Modeling and Analysis of Modal Switching in Networked Transport Systems

We consider networked transport systems defined on directed graphs: the dynamics on the edges correspond to solutions of transport equations with space dimension one. In addition to the graph setting, a major consideration is the introduction and propagation of discontinuities in the solutions when the system may discontinuously switch modes, naturally or as a hybrid control. This kind of switching has been extensively studied for ordinary differential equations, but not much so far for systems governed by partial differential equations. In particular, we give well-posedness results for switching as a control, both in finite horizon open loop operation and as feedback based on sensor measurements in the system.     

Needle-like supramolecular amphiphilic assembly constructed by the host–guest interaction between calixpyridinium and methotrexate disodium

In this work, the host–guest interaction between calixpyridinium and the anionic anticancer drug methotrexate disodium was explored in water. Unexpectedly, an interesting anisotropic needle-like rather than an ordinary isotropic spherical supramolecular amphiphilic assembly was fabricated by the complexation of calixpyridinium with methotrexate disodium. It is the second anionic guest to be discovered to form the non-spherical supramolecular assembly upon complexation with calixpyridinium. This discovery implies the possibility to construct various topological nanostructures based on the host–guest interactions between calixpyridinium and the anionic drugs in the future. The resulting calixpyridinium–drug assemblies with different morphologies may have the diverse potentials to adjust the efficacies of anionic drugs.     

Synthesis, crystal structures, and luminescent properties of two types of lanthanide phosphonates

Hydrothermal reactions of different lanthanide(III) salts with an amino-diphosphonate ligand (H₄L=C₆H₅CH₂N(CH₂PO₃H₂)₂) led to two series of lanthanide phosphonates, namely, Ln(H₂L)(H₃L) (Ln=La, 1; Pr, 2; Nd, 3; Sm, 4; Eu, 5; Gd, 6; Tb, 7). Compounds 1-5 feature a one-dimensional (1D) chain structure in which dimers of two edge-sharing LnO₈ polyhedra are interconnected by bridging phosphonate groups, such 1D arrays are further interlinked via strong hydrogen bonds between non-coordinated phosphonate oxygen atoms into a two-dimensional (2D) layer with the phenyl groups of the ligands orientated toward the interlayer space. Compounds 6 and 7 also show a different 1D array in which the LnO₆ octahedra are bridged by phosphonate groups via corner-sharing, such chains are also further interlinked by hydrogen bonds into a 2D supramolecular layer. Compounds 5 and 7 emit red and green light with a lifetime of 2.1 and 3.7 ms, respectively.     

Hydrogels: From soft contact lenses and implants to self‐assembled nanomaterials

Hydrogels were the first biomaterials designed for clinical use. Their discovery and applications as soft contact lenses and implants are presented. This early hydrogel research served as a foundation for the expansion of biomedical polymers research into new directions: design of stimuli sensitive hydrogels that abruptly change their properties upon application of an external stimulus (pH, temperature, solvent, electrical field, biorecognition) and hydrogels as carriers for the delivery of drugs, peptides, and proteins. Finally, pathways to self‐assembly of block and graft copolymers into hydrogels of precise 3D structures are introduced. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5929–5946, 2009     

Molecular Recognition in Self‐Assembled Integrated Circuits: Getting Smaller while under Control

Available in small print : Block copolymer lithography has great potential for reducing the size and fabrication time of integrated circuits. Hydrogen‐bonding‐mediated molecular recognition in self‐assembly processes can be used to produce highly ordered square arrays of block copolymers on the surface of a silicon substrate (see picture).

     

Understanding the Supramolecular Self‐Assembly of the Fullerene Derivative PCBM on Gold Surfaces

We report a DFT study on the self‐assembly of the fullerene derivative PCBM on the Au(111) surface. Recent STM experiments (Angew. Chem. 2007 , 119, 8020–8023^[1]) show a coverage‐dependent transition of the adsorption and self‐assembly of PCBM on this surface. To understand the origin of this observation, we compute the geometries and relative energies of ten PCBM dimers and four tetramers. The calculations show that the self‐assembly of PCBM at high coverage is mainly controlled by hydrogen bonding between the PCBM tails. Due to the large size of the fullerene cage, the hydrogen bonds are formed far away from the surface; hence they are very similar to those found in the gas phase. This picture successfully explains the observed site‐insensitive adsorption at high coverage and the 2D arrangement of PCBM on the surface.     

Mesoporous carbon materials: synthesis and modification

Porous carbon materials are of interest in many applications because of their high surface area and physicochemical properties. Conventional syntheses can only produce randomly porous materials, with little control over the pore-size distributions, let alone mesostructures. Recent breakthroughs in the preparation of other porous materials have resulted in the development of methods for the preparation of mesoporous carbon materials with extremely high surface areas and ordered mesostructures, with potential applications as catalysts, separation media, and advanced electronic materials in many scientific disciplines. Current syntheses can be categorized as either hard-template or soft-template methods. Both are examined in this Review along with procedures for surface functionalization of the carbon materials obtained.     

Novel single-crystal-to-single-crystal anion exchange and self-assembly of luminescent d(10) metal (Cd(II), Zn(II), and Cu(I)) complexes containing C(3)-symmetrical ligands

Ligands L1 and L2' (L1=N,N',N'-tris(4-pyridyl)trimesic amide, L2'=N,N',N'-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide) belonging to an interesting family of tripyridyltriamides with C(3)-symmetry have been utilized to construct 3D porous or hydrogen-bonded frameworks. Through a novel single-crystal-to-single-crystal anion-exchange process, [Cd(L1)(2)(ClO(4))(2)](n) (1c) can be obtained from [Cd(L1)(2)Cl(2)](n) (1b) in the presence of ClO(4)(-) anions. This anion-exchange process is highly selective and only the substitution of Cl(-) by ClO(4)(-) or PF(6)(-) could be realized; Cl(-) was found not to be substituted by BPh(4)(-). This demonstrates that the exchange process depends on the size of the anions in relation to the size of the cavities in the host material (ca. 7.5 A). In addition, the anion-exchange properties of 1 b have also been investigated by means of powder X-ray diffraction (PXRD), elemental analysis (EA), and infrared absorption spectroscopy (IR). Structurally, [Zn(L1)(NO(3))(2)](n)(2) consists of a 2D coordination network with five-coordinate Zn(II) ions. Surprisingly, different trigonal-bipyramidal Zn(II) ions propagate to form distinct respective sheet structures, A and B, which are packed in an A-B-A-B manner in the crystal lattice, and these are hydrogen-bonded to give a 3D extended framework. The molecular structure of [CuI(L2')](n)(3) shows that the Cu(I) ion adopts a distorted tetrahedral geometry, and 3 also forms a 2D coordination network. Significantly, this 2D coordination network is further assembled into a remarkable 3D homochiral framework through triple hydrogen bonding and pi...pi interactions. All of these 3D coordination polymers and/or hydrogen-bonded frameworks are luminescent in the solid state, and their solid-state luminescent properties have been investigated at room temperature and/or at 77 K.     

DNA tile based self-assembly: building complex nanoarchitectures.

DNA tile based self-assembly provides an attractive route to create nanoarchitectures of programmable patterns. It also offers excellent scaffolds for directed self-assembly of nanometer-scale materials, ranging from nanoparticles to proteins, with potential applications in constructing nanoelectronic/nanophotonic devices and protein/ligand nanoarrays. This Review first summarizes the currently available DNA tile toolboxes and further emphasizes recent developments toward self-assembling DNA nanostructures with increasing complexity. Exciting progress using DNA tiles for directed self-assembly of other nanometer scale components is also discussed.     

Novel Water‐Soluble Shape‐Regulatable Luminescent Nanoparticles by Non‐Covalently Bonded Self‐Assembly

Summary: Novel non‐covalently connected water‐soluble nanoparticles that contain poly(fluorene‐co‐phenylene) with hydroxy‐capped alkoxy side chains (PF3BOH) and poly(acrylic acid) (PAA) have been obtained and characterized. With different proportions of PF3BOH and PAA, the shape and size of the nanoparticles can be regulated. The nanoparticles are quite stable in water with no precipitate being observed after weeks. Transmission electron microscopy and dynamic laser light scattering are used to confirm the morphology of the PF3BOH/PAA nanoparticles. Their optical properties have been investigated and show similar optoelectronic properties to a PF3BOH solid film although they do not undergo aggregation.

TEM images of the nanoparticles obtained upon varying the PAA/PF3BOH content.