Reduction-enhanced water flux through layered graphene oxide (GO) membranes stabilized with H3O+ and OH- ions.

Graphene oxide (GO) is one of the most promising candidates for next generation of atomically thin membranes. Nevertheless, one of the major issues for real world application of GO membranes is their undesirable swelling in an aqueous environment. Recently, we demonstrated that generation of H3O+ and OH- ions (e.g., with an external electric field) in the interlayer gallery could impart aqueous stability to the layered GO membranes (A. Gogoi, ACS Appl. Mater. Interfaces, 2022, 14, 34946). This, however, compromises the water flux through the membrane. In this study, we report on reducing the GO nanosheets as a solution to this issue. With the reduction of the GO nanosheets, the water flux through the layered GO membrane initially increases and then decreases again beyond a certain degree of reduction. Here, two key factors are at play. Firstly, the instability of the H-bond network between water molecules and the GO nanosheets, which increases the water flux. Secondly, the pore size reduction in the interlayer gallery of the membranes, which decreases the water flux. We also observe a significant improvement in the salt rejection of the membranes, due to the dissociation of water molecules in the interlayer gallery. In particular, for the case of 10% water dissociation, the water flux through the membranes can be enhanced without altering its selectivity. This is an encouraging observation as it breaks the traditional tradeoff between water flux and salt rejection of a membrane.

Synthesis of benzimidazole-fused 1,4-benzoxazepines and benzosultams spiro-connected to a 2-oxindole core via a tandem epoxide-opening/SNAr approach.

While hundreds of literature reports describe the preparation of spirooxindole-based five- and six-membered heterocycles, the construction of seven-membered heterocyclic rings spiro-connected to a 2-oxindole core has so far been less developed. Herein, we disclose a base-mediated (4 + 3) annulation of spiro-epoxyoxindoles and 2-(2-fluoroaryl)-1H-benzoimidazoles or 2-fluoro-N-arylbenzenesulfonamides toward the synthesis of two new classes of spirooxindole-based polycyclic systems. Mechanistically, this conceptually simple and high atom-economical reaction proceeds via an SN2-like intermolecular epoxide ring-opening, accompanied by a concomitant intramolecular SNAr reaction. From a synthetic aspect, the notable features of the process are its full regioselectivity, operational simplicity using readily available substrates under transition-metal-free conditions, high yields, and broad substrate scope.

An epoxide-opening cyclization/double Smiles rearrangement cascade approach to N-aryl-1,4-benzoxazines and N-arylindolines.

Reported herein is a transition-metal-free protocol for a regio- and diastereoselective synthesis of hydroxyalkyl group-embedded N-arylbenzo[b][1,4]oxazines and N-arylindolines based on an epoxide-opening cyclization/double Smiles rearrangement cascade of p-nosylamide-tethered epoxides. To the best of our knowledge, this is the first report of the integration of epoxide-opening cyclization with Smiles rearrangement in a cascade fashion, enabling simultaneous construction and N-arylation of N-heterocycles. The reaction employs substrates derived from commercially available 2-nitrophenols and easily accessible allylic halides/alcohols, and exhibits a broad substrate scope and delivers the products in high yields.

Arresting Aqueous Swelling of Layered Graphene-Oxide Membranes with H3O+ and OH- Ions.

Over the past decade, graphene oxide (GO) has emerged as a promising membrane material with superior separation performance and intriguing mechanical/chemical stability. However, its practical implementation remains very challenging primarily because of its undesirable swelling in an aqueous environment. Here, we demonstrated that dissociation of water molecules into H3O+ and OH- ions inside the interlayer gallery of a layered GO membrane can strongly affect its stability and performance. We reveal that H3O+ and OH- ions form clusters inside the GO laminates that impede the permeance of water and salt ions through the membrane. Dynamics of those clusters is sensitive to an external ac electric field, which can be used to tailor the membrane performance. The presence of H3O+ and OH- ions also leads to increased stability of the hydrogen bond (H-bond) network among the water molecules and the GO layers, which further reduces water permeance through the membrane, while crucially imparting stability to the layered GO membrane against undesirable swelling.

Effect of an ionic environment on membrane fouling: a molecular dynamics study.

The effect of the ionic environment on membrane fouling was investigated for polyamide (PA) and graphene oxide (GO) membranes using equilibrium molecular dynamics (MD) simulations. For each of these membranes, bovine serum albumin (BSA) was considered as the model foulant. The effect of the foulant on the membranes is investigated at seawater concentration and also in a normal aqueous environment. We investigated the translational and rotational motion of the protein relative to the membrane, interaction energy between the protein and the membrane surface, structural changes in the protein, and ion distribution around the protein and the membrane surface for all the systems. We found that the effects of ions were very different on both the membranes. Specifically, with an increase in ionic strength, the repulsion between the protein and membrane was observed in the case of GO, while for PA, no significant changes were observed for the same. Also, the ion distribution around the protein and the membrane surface were found to be different. In particular, for GO, there were more number of chloride ions around the protein and the membrane than that of sodium ions, which was probably the reason for the repulsion in the case of GO. However, in the case of PA, the membrane surface did not exhibit any affinity towards a specific ion, and the protein in the case of PA was surrounded by more number of sodium ions than chloride ions.

Influence of the presence of cations on the water and salt dynamics inside layered graphene oxide (GO) membranes.

Although over the past few years, graphene oxide (GO) has emerged as a promising membrane material, the applicability of layered GO membranes in water purification/seawater desalination is still a challenging issue because of the undesirable swelling of GO laminates in the aqueous environment. One of the ways to tune the interlayer spacing and to arrest the undesirable swelling of layered GO membranes in the aqueous environment is to intercalate the interlayer spacing of the GO laminates with cations. Although the cation intercalation imparts stabilization to GO laminates in the aqueous environment, their effect on the performance of the membrane is yet to be addressed in detail. In the present study we have investigated the effect of cation intercalation on the performance of layered GO membranes using molecular dynamics simulation. For the same interlayer spacing, the cation intercalated layered GO membranes have a higher water flux as compared to the corresponding pristine layered GO membranes. In the presence of the cations, the water molecules inside the interlayer gallery get more compactly packed. The presence of the cations also increases the stability of the hydrogen bond network among the water molecules inside the membrane. This can be attributed to slow water reorientation dynamics inside the interlayer gallery in the presence of the cations. The synergistic effect of all these changes is that the water permeability through the cation intercalated layered GO membranes is higher as compared to that through the corresponding pristine layered GO membranes. On the other hand, the intercalation of the cations (K+, Mg2+) leads to higher rejection of Na+ ions whereas the rejection of Cl- ions slightly decreases.

Climate Change, Health and Mosquito-Borne Diseases: Trends and Implications to the Pacific Region.

Climate change is known to affect Pacific Island nations in a variety of ways. One of them is by increasing the vulnerability of human health induced by various climate change impacts, which pose an additional burden to the already distressed health systems in the region. This paper explores the associations between climate change and human health on the one hand, and outlines some of the health care challenges posed by a changing climate on the other. In particular, it describes the links between climate variations and the emergence of climate-sensitive infectious diseases, such as the mosquito-borne diseases dengue, chikungunya, and Zika. The paper also presents a summary of the key findings of the research initiatives Climate Change and Prevalence Study of ZIKA Virus Diseases in Fiji and the findings from the World Mosquito Program as two examples of public health action in the Pacific region.

What governs the nature of fouling in forward osmosis (FO) and reverse osmosis (RO)? A molecular dynamics study.

Membrane fouling is a performance hampering phenomenon, which impacts forward osmosis (FO) and reverse osmosis (RO) differently. Experiments have found that the fouling layer structure for FO and RO is very different, but the reasons are not yet very clear, and hence a mechanistic understanding of the fouling in FO and RO is indispensable. Here we used molecular dynamics (MD) simulations to characterize the nature of fouling in FO and RO. Lysozyme and layered graphene oxide (GO) were used as typical representatives of the model foulant and desalination membrane, respectively. It was found that protein-solvent and protein-ion interactions are at the core of the structural differences between RO and FO. In particular, we suggest hydration repulsion and charge screening as probable mechanisms, which lead to different fouling layer structures in FO and RO. Also, a probable mechanism of lysozyme adsorption on the GO surface is proposed, which is based on the transport of protein towards the surface due to hydraulic pressure and Coulombic interactions induced between basic residues of lysozyme (arginine, lysine) facing the surface and oxygen-rich functional groups present on the GO surface. Both hydraulic pressure and Coulombic interactions acted synergistically, which led to lysozyme adsorption on the GO surface. Furthermore, the effect of initial protein orientation on protein-membrane interaction was also explored and was found to be an important factor in determining the nature of interaction and the time scale within which an adsorption event could be observed. This study facilitates the current understanding of the fouling in FO and RO and provides a probable molecular mechanism of how fundamental forces such as hydration repulsion and electrostatic interaction make fouling structurally different in FO and RO.

Effect of graphene oxide (GO) nanosheet sizes, pinhole defects and non-ideal lamellar stacking on the performance of layered GO membranes: an atomistic investigation.

The effect of non-idealities, namely pinhole defects and non-ideal lamellar stacking of nanosheets, on the performance of size-differentiated graphene oxide (GO) laminates is investigated using equilibrium molecular dynamics (MD) simulations. With the increase in sizes of the constituent GO nanosheets the water permeability of the layered GO membranes decreases and salt rejection increases. But with the inclusion of non-idealities the difference in water permeability between these membranes substantially reduced. The pinholes on the GO nanosheets provide shorter routes for trans-sheet flow, thereby increasing the water permeability of the membranes. The non-ideal stacking of the nanosheets without pinhole defects results in slight reduction in water permeability because of blockage of permeation pathways inside the membranes. However, with pinhole defects non-ideal stacking becomes favorable for water permeation through the layered GO membranes; as this time the non-ideal stacking leads to formation of voids inside the membranes, which act as routes for shorter permeation pathways. The effect of these non-idealities is more significant for layered GO membranes composed of large GO nanosheets. Although the water permeability through the layered GO membrane is greatly enhanced because of these non-idealities (about 10 times), the corresponding variation in the salt rejection is very low (<2%).

Aggregation-Induced Emission Active Metal-Free Chemosensing Platform for Highly Selective Turn-On Sensing and Bioimaging of Pyrophosphate Anion.

We report the synthesis of a metal-free chemosensor for highly selective sensing of pyrophosphate (PPi) anion in physiological medium. The novel phenylbenzimidazole functionalized imine containing chemosensor (L; [2,6-bis(((4-(1H-benzo[d]imidazol-2-yl)phenyl)imino) methyl)-4 methyl phenol]) could sense PPi anion through "turn-on" colorimetric and fluorimetric responses in a very competitive environment. The overall sensing mechanism is based on the aggregation-induced emission (AIE) phenomenon. Moreover, a real time in-field device application was demonstrated by sensing PPi in paper strips coated with L. Interestingly, detection of intracellular PPi ions in model human cells could also be possible by fluorescence microscopic studies without any toxicity to these cells.

Anion complexation with cyanobenzoyl substituted first and second generation tripodal amide receptors: crystal structure and solution studies.

Anion complexation properties of two new tripodal amide receptors have been extensively studied here. Two tripodal receptors have been synthesized from the reaction of cyanobenzoyl acid chloride with two tri-amine building blocks such as (i) tris(2-aminoethyl)amine and (ii) tris(2-(4-aminophenoxy)ethyl)amine, which resulted in the first (L1) and second (L2) generation tripodal amides respectively. A detailed comparison of their coordination behavior with anions is also described by crystallographic and solution state experiments. The crystal structure demonstrates various types of spatial orientations of tripodal arms in two receptors and concomitantly interacts with anions distinctively. Intramolecular H-bonding between amide N­H and CO prevents opening of the receptor cavity in the crystal, which leads to a locked conformation of L1 having C(3v) symmetry and makes amide hydrogen unavailable for the anion which results in side cleft anion binding. However, in L2 we conveniently shift the anion binding sites to a distant position which increases cavity size as well as rules out any intramolecular H-bonding between amide N­H and CO. The crystal structure shows a different orientation of the arms in L2; it adopts a quasi-planar arrangement with C(2v) symmetry. In the crystal structure two arms are pointed in the same direction and while extending the contact the third arm is H-bonded with the apical N-atom through a ­CN group, making a pseudo capsular cavity where the anion interacts. Most importantly spatial reorientation of the receptor L2 from a C(2v) symmetry to a folded conformation with a C(3v) symmetry was observed only in the presence of an octahedral SiF6(2-) anion and forms a sandwich type complex. Receptors L1 and L2 are explored for their solution state anion binding abilities. The substantial changes in chemical shifts were observed for the amide (-NH) and aromatic hydrogen (-CH) (especially for F(-)), indicating the role of these hydrogens in anion binding. The anion interacts with receptor L2 more strongly than L1 as confirmed by 1H NMR titration upon monitoring the -NH signal.