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•Nanocellulose based membrane with ultrathin graphene oxide top layer was developed.•Ultrahigh flux (18,123 Lm−2h−1 bar−1) attributable to water transport nanochannels.•Membranes had ...excellent dry and wet mechanical properties.•Efficient retention of dyes (92%–99%) via adsorption and size exclusion.•The layered structure impacts membrane functionality.
Ultrathin graphene oxide (GO) layer was fabricated on cellulose nanofiber (CNF) membrane to achieve robust crosslinker free layered membrane with synergistic water flux and separation performance. Unlike pristine cellulosic or GO membranes, GO-CNF hybrid membranes exhibited significantly improved mechanical stability in both dry and wet states. All membranes showed negative surface zeta potential. GO: CNF membrane (1:100) exhibited significantly high water flux (18,123 ± 574 Lm−2 h−1 bar−1); higher than that of CNF membrane or the hydrophilic commercial reference membrane with comparable pore structure (Nylon 66, 0.2 μm). We hypothyse that a unique surface structure of “standing inserted GO nanosheets” observed at low concentrations of GO contributes enormously to its ultrafast water permeability through creation of numerous water transport nanochannels. The aniosptropic layered membranes exhibited >90% rejection of positively and negatively charged dyes through a combination of electrostatic interaction, hydrophobic interactions and molecular size exclusion. Construction of an ultrathin GO layer on CNF offers a unique and efficient way to prepare highly functional, economical and scalable water purification membranes having significant advantage with respect to flux, mechanical stability and rejection of dyes compared to isotropic membrane with GO nanosheets randomly dispersed in the cellulose nanofibrous network.
Nanocellulose, graphene oxide (GO), and their combinations there off have attracted great attention for the application of water purification recently because of their unique adsorption capacity, ...mechanical characteristics, coordination with transition metal ions, surface charge density, and so on. In the current study, (2,2,6,6-tetramethylpiperidine-1-oxylradical) (TEMPO)-mediated oxidized cellulose nanofibers (TOCNF) and GO sheets or graphene oxide nanocolloid (nanoGO) biohybrids were prepared by vacuum filtration method to obtain self-assembled adsorbents and membranes for water purification. The porous biohybrid structure, studied using advanced microscopy techniques, revealed a unique networking and self-assembling of TOCNF, GO, and nanoGO, driven by the morphology of the GO phase and stabilized by the intermolecular H-bonding between carboxyl groups and hydroxyl groups. The biohybrids exhibited a promising adsorption capacity toward Cu(II) due to TOCNF and formed a unique “arrested state” in water because of ionic cross-linking between adsorbed Cu(II) and the negatively charged TOCNF and GO phase. The mechanical performance of the freestanding biohybrid membranes investigated using PeakForce Quantative NanoMechanics characterization confirmed the enhanced modulus of the hybrid membrane compared to that of the TOCNF membrane. Besides, the TOCNF+nanoGO membrane shows unique hydrolytic stability and recyclability even under several cycles of adsorption and desorption and strong sonication. This study shows that TOCNF and nanoGO hybrids can generate new water-cleaning membranes with synergistic properties because of their high adsorption capacity, flexibility, hydrolytic stability, and mechanical robustness.
The self-assembly of nanocellulose and graphene oxide into highly porous biohybrid materials has inspired the design and synthesis of multifunctional membranes for removing water pollutants. The ...mechanisms of self-assembly, metal ion capture, and cluster formation on the biohybrids at the nano- and molecular scales are quite complex. Their elucidation requires evidence from the synergistic combination of experimental data and computational models. The AFM-based microscopy studies of (2,2,6,6-tetramethylpiperidine-1-oxylradical)-mediated oxidized cellulose nanofibers (TOCNFs), graphene oxide (GO), and their biohybrid membranes provide strong, direct evidence of self-assembly; small GO nanoparticles first attach and accumulate along a single TOCNF fiber, while the long, flexible TOCNF filaments wrap around the flat, wide GO planes, thus forming an amorphous and porous biohybrid network. The layered structure of the TOCNFs and GO membrane, derived from the self-assembly and its surface properties before and after the adsorption of Cu(II), is investigated by advanced microscopy techniques and is further clarified by the ReaxFF molecular dynamics (MD) simulations. The dynamics of the Cu(II)-ion capture by the TOCNF and GO membranes in solution and the ion cluster formation during drying are confirmed by the MD simulations. The results of this multidisciplinary investigation move the research one step forward by disclosing specific aspects of the self-assembly behavior of biospecies and suggesting effective design strategies to control the pore size and robust materials for industrial applications.
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•AFM probes functionalised with cellulose nanocrystals and nanofibers successfully.•Nanocellulose adhesion with Cu(II) and dye quantified using AFM force spectroscopy•Adhesion force ...explained by electrostatic interactions and surface charge density.•Models reveal clustering or stacking that maximize interaction with nanocellulose.
Atomic Force Microscope (AFM) probes were successfully functionalized with two types of nanocellulose, namely 2,2,6,6-tetramethylpiperidine-1-oxylradical (TEMPO)-mediated oxidized cellulose nanofibers (TOCNF) and cellulose nanocrystals (CNC) and used to study interfacial interactions of nanocellulose with Cu(II) ions and the Victoria blue B dye in liquid medium. TOCNF modified tip showed higher adhesion force due to adsorption of Cu(II) ions and dye molecules compared to CNC ones. Exploring the adsorption properties through classical reactive molecular dynamics simulations (ReaxFF) at the atomic scale confirmed that the Cu(II) ions promptly migrated and adsorbed onto the nanocelluloses through the co-operative chelating action of carboxyl and hydroxyl species. The adsorbed Cu(II) ions showed the tendency to self-organize by forming nano-clusters of variable size, whereas the dye adopted a flat orientation to maximize its adsorption. The satisfactory agreement between the two techniques suggests that functionalized AFM probes can be successfully used to study nanocellulose surface interactions in dry or aqueous environment.
Hydrogen sulfide (H2S) is a hazardous and corrosive byproduct generated during heavy oil recovery, particularly during hot water flooding. Previous studies on factors influencing H2S generation ...during hot water flooding have been mainly focused on high temperatures (>250 °C), which may not accurately represent reservoir conditions. Moreover, the concentration of H2S produced by hot water flooding at low temperatures exceeds the standard. In this study, experiments were conducted on hot water flooding at low temperatures (110–150 °C). The mechanism of reactants and reaction conditions on H2S generation was investigated. The results showed that thermochemical sulfate reduction (TSR) was the primary reaction type responsible for H2S generation, while aquathermolysis and pyrite oxidation reactions weakly or did not occur. The reactivity of TSR was directly proportional to reaction temperature and time, while inversely proportional to reaction pH. The formation of oxidants (MgSO4CIP and HSO4 –) was also found to be crucial for TSR initiation. Unstable organic sulfur-containing compounds were oxidized to produce CO2, H2S, SO3, and solid bitumen, which further sustained the autocatalytic reaction. Low temperature TSR was found to consume the saturated fraction in heavy oil and convert inorganic sulfur to organic sulfide. The increase in pH inhibited the conversion of inorganic sulfur to organic sulfur, resulting in a higher percentage of the saturated fraction. This study provides new insights into the low temperature TSR reaction mechanism and the origin of H2S, which can aid in better understanding and mitigation of the associated risks during heavy oil recovery.
Based on the previous synthesis of tetracyclic and tricyclic benzimidazoles starting from 1,4:3,6-dianhydro-d-fructose and o-phenylenediamines, a series of 5(6)-amino substituted tetracyclic and ...tricyclic benzimidazolequinones were obtained through the oxidation of 4,7-dimethoxy-benzimidazole analogues with bis(trifluoroacetoxy)iodobenzene (PIFA) and subsequent substitution with various aliphatic and aromatic amines. Biological evaluations of the target benzimidazolequinones indicated that all the arylamino-substituted benzimidazolequinones possess potent antitumour activity against human gastric cancer cells (MGC-803), especially compound a21–2. Furthermore, compound a21–2 inhibits gastric cancer cells proliferation and cell colony formation. Mechanistic investigations showed that compound a21–2 induces ROS production, which subsequently causes DNA damage and activation of ATM/Chk2, leading to G2/M phase arrest. ROS activates the c-Jun N-terminal kinase (JNK) pathway to induce mitochondrial-mediated apoptosis. In vivo studies showed that compound a21–2 inhibits the growth of tumours in nude mice without significant systemic toxicity. These findings suggest that compound a21–2 represents a promising candidate antitumour drug.
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•Synthesis of multicyclic benzimidazolequinones from 1,4:3,6-dianhydro-d-fructose.•Potent antitumour drug candidate against human gastric cancer cells.•Activation of ROS/JNK pathway to induce cancer cell apoptosis.•ROS-mediated DNA damage triggers ATM-Chk2 pathway-dependent G2/M arrest.•Anti-tumour effect in vivo without obvious systemic toxicity in nude mice.
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