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Commercial adhesives typically fall into two categories: structural or pressure sensitive. Structural glues rely on covalent bonds formed during curing and provide high tensile strength whilst pressure-sensitive adhesives use physical bonding to provide weaker adhesion, but with considerable convenience for the user. Here, a new class of adhesive is presented that is also reversible, with a bond strength intermediate between those of pressure-sensitive and structural adhesives. Complementary water-based formulations incorporating oppositely charged polyelectrolytes form electrostatic bonds that may be reversed through immersion in a low or high pH aqueous environment. This electrostatic adhesive has the advantageous property that it exhibits good adhesion to low-energy surfaces such as polypropylene. Furthermore, it is produced by the emulsion copolymerization of commodity materials, styrene and butyl acrylate, which makes it inexpensive and opens the possibility of industrial production. Bio-based materials have been also integrated into the formulations to further increase sustainability. Moreover, unlike other water-based glues, adhesion does not significantly degrade in humid environments. Because such electrostatic adhesives do not require mechanical detachment, they are appropriate for the large-scale recycling of, e.g., bottle labels or food packaging. The adhesive is also suitable for dismantling components in areas as varied as automotive parts and electronics.
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This Feature Article evaluates ongoing efforts to adapt adhesives toward the goal of zero-waste living and suggests the most promising future directions. Adhesives are not always considered in zero-waste manufacturing because they represent only a small fraction of a product and offer no additional functionality. However, their presence restricts the reintegration of constituent parts into a circular economy, so a new generation of adhesives is required. Furthermore, their production often leads to harmful pollutants. Here, two main approaches toward addressing these problems are considered: first, the use of natural materials that replace petroleum-based polymers from which conventional adhesives are made and second, the production of dismantlable adhesives capable of debonding on demand with the application of an external stimulus. These approaches, either individually or combined, offer a new paradigm in zero-waste industrial production and consumer applications.
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Adesivos , Indústrias , PolímerosRESUMO
I review experimental developments in the growth and application of surface-grafted weak polyelectrolytes (brushes), concentrating on their surface, tribological, and adhesive and bioadhesive properties, and their role as actuators.
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Polímeros , Polieletrólitos , Propriedades de SuperfícieRESUMO
Attachment assays of a Pseudomonas isolate to fused silica slides showed that treatment with DNaseI significantly inhibited cellular adsorption, which was restored upon DNA treatment. These assays confirmed the important role of extracellular DNA (eDNA) adsorption to a surface. To investigate the eDNA adsorption mechanism, single-molecule force spectroscopy (SMFS) was used to measure the adsorption of eDNA to silicon surfaces in the presence of different concentrations of sodium and calcium ions. SMFS reveals that the work of adhesion required to remove calcium-bound eDNA from the silicon oxide surface is substantially greater than that for sodium. Molecular dynamics simulations were also performed, and here, it was shown that the energy gain in eDNA adsorption to a silicon oxide surface in the presence of calcium ions is small and much less than that in the presence of sodium. The simulations show that the length scales involved in eDNA adsorption are less in the presence of sodium ions than those in the presence of calcium. In the presence of calcium, eDNA is pushed above the surface cations, whereas in the presence of sodium ions, short-range interactions with the surface dominate. Moreover, SMFS data show that increasing [Ca2+] from 1 to 10 mM increases the adsorption of the cations to the silicon oxide surface and consequently enhances the Stern layer, which in turn increases the length scale associated with eDNA adsorption.
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Fluorescence correlation spectroscopy was used to show that the temperature-dependent diffusion coefficient of poly(ethylene oxide) (PEO) adsorbed on polystyrene and different poly(alkyl methacrylate) (PAMA) films in aqueous solution exhibited a maximum close to (but below) the surface glass transition temperature, Tgs, of the film. This elevated diffusion was observed over a small range of temperatures below Tgs for these surfaces, and at other temperatures, the diffusion was similar to that on silicon, although the diffusion coefficient for PEO on polystyrene at temperatures above Tgs did not completely decrease to that on silicon, in contrast to the PAMA surfaces. It is concluded that the enhanced surface mobility of the films near the surface glass transition temperature induces conformational changes in the adsorbed PEO. The origin of this narrow and dramatic increase in diffusion coefficient is not clear, but it is proposed that it is caused by a coupling of a dominant capillary mode in the liquid surface layer with the polymer. Friction force microscopy experiments also demonstrate an unexpected increase in friction at the same temperature as the increase in diffusion coefficient.
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The presence of excited-states and charge-separated species was identified through UV and visible laser pump and visible/near-infrared probe femtosecond transient absorption spectroscopy in spin coated films of poly[N-9â³-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) nanoparticles and mesoparticles. Optical gain in the mesoparticle films is observed after excitation at both 400 and 610 nm. In the mesoparticle film, charge generation after UV excitation appears after around 50 ps, but little is observed after visible pump excitation. In the nanoparticle film, as for a uniform film of the pure polymer, charge formation was efficiently induced by UV excitation pump, while excitation of the low energetic absorption states (at 610 nm) induces in the nanoparticle film a large optical gain region reducing the charge formation efficiency. It is proposed that the different intermolecular interactions and molecular order within the nanoparticles and mesoparticles are responsible for their markedly different photophysical behavior. These results therefore demonstrate the possibility of a hitherto unexplored route to stimulated emission in a conjugated polymer that has relatively undemanding film preparation requirements.
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Carbazóis/química , Nanopartículas/química , Polímeros/química , Compostos de Enxofre/química , SemicondutoresRESUMO
Polyelectrolyte adhesives, either poly[2-(dimethylamino)ethyl methacrylate] or poly(methacrylic acid), functionalized with a surface-active calix[4]resorcinarene were grafted onto silicon wafers. Adhesion studies on these grafted-to brushes using polyelectrolyte hydrogels of opposite charge showed that it is the calix[4]resorcinarene, rather than adsorption of polyelectrolyte monomers, that adheres the brush to the silicon substrate. The adhesion measured was similar to that measured using polymers grafted from the surface, and was stronger than a control layer of poly(vinyl acetate) under the same test conditions. The limiting factor was determined to be adhesive failure at the hydrogel-brush interface, rather than the brush-silicon interface. Therefore, the adhesion has not been adversely affected by changing from a grafted-from to a grafted-to brush, demonstrating the possibility of a one-pot approach to creating switchable adhesives.
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Dynamic single-molecule force spectroscopy was performed to monitor the unbinding of fibronectin with the proteoglycans syndecan-4 (SDC4) and decorin and to compare this with the unbinding characteristics of α5ß1-integrin. A single energy barrier was sufficient to describe the unbinding of both SDC4 and decorin from fibronectin, whereas two barriers were observed for the dissociation of α5ß1-integrin from fibronectin. The outer (high-affinity) barriers in the interactions of fibronectin with α5ß1-integrin and SDC4 are characterized by larger barrier heights and widths and slower dissociation rates than those of the inner (low-affinity) barriers in the interactions of fibronectin with α5ß1-integrin and decorin. These results indicate that SDC4 and (ultimately) α5ß1-integrin have the ability to withstand deformation in their interactions with fibronectin, whereas the decorin-fibronectin interaction is considerably more brittle.
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Decorina/metabolismo , Fibronectinas/metabolismo , Integrina alfa5beta1/metabolismo , Sindecana-4/metabolismo , Sítios de Ligação , Decorina/química , Fibronectinas/química , Humanos , Integrina alfa5beta1/química , Ligação Proteica , Sindecana-4/química , TermodinâmicaRESUMO
Force spectroscopy was used to show that extracellular DNA (eDNA) has a pre-eminent structural role in a biofilm. The adhesive behavior of extracellular polymeric substances to poly(ethylene terephthalate), a model hydrophobic surface, was measured in response to their degradation by hydrolytic enzymes known for their biofilm dispersion potential: DNaseI, protease, cellulase, and mannanase. Only treatment with DNaseI significantly decreased the adhesive force of the model bacterium Micrococcus luteus with the surface, and furthermore this treatment almost completely eliminated any components of the biofilm maintaining the adhesion, establishing a key structural role for eDNA.
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Biofilmes , DNA Bacteriano/metabolismo , Espaço Extracelular/metabolismo , Micrococcus luteus/citologia , Micrococcus luteus/fisiologia , Aderência Bacteriana , Desoxirribonuclease I/metabolismo , Hidrólise , Polissacarídeos Bacterianos/metabolismoRESUMO
Small-angle neutron scattering (SANS) and neutron spin-echo (NSE) have been used to investigate the temperature-dependent solution behaviour of highly-branched poly(N-isopropylacrylamide) (HB-PNIPAM). SANS experiments have shown that water is a good solvent for both HB-PNIPAM and a linear PNIPAM control at low temperatures where the small angle scattering is described by a single correlation length model. Increasing the temperature leads to a gradual collapse of HB-PNIPAM until above the lower critical solution temperature (LCST), at which point aggregation occurs, forming disperse spherical particles of up to 60 nm in diameter, independent of the degree of branching. However, SANS from linear PNIPAM above the LCST is described by a model that combines particulate structure and a contribution from solvated chains. NSE was used to study the internal and translational solution dynamics of HB-PNIPAM chains below the LCST. Internal HB-PNIPAM dynamics is described well by the Rouse model for non-entangled chains.
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Following controlled photodeprotection of a 2-nitrophenylpropyloxycarbonyl-protected (aminopropyl)triethoxysilane (NPPOC-APTES) film and subsequent derivatization with a bromoester-based initiator, poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC) brushes with various grafting densities were grown from planar silicon substrates using atom transfer radical polymerization (ATRP). The grafting density correlated closely with the extent of deprotection of the NPPOC-APTES. The coefficient of friction for such PMPC brushes was measured by friction force microscopy in water and found to be inversely proportional to the grafting density due to the osmotic pressure that resists deformation. Deprotection of NPPOC-APTES via near-field photolithography using a range of writing rates enabled the fabrication of neighboring nanoscopic polymeric structures with dimensions ranging from 100 to 1000 nm. Slow writing rates enable complete deprotection to occur; hence, polymer brushes are formed with comparable thicknesses to macroscopic brushes grown under the same conditions. However, the extent of deprotection is reduced at higher writing rates, resulting in the concomitant reduction of the brush thickness. The coefficient of friction for such polymer brushes varied smoothly with brush height, with lower coefficients being obtained at slower writing rate (increasing initiator density) because the solvated brush layer confers greater lubricity. However, when ultrasharp probes were used for nanotribological measurements, the coefficient of friction increased with brush thickness. Under such conditions, the radius of curvature of the tip is comparable to the mean spacing between brush chains, allowing the probe to penetrate the brush layer leading to a relatively large contact area.
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The mechanical properties of Rhodococcus RC291 were measured using force spectroscopy equipped with a bacterial cell probe. Rhodococcal cells in the late growth stage of development were found to have greater adhesion to a silicon oxide surface than those in the early growth stage. This is because there are more extracellular polymeric substances (EPS) that contain nonspecific binding sites available on the cells of late growth stage. It is found that EPS in the late exponential phase are less densely bound but consist of chains able to extend further into their local environment, while the denser EPS at the late stationary phase act more to sheath the cell. Contraction and extension of the EPS could change the density of the binding sites, and therefore affect the magnitude of the adhesion force between the EPS and the silicon oxide surface. By treating rhodococcal EPS as a surface-grafted polyelectrolyte layer and using scaling theory, the interaction between EPS and a solid substrate was modelled for the cell approaching the surface which revealed that EPS possess a large capacity to store charge. Changing the pH of the surrounding medium acts to change the conformation of EPS chains.
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Polissacarídeos Bacterianos/química , Rhodococcus/química , Dióxido de Silício/química , Aderência Bacteriana , Sítios de Ligação , Concentração de Íons de Hidrogênio , Microscopia de Força Atômica , Conformação Molecular , Sondas Moleculares/química , Polilisina/química , Eletricidade Estática , Propriedades de SuperfícieRESUMO
A quantitative investigation of the responses of surface-grown biocompatible brushes of poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) to different types of salt has been carried out using ellipsometry, quartz crystal microbalance (QCM) measurements, and friction force microscopy. Both cations and anions of varying valency over a wide range of concentrations were examined. Ellipsometry shows that the height of the brushes is largely independent of the ionic strength, confirming that the degree of swelling of the polymer is independent of the ionic character of the medium. In contrast, QCM measurements reveal significant changes in mass and dissipation to the PMPC brush layer, suggesting that ions bind to phosphorylcholine (PC) groups in PMPC molecules, which results in changes in the stiffness of the brush layer, and the binding affinity varies with salt type. Nanotribological measurements made using friction force microscopy show that the coefficient of friction decreases with increasing ionic strength for a variety of salts, supporting the conclusion drawn from QCM measurements. It is proposed that the binding of ions to the PMPC molecules does not change their hydration state, and hence the height of the surface-grown polymeric brushes. However, the balance of the intra- and intermolecular interactions is strongly dependent upon the ionic character of the medium between the hydrated chains, modulating the interactions between the zwitterionic PC pendant groups and, consequently, the stiffness of the PMPC molecules in the brush layer.
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For environmentally-switchable adhesive systems to be reused repeatedly, the adhesive strength must not deteriorate after each adhesion cycle. An important criterion to achieve this goal is that the integrity of the interface must be retained after each adhesion cycle. Furthermore, in order to have practical benefits, reversing the adhesion must be a relatively rapid process. Here, a double-network hydrogel of poly(methacrylic acid) and poly[oligo(ethylene glycol)methyl ether methacrylate] is shown to undergo adhesive failure during pH-switchable adhesion with a grafted (brush) layer of polycationic poly[2-(diethyl amino)ethyl methacrylate], and can be reused at least seven times. The surfaces are attached at pH 6 and detached at pH 1. A single-network hydrogel of poly(methacrylic acid), also exhibits pH-switchable adhesion with poly[2-(diethyl amino)ethyl methacrylate] but cohesive failure leads to an accumulation of the hydrogel on the brush surface and the hydrogel can only be reused at different parts of that surface. Even without an environmental stimulus (i.e. attaching and detaching at pH 6), the double-network hydrogel can be used up to three times at the same point on the brush surface. The single-network hydrogel cannot be reused under such circumstances. Finally, the time taken for the reuse of the double-network hydrogel is relatively rapid, taking no more than an hour to reverse the adhesion.
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Fluorescence spectroscopy on a series of aqueous solutions of poly(acrylic acid) containing a luminescent label showed that polymers with molar mass, Mn < 16.5 kDa did not exhibit a pH responsive conformational change, which is typical of higher molar mass poly(acrylic acid). Below this molar mass, polymers remained in an extended conformation, regardless of pH. Above this molar mass, a pH-dependent conformational change was observed. Diffusion-ordered nuclear magnetic resonance spectroscopy confirmed that low molar mass polymers did not undergo a conformational transition, although large molar mass polymers did exhibit pH-dependent diffusion.
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Measurements have been performed on thermally equilibrated conjugated-polymer/insulating-polymer bilayers, using specular and off-specular neutron reflectivity. While specular reflectivity is only sensitive to the structure normal to the sample, off-specular measurements can probe the structure of the buried polymer/polymer interface in the plane of the sample. Systematic analysis of the scattering from a set of samples with varying insulating-polymer-thickness, using the distorted-wave Born approximation (DWBA), has allowed a robust determination of the intrinsic width at the buried polymer/polymer interface. The quantification of this width (12 Å ± 4 Å) allows us to examine aspects of the conjugated polymer conformation at the interface, by appealing to self-consistent field theory (SCFT) predictions for equilibrium polymer/polymer interfaces in the cases of flexible and semi-flexible chains. This analysis enables us to infer that mixing at this particular interface cannot be described in terms of polymer chain segments that adopt conformations similar to a random walk. Instead, a more plausible explanation is that the conjugated polymer chain segments become significantly oriented in the plane of the interface. It is important to point out that we are only able to reach this conclusion following the extensive analysis of reflectivity data, followed by comparison with SCFT predictions. It is not simply the case that conjugated polymers would be expected to adopt this kind of oriented conformation at the interface, because of their relatively high chain stiffness. It is the combination of a high stiffness and a relatively narrow intrinsic interfacial width that results in a deviation from flexible chain behaviour.
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The temperature and pH-dependent diffusion of poly(glycerol monomethacrylate)-block-poly(2-hydroxypropyl methacrylate) nanoparticles prepared via polymerization-induced self-assembly in water is characterized using fluorescence correlation spectroscopy (FCS). Lowering the solution temperature or raising the solution pH induces a worm-to-sphere transition and hence an increase in diffusion coefficient by a factor of between four and eight. FCS enables morphological transitions to be monitored at relatively high copolymer concentrations (10% w/w) compared to those required for dynamic light scattering (0.1% w/w). This is important because such transitions are reversible at the former concentration, whereas they are irreversible at the latter. Furthermore, the FCS data suggest that the thermal transition takes place over a very narrow temperature range (less than 2 °C). These results demonstrate the application of FCS to characterize order-order transitions, as opposed to order-disorder transitions.
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Polímeros/química , Espectrometria de Fluorescência/métodos , Água/químicaRESUMO
The frictional behaviour of end-grafted poly[2-(dimethyl amino)ethyl methacrylate] films (brushes) has been shown by friction force microscopy to be a strong function of pH in aqueous solution. Data were acquired using bare silicon nitride and gold-coated tips, and gold coated probes that were functionalized by the deposition of self-assembled monolayers. At the extremes of pH (pH = 1, 2, and 12), the friction-load relationship was found to be linear, in agreement with Amontons' law of macroscopic friction. However, at intermediate pH values, the data were fitted by single asperity contact mechanics models; both Johnson-Kendall-Roberts (JKR) and Derjaguin-Muller-Toporov models were observed, with JKR behaviour fitting the data better at relatively neutral pH.
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Metacrilatos/química , Nylons/química , Poliaminas/química , Concentração de Íons de Hidrogênio , PolieletrólitosRESUMO
Friction force microscopy has been used to demonstrate that biocompatible, lubricious poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC) brushes exhibit different frictional properties depending on the medium (methanol, ethanol, 2-propanol, and water; the latter also with different quantities of added salt). The chemical functionalization of the probe (amine-, carboxylic acid-, and methyl-terminated probes were used) is not as important as the medium in determining the contact mechanics. For solvents such as methanol, where the adhesion between AFM probe and PMPC brushes is negligible, a linear friction-load relationship is observed. In contrast, the friction-load plot is nonlinear in ethanol or water, media in which stronger adhesion is measured. For ethanol, the data indicate Johnson-Kendall-Roberts (JKR) mechanics, whereas the Derjaguin-Muller-Toporov (DMT) model provided a good fit for the data acquired in water. Contact mechanics on zwitterionic PMPC brushes immersed in aqueous solutions of varying ionic strength followed the same trend, with high adhesion energies being correlated with a nonlinear friction-load relationship. These results can be rationalized by treating the friction force as the sum of a load-dependent term, attributed to molecular plowing, and an area-dependent shear term. In a good solvent for PMPC such as methanol, the shear term is negligible and the sliding interaction is dominated by molecular plowing. However, the adhesion energy is significantly larger in water and ethanol and the shear term is no longer negligible.
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Materiais Biocompatíveis/química , Polímeros/química , Fricção , Microscopia de Força Atômica , Modelos Teóricos , Propriedades de SuperfícieRESUMO
We have studied the pH-dependent interaction between mycolic acid (MA) monolayers and hydrophobic and hydrophilic surfaces using molecular (colloidal probe) force spectroscopy. In both cases, hydrophobic and hydrophilic monolayers (prepared by Langmuir-Blodgett and Langmuir-Schaefer deposition on silicon or hydrophobized silicon substrates, respectively) were studied. The force spectroscopy data, fitted with classical DLVO (Derjaguin, Landau, Verwey, and Overbeek) theory to examine the contribution of electrostatic and van der Waals forces, revealed that electrostatic forces are the dominant contribution to the repulsive force between the approaching colloidal probe and MA monolayers. The good agreement between data and the DLVO model suggest that beyond a few nm away from the surface, hydrophobic, hydration, and specific chemical bonding are unlikely to contribute to any significant extent to the interaction energy between the probe and the surface. The pH-dependent conformation of MA molecules in the monolayer at the solid-liquid interface was studied by ellipsometry, neutron reflectometry, and with a quartz crystal microbalance. Monolayers prepared by the Langmuir-Blodgett method demonstrated a distinct pH-responsive behaviour, while monolayers prepared by the Langmuir-Schaefer method were less sensitive to pH variation. It was found that the attachment of water molecules plays a vital role in determining the conformation of the MA monolayers.