Graphene oxide membranes-partially oxidized, stacked sheets of graphene-can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes-that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)-are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with angstrom precision using K+, Na+, Ca2+, Li+ or Mg2+ ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) should have a much stronger cation-π interaction with the graphene sheet than Na+ has, suggesting that other ions could be used to produce a wider range of interlayer spacings.

Ion sieving in graphene oxide membranes via cationic control of interlayer spacing

Fragmentation Methods: A Route to Accurate Calculations on Large Systems Mark S. Gordon,* Dmitri G. Fedorov, Spencer R. Pruitt, and Lyudmila V. Slipchenko Department of Chemistry and Ames Laboratory, Iowa State University, Ames Iowa 50011, United States Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States

Fragmentation methods: a route to accurate calculations on large systems.

Cation-π interaction: its role and relevance in chemistry, biology, and material science.

Minerals and organic matter (OM) may form intricate associations via myriad interactions. In soils, the associations of OM with mineral surfaces are mainly investigated because of their role in determining the long-term retention of OM. OM “must decay in order to release the energy and nutrients that drive live processes all over the planet” ( Janzen, 2006 ). Thus, the processes and mechanisms that retain OM in soil are a central concern to very different branches of environmental research. An agronomist may want to synchronize periods of high nutrient and energy release with the growth stages of a crop. An environmental chemist may wish to either immobilize an organic soil contaminant or enhance its decomposition into less harmful metabolites, while climate scientists need to understand the processes that mediate the production of potent greenhouse gases from decomposing OM. Associations of OM with pedogenic minerals (henceforth termed mineral–organic associations (MOAs)) are known to be key controls in these and many other processes. Here we strive to present an overview of the current knowledge on MOAs and identify key questions and future research needs.

Chapter One – Mineral–Organic Associations: Formation, Properties, and Relevance in Soil Environments

Self-assembling systems play a significant role in physiological functions and have therefore attracted tremendous attention due to their great potential for applications in energy, biomedicine and nanotechnology. Peptides, consisting of amino acids, are among the most popular building blocks and programmable molecular motifs. Nanostructures and materials assembled using peptides exhibit important potential for green-life new technology and biomedical applications mostly because of their bio-friendliness and reversibility. The formation of these ordered nanostructures pertains to the synergistic effect of various intermolecular non-covalent interactions, including hydrogen-bonding, π–π stacking, electrostatic, hydrophobic, and van der Waals interactions. Therefore, the self-assembly process is mainly driven by thermodynamics; however, kinetics is also a critical factor in structural modulation and function integration. In this review, we focus on the influence of thermodynamic and kinetic factors on structural assembly and regulation based on different types of peptide building blocks, including aromatic dipeptides, amphiphilic peptides, polypeptides, and amyloid-relevant peptides.

Peptide self-assembly: thermodynamics and kinetics

Cooperativity in Noncovalent Interactions.

An exhaustive study on the clusters of benzene (Bz)n, n=2–8, at MP2/6-31++G∗∗ level of theory is reported. The relative strengths of CH-π and π-π interactions in these aggregates are examined, which eventually govern the pattern of cluster formation. A linear scaling method, viz., molecular tailoring approach (MTA), is efficiently employed for studying the energetics and growth patterns of benzene clusters consisting up to eight benzene (Bz) units. Accuracy of MTA-based calculations is appraised by performing the corresponding standard calculations wherever possible, i.e., up to tetramers. For benzene tetramers, the error introduced in energy is of the order of 0.1 mH (∼0.06 kcal/mol). Although for higher clusters the error may build up, further corrections based on many-body interaction energy analysis substantially reduce the error in the MTA-estimate. This is demonstrated for a prototypical case of benzene hexamer. A systematic way of building up a cluster of n monomers (n-mer) which employs molecular ...

Ab initio investigation of benzene clusters: molecular tailoring approach.

Ab initio and DFT computations were carried out on four distinct hydrogen-bonded arrangements of water clusters (H2O)n, n = 2−20, represented as W1D, W2D, W2DH, and W3D. The variation in the strength of hydrogen bond as a function of the chain length is studied. In all the four cases, there is a substantial cooperative interaction, albeit in different degrees. The effect of basis set superposition error (BSSE) on the complexation energy of water clusters has been analyzed. Atoms in molecules (AIM) analysis performed to evaluate the nature of the hydrogen bonding shows a high correlation between hydrogen bond strength and the trends in complexation energy. Solvated water clusters exhibit lower complexation energies compared to corresponding gas-phase geometries on PCM (polarized continuum model) optimization. The feasibility of stripping an electron or addition of an electron increases dramatically as the cluster size increases. Although W3D caged structures are stable for neutral clusters, the helical W2D...

Hydrogen Bonding in Water Clusters and Their Ionized Counterparts

Insights into the formation of hydrogen bonded clusters are of outstanding importance and quantum chemical calculations play a pivotal role in achieving this understanding. Structure and energetic comparison of linear, circular and standard forms of (acetamide)n clusters (n = 1–15) at the B3LYP/D95** level of theory including empirical dispersion correction reveals significant cooperativity of hydrogen bonding and size dependent structural preference. A substantial amount of impact of BSSE is observed in these calculations as the cluster size increases irrespective of the kind of arrangement. The interaction energy per monomer increases from dimer to 15mer by 90% in the case of the circular arrangement, by 76% in the case of the linear arrangement and by 34% in the case of the standard arrangement respectively. The cooperativity in hydrogen bonding is also manifested by a regular decrease in average O⋯H and C–N bond distances, while average CO and N–H bond lengths increase with increasing cluster size. Atoms-In-Molecules (AIM) analysis is used to characterize the nature of hydrogen bonding between the acetamide molecules in the cluster on the basis of electron density (ρ) values obtained at the bond critical point. An analysis of N–H bond stretching frequencies as a function of the cluster size shows a marked red shift as the cluster size increases from 1 to 15.

A. Subha Mahadevi

Papers

Cation-π interaction: its role and relevance in chemistry, biology, and material science.

Cooperativity in Noncovalent Interactions.

Ab initio investigation of benzene clusters: molecular tailoring approach.

Hydrogen Bonding in Water Clusters and Their Ionized Counterparts

A theoretical study on structural, spectroscopic and energetic properties of acetamide clusters [CH3CONH2] (n = 1–15)