Functionalized graphene oxide tablets for sample preparation of drugs in biological fluids: Extraction of ritonavir, a HIV protease inhibitor, from human saliva and plasma using LC-MS/MS.

In this work, graphene oxide-based tablets (GO-Tabs) were prepared by applying a thin layer of functionalized GO on a polyethylene substrate. The GO was functionalized with amine groups (-NH2 ) by poly(ethylene glycol)bis(3-aminopropyl) terminated (GO-NH2 -PEG-NH2 ). The functionalized GO-Tabs were used for the extraction of ritonavir (RTV) in human saliva samples. RTV in plasma and saliva samples was analyzed using LC-MS/MS. Gradient LC system with MS/MS in the positive-ion mode [electrospray ionization (ESI+)] was used. The transitions m/z 721 → 269.0 and m/z 614 → 421 were used for RTV and the internal standard indinavir, respectively. This study determined the human immunodeficiency virus protease inhibitor RTV in human saliva samples using functionalized GO-Tab and LC-MS/MS, and the method was validated. The standard calibration curve for plasma and saliva samples was constructed from 5.0 to 2000 nmol L-1 . The limit of detection was 0.1 nmol L-1 , and the limit of quantification was 5.0 nmol L-1 in both plasma and saliva matrices. The intra- and inter-assay precision values were found to be between 1.5 and 5.8%, and the accuracy values ranged from 88.0 to 108% utilizing saliva and plasma samples. The extraction recovery was more than 80%, and the presented functionalized GO-Tabs could be reused for more than 10 extractions without deterioration in recovery.

Disinfection of Bacteria in Water by Capacitive Deionization.

Clean water is one of the primary UN sustainable development goals for 2,030 and sustainable water deionization and disinfection is the backbone of that goal. Capacitive deionization (CDI) is an upcoming technique for water deionization and has shown substantial promise for large scale commercialization. In this study, activated carbon cloth (ACC) electrode based CDI devices are used to study the removal of ionic contaminants in water and the effect of ion concentrations on the electrosorption and disinfection functions of the CDI device for mixed microbial communities in groundwater and a model bacterial strain Escherichia coli. Up to 75 % of microbial cells could be removed in a single pass through the CDI unit for both synthetic and groundwater, while maintaining the salt removal activity. Mortality of the microbial cells were also observed during the CDI cell regeneration and correlated with the chloride ion concentrations. The power consumption and salt removal capacity in the presence and absence of salt were mapped and shown to be as low as 0.1 kWh m-3 and 9.5 mg g-1, respectively. The results indicate that CDI could be a viable option for single step deionization and microbial disinfection of brackish water.

An Easy-to-Use Tool for Modeling the Dynamics of Capacitive Deionization.

Capacitive deionization is an emerging method of desalinating brackish water that has been presented as an alternative to the widely applied technologies such as reverse osmosis. However, for the technology to find more widespread use, it is important not only to improve its efficiency but also to make its modeling more accessible for researchers. In this work, a program has been developed and provided as an open-source with which a user can simulate the performance of a capacitive deionization system by simply entering the basic experimental conditions. The usefulness of this program was demonstrated by predicting how the effluent concentration in a continuous-mode constant-voltage operation varies with time, as well as how it depends on the flow rate, applied voltage, and inlet ion concentration. Finally, the generality of the program has been demonstrated using data from reports in the literature wherein various electrode materials, cell structures, and operational modes were used. Thus, we conclude that the model, termed the dynamic Langmuir model, could be an effective and simple tool for modeling the dynamics of capacitive deionization.

Nanoparticulate Dielectric Overlayer for Enhanced Electric Fields in a Capacitive Deionization Device.

The magnitude and distribution of the electric field between two conducting electrodes of a capacitive deionization (CDI) device plays an important role in governing the desalting capacity. A dielectric coating on these electrodes can polarize under an applied potential to modulate the net electric field and hence the salt adsorption capacity of the device. Using finite element models, we show the extent and nature of electric field modulation, associated with changes in the size, thickness, and permittivity of commonly used nanostructured dielectric coatings such as zinc oxide (ZnO) and titanium dioxide (TiO2). Experimental data pertaining to the simulation are obtained by coating activated carbon cloth (ACC) with nanoparticles of ZnO and TiO2 and using them as electrodes in a CDI device. The dielectric-coated electrodes displayed faster desalting kinetics of 1.7 and 1.55 mg g-1 min-1 and higher unsaturated specific salt adsorption capacities of 5.72 and 5.3 mg g-1 for ZnO and TiO2, respectively. In contrast, uncoated ACC had a salt adsorption rate and capacity of 1.05 mg g-1 min-1 and 3.95 mg g-1, respectively. The desalting data is analyzed with respect to the electrical parameters of the electrodes extracted from cyclic voltammetry and impedance measurements. Additionally, the obtained results are correlated with the simulation data to ascertain the governing principles for the changes observed and advances that can be achieved through dielectric-based electrode modifications for enhancing the CDI device performance.

Bioinspired nanocoatings for biofouling prevention by photocatalytic redox reactions.

Aquaculture is a billion dollar industry and biofouling of aquaculture installations has heavy economic penalties. The natural antifouling (AF) defence mechanism of some seaweed that inhibits biofouling by production of reactive oxygen species (ROS) inspired us to mimic this process by fabricating ZnO photocatalytic nanocoating. AF activity of fishing nets modified with ZnO nanocoating was compared with uncoated nets (control) and nets painted with copper-based AF paint. One month experiment in tropical waters showed that nanocoatings reduce abundances of microfouling organisms by 3-fold compared to the control and had higher antifouling performance over AF paint. Metagenomic analysis of prokaryotic and eukaryotic fouling organisms using next generation sequencing platform proved that nanocoatings compared to AF paint were not selectively enriching communities with the resistant and pathogenic species. The proposed bio-inspired nanocoating is an important contribution towards environmentally friendly AF technologies for aquaculture.

Influence of Atomic Hydrogen, Band Bending, and Defects in the Top Few Nanometers of Hydrothermally Prepared Zinc Oxide Nanorods.

We report on the surface, sub-surface (top few nanometers) and bulk properties of hydrothermally grown zinc oxide (ZnO) nanorods (NRs) prior to and after hydrogen treatment. Upon treating with atomic hydrogen (H*), upward and downward band bending is observed depending on the availability of molecular H2O within the structure of the NRs. In the absence of H2O, the H* treatment demonstrated a cleaning effect of the nanorods, leading to a 0.51 eV upward band bending. In addition, enhancement in the intensity of room temperature photoluminescence (PL) signals due to the creation of new surface defects could be observed. The defects enhanced the visible light activity of the ZnO NRs which were subsequently used to photocatalytically degrade aqueous phenol under simulated sunlight. On the contrary, in the presence of H2O, H* treatment created an electronic accumulation layer inducing downward band bending of 0.45 eV (~1/7th of the bulk ZnO band gap) along with the weakening of the defect signals as observed from room temperature photoluminescence spectra. The results suggest a plausible way of tailoring the band bending and defects of the ZnO NRs through control of H2O/H* species.

Enhancement in ion adsorption rate and desalination efficiency in a capacitive deionization cell through improved electric field distribution using electrodes composed of activated carbon cloth coated with zinc oxide nanorods.

Electrodes composed of activated carbon cloth (ACC) coated with zinc oxide (ZnO) nanorods are compared with plain ACC electrodes, with respect to their desalination efficiency of a 17 mM NaCl solution at different applied potentials. Polarization of the ZnO nanorods increased the penetration depth and strength of the electric field between the electrodes, leading to an increase in the capacitance and charge efficiency at reduced input charge ratios. Uniform distribution of the electric field lines between two electrodes coated with ZnO nanorods led to faster ion adsorption rates, reduced the electrode saturation time, and increased the average desalination efficiency by ∼45% for all applied potentials. The electrodes were characterized for active surface area, capacitance from cyclic voltammetry, theoretical assessment of surface area utilization, and the magnitude of electric field force acting on an ion of unit charge for each potential.