Danijela Gregurec

Highly Efficient Transition Metal Nanoparticle Catalysts in Aqueous Solutions

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.

Precise localization of metal nanoparticles in dendrimer nanosnakes or inner periphery and consequences in catalysis.

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.

Stability of polyelectrolyte multilayers in oxidizing media: a critical issue for the development of multilayer based membranes for nanofiltration

Polyelectrolyte multilayers (PEMs) for nanofiltration and reverse osmosis are fabricated by means of the Layer by Layer technique from the negatively charged poly(sodium 4-styrenesulfonate) (PSS) and polycations with primary, secondary, tertiary, and quaternary amines. PEMs stability is studied after treatment with the oxidizing agent sodium hypochlorite (NaOCl), in the same conditions as in membrane modulus cleaning. PEM assembly and mass changes after treatment with NaOCl are studied with the Quartz Crystal Microbalance. The chemical composition of the PEMs after the treatment with NaOCl is studied by X-ray photoelectron spectroscopy. The oxidation of polycations in bulk is studied by UV–vis. The PEMs fabricated with poly(diallydimethylammonium chloride) (PDADMAC) and poly(vinylbenzyltrimethylammonium chloride) (PVBTMAC), bearing quaternary amines, show the highest chemical stability and smallest mass variations after oxidation. PEMs including other polycations bearing quaternary amines and polycations with primary, secondary, and tertiary amines are either fully removed or significantly changed chemically.

Redox-Robust Pentamethylferrocene Polymers and Supramolecular Polymers, and Controlled Self-Assembly of Pentamethylferricenium Polymer-Embedded Ag, AgI, and Au Nanoparticles.

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.

Enhancing orthopedic implant bioactivity: refining the nanotopography

Advances in nanotechnology open up new possibilities to produce biomimetic surfaces that resemble the cell in vivo growth environment at a nanoscale level. Nanotopographical changes of biomaterials surfaces can positively impact the bioactivity and ossointegration properties of orthopedic and dental implants. This review introduces nanofabrication techniques currently used or those with high potential for use as surface modification of biomedical implants. The interactions of nanotopography with water, proteins and cells are also discussed, as they largely determine the final success of the implants. Due to the well-documented effects of surface chemistry and microtopography on the bioactivity of the implant, we here elaborate on the ability of the nanofabrication techniques to combine the dual (multi) modification of surface chemistry and/or microtopography.

Bioinspired titanium coatings: self-assembly of collagen–alginate films for enhanced osseointegration

Achieving long term osseointegration is fundamental to the development of successful bone implants. A key aspect for improving long term osseointegration on titania surfaces is to gain control of nano- and microscale features. The so called biological approach is applied here to modify the surface of titania by coating it with a self-assembled and chemically crosslinked biopolymer film made of alginate and collagen. The biofilm coated titania closely mimics the bone extracellular matrix in bio-morphology and mechanical properties. Biofilms are prepared using the layer by layer technique combined with carbodiimide chemistry to achieve a stable and compact structure. Alginate-collagen coatings display fibrillar morphology with an apparent fiber diameter of ∼50 nm and lengths ranging from a few hundred nanometers to ∼3 μm, mimicking therefore the extracellular matrix of the bone in fiber length and extent. Osteoblast MC3T3-E1 cells showed enhanced adhesion on the coated surface compared to the bare titania and a superior biological activity of the alginate-terminated coating that interfaces the cells in biological fluids.

Liquid–Liquid Interfacial Electron Transfer from Ferrocene to Gold(III): An Ultrasimple and Ultrafast Gold Nanoparticle Synthesis in Water under Ambient Conditions

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-vinylmethylpyrrolidone) 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)nAuNPs.

Role of Hydrogen Bonding and Polyanion Composition in the Formation of Lipid Bilayers on Top of Polyelectrolyte Multilayers

The self-assembly of mixed vesicles of zwitterionic phosphatidylcholine (PC) and anionic phosphatidylserine (PS) phospholipids on top of polyelectrolyte multilayers (PEMs) of poly(allylamine hydrochloride) (PAH), as a polycation, and polystyrenesulfonate (PSS), as a polyanion, is investigated as a function of the vesicle composition by means of the quartz crystal microbalance with dissipation (QCM-D), cryo-transmission electron microscopy (Cryo-TEM), atomic force microscopy (AFM), and atomic force spectroscopy (AFS). Vesicles with molar percentages of PS between 50% and 70% result in the formation of lipid bilayers on top of the PEMs. Vesicles with over 50% of PC or over 80% of PS do not assembly into bilayers. AFS studies performed with a PAH-modified cantilever approaching and retracting from the lipid assemblies reveal that the main interaction between PAH and the lipids takes place through hydrogen bonding between the amine groups of PAH and the carboxylate and phosphate groups of PS and with the phosphate groups of PC. The interaction of PAH with PS is much stronger than with PC. AFS measurements on assemblies with 50% PC and 50% PS revealed similar adhesion forces to pure PS assemblies, but the PAH chains can reorganize much better on the lipids as a consequence of the presence of PC. QCM-D experiments show that vesicles with a lipid composition of 50% PC and 50% PS do not form bilayers if PSS is replaced by alginate (Alg) or poly(acrylic acid) (PAA).

High Resistivity Lipid Bilayers Assembled on Polyelectrolyte Multilayer Cushions: An Impedance Study

Supported membranes on top of polymer cushions are interesting models of biomembranes as cell membranes are supported on a polymer network of proteins and sugars. In this work lipid vesicles formed by a mixture of 30% 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 70% 1,2-dioleoyl-sn-glycero-3-phospho-l-serine (DOPS) are assembled on top of a polyelectrolyte multilayer (PEM) cushion of poly(allylamine hydrochloride) (PAH) and poly(styrene sodium sulfonate) (PSS). The assembly results in the formation of a bilayer on top of the PEM as proven by means of the quartz crystal microbalance with dissipation technique (QCM-D) and by cryo-transmission electron microscopy (cryo-TEM). The electrical properties of the bilayer are studied by electrochemical impedance spectroscopy (EIS). The bilayer supported on the PEMs shows a high resistance, on the order of 10(7) Ω cm(2), which is indicative of a continuous, dense bilayer. Such resistance is comparable with the resistance of black lipid membranes. This is the first time that such values are obtained for lipid bilayers supported on PEMs. The assembly of polyelectrolytes on top of a lipid bilayer decreases the resistance of the bilayer up to 2 orders of magnitude. The assembly of the polyelectrolytes on the lipids induces defects or pores in the bilayer which in turn prompts a decrease in the measured resistance.

Impact of thermal annealing on wettability and antifouling characteristics of alginate poly-l-lysine polyelectrolyte multilayer films

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.