4-nitrophenol optical sensing with N doped oxidized carbon dots.

In this work, we report a facile strategy for 4-nitrophenol (4-NP) sensing using highly luminescent nitrogen-doped oxidized carbon dots. The quenching of fluorescence (turn OFF), with the addition of trace amounts of organic pollutant (4-NP) in NOCDs, has been attributed to the complete reduction of nitrogen-doped oxidized carbon dots (NOCDs) to reduced nitrogen-doped oxidized carbon dots (rNOCDs) and its formation was confirmed by infrared, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The chemical changes in oxygen-containing functional groups of NOCDs, in the presence of 4-NP, are elucidated and corresponding characterization through XPS reveals the changes in the peak intensities of CC (284.5 eV) and OCO (288.6 eV), indicating a decrement in hydroxyl groups that hinder its complete reduction to NOCDs. The sensitivity of NOCDs towards 4-NP has been tested in spiked tap water in the concentration range 2 µM to 2 mM with the minimum detection limit of 2 µM (linear detection range from 2 to 100 µM with regression coefficient R2 =0.99). The proposed simple sensing platform can be used to reduce NOCDs and simultaneously sense low concentrations of 4-NP. Finally, an effective treatment to improve the reduction of nitrogen-doped graphene oxide is proposed.

Simultaneous intercalated assembly of mesostructured hybrid carbon nanofiber/reduced graphene oxide and its use in electrochemical sensing.

Polyacrylonitrile nonwovens intercalated with graphene oxide (GO) sheets were prepared by a simultaneous electrospinning-spray deposition system. These hybrid nonwovens were carbonized in a two-stage process to obtain a mesostructured hybrid carbon containing carbon nanofibers (CNF) and reduced GO sheets (CNF/RGO). During the carbonization process, the CNF act as spacers between the RGO layers to prevent their compactation and restacking resulting in a three-dimensional structure. The presence of RGO increases the electrical conductivity in the CNF/RGO material. The resulting hybrid carbon is nitrogen-doped as indicated by x-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy. This N-doped porous carbon was used to prepare electrodes with improved sensitivity for the electrochemical detection of L-cysteine.

Robust water desalination membranes against degradation using high loads of carbon nanotubes.

Chlorine resistant reverse osmosis (RO) membranes were fabricated using a multi-walled carbon nanotube-polyamide (MWCNT-PA) nanocomposite. The separation performance of these membranes after chlorine exposure (4800 ppm·h) remained unchanged (99.9%) but was drastically reduced to 82% in the absence of MWCNT. It was observed that the surface roughness of the membranes changed significantly by adding MWCNT. Moreover, membranes containing MWCNT fractions above 12.5 wt.% clearly improved degradation resistance against chlorine exposure, with an increase in water flux while maintaining salt rejection performance. Molecular dynamics and quantum chemical calculations were performed in order to understand the high chemical stability of the MWCNT-PA nanocomposite membranes, and revealed that high activation energies are required for the chlorination of PA. The results presented here confirm the unique potential of carbon nanomaterials embedded in polymeric composite membranes for efficient RO water desalination technologies.

Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin.

Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection.

Biocatalytic synthesis of polypyrrole powder, colloids, and films using horseradish peroxidase.

Polypyrrole was synthesized in high yield by a biocatalytic method in mild aqueous media using hydrogen peroxide as oxidizer. A redox mediator, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) diammonium salt, was used to oxidize the pyrrole. ABTS is a very effective peroxidase substrate, which was enzymatically oxidized to generate a radical cation that in turn was able to chemically oxidize pyrrole. This indirect biocatalytic method was implemented because pyrrole is not a substrate of horseradish peroxidase, however, the polymerization process was successfully optimized and later adapted to prepare also polypyrrole thin films and water dispersible polypyrrole colloids. The polypyrrole powder and colloids were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, electrical conductivity, and thermogravimetric analysis. In addition, the deposition of the polypyrrole thin film was monitored using a quartz-crystal microbalance and its morphology studied by optical and scanning electron microscopy. The biocatalytic polymerization of pyrrole results in a polymer spectroscopically very similar to chemically synthesized polypyrrole.