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).

Citrate functionalized gold nanoparticles assisted micro extraction of L-cysteine in milk and water samples using Fourier transform infrared spectroscopy.

This paper describes the sensing application of citrate functionalized gold nanoparticles (AuNPs) employing for the determination of L-cysteine in food and water samples. It is established with diffuse reflectance Fourier transform infrared (DRS-FTIR) spectroscopic analysis. The disappearance of the thiol (-SH) band in the FTIR spectra and the shift in the peaks of the amino group (NH3+) and carboxylate group (-COO-) indicated the Au-S interaction and the aggregation of the NPs. The signal intensity of L-cysteine was enhanced due to hot-spots formed by the aggregation of AuNPs producing the effective absorption of electromagnetic radiation in the IR region for molecular vibration. The relationship between AuNPs and L-cysteine was theoretically investigated by the Density Function Theory (DFT) based on LANL2DZ with the aid of the Gaussian 09 (C.01) software. Interaction between AuNPs and L-cysteine molecules resulted to a shift to higher wavelengths in the plasmon bands, further verified by transmission electron microscopes (TEM), which have indicated random aggregated particles. Further dynamic light scattering (DLS) measurements showed a relatively high degree of polydispersity confirming the aggregation of the particles. Under optimized conditions, the calibration curve showed a good linearity range from 20 to 150 µg mL-1 with a correlation coefficient (R2) 0.990. The limit of detection and quantification were 1.04 and 3.44 µg mL-1, respectively by DRS-FTIR. This modified AuNPs sample was used successfully in milk and water samples with adequate results to determine L-cysteine.

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.

L-cysteine modified silver nanoparticles for selective and sensitive colorimetric detection of vitamin B1 in food and water samples.

The use of L-cysteine modified silver nanoparticles (Cys-capped AgNPs) as a colorimetric probe for determination of vitamin B1 (thiamine) is described in the present work. This method is based on the measurement of red shift of localized surface plasmon resonance (LSPR) band of Cys-capped AgNPs in the region of 200-800 nm. The color of Cys-capped AgNPs was changed from yellow to colorless by the addition of vitamin B1. The mechanism for detection of vitamin B1 is based on the electrostatic interaction between positively charged vitamin B1, which causes the red shift of LSPR band from 390 nm to 580 nm. The interaction between Cys-capped AgNPs and vitamin B1 was theoretically explored by density function theory (DFT) using LANL2DZ basis sets with help of Gaussian 09 (C.01) program. The morphology, size distribution and optical properties of Cys-capped AgNPs were characterized by transmission electron microscope (TEM), UV-Visible spectrophotometry, Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering (DLS) techniques. The method is linear in the range of 25-500 µg mL-1 with correlation coefficient (R2) 0.992 and limit of detection of 7.0 µg mL-1. The advantages of using Cys-capped AgNPs as a chemical sensor in colorimetry assay are being simple, low cost and selective for detection of vitamin B1 from food (peas, grapes and tomato) and environmental (river, sewage and pond) water samples.

Smartphone coupled with paper-based chemical sensor for on-site determination of iron(III) in environmental and biological samples.

We report a smartphone-paper-based sensor impregnated with cetyltrimethylammonium bromide modified silver nanoparticles (AgNPs/CTAB) for determination of Fe3+ in water and blood plasma samples. The methodology for determination of Fe3+ is based on the change in signal intensity of AgNPs/CTAB fabricated on a paper substrate after the deposition of analyte, using a smartphone followed by processing with ImageJ software. The mechanism of sensing for detection and determination of Fe3+ is based on the discoloration of AgNPs which impregnated the paper substrate. The discoloration is attributed to the electron transfer reaction taking place on the surface of NPs in the presence of CTAB. Fe3+ was determined when the paper was impregnated with 1 mM AgNPs for 5 min of reaction time and the substrate was kept under acidic conditions. The linear range for determination of total iron in terms of Fe3+ was 50-900 µg L-1 with a limit of determination (LOD) of 20 µg L-1 and coefficient of variation (CV) of 3.2%. The good relative recovery of 91.3-95.0% and interference studies showed the selectivity of the method for determination of total iron in water and blood plasma samples. Smartphone-paper-based sensors have advantages of simplicity, rapidity, user-friendliness, low cost, and miniaturization of the method for on-site determination of total iron compared to methods that require sophisticated analytical instruments. Graphical abstract Smartphone-paper-based sensor with cetyltrimethylammonium bromide modified silver nanoparticles for determination of Fe3+ in water and blood plasma samples.

Removal of endrin and dieldrin isomeric pesticides through stereoselective adsorption behavior on the graphene oxide-magnetic nanoparticles.

A novel stereoselective removal behavior of isomeric endrin and dieldrin pesticides from sample solution is demonstrated using nanocomposite of graphene oxide (GO) and iron oxide (Fe3O4) magnetic nanoparticles (MNPs). The removal efficiency of endrin and dieldrin was found higher when GO-MNPs was used as a separating probe than the individual use of GO and MNPs. The removal efficiency of both the pesticides was found to be more favorable when the dosage amount of GO-MNPs was 30 mg for 30-min contact time with pH 4.0 at room temperature. The good correlation of determination (R 2) with 0.975 and 0.973 values obtained for endrin and dieldrin, respectively demonstrated a well fitting of Langmuir adsorption isotherm model. The higher removal percentage (86.0%) and higher slope value of Langmuir adsorption isotherm were estimated for endrin compared to dieldrin (74.0%). The reason for higher adsorption percentage of endrin is due to the endo-position of oxygen atom in molecule favors more interaction of molecules with GO-MNPs compared to the exo-position of oxygen present in dieldrin. In addition, the higher value of R 2 for endrin and dieldrin demonstrated better suitability of pseudo-first-order and pseudo-second-order kinetic models, respectively. The advantages of the present method are use of simple UV-vis spectrophotometry for monitoring and low-cost use of GO-MNPs nanomaterial for the removal of pesticides from sample solution.

Onsite-detection of barium and nickel from river, pond and tap water samples using gold nanoparticles as a chemical sensor.

We report a simple, selective and sensitive colorimetric assay for onsite determination of Ni(II) and Ba(II) from river, pond and tap water samples using the localized surface plasmon resonance (LSPR) of malonate capped gold nanoparticles (AuNPs) as a chemical sensor. The method is based on the color change and red shift of LSPR absorption band in visible region that caused by the aggregation of NPs because of the coordination complex between Ba(II) and Ni(II) with carboxylate ions of malonate capped AuNPs. The determination of Ba(II) and NI(II) in a same sample was performed by masking one of the analyte at a time, EDTA was used to mask Ni(II) for detection of Ba(II) and dilute H2SO4 was used to mask the Ba(II) for detection of Ni(II). The linear range for quantitative determination of Ba(II) and NI(II) were found in the range of 15-500 and 10-500ngmL-1 with a limit of detection of 5 and 3ngmL-1, respectively. The advantages of the AuNPs based chemical sensor is found to be simple, rapid and sensitive as well as it can be applied at the sample source for trace detection of Ba(II) and Ni(II) in various environmental samples.

Application of platinum nanoparticles as affinity probe and matrix for direct analysis of small biomolecules and microwave digested proteins using matrix-assisted laser desorption/ionization mass spectrometry.

We report the use of platinum nanoparticles (PtNPs) for analysis of amino acids, peptides, proteins and microwave digested proteins (lysozyme and bovine serum albumin) without any tedious washing and separation procedures prior to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the present study, PtNPs play three functions, such as matrix, affinity probe and acceleration of protein digestion by absorbing the microwave irradiation. Good signal intensity of the target molecules from the sample was obtained when laser energy, NPs concentration and incubation time were set to 35 µJ, 25 nM and 30 min, respectively. In addition, higher numbers of peptide sequence were obtained for microwave digested lysozyme protein using PtNPs as compared to previously reported methods for analysis of digested protein in MALDI-MS. Thus, the present method is a simple, rapid and one step preparation method for the analysis of amino acids, peptides, proteins and digested proteins in MALDI-TOF-MS without the need for any tedious purifications and washing procedures.

Quantum dots laser desorption/ionization MS: multifunctional CdSe quantum dots as the matrix, concentrating probes and acceleration for microwave enzymatic digestion for peptide analysis and high resolution detection of proteins in a linear MALDI-TOF MS.

We report the first use of functionalized cadmium selinide quantum dots (CdSe QDs) with 11-mercaptoundecanoic acid (MUA) as the matrix for the selective ionization of proteins with high resolution and rapid analysis of amino acids and peptides by using quantum dots laser desorption/ionization mass spectrometry (QDLDI-MS). The mercaptocarboxylic groups of CdSe QDs have been known to be an effective affinity probe to interact with the biomolecules at low abundance level. Using these QDs as the matrix, sensitivity of the method was greatly enhanced and the LOQ of peptides was found to be 100 pM with RSD <10%. The QDLDI-MS is capable for the selective ionization of insulin, lysozyme and myoglobin with high resolution, which is not observed with sinapic acid (SA) as the matrix. The QDLDI-MS technique offers many advantages for the analysis of amino acids, peptides and proteins with regard to simplicity, rapidity, sensitivity and the mass spectra were generated in the presence of signal suppressors such as urea and Trition X-100. In addition, the CdSe QDs have been successfully applied as preconcentrating probes for the analysis of digested peptides in lysozyme from chicken egg white by microwave-assisted enzymatic digestion. This indicates that the QDs are able to absorb radiation from microwave and their ability to trap peptides from microwave-digested lysozyme. These results demonstrate that the CdSe QDs are promising candidates for the selective ionization of the analytes with an accurate platform to the rapid screening of biomolecules.

Single drop microextraction using silver nanoparticles as electrostatic probes for peptide analysis in atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry and comparison with gold electrostatic probes and silver hydrophobic probes.

Single drop microextraction using tetraalkylammonium bromide coated silver nanoparticles (SDME-AgNPs) prepared in toluene has been successfully applied as electrostatic affinity probes to preconcentrate peptide mixtures in biological samples prior to atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry (AP-MALDI-MS) analysis. This approach is based on the isoelectric point (pI) of peptides and surface charge of AgNPs. Using the SDME-AgNPs technique, from a peptide mixture, Met- and Leu-enkephalins (Met-enk and Leu-enk) were extracted into a droplet of toluene containing AgNPs, but not the neutral peptides (gramicidins). The best peptide extraction efficiency for SDME-AgNPs was observed with the optimized parameters: extraction time 2 min, sample agitation rate 240 rpm, and sample pH 7. The limits of detection (LODs) of the SDME-AgNPs/AP-MALDI-MS technique for Met-enk and Leu-enk peptides were 160 and 210 nM, respectively. Furthermore, the application of the technique has been shown for the analysis of peptides from a sample containing high matrix interferences such as 1% Triton X-100 and 6 M urea. Finally, this approach has been compared with the SDME-AuNPs technique and the results have clearly revealed that the SDME-AgNP affinity probe exhibits higher affinity to extract the sulfur-bearing peptide (Met-enk). We also compared this electrostatic affinity probe of AgNPs with the previously demonstrated hydrophobic affinity probe of AgNPs and found that the electrostatic probe can greatly reduce the extraction time from 1.5 h to 2 min. This is due to the fact that electrostatic attraction forces are much stronger than the hydrophobic attraction forces. Therefore, we concluded that the electrostatic affinity probe based on SDME-AgNPs coupled with AP-MALDI-MS is a high-throughput technique for the analysis of low-abundance peptides from biological samples containing complex matrices.

Applications of silver nanoparticles capped with different functional groups as the matrix and affinity probes in surface-assisted laser desorption/ionization time-of-flight and atmospheric pressure matrix-assisted laser desorption/ionization ion trap mass spectrometry for rapid analysis of sulfur drugs and biothiols in human urine.

A strategy is presented for the analysis of sulfur drugs and biothiols using silver nanoparticles (AgNPs) capped with different functional groups as the matrix and affinity probes in surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI-TOF MS) and atmospheric pressure-matrix assisted laser desorption/ionization ion trap mass spectrometry (AP-MALDI-ITMS). Biothiols adsorbed on the surface of AgNPs through covalent bonding were subjected to ultraviolet (UV) radiation that enabled desorption and ionization due to the excellent photochemical property of NPs. The proposed method has been successfully applied for the determination of cysteine and homocysteine in human urine samples using an internal standard. The limit of detection (LOD) and limit of quantification (LOQ) for cysteine and homocysteine in urine sample are 7 and 22 nM, respectively, with a relative standard deviation (RSD) of <10%. The advantages of the present method compared with the methods reported in the literature for biothiol analysis are simplicity, rapidity and sensitivity without the need for time-consuming separation and tedious preconcentration processes. Additionally, we also found that the bare AgNPs can be directly used as the matrix in MALDI-TOF MS for the analysis of sulfur drugs without the addition of an extra proton source.

Reverse micellar microextraction for rapid analysis of thiol-containing peptides and amino acids by atmospheric-pressure matrix-assisted laser desorption/ionization ion trap and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Simple, rapid and inexpensive one-step reverse micellar microextraction (RMME) procedures were combined with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for the determination of thiol-containing peptides and amino acids. In this investigation, a thiol-containing peptide (HW6) was chosen as model compound to understand the mechanism of RMME. The electrostatic interactions between the thiol-containing peptide and reverse micelles were proposed to be reason for the transfer of analytes from the aqueous phase to the organic phase. Reverse micelles were formed by the cationic surfactant, methyltrioctylammonium chloride (MTOAC). The best extraction efficiency of HW6 was obtained under the following conditions: pH 11.0, ionic strength 5.0 mM of KCl and micelle concentration 7.0 mM of MTOAC. The limits of detection (LODs) obtained for HW6 in water, urine and plasma samples were 0.15, 0.19 and 0.28 microM, respectively, with relative standard deviation (RSD) values in the range +/-8.8-10.5%. The sensitivity obtained in water by the present method was 45-fold higher than that of the conventional use of atmospheric-pressure (AP)-MALDI MS. Furthermore, the applicability of the proposed approach was extended for the determination of thiol-containing amino acids in sample solutions by using MALDI time-of-flight (TOF) MS.

Modified silver nanoparticle as a hydrophobic affinity probe for analysis of peptides and proteins in biological samples by using liquid-liquid microextraction coupled to AP-MALDI-ion trap and MALDI-TOF mass spectrometry.

A new approach of using modified silver nanoparticles (AgNPs) in toluene as hydrophobic affinity probes for the separation and preconcentration of peptides and proteins in biological samples prior to atmospheric pressure-matrix assisted laser desorption/ionization (AP-MALDI) ion trap mass spectrometry and matrix assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry has been successfully demonstrated. To our best knowledge, for the first time, the modified AgNPs with hydrophobic ligands, such as dodecanethiol (DT) and octadecanethiol (OT) in toluene, were used for the liquid-liquid microextraction (LLME) of peptides and proteins through the hydrophobic interactions. In the present investigation, gramicidin was chosen as a model compound to assess the hydrophobic extraction with the modified AgNPs. The optimum extraction efficiency of gramicidine was observed at pH 7.0 for 1.5 h of extraction time with 7% addition of salt. Compared to the conventional use of AP-MALDI-MS, a 266-388-fold improvement in the limit of detection (LOD) for gramicidin was obtained in urine and plasma samples. The lowest concentration of gramicidin that was detected by using modified AgNPs in urine and plasma samples was 0.13 and 0.16 microM, respectively. Furthermore, the proposed method was demonstrated for the extraction of other long chain proteins, like myoglobin, ubiquitin, and bovine serum albumin, in a sample solution by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The major feature of the newly synthesized modified AgNPs was that the target species could be efficiently separated and preconcentrated without sample loss prior to MALDI-MS detection for the sensitive and effective analysis of peptides and proteins in biological samples.

Ultrasonication followed by single-drop microextraction combined with GC/MS for rapid determination of organochlorine pesticides from fish.

A novel, rapid and simple sample pretreatment technique termed ultrasonication followed by single-drop micro-extraction (U-SDME) has been developed and combined with GC/MS for the determination of organochlorine pesticides (OCPs) in fish. In the present work, the lengthy procedures generally used in the conventional methods like, Soxhlet extraction, supercritical fluid extraction, pressurized liquid extraction and microwave assisted solvent extraction for extraction of OCPs from fish tissues are minimized by the use of two simple extraction procedures. Firstly, OCPs from fish were extracted in organic solvent with ultrasonication and then subsequently preconcentrated by single-drop micro-extraction (SDME). Extraction parameters of ultrasonication and SDME were optimized in spiked sample solution in order to obtain efficient extraction of OCPs from fish tissues. The calibration curves for OCPs were found to be linear between 10-1000 ng/g with correlation of estimations in the range 0.990-0.994. The recoveries obtained in blank fish tissues were ranged from 82.1 to 95.3%. The LOD and RSD for determination of OCPs in fish were 0.5 ng/g and 9.4-10.0%, respectively. The proposed method was applied for the determination of bioconcentration factor in fish after exposure to different concentrations of OCPs in cultured water. The present method avoids the co-extraction of lipids, long extraction steps (>12 h) and large amount of organic solvent for the separation of OCPs. The main advantages of the present method are rapid, selective, sensitive and low cost for the determination of OCPs in fish.

Rapid determination of caffeine in one drop of beverages and foods using drop-to-drop solvent microextraction with gas chromatography/mass spectrometry.

A simple and rapid sample cleanup and preconcentration method for the quantitative determination of caffeine in one drop of beverages and foods by gas chromatography/mass spectrometry (GC/MS) has been proposed using drop-to-drop solvent microextraction (DDSME). The best optimum experimental conditions for DDSME were: chloroform as the extraction solvent, 5 min extraction time, 0.5 microL exposure volume of the extraction phase and no salt addition at room temperature. The optimized methodology exhibited good linearity between 0.05 and 5.0 microg/mL with correlation coefficient of 0.980. The relative standard deviation (RSD) and limits of detection (LOD) of the DDSME/GC/MS method were 4.4% and 4.0 ng/mL, respectively. Relative recovery of caffeine in beverages and foods were found to be 96.6-101%, which showing good reliability of this method. This DDSME excludes the major disadvantages of conventional method of caffeine extraction, like large amount of organic solvent and sample consumption and long sample pre-treatment process. So, this approach proves that the DDSME/GC/MS technique can be applied as a simple, fast and feasible diagnosis tool for environmental, food and biological application for extremely small amount of real sample analysis.