurred in a very broad linear range of QC (25-600 nM) enabled QC to be sensed quantitatively with the limit of detection of QC (1.35 nM), being the lowest ever reported to date. The quenching phenomena that caused such excellent sensitivity could be accounted for by combined effects of static quenching/radiation-free complex formation and inner filter effects (IFE) of Ti3C2 MX-QDs with QC. SIGNIFICANCE: In addition, the quenching-based detection demonstrated excellent specificity against structurally relevant interferants. Therefore, the presented sensing strategies with Ti3C2 MX-QDs-based fluorescence quenching can be one of the strongest candidates as a reliable and cost-effective solution to highly sensitive quantification of QC in food samples.

Yellow Emissive Carbon Dots - A Robust Nanoprobe for Highly Sensitive Quantification of Jaundice Biomarker and Mitochondria Targeting in Cancer Cells.

The abnormally high level of bilirubin (BR) in biofluids (human serum and urine) indicates a high probability of jaundice and liver dysfunction. However, quantification of BR as the Jaundice biomarker is difficult due to the interference of various biomolecules in serum and urine. To address this issue, we developed a fluorescence-based detection strategy, for which yellow emissive carbon dots (YCDs) were produced from a one-step solvothermal process using phloroglucinol and thionin acetate as chemical precursors. The as-fabricated YCDs exhibited a strong fluorescence peak at the wavelength of 542 nm upon excitation at 390 nm. We used YCDs for detecting BR through the fluorescence turn-off mechanism, unveiling the excellent sensitivity in the linear range of 0.5-12.5 µM with a limit of detection (LOD) of 9.62 nM, which was far below the clinically relevant range. The analytical nanoprobe also offered excellent detection specificity for quantifying BR in real samples. Moreover, the biocompatible fluorescent nanoprobe was successfully employed to target mitochondria in live cancer cells. A colocalization study confirmed that YCDs possessed the ability to target mitochondria and overlapped completely with MitoTracker Red. The developed nanoprobe of YCDs turned out to be straightforward in their synthesis, noninvasive, and can be utilized for biomedical sensors to diagnose the onset of jaundice as well as for mitochondria targeting.

Smartphone-enabled colorimetric visual quantification of highly hazardous trivalent chromium ions in environmental waters and catalytic reduction of p-nitroaniline by thiol-functionalized gold nanoparticles.

High-efficiency sensing systems for extremely hazardous chromium (Cr(III)) ions are important due to their detrimental effects on human health and the environment. We employed a spectrophotometric method combined with a smartphone (red, green, and blue (RGB) color ratio)-based detection platform to realize the quick, visually quantifiable in situ detection of Cr(III) ions using surface plasmon resonance (SPR)-aided colorimetry. For optical sensing nanoprobes, we synthesized the 2-Mercapto-5-methyl-1,3,4-thiadiazole (MMT)-modified gold nanoparticles (MMT-AuNPs) using a wet chemical method. By way of a coordination reaction, the Cr(III) ions induce the as-prepared MMT-AuNPs to aggregate and subsequently change the SPR wavelength band. The freshly synthesized MMT-AuNPs exhibited a wine-red color. While Cr(III) ions interact with the MMT-AuNPs, the color of the latter evolved from wine red to purple, thus facilitating visual monitoring. The SPR-relevant color change allowed the quantitative sensing of Cr(III) ions in the range of 40-128 nM, with the limit of detection of 6.93 nM when employing the spectrophotometric method and 12.4 nM when using the smartphone RGB color ratio. Furthermore, we developed the spectrophotometric technique that used the smartphone RGB color ratio for on-site analysis of Cr(III) ions in environmental water samples, indicating the possibility of its chemo-sensing applications for portable quantitative detection devices. Additionally, the catalytic performance of the MMT-AuNPs was demonstrated by the reduction of p-nitroaniline in the presence of sodium borohydride. It was interestingly unveiled that the MMT-AuNPs showed outstanding catalytic performance with a catalytic rate constant of 6.31 × 10-3 s-1.

Nitrogen- and Sulfur-Codoped Strong Green Fluorescent Carbon Dots for the Highly Specific Quantification of Quercetin in Food Samples.

Carbon dots (CDs) doped with heteroatoms have garnered significant interest due to their chemically modifiable luminescence properties. Herein, nitrogen- and sulfur-codoped carbon dots (NS-CDs) were successfully prepared using p-phenylenediamine and thioacetamide via a facile process. The as-developed NS-CDs had high photostability against photobleaching, good water dispersibility, and excitation-independent spectral emission properties due to the abundant amino and sulfur functional groups on their surface. The wine-red-colored NS-CDs exhibited strong green emission with a large Stokes shift of up to 125 nm upon the excitation wavelength of 375 nm, with a high quantum yield (QY) of 28%. The novel NS-CDs revealed excellent sensitivity for quercetin (QT) detection via the fluorescence quenching effect, with a low detection limit of 17.3 nM within the linear range of 0-29.7 µM. The fluorescence was quenched only when QT was brought near the NS-CDs. This QT-induced quenching occurred through the strong inner filter effect (IFE) and the complex bound state formed between the ground-state QT and excited-state NS-CDs. The quenching-based detection strategies also demonstrated good specificity for QT over various interferents (phenols, biomolecules, amino acids, metal ions, and flavonoids). Moreover, this approach could be effectively applied to the quantitative detection of QT (with good sensing recovery) in real food samples such as red wine and onion samples. The present work, consequently, suggests that NS-CDs may open the door to the sensitive and specific detection of QT in food samples in a cost-effective and straightforward manner.

Cysteamine-decorated gold nanoparticles for plasmon-based colorimetric on-site sensors for detecting cyanide ions using the smart-phone color ratio and for catalytic reduction of 4-nitrophenol.

In this paper, we have reported the cyanide ions (CN-) sensing in environmental water samples using cysteamine-capped gold nanoparticles (Cyst-AuNPs) by spectrophotometric, colorimetric, and smartphone-based RGB color detection. The surface plasmon resonance shift at around 525 nm for the Cyst-AuNPs could be used to detect quantitatively the amounts of CN- with concomitant alteration of their color from wine red to purple visualized by the naked eye. For the first time, the Cyst-AuNPs-based visual sensing of CN- was performed using smartphone-based detection with its detection limit of 159 × 10-9 M, ten times lower than that of the highest tolerance level (2 × 10-6 M) permitted by the world health organization. The Cyst-AuNPs displayed excellent specificity for detecting the concentration of 30 × 10-6 M even amid the presence of other interfering inorganic anions with their concentrations about five times higher than it. Environmental real water samples were used to arrange the three different CN- concentrations for plasmon-based colorimetric detection and smartphone-based method. Additionally, the catalytic performance of Cyst-AuNPs was demonstrated for the fast catalytic conversion of hazardous 4-nitrophenol (selected environmental contaminant) to the analogous amino aromatic compounds. A chemical kinetic study showed the conversion rate to be estimated as 1.65 × 10-2 s-1. Cyst-AuNPs can find an application in colorimetric sensing of CN- while being able to be utilized as a catalytic nanomaterial for ecological remedies associated with health care.

Optical Sensing of Toxic Cyanide Anions Using Noble Metal Nanomaterials.

Water toxicity, one of the major concerns for ecosystems and the health of humanity, is usually attributed to inorganic anions-induced contamination. Particularly, cyanide ions are considered one of the most harmful elements required to be monitored in water. The need for cyanide sensing and monitoring has tempted the development of sensing technologies without highly sophisticated instruments or highly skilled operations for the objective of in-situ monitoring. Recent decades have witnessed the growth of noble metal nanomaterials-based sensors for detecting cyanide ions quantitatively as nanoscience and nanotechnologies advance to allow nanoscale-inherent physicochemical properties to be exploited for sensing performance. Particularly, noble metal nanostructure e-based optical sensors have permitted cyanide ions of nanomolar levels, or even lower, to be detectable. This capability lends itself to analytical application in the quantitative detection of harmful elements in environmental water samples. This review covers the noble metal nanomaterials-based sensors for cyanide ions detection developed in a variety of approaches, such as those based on colorimetry, fluorescence, Rayleigh scattering (RS), and surface-enhanced Raman scattering (SERS). Additionally, major challenges associated with these nano-platforms are also addressed, while future perspectives are given with directions towards resolving these issues.

Smart phone assisted quinoline-hemicyanine based fluorescent probe for the selective detection of glutathione and the application in living cells.

Quinoline appended hemicyanine 6MIM with strong ICT character was successfully synthesized through simple condensation reaction of 6-methoxy-2-chloro-3-formyl quinoline with 2-benzothiazolinium iodide. The photophysical characteristics of synthesized probe revealed that it would selectively detect glutathione (GSH) when it compared with different amino acids including biothiols and the detection limit is found to be 100 nM. The turn off sensor is due to thiol-halogen SNAr nucleophilic substitution between 6MIM and thiol group in glutathione. More importantly, the biosensor 6MIM was effectively applied in the fluorescence bioimaging of GSH in living cells with low cell toxicity. The colorimetric detectable color change of 6MIM-GSH has been effectively integrated with smartphone assisted RGB color value application with lowest detection value of 120 nM.

Red emitting human serum albumin templated copper nanoclusters as effective candidates for highly specific biosensing of bilirubin.

In this paper, we report a new type of human serum albumin (HSA) stabilized red emissive copper nanoclusters (HSA-CuNCs) were prepared at room temperature and HSA-CuNCs were applied to identify the bilirubin in human urine and blood serum samples. The emission characteristics of synthesized HSA-CuNCs were pH responsive to that the intensity of emission enhanced quickly with varying the pH range from 12 to 6. Emission spectral signal of HSA-CuNCs was found as reduced well with the raise in the amounts of bilirubin attributed to strong binding attraction leads to the non-fluorescent complex formation of HSA-CuNCs with bilirubin. Due to the strong affinity between the nanoprobe and analyte, the red emissive HSA-CuNCs illustrates more specific for the detection bilirubin over the different potential interfering molecules. Two good linear relationships were distinguished the relative emission intensity of HSA-CuNCs versus bilirubin concentrations range from 1.25 × 10-6 to 7.50 × 10-6 M and 5.00 × 10-6 to 2.875 × 10-5 M with lowest limit of detection was determined as 35.00 × 10-9 M and 145.00 × 10-9 M (S/N = 3), respectively. Furthermore, this methodology was effectively used in the quantification of bilirubin in clinical (real) samples. In addition, this fluorometric method offers cost-effective, easy, highly specific and ultrasensitive optical platform for the determination of bilirubin.

New insights into the binding interaction of food protein ovalbumin with malachite green dye by hybrid spectroscopic and molecular docking analysis.

Communicated by Ramaswamy H. Sarma.

Investigation of binding interactions between BSA and [EPMpyr][Sal] through spectroscopy studies, thermophysical and thermodynamic properties.

The intensity of research, probing the interactions between proteins and ionic liquid (IL), has been increasing and parallels the fast-growing applications of ILs in biotechnology. The specific aspects which have attracted the involvement of researchers are stabilization, separation, biochemical and enzymatic reactions of proteins. In this work the synthesis of IL, epoxypropyl and N-methyl substituted 2­oxopyrrolidinium cation with salicylate anion, [EPMpyr][Sal], and its interaction with aqueous BSA{BSA(aq)-[EPMpyr][Sal]}. Measurements of thermophysical properties (density (ρ), and speed of sound (u)) showed that both moderately strong and weak interactions occur on treatment of BSA with that chosen IL. H-bond formation, dipole-dipole interactions and ionic interactions occurring in this system were investigated via thermophysical and thermodynamic properties as well as spectroscopic data. Thermodynamic data (excess molar volume (VmE), isentropic compressibility (ks), deviation in isentropic compressibility (∆ks) and intermolecular free length (Lf)) showed that there were stronger interaction between IL and BSA at higher temperature. The data from all the studies were correlated with Redlich Kister polynomial equation. The blue shift observed in the fluorescent spectra was interpreted to indicate that thetryptophan (Trp) residue of BSA moves to a more hydrophobic environment. It was also observed that the addition of more IL to BSA resulted in denaturation of BSA due to high hydrophobic nature of IL. Circular dichroism studies show that there were significant changes in the fine structure of BSA on interaction with IL. From the FTIR spectra the position of H-bond in the secondary structure of BSA was deduced.

Synthesis of novel 1,10-phenanthroline derivatives and it used as probes for sensitive detection of Zn2+ and Cd2+ metal ions - Spectroscopic and theoretical approach.

A novel class of unexpected 1,10-phenanthrolinederivatives were synthesized from 2,3-dihydroacridin-4(1H)-ones with 3-aminonaphthalen-2-carboxylic acid in presence of phosphorus oxychloride at 130°C and simple perceptive emission intensity increasing assay was developed effectively to detect the very low concentrations of Zn2+ and Cd2+ ions. Emission intensity of compounds 3(a-c) directly related to the concentrations of Zn2+ and Cd2+ ions was due to metal chelating enhanced fluorescence (CHEF) effect and also its further validated by fluorescence lifetime measurement. Furthermore, the sensing mechanism for compounds 3(a-c) of Zn2+ and Cd2+ were sustained by theoretical calculations. Computational analysis results reveals that compounds 3(a-c) are more interested in Zn2+ ions than that of Cd2+ ions, while, compound 3c is more interested with Zn2+ and Cd2+ ions than those of the rest of the compounds. In addition, this proposed detection analysis has the direct application for monitoring Zn2+ and Cd2+ concentrations in tap and drinking water samples.

Coumarin based hydrazone as an ICT-based fluorescence chemosensor for the detection of Cu2+ ions and the application in HeLa cells.

We have constructed a new coumarin based fluorescence probe BENZPYR with ICT character through condensation of N, N-diethylamino-3-acetyl coumarin with 2-hydrazinobenzothiazole. The absorbance and fluorescence spectral characteristics of BENZPYR revealed that the chemosensor can specifically detect for Cu2+ ions over other different metal ions and the lowest limit of detection was found in nano molar range. The turn off sensor of BENZPYR is related to chelation enhanced quenching (CHEQ) and intramolecular charge transfer (ICT) processes were serve as excellent fluorescent detection of Cu2+ ions in DMF medium. Fluorescence microscopy experiments revealed that probe BENZPYR may have application as a fluorophore to detect the Cu2+ in living cells. The simulated DFT analysis of electronic and structural properties and also UV-vis absorption spectra are in well accordance with the experimental UV-vis absorption spectra.

Protein-Localized Bright-Red Fluorescent Gold Nanoclusters as Cyanide-Selective Colorimetric and Fluorometric Nanoprobes.

Herein, we describe a bright-red-emitting ovalbumin-protected gold nanoclusters (OVA-AuNCs) that were prepared and applied as a luminescent probe for a simple, rapid, and highly sensitive determination of cyanide ions (CN- ions) based on an emission quenching and colorimetric method. Initially, an intense red-emissive fluorescence of the OVA-AuNCs successfully disappeared upon the addition of CN- ions. The resultant emission-quenching process involved CN- ions etching the OVA-AuNC surface, which produced AuCN2 - complexes in the presence of ambient oxygen. Under optimized experimental conditions, the relative emission intensity is inversely relative to CN- ion concentrations ranging from 5.00 × 10-7 to 75.00 × 10-7 mol/L with a linear correlation coefficient of 0.9932. Furthermore, OVA-AuNC-based optical detection systems on both colorimetric and fluorometric assays were tested, which expose highly sensitive and specific determination of CN- ions, and it is easily visualized by the naked eye (day light and UV light). Because of the distinct Elsner reaction between Au atoms of OVA-AuNCs and CN- ions, the recent nanoprobe offered ultrasensitivity and good selectivity with the lowest limit of detection value of 68.00 × 10-9 mol/L. In addition, this fluorescence "turn-off" CN- ion detection method was executed in real water samples. The demonstrated route of OVA-AuNC preparation is extremely easy and quick, making the proposed selective and sensitive CN- ion sensing assay based on the fluorescence response of the OVA-AuNCs for numerous practical applications.

Fluorescence Sensing Approach for High Specific Detection of 2,4,6-Trinitrophenol Using Bright Cyan Blue Color-Emittive Poly(vinylpyrrolidone)-Supported Copper Nanoclusters as a Fluorophore.

In this paper, we illustrate an efficient, convenient, and simplistic fluorescence technique for the specific identification for nitro explosive 2,4,6-trinitrophenol (TNP) in 100% water medium by bright cyan blue color-emitting poly(vinylpyrrolidone)-supported copper nanoclusters (PVP-CuNCs) as a fluorescence probe. PVP-CuNCs exhibited linear fluorescence quenching response toward the increasing concentration of TNP analyte. Surprisingly, TNP only reduces the emission signal of PVP-CuNCs, whereas various nitro explosives cause very slight reducing emission intensity, validating the good specificity of the PVP-CuNC probe toward TNP. The highest Stern-Volmer quenching constant (K sv) value of 1.03 × 107 dm3 mol-1 and the extremely lowest limit of detection of 81.44 × 10-12 mol dm-3 were achieved solely for TNP in 100% water medium which is astonishing and exclusive for this nanoprobe. The sensing pathway for the high sensitivity of PVP-CuNCs assay to quantify the TNP is expected to combine with the inner filter effect process and static quenching. The static quenching mechanism between TNP and PVP-CuNCs is further verified by fluorescence decay measurements. Furthermore, the developed fluorescence sensing platform is applied for the quantification of a trace amount of TNP in real samples named dam water, sea water, and match stick.