Chemical fractionation of particulate-bound metal(loid)s to evaluate their bioavailability, sources and associated cancer risk in India.

Eleven potentially toxic metal(loid)s (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn), proven source markers of mineral based coal-fired industrial emissions and vehicular exhausts, were analysed using the four steps sequential extraction method to evaluate metal(loid)s concentration, in total and fractions of bioavailable and non-bioavailable for fine (PM2.5) and coarse (PM10-2.5) particulate modes. A total of 26-day-wise samples with three replications (total number of samples = 78) were collected in January-December 2019 for each PM10 and PM2.5 at an urban-residential site in India. In both the coarse and fine particulate modes, Pb and Cr have respectively shown the highest and lowest total concentrations of the measured metal(loid)s, indicating the presence of coal-fired power plants and heavy vehicular activities near to study area. In addition, Mn has shown highest bioavailable fraction for both coarse and fine particulate modes. More than 50 % of metal(loid)s concentration, in total to a bioavailable fraction (BAF) were observed in case of As, Cd, Cr, Co, Mn, Ni, and Pb of PM2.5. Mn and Zn have shown similar behaviour in the case of coarse particulate mode. Source apportionment of metal(loid)s bioavailable fractions using positive matrix factorization (PMF 5.0) has found three significant sources: crustal and natural dust (30.04 and 39 %), road traffic (49.57 and 20 %), and industrial emission (20.39 and 41 %) for coarse and fine particulate mode, respectively. Cancer risk through the inhalation pathway was high in total concentration but lower in BAF concentration in both age groups (children and adults).

Interaction of Folic Acid with Mn2+ Doped CdTe/ZnS Quantum Dots: In Situ Detection of Folic Acid.

To utilize the nanomaterials as an effective carrier for the drug delivery applications, it is important to study the interaction between nanomaterials and drug or biomolecules. In this study GSH functionalized Mn2+-doped CdTe/ZnS QDs has been utilized as a model nanomaterial due to its high luminescence property. Folic acid (FA) gradually quenches the FL of GSH functionalized Mn2+ - doped CdTe/ZnS QDs. The Stern-Volmer quenching constant (Ksv), binding constant (Ks) and effective quenching constant (Ka) for the FA-QDs system is calculated to be 1.32 × 105 M-1, 1.92 × 105 and 0.27 × 105 M-1, respectively under optimized condition (Temp. 300 K, pH 8.0, incubation time 40 min.). The effects of temperature, pH, and incubation time on FA-QDs system have also been studied. Statistical analysis of the quenched FL intensity versus FA concentration revealed a linear range from 1 × 10-7 to 5.0 × 10-5 for FA detection. The LOD of the current nano-sensor for FA was calculated to be 0.2 µM. The effect of common interfering metal ions and other relevant biomolecules on the detection of FA (12.0 µM) have also been investigated. L-cysteine and glutathione displayed moderate effect on FA detection. Similarly, the common metal ions (Na+, K+, Ca2+ and Mg2+) produced minute interference while Zn2+ Cu2+ and Fe3+ exert moderate interference. Toxic metal ions (Hg2+ and Pb2+) produced severe interferences in FA detection.Graphical abstract GSH-Mn2+ CdTe/ZnS QDs based Fluorescence Nanosensor for Folic acid.

Colorimetric determination of L-cysteine in milk samples with surface functionalized silver nanoparticles.

A simple, selective and sensitive method is proposed for determination of cysteine (Cys) in milk samples using ionic liquid functionalized silver nanoparticles (ILs-AgNPs) as a colorimetric probe. ILs-AgNPs was synthesized by simple reduction method using silver nitrate as a precursor and sodium borohydride as a reducing agent and functionalized with ILs to prevent particles from self-aggregation. The sensing mechanism has been dependent on the color change of ILs-AgNPs and red shift of absorption band from 395 nm to 560 nm in the visible region, which is found proportional to the concentration of target analyte in sample. ILs-AgNPs was characterized in absence and presence of Cys by UV-vis, Fourier transform-infrared (FTIR) spectroscopy, transmission electron microscope (TEM) and dynamic light scattering (DLS). The linear range was acquired in the range of 0-100 ng mL-1, with correlation coefficient (R2) of 0.996 and limit of detection (LOD) of 4.0 nM. The binding mechanism and interactions between Cys and ILs-AgNPs was confirmed by calculating the binding constant and thermodynamic parameters such as enthalpy (∆H), entropy (∆S) and Gibb's free energy (∆G). The use of ILs-AgNPs exhibited high colorimetric selectivity for Cys in milk samples in presence of other amino acids. This proposed strategy possessed the advantages of simplicity and selectivity, hence is applied for analysis of Cys in milk samples.

Glycosylated-imidazole aldoximes as reactivators of pesticides inhibited AChE: Synthesis and in-vitro reactivation study.

The present armamentarium of commercially available antidotes provides limited protection against the neurological effects of organophosphate exposure. Hence, there is an urgent need to design and develop molecules that can protect and reactivate inhibited-AChE in the central nervous system. Some natural compounds like glucose and certain amino acids (glutamate, the anion of glutamic acid) can easily cross the blood brain barrier although they are highly polar. Glucose is mainly transported by systems like glucose transporter protein type 1 (GLUT1). For this reason, a series of non-quaternary and quaternary glycosylated imidazolium oximes with different alkane linkers have been designed and synthesized. These compounds were evaluated for their in-vitro reactivation ability against pesticide (paraoxon-ethyl and paraoxon-methyl) inhibited-AChE and compared with standards antidote AChE reactivators pralidoxime and obidoxime. Several physicochemical properties including acid dissociation constant (pKa), logP, logD, HBD and HBA, have also been assessed for reported compounds. Out of the synthesized compounds, three have exhibited comparable potency with a standard antidote (pralidoxime).

CdTe QD-based inhibition and reactivation assay of acetylcholinesterase for the detection of organophosphorus pesticides.

An enzyme immobilized glutathione (GSH)-capped CdTe quantum dot (QD)-based fluorescence assay has been developed for monitoring organophosphate pesticides. In principle, GSH-capped CdTe QDs exhibit higher sensitivity towards H2O2 produced from the active enzymatic reaction of acetylcholinesterase (AChE) and choline oxidase (CHOx), which results in the fluorescence (FL) "turn-off" of the GSH-capped CdTe QDs. A "turn-on" FL of the CdTe QDs at 520 nm was recovered in the presence of organophosphate (OP). The FL changes of the GSH-capped CdTe QD/AChE/CHOx biosensor reasonably correspond to the amount of OP pesticides. The detection limit of the CdTe/AChE/CHOx biosensor towards paraoxon, dichlorvos, malathion and triazophos was 1.62 × 10-15 M, 75.3 × 10-15 M, 0.23 × 10-9 M and 10.6 × 10-12 M, respectively. The GSH-capped CdTe QDs/AChE/CHOx biosensor was applied as a FL nanoprobe for assaying the enzymatic activity of AChE. The inhibited AChE was reactivated up to 94% using pyridine oximate (2-PyOx-), and functionalized pyridinium oximates (4-C12PyOx- and 4-C18PyOx-) of varying chain lengths. It was found that the reactivation potency of the tested oximes varied with the chain length of the oximes. This biosensing system offers the promising benefit for the determination of the OP pesticides in food, water and environmental samples.

Antibacterial properties of amino acid functionalized silver nanoparticles decorated on graphene oxide sheets.

Graphene oxide (GO) sheets decorated with amino acid L-cysteine (L-cys) functionalized silver nanoparticles (GO-L-cys-Ag) was synthesized by AgNO3, trisodium citrate, and NaBH4. GO-L-cys-Ag nanocomposite was characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectra, ultraviolet-visible (UV-vis) absorption spectra, which demonstrated that a diameter of L-cys-AgNPs compactly deposited on GO. Antibacterial activity tests of GO-L-cys-Ag nanocomposite were carried out using Escherichia coli MTCC 1687 and Staphylococcus aureus MTCC 3160 as model strains of Gram-negative and Gram-positive bacteria, respectively. The effect of bactericide dosage on antibacterial activity of GO-L-cys-Ag nanocomposite was examined by plate count, well diffusion and broth dilution methods. Morphological observation of bacterial cells by scanning electron microscope (SEM) showed that GO-L-cys-Ag nanocomposite was more destructive to cell membrane of Escherichia coli than that of Staphylococcus aureus. The above technique establish that the bactericidal property of GO-L-cys-Ag nanocomposite with wide range of applications in biomedical science.

Surface plasmon resonance based spectrophotometric determination of medicinally important thiol compounds using unmodified silver nanoparticles.

The determination of thiol based biological molecules and drugs, such as cysteine (Cys) (I), α-lipoic acid (II), and sodium 2-sulfanylethane sulphonate (Mesna (III)) in human plasma are becoming progressively more important due to the growing body of knowledge about their essential role in numerous biological pathways. Herein we demonstrate a sensitive colorimetric sensor for the determination of medicinally important thiol drugs based on aggregation of the citrate capped silver nanoparticles (Ag NPs). This approach exploited the high affinity of thiols towards the Ag NPs surface which could tempt replacement of the citrate shell by the thiolate shell of target molecules, resulting in aggregation of the NPs through intermolecular electrostatic interaction or hydrogen-bonding. Because of aggregation, the plasmon band at around 400nm decreases gradually, along with the appearance of a new band connoting a red shift. The calibration curves are derived from the intensity ratios of A530/A400, which display a linear relation in the range of 1µM-150µM, 5µM-200µM and 10µM-130µM, respectively. The obtained detection limits (3σ) were found to be 1.5µM, 5.6µM and 10.2µM for compound I-III, respectively. The proposed method has been successfully applied for the detection of thiol compounds in real samples.

Green Luminescent CdTe Quantum Dot Based Fluorescence Nano-Sensor for Sensitive Detection of Arsenic (III).

Arsenic (As3+) is a hazardous and ubiquitous element; hence the quantitative detection of arsenic in various kinds of environmental sample is an important issue. Herein, we reported L-cysteine capped CdTe Quantum dot based optical sensor for the fluorometric detection of arsenic (III) in real water sample. The method is based on the fluorescence quenching of QDs with the addition of arsenic solution that caused the reduction in fluorescence intensity due to strong interaction between As3+ and L-cysteine to form As(Cys)3. The calibration curve was linear over 2.0 nM-0.5 µM arsenic with limit of detection (LOD) of 2.0 nM, correlation coefficient (r2) of 0.9698, and relative standard deviation (RSD %) of 5.2%. The Stern-Volmer constant for the quenching of CdTe QDs with As3+ at optimized condition was evaluated to be 1.17 × 108 L mol-1 s-1. The feasibility of the sensor has been analyzed by checking the inference of common metal ions available in the water such as K+, Na+, Mg2+, Ca2+, Ba2+, Cu2+, Ni2+, Zn2+, Al3+, Co2+, Cr2+, Fe3+ and its higher oxidation state As5+. Graphical Abstract Schematic representation of As3+ detection by L-Cysteine capped CdTe QDs.