Suguna Perumal

Facile synthesis of zinc oxide nanoparticles decorated graphene oxide composite via simple solvothermal route and their photocatalytic activity on methylene blue degradation.

Zinc oxide nanoparticles decorated graphene oxide (ZnO@GO) composite was synthesized by simple solvothermal method where zinc oxide (ZnO) nanoparticles and graphene oxide (GO) were synthesized via simple thermal oxidation and Hummers method, respectively. The obtained materials were thoroughly characterized by various physico-chemical techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Raman spectrum shows the intensity of D to G value was close to one which confirms the obtained GO and ZnO@GO composite possesses moderate graphitization. TEM images shows the ZnO nanoparticles mean size of 15±5nm were dispersed over the wrinkled graphene layers. The photocatalytic performance of ZnO@GO composite on degradation of methylene blue (MB) is investigated and the results show that the GO plays an important role in the enhancement of photocatalytic performance. The synthesized ZnO@GO composite achieves a maximum degradation efficiency of 98.5% in a neutral solution under UV-light irradiation for 15min as compared with pure ZnO (degradation efficiency is 49% after 60min of irradiation) due to the increased light absorption, the reduced charge recombination with the introduction of GO. Moreover, the resulting ZnO@GO composite possesses excellent degradation efficiency as compared to ZnO nanoparticles alone on MB.

Highly fluorescent nitrogen-doped carbon dots derived from Phyllanthus acidus utilized as a fluorescent probe for label-free selective detection of Fe3+ ions, live cell imaging and fluorescent ink

A facile, economical and one-step hydrothermal method is used to synthesize highly durable fluorescent nitrogen-doped carbon dots (FNCDs) by utilizing Phyllanthus acidus (P. acidus) and aqueous ammonia as the carbon and nitrogen sources, respectively. The synthesized FNCDs have an average size of 4.5±1nm and showed bright blue fluorescence under the irradiation of UV-light at an excitation wavelength of 365nm. It exhibits a quantum yield (QY) of 14% at an excitation wavelength of 350nm with maximum emission at 420nm. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy characterizations clearly showed the formation of FNCDs that predominantly consists of nitrogen and hydroxyl groups which can provide more adsorption sites. In addition, the above study reveals the successful bonding of nitrogen with carbon (C-N) in the FNCDs. The synthesized FNCDs with high QY can be used as efficient fluorescent probes for the detection of Fe3+. Based on the linear relationship between normalized fluorescence intensity and concentration of Fe3+ ions, the prepared FNCDs can be used for label-free sensitive and selective detection of Fe3+ ions in a wide concentration range of 2-25μM with a detection limit of 0.9μM. The present study proves that synthesized FNCDs has durable fluorescence, soluble in water very well and thus act as a promising candidate for the diverse applications such as label-free sensitive and selective detection of Fe3+, fluorescent ink and cellular imaging with good biocompatibility and low cytotoxicity.

Highly graphitic carbon nanosheets synthesized over tailored mesoporous molecular sieves using acetylene by chemical vapor deposition method

Graphitic carbon nanosheets (GCNS) were synthesized using mesoporous Ti-MCM-41 molecular sieves as catalytic template and acetylene as carbon precursor following chemical vapor deposition method, under atmospheric pressure. The mesoporous Ti-MCM-41 molecular sieves with various Si/Ti ratios were synthesized by direct hydrothermal method. The materials so obtained were characterized by various physico-chemical techniques such as X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. The analytical results indicated that the obtained GCNS possess high thermal stability and good graphitization with an inter layer distance of around 3.45 A. The influence of reaction parameters such as temperature and catalytic templates was studied to improve the quality and quantity of GCNS. The excellent graphitized GCNS material on a large scale was achieved from Ti-MCM-41 at moderate reaction temperature. This work proposes a way for the large scale synthesis of GCNS with applications suitable for nanoelectronics, nanocomposites and so on.

PVP-b-PEO block copolymers for stable aqueous and ethanolic graphene dispersions

The ability to disperse pristine (unfunctionalized) graphene is important for various applications, coating, nanocomposites, and energy related systems. Herein we report that amphiphilic copolymers of poly(4-vinyl pyridine)-block-poly(ethylene oxide) (PVP-b-PEO) are able to disperse graphene with high concentrations about 2.6mg/mL via sonication and centrifugation. Ethanolic and aqueous highly-ordered pyrolytic graphite (HOPG) dispersions with block copolymers were prepared and they were compared with the dispersions stabilized by P-123 Pluronic® (P123) and poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) synthesized. Transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman and UV-visible spectroscopic studies confirmed that PVP-b-PEO block copolymers are better stabilizers for HOPG graphene than P123 and PS-b-PEO. X-ray photoelectron spectroscopy and force-distance (F-d) curve analyses revealed that the nitrogen of vinyl pyridine plays a vital role in better attractive interaction with surface of graphene sheet. Thermogravimetric analysis showed that larger amount of PVP-b-PEO was adsorbed onto graphene with longer poly(4-vinyl pyridine) (PVP) block length and in aqueous medium, respectively, and which was consistent with electrical conductivity decreases. This study presents the dispersion efficiency of graphene using PVP-b-PEO varies substantially depending on the lengths of their hydrophobic (PVP) domains.

High-concentration graphene dispersion stabilized by block copolymers in ethanol

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion.

Amphiphilic Fluorinated Block Copolymer Synthesized by RAFT Polymerization for Graphene Dispersions

Despite the superior properties of graphene, the strong π–π interactions among pristine graphenes yielding massive aggregation impede industrial applications. For non-covalent functionalization of highly-ordered pyrolytic graphite (HOPG), poly(2,2,2-trifluoroethyl methacrylate)-block-poly(4-vinyl pyridine) (PTFEMA-b-PVP) block copolymers were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization and used as polymeric dispersants in liquid phase exfoliation assisted by ultrasonication. The HOPG graphene concentrations were found to be 0.260–0.385 mg/mL in methanolic graphene dispersions stabilized with 10 wt % (relative to HOPG) PTFEMA-b-PVP block copolymers after one week. Raman and atomic force microscopy (AFM) analyses revealed that HOPG could not be completely exfoliated during the sonication. However, on-line turbidity results confirmed that the dispersion stability of HOPG in the presence of the block copolymer lasted for one week and that longer PTFEMA and PVP blocks led to better graphene dispersibility. Force–distance (F–d) analyses of AFM showed that PVP block is a good graphene-philic block while PTFEMA is methanol-philic.

Hydrothermal conversion of Magnolia liliiflora into nitrogen-doped carbon dots as an effective turn-off fluorescence sensing, multi-colour cell imaging and fluorescent ink

The present work illustrates the potential uses of nitrogen-doped multi-fluorescent carbon dots (N-CDs) for Fe3+ sensing, cellular multi-colour imaging, and fluorescent ink. N-CDs were synthesized using Magnolia liliiflora flower by the simple hydrothermal method. The resulted N-CDs was found to be nearly spherical in shape with the size of about 4 ± 1 nm and showed competitive quantum yield around 11%. The synthesized N-CDs with uniform size distribution and high content of nitrogen and oxygen-bearing functional groups exhibit excellent dispersibility in aqueous media. The N-CDs were able to detect a high concentration of Fe3+ ions (1-1000 μM) with a limit of detection is about 1.2 μM by forming N-CDs-Fe3+ complex due to the functional groups such as nitrogen, carbonyl and carboxyl on the surface of N-CDs. Thus they could be used to remove pollutants from industrial wastewater. The electronic charge on the surface of the N-CDs and N-CDs-Fe3+ complex (zeta potential) is around -36 and 18 mV, respectively. In addition, these N-CDs show excitation-dependent fluorescence that was utilized for multi-colour in vitro cellular imaging in rat liver cells (Clone 9 hepatocytes). The N-CDs are rapidly uptake in the cell cytoplasm and showed high cytocompatibility on cellular morphology. Moreover, as the N-CDs possess strong fluorescence and anti-coagulation they could be utilized in fluorescent ink pens.

Interaction of Zwitterionic and Ionic Monomers with Graphene Surfaces

Measurement of the interaction force between two materials provides important information on various properties, such as adsorption, binding, or compatibility for coatings, adhesion, and composites. The interaction forces of zwitterionic and ionic monomers with graphite platelets (G) and reduced graphene oxide (rGO) surfaces were systematically investigated by atomic force microscopy (AFM) in air and water. The monomers examined were 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate (MPC), [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBE), [2-(acryloyloxy)ethyl]trimethylammonium chloride (ATC), and 2-methyl-2-propene-1-sulfonic acid sodium (MSS). The AFM studies revealed that MSS and SBE monomers with sulfonate units have stronger interaction forces with G surface in air and that MPC and ATC monomers with quaternary ammonium units have higher interaction forces in water. In the case of rGO surface, the monomers with quaternary ammonium units showed stronger interactions regardless of the medium. These interactions could be rationalized by the interaction mechanism between the monomers with graphene surfaces, such as cation-π for MPC and ATC and anion-π for MSS and SBE. Overall, cation-π interactions were effective in water, whereas anion-π interactions are effective in air with G surface. The adhesion values of MPC, SBE, ATC, and MSS on rGO were lower than the values measured on G surface. Among the monomers, MPC showed the highest dispersibility for aqueous graphene dispersions. Further, the adsorption of MPC on G and rGO surfaces was verified by high-resolution transmission electron microscopy and X-ray diffraction patterns.

An ultrasensitive photoelectrochemical biosensor for glucose based on bio-derived nitrogen-doped carbon sheets wrapped titanium dioxide nanoparticles

In this work, an ultra-sensing photoelectrochemical (PEC) glucose biosensor has been constructed from the bio-derived nitrogen-doped carbon sheets (NDC) wrapped titanium dioxide nanoparticles (NDC-TiO2 NPs) followed by the covalent immobilization of glucose oxidase (GODx) on them (designated as a GODx/NDC-TiO2NPs/ITO biosensor). Initially, the TiO2 NPs was synthesized by sol-gel method and then NDC-TiO2 NPs was synthesized utilizing a green source of Prunus persica (peach fruit) through a simple hydrothermal process. The synthesized NDC-TiO2 NPs composite was characterized by FESEM, HRTEM, Raman spectroscopy, XRD, ATR-FTIR spectroscopy and XPS to determine composition and phase purity. These fabricated GODx/NDC-TiO2NPs/ITO biosensor exhibited a good charge separation, highly enhanced and stable photocurrent responses with switching PEC behavior under the light (λ > 400 nm). As a result, GODx/NDC-TiO2NPs/ITO PEC glucose sensor exhibits a good photocurrent response to detection of glucose concentrations (0.05-10 μM) with an ultra-low detection limit of 13 nM under optimized PEC experimental conditions. Also, the PEC glucose sensor revealed a high selectivity, good stability, long time durability, and capability to analyze the glucose levels in real human serum. Also, the further development of this work may provide new insights into preparing other bio-derived carbon nanostructure-based photocatalysts for PEC applications.

Preparation of urushiol-containing poly(methyl methacrylate) copolymers for antibacterial and antifouling coatings

Synthesis of an eco-friendly and efficient antibacterial and antifouling coatings is presented by exploiting urushiol, a natural varnishing material. Since urushiol has inherent outstanding surface-protecting and antimicrobial properties, a series of poly (methyl methacrylate)-urushiol polymer compositions were prepared and fabricated into films. The prepared films were subjected to antimicrobial and antifouling studies. The polymer systems were characterized by various physico-spectroscopic techniques such as 1H NMR, Fourier transform infrared spectroscopy, differential scanning calorimetry, atomic force microscopy, and thermal gravimetric analysis. The confocal laser scanning micrographs, obtained for Pseudomonas aeruginosa biofilm formation, demonstrated an excellent antimicrobial response of the urushiol-incorporated polymers against this bacterial strain. We also demonstrated an inhibitory attachment effect against Navicula incerta, a fouling microalgal strain.