Size-Controlled Formation of Polymer Janus Discs.

A straightforward method is presented for the preparation of nano- to micrometer-sized Janus discs with controlled shape, size, and aspect ratio. The method relies on cross-linkable ABC triblock terpolymers and involves first the preparation of prolate ellipsoidal microparticles by combining Shirasu porous glass (SPG) membrane emulsification with evaporation-induced confinement assembly (EICA). By varying the pore diameter of the SPG membrane, we produce Janus discs with controlled size distributions centered around hundreds of nanometers to several microns. We further transferred the discs to water by mild sulfonation of PS to polystyrene sulfonic acid (PSS) and verified the Janus character by subsequent labelling with cationic nanoparticles. Finally, we show that the sulfonated Janus discs are amphiphilic and can be used as efficient colloidal stabilizers for oil-in-water (O/W) emulsions.

Towards field-effect controlled graphene-enhanced Raman spectroscopy of cobalt octaethylporphyrin molecules.

During the last decade graphene-enhanced Raman spectroscopy has proven to be a powerful tool to detect and analyze minute amounts of molecules adsorbed on graphene. By using a graphene-based field-effect device the unique opportunity arises to gain a deeper insight into the coupling of molecules and graphene as graphene's Fermi level can be controlled by the transistor`s gate voltage. However, the fabrication of such a device comes with great challenges because of contaminations stemming from processing the device inevitably prevent direct adsorption of the molecules onto graphene rendering it unsuitable for field-effect controlled graphene-enhanced Raman spectroscopy measurements/experiments. In this work, we solve this problem by establishing two different fabrication procedures for such devices, both of which are in addition compatible with large area and scalable production requirements. As a first solution, selective argon cluster irradiation is shown to be an efficient way to remove resist residues after processing. We provide evidence that after the irradiation the enhancement of the molecular Raman signal can indeed be measured, demonstrating that this procedure cleans graphene's surface sufficiently enough for direct molecular adsorption. As a second solution, we have developed a novel stacking method to encapsulate the molecules in between two graphene layers to protect the underlying graphene and molecular layer from the harsh conditions during the photolithography process. This method combines the advantages of dry stacking, which leads to a perfectly clean interface, and wet stacking processes, which can easily be scaled up for large area processing. Both approaches yield working graphene transistors with strong molecular Raman signals stemming from cobalt octaehtylporphyrin, a promising and prototypical candidate for spintronic applications, and are therefore suitable for graphene based molecular sensing applications.

Terpolymer Multicompartment Nanofibers as Templates for Hybrid Pt Double Helices.

Hybrid inorganic/block copolymer (BCP) materials have become increasingly relevant for application in heterogeneous catalysis, microelectronics, and nanomedicine. While block copolymer templates are widely used for the formation of inorganic nanostructures, multicompartment templates could give access to more complex shapes and inner structures that are challenging to obtain with traditional processes. Here, we report the formation and characterization of hybrid platinum/polymer helices using multicompartment nanofibers (MCNFs) of polystyrene-block-polybutadiene-block-poly(tert-butyl methacrylate) (PS-b-PB-b-PT) triblock terpolymers as templates. Cross-linking of a PS-b-PB-b-PT helix-on-cylinder morphology resulted in uniform nanofibers with a diameter of 90 nm and a length of several micrometers, as well as an inner PB double helix (diameter 35 nm, pitch 25 nm, core 12 nm). The PB double helix served as template for the sol-gel reaction of H2PtCl6 into hybrid Pt double helices (Pt@MCNFs) as verified by STEM, electron tomography, AFM, and SEM. Carbonization of the Pt hybrids into Pt decorated carbon nanofibers (Pt@C) was followed in situ on a TEM heating state. Gradual heating from 25 to 1000 °C induced fusion of amorphous Pt NPs into larger crystalline Pt NP, which sheds light on the aging of Pt NPs in BCP scaffolds under high temperature conditions. The Pt@MCNFs were further sulfonated and incorporated into a filter to catalyze a model compound in a continuous flow process.

Laser-Induced Functionalization of Organo/Carbon Interfaces for Selective Adsorption of Au Nanoparticles in Microsized Domains.

Laser microprocessing of highly oriented pyrolytic graphite (HOPG) in conjunction with chemical functionalization routines is used to fabricate functional microsized domains. Infrared and Auger electron spectroscopy, contact angle measurements, and electron microscopy are used for characterization of laser-fabricated structures. HOPG samples are coated with alkylsiloxane monolayers. Laser-induced bromination of coated HOPG samples in gaseous bromine is carried out using a microfocused laser beam at a wavelength of 514 nm and 1/e2 laser spot diameter of about 2 µm. Subsequent azidation and amination results in functional domains with sizes in the range of 1.2 to 40 µm and more. At low laser powers and irradiation times fully functionalized circular-shaped structures are formed. At high laser powers and irradiation times laser processing results in decomposition of the organic monolayer and substrate in the center of the structures yielding donut-shaped structures. After laser processing and chemical transformation Au nanoparticles are selectively adsorbed onto the functional domains. This provides an opportunity to build up functional nanoparticle microarrays on carbon-based materials, e.g., for applications in sensing and electrocatalysis.

Improved Antifouling Properties of Polydimethylsiloxane Films via Formation of Polysiloxane/Polyzwitterion Interpenetrating Networks.

Nonspecific adsorption of proteins is a challenging problem for the development of biocompatible materials, as well as for antifouling and fouling-release coatings, for instance for the marine industry. The concept of preparing amphiphilic systems based on low surface energy hydrophobic materials via their hydrophilic modification is being widely pursued. This work describes a novel two-step route for the preparation of interpenetrating polymer networks of otherwise incompatible poly(dimethylsiloxane) and zwitterionic polymers. Changes in surface hydrophilicity as well as surface charge at different pH values are investigated. Characterization using atomic force microscopy provides thorough insight into surface changes upon hydrophilic modification. Protein fouling of the materials is assessed using fibrinogen as a model protein.

Poly(N,N-dimethylaminoethyl methacrylate) Brushes: pH-Dependent Switching Kinetics of a Surface-Grafted Thermoresponsive Polyelectrolyte.

The temperature-dependent switching behavior of poly(N,N-dimethylaminoethyl methacrylate) brushes in alkaline, neutral, and acidic solutions is examined. A novel microscopic laser temperature-jump technique is employed in order to study characteristic thermodynamic and kinetic parameters. Static laser micromanipulation experiments allow one to determine the temperature-dependent variation of the swelling ratio. The data reveal a strong shift of the volume phase transition of the polymer brushes to higher temperatures when going from pH = 10 to pH = 4. Dynamic laser micromanipulation experiments offer a temporal resolution on a submillisecond time scale and provide a means to determine the intrinsic rate constants. Both the swelling and the deswelling rates strongly decrease in acidic solutions. Complementary experiments using in situ atomic force microscopy show an increased polymer layer thickness at these conditions. The data are discussed on the basis of pH-dependent structural changes of the polymer brushes including protonation of the amine groups and conformational rearrangements. Generally, repulsive electrostatic interactions and steric effects are assumed to hamper and slow down temperature-induced switching in acidic solutions. This imposes significant restrictions for smart polymer surfaces, sensors, and devices requiring fast response times.

Photothermal laser fabrication of micro- and nanostructured chemical templates for directed protein immobilization.

Photothermal patterning of poly(ethylene glycol) terminated organic monolayers on surface-oxidized silicon substrates is carried out using a microfocused beam of a CW laser operated at a wavelength of 532 nm. Trichlorosilane and trimethoxysilane precursors are used for coating. Monolayers from trimethoxysilane precursors show negligible unspecific protein adsorption in the background, i.e., provide platforms of superior protein repellency. Laser patterning results in decomposition of the monolayers and yields chemical templates for directed immobilization of proteins at predefined positions. Characterization is carried out via complementary analytical methods including fluorescence microscopy, atomic force microscopy, and scanning electron microscopy. Appropriate labeling techniques (fluorescent markers and gold clusters) and substrates (native and thermally oxidized silicon substrates) are chosen in order to facilitate identification of protein adsorption and ensure high sensitivity and selectivity. Variation of the laser parameters at a 1/e(2) spot diameter of 2.8 µm allows for fabrication of protein binding domains with diameters on the micrometer and nanometer length scale. Minimum domain sizes are about 300 nm. In addition to unspecific protein adsorption on as-patterned monolayers, biotin-streptavidin coupling chemistry is exploited for specific protein binding. This approach represents a novel facile laser-based means for fabrication of protein micro- and nanopatterns. The routine is readily applicable to femtosecond laser processing of glass substrates for the fabrication of transparent templates.

Photothermal laser microsintering of nanoporous gold.

Photothermal processing of nanoporous gold using a microfocused continuous-wave laser at a wavelength of 532 nm and a 1/e(2) spot diameter of 2.9 µm has been studied. In addition, complementary experiments have been carried out via conventional annealing. Scanning electron microscopy has been used for characterization. Local laser irradiation at distinct laser powers and pulse lengths results in coarsening of the porous gold structures. During laser processing the pore size of the native nanoporous gold increases to maximum values in the range of 0.25-3 µm. The affected areas exhibit lateral dimensions in the range of 2-10 µm. Overall two regions are distinguished. An inner region, where large pores and ligaments are formed and an outer region, where the pore size and ligament size gradually change and approach the feature sizes of the native material. A qualitative thermokinetic model allows one to reproduce the experimentally observed dependence of the laser-induced morphologies on the laser parameters. On the basis of this model the underlying processes are attributed to sintering and melting of the gold structures. The presented results demonstrate the prospects of photothermal laser processing in engineering porous gold with spatially varying porosities on micrometer to nanometer length scales.

Dose-dependent surface endothelialization and biocompatibility of polyurethane noble metal nanocomposites.

Surface pre-endothelialization is a promising approach to improve the hemocompatibility of implants, medical devices, and artificial organs. To promote the adhesive property of thermoplastic polyurethane (TPU) for endothelial cells (ECs), up to 1 wt % of gold (Au) or platinum (Pt) nanoparticles, fabricated by pulsed laser ablation in polymer solution, were embedded into the polymer matrix. The analysis of these nanocomposites showed a homogenous dispersion of the nanoparticles, with average diameters of 7 nm for Au or 9 nm for Pt. A dose-dependent effect was found when ECs were seeded onto nanocomposites comprising different nanoparticle concentrations, resulting in a fivefold improvement of proliferation at 0.1 wt % nanoparticle load. This effect was associated with a nanoparticle concentration-dependent hydrophilicity and negative charge of the nanocomposite. In dynamic flow tests, nanocomposites containing 0.1 wt % Au or Pt nanoparticles allowed for the generation of a confluent and resistant EC layer. Real-time polymerase chain reaction quantification of specific markers for EC activation indicated that ECs cultivated on nanocomposites remain in an inactivated, nonthrombogenic and noninflammatory state; however, maintain the ability to trigger an inflammatory response upon stimulation. These findings were confirmed by a platelet and leukocyte adhesion assay. The results of this study suggest the possible applicability of TPU nanocomposites, containing 0.1 wt % Au or Pt nanoparticles, for the generation of pre-endothelialized surfaces of medical devices.

Hofmeister effect of sodium halides on the switching energetics of thermoresponsive polymer brushes.

A laser temperature-jump technique is used to probe the impact of sodium halides on the temperature-dependent switching kinetics and thermodynamics of poly(N-isopropylacrylamide) brushes. An analysis on the basis of a two-state model reveals van't Hoff enthalpy and entropy changes. Sodium halides increase the endothermicity and the entropic gain of the switching process below and above Tc following the Hofmeister series: NaCl > NaBr > NaI. In contrast, enthalpic and entropic changes at Tc remain virtually unaffected. This provides an unprecedented insight into the underlying switching energetics of this classic stimuli-responsive polymer. Because of its model character, these results represent an essential reference on the way to unpuzzle the molecular driving forces of the Hofmeister effect.

Photothermal micro- and nanopatterning of organic/silicon interfaces.

Photothermal laser processing of organic monolayers on oxide-free silicon substrates under ambient conditions is investigated. Organic monolayers on Si(100) and Si(111) substrates are prepared via hydrosilylation of H-terminated silicon samples in neat 1-hexadecene and 1-hexadecyne, respectively. Laser processing at lambda = 514 nm and a 1/e(2) spot diameter of 2.6 microm results in local decomposition of the monolayers and oxidation of the exposed substrate. In agreement with the high thermal and chemical stability of these monolayers, a thermokinetic analysis of the data from experiments at distinct laser powers and pulse lengths points to a highly activated process. As a result, processing is strongly nonlinear and allows for subwavelength patterning, with line widths between 0.4 and 1.4 microm. Most remarkably, upon fabrication of dense line patterns, narrow organic monolayer stripes with sharp edges and lateral dimensions of 80 nm are formed. This opens up new perspectives in photothermal engineering of organic/silicon interfaces, e.g., for hybrid microelectronic and sensor applications.

Surface-initiated polymerization on laser-patterned templates: morphological scaling of nanoconfined polymer brushes.

Nonlinear laser processing of silane-based monolayers is used to fabricate nanostructured chemical templates for the selective growth of polymer brushes in confined domains via surface-initiated polymerization (SIP). Upon varying the laser parameters, reactive domains with lateral dimensions from several micrometers down to the sub-100-nm range are fabricated. This provides a versatile means for studying the morphological scaling behavior of confined polymer brushes. Here, the surface-initiated growth of a stimuli-responsive polymer, poly(N-isopropylacrylamide) (PNiPAAm), via atom transfer radical polymerization (ATRP) is investigated. Polymer chains at the domain boundaries extend into the surrounding polymer-free areas. For this reason the width of confined polymer brushes is significantly larger than that of the underlying domains. Within experimental error, though, the excess width does not depend on the domain size. In contrast, the brush height decreases more and more when the domain size falls below a certain value. Simple considerations point to a geometrical scaling relation between height and width of the polymer brushes. These results are considered as essential for implementation of SIP routines in laser-assisted fabrication schemes targeting micro- and nanofluidic applications.

Direct laser patterning of soft matter: photothermal processing of supported phospholipid multilayers with nanoscale precision.

Direct laser patterning of supported phospholipid multilayers is investigated. Spin coating is used to fabricate stacked bilayers of 1,2-dioleoyl-sn-glycero-3-phosphate (DOPA). Photothermal processing with a focused laser beam at lambda = 514 nm allows removal of the coating at predefined positions without causing any significant change in adjacent areas. Moreover, processing with nanoscale precision is feasible despite the soft and fluid nature of phospholipid films. In particular, holes with diameters from 1.8 microm down to 300 nm and below are fabricated by using a 1/e(2) laser spot size of about 2.5 microm. In addition, patterning is also very flexible and can be carried out over macroscopic length scales and at short processing times. Considering these features photothermal laser processing constitutes a powerful tool for micro- and nanopatterning of phospholipid films.

1D nanofabrication with a micrometer-sized laser spot.

A simple laser-assisted procedure for the fabrication of functional organic nanostructures is demonstrated. Native silicon samples are coated with alkylsiloxane monolayers and patterned with a focused beam of an Ar(+) laser (lambda = 514 nm). After patterning, the coating is chemically functionalized following a robust preparation scheme. Despite a laser spot diameter of about 2.5 mum, this routine allows for the fabrication of well-confined organosiloxane stripes with widths below 100 nm. As shown, these structures provide a versatile means for building ordered surface architectures of nanoscopic components. In particular, gold nanoparticles (d = 16 nm) self-assemble into one-dimensional arrangements, such as single chains.

Size-selective protein adsorption to polystyrene surfaces by self-assembled grafted poly(ethylene glycols) with varied chain lengths.

We report about the surface modification of polystyrene (PSt) with photoreactive alpha-4-azidobenzoyl-omega-methoxy poly(ethylene glycol)s (ABMPEG) of three different molecular weights (MWs of approximately 2, approximately 5, and approximately 10 kg/mol) and with two poly(ethylene glycol)/poly(propylene glycol) triblock copolymers (PEG-PPG-PEG) of about identical PEG/PPG ratio (80/20, w/w) and MW(PEG) of approximately 3 and approximately 6 kg/mol, all via adsorption from aqueous solutions. For ABMPEGs, an additional UV irradiation was used for photografting to the PSt. Contact angle (CA) and atomic force microscopy data revealed pronounced differences of the hydrophilicity/hydrophobicity and topography of the surfaces as a function of PEG type and concentration used for the modification. In all cases, an incomplete coverage of the PSt was observed even after modification at the highest solution concentrations (10 g/L). However, clear differences were seen between PEG-PPG-PEGs and ABMPEGs; only for the latter was a nanoscale-ordered interphase structure with an influence of MW(PEG) on the PEG density observed; after modification at the same solution concentrations, the density was significantly higher for lower MW(PEG). The adsorption of three proteins, myoglobin (Mgb), bovine serum albumin (BSA), and fibrinogen to the various surfaces was analyzed by surface plasmon resonance. Pronounced differences between the two PEG types with respect to the reduction of protein adsorption were found. At high, but still incomplete, surface coverage and similar CA, the shielding of ABMPEG layers toward the adsorption of Mgb and BSA was much more efficient; e.g., the adsorbed Mgb mass relative to that of unmodified PSt was reduced to 10% for ABMPEG 2 kg/mol while for both PEG-PPG-PEGs the Mgb mass was still around 100%. In addition, for the ABMPEG layers an effect of MW(PEG) on adsorbed protein mass-decrease with decreasing MW-could be confirmed; and the highest Mgb/BSA selectivities were also observed. A "two-dimensional molecular sieving", based on PEG molecules having a nanoscale order at the hydrophobic substrate polymer surface has been proposed, and the main prerequisites were the use of PEG conjugates which are suitable for an "end-on" grafting (e.g., ABMPEGs), the use of suitable (not too high) concentrations for the surface modification via adsorption/self-assembly, optionally the photografting on the substrate (possible only for ABMPEG), and presumably, a washing step to remove the excess of unbound PEGs. The results of this study also strongly support the hypothesis that the biocompatibility of hydrophobic materials can be very much improved by PEG modifications at surface coverages that are incomplete but have an ordered layer structure controlled by the size and steric interactions of surface-bound PEGs.

Preparation of submicron-structured alkylsiloxane monolayers using prepatterned silicon substrates by laser direct writing.

A new constructive method for the preparation of laterally structured alkylsiloxane monolayers is demonstrated. Laser direct writing has been used to create oxide patterns on H-terminated Si(100) samples under ambient conditions. Depending on the laser power and the writing speed, oxide structures with a lateral resolution below 500 nm are prepared routinely. The patterned samples are suitable as temporary templates for the preparation of laterally structured octadecylsiloxane monolayers. Prior to immersion in an octadecyltrichlorosilane solution, however, hydration of the samples in water is essential to facilitate a selective coating of the oxidized areas. After coating, atomic force microscopy reveals the formation of octadecylsiloxane islands exclusively on top of the oxide lines.

Nanostructured silicon surfaces via nanoporous alumina.

Nanostructured silicon surfaces are generated using nanoporous alumina membranes as stamps to imprint PMMA films on silicon, followed by reactive ion etching (RIE).