Late transition-metal nanoparticles were synthesized using Na naphthalenide reduction of salts followed by salting-out purification catalyse click, redox and coupling reactions.

Polyelectrolyte multilayers (PEMs) have many potential applications in tissue engineering and regenerative medicine. However, the softness of biocompatible PEMs results in limited cell adhesion. A novel strategy for the enhancement of cell adhesion on PEMs based on thermal annealing is presented here. The impact of thermal annealing at 37 ºC of poly‐l‐lysine (PLL) and alginate (Alg) polyelectrolyte multilayers on the adhesion of human lung cancer A549 and myoblast C2C12 cell lines is studied. The properties of the PEMs after annealing are characterized by means of the quartz crystal microbalance with dissipation, atomic force microscopy, atomic force spectroscopy, zeta potential, and contact angle measurements. After annealing, PLL/Alg PEMs become smoother displaying an increase in stiffness. Furthermore, PEMs become more hydrophobic, with an increase in contact angle from 36° to 90°. Additionally, the surface charge decreases and protein deposition on PEMs significantly diminishes after annealing. Cell adhesion, measured by the projected average cell spreading and focal contact formation, is remarkably improved for the annealed PEMs.

A tris(triazolyl)-polyethylene glycol amphiphilic ligand is designed and successfully used as highly efficient catalyst in combination with various transition metal nanoparticles in click reactions, Suzuki—Miyaura couplings, as well as transfer hydrogenation reactions.

A polyelectrolyte multilayer (PEM) membrane of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium 4‐styrenesulfonate) (PSS) is deposited on top of a thick‐layer micrometer range of multiwalled carbon nanotubes (MWCNTs) assembled on a porous silicon carbide (SiC) tubular membrane support. MWCNTs are assembled “layer‐by‐layer” alternating oxidized CNTs and poly(allylamine hydrochloride)‐modified CNTs. The MWCNTs layer is crosslinked by annealing after the assembly. The MWCNT layer acts as a spacer between the PDADMAC/PSS PEM and the SiC support. The MWCNT support increases water permeability in 42% compared with the PEMs deposited without MWCNTs. Hybrid MWCNT–PEM membranes show high rejection for divalent ions, which increases directly with flux. A rejection up to 92% is measured for MgSO4 and there is up to a 60% rejection difference between MgCl2 and NaCl, making the hybrid MWCNT–PEMs highly appealing for nanofiltration and monovalent and divalent ion separations image

Understanding the relationship between the location of nanoparticles (NPs) in an organic matrix and their catalytic performances is essential for catalyst design. Here we show that catalytic activities of Au, Ag and CuNPs stabilized by dendrimers using coordination to intradendritic triazoles, galvanic replacement or stabilization outside dendrimers strongly depends on their location. AgNPs are found at the inner click dendrimer periphery, whereas CuNPs and AuNPs are encapsulated in click dendrimer nanosnakes. AuNPs and AgNPs formed by galvanic replacement are larger than precursors and only partly encapsulated. AuNPs are all the better 4-nitrophenol reduction catalysts as they are less sterically inhibited by the dendrimer interior, whereas on the contrary CuNPs are all the better alkyne azide cycloaddition catalysts as they are better protected from aerobic oxidation inside dendrimers. This work highlights the role of the location in macromolecules on the catalytic efficiency of metal nanoparticles and rationalizes optimization in catalyst engineering.

Ferrocene (Fc) in ether reduces HAuCl4 in water within seconds under ambient conditions in air upon stirring, forming ferricinium chloride stabilized water-soluble 20 nm gold nanoparticles (AuNPs) that are redispersible in the presence of poly(N-vinylmethylpyrro-lidone) or NaBH4 + thiol. After reduction with NaBH4 yielding Fc and 26 nm sodium poly(hydroxyborate) stabilized AuNPs, the core size no longer changes following reactions with thiols providing (RS)(n)AuNPs.

A ligand design is proposed for transition metal nanoparticle (TMNP) catalysts in aqueous solution. Thus, a tris(triazolyl)-polyethylene glycol (tris-trz-PEG) amphiphilic ligand, 2, is used for the synthesis of very small TMNPs with Fe, Co, Ni, Cu, Ru, Pd, Ag, Pt, and Au. These TMNP-2 catalysts were evaluated and compared for the model 4-nitrophenol reduction, and proved to be extremely efficient. High catalytic efficiencies involving the use of only a few ppm metal of PdNPs, RuNPs, and CuNPs were also exemplified in Suzuki-Miyaura, transfer hydrogenation, and click reactions, respectively.

Polyelectrolyte multilayers (PEMs) of poly-l-lysine (PLL) and alginic acid sodium salt (Alg) are fabricated applying the layer by layer technique and annealed at a constant temperature; 37, 50 and 80°C, for 72h. Atomic force microscopy reveals changes in the topography of the PEM, which is changing from a fibrillar to a smooth surface. Advancing contact angle in water varies from 36° before annealing to 93°, 77° and 95° after annealing at 37, 50 and 80°C, respectively. Surface energy changes after annealing were calculated from contact angle measurements performed with organic solvents. Quartz crystal microbalance with dissipation, contact angle and fluorescence spectroscopy measurements show a significant decrease in the adsorption of the bovine serum albumin protein to the PEMs after annealing. Changes in the physical properties of the PEMs are interpreted as a result of the reorganization of the polyelectrolytes in the PEMs from a layered structure into complexes where the interaction of polycations and polyanions is enhanced. This work proposes a simple method to endow bio-PEMs with antifouling characteristics and tune their wettability.

Polymer brushes of poly[2-(methacryloyloxy)ethyl]trimethylammonium chloride (PMETAC) and poly(sulfo propyl methacrylate) (PSPM) were synthesized by Atomic Transfer Radical Polymerization from planar and colloidal surfaces. Polymer brush growth was followed by QCMD and the water content determined by combined QCMD and elipsometry. From the water content the percentage of water lost during the brush collapse with the ionic strength could be obtained.Highly charged PSPM brushes were indented by Atomic Force Microscopy at different ionic strengths. The force response was fitted to a phenomenological equation analogous to the equation of state of a compressible fluid. Internal energy and brush compressibility were obtained as a function of ionic strength.Spherical brushes of PMETAC and PSPM display an invariance of the zeta potential with ionic strength in the range from 20 mM to 200 mM NaCl, the zeta potential remains almost constant. This invariance can be explained applying a hairy surface approach.

The design of redox-robust polymers is called for in view of interactions with nanoparticles and surfaces toward applications in nanonetwork design, sensing, and catalysis. Redox-robust triazolylbiferrocenyl (trzBiFc) polymers have been synthesized with the organometallic group in the side chain by ring-opening metathesis polymerization using Grubbs-III catalyst or radical polymerization and with the organometallic group in the main chain by Cu(I) azide alkyne cycloaddition (CuAAC) catalyzed by [Cu(I)(hexabenzyltren)]Br. Oxidation of the trzBiFc polymers with ferricenium hexafluorophosphate yields the stable 35-electron class-II mixed-valent biferrocenium polymer. Oxidation of these polymers with Au(III) or Ag(I) gives nanosnake-shaped networks (observed by transmission electron microscopy and atomic force microscopy) of this mixed-valent Fe(II)Fe(III) polymer with encapsulated metal nanoparticles (NPs) when the organoiron group is located on the side chain. The factors that are suggested to be synergistically responsible for the NP stabilization and network formation are the polymer bulk, the trz coordination, the nearby cationic charge of trzBiFc, and the inter-BiFc distance. For instance, reduction of such an oxidized trzBiFc-AuNP polymer to the neutral trzBiFc-AuNP polymer with NaBH4 destroys the network, and the product flocculates. The polymers easily provide modified electrodes that sense, via the oxidized Fe(II)Fe(III) and Fe(III)Fe(III) polymer states, respectively, ATP(2-) via the outer ferrocenyl units of the polymer and Pd(II) via the inner Fc units; this recognition works well in dichloromethane, but also to a lesser extent in water with NaCl as the electrolyte.

The ability to engineer surfaces at the supramolecular level by controlled integration of specific chemical units through substrate‐independent methodologies represents one of the new paradigms of contemporary materials science. Here, a method is reported to form multifunctional supramolecular coatings through simple dip‐coating of substrates in an aqueous solution of polyamine in the presence of phosphate anions. The chemical richness and versatility of polyamines are exploited as phosphate receptors to form thin functional films on a broad variety of substrates, ranging from metal to carbonaceous surfaces. It is shown that the simple derivatization of pendant amino groups of polyallylamine precursors with different chemical groups can endow films with predefined responsiveness or multiple functions—this translates into one‐pot and one‐step preparation of substrate‐adherent films displaying built‐in functions. It is believed that the flexibility, speed, and versatility with which this method provides such robust functional films make it very attractive for preparing samples of fundamental and technological interest.

Cerium Oxide nanoparticles (CeO(2-x) NPs) are modified with polymer brushes of negatively charged poly (3-sulfopropylmethacrylate) (PSPM) and positively charged poly (2-(methacryloyloxy)ethyl-trimethylammonium chloride) (PMETAC) by Atom Transfer Radical Polymerisation (ATRP). CeO(2-x) NPs are fluorescently labelled by covalently attaching Alexa Fluor® 488/Fluorescein isothiocyanate to the NP surface prior to polymerisation. Cell uptake, intracellular distribution and the impact on the generation of intracellular Reactive Oxygen Species (ROS) with respect to CeO(2-x) NPs are studied by means of Raman Confocal Microscopy (CRM), Transmission Electron Microscopy (TEM) and Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). PSPM and PMETAC coated CeO(2-x) NPs show slower and less uptake compared to uncoated Brush modified NPs display a higher degree of co-localisation with cell endosomes and lysosomes after 24 h of incubation. They also show higher co-localisation with lipid bodies when compared to unmodified CeO(2-x) NPs. The brush coating does not prevent CeO(2-x) NPs from displaying antioxidant properties.

We report the first pentamethylferrocene (PMF) polymers and the redox chemistry of their robust polycationic pentamethylferricenium (PMFium) analogues. The PMF polymers were synthesized by ring-opening metathesis polymerization (ROMP) of a PMF-containing norbornene derivative by using the third-generation Grubbs ruthenium metathesis catalyst. Cyclic voltammetry studies allowed us to determine confidently the number of monomer units in the polymers through the Bard-Anson method. Stoichiometric oxidation by using ferricenium hexafluorophosphate quantitatively and instantaneously provided fully stable (even in aerobic solutions) blue d(5) Fe(III) metallopolymers. Alternatively, oxidation of the PMF-containing polymers was conducted by reactions with Ag(I) or Au(III) , to give PMFium polymer-embedded Ag and Au nanoparticles (NPs). In the presence of I2 , oxidation by using Ag(I) gave polymer-embedded Ag/AgI NPs and AgNPs at the surface of AgI NPs. Oxidation by using Au(III) also produced an Au(I) intermediate that was trapped and characterized. Engineered single-electron transfer reactions of these redox-robust nanomaterial precursors appear to be a new way to control their formation, size, and environment in a supramolecular way.

A novel and facile method was developed to produce hybrid graphene oxide (GO)–polyelectrolyte (PE) capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH) and polystyrenesulfonate sodium salt (PSS). Capsules where characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS) and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies.

Regenerable polyelectrolyte multilayers (PEMs) are prepared on the basis of a sacrificial block of polyelectrolyte on the top of a non‐removable PEM. Poly(allylamine hydrochloride) (PAH) and polyestyrene sulfonate (PSS) PEMs with a block of poly(diallylmethylammonium chlor­ide) (PDADMAC)/PSS on top; PAH/PSS with PDADMAC/poly(acrylic acid) (PAA) on top; and poly­ethylenimine (PEI)/PSS with PEI/PAA on top are fabricated. The top PDADMAC/PSS and PEI/PAA blocks are removed by interaction with (1‐tetradecyl) trimethylammonium bromide and sodium dodecylsulfate surfactants, respectively, whereas PDADMAC/PAA is removed by exposure them to basic pH. The supporting PEMs are not removed. The PEMs are coated with bovine serum albumin (BSA) as a model foulant. The top block is removed together with the BSA. After removal of the top block, the film is regenerated by assembling polyelectrolyte layers with the same composition as the original top block. Removal and regeneration are followed by quartz crystal microbalance measurements with dissipation, atomic force microscopy, fluorescence spectroscopy, and X‐ray photon electron spectroscopy. image

Hybrid polyelectrolyte multilayer systems were fabricated on top of planar surfaces and colloidal particles via layer by layer (LbL) assembly of polystyrene sulphonate (PSS) and polybenzyl methacrylate-block-poly(dimethylamino)ethyl methacrylate (PBzMA-b-PDMAEMA) polymersomes. Polymersomes were prepared by self assembly of PBzMA-b-PDMAEMA copolymer, synthesised by group transfer polymerisation. Polymersomes display a diameter of 270 nm and a shell thickness of 11nm. Assembly on planar surfaces was followed by means of the Quartz Crystal Microbalance with Dissipation (QCM-D) and Atomic Force Microscopy (AFM). Detailed information on the assembly mechanism and surface topology of the polymersome/polyelectrolyte films was thereby obtained. The assembly of polymersomes and PSS on top of silica particles of 500 nm in diameter was confirmed by ζ-potential measurements. Confocal laser scanning microscopy (CLSM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that polymersome/PSS coated silica particles increase in total diameter up to 3-5μm. This hints toward the formation of densely packed polymersome layers. In addition, CLSM showed that polymersome/PSS films exhibit a high loading capacity that could potentially be used for encapsulation and delivery of diverse chemical species. These results provide an insight into the formation of multilayered films with compartmentalised hydrophilic/hydrophobic domains and may lead to the successful application of polymersomes in surface-engineered colloidal systems.

ABSTRACT The combination of Quartz Crystal Microbalance and ellipsometry to quantify polyelectrolyte brush hydration and how this impacts on the study of brush collapse is discussed here. Recent articles study collapse after quantifying hydration of poly (2‐methacryloyloxy ethyl trimethyl ammonium chloride) (PMETAC) and poly(potassium sulfo propyl methacrylate). Water lost increases with ionic strength but only a 50% of their water content is lost at 1 M NaCl. For PMETAC brushes the exchange of Cl − by ClO 4 − is more effective, causing 50% lost at 0.05 M. The hydration and water lost for PMETAC brushes synthesized from thiol monolayers with variable density of initiators from 1 to 100% show that the freely entrapped water of the brushes is around a 10%. Irrespectively of initiator percentage the brush does not lose at 1 M NaCl more than 50% of the original water content. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1068–1072