The preparation of poly(isobutylene) (PIB) nanoparticles via cationic emulsion polymerization is presented. As a requirement, an oil-in-perfluoroalkane nonaqueous emulsion is developed, which is inert under the carbocationic polymerization conditions. To stabilize the dichloromethane/hexane droplets in the fluorinated, continuous phase, an amphiphilic block copolymer emulsifier is prepared containing PIB and 1H,1H-perfluoroalkylated poly(pentafluorostyrene) blocks. This system allows for the polymerization of isobutylene with number-average molecular weights (M¯n) up to 27 000 g mol(-1) . The particle morphologies are characterized via dynamic light scattering and electron microscopy. For M¯n > 20 000 g mol(-1) , the particles exhibit shape-persistence at room temperature and are ?100 nm in diameter.
Fluorinated surfactants with short perfluoroalkyl chains (R(F)) as potential substitutes for the environmentally questionable, long R(F) systems are presented. Three types of nonionic hydrophilic-fluorophilic amphiphiles are synthesized and evaluated based on surface activity in equilibrated (static) and non-equilibrated (dynamic) states. Furthermore, several mono- and disaccharide-based fluorosurfactants are also examined as potential non-bioaccumulative alternatives. A correlation between the chemical structure and resulting surface properties is made by comparing R(F) length, number and size, alkyl-spacer, and hydrophilic moieties. Based on dynamic and static surface tension experiments, the effects of surfactant structure are summarized to provide a basis for the future design of fluorosurfactants. We have found that surfactants with more perfluorinated chains tend to have a higher surface tension reduction, but typically result in slower dynamic behaviors. Using the presented structural characteristics, surfactants with R(F)<4 can be prepared with static surface tensions as low as 18.1 mN/m or reduce surface tension within milliseconds.
Proton-conducting networks (NETs) were prepared successfully by the insertion of phosphonated nanochannels into organic-inorganic hybrid materials that contain Al(3+) as the connector and hexakis(p-phosphonatophenyl)benzene (HPB) as the linker. Noncomplexed phosphonic acid groups remain in the framework, which depends on the ratio of both compounds, to yield a proton conductivity in the region of 10(-3) S cm(-1). This conductivity can be further improved and values as high as Nafion, a benchmark proton-exchange membrane for fuel cell applications, can be obtained by filling the network pores with intrinsic proton conductors. As a result of their sponge-like morphology, aluminum phosphonates adsorb conductive small molecules such as phosphonic acids, which results in a very high proton conductivity of approximately 5 × 10(-2) S cm(-1) at 120 °C and 50 % relative humidity (RH). Contrary to Nafion, the doped networks show a remarkably low temperature dependence of proton conductivity from external humidification. This effect indicates a transport mechanism that is different to the water vehicle mechanism. Furthermore, the materials exhibit an activation energy of 40 kJ mol(-1) at 15 % RH that starts to diminish to 10 kJ mol(-1) at 80 % RH, which is even smaller than the corresponding values obtained for Nafion 117.
In the ideal case, a precise synthesis yields molecules with a constitutional as well as a conformational perfectness. Such a case of precision is demonstrated by the synthesis of semi-rigid amphiphilic polyphenylene dendrimers (PPDs). Polar sulfonate groups are precisely placed on their periphery in such a manner that patches of polar and non-polar regions are created. Key structural features are the semi-rigid framework and shape-persistent nature of PPDs since the limited flexibility introduces a nano-phase-separated amphiphilic rim of the dendrimer. This results in both attractive and repulsive interactions with a given solvent. Frustrated solvent structures then lead to a remarkable solubility in solvents of different polarity such as toluene, methanol, and water or their mixtures. Water solubility combined with defined surface structuring and variable hydrophobicity of PPDs that resemble the delicate surface textures of proteins are important prerequisites for their biological and medical applications based upon cellular internalization.
Free-standing nanomembranes with molecular or atomic thickness are currently explored for separation technologies, electronics, and sensing. Their engineering with well-defined structural and functional properties is a challenge for materials research. Here we present a broadly applicable scheme to create mechanically stable carbon nanomembranes (CNMs) with a thickness of ~0.5 to ~3 nm. Monolayers of polyaromatic molecules (oligophenyls, hexaphenylbenzene, and polycyclic aromatic hydrocarbons) were assembled and exposed to electrons that cross-link them into CNMs; subsequent pyrolysis converts the CNMs into graphene sheets. In this transformation the thickness, porosity, and surface functionality of the nanomembranes are determined by the monolayers, and structural and functional features are passed on from the molecules through their monolayers to the CNMs and finally on to the graphene. Our procedure is scalable to large areas and allows the engineering of ultrathin nanomembranes by controlling the composition and structure of precursor molecules and their monolayers.
Polypeptides are successfully incorporated into poly(l-lactide) (PLLA) chains in a ring-opening polymerization (ROP) of l-lactide by using them as initiators. The resulting ABA triblock copolymers possess molecular weights up to 11000 g·mol(-1) and polydispersities as low as 1.13, indicating the living character of the polymerization process. In a nonaqueous emulsion, peptide-initiated polymerization of l-lactide leads to well-defined nanoparticles, consisting of PLLA-block-peptide-block-PLLA copolymer. These nanoparticles are easily loaded by dye-encapsulation and transferred into aqueous media without aggregation (average diameter of 100 nm) or significant dye leakage. Finally, internalization of PLLA-block-peptide-block-PLLA nanoparticles by HeLa cells is demonstrated by a combination of coherent anti-Stokes Raman spectroscopy (CARS) and fluorescence microscopy. This demonstrates the promise of their utilization as cargo delivery vehicles.
Polymeric and composite microspheres can be synthesized without solvents or process liquids by using superamphiphobic surfaces. In this method, the repellency of superamphiphobic layers to monomers and polymer melts and the extremely low adhesion to particles are taken advantage of.
To study charge-dependent interactions of nanoparticles (NPs) with biological media and NP uptake by cells, colloidal gold nanoparticles were modified with amphiphilic polymers to obtain NPs with identical physical properties except for the sign of the charge (negative/positive). This strategy enabled us to solely assess the influence of charge on the interactions of the NPs with proteins and cells, without interference by other effects such as different size and colloidal stability. Our study shows that the number of adsorbed human serum albumin molecules per NP was not influenced by their surface charge. Positively charged NPs were incorporated by cells to a larger extent than negatively charged ones, both in serum-free and serum-containing media. Consequently, with and without protein corona (i.e., in serum-free medium) present, NP internalization depends on the sign of charge. The uptake rate of NPs by cells was higher for positively than for negatively charged NPs. Furthermore, cytotoxicity assays revealed a higher cytotoxicity for positively charged NPs, associated with their enhanced uptake.
Titanium that is covered with a native oxide layer is widely used as an implant material; however, it is only passively incorporated in the human bone. To increase the implant-bone interaction, one can graft multifunctional phosphonic compounds onto the implant material. Phosphonate groups show excellent adhesion properties onto metal oxide surfaces such as titanium dioxide, and therefore, they can be used as anchor groups. Here, we present an alternative coating material composed of phosphonate surface-functionalized polystyrene nanoparticles synthesized via free radical copolymerization in a direct (oil-in-water) miniemulsion process. Two types of functional monomers, namely, vinylphosphonic acid (VPA) and vinylbenzyl phosphonic acid (VBPA), were employed in the copolymerization reaction. Using VBPA as a comonomer leads to particles with a higher density of surface phosphonate groups in comparison to those obtained with VPA. VBPA-functionalized particles were used for the coating formation on the titanium surface. The particles monolayer was investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM) employing titanium and silicium tip with the native OH groups. Force versus distance curves proves the strong adhesion between the phosphonated particles and the titanium (or silicium) surfaces in contrast to the nonfunctionalized polystyrene particles. Finally, as a proof of concept, the particles adhered to the surface were further used to nucleate hydroxyapatite, which has high potential for bioimplants.
The preparation of nanosized, molecularly imprinted polymer particles by nonaqueous emulsion polymerization is presented. Monodisperse cross-linked polymer nanospheres with a diameter of around 100?nm were synthesized using a standard monomer mixture of methacrylic acid and ethylene dimethacrylate, containing (±)-propranolol as a template. The rebinding efficiency of the resulting particles was determined by batch rebinding tests and isothermal titration calorimetry (ITC). The results indicate that the proposed imprinting process under nonaqueous conditions lead to particles with an enhanced capacity of template rebinding compared to both nonimprinted ones and to particles obtained by more conventional emulsion polymerization in water.
We studied the fluorescence enhancement of a dye-loaded polyphenylene dendrimer in a gap of 2-3 nm between a silver film and single silver particles with an average diameter of 80 nm. This sphere-on-plane geometry provides a controllable plasmonic resonator with a defined dye position. A strong fluorescence signal was seen from all particles, which was at least 1000 times stronger than the signal from the plane dye-coated metal surface. The fluorescence emission profile varied between the particles and showed light emission at higher energies than the free dye, which we assigned to hot luminescence. The maximum fluorescence emission peak shifted along with the scattering maximum of the plasmonic resonance. Two classes of scattering resonators could be distinguished. Up to a significant line-broadening, the response of the "sphere-on-plane"-like cases resembled the theoretical prediction for a perfect sphere-on-plane geometry. Resonators which deviate strongly from this ideal scenario were also found. Electron microscopy did not show significant differences between these two classes, suggesting that the variations in the optical response are due to nanoscale variations of shape and roughness in the gap region. The strong modifications of the dye emission spectrum suggested the presence of physical mechanisms at very small metal/dye separations, which are beyond a simple wavelength-dependent enhancement factor.
Two novel phosphonic acid-based "dry" proton exchange membrane materials that may allow for fuel cell operation above 100 degrees C have been prepared and characterized via solid-state 1H and 2H MAS NMR spectroscopy. We obtained information on both the nature of hydrogen bonding and local proton mobilities among phosphonic acid moieties. In particular, 2H MAS NMR line shape analysis yielded apparent activation energies of the underlying motional processes. Using this approach, we have investigated both a model compound and a novel PEM system. It was found that the relation of estimated hydrogen-bond strength and local proton mobility accessible by solid-state NMR and bulk proton conductivity is complex. Improvements through admixture of a second component with protogenic groups are suggested.
Let the protons flow: The synthesis of a core-shell macromolecule bearing phosphonic acids is presented. The rigid central core serves as a scaffold to stabilize the flexible polymer shells. Pronounced proton conductivity is obtained under humidified conditions. The self-assembly of such dendritic macromolecules by electrostatic interactions on a modified gold substrate is investigated and characterized.
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