General Photo‐Patterning of Polyelectrolyte Thin Films via Efficient Ionic Bis(Fluorinated Phenyl Azide) Photo‐Crosslinkers and their Post‐Deposition Modification

We have extended the well known bisfluorinated(phenyl azide) (bisFPA) methodology to develop an ionic bisFPA process suitable for photo‐crosslinking a wide variety of polyelectrolyte thin films. The crosslinking efficiencies (0.1–1.0 crosslink per photo‐reaction) are sufficiently high for the gel fraction to exceed 80 % for crosslinker concentrations of only a few weight %. This method is based on the photo‐induced formation of singlet nitrenes from FPAs and their insertion into unactivated C–H or other bonds, which thus general and not dependent on the presence of specific chemical functional groups. By derivatizing with ionic charge groups, we obtained ionic bisFPAs that can be properly dispersed into polyelectrolyte thin films. The sorbed moisture always present in these films however severely limits the photo‐crosslinking efficiency, apparently through nitrene protonation and intersystem crossing. This can be avoided by dehydration of the films, in some cases, to 130 °C for 10 min in nitrogen before photo‐exposure. We found that efficient photo‐crosslinking can then be achieved for polyelectrolytes even when they have nucleophilic groups. These include poly(styrenesulfonic acid) and their salts, poly(acrylic acid) and their salts, poly(dimethyldiallylammonium salts), as well as the electrically‐conducting poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonic acid) complex (PEDT:PSSH). We further demonstrate using this ionic bisFPA methodology both photo‐patterning and post‐deposition chemical modifications of polyelectrolyte thin films. This opens broad new possibilities in membrane, sensor and actuator technologies, as well as for organic semiconductor plastic electronics (such as field‐effect transistors) and polyelectrolyte‐based devices.     

A Biomimetic Actuator Based on an Ionic Networking Membrane of Poly(styrene‐alt‐maleimide)‐Incorporated Poly(vinylidene fluoride)

A novel electro‐active polymer actuator employing the ionic networking membrane of poly(styrene‐alt‐maleimide) (PSMI)‐incorporated poly(vinylidene fluoride) (PVDF) was developed to improve the electrical and mechanical performance of the artificial muscles. The main drawback of the previous ionic polymer‐metal composite actuator was the straightening‐back and relaxation under the constant voltage excitation. The present ionic networking membrane actuator overcomes the relaxation of the ionic polymer‐metal composite actuator under the constant voltage and also shows much larger tip displacement than that of the Nafion‐based actuator. Under the simple harmonic stimulus, the measured mechanical displacement was comparable to that of the Nafion‐based actuator. The excellent electromechanical response of the current polymer actuator is attributed to two factors: the inherent large ionic‐exchange capacity and the unique hydrophilic nano‐channels of the ionic networking membrane. The electro‐active polymer actuator of PSMI‐incorporated PVDF can be a promising smart material and may possibly diversify niche applications in biomimetic motion.     

Electrospun Ionomeric Fibers with Anion Conducting Properties

Anion conductive nanofiber mats from FAA‐3 ionomers are obtained by electrospinning. Depending on the solvent used in the precursor solution, nanofibers with either nonhollow cylindrical or flat ribbon‐like cross‐sections are prepared. The anion conductivity and water uptake of the ionomeric nanofiber mats are measured as a function of the relative humidity in the 10–90% range and compared to that of a solid membrane cast from the same ionomer. In addition, the anion conductivity of an isolated single fiber of the ionomer is measured for the first time. The anion conductivity of the electrospun single fiber is found to be higher than that of the mats, which is, in turn, one order of magnitude higher than that of the solid ionomer membrane. The higher conductivity of the mats relative to the solid membrane (in both in‐plane and through‐plane directions) is found to be related to the variation in water uptake, which stems from the morphological distinctions. These results increase the understanding of the electrospinning process of ionomers, toward the development and design of new anion conductive ionomer fibers, useful for high performance electrochemical devices.     

Nanostructure/Swelling Relationships of Bulk and Thin‐Film PFSA Ionomers

Perfluorinated sulfonic acid (PFSA) ionomers are the most widely used solid electrolyte in electrochemical technologies due to their remarkable ionic conductivity with simultanous mechanical stability, imparted by their phase‐separated morphology. In this work, the morphology and swelling of PFSA ionomers (Nafion and 3M) as bulk membranes (>10 μm) and dispersion‐cast thin films (<100 nm) are investigated to identify the roles of equivalent weight (EW) and side‐chain length across lengthscales. Humidity‐dependent structural changes as well as different PFSA chemistries are explored in the thin‐film regime, allowing for the development of thickness‐EW phase diagrams. The ratio of macroscopic (thickness) to nanoscopic (domain spacing) swelling during hydration is found to be affine (1:1) in thin films, but increases as the thickness approaches bulk values, revealing the existence of a mesoscale organization governing the multiscale swelling in PFSAs. Ionomer chemistry, in particular EW, is found to play a key role in altering the confinement‐driven structural changes, including thin‐film anisotropy, with phase separation becoming weaker as the film thickness is reduced below 25 nm or as EW is increased. For the lower‐EW 3M PFSA ionomers, confinement appears to induce even stronger phase separation accompanied by domain alignment parallel to the substrate.     

Protein Adsorption on Grafted Zwitterionic Polymers Depends on Chain Density and Molecular Weight

This study demonstrates that protein adsorption on end‐grafted, zwitterionic poly(sulfobetaine) (pSBMA) thin films depends on the grafting density, molecular weight, and ionic strength. Zwitterionic polymers exhibit ultralow nonspecific fouling (protein adsorption) and excellent biocompatibility. This picture contrasts with a recent report that soluble pSBMA chains bind proteins and alter the protein folding stability. To address this apparent contradiction, the dependence of protein adsorption on the chain grafting parameters is investigated: namely, the grafting density, molecular weight, and ionic strength. Studies compared the adsorption of phosphoglycerate kinase and positively charged lysozyme versus the scaled grafting parameter s/2R_F, where s is the distance between grafting sites and R_F is the Flory radius. Plots of the adsorbed protein amount versus s/2R_F exhibit a bell‐shaped curve, with a maximum near s/2R_F ≈ 1 and an amplitude that decreases with ionic strength. This behavior is qualitatively consistent with theoretical models for colloid interactions with weakly attractive, grafted chains. The results confirm that proteins do adsorb to pSBMA thin films, and they suggest an underlying mechanism. Comparisons with polymer models further identify design rules for pSBMA films that effectively repel protein.     

Solid Polymer Electrolytes Based on Ionic Graft Polymers: Effect of Graft Chain Length on Nano‐Structured,Ionic Networks

The length of graft chains in graft polymers is controlled in order to dictate the formation of a nanochannel network of ions in a non‐ionic matrix. Graft polymers were prepared by copolymerization of styrene with poly(sodium styrene sulfonate) (PSSNa) macromonomers. The latter were prepared with controlled molecular weight and narrow polydispersity by stable free radical polymerization. Phase separation of ionic aggregates occurs to a greater extent in films prepared from amphiphilic polymers possessing longer graft chains. Films prepared from polymers containing low ion content comprise of isolated ionic domains and exhibit low ionic conductivity. Increasing the ion content with the membrane, by increasing the number density of ionic graft chains in the polymer, results in ionic domains that coalesce into a network of nanochannels, and a dramatic increase in ion conductivity is observed. The ionic network is developed to a greater extent for films based on longer ionic graft chain polymers; an observation explained on the basis of phase separation.     

Mosaic,Single‐Crystal CaCO3 Thin Films Fabricated on Modified Polymer Templates

Mosaic, single‐crystal CaCO₃ thin films have been prepared on modified poly(ethylene terephthalate) (PET) templates. Surface modification of PET through the introduction of carboxylic acid groups (COOH‐PET), and the subsequent physical and chemical adsorption of poly(allylamine hydrochloride) (PAH) at pH 8 (PAH8‐PET) and pH 11 (PAH11‐PET), afford template surfaces that influenced the phase transition of an amorphous CaCO₃ (ACC) films during crystallization in air. Macroscopic ACC thin films are prepared on modified PET films in the presence of poly(acrylic acid). Polycrystalline, spherulitic vaterite (CaCO₃) films are observed to form on native PET and PAH11‐PET, while mosaic, single‐crystal calcitic (CaCO₃) films form on COOH‐PET and PAH8‐PET templates. These results confirm that single‐crystal CaCO₃ growth patterns are dependent on the surface characteristics of the PET template. We infer therefore, that the nucleation and growth of ceramic films on polymeric templates can be controlled by chemical modification of the polymeric template surface, and by the subsequent attachment of ionic polyelectrolytes.     

Capillary Force Lithography: A Versatile Tool for Structured Biomaterials Interface Towards Cell and Tissue Engineering

This Feature Article aims to provide an in‐depth overview of the recently developed molding technologies termed capillary force lithography (CFL) that can be used to control the cellular microenvironment towards cell and tissue engineering. Patterned polymer films provide a fertile ground for controlling various aspects of the cellular microenvironment such as cell–substrate and cell–cell interactions at the micro‐ and nanoscale. Patterning thin polymer films by molding typically involves several physical forces such as capillary, hydrostatic, and dispersion forces. If these forces are precisely controlled, the polymer films can be molded into the features of a polymeric mold with high pattern fidelity and physical integrity. The patterns can be made either with the substrate surface clearly exposed or unexposed depending on the pattern size and material properties used in the patterning. The former (exposed substrate) can be used to adhere proteins or cells on pre‐defined locations of a substrate or within a microfluidic channel using an adhesion‐repelling polymer such as poly(ethylene glycol) (PEG)‐based polymer and hyaluronic acid (HA). Also, the patterns can be used to co‐culture different cells types with molding‐assisted layer‐by‐layer deposition. In comparison, the latter (unexposed substrate) can be used to control the biophysical surrounding of a cell with tailored mechanical properties of the material. The surface micropatterns can be used to engineer cellular and multi‐cellular architecture, resulting in changes of the cell shape and the cytoskeletal structures. Also, the nanoscale patterns can be used to affect various aspects of the cellular behavior, such as adhesion, proliferation, migration, and differentiation.     

Self‐Organized Gradient Hole Injection to Improve the Performance of Polymer Electroluminescent Devices

A new approach to forming a gradient hole‐injection layer in polymer light‐emitting diodes (PLEDs) is demonstrated. Single spin‐coating of hole‐injecting conducting polymer compositions with a perfluorinated ionomer results in a work function gradient through the layer formed by self‐organization, which leads to remarkably efficient single‐layer PLEDs (ca. 21 cd A^–1). The device lifetime is significantly improved (ca. 50 times) compared with the conventional hole‐injection layer, poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonate). These results are a good example for demonstrating that the shorter lifetime of PLEDs compared with small‐molecule‐based organic LEDs (SM‐OLEDs) is not mainly due to the inherent degradation of the polymeric emitter itself. Hence, the results open the way to further improvements of PLEDs for real applications to large‐area, high‐resolution, and full‐color flexible displays.     

Novel Engineered Ion Channel Provides Controllable Ion Permeability for Polyelectrolyte Microcapsules Coated with a Lipid Membrane

The development of nanostructured microcapsules based on a biomimetic lipid bilayer membrane (BLM) coating of poly(sodium styrenesulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) polyelectrolyte hollow microcapsules is reported. A novel engineered ion channel, gramicidin (bis‐gA), incorporated into the lipid membrane coating provides a functional capability to control transport across the microcapsule wall. The microcapsules provide transport and permeation for drug‐analog neutral species, as well as positively and negatively charged ionic species. This controlled transport can be tuned for selective release biomimetically by controlling the gating of incorporated bis‐gA ion channels. This system provides a platform for the creation of “smart” biomimetic delivery vessels for the effective and selective therapeutic delivery and targeting of drugs.     

Controlled Degradability of Polysaccharide Multilayer Films In Vitro and In Vivo

This article demonstrates the possibility of tuning the degradability of polysaccharide multilayer films in vitro and in vivo. Chitosan and hyaluronan multilayer films (CHI/HA) were either native or crosslinked using a water soluble carbodiimide, 1‐ethyl‐3‐(3‐dimethylamino‐propyl)carbodiimide (EDC) at various concentrations in combination with N‐hydroxysulfosuccinimide. The in‐vitro degradation of the films in contact with lysozyme and hyaluronidase was followed by quartz crystal microbalance measurements, fluorimetry, and confocal laser scanning microscopy after labeling of the chitosan with fluorescein isothiocyanate (CHI^FITC). The native films were subjected to degradation by these enzymes, and the crosslinked films were more resistant to enzymatic degradation. Films made of chitosan of medium molecular weight were more resistant than films made of chitosan‐oligosaccharides. The films were also brought in contact with plasma, which induced a change in film structure for the native film but did not have any effect on the crosslinked film. The in‐vitro study shows that macrophages can degrade all types of films and internalize the chitosan. The in‐vivo degradation of the films implanted in mouse peritoneal cavity for a week again showed an almost complete degradation of the native films, whereas the crosslinked films were only partially degraded. Taken together, these results suggest that polysaccharide multilayer films are of potential interest for in‐vivo applications as biodegradable coatings, and that degradation can be tuned by using chitosan of different molecular weights and by controlling film crosslinking.     

Perfluorinated Ionomer‐Modified Hole‐Injection Layers: Ultrahigh‐Workfunction but Nonohmic Contacts

Recently it has been reported that Nafion oligomers, i.e., 2‐(2‐sulfonatotetrafluoroethoxy)‐2‐trifluoromethyltrifluoroethoxyfunctionalized oligotetrafluoroethylenes, also called perfluorinated ionomers (PFIs), can be blended into poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDT:PSSH) films to increase their workfunctions beyond 5.2 eV. These PFI‐modified films are useful for energy‐level alignment studies, and have been proposed as hole‐injection layers (HILs). It is shown here however that these HILs do not provide sufficiently fast hole transfer into adjacent polymer semiconductor layers with ionization potentials deeper than ≈5.2 eV. X‐ray and ultraviolet photoemission spectroscopies reveal that these HILs exhibit a molecularly‐thin PFI overlayer that sets up a surface dipole that provides the ultrahigh workfunction. This dipolar layer persists even when the subsequent organic semiconductor layer is deposited, as evidenced by measurements of the diode built‐in potentials. As a consequence, the PFI‐modified HILs produce a higher contact resistance, and a lower equilibrium density of holes at the semiconductor contact than might have been expected from simple thermodynamic considerations of the reduction in hole‐injection barrier. Thus the use of insulating dipolar surface layers at the charge‐injection contact to tune its workfunction to match the relevant transport level of the semiconductor is of limited utility to achieve ohmic contact in these devices.     

Phase Segregation in Thin Films of Conjugated Polyrotaxane– Poly(ethylene oxide) Blends: A Scanning Force Microscopy Study

Scanning force microscopy (SFM) is used to study the surface morphology of spin‐coated thin films of the ion‐transport polymer poly(ethylene oxide) (PEO) blended with either cyclodextrin (CD)‐threaded conjugated polyrotaxanes based on poly(4,4′‐diphenylene‐vinylene) (PDV), β‐CD–PDV, or their uninsulated PDV analogues. Both the polyrotaxanes and their blends with PEO are of interest as active materials in light‐emitting devices. The SFM analysis of the blended films supported on mica and on indium tin oxide (ITO) reveals in both cases a morphology that reflects the substrate topography on the (sub‐)micrometer scale and is characterized by an absence of the surface structure that is usually associated with phase segregation. This observation confirms a good miscibility of the two hydrophilic components, when deposited by using spin‐coating, as suggested by the luminescence data on devices and thin films. Clear evidence of phase segregation is instead found when blending PEO with a new organic‐soluble conjugated polymer such as a silylated poly(fluorene)‐alt‐poly(para‐phenylene) based polyrotaxane (THS–β‐CD–PF–PPP). The results obtained are relevant to the understanding of the factors influencing the interfacial and the intermolecular interactions with a view to optimizing the performance of light‐emitting diodes, and light‐emitting electrochemical cells based on supramolecularly engineered organic polymers.     

Understanding the Origin of the 535 nm Emission Band in Oxidized Poly(9,9‐dioctylfluorene): The Essential Role of Inter‐Chain/Inter‐Segment Interactions

We present a careful study of the effects of photo‐oxidation on the emissive properties of poly(9,9‐dioctylfluorene) (PFO) that addresses important issues raised by a recent flurry of publications concerning the degradation of blue light‐emitting, fluorene‐based homo‐ and copolymers. The photoluminescence (PL) spectra of thin PFO films oxidized at room temperature comprise two major components, namely a vibronically structured blue band and a green, structureless component, referred to hereafter as the ‘g‐band’. These are common features in a wide range of poly(fluorene)s (PFs) and whilst the former is uniformly accepted to be the result of intra‐chain, fluorene‐based, singlet‐exciton emission, the origin of the ‘g‐band’ is subject to increasing debate. Our studies, described in detail below, support the proposed formation of oxidation‐induced fluorenone defects that quench intra‐chain, singlet‐exciton emission and activate the g‐band emission. However, whilst these fluorenone defects are concluded to be necessary for the g‐band emission to be observed, they are considered not to be, alone, sufficient. We show that inter‐chain/inter‐segment interactions are required for the appearance of the g‐band in the PL spectra of PFO and propose that the g‐band is attributable to emission from fluorenone‐based excimers rather than from localized fluorenone π–π* transitions as recently suggested.     

Poly(arylene piperidinium) Hydroxide Ion Exchange Membranes: Synthesis,Alkaline Stability,and Conductivity

A series of poly(arylene piperidinium)s (PAPipQs) devoid of any alkali‐sensitive aryl ether bonds or benzylic sites are prepared and studied as anion exchange membranes (AEMs) for alkaline fuel cells. First, the excellent alkaline stability of the model compound 4,4‐diarylpiperidinium is confirmed. Medium molecular weight poly(arylene piperidine)s are then synthesized in polycondensations of N‐methyl‐4‐piperidone and either bi‐ or terphenyl via superelectrophilic activation in triflic acid. Film‐forming PAPipQs are subsequently prepared in Menshutkin reactions with methyl, butyl, hexyl, and octyl halides, respectively. AEMs based on poly(terphenyl dimethylpiperidinium) show the best performance with no structural degradation detectable by ¹H NMR spectroscopy after storage in 2 m aq. NaOH at 60 °C after 15 d, and a mere 5% ionic loss at 90 °C. In the fully hydrated state these AEMs reach an OH^? conductivity of 89 mS cm^?1 at 80 °C. The presence of longer pendant N‐alkyl chains (butyl to octyl) is found to significantly promote Hofmann ring‐opening elimination reactions and the degradation rate increases with increasing alkyl chain length. The results of the present study demonstrate that PAPipQs are efficiently prepared from readily available monomers and show excellent alkaline stability and OH^? conductivity when devoid of pendant N‐alkyl chains.     

Supported Lipid Bilayer Assembly on PEDOT:PSS Films and Transistors

Lipid bilayers are widely employed as a model system to investigate interactions between cells and their environment. Supported lipid bilayers (SLB) with integrated transmembrane proteins are emerging as a preferred platform for sensing applications. Challenges lie in the generation of SLB on surfaces which allow transduction of signals for characterization of lipid bilayer and incorporated transmembrane proteins. For the first time, the formation of SLBs is shown on films of the conducting polymer, poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS), using traditional methods for characterizing lipid bilayer quality and function (QCM‐D, FRAP) combined with impedance spectroscopy. Further, partial formation of SLBs on PEDOT:PSS based organic electrochemical transistors (OECTs) is successfully demonstrated, as well as the ability to integrate and sense the ion pore α‐hemolysin, confirming the sensitivity of the OECT as a transducer of biological membrane function. This work represents a highly promising first step toward the use of such OECTs for functional readout of transmembrane proteins in their native environment.     

Multivalent‐Ion‐Mediated Stabilization of Hydrogen‐Bonded Multilayers

Hydrogen‐bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)‐co‐(maleic acid)] (PSSMA) and poly(N‐isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce⁴⁺ or Fe³⁺) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce⁴⁺‐ and Fe³⁺‐stabilized films, respectively), film loss is negligible. This provides a stark contrast with non‐stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen‐bonded structures non‐covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe³⁺‐treated films to iodide solutions.     

A Critical Revision of the Nano‐Morphology of Proton Conducting Ionomers and Polyelectrolytes for Fuel Cell Applications

A few aspects of the nano‐morphology of hydrated Nafion and other ionomers and polyelectrolytes in their acid form are revisited by examining the evolution of small angle X‐ray scattering (SAXS) data which are recorded for a wide range of water volume fractions (Φ_water ≈ 7–56 vol%). A consistency check with the recent “parallel cylinder model” discloses that this is most likely biased by a large uncertainty of the experimentally determined water content. We rather find our data to be consistent with locally flat and narrow (around 1 nm) water domains . The formation of relatively thin water “films” is suggested to be a common feature of many ionomers and polyelectrolytes, and the underlying driving force is most likely electrostatics within these highly dissociated systems. The water films may act as a charged (e.g., with positive protonic charge carriers) “glue”, keeping together the oppositely charged polymer structures. While this interaction tends to produce flat morphologies, the formation process is suggested to be constraint by limited conformational degrees of freedom of the corresponding polymer and the interactions between polymer backbones. This may leave severe tortuosities on larger scales which depend on the sample history (including swelling, de‐swelling, aging, stretching, and pressing).     

Defect‐Tolerant Nanocomposites through Bio‐Inspired Stiffness Modulation

A biologically inspired, multilayer laminate structural design is deployed into nanocomposite films of graphene oxide‐poly(methyl methacrylate) (GO‐PMMA). The resulting multilayer GO‐PMMA films show greatly enhanced mechanical properties compared to pure‐graphene‐oxide films, with up to 100% increases in stiffness and strength when optimized. Notably, a new morphology is observed at fracture surfaces: whereas pure‐graphene‐oxide films show clean fracture surfaces consistent with crack initiation and propagation perpendicular to the applied tensile load, the GO‐PMMA multilayer laminates show terracing consistent with crack stopping and deflection mechanisms. As a consequence, these macroscopic GO‐PMMA films become defect‐tolerant and can maintain their tensile strengths as their sample volumes increase. Linear elastic fracture analysis supports these observations by showing that the stiffness modulation introduced by including PMMA layers within a graphene oxide film can act to shield or deflect cracks, thereby delaying failure and allowing the material to access more of its inherent strength. Together, these data clearly demonstrate that desirable defect‐tolerant traits of structural biomaterials can indeed be incorporated into graphene‐ oxide‐based nanocomposites.     

Single‐Molecule Tracking of Fibrinogen Dynamics on Nanostructured Poly(ethylene) Films

Using fibrinogen (Fg) protein as a probe molecule, mapping using accumulated probe trajectories (MAPT) is performed on nanostructured melt‐drawn high‐density poly(ethylene) (HDPE) films composed of well‐oriented crystalline patches separated by amorphous regions. The spatially grouped molecular trajectories allow for identification of regions with distinct surface properties (i.e., crystalline vs. amorphous) while simultaneously determining the characteristic dynamic protein behavior within those regions. In the presence of solution with a sufficiently high Fg concentration, discrete patches of a dense, ordered protein layer form (presumably on crystalline HDPE regions), leading to a dramatic rise in the surface residence time (by more than two orders of magnitude) of molecules incorporated into the film. Within this ordered Fg layer, individual molecules exhibit slow anisotropic lateral diffusion; the mobility is restricted by the nanostructure boundaries of the underlying HDPE. On HDPE films at low Fg surface coverage, or on films that have been rendered hydrophilic with Ar plasma, short surface residence times and fast, isotropic diffusion are observed. These results demonstrate the ability of spatially resolved single‐molecule tracking to provide mechanistic information about biomolecule‐surface interactions in a highly heterogeneous environment.