Design of Hybrid Electrochromic Materials with Large Electrical Modulation of Plasmonic Resonances.

We present a rational approach to fabricating plasmonically active hybrid polymer-metal nanomaterials with electrochemical tunability of the localized surface plasmon resonances (LSPRs) of noble metal nanostructures embedded in an electroactive polymer matrix. The key requirement for being able to significantly modulate the LSPR band position is a close overlap between the refractive index change [Δn(λ)] of a stimuli-responsive polymeric matrix and the intrinsic LSPR bands. For this purpose, gold nanorods with a controlled aspect ratio, synthesized to provide high refractive index sensitivity while maintaining good oxidative stability, were combined with a solution-processable electroactive and electrochromic polymer (ECP): alkoxy-substituted poly(3,4-propylenedioxythiophene) [PProDOT(CH2OEtHx)2]. Spectral characteristics of the ECP, in particular the Δn(λ) variation, were evaluated as the material was switched between oxidized and reduced states. We fabricated ultrathin plasmonic electrochromic hybrid films consisting of gold nanorods and ECP that exhibited a large, stable, and reversible LSPR modulation of up to 25-30 nm with an applied electrical potential. Finite-difference time-domain (FDTD) simulations confirm a good match between the experimentally measured refractive index change in the ECP and the plasmonic response during electrochemical modulations.

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.

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.

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.

Silver nanocube aggregation gradient materials in search for total internal reflection with high phase sensitivity.

We fabricated monolayer coatings of a silver nanocube aggregation to create a step-wise optical strip by applying different surface pressures during slow Langmuir-Blodgett deposition. The varying amount of randomly distributed nanocube aggregates with different surface coverages in gradient manner due to changes in surface pressure allows for continuous control of the polarization sensitive absorption of the incoming light over a broad optical spectrum. Optical characterization under total internal reflection conditions combined with electromagnetic simulations reveal that the broadband light absorption depends on the relative orientation of the nanoparticles to the polarization of the incoming light. By using computer simulations, we found that the electric field vector of the s-polarized light interacts with the different types of silver nanocube aggregations to excite different plasmonic resonances. The s-polarization shows dramatic changes of the plasmonic resonances at different angles of incidence (shift of 64 nm per 10° angle of incidence). With a low surface nanocube coverage (from 5% to 20%), we observed a polarization-selective high absorption of 80% (with an average 75%) of the incoming light over a broad optical range in the visible region from 400 nm to 700 nm. This large-area gradient material with location-dependent optical properties can be of particular interest for broadband light absorption, phase-sensitive sensors, and imaging.

Light-responsive plasmonic arrays consisting of silver nanocubes and a photoisomerizable matrix.

We report on the synthesis of novel branched organic-inorganic azo-polyhedral oligomeric silsesquioxane (POSS) conjugates (Azo-POSS) and their use as a stable active medium to induce reversible plasmonic modulations of embedded metal nanostructures. A dense monolayer of silver nanocubes was deposited on a quartz substrate using the Langmuir-Blodgett technique and subsequently coated with an ultrathin Azo-POSS layer. The reversible light-induced photoisomerization between the trans and cis states of the azobenzene-terminated branched POSS material results in significant changes in the refractive index (up to 0.17) at a wavelength of 380 nm. We observed that the pronounced and reversible change in the surrounding refractive index results in a corresponding hypsochromic plasmonic shift of 6 nm in the plasmonic band of the embedded silver nanocubes. The reversible tuning of the plasmonic modes of noble-metal nanostructures using a variable-refractive-index medium opens up the possibility of fabricating photoactive, hybrid, ultrathin coatings with robust, real-time, photoinitiated responses for prospective applications in photoactive materials that can be reversibly tuned by light illumination.

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.

Exploring strain-promoted 1,3-dipolar cycloadditions of end functionalized polymers.

Strain-promoted 1,3-dipolar cycloaddition of cyclooctynes with 1,3-dipoles such as azides, nitrones, and nitrile oxides, are of interest for the functionalization of polymers. In this study, we have explored the use of a 4-dibenzocyclooctynol (DIBO)-containing chain transfer agent in reversible addition-fragmentation chain transfer polymerizations. The controlled radical polymerization resulted in well-defined DIBO-terminating polymers that could be modified by 1,3-dipolar cycloadditions using nitrones, nitrile oxides, and azides having a hydrophilic moiety. The self-assembly properties of the resulting block copolymers have been examined. The versatility of the methodology was further demonstrated by the controlled preparation of gold nanoparticles coated with the DIBO-containing polymers to produce materials that can be further modified by strain-promoted cycloadditions.

Electrically tunable plasmonic behavior of nanocube-polymer nanomaterials induced by a redox-active electrochromic polymer.

We present a plasmon-active hybrid nanomaterial design with electrochemical tunability of the localized surface plasmon resonances. The plasmonic-active nanostructures are composed of silver nanocube aggregates embedded into an electrochromic polymer coating on an indium tin oxide electrode with the nanocube aggregation controlled by the surface pressure. Such polymer-nanocube hybrid nanomaterials demonstrated unique tunable plasmonic behavior under an applied electrochemical potential. A significant reversible experimental peak shift of 22 nm at an electrical potential of 200 mV has been achieved in these measurements. Finite-difference time-domain (FDTD) simulations show that, under full oxidation potential, a maximal spectral shift of ca. 80 nm can be potentially achieved, which corresponds to a high sensitivity of 178 nm per refractive index unit. Furthermore, FDTD modeling suggests that the electrochemically controlled tunability of plasmonic peaks is caused by reversible changes in the refractive index of the electrochromic polymer coating caused by oxidation or reduction reactions under external electrical potential. Consequently, we define the orthogonal plasmonic resonance shift as a shift that is orthogonal to the redox process responsible for the refractive index change. On the basis of these results, we suggest that the combination of anisotropic nanostructures and electrochromic matrix has the potential to reversibly electrically tune plasmonic resonances over the full visible spectrum.

Multi-Functionalization of Polymers by Strain-Promoted Cycloadditions.

We report here a synthetic route to oxime, azide and nitrone-bearing copolymers via reversible addition-fragmentation chain transfer copolymerization of 4-vinylbenzaldehyde and 1-(chloromethyl)-4-vinylbenzene with styrene. The azide and nitrone moieties could be employed in strain-promoted 1,3-dipolar cycloadditions with various functionalized dibenzocyclooctynols (DIBO) for metal-free post-functionalization of the polymers. In situ oxidation of the oximes with hypervalent iodine gave nitrile oxides, which could also be employed as 1,3-dipoles for facile cycloadditions with DIBO derivatives. Kinetic measurements demonstrated that the pendant nitrile oxides reacted approximately twenty times faster compared to similar cycloadditions with azides. A block copolymer, containing azide and oxime groups in segregated blocks, served as a scaffold for attachment of hydrophobic and hydrophilic moieties by sequential strain-promoted alkyne-azide and strain-promoted alkyne-nitrile oxide cycloadditions. This sequential bi-functionalization approach made it possible to prepare in a controlled manner multi-functional polymers that could self-assemble into well-defined nanostructures.

Polar dibenzocyclooctynes for selective labeling of extracellular glycoconjugates of living cells.

Although strain-promoted alkyne-azide cycloadditions (SPAAC) have found wide utility in biological and material sciences, the low polarity and limited water solubility of commonly used cyclooctynes represent a serious shortcoming. To address this problem, an efficient synthetic route has been developed for highly polar sulfated dibenzocyclooctynylamides (S-DIBO) by a Friedel-Crafts alkylation of 1,2-bis(3-methoxyphenyl)ethylamides with trichlorocyclopropenium cation followed by a controlled hydrolysis of the resulting dichlorocyclopropenes to give bis(3-methoxyphenyl)cyclooctacyclopropenones, which were subjected to methoxy group removal of the phenols, O-sulfation, and photochemical unmasking of the cyclopropenone moiety. Accurate rate measurements of the reaction of benzyl azide with various dibenzylcyclooctyne derivatives demonstrated that aromatic substitution and the presence of the amide function had only a marginal impact on the rate constants. Biotinylated S-DIBO 8 was successfully used for labeling azido-containing glycoconjugates of living cells. Furthermore, it was found that the substitution pattern of the dibenzylcyclooctynes influences subcellular location, and in particular it has been shown that DIBO derivative 4 can enter cells, thereby labeling intra- and extracellular azido-modified glycoconjugates, whereas S-DIBO 8 cannot pass the cell membrane and therefore is ideally suited for selective labeling of cell surface molecules. The ability to selectively label cell surface molecules will yield unique opportunities for glycomic analysis and the study of glycoprotein trafficking.

Convergent assembly and surface modification of multifunctional dendrimers by three consecutive click reactions.

Multifunctional dendrimers bearing two or more surface functionalities have the promise to provide smart drug delivery devices that can for example combine tissue targeting and imaging or be directed more precisely to a specific tissue or cell type. We have developed a concise synthetic methodology for efficient dendrimer assembly and heterobifunctionalization based on three sequential azide-alkyne cycloadditions. The methodology is compatible with biologically important compounds rich in chemical functionalities such as peptides, carbohydrates, and fluorescent tags. In the approach, a strain-promoted azide-alkyne cycloaddition (SPAAC) between polyester dendrons modified at the focal point with an azido and 4-dibenzocyclooctynol (DIBO) moiety provided dendrimers bearing terminal and TMS-protected (TMS=trimethylsilyl) alkynes at the periphery. The terminal alkynes were outfitted with azido-modified polyethylene glycol (PEG) chains or galactosyl residues by using Cu(I) -catalyzed azide-alkyne cycloadditions (CuAAC). Next, a one-pot TMS deprotection and second click reaction of the resulting terminal alkyne with azido-containing compounds gave multifunctional dendrimers bearing complex biologically active moieties at the periphery.

Metal-free sequential [3 + 2]-dipolar cycloadditions using cyclooctynes and 1,3-dipoles of different reactivity.

Although metal-free cycloadditions of cyclooctynes and azides to give stable 1,2,3-triazoles have found wide utility in chemical biology and material sciences, there is an urgent need for faster and more versatile bioorthogonal reactions. We have found that nitrile oxides and diazocarbonyl derivatives undergo facile 1,3-dipolar cycloadditions with cyclooctynes. Cycloadditions with diazocarbonyl derivatives exhibited similar kinetics as compared to azides, whereas the reaction rates of cycloadditions with nitrile oxides were much faster. Nitrile oxides could conveniently be prepared by direct oxidation of the corresponding oximes with BAIB, and these conditions made it possible to perform oxime formation, oxidation, and cycloaddition as a one-pot procedure. The methodology was employed to functionalize the anomeric center of carbohydrates with various tags. Furthermore, oximes and azides provide an orthogonal pair of functional groups for sequential metal-free click reactions, and this feature makes it possible to multifunctionalize biomolecules and materials by a simple synthetic procedure that does not require toxic metal catalysts.