Surface-grafted Polymer Research Articles

Binding of mucin to water-soluble and surface-grafted boronate-containing polymers

The binding of mucin to water-soluble copolymers of N,N-dimethylacrylamide and N-acryloyl-m-aminophenylboronic acid grafted on the surface of glass is studied. Atomic force microscopy studies show that many graft copolymer islands 20-200 nm in diameter and 50 nm in height occur on the modified surface of flat glass. Owing to the presence of phenyl boronate groups, the copolymer behaves as a weak polyelectrolyte (pK(a) = 9.0) and, in the grafted state in an aqueous solution, experiences reversible transitions between states with higher and lower degrees of ionization. As evidenced by spectral correlation interferometry, this phenomenon brings about a change in the thickness of the grafted layer by approximately 0.5 nm. The ability of phenyl boronate groups to form cyclic esters with diol and polyol groups results in complexation of the soluble copolymer with mucin oligosaccharides and entails the appearance of slowly growing submicron particles formed by similarly charged polymers. The specificity of complexation is confirmed by dissolution of particles in the presence of fructose: a saccharide with a strong affinity for phenyl boronate groups. The binding of mucin to glass, which is chemically modified with the above copolymer, leads to formation of an adsorption layer with a thickness of 1.2-1.8 nm. Thus, boronate-containing copolymers are suitable for preparing carriers with controllable adsorption properties with respect to polyols, including mucinlike proteins of cellular glycocalyxes. (Less)

An experimental-theoretical analysis of protein adsorption on peptidomimetic polymer brushes.

Surface-grafted water-soluble polymer brushes are being intensely investigated for preventing protein adsorption to improve biomedical device function, prevent marine fouling, and enable applications in biosensing and tissue engineering. In this contribution, we present an experimental-theoretical analysis of a peptidomimetic polymer brush system with regard to the critical brush density required for preventing protein adsorption at varying chain lengths. A mussel adhesive-inspired DOPA-Lys (DOPA = 3,4-dihydroxy-phenylalanine; Lys = lysine) pentapeptide surface grafting motif enabled aqueous deposition of our peptidomimetic polypeptoid brushes over a wide range of chain densities. Critical densities of 0.88 nm(-2) for a relatively short polypeptoid 10-mer to 0.42 nm(-2) for a 50-mer were identified from measurements of protein adsorption. The experiments were also compared with the protein adsorption isotherms predicted by a molecular theory. Excellent agreements in terms of both the polymer brush structure and the critical chain density were obtained. Furthermore, atomic force microscopy (AFM) imaging is shown to be useful in verifying the critical brush density for preventing protein adsorption. The present coanalysis of experimental and theoretical results demonstrates the significance of characterizing the critical brush density in evaluating the performance of an antifouling polymer brush system. The high fidelity of the agreement between the experiments and molecular theory also indicate that the theoretical approach presented can aid in the practical design of antifouling polymer brush systems.

Efficient One‐Pot Synthesis of Water‐Compatible Molecularly Imprinted Polymer Microspheres by Facile RAFT Precipitation Polymerization

Molecular imprinting is a versatile and straightforward method for the preparation of polymer receptors with tailor-made recognition sites. Despite the tremendous progress made in this field, many challenges still remain to be addressed. In particular, it has been shown that the presently developed molecularly imprinted polymers (MIPs) are normally only organic solvent compatible and they mostly fail to show specific template bindings in pure aqueous solutions, thus significantly limiting their practical applications in the field of biotechnology. Although some approaches, which either use specifically designed functional monomers or apply the conventional imprinting protocol, have been developed for the preparation of MIPs with molecular recognition ability under aqueous conditions, versatile approaches for the preparation of MIPs that are applicable in pure aqueous environments are still rare. Herein, we report a new and efficient one-pot approach to obtain pure-water-compatible and narrowly dispersed MIP microspheres with surface-grafted hydrophilic polymer brushes by facile reversible addition/fragmentation chaintransfer (RAFT) precipitation polymerization (RAFTPP), mediated by hydrophilic macromolecular chain-transfer agents (Macro-CTAs; Scheme 1). The presence of hydrophilic polymer brushes on MIP microspheres significantly improved their surface hydrophilicity and dramatically reduced their hydrophobic interactions with template molecules in pure aqueous media, thus leading to their water compatibility. The easy availability of many different hydrophilic Macro-CTAs (by either RAFT polymerization of hydrophilic monomers or hydrophilic polymer end group modification), together with the versatility of RAFTPP for the controlled preparation of MIP microspheres, makes this strategy highly applicable for the design of hydrophilic and water-compatible MIPs. Two strategies have been developed for the synthesis of water-compatibleMIPs by improving their surface hydrophilicity; these strategies involve the use of a hydrophilic comonomer, functional monomer, or crosslinker in the molecular imprinting process, and the postmodification of the preformed MIPs. Although simple in principle, the former strategy either requires time-consuming optimization of MIP formulation components or can only be applied in some special systems. In comparison, the latter strategy, which involves the surface grafting of hydrophilic polymer layers, has proven highly attractive because it not only significantly improves the MIPs surface hydrophilicity, but also provides a protective layer to prevent protein molecules from blocking their imprinting sites in biological solutions. Very recently, we have successfully prepared pure-water-compatible MIP microspheres by the controlled grafting of hydrophilic polymer layers onto the preformed MIP particles. Compared with this two-step approach, the new strategy presented herein allows the more efficient controlled synthesis of pure-water-compatible MIP microspheres with surface-grafted hydrophilic polymer brushes by a one-pot RAFTPP method. To show proof-of-principle for our strategy, a model noncovalent molecular imprinting system was chosen because Scheme 1. Chemical structures of the utilized RAFT agents (including hydrophilic Macro-CTAs and CDB) and the schematic protocol for the one-pot preparation of water-compatible MIP microspheres by RAFT precipitation polymerization.

A substrate-independent method for surface grafting polymer layers by atom transfer radical polymerization: Reduction of protein adsorption

A general method for producing low-fouling biomaterials on any surface by surface-initiated grafting of polymer brushes is presented. Our procedure uses radiofrequency glow discharge thin film deposition followed by macro-initiator coupling and then surface-initiated atom transfer radical polymerization (SI-ATRP) to prepare neutral polymer brushes on planar substrates. Coatings were produced on substrates with variable interfacial composition and mechanical properties such as hard inorganic/metal substrates (silicon and gold) or flexible (perfluorinated poly(ethylene-co-propylene) film) and rigid (microtitre plates) polymeric materials. First, surfaces were functionalized via deposition of an allylamine plasma polymer thin film followed by covalent coupling of a macro-initiator composed partly of ATRP initiator groups. Successful grafting of a hydrophilic polymer layer was achieved by SI-ATRP of N, N′-dimethylacrylamide in aqueous media at room temperature. We exemplified how this method could be used to create surface coatings with significantly reduced protein adsorption on different material substrates. Protein binding experiments using labelled human serum albumin on grafted materials resulted in quantitative evidence for low-fouling compared to control surfaces.

Precise control of surface physicochemical properties for electrospun fiber mats by surface-initiated radical polymerization

Non-woven fiber mats were fabricated with the electrospinning method using poly(methyl methacrylate)-co-poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) in various solvents. The surface morphology of the electrospun fibers depended on the solvent vapor pressure and polymer concentration. Surface-initiated atom transfer radical polymerization (ATRP) with 3-(N-2-methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate), 2-hydroxyethyl methacrylate or 2-(perfluorooctyl)ethyl acrylate generated surface-grafted polymers, as determined by X-ray photoelectron spectroscopy. Scanning electron microscopic observation revealed that the apparent fiber morphology did not change upon modification. The atomic force microscopic images of the grafted fiber cross-sections indicated that monomers and solvents penetrated slightly into the fibers and polymerization occurred at both internal and external initiation sites. Physicochemical properties, such as contact angle, hydrophobicity and hydrophilicity, and wettability, could be altered by the proper selection of substrates (spin-coated flat films or the variously prepared non-woven fiber mats). We have successfully prepared hydrophilic and hydrophobic fiber surfaces by a combination of the electrospinning protocol and surface-initiated ATRP. Functional non-woven fiber mats were prepared by combining the electrospinning method and surface-initiated atom transfer radical polymerization (ATRP). The surface-initiated ATRP of 3-(N-2-methacryloyloxyethyl-N,N-dimethyl) ammonatopropanesulfonate), 2-hydroxyethyl methacrylate and 2-(perfluorooctyl)ethyl acrylate proceeded successfully from the fiber surface of poly(methyl methacrylate)-co-poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) without any structural changes. A grafted layer after the surface-initiated ATRP was observed by atomic force microscopy. Static contact angles against water were also evaluated to discuss the relationship between the roughness of the electrospun non-woven fiber mats and wettability.

Surface-Grafted Polymers from Electropolymerized Polythiophene RAFT Agent

The synthesis of grafted homopolymer and block copolymer films is reported using a surface-initiated reversible addition−fragmentation chain transfer (SI-RAFT) polymerization from electropolymerized polythiophene on indium tin oxide (ITO) and Au electrode surfaces. The polythiophene macro-RAFT agent was electrodeposited by cyclic voltammetry (CV) from thiobenzoate-functionalized terthiophene monomers. The ultrathin films on Au surfaces were investigated using atomic force microscopy (AFM), static contact angle, X-ray photoelectron spectroscopy (XPS), and ellipsometry. On the other hand, the RAFT agent-modified ITO substrate was monitored by UV−vis to track the electropolymerization of the RAFT agent and formation of π-conjugated polymer. Molecular weight (MW) and polydispersity index (PDI) were determined from sacrificial polymerization in solution. AFM imaging revealed typical polymer layer morphology for the films. Investigation of film thicknesses by ellipsometry and AFM profilometry gave comparable re...

Electrochemically crosslinked surface-grafted PVK polymer brushes as a hole transport layer for organic photovoltaics

Electrochemically crosslinked surface-grafted poly(N-vinylcarbazole) (PVK) brushes as hole transport layers (HTLs) on a photovoltaic device have been demonstrated using SI-RAFT polymerization. Comparable performance to PEDOT:PSS/P3HT:PCBM based devices was achieved. A main advantage is strong adhesion to ITO with a possible long-term stability against acid dopants and oxygen.

Binary Polymer Brushes on Silica@Polymer Hybrid Nanospheres and Hollow Polymer Nanospheres by Combined Alkyne−Azide and Thiol−Ene Surface Click Reactions

Silica@polymer core−shell hybrid nanospheres and air@polymer hollow nanospheres with surface-grafted binary polymer brushes were synthesized by a combination of sol−gel reaction, distillation−precipitation polymerization, and dual “click” reactions (alkyne−azide and thiol−ene “click” chemistry). Initially, 179 nm silica@poly(methacrylic acid-co-propargyl methacrylate-co-divinylbenzene) (SiO2@P(MAA-co-PMA-co-DVB)) core−shell hybrid nanospheres were prepared by distillation−precipitation copolymerization of MAA, PMA, and DVB in acetonitrile, using the 151 nm silica nanospheres from sol−gel reaction as templates. The propargyl groups from PMA and residual C═C double bonds from DVB on the SiO2@P(MAA-co-PMA-co-DVB) core−shell hybrid nanospheres provided dual clickable functionalities for the respective alkyne−azide and thiol−ene reactions with the azido-terminated hydrophobic polystyrene (PS-N3, Mn = 2550 g/mol) and thiol-terminated hydrophilic poly(ethylene glycol) (PEG-SH, Mn = 5000 g/mol). Finally, hairy ho...

Synthesis of thermosensitive polymer/mesoporous silica composite and its temperature dependence of anion exchange property

An anion exchanger consisting of amino-functionalized MCM-41 type mesoporous silica coated with temperature-responsive polymer, poly( N-isopropylacrylamide) (PNIPAM), was synthesized in this study. The structure of this composite was characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and elemental analysis. The XRD pattern showed that the synthesized composite had the ordered hexagonal structure and the interplanar spacing, d 100, was around 40 Å. The amount of surface-grafted thermosensitive polymer was estimated to be about 0.8 wt.% by elemental analysis. The adsorption–desorption behavior of methyl orange in this synthesized material depended on the temperature of aqueous solution: at 25 °C, the reversible adsorption–desorption of methyl orange was repeated with changing pH of the solution; at 40 °C, the methyl orange was not adsorbed and desorbed independent of pH of the solution.

One-Pot Preparation of Ferrocene-Functionalized Polymer Brushes on Gold Substrates by Combined Surface-Initiated Atom Transfer Radical Polymerization and “Click Chemistry”

A gold substrate with surface-grafted ferrocene functional polymer brushes, or Au-g-PFTMA surface [PFTMA = poly(5-ferrocene-triazolyl methacrylate)], was prepared by a combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and "click chemistry" in one pot, in the presence of 2-azidoethyl methacrylate (AzEMA), ethynyl ferrocene, CuBr catalyst, CuBr(2) deactivator, and pentamethyldiethylenetriamine ligand. Thus, SI-ATRP of AzEMA from the Au substrate (the "grafting from" process) and click chemistry of the ethynyl ferrocene to the azide functional group of AzEMA (the "grafting to" process) proceeded simultaneously to produce the functional PFTMA brushes on the Au surface. Kinetic studies suggest that the reaction involving simultaneous SI-ATRP and click chemistry is still consistent with a controlled/"living" process. The composition and physical properties of the modified gold surface were analyzed by X-ray photoelectron spectroscopy, water contact angle measurement, and cyclic voltammetry. The redox-responsive properties of the ferrocene-functionalized polymer brushes on the Au-g-PFTMA surface were demonstrated in the reversible loading-unloading step of the β-cyclodextrin polymer via host-guest interaction.

Attachment and detachment of bacteria on surfaces with tunable and switchable wettability

Controlling accumulations of unwanted biofilms requires an understanding of the mechanisms that organisms use to interact with submerged substrata. While the substratum properties influencing biofilm formation are well studied, those that may lead to cellular or biofilm detachment are not. Surface-grafted stimuli-responsive polymers, such as poly (N-isopropylacrylamide) (PNIPAAm) release attached cells upon induction of environmentally-triggered phase changes. Altering the physicochemical characteristics of such polymeric systems for systematically studying release, however, can alter the phase transition. The physico-chemical changes of thin films of PNIPAAm grafted from initiator-modified self-assembled monolayers (SAMs) of ω-substituted alkanethiolates on gold can be altered by changing the composition of the underlying SAM, without affecting the overlying polymer. This work demonstrates that the ability to tune such changes in substratum physico-chemistry allows systematic study of attachment and release of bacteria over a large range of water contact angles. Such surfaces show great promise for studying a variety of interactions at the biointerface. Understanding of the source of this tunability will require further studies into the heterogeneity of such films and further investigation of interactions beyond those of water wettability.

Characterization and molecular engineering of surface-grafted polymer brushes across the length scales by atomic force microscopy

With the advent of regulated, surface initiated polymerizations, specifically using controlled radical approaches, the choice of polymerizable compounds and the control over grafting chemistry have seen tremendous advancement. New analysis techniques and approaches are now needed to characterize these brushes with molecular precision. In addition, spatial structure control at the nanoscale, and tuning of thickness as well as composition of the brushes, have become feasible by utilizing recently developed enabling molecular nanofabrication approaches. Atomic force microscopy (AFM) is a powerful analytical tool for the characterization of polymer brushes, as well as for the fabrication of brush structures across the length scales. AFM has been used to investigate polymer brushes in a number of ways including imaging surface morphologies, measuring brush thickness, estimating the value of number average molar mass, observing stimulus responsive behavior and probing surface mechanical properties. In addition, AFM based methods such as nanoscratching, dip-pen nanolithography (DPN) and scanning probe oxidation (SPO) have been also employed for the nanofabrication of patterned polymer brushes. This feature article gives a short account of this field and highlights recent advances.

Selective solid-phase extraction of trace thorium(IV) using surface-grafted Th(IV)-imprinted polymers with pyrazole derivative

A new pyrazole derivative 1-phenyl-3-methylthio-4-cyano-5-acrylicacidcarbamoyl-pyrazole (PMTCAACP) was synthesized and chosen as a complexing monomer for the preparation of surface-grafted ion-imprinted polymers for selective solid-phase extraction of thorium(IV). The silica gel, modified with maleic anhydride, was prepared as a carrier material. In the ion-imprinting process, Th(IV) was complexed with PMTCAACP, and then imprinted in the polymers grafted to the surface of modified silica gel. Subsequently, the template Th(IV) ions were removed with 6 mol/L HCl solution. The obtained ion-imprinted particles for Th(IV) showed specific recognition, and rapid adsorption and desorption kinetics process. The maximum static and total dynamic adsorption capacity of the ion-imprinted polymers (IIPs) for Th(IV) was 64.8 and 37.4 mg/g, respectively. The relative selectivity coefficient values of the imprinted adsorbent for Th(IV)/U(VI), Th(IV)/Ce(III), Th(IV)/La(III), and Th(IV)/Zr(IV) were 72.9, 89.6, 93.8, and 137.2 times greater than non-imprinted matrix, respectively. The interference effect of common cations tested did not interfere with the recovery of Th(IV). The enhancement factor of 20.2, the detection limit of 0.43 microg/L, and the precision of 2.47% (n=7) of the method under the optimized conditions were obtained. Additionally, the calibration curve (r=0.9993) was linear in the range of 1.43-103 microg/L of thorium(IV). The prepared IIPs were shown to be promising for solid-phase extraction coupled with UV-vis spectrophotometry for determination of trace Th(IV) in real samples.

Interaction Forces and Reversible Collapse of a Polymer Brush-Gated Nanopore

Nanopores are ubiquitous in nature and technology, yet relatively little is known about how surface-grafted polymers can affect the interaction forces at the pore. By fabricating Au nanorings on Si substrates, we have constructed a unique experimental platform that allows for direct atomic force microscope (AFM) measurements to be made on polyethylene glycol (PEG) chains locally anchored onto a geometric pore surface. Force measurements show that the PEG gives rise to a steric repulsive barrier that envelops the entire nanoring, signifying polymer brush formation. This is confirmed by a direct imaging of the PEG brush, which reversibly collapses by switching between poor and good solvent conditions to "open" and "close" the pore, respectively. From the view of interaction forces, these results highlight possible functionalities in which polymer brushes may play a role in minimizing fouling/clogging effects in synthetic nanopores and biological nuclear pore complexes (NPCs). By the mechanism of a reversible collapse, this work illustrates how polymer brush-gated nanopores may be used as nonfouling sieves for small molecules and/or solvent-controlled chemical valves that regulate solute traffic.

Surface-initiated atom transfer radical polymerization—a technique to develop biofunctional coatings

The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer coatings is discussed briefly in order to provide a readily accessible survey. The potential for achieving a range of well-defined biofunctionalities, such as inhibition of non-specific fouling, immobilization of biomolecules, separation of proteins, adsorbents for proteins or cells, antibacterial activity, and encapsulation of drugs in particular provided by these surface-grafted polymers is described.

Controlled Nitroxide-Mediated Styrene Surface Graft Polymerization with Atmospheric Plasma Surface Activation

Polymer layer growth by free radical graft polymerization (FRGP) and controlled nitroxide-mediated graft polymerization (NMGP) of polystyrene was achieved by atmospheric pressure hydrogen plasma surface activation of silicon. Kinetic polystyrene layer growth by atmospheric pressure plasma-induced FRGP (APPI-FRGP) exhibited a maximum surface-grafted layer thickness (125 A after 20 h) at an initial monomer concentration of [M] 0 = 2.62 M at 85 degrees C. Increasing both the reaction temperature ( T = 100 degrees C) and initial monomer concentration ([M] 0 = 4.36 M) led to an increased initial film growth rate but a reduced polymer layer thickness, due to uncontrolled thermal initiation and polymer grafting from solution. Controlled atmospheric pressure plasma-induced NMGP (APPI-NMGP), using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), exhibited a linear increase in grafted polystyrene layer growth with time due to controlled surface graft polymerization as well as reduced uncontrolled solution polymerization and polymer grafting, resulting in a polymer layer thickness of 285 A after 60 h at [TEMPO] = 10 mM, [M] 0 = 4.36 M, and T = 120 degrees C. Atomic force microscopy (AFM) surface analysis demonstrated that polystyrene-grafted surfaces created by APPI-NMGP exhibited a high surface density of spatially homogeneous polymer features with a low root-mean-square (RMS) surface roughness ( R rms = 0.36 nm), similar to that of the native silicon surface ( R rms = 0.21 nm). In contrast, polymer films created by APPI-FRGP at [M] 0 = 2.62 M demonstrated an increase in polymer film surface roughness observed at reaction temperatures of 85 degrees C ( R rms = 0.55 nm) and 100 degrees C ( R rms = 1.70 nm). The present study concluded that the current approach to APPI controlled radical polymerization may be used to achieve a grafted polymer layer with a lower surface roughness and a higher fractional coverage of surface-grafted polymers compared to both conventional FRGP and APPI-FRGP.

Synthesis and applications of surface-grafted Th(IV)-imprinted polymers for selective solid-phase extraction of thorium(IV)

A new functional monomer N-( o-carboxyphenyl)maleamic acid (CPMA) was synthesized and chosen for the preparation of surface-grafted ion-imprinted polymers (IIPs) specific for thorium(IV). Polymerizable double bond was introduced to silica gel surface by amidation reaction between –NH 2 and maleic anhydride. In the ion-imprinting process, thorium(IV) was complexed with the carboxyl groups, then was imprinted in the polymers grafted to the silica gel surface. The imprinted Th(IV) was removed with 3 mol L −1 HCl. The obtained imprinted particles exhibited excellent selectivity and rapid kinetics process for Th(IV). The relatively selective factor ( α r) values of Th(IV)/La(III), Th(IV)/Ce(III), Th(IV)/Nd(III), Th(IV)/U(VI), and Th(IV)/Zr(IV) were 85.7, 88.9, 26.6, 64.4, and 433.8, respectively, which were greater than 1. The precision (R.S.D.), the detection limit (3 σ), and the quantification limit (10 σ) of the method were 1.9%, 0.51 ng mL −1 and 1.19 ng mL −1, respectively. The prepared IIPs as solid-phase extractants were successfully applied for the preconcentration of trace thorium in natural and certified samples prior to its determination by inductively coupled plasma atomic emission spectrometry (ICP-AES) with satisfactory results.

Reversibly cross-linked surface-grafted polymer brushes.

Reversibly cross-linked surface-grafted polymer brushes.

Modeling of Protein Interactions with Surface-Grafted Charged Polymers. Correlations between Statistical Molecular Modeling and a Mean Field Approach

Ion exchange media involving charge groups attached to flexible polymers are widely used for protein purification. Such media often provide enhanced target protein purity and yield. Yet, little is understood about protein interaction with such media at the molecular level, or how different media architectures might affect separation performance. To gain a better understanding of such adsorptive systems, statistical mechanical perturbation calculations, utilizing a Debye-Hückel potential, were performed on surface-grafted charged polymers and their interaction with model proteins. The studied systems were weakly charged, and the polymers were linear and relatively short (degree of polymerization is 30). Segment distributions from the surface were also determined. The interaction of spherical model protein particles of 12-30 A radius were investigated with respect to polymer grafting density, distance from matrix surface, protein charge, and ionic strength. The partitioning coefficient of the model proteins was determined for different distances from the surface. An empirical mean field theory that scales the entropy of the protein with the square of the protein radius correlates well to Monte Carlo statistical modeling results. Upon adsorption to the polymer layers, the model proteins exhibit a critical surface charge density that is proportional to the ionic strength, independent of the grafting density, and appears to be a fundamental determinant of protein adsorption. Partitioning of protein-like nanoparticles to the charged polymer surface is only favored above the particle critical charge density.

Reversible Switching of Microtubule Motility Using Thermoresponsive Polymer Surfaces

We report a novel approach for the dynamic control of gliding microtubule motility by external stimuli. Our approach is based on the fabrication of a composite surface where functional kinesin motor-molecules are adsorbed onto a silicon substrate between surface-grafted polymer chains of thermoresponsive poly(N-isopropylacrylamide). By external temperature control between 27 and 35 degrees C, we demonstrate the reversible landing, gliding, and releasing of motor-driven microtubules in response to conformational changes of the polymer chains. Our method represents a versatile means to control the activity of biomolecular motors, and other surface-coupled enzyme systems, in bionanotechnological applications.