Using functionalized asphaltenes as effective adsorbents for the removal of chromium and lead metal ions from aqueous solution.

For the first time, functionalized asphaltene has been designed, synthesized, and used for the removal of heavy metals from the water. Asphaltene was separated from the crude oil with the addition of n-alkanes. Asphaltene having a complex chemical structure including multilayered and clustered aromatic fused rings bearing aliphatic chains. Asphaltene also contains heteroatoms like N, S, and O atoms along with Ni and V as prominent trace metals. On functionalization of asphaltene with nitric acid, the aliphatic chains and some of the naphthenic rings broke down and developed -COOH, -CO, C-O, and other oxygen functional groups which are playing key roles as surface-active agents in the removal of the heavy metals via chemisorption. The study was conducted using different parameters such as dose, time, pH, and concentration. The adsorption efficiency for this material at pH 4 is excellent for the removal of chromium and lead. The Langmuir, Freundlich and Temkin adsorption isotherm models as well as Lagergren pseudo second-order kinetic model were investigated. The positive enthalpies ΔHs confirm that the adsorption process is endothermic and the negative free energies ΔGs confirm the spontaneity of the process. The good efficiency of the adsorption implies the efficacy in the removal of the heavy metal ions, as well as the good efficiency in desorption, which implies the excellent recovery of the adsorbent. The effective reusability of this adsorbent makes it applicable for industrial water treatment from contaminants.

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.

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.

Facile Green Synthesis of BCN Nanosheets as High-Performance Electrode Material for Electrochemical Energy Storage.

Two-dimensional hexagonal boron carbon nitride (BCN) nanosheets (NSs) were synthesized by new approach in which a mixture of glucose and an adduct of boric acid (H3 BO3 ) and urea (NH2 CONH2 ) is heated at 900 °C. The method is green, scalable and gives a high yield of BCN NSs with average size of about 1 µm and thickness of about 13 nm. Structural characterization of the as-synthesized material was carried out by several techniques, and its energy-storage properties were evaluated electrochemically. The material showed excellent capacitive behaviour with a specific capacitance as high as 244 F g(-1) at a current density of 1 A g(-1) . The material retains up to 96 % of its initial capacity after 3000 cycles at a current density of 5 A g(-1) .

Inner-filter effect of nitrogen-doped carbon quantum dots-MnO2 nanotubes for smartphone-integrated dual-mode sensing of glutathione and captopril.

Nitrogen-doped carbon quantum dots (N-CQDs) exhibit unique fluorescence properties and are considered one of the best candidates for the development of fluorescence-based sensors for the detection of many analytes. In this work, a smartphone-assisted fluorescent sensor has been developed using N-CQDs and MnO2 nanotubes (MnO2 NTs) for the detection of glutathione (GSH) and captopril (CAP). N-CQDs were facilely synthesized via the solvothermal method, where o-phenylenediamine (o-PD) and urea were used as nitrogen precursors. Likewise, MnO2 NTs were synthesized using the hydrothermal method. Relying on the excellent fluorescence quenching ability of MnO2 NTs, a nanocomposite of N-CQDs and MnO2 NTs is prepared, wherein the fluorescence intensity of N-CQDs was effectively quenched in the presence of MnO2 NTs via the inner-filter effect (IFE). The addition of thiolated compounds (GSH and CAP) helped in the recovery of the fluorescence of N-CQDs by triggering the redox reaction and decomposing the MnO2 NTs. An investigation of fluorescence along with smartphone-based studies by evaluating the gray measurement using Image J software showed a great response towards GSH and CAP providing LODs of 4.70 µM and 5.22 µM (fluorometrically) and 5.76 µM and 2.81 µM (smartphone-based), respectively. The practical applicability of the sensing system has been verified using human blood plasma samples.

ß-Cyclodextrin Stabilized Nanoceria for Hydrolytic Cleavage of Paraoxon in Aqueous and Cationic Micellar Media.

Beta-cyclodextrin (ß-CD) stabilized cerium oxide nanoparticles (ß-CD@CeO2 NPs) were synthesized through a hydrothermal route. The electronic properties, surface functional group, surface composition, size, and morphologies of the as-synthesized ß-CD@CeO2 NPs were characterized using UV-visible spectroscopy, FTIR analysis, high resolution X-ray photoelectron spectroscopy (HRXPS), high resolution transmission electron microscopy (HRTEM), and field emission scanning electron microscopy (FESEM). The pH-dependent variation of the ζ-potential of ß-CD@CeO2 NPs and the catalytic activity of the NPs for the hydrolysis of paraoxon were investigated. The observed pseudo-first-order rate constant (kobs) for the hydrolysis of paraoxon is increased with increasing pH and the ζ-potential of ß-CD@CeO2 NPs. The kinetics and mechanism of hydrolysis of paraoxon in the aqueous and cationic micellar media have been discussed.

A portable smartphone-assisted digital image fluorimetry for analysis of methiocarb pesticide in vegetables: Nitrogen-doped carbon quantum dots as a sensing probe.

The increasing use of pesticides in the agriculture fields strengthen the crop production to meet the needs of increasing population. The residues in water and food materials cause several health hazards. Herein, nitrogen-doped carbon quantum dot (N-CQDs) is designed for determination of methiocarb pesticide in vegetables by fluorescent paper sensor and compared the results with fluorimetry. The fluorescent paper-based detection is performed by recording the change in fluorescence of N-CQDs with introduction of methiocarb using smartphone and ImageJ software. Good linear range was acquired for analysis of methiocarb from 10 to 1000 µgL-1 with a low detection limit (LOD) of 3.5 µgL-1 in fluorimetry; and 700-10,000 µgL-1 with a LOD of 500 µgL-1 in fluorescent paper sensor. A better recovery from 92.0 to 95.4% illustrating the selectivity of both methods for analysis of methiocarb in vegetables. Thus, the advantage of using N-CQDs as a fluorescent sensor for analysis of methiocarb in vegetables is instrument free, portable and user-friendly.

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).

A simple and cost-effective paper-based and colorimetric dual-mode detection of arsenic(iii) and lead(ii) based on glucose-functionalized gold nanoparticles.

We report a simple and cost-effective paper-based and colorimetric dual-mode detection of As(iii) and Pb(ii) based on glucose-functionalized gold nanoparticles under optimized conditions. The paper-based detection of As(iii) and Pb(ii) is based on the change in the signal intensity of AuNPs/Glu fabricated on a paper substrate after the deposition of the analyte using a smartphone, followed by processing with the ImageJ software. The colorimetric method is based on the change in the color and the red shift of the localized surface plasmon resonance (LSPR) absorption band of AuNPs/Glu in the region of 200-800 nm. The red shift (Δλ) of the LSPR band observed was from 525 nm to 660 nm for As(iii) and from 525 nm to 670 nm for Pb(ii). The mechanism of dual-mode detection is due to the non-covalent interactions of As(iii) and Pb(ii) ions with glucose molecule present on the surface AuNPs, resulting in the aggregation of novel metal nanoparticles. The calibration curve gave a good linearity range of 20-500 µg L-1 and 20-1000 µg L-1 for the determination of As(iii) and Pb(ii) with the limit of detection of 5.6 µg L-1 and 7.7 µg L-1 for both metal ions, respectively. The possible effects of different metal ions and anions were also investigated but did not cause any significant interference. The employment of AuNPs/Glu is successfully demonstrated for the determination of As(iii) and Pb(ii) using paper-based and colorimetric sensors in environmental water samples.

Thermodynamic investigation of the interaction between ionic liquid functionalized gold nanoparticles and human serum albumin for selective determination of glutamine.

The excellent biocompatible and monodispersed gold nanoparticles (AuNPs) functionalized by amino based ionic liquid (IL) have been synthesized for the demonstration of their interaction with human serum albumin (HSA). Amino based IL stabilizes the surface of AuNPs and provides a colorimetric sensor platform. The size of synthesized IL-AuNPs was identified by use of transmission electron microscopy (TEM) and dynamic light scattering (DLS) techniques. Molecular interaction of functionalized AuNPs with HSA have been investigated using multispectroscopic techniques, such as UV-Vis, fluorescence and Fourier transform infra-red (FT-IR) spectroscopy. The fluorescence and synchronous fluorescent intensity together indicated that IL-AuNPs exhibits a strong ability to quench the intrinsic fluorescence of HSA via a dynamic quenching mechanism. Moreover, the binding constant (K a), Stern-Volmer quenching constant (K SV) and different thermodynamic parameters, namely Gibb's free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) have been evaluated at different temperatures. This interactive study focuses on the nature of surface modification of IL-AuNPs via HSA for selective detection of glutamine (Glu) with a lower limit of detection of 0.67 nM in the linear range of 10-100 nM for Glu.

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.

Uncovering the origin of enhanced field emission properties of rGO-MnO2 heterostructures: a synergistic experimental and computational investigation.

The unique structural merits of heterostructured nanomaterials including the electronic interaction, interfacial bonding and synergistic effects make them attractive for fabricating highly efficient optoelectronic devices. Herein, we report the synthesis of MnO2 nanorods and a rGO/MnO2 nano-heterostructure using low-cost hydrothermal and modified Hummers' methods, respectively. Detailed characterization and confirmation of the structural and morphological properties are done via X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM). Compared to the isolated MnO2 nanorods, the rGO/MnO2 nano-heterostructure exhibits impressive field emission (FE) performance in terms of the low turn-on field of 1.4 V µm-1 for an emission current density of 10 µA cm-2 and a high current density of 600 µA cm-2 at a relatively very low applied electric field of 3.1 V µm-1. The isolated MnO2 nanorods display a high turn-on field of 7.1 for an emission current density of 10 µA cm-2 and a low current density of 221 µA cm-2 at an applied field of 8.1 V µm-1. Besides the superior FE characteristics of the rGO/MnO2 nano-heterostructure, the emission current remains quite stable over the continuous 2 h period of measurement. The improvement of the FE characteristics of the rGO/MnO2 nano-heterostructure can be ascribed to the nanometric features and the lower work function (6.01 and 6.12 eV for the rGO with 8% and 16% oxygen content) compared to the isolated α-MnO2(100) surface (Φ = 7.22 eV) as predicted from complementary first-principles electronic structure calculations based on density functional theory (DFT) methods. These results suggest that an appropriate coupling of rGO with MnO2 nanorods would have a synergistic effect of lowering the electronic work function, resulting in a beneficial tuning of the FE characteristics.

A colorimetric nanoprobe based on enzyme-immobilized silver nanoparticles for the efficient detection of cholesterol.

A large number of cardiovascular diseases have recently become of serious concern throughout the world. Herein, we developed a colorimetric probe based on functionalized silver nanoparticles (AgNPs) for the efficient sensing of cholesterol, an important cardiovascular risk marker. A simple sodium borohydride reduction method was employed to synthesize the AgNPs. The cholesterol oxidase (ChOx)-immobilized AgNPs interact with free cholesterol to produce H2O2 in proportion to the concentration of cholesterol, resulting in decreased AgNP absorbance (turn-off) at 400 nm due to electron transfer between the AgNPs and H2O2. The response of the sensor can also be observed visually. The absorption intensity of the AgNPs is recovered (turn-on) upon the addition of sodium dodecyl sulfate due to the inhibition of ChOx. This on-off mechanism was effectively applied to detect cholesterol within the concentration range 10-250 nM with a low detection limit of approximately 0.014 nM. Moreover, the selectivity of the sensor toward cholesterol was analyzed in the presence of a range of interfering organic substances such as glucose, urea, and sucrose. Finally, the potential of the proposed sensor was evaluated using real samples.

Ammonia-modified graphene sheets decorated with magnetic Fe3O4 nanoparticles for the photocatalytic and photo-Fenton degradation of phenolic compounds under sunlight irradiation.

Synthesis of easily separable and eco-friendly efficient catalyst with both photocatalytic and photo-Fenton degradation properties is of great importance for environment remediation application. Herein, ammonia-modified graphene (AG) sheets decorated with Fe3O4 nanoparticles (AG/Fe3O4) as a magnetically recoverable photocatalyst by a simple in situ solution chemistry approach. First, we have functionalized graphene oxide (GO) sheets by amide functional group and then Fe3O4 nanoparticles (NPs) are doped onto the functionalized GO surface. The AG/Fe3O4 nanocomposite showed efficient photocatalytic activity towards degradation of phenol (92.43%), 2-nitrophenol (2-NP) (98%) and 2-chlorophenol (2-CP) (97.15%) within 70-120min. Consequently, in case of photo-Fenton degradation phenomenon, 93.56% phenol, 98.76% 2-NP and 98.06% of 2-CP degradation were achieved within 50-80min using AG/Fe3O4 nanocomposite under sunlight irradiation. The synergistic effect between amide functionalized graphene and Fe3O4 nanoparticles (NPs) enhances the photocatalytic activity by preventing the recombination rate of electron-hole-pair in Fe3O4 NPs. Furthermore, the remarkable reusability of the AG/Fe3O4 nanocomposite was observed up to ten cycles during the photocatalytic degradation of these phenolic compounds.

Facile Synthesis of Unique Cellulose Triacetate Based Flexible and High Performance Gel Polymer Electrolyte for Lithium Ion Batteries.

Lithium ion batteries (LIBs) with polymer based electrolytes have attracted enormous attention due to the possibility of fabricating intrinsically safer and flexible devices. However, economical and eco-friendly sustainable technology is an oncoming challenge to fulfill the ever increasing demand. To circumvent this issue, we have developed a gel polymer electrolyte (GPE) based on renewable polymers like cellulose triacetate and poly(polyethylene glycol methacrylate) p(PEGMA) using a photo polymerization technique. Cellulose triacetate offers good mechanical strength with improved ionic conductivity, owing to its ether and carbonyl functional groups. It is observed that the presence of an open network has a critical impact on lithium ion transport. At room temperature, GPE PC exhibits an optimal ionic conductivity of 1.8 × 10-3 S cm-1 and transference number of 0.7. Interestingly, it affords an excellent electrochemical stability window up to 5.0 V vs Li/Li+. GPE PC shows a discharge capacity of 164 mAhg-1 after the first cycle when evaluated in a Li/GPE/LiFePO4 cell at 0.5 C-rate. Interfacial compatibility of GPE PC with lithium metal improves the overall cycling performance. This system provides a guiding principle toward a future renewable and flexible electrolyte design for flexible LIBs (FLIBs).

Nucleophilic attack of salicylhydroxamate ion at C=O and P=O centers in cationic micellar media.

The reaction between the salicylhydroxamate anion (SHA(-)) and p-nitrophenyl benzoate (PNPB), tris(3-nitrophenyl)phosphate (TRIS), and bis(2,4-dinitrophenyl)phosphate (BDNPP) have been examined kinetically. The α-nucleophile, SHA(-), incorporated into cetyltrimethylammonium bromide (CTAB) micelles accelerates dephosphorylation of tris(3-nitrophenyl)phosphate (TRIS) over the pH range 6.7-11.4. With a 1.0 mM of SHA in CTAB, the nucleophilicity of SHA followed the order of reactivity, PNPB (C=O, carboxylate ester) > TRIS (P=O, triester) > BDNPP (P=O, diester), and monoanionic SHA(-) and dianionic SA(2-) are the reactive species. The critical micelle concentration, cmc, of cetyltrimethylammonium bromide (CTAB) decreases and the fractional ionization constant, α, increases with increasing the concentration of SHA(-). Addition of 1 and 10 mM SHA under the reaction conditions (pH 9.2, borate buffer) led to saturation of the micellar surface and provided qualitative information for the micellar incorporation of hydroxamate ion. Plots of the pseudo-first-order rate constant, k(obs), log k(obs), fraction of hydroxamic acid ionized, α(SHA(-)) and α(SA(2-)), vs pH showed bifunctional nucleophilicity of hydroxamic acid under micellar condition. Plotting k(obs) vs [SHA](T) gave a straight line with intercept k(0). This indicates that hydroxamate ions are very strong nucleophiles for nucleophilic attack at the C and P center. The pseudo-first-order rate constant-surfactant profiles show micelle-assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase.