There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Fast parallel algorithms for short-range molecular dynamics

Graphenes as potential material for electronics.

Membranes have an increasingly important role in alleviating water scarcity and the pollution of aquatic environments. Promising molecular-level design approaches are reviewed for membrane materials, focusing on how these materials address the urgent requirements of water treatment applications.

Materials for next-generation desalination and water purification membranes

BACKGROUND Synthetic membranes are used for desalination, dialysis, sterile filtration, food processing, dehydration of air and other industrial, medical, and environmental applications due to low energy requirements, compact design, and mechanical simplicity. New applications are emerging from the water-energy nexus, shale gas extraction, and environmental needs such as carbon capture. All membranes exhibit a trade-off between permeability—i.e., how fast molecules pass through a membrane material—and selectivity—i.e., to what extent the desired molecules are separated from the rest. However, biological membranes such as aquaporins and ion channels are both highly permeable and highly selective. Separation based on size difference is common, but there are other ways to either block one component or enhance transport of another through a membrane. Based on increasing molecular understanding of both biological and synthetic membranes, key design criteria for new membranes have emerged: (i) properly sized free-volume elements (or pores), (ii) narrow free-volume element (or pore size) distribution, (iii) a thin active layer, and (iv) highly tuned interactions between permeants of interest and the membrane. Here, we discuss the permeability/selectivity trade-off, highlight similarities and differences between synthetic and biological membranes, describe challenges for existing membranes, and identify fruitful areas of future research. ADVANCES Many organic, inorganic, and hybrid materials have emerged as potential membranes. In addition to polymers, used for most membranes today, materials such as carbon molecular sieves, ceramics, zeolites, various nanomaterials (e.g., graphene, graphene oxide, and metal organic frameworks), and their mixtures with polymers have been explored. Simultaneously, global challenges such as climate change and rapid population growth stimulate the search for efficient water purification and energy-generation technologies, many of which are membrane-based. Additional driving forces include wastewater reuse from shale gas extraction and improvement of chemical and petrochemical separation processes by increasing the use of light hydrocarbons for chemicals manufacturing. OUTLOOK Opportunities for advancing membranes include (i) more mechanically, chemically, and thermally robust materials; (ii) judiciously higher permeability and selectivity for applications where such improvements matter; and (iii) more emphasis on fundamental structure/property/processing relations. There is a pressing need for membranes with improved selectivity, rather than membranes with improved permeability, especially for water purification. Modeling at all length scales is needed to develop a coherent molecular understanding of membrane properties, provide insight for future materials design, and clarify the fundamental basis for trade-off behavior. Basic molecular-level understanding of thermodynamic and diffusion properties of water and ions in charged membranes for desalination and energy applications such as fuel cells is largely incomplete. Fundamental understanding of membrane structure optimization to control transport of minor species (e.g., trace-organic contaminants in desalination membranes, neutral compounds in charged membranes, and heavy hydrocarbons in membranes for natural gas separation) is needed. Laboratory evaluation of membranes is often conducted with highly idealized mixtures, so separation performance in real applications with complex mixtures is poorly understood. Lack of systematic understanding of methodologies to scale promising membranes from the few square centimeters needed for laboratory studies to the thousands of square meters needed for large applications stymies membrane deployment. Nevertheless, opportunities for membranes in both existing and emerging applications, together with an expanding set of membrane materials, hold great promise for membranes to effectively address separations needs.

http://science.sciencemag.org/content/sci/356/6343/eaab0530.full.pdf

Maximizing the right stuff: The trade-off between membrane permeability and selectivity

Aqueous solutions of tri-block co-polymer surfactants are able to aggregate into a rich variety of microstructures, which can exhibit different rheological behaviors. In this work, we study the diversity of structures detected in aqueous solutions of Pluronic L64 at various concentrations and temperatures by experimental rheometry and dissipative particle dynamics (DPD) simulations. Mixtures of Pluronic L64 in water (ranging from 0 to 90 wt% Pluronic L64) have been studied in both linear and non-linear regimes by oscillatory and steady shear flow. The measurements allowed for the determination of a complete rheological phase diagram of the Pluronic L64–water system. The linear and non-linear regimes have been compared to equilibrium and non-equilibrium DPD bulk simulations of similar systems obtained by using the software LAMMPS. The molecular results are capable of reproducing the equilibrium structures, which are in complete agreement with the ones predicted through experimental linear rheology. The simulations also depict micellar microstructures after long time periods when a strong flow is applied. These structures are directly compared, from a qualitative point of view, with the corresponding experimental results and differences between the equilibrium and non-equilibrium phase diagrams are highlighted, proving the capability of detecting morphological changes caused by deformation in both experiments and DPD simulations. The effect of temperature on the rheology of the systems has been eventually investigated and compared with the already existing non-rheological phase diagram.

An experimental rheological phase diagram of a tri-block co-polymer in water validated against dissipative particle dynamics simulations

Series of propene-norbornene (P-N) copolymers were synthesized in the presence of two C 2 symmetric zirconocenes, rac-Et(Indenyl) 2 ZrCl 2 (1) and rac-Me 2 Si(Indenyl) 2 ZrCl 2 (2), and of the C s symmetric zirconocene Me 2 C(Cp)(Fluorenyl)ZrCl 2 (3) with MAO as cocatalyst. P-N copolymers were characterized by 13 C NMR spectroscopy, SEC, and DSC. A first assignment of the main 13 C NMR signals of P-N copolymers obtained with 1 and 2 containing isolated N units was obtained on the basis of DEPT experiments and by comparison with isotactic polypropene (i-PP) and E-N copolymer spectra. Ab initio theoretical 13 C NMR chemical shifts, combined with R.I.S. statistics of the P-N chain, gave important detailed indications for the assignment of the complex 13 C spectra of these copolymers. Such assignments were used to estimate the N copolymer content. The comparison of N content values obtained from the areas of different regions of the spectra reveals that 1,3 propene misinsertions are formed in greater amount as the [N]/[P] ratio of the feed increases. This may be due to the steric hindrance of the Mt-tertiary carbon bond when N is the last inserted unit, which makes difficult the next propene insertion and causes the low polymerization activities, molecular masses and Tg. The spectra of P-N copolymers obtained with 3 revealed to be even more complex. A limited assignment of the spectrum has been achieved. This allowed us to evaluate the N content in the copolymers and to evidence the low tendency of the C s symmetric 3 to give 1,3 propene misinsertions in P-N copolymers. This is in agreement with the results observed with this catalyst in propene homopolymerization.

Propene-norbornene copolymers: Synthesis and microstructure

We report the wetting behavior of graphitic surface–water interfaces through the calculation of the local stress tensor based on the Irving–Kirkwood–Noll theory using detailed atomistic molecular d...

Role of Long-Range Electrostatic Interactions and Local Topology of the Hydrogen Bond Network in the Wettability of Fully and Partially Wetted Single and Multilayer Graphene

Performing molecular dynamics simulations on model systems we study the structural changes and thermodynamic stability of polymers of varying topology (linear and star-shaped) at interface between two liquids. We find that homopolymers are attracted to the interface in both good and poor solvent conditions showing that they are surface active molecules even though not amphiphilic. In most cases changing polymer topology had only a minor effect on the desorption free energy. A noticeable dependence on polymer topology is only seen for relatively high molecular weight polymers at interface between two good solvents. Examining separately the enthalpic and entropic components of the desorption free energy suggests that its largest contribution is the decrease in the enthalpic part of interfacial free energy caused by the adsorption of the polymer at the interface. Finally we propose a simple method to qualitatively predict the trend of the interfacial free energy as a function of the polymer molecular weight.

Thermodynamics of linear and star polymers at fluid interfaces

We employ atomistic molecular dynamics simulations to investigate the effect that the incorporation of the nonionic amphiphilic copolymer known as Pluronic L64 has on the mechanical stability of a DPPC membrane. The simulations reveal that the incorporation of the polymer chains leads to membranes that can sustain increasing mechanical stresses. Analysis of mechanical, structural, and dynamic properties of the membrane shows that the polymer chains interact strongly with the lipids in the vicinity, restraining their mobility and imparting better mechanical stability to the membrane. The hybrid membranes under tension remain thicker, more ordered, and stiffer in comparison to their lipid analogues. Trans-bilayer lipid movements (flip-flop) are observed and appear to be triggered by the presence of the polymer chains. A careful analysis of the pore formation under high tensions reveals two distinctive mechanisms that depend on the distribution of the hydrophilic polymer blocks in the bilayer. Finally, the r...

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Paola Carbone

Papers

An experimental rheological phase diagram of a tri-block co-polymer in water validated against dissipative particle dynamics simulations

Propene-norbornene copolymers: Synthesis and microstructure

Role of Long-Range Electrostatic Interactions and Local Topology of the Hydrogen Bond Network in the Wettability of Fully and Partially Wetted Single and Multilayer Graphene

Thermodynamics of linear and star polymers at fluid interfaces

How the Incorporation of Pluronic Block Copolymers Modulates the Response of Lipid Membranes to Mechanical Stress