Polymer Stereocomplexation as a Scalable Platform for Nanoparticle Assembly.

DNA-mediated assembly of inorganic particles has demonstrated to be a powerful approach for preparing nanomaterials with a range of interesting optical and electrical properties. Building on this inspiration, we describe a generalizable gram-scale method to assemble nanoparticles through the formation of poly(methyl methacrylate) (PMMA) triple-helices. In this work, alkene-terminated syndiotactic (st-) and isotactic (it-) PMMA polymers were prepared and subsequently functionalized to afford nanoparticle ligands. Nanoparticles with complementary st- and it-PMMA ligands could then be spontaneously assembled upon mixing at room temperature. This process was robust and fully reversible through multiple heating and cooling cycles. The versatility of PMMA stereocomplexation was highlighted by assembling hybrid structures composed of nanoparticles of different compositions (e.g., Au and quantum dots) and shapes (e.g., spheres and rods). These initial demonstrations of nanoparticle self-assembly from inexpensive PMMA-based materials present an attractive alternative to DNA-based nanomaterials.

Molecular mapping of poly(methyl methacrylate) super-helix stereocomplexes.

In this study, by using X-ray powder diffraction profiles as blueprints, we successfully mapped the most probable molecular-level structural arrangement of the PMMA super-helix stereocomplexes through molecular dynamic simulations. Molecular-level resolution of the PMMA triple-helix supramolecule was not previously achievable by experimental methods. After constructing molecular models of stereo-regular complexes composed of linear it- and st-PMMAs, our all-atom molecular dynamics simulations identified the stereocomplex structure that best reproduces experimental diffraction profiles and thermodynamic properties as a double helix of isotactic (it-)PMMA with a helical pitch of 1.8 nm and 9 units per turn surrounded by a single helix of syndiotactic (st-)PMMA with an average helical pitch of 0.9 nm and 20 units per turn. The it-/st- complexing stoichiometry in the PMMA triple-helix is therefore 9 : 20. This presents the first all-atom model of the it-/st-PMMA triple-helix stereocomplex that accurately fits experimental X-ray diffraction profiles. In addition, the simulation results revealed the outer st-PMMA helix of the PMMA stereocomplex has a fiber diameter of at least 1.85 nm and adopts a non-ideal helical geometry. Furthermore, through dynamic simulations, surprising new sights into the effect of the structural configuration of the PMMA stereocomplex (i.e., helical pitch and direction, and tilt angle) on the physical properties of their crystal structures were obtained. Those crystal properties include X-ray diffraction profile, packing density, chain-chain spacing, chain width and cohesive energy density.

Stereospecific cyclic poly(methyl methacrylate) and its topology- guided hierarchically controlled supramolecular assemblies.

In this study, the stereocomplexation between a novel stereospecific cyclic vinyl polymer, that is, cyclic syndiotactic poly(methyl methacrylate) (st-PMMA), with the complementary linear isotactic (it-) PMMA was investigated. Surprising new insight into the effects of the topology (i.e., end groups), size, and tacticity of the assembling components on stereocomplex formation was obtained. Characterization of the stereocomplexes revealed that the self-assembly of cyclic st-PMMAs and linear it-PMMAs resulted in the formation of an unprecedented "polypseudorotaxane-type" supramolecular assembly. This stereocomplex exhibited remarkably different physical properties as compared to the conventional PMMA triple-helix stereocomplex as a result of the restricted topology imposed by the cyclic st-PMMA assembling component.

[Ecological service assessment of human-dominated freshwater ecosystem with a case study in Yangzhou Prefecture, China.

Freshwater ecosystems provide a host of services to humanity. These services are now rapidly being lost, not least because of the inability of making the impacts measurable. To overcome this obstacle, assessment frameworks for freshwater ecosystem services are needed. A simple water equivalent framework to assess the ecological services provided by freshwater ecosystems was developed in this study. It translated the occupation of freshwater ecosystem services into biologically freshwater volumes and then compares this consumption to the freshwater throughput, that is, the ecological capacity available in this region. In this way, we use the example of Yangzhou Prefecture, to account the main categories of human occupation of water ecosystem services. The result showed that there is a huge gap between the consumption and the supply of freshwater ecosystem services. This must encourage local government to make land-use and water management decisions both economically rational and environmentally sound.