Weinan Xu

Ultrarobust Transparent Cellulose Nanocrystal‐Graphene Membranes with High Electrical Conductivity

Ultra-robust nanomembranes possessing high mechanical strength combined with excellent stiffness and toughness rarely achieved in nanocomposite materials are presented. These are fabricated by alternately depositing 1D cellulose nanocrystals and 2D graphene oxide nanosheets by using a spin assisted layer-by-layer assembly technique. Such a unique combination of 1D and 2D reinforcing nanostructures results in layered nanomaterials.

Competitive Adsorption of Dopamine and Rhodamine 6G on the Surface of Graphene Oxide

Competitive adsorption-desorption behavior of popular fluorescent labeling and bioanalyte molecules, Rhodamine 6G (R6G) and dopamine (DA), on a chemically heterogeneous graphene oxide (GO) surface is discussed in this study. Individually, R6G and DA compounds were found to adsorb rapidly on the surface of graphene oxide as they followed the traditional Langmuir adsorption behavior. FTIR analysis suggested that both R6G and DA molecules predominantly adsorb on the hydrophilic oxidized regions of the GO surface. Thus, when R6G and DA compounds were adsorbed from mixed solution, competitive adsorption was observed around the oxygen-containing groups of GO sheets, which resulted in partial desorption of R6G molecules from the surface of GO into the solution. The desorbed R6G molecules can be monitored by fluorescence change in solution and was dependent on the DA concentration. We suggest that the efficient competitive adsorption of different strongly bound bioanalytes onto GO-dye complex can be used for the development of sensitive and selective colorimetric biosensors.

Nondestructive Light-Initiated Tuning of Layer-by-Layer Microcapsule Permeability

A nondestructive way to achieve remote, reversible, light-controlled tunable permeability of ultrathin shell microcapsules is demonstrated in this study. Microcapsules based on poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) star polyelectrolyte and poly(sodium 4-styrenesulfonate) (PSS) were prepared by a layer-by-layer (LbL) technique. We demonstrated stable microcapsules with controlled permeability with the arm number of a star polymer having significant effect on the assembly structure: the PMETAI star with 18 arms shows a more uniform and compact assembly structure. We observed that in contrast to regular microcapsules from linear polymers, the permeability of the star polymer microcapsules could be dramatically altered by photoinduced transformation of the trivalent hexacyanocobaltate ions into a mixture of mono- and divalent ions by using UV irradiation. The reversible contraction of PMETAI star polyelectrolyte arms and the compaction of star polyelectrolytes in the presence of multivalent counterions are considered to cause the dramatic photoinduced changes in microcapsule properties observed here. Remarkably, unlike the current mostly destructive approaches, the light-induced changes in microcapsule permeability are completely reversible and can be used for light-mediated loading/unloading control of microcapsules.

Architecture, Assembly, and Emerging Applications of Branched Functional Polyelectrolytes and Poly(ionic liquid)s

Branched polyelectrolytes with cylindrical brush, dendritic, hyperbranched, grafted, and star architectures bearing ionizable functional groups possess complex and unique assembly behavior in solution at surfaces and interfaces as compared to their linear counterparts. This review summarizes the recent developments in the introduction of various architectures and understanding of the assembly behavior of branched polyelectrolytes with a focus on functional polyelectrolytes and poly(ionic liquid)s with responsive properties. The branched polyelectrolytes and poly(ionic liquid)s interact electrostatically with small molecules, linear polyelectrolytes, or other branched polyelectrolytes to form assemblies of hybrid nanoparticles, multilayer thin films, responsive microcapsules, and ion-conductive membranes. The branched structures lead to unconventional assemblies and complex hierarchical structures with responsive properties as summarized in this review. Finally, we discuss prospectives for emerging applications of branched polyelectrolytes and poly(ionic liquid)s for energy harvesting and storage, controlled delivery, chemical microreactors, adaptive surfaces, and ion-exchange membranes.

Multicompartmental Microcapsules with Orthogonal Programmable Two-Way Sequencing of Hydrophobic and Hydrophilic Cargo Release.

Multicompartmental responsive microstructures with the capability for the pre-programmed sequential release of multiple target molecules of opposite solubility (hydrophobic and hydrophilic) in a controlled manner have been fabricated. Star block copolymers with dual-responsive blocks (temperature for poly(N-isopropylacrylamide) chains and pH for poly(acrylic acid) and poly(2-vinylpyridine) arms) and unimolecular micellar structures serve as nanocarriers for hydrophobic molecules in the microcapsule shell. The interior of the microcapsule can be loaded with water-soluble hydrophilic macromolecules. For these dual-loaded microcapsules, a programmable and sequential release of hydrophobic and hydrophilic molecules from the shell and core, respectively, can be triggered independently by temperature and pH variations. These stimuli affect the hydrophobicity and chain conformation of the star block copolymers to initiate out-of-shell release (elevated temperature), or change the overall star conformation and interlayer interactions to trigger increased permeability of the shell and out-of-core release (pH). Reversing stimulus order completely alters the release process.

Star-Shaped Molecules with Polyhedral Oligomeric Silsesquioxane Core and Azobenzene Dye Arms

We synthesized a series of hybrid nanomaterials combining organic dyes with polyhedral oligomeric silsesquioxanes (POSS) based on three different azobenzenes: monoazobenzene (4-phenylazophenol), bis-azobenzene (Disperse Yellow 7 and Fast Garnet derivative), and push-pull azobenzene (Disperse Red 1) via hydrosilylation coupling. The azo-functionalized POSS compounds possess high thermal stability, and their branched architecture resulted in effective suppression of molecular aggregation and allowed for direct imaging of individual dye-POSS structures with expected molecular dimensions. Stable, uniform, smooth, and ultrathin nanocomposite films with mixed silica-organic composition and relatively low refractive indices can be fabricated from all azo-POSS branched conjugates. Finally, the photoisomerization behavior of POSS-conjugated 4-phenylazophenol was investigated in solution as well as in ultrathin nanocomposite film. We found that conjugation to POSS core did not affect the kinetics of trans-cis photoisomerization and thermal cis-trans relaxation. Furthermore, rapid and reversible photoisomerization was observed in azo-POSS nanocomposite films. We suggest that the highly stable branched azo-POSS conjugates with high dye grafting density described here can be considered for nanometer-sized photoswitches, active layer material with optical-limiting properties, and a medium with photoinduced anisotropy for optical storage.

Star Polymer Unimicelles on Graphene Oxide Flakes

We report the interfacial assembly of amphiphilic heteroarm star copolymers (PSnP2VPn and PSn(P2VP-b-PtBA)n (n = 28 arms)) on graphene oxide flakes at the air-water interface. Adsorption, spreading, and ordering of star polymer micelles on the surface of the basal plane and edge of monolayer graphene oxide sheets were investigated on a Langmuir trough. This interface-mediated assembly resulted in micelle-decorated graphene oxide sheets with uniform spacing and organized morphology. We found that the surface activity of solvated graphene oxide sheets enables star polymer surfactants to subsequently adsorb on the presuspended graphene oxide sheets, thereby producing a bilayer complex. The positively charged heterocyclic pyridine-containing star polymers exhibited strong affinity onto the basal plane and edge of graphene oxide, leading to a well-organized and long-range ordered discrete micelle assembly. The preferred binding can be related to the increased conformational entropy due to the reduction of interarm repulsion. The extent of coverage was tuned by controlling assembly parameters such as concentration and solvent polarity. The polymer micelles on the basal plane remained incompressible under lateral compression in contrast to ones on the water surface due to strongly repulsive confined arms on the polar surface of graphene oxide and a preventive barrier in the form of the sheet edges. The densely packed biphasic tile-like morphology was evident, suggesting the high interfacial stability and mechanically stiff nature of graphene oxide sheets decorated with star polymer micelles. This noncovalent assembly represents a facile route for the control and fabrication of graphene oxide-inclusive ultrathin hybrid films applicable for layered nanocomposites.

Branched Polyhedral Oligomeric Silsesquioxane Nanoparticles Prepared via Strain-Promoted 1,3-Dipolar Cycloadditions

Conjugation of small organic molecules and polymers to polyhedral oligosilsesquioxane (POSS) cores results in novel hybrid materials with unique physical characteristics. We report here an approach in which star-shaped organic-inorganic scaffolds bearing eight cyclooctyne moieties can be rapidly functionalized via strain-promoted azide-alkyne cycloaddition (SPAAC) to synthesize a series of nearly monodisperse branched core-shell nanoparticles with hydrophobic POSS cores and hydrophilic arms. We established that SPAAC is a robust method for POSS core octafunctionalization with the reaction rate constant of 1.9 × 10(-2) M(-1) s(-1). Functionalization with poly(ethylene glycol) (PEG) azide, fluorescein azide, and unprotected lactose azide gave conjugates which represent different classes of compounds: polymer conjugates, fluorescent dots, and bioconjugates. These resulting hybrid compounds were preliminarily tested for their ability to self-assemble in solution and at the air-water interface. We observed the formation of robust smooth Langmuir monolayers with diverse morphologies. We found that polar lactose moieties are completely submerged into the subphase whereas the relatively hydrophobic fluorescein arms had extended conformation at the interface, and PEG arms were partially submerged. Finally, we observed the formation of stable micelles with sizes between 70 and 160 nm in aqueous solutions with size and morphology of the structures dependent on the molecular weight and the type of the peripheral hydrophilic moieties.

Linear and Star Poly(ionic liquid) Assemblies: Surface Monolayers and Multilayers

The surface morphology and organization of poly(ionic liquid)s (PILs), poly[1-(4-vinylbenzyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] are explored in conjunction with their molecular architecture, adsorption conditions, and postassembly treatments. The formation of stable PIL Langmuir and Langmuir-Blodgett (LB) monolayers at the air-water and air-solid interfaces is demonstrated. The hydrophobic bis(trifluoromethylsulfonyl)imide (Tf2N-) is shown to be a critical agent governing the assembly morphology, as observed in the reversible condensation of LB monolayers into dense nanodroplets. The PIL is then incorporated as an unconventional polyelectrolyte component in the layer-by-layer (LbL) films of hydrophobic character. We demonstrate that the interplay of capillary forces, macromolecular mobility, and structural relaxation of the polymer chains influence the dewetting mechanisms in the PIL multilayers, thereby enabling access to a diverse set of highly textured, porous, and interconnected network morphologies for PIL LbL films that would otherwise be absent in conventional LbL films. Their compartmentalized internal structure is relevant to molecular separation membranes, ultrathin hydrophobic coatings, targeted cargo delivery, and highly conductive films.

Structural Study of Star Polyelectrolytes and Their Porous Multilayer Assembly in Solution

Star polyelectrolytes with responsive properties to external stimuli, such as pH, temperature and ionic condition, were utilized to fabricate layer-by-layer (LbL) microcapsules . The microstructure of star polyelectrolytes was first studied in semi-dilute solution by in situ small-angle neutron scattering (SANS). These measurements show that with the addition of salts, arms of strong cationic star polyelectrolytes will contract and the spatial ordering of the stars would be interrupted. SANS measurements were also performed on the microcapsules in order to study their internal structure and responsive properties in solution. The results show that with the increase of shell thickness, microcapsules undergo a change of fractal dimension. Microcapsules with thinner shell have a surface fractal structure with rough interface, while those with thicker shell generally have a mass fractal structure of 3D random network. With the change of surrounding environment (pH, temperature, or ionic condition), the morphology and permeability of microcapsules are changed concurrently, for example, with the addition of multivalent salt, there is a surface- to mass-fractal transition, with the correlation length decreasing by around 50 %. This study provides insight into the mechanism of the responsiveness of novel star polyelectrolytes and their assembled multilayer structures.