Probing the Interaction of Heavy and Transition Metal Ions with Silver Nanoparticles Decorated on Graphene Quantum Dots by Spectroscopic and Microscopic Methods.

We report a comprehensive study of the interaction of transition and heavy metal ions with graphene quantum dots-capped silver nanoparticles (AgGQDs) using different spectroscopic and microscopic techniques. High-resolution transmission electron microscopy studies show that the interaction of metal ions with AgGQDs leads to the formation of metal oxides, the formation of zerovalent metals, and the aggregation of Ag nanoparticles (AgNPs). The metal ions may interact with AgGQDs through selective coordination with -OH and -COOH functionalities, adsorption on the graphene moiety, and directly to AgNPs. For instance, the interaction of Cd2+ with AgGQDs altered the spherical shape of AgNPs into a chain-like structure. On the contrary, the formation of PbO is observed after the addition of Pb2+ to AgGQDs. Interestingly, the interaction of AgGQDs with Hg2+ results in the complete dissolution of Ag0 from the surface of GQDs and subsequent deposition of Hg0 on the graphene moiety of GQDs. Unlike transition metal ions, Cd2+, Pb2+, and Hg2+ can adsorb strongly on the graphene surface at the bridge, hollow, and top sites, respectively. This special interaction of heavy metal ions with the graphene surface would decide the mechanistic pathway in which the reaction proceeds. The transition metal ions Cu2+, Zn2+, Co3+, Mn2+, Ni2+, and Fe3+ induced the aggregation of AgNPs.

Formation of Mercury Droplets at Ambient Conditions through the Interaction of Hg(II) with Graphene Quantum Dots.

Unlike other metals, Hg forms droplets at ambient conditions when a Hg(II) salt interacts with hydroxyl-enriched graphene quantum dots (HEGQDs). The hydroxylation of GQD surface is evident from FT-IR, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) techniques. The scanning electron microscopy images of Hg(II)-HEGQDs incubated for 0, 1, 24, and 168 h show Hg droplets with the size of 0.1, 0.3, 0.8, and 2 µm, respectively. The XPS studies confirm the presence of Hg(0) and also reveal a noticeable decline in the composition percentage of C-O, whereas a marked increase is observed in the C═O composition percentage. The pathway for the formation of droplets induces immediate reduction of Hg(II) to Hg(0) by both hydroxyl groups and π electron cloud present on the surface of HEGQDs, followed by coalescence. The formed Hg(0) is then strongly adsorbed on the hollow sites of graphene and acts as a nucleation site for the growth of droplets. The kinetics of the reaction obeys LaMer Burst nucleation followed by coalescent growth in addition to autocatalytic reduction and finally follows the Oswald ripening mechanism. The internal pressure of Hg droplets gradually decreases as the radius of the drop increases over the incubation time and liquid-rhombohedral transformation is likely to take place at a radius of 0.8 nm.

Unusual Reactivity of Graphene Quantum Dot-Wrapped Silver Nanoparticles with Hg(II): Spontaneous Growth of Hg Flowers and Their Electrocatalytic Activity.

The galvanic reaction (GR) between a graphene quantum dot (GQD)-stabilized AgNP (Ag-GQD)-modified glassy carbon (GC) surface and Hg(II) leads to complete dissolution of AgNPs within 15 min and subsequent growth of Hg(0) as a "flower" on the GQD surface. This is unusual because generally the GR of bulk Ag/AgNPs with Hg(II) leads to the formation of a Hg-Ag amalgam/core shell structure. The appearance of peaks at 99.9 and 103.9 eV in X-ray photoelectron spectroscopy confirms Hg(0) on GQDs, whereas the disappearance of a peak at 370 eV indicates complete dissolution of Ag(0). When 200 ppm Hg(II) interacts with Ag-GQDs for 10 min, coalescence of AgNPs takes place along with the formation of Hg(0) petals separately. However, Hg(0) is grown as a flower with 2 µm size, and complete dissolution of AgNPs occurs subsequently after 15 min. The reason for anti-amalgamation is the direct deposition of Hg(0) by the available oxygen functional groups, followed by its strong adsorption on the graphene surface of GQDs. The subsequent growth of Hg(0) as a flower is due to the GR between AgNPs and Hg(II). Interestingly, the Hg flower-GQD-modified GC electrode acts as a good electrocatalyst toward H2O2 reduction by decreasing its overpotential by 150 mV in contrast to GC/Ag-GQDs.

Conducting Polymers as Versatile Tools for the Electrochemical Detection of Cancer Biomarkers.

The detection of cancer biomarkers has recently become an established method for the early diagnosis of cancer. The sensitive analysis of specific biomarkers can also be clinically applied for the determination of response to treatment and monitoring of disease progression. Because of the ultra-low concentration of cancer biomarkers in body fluids, diagnostic tools need to be highly sensitive and specific. Conducting polymers (CPs) are particularly known to exhibit numerous features that enable them to serve as excellent materials for the immobilization of biomolecules and the facilitation of electron transfer. Their large surface area, porosity, and the presence of functional groups provide CPs with binding sites suitable for capturing biomarkers, in addition to their sensitive and easy detection. The aim of this review is to present a comprehensive summary of the available electrochemical biosensors based on CPs and their composites for the ultrasensitive detection of selected cancer biomarkers. We have categorized the study based on different types of targeted biomarkers such as DNAs, miRNAs, proteins, enzymes, neurotransmitters and whole cancer cells. The sensitivity of their detection is enhanced by the presence of CPs, providing a limit of detection as low as 0.5 fM (for miRNA) and 10 cells (for the detection of cancer cells). The methods of multiplex biomarker detection and cell capture are indicated as the most promising category, since they furnish more accurate and reliable results. Ultimately, we discuss the available CP-based electrochemical sensors and promising approaches for facilitating cancer diagnosis and treatment.

Bioengineered magnetic graphene oxide microcomposites for bioremediation of chromium in ex situ - A novel strategy for aggrandized recovery by electromagnetic gadgetry.

Novel magnetic microcomposites consisting of graphene oxide and iron oxide was synthesized to immobilize metabolically versatile Paracoccus sp. MKU1 and Leucobacter sp. AA7 and tested for the simultaneous adsorption and enhanced biological detoxification of hexavalent chromium (Cr(VI)) from tannery wastewater. This study reports highest chromium adsorption of 272.6 mg/g and 179.3 mg/g with complete reduction of Cr(VI) to Cr(III) by the microcomposites of AA7 and MKU1 from wastewater in a bioreactor (10 L) at large-scale for first time in ex situ. Furthermore, both the microcomposites displayed an enhanced detoxification of tannery wastewater by reducing various physicochemical conditions such as ammonia, nitrate, TDS, fluoride, CaCO3, Ca, Mg, NO3 and SO2 under the permissible limits. Use of electromagnetic device for magnetic microcomposites recovery from bioreactor yielded a maximum of 88% and 80.6% recovery for AA7 and MKU1, respectively. The rate of chromium recuperation achieved following desorption from the microcomposites of AA7 and MKU1 was 90.71% and 93.97%, respectively. Thus, the multifarious benefits including adsorption, metabolic detoxification, recovery, and recuperation by single functional microcomposites seems to be an intriguing and profitable approach for practicing in real-time operations to effectively remove heavy metals from the contaminated wastewater for environmental protection.

Bioengineered Graphene Oxide Microcomposites Containing Metabolically Versatile Paracoccus sp. MKU1 for Enhanced Catechol Degradation.

Paracoccus sp. MKU1, a metabolically versatile bacterium that encompasses diverse metabolic pathways in its genome for the degradation of aromatic compounds, was investigated for catechol bioremediation here for the first time to our knowledge. Paracoccus sp. MKU1 degraded catechol at an optimal pH of 7.5 and a temperature of 37 °C, wherein 100 mg/L catechol was completely mineralized in 96 h but required 192 h for complete mineralization of 500 mg/L catechol. While investigating the molecular mechanisms of its degradation potential, it was unveiled that Paracoccus sp. MKU1 employed both the ortho and meta pathways by inducing the expression of catechol 1,2-dioxygenase (C12O) and catechol 2,3-dioxygenase (C23O), respectively. C23O expression at transcriptional levels was significantly more abundant than C12O, which indicated that catechol degradation was primarily mediated by extradiol cleavage by MKU1. Furthermore, poly(MAA-co-BMA)-GO (PGO) microcomposites containing Paracoccus sp. MKU1 were synthesized, which degraded catechol (100 mg/L) completely within 48 h with excellent recycling performance for three cycles. Thus, PGO@Paracoccus microcomposites proved to be efficient in catechol degradation at not only faster rates but also with excellent recycling performances than free cells. These findings accomplish that Paracoccus sp. MKU1 could serve as a potential tool for bioremediation of catechol-polluted industrial wastewater and soil.