Clicked into Place: Biomimetic Copolymer Adhesive for Covalent Conjugation of Functionalities.

Polydopamines (PDA) are a popular class of materials and promising candidates as adhesives for new fastening techniques. PDA layers can be formed on a wide range of substrates in various environments. Here, we present a novel method for functionalizing PDA-based copolymer films by using click chemistry. These copolymers adhere strongly to various surfaces and simultaneously have active groups that allow the attachment of functional groups. We discuss the coupling of two types of chitosan and a rhodamine B dye molecule to the alkyne groups of the copolymers by employing click reactions. Azidopropyl methacrylate (AzMA), methyl methacrylate (MMA), and dopamine methacrylamide (DOMA) are copolymerized and codeposited with (3-aminopropyl)triethoxysilane on silicon wafers, polyethylene (PE), and polytetrafluoroethylene (PTFE). AzMA provides the surfaces with azides for use in click reactions, MMA functions to control the polymer as a nonfunctional diluent, whereas DOMA provides adhesion, as well as cross-linking groups. After codeposition, the dyes are grafted to the copolymer to illustrate the ability of the films to link functional groups covalently. Fourier transform infrared spectroscopy confirms the successful click reaction in solution, and atomic force microscopy shows the surface morphologies following grafting. Fluorescence microscopy provides evidence of successful grafting. As an example of a possible application, layers exhibiting antifouling properties are prepared. Chitosan grafted to PE is tested for antifouling performance. These functionalized layers show nonspecific inhibition of protein adsorption. We find that chitosan can lower the adsorption of fluorescein-labeled bovine serum albumin (BSA) protein by more than 90% for the best performing fluorescein-labeled BSA protein and by more than 90% for the best-performing layer. These results demonstrate the viability of our PDA-based copolymers for surface functionalization through click chemistry grafting at challenging adhesion to surfaces.

Suppression of the Coffee Ring Effect in a Single Solvent-Based Silicon Nanoparticle Ink.

Silicon (Si) is made printable by dispersing Si nanoparticles in a single organic solvent. Viscoelastic properties of the prepared inks as well as the uniformity of inkjet-printed thin films are investigated in dependence on the Si volume fraction. It has been demonstrated that no ink additives are needed to completely suppress the occurrence of the coffee ring effect. This is obtained by increasing the ink's volume fraction to induce gelation in order to generate elasticity. The printability of our inks is investigated in terms of Weber, Reynolds, and Ohnesorge numbers and found to be maintained even at high particle loads due to shear-thinning viscosity behavior. When printed onto tungsten (W) substrates, Si inks with ϕ(Si) = 0.4% and ϕ(Si) = 2.1% leave a ring stain after drying, whereas coffee rings are absent for inks with ϕ(Si) = 3.0% and above. The reason for this is a significant ink elasticity achieved by the buildup of a gel network for higher particle loads, which leads to thixotropy-like properties. These are low viscosity for printability and elevated elasticity during ink drying, made possible by a breakup of the gel network during drop formation in conjunction with a rapid network reformation after deposition.

Engineering of Adhesion at Metal-Poly(lactic acid) Interfaces by Poly(dopamine): The Effect of the Annealing Temperature.

Control over adhesion at interfaces from strong bonding to release between thermoplastic polymers (TPs) and metal oxides is highly significant for polymer composites. In this work, we showcase a simple and inexpensive method to tune adhesion between a TP of growing interest, poly(lactic acid) (PLA), and two commercial metal alloys, based on titanium and stainless steel. This is realized by coating titanium and stainless steel wires with polydopamine (PDA), thermally treating them under vacuum at temperatures ranging from 25 to 250 °C, and then comolding them with PLA to form pullout specimens for adhesion tests. Pullout results indicate that PDA coatings treated at low temperatures up to a given threshold significantly improve adhesion between PLA and the metals. Conversely, at higher PDA annealing temperatures beyond the threshold, interfacial bonding gradually declines. The excellent control over interfacial adhesion is attributed to the thermally induced transformation of PDA. In this work, we show using thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared, and 13C solid-state NMR that the extent of the thermal transformation is dependent on the annealing temperature. By selecting the annealing temperature, we vary the concentration of primary amine and hydroxyl groups in PDA, which influences adhesion at the metal/PLA interface. We believe that these findings contribute to optimizing and broadening the applications of PDA in composite materials.

Dopamine-Based Copolymer Bottlebrushes for Functional Adhesives: Synthesis, Characterization, and Applications in Surface Engineering of Antifouling Polyethylene.

Nonpolar materials like polyolefins are notoriously challenging substrates for surface modification. However, this challenge is not observed in nature. Barnacle shells and mussels, for example, utilize catechol-based chemistry to fasten themselves onto all kinds of materials, such as boat hulls or plastic waste. Here, a design is proposed, synthesized, and demonstrated for a class of catechol-containing copolymers (terpolymers) for surface functionalization of polyolefins. Dopamine methacrylamide (DOMA), a catechol-containing monomer, is incorporated into a polymer chain together with methyl methacrylate (MMA) and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). DOMA serves as adhesion points, BIEM provides functional sites for subsequent "grafting from" reactions, and MMA provides the possibility for concentration and conformation adjustment. First, the adhesive capabilities of DOMA are demonstrated by varying its content in the copolymer. Then, terpolymers are spin-coated on model Si substrates. Subsequently, the atom transfer initiator (ATRP) initiating group is used to graft a poly(methyl methacrylate) (PMMA) layer from the copolymers, with 40% DOMA content providing a coherent PMMA film. To demonstrate functionalization on a polyolefin substrate, the copolymer is spin-coated on high-density polyethylene (HDPE) substrates. A POEGMA layer is grafted from the ATRP initiator sites on the terpolymer chain on the HDPE films to provide antifouling characteristics. Static contact angle values and Fourier transform infrared (FTIR) spectra confirm the presence of POEGMA on the HDPE substrate. Finally, the anticipated antifouling functionality of grafted POEGMA is demonstrated by observing the inhibition of nonspecific adsorption of the fluorescein-modified bovine serum albumin (BSA) protein. The poly(oligoethylene glycol methacrylate) POEGMA layers grafted on 30% DOMA-containing copolymers on HDPE show optimal antifouling performance exhibiting a 95% reduction of BSA fluorescence compared to nonfunctionalized and surface-fouled polyethylene. These results demonstrate the successful utilization of catechol-based materials for functionalizing polyolefin surfaces.

Adhesion Engineering in Polymer-Metal Comolded Joints with Biomimetic Polydopamine.

Joints that connect thermoplastic polymer matrices (TPMs) and metals, which are obtained by comolding, are of growing importance in numerous applications. The overall performance of these constructs is strongly impacted by the TPM-metal interfacial strength, which can be tuned by tailoring the surface chemistry of the metal prior to the comolding process. In the present work, a model TPM-metal system consisting of poly(methyl methacrylate) (PMMA) and titanium is used to prepare comolded joints. The interfacial adhesion is quantified by wire pullout experiments. Pullout tests prior to and following surface modification are performed and analyzed. Unmodified wires show poor interfacial strength, with a work of adhesion (Ga) value of 3.8 J m-2. To enhance interfacial adhesion, a biomimetic polydopamine (PDA) layer is first deposited on titanium followed by a second layer of a poly(methyl methacrylate-co-methacrylic acid) (P(MMA-co-MAA)) copolymer prior to comolding. During processing, the MAA moieties of the copolymer thermally react with PDA, forming amide bonds, while MMA promotes the formation of secondary bonds and molecular interdigitation with the PMMA matrix. Control testing reveals that neither PDA nor the copolymer provides a substantial increase in adhesion. However, when used in combination, a significant increase in adhesion is detected. This observation indicates a pronounced synergistic effect between the two layers that strengthens the PMMA-titanium bonding. Enhanced adhesion is optimized by tuning the MMA-to-MAA ratio of the copolymer, which shows a maximum at a 24% MAA content and a greatly increased Ga value of 155 J m-2; this value corresponds to a 40-fold increase. Further growth in the Ga values at higher MAA contents is hindered by the thermal cross-linking of MAA; MAA contents above 24% restrict the formation of secondary bonds and molecular interdigitation with the PMMA chains. Our results provide new design principles to produce thermoplastic-metal comolded joints with strong interfaces.

Designer Core-Shell Nanoparticles as Polymer Foam Cell Nucleating Agents: The Impact of Molecularly Engineered Interfaces.

The interface between nucleating agents and polymers plays a pivotal role in heterogeneous cell nucleation in polymer foaming. We describe how interfacial engineering of nucleating particles by polymer shells impacts cell nucleation efficiency in CO2 blown polymer foams. Core-shell nanoparticles (NPs) with a 80 nm silica core and various polymer shells including polystyrene (PS), poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and poly(acrylonitrile) (PAN) are prepared and used as heterogeneous nucleation agents to obtain CO2 blown PMMA and PS micro- and nanocellular foams. Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy are employed to confirm the successful synthesis of core-shell NPs. The cell size and cell density are determined by scanning electron microscopy. Silica NPs grafted with a thin PDMS shell layer exhibit the highest nucleation efficiency values, followed by PAN. The nucleation efficiency of PS- and PMMA-grafted NPs are comparable with the untreated particles and are significantly lower when compared to PDMS and PAN shells. Molecular dynamics simulations (MDS) are employed to better understand CO2 absorption and nucleation, in particular to study the impact of interfacial properties and CO2-philicity. The MDS results show that the incompatibility between particle shell layers and the polymer matrix results in immiscibility at the interface area, which leads to a local accumulation of CO2 at the interfaces. Elevated CO2 concentrations at the interfaces combined with the high interfacial tension (caused by the immiscibility) induce an energetically favorable cell nucleation process. These findings emphasize the importance of interfacial effects on cell nucleation and provide guidance for designing new, highly efficient nucleation agents in nanocellular polymer foaming.

Bubble Seeding Nanocavities: Multiple Polymer Foam Cell Nucleation by Polydimethylsiloxane-Grafted Designer Silica Nanoparticles.

We describe a successful strategy to substantially enhance cell nucleation efficiency in polymer foams by using designer nanoparticles as nucleating agents. Bare and poly(dimethylsilane) (PDMS)-grafted raspberry-like silica nanoparticles with diameters ranging from ∼80 nm to ∼200 nm were synthesized and utilized as highly efficient cell nucleators in CO2-blown nanocellular polymethyl methacrylate (PMMA) foams. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller measurements, and transmission electron microscopy. The cell size and cell density of the obtained PMMA micro- and nanocellular foams were determined by scanning electron microscopy. The results show that increased surface roughness enhances the nucleation efficiency of the designer silica particles. This effect is ascribed to a decreased nucleation free energy for foam cell nucleation in the nanocavities at the melt-nucleator interface. For PDMS grafted raspberry-like silica nanoparticles with diameters of 155 and 200 nm, multiple cell nucleation events were observed. These hybrid particles had nucleation efficiencies of 3.7 and 6.2, respectively. The surprising increase in nucleation efficiency to above unity is ascribed to the significant increase in CO2 absorption and capillary condensation in the corresponding PMMA during saturation. This increase results in the presence of large amounts of the physical blowing agent close to energetically favorable nucleation points. Additionally, it is shown that as a consequence of cell coalescence, the increased number of foam cells is rapidly reduced during the first seconds of foaming. Hence, the design of highly efficient nucleating particles, as well as careful selection of foam matrix materials, seems to be of pivotal importance for obtaining polymer cellular materials with cell dimensions at the nanoscale. These findings contribute to the fabrication of polymer foams with high thermal insulation capacity and have relevance in general to the area of cellular materials.

Printing "Smart" Inks of Redox-Responsive Organometallic Polymers on Microelectrode Arrays for Molecular Sensing.

Printing arrays of responsive spots for multiplexed sensing with electrochemical readout requires new molecules and precise, high-throughput deposition of active compounds on microelectrodes with spatial control. We have designed and developed new redox-responsive polymers, featuring a poly(ferrocenylsilane) (PFS) backbone and side groups with disulfide units, which allow an efficient and stable bonding to Au substrates, using sulfur-gold coupling chemistry in a "grafting-to" approach. The polymer molecules can be employed for area selective molecular sensing following their deposition by high-precision inkjet printing. The new PFS derivatives, which serve as "molecular inks", were characterized by 1H NMR, 13C NMR, and FTIR spectroscopies and by gel permeation chromatography. The viscosity and surface tension of the inks were assessed by rheology and pendant drop contact angle measurements, respectively. Commercial microelectrode arrays were modified with the new PFS ink by using inkjet printing in the "drop-on-demand" mode. FTIR spectroscopy, AFM, and EDX-SEM confirmed a successful, spatially localized PFS modification of the individual electrodes within the sensing cells of the microelectrode arrays. The potential application of these devices to act as an electrochemical sensor array was demonstrated with a model analyte, ascorbic acid, by using cyclic voltammetry and amperometric measurements.

Size-Dependent Submerging of Nanoparticles in Polymer Melts: Effect of Line Tension.

Adhesion of nanoparticles to polymer films plays a key role in various polymer technologies. Here we report experiments that reveal how silica nanoparticles adhere to a viscoelastic PMMA film above the glass transition temperature. The polymer was swollen with CO2, closely matching the conditions of nanoparticle-nucleated polymer foaming. It is found that the degree by which the particles sink into the viscoelastic substrate is strongly size dependent and can even lead to complete engulfment for particles of diameter below 12 nm. These findings are explained quantitatively by a thermodynamic analysis, combining elasticity, capillary adhesion, and line tension. We argue that line tension, here proposed for the first time in elastic media, is responsible for the nanoparticle engulfment.

Silica-Assisted Nucleation of Polymer Foam Cells with Nanoscopic Dimensions: Impact of Particle Size, Line Tension, and Surface Functionality.

Core-shell nanoparticles consisting of silica as core and surface-grafted poly(dimethylsiloxane) (PDMS) as shell with different diameters were prepared and used as heterogeneous nucleation agents to obtain CO2-blown poly(methyl methacrylate) (PMMA) nanocomposite foams. PDMS was selected as the shell material as it possesses a low surface energy and high CO2-philicity. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy. The cell size and cell density of the PMMA micro- and nanocellular materials were determined by scanning electron microscopy. The cell nucleation efficiency using core-shell nanoparticles was significantly enhanced when compared to that of unmodified silica. The highest nucleation efficiency observed had a value of ∼0.5 for nanoparticles with a core diameter of 80 nm. The particle size dependence of cell nucleation efficiency is discussed taking into account line tension effects. Complete engulfment by the polymer matrix of particles with a core diameter below 40 nm at the cell wall interface was observed corresponding to line tension values of approximately 0.42 nN. This line tension significantly increases the energy barrier of heterogeneous nucleation and thus reduces the nucleation efficiency. The increase of the CO2 saturation pressure to 300 bar prior to batch foaming resulted in an increased line tension length. We observed a decrease of the heterogeneous nucleation efficiency for foaming after saturation with CO2 at 300 bar, which we attribute to homogenous nucleation becoming more favorable at the expense of heterogeneous nucleation in this case. Overall, it is shown that the contribution of line tension to the free energy barrier of heterogeneous foam cell nucleation must be considered to understand foaming of viscoelastic materials. This finding emphasizes the need for new strategies including the use of designer nucleating particles to enhance the foam cell nucleation efficiency.

Optical imaging beyond the diffraction limit by SNEM: effects of AFM tip modifications with thiol monolayers on imaging quality.

Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast.

Scanning thermal lithography of tailored tert-butyl ester protected carboxylic acid functionalized (meth)acrylate polymer platforms.

In this paper, we report on the development of tailored polymer films for high-resolution atomic force microscopy based scanning thermal lithography (SThL). In particular, full control of surface chemical and topographical structuring was sought. Thin cross-linked films comprising poly(tert-butyl methacrylate) (MA(20)) or poly(tert-butyl acrylate) (A(20)) were prepared via UV initiated free radical polymerization. Thermogravimetric analysis (TGA) and FTIR spectroscopy showed that the heat-induced thermal decomposition of MA(20) by oxidative depolymerization is initially the primary reaction followed by tert-butyl ester thermolysis. By contrast, no significant depolymerization was observed for A(20). For A(20) and MA(20) (at higher temperatures and/or longer reaction times) the thermolysis of the tert-butyl ester liberates isobutylene and yields carboxylic acid groups, which react further intramolecularly to cyclic anhydrides. The values of the apparent activation energies (E(a)) for the thermolysis were calculated to be 125 ± 13 kJ mol(-1) and 116 ± 7 kJ mol(-1) for MA(20) and A(20), respectively. Both MA(20) and A(20) films showed improved thermomechanical stability during SThL compared to non cross-linked films. Carboxylic acid functionalized lines written by SThL in A(20) films had a typically ~10 times smaller width compared to those written in MA(20) films regardless of the tip radius of the heated probe and did not show any evidence for thermochemically or thermomechanically induced modification of film topography. These observations and the E(a) of 45 ± 3 kJ mol(-1) for groove formation in MA(20) estimated from the observed volume loss are attributed to oxidative thermal depolymerization during SThL of MA(20) films, which is considered to be the dominant reaction mechanism for MA(20). The smallest line width values obtained for MA(20) and A(20) films with SThL were 83 ± 7 nm and 21 ± 2 nm, whereas the depth of the lines was below 1 nm, respectively.

Nanoscale thermal AFM of polymers: transient heat flow effects.

Thermal transport around the nanoscale contact area between the heated atomic force microscopy (AFM) probe tip and the specimen under investigation is a central issue in scanning thermal microscopy (SThM). Polarized light microscopy and AFM imaging of the temperature-induced crystallization of poly(ethylene terephthalate) (PET) films in the region near the tip were used in this study to unveil the lateral heat transport. The radius of the observed lateral surface isotherm at 133 °C ranged from 2.2 ± 0.5 to 18.7 ± 0.5 µm for tip-polymer interface temperatures between 200 and 300 °C with contact times varying from 20 to 120 s, respectively. In addition, the heat transport into polymer films was assessed by measurements of the thermal expansion of poly(dimethyl siloxane) (PDMS) films with variable thickness on silicon supports. Our data showed that heat transport in the specimen normal (z) direction occurred to depths exceeding 1000 µm using representative non-steady-state SThM conditions (i.e., heating from 40 to 180 °C at a rate of 10 °C s(-1)). On the basis of the experimental results, a 1D steady-state model for heat transport was developed, which shows the temperature profile close to the tip-polymer contact. The model also indicates that ≤1% of the total power generated in the heater area, which is embedded in the cantilever end, is transported into the polymer through the tip-polymer contact interface. Our results complement recent efforts in the evaluation and improvement of existing theoretical models for thermal AFM, as well as advance further developments of SThM for nanoscale thermal materials characterization and/or manipulation via scanning thermal lithography (SThL).

Atomic force microscopy based thermal lithography of poly(tert-butyl acrylate) block copolymer films for bioconjugation.

In this paper, we report on the local thermal activation of thin polymer films for area-selective surface chemical modification on micrometer and nanometer length scales. The thermally induced activation of tert-butyl ester moieties in polystyrene- block-poly(tert-butyl acrylate) (PS- b-PtBA) block copolymer films leads to the formation of pending carboxylic acid groups, which are among the versatile functionalities for subsequent bioconjugation. From Fourier transform infrared (FTIR) spectroscopic analyses, the apparent activation energy (Ea) for the tert-butyl ester deprotection in thin films was calculated to be 93 +/- 12 kJ/mol, which is in good agreement with values reported for the bulk. The availability of the deprotected carboxylic acid groups in subsequent wet chemical grafting reactions on neat thermolyzed films was confirmed by covalently immobilizing fluoresceinamine and amino end-functionalized poly(ethylene glycol) (PEG-NH2) using established 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS) chemistry. Local thermal deprotection on micrometer and sub-micrometer length scales was achieved by scanning thermal microscopy using an atomic force microscope with heatable probe tips. Passivating PEG and fluoresceinamine layers were selectively covalently coupled to locally deprotected areas as small as 370 nm x 580 nm.