Direct nanopatterning of silsesquioxane/poly(ethylene glycol) blends with high stability and nonfouling properties

A free‐radical‐polymerizable SSQ/PEG blend with direct patternability has been proposed as an ideal nonfouling material for nanostructure‐based biomedical applications. Cured SSQ/PEG networks show an UV transparency of >90% at 365 nm, high resistance to organic/aqueous solutions, hydrophilicity and Young's moduli of 1.898–2.815 GPa. SSQ/PEG patterns with 25‐nm linewidths, 25‐nm spacing, and an aspect ratio of 4:1 were directly fabricated on transparent substrates by UV embossing, and cured SSQ/PEG networks with long‐term stability under chemical, thermal, and biological stress showed strong resistance to the nonspecific adsorption of biomolecules. These characteristics may offer a new strategy for the development of a number of medical nanodevice applications such as labs‐on‐a‐chip.

     

Direct force measurement of the stability of poly(ethylene glycol)-polyethylenimine graft films

The stability and passivity of poly(ethylene glycol)-polyethylenimine (PEG-PEI) graft films are important for their use as antifouling coatings in a variety of biotechnology applications. We have used AFM colloidal-probe force measurements combined with optical reflectometry to characterize the surface properties and stability of PEI and dense PEG-PEI graft films on silica. Initial contact between bare silica probes and PEI-modified surfaces yields force curves that exhibit a long-range electrostatic repulsion and short-range attraction between the surfaces, indicating spontaneous desorption of PEI in the aqueous medium. Further transfer of PEI molecules to the probe occurs with subsequent application of forces between FR = 300 and 500 microN/m. The presence of PEG reduces the adhesive properties of the PEI surface and prevents transfer of PEI molecules to the probe with continuous contact, though an initial desorption of PEI still occurs. Glutaraldehyde crosslinking of the graft films prevents both the initial desorption and subsequent transfer of the PEI, resulting in sustained attractive interaction forces of electrostatic origin between the negatively charged probe and the positively charged copolymer graft films.     

Investigation of the hydration of nonfouling material poly(ethylene glycol) by low-field nuclear magnetic resonance

The strong surface hydration layer of nonfouling materials plays a key role in their resistance to nonspecific protein adsorption. Poly(ethylene glycol) (PEG) is an effective example of materials that can resist nonspecific protein adsorption and cell adhesion. Thus, the strong interaction between water molecules and PEG was investigated through each T(2) component in water/PEG mixtures using multiexponential inversion of T(2) relaxation time measured by the Carr-Purcell-Meiboom-Gill (CPMG) sequence of low-field nuclear magnetic resonance (LF-NMR). Results show that about one water molecule is tightly bound with one ethylene glycol (EG) unit, and additional water molecules over 1:1 ratio mainly swell the PEG matrix and are not tightly bound with PEG. This result was also supported by the endothermic behavior of water/PEG mixtures measured by differential scanning calorimetry (DSC). It is believed that the method developed could be also applied to investigate various interactions between macromolecules and other small molecules without using deuterium samples, which might open a novel route to quantitatively measure guest-host interactions in the future.     

Crystal growth rate in ultrathin films of poly(ethylene oxide)

Many dynamical properties of polymers, including segmental relaxation and chain diffusion, exhibit anomalies in thin‐film samples. We extend the studies of thin‐film dynamics to the case of semicrystalline polymers and present a study of the crystal growth rate for thin films of poly(ethylene oxide). We used optical microscopy and quartz crystal microbalance techniques to characterize the kinetics of crystallization for films with thicknesses from 40 to 1000 nm for a range of temperatures near the melting point. A remarkable slowing down of the crystal growth is observed at all temperatures studied for films with a thickness of less than ～100 nm. The results can be used to suggest reductions of the mobility of chains at the crystal/amorphous interface. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2615–2621, 2001     

Morphology of ultrathin polymer films based on poly(ethylene oxide) blends

The structure of ultrathin (15–200 nm) films of two types prepared from polymer blends based on PEO (the crystallizable component), namely, PEO-poly(arylene sulfone oxide) (the amorphous component) and PEO-PB (the amorphous component), has been studied by atomic force microscopy. The content of PEO in both blends is 76 wt %. Ultrathin blend films have been applied on a Si substrate via substrate dipping into dilute solutions of polymer blends in chloroform at room temperature. The rate of the substrate lift has been varied from 0.1 to 1 mm/min. The amorphous-amorphous separation takes place during formation of ultrathin films of the above blends in the course of the substrate lift at the stage of gelation. The crystallization of PEO and dewetting in the resulting two-phase blend gels depend on the rate of the substrate lift and the rigidity of macromolecules of the amorphous component. Moreover, the predominant interaction of the substrate with one of the components plays a significant role in structure formation of ultrathin films of both polymer blends.     

Synthesis and characterization of ultrathin WO3 nanodisks utilizing long-chain poly(ethylene glycol)

Metal oxide nanostructures hold great potential for photovoltaic (PV), photoelectrochemical (PEC), and photocatalytic applications. Whereas thin films of various materials of both nanoparticle and nanorod morphologies have been widely investigated, there have been few inquiries into nanodisk structures. Here, we report the synthesis of ultrathin WO3 nanodisks using a wet chemical route with poly(ethylene glycol) (PEG) as a surface modulator. The reported nanodisk structure is based on the interaction of the nonionic 10000 g/mol PEG molecules with tungsten oxoanion precursors. The WO3 nanostructures formed are dominated by very thin disks with dimensions on the nanometer to micrometer scale. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images reveal the structures to have dimensions on the order of 350-1000 nm in length, 200-750 nm in width, and 7-18 nm in thickness and possessing textured single-crystalline features. A number of analytical techniques were used to characterize the WO3 nanodisks, including selected-area electron diffraction (SAED), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), Raman scattering spectroscopy, UV-visible spectrophotometry, and cyclic voltammetry (CV). The growth of the WO3 nanodisks was inhibited in the [010] crystal direction, leading to ultrathin morphologies in the monoclinic crystal phase. The large flat surface area and high aspect ratio of the WO3 nanodisks are potentially useful in PEC cells for hydrogen production via direct water splitting, as has been demonstrated in a preliminary experiment with external bias.     

Protein adhesion on silicon-supported hyperbranched poly(ethylene glycol) and poly(allylamine) thin films

Hyperbranching poly(allylamine) (PAAm) and poly(ethylene glycol) (PEG) on silicon and its effect on protein adhesion was investigated. Hyperbranching involves sequential grafting of polymers on a surface with one of the components having multiple reactive sites. In this research, PAAm provided multiple amines for grafting PEG diacrylate. Current methodologies for generating PEG surfaces include PEG-silane monolayers or polymerized PEG networks. Hyperbranching combines the nanoscale thickness of monolayers with the surface coverage afforded by polymerization. A multistep approach was used to generate the silicon-supported hyperbranched polymers. The silicon wafer surface was initially modified with a vinyl silane followed by oxidation of the terminal vinyl group to present an acid function. Carbodiimide activation of the surface carboxyl group allowed for coupling to PAAm amines to form the first polymer layer. The polymers were hyperbranched by grafting alternating PEG and PAAm layers to the surface using Michael addition chemistry. The alternating polymers were grafted up to six total layers. The substrates remained hydrophilic after each modification. Static contact angles for PAAm (32-44 degrees) and PEG (33-37 degrees) were characteristic of the corresponding individual polymer (30-50 degrees for allylamine, 34-42 degrees for PEG). Roughness values varied from approximately 1 to 8 nm, but had no apparent affect on protein adhesion. Modifications terminating with a PEG layer reduced bovine serum albumin adhesion to the surface by approximately 80% as determined by ELISA and radiolabel binding studies. The hyperbranched PAAm and PEG surfaces described in this paper are nanometer-scale, multilayer films capable of reducing protein adhesion.     

Influence of copolymeric poly(diethylene glycol) terephthalate on the thermal stability of poly(ethylene terephthalate)

Copolymers of poly(ethylene terephthalate) (PET) containing 1–24% poly(diethylene glycol)terephthalate (PDEGT) were prepared and characterized by infrared spectra. The energy and entropy of activation for the thermal degradation were measured for these copolymers and for the PDEGT. These activation energies and energies and entropies were found to decrease steadily with increasing diethylene glycol content. From these measurements the mechanism of degradation of PDEGT was found to be different from that of PET. Fibers prepared from seven different copolymeric compositions were heat-aged at 121°C and 204°C for 24 hr. From the changes observed in intrinsic viscosity, per cent ether, hydroxyl and carboxyl endgroups during heat aging it became apparent that the mechanisms for decomposition are operative below melt temperatures and can rapidly destroy such copolymers.     

Hofmeister effects on the colloidal stability of poly(ethylene glycol)-decorated nanoparticles

The colloidal stability of poly(ethylene glycol)-decorated poly(methyl methacrylate), PMMA/Tween-20, particles was investigated by means of phase separation measurements, in the presence of sodium fluoride (NaF), sodium chloride, sodium bromide, sodium nitrate, or sodium thiocyanate (NaSCN) at 1.0?mol?L^?1. Following Hofmeister's series, the dispersions of PMMA/Tween-20 destabilized faster in the presence of NaF than with NaSCN. After the phase separation, the systems were homogenized and except for the dispersions in NaF, re-dispersed particles took longer to destabilize, indicating that anions adsorbed on the particles, creating a new surface. Except for F^? ions, the adsorption of anions on the polar outmost shell was evidenced by means of tensiometry and small-angle X-ray scattering measurements. Fluoride ions induced the dehydration of the polar shell, without affecting the polar shell electron density, and the formation of very large aggregates. A model was proposed to explain the colloidal behavior in the presence of Hofmeister ions.     

Segmented block copolymers of poly(ethylene glycol) and poly(ethylene terephthalate)

A new series of segmented copolymers were synthesized from poly(ethylene terephthalate) (PET) oligomers and poly(ethylene glycol) (PEG) by a two‐step solution polymerization reaction. PET oligomers were obtained by glycolysis depolymerization. Structural features were defined by infrared and nuclear magnetic resonance (NMR) spectroscopy. The copolymer composition was calculated via ¹H NMR spectroscopy. The content of soft PEG segments was higher than that of hard PET segments. A single glass‐transition temperature was detected for all the synthesized segmented copolymers. This observation was found to be independent of the initial PET‐to‐PEG molar ratio. The molar masses of the copolymers were determined by gel permeation chromatography (GPC). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4448–4457, 2004     

Dense passivating poly(ethylene glycol) films on indium tin oxide substrates

We describe the formation and characterization of surface-passivating poly(ethylene glycol) (PEG) films on indium tin oxide (ITO) glass substrates. PEG chains with a molecular weight of 2000 and 5000 D were covalently attached to the substrates in a systematic approach using different coupling schemes. The coupling strategies included the direct grafting with PEG-silane, PEG-methacrylate, and PEG-bis(amine), as well as the two-step functionalization with aldehyde-bearing silane films and subsequent coupling with PEG-bis(amine). Elemental analysis by X-ray photoelectron spectroscopy (XPS) confirmed the successful surface modification, and XPS and ellipsometry provided values for film thicknesses. XPS and ellipsometry thickness values were almost identical for PEG-silane films but differed by up to 400% for the other PEG layers, suggesting a homogeneous layer for PEG-silane but an inhomogeneous distribution for other PEG coatings on the molecularly rough ITO substrates. Atomic force microscopy (AFM) and water contact angle goniometry confirmed the different degrees of surface homogeneity of the polymer films, with PEG-silane reducing the AFM rms surface roughness by 50% and the water contact angle hysteresis by 75% compared to uncoated ITO. The ability of the PEG layers to passivate the substrate against the nonspecific adsorption of biopolymers was tested using fluorescence-labeled immunoglobulin G and DNA oligonucleotides in combination with fluorescence microscopy. The results indicate a positive relationship between film density and homogeneity on one hand and the ability to passivate against biopolymer adhesion on the other hand. The most homogeneous layers prepared with PEG-silane reduced the nonspecific adsorption of fluorescence-labeled DNA by a factor of 300 compared to uncoated ITO. In addition, the study finds that the ratio of film thicknesses derived by ellipsometry and XPS is a useful parameter to quantify the structural integrity of PEG layers on molecularly rough ITO surfaces. The findings may be applied to characterize PEG or other polymeric films on similarly coarse substrates.     

Effect of poly(ethylene glycol) on the dielectric properties of poly(vinylidene fluoride)/BiFeO<Subscript>3</Subscript>/poly(ethylene glycol) composite films for electronic applications

In the present work a series of poly(vinylidene fluoride)/BiFeO₃/poly(ethylene glycol) composite films were prepared by solvent casting method with poly(vinylidene fluoride) as polymer matrix, bismuth ferrite as ceramic filler and poly(ethylene glycol) as binding agent as well as enhancer. The structural analysis of the composite films by X-ray diffraction confirms that the composites have a distorted rhombohedral structure. The micro-structural analysis shows that the use of poly(ethylene glycol)in the composite films enhances the homogeneity as well as compatibility of BiFeO₃ particles within the poly(vinylidene fluoride) matrix. The dielectric and electrical study done by impedance analyzer reveals that with an increase in poly(ethylene glycol) concentration, there is a subsequent increase in dielectric constant as well as AC electrical conductivity. Finally, the ferroelectric behavior of the composite confirms that the ferroelectric properties of the composites are enhanced by the addition of BiFeO₃ with an increase in poly(ethylene glycol) concentrations. These preliminary results give an idea for possible applications of this type of composites in the field of electronic applications.     

Antifouling properties of poly(methyl methacrylate) films grafted with poly(ethylene glycol) monoacrylate immersed in seawater

Biofouling of all structures immersed in seawater constitutes an important problem, and many strategies are currently being developed to tackle it. In this context, our previous work shows that poly(ethylene glycol) monoacrylate (PEGA) macromonomer grafted on preoxidized poly(methyl methacrylate) (PMMAox) films exhibits an excellent repellency against the bovine serum albumin used as a model protein. This study aims to evaluate the following: (1) the prevention of a marine extract material adsorption by the modified surfaces and (2) the antifouling property of the PEGA-g-PMMAox substrates when immersed in natural seawater during two seasons (season 1: end of April-beginning of May 2007, and season 2: end of October-beginning of November 2007). The antifouling performances of the PEGA-g-PMMAox films are investigated for different PEG chain lengths and macromonomer concentrations into the PEGA-based coatings. These two parameters are followed as a function of the immersion time, which evolves up to 14 days. The influence of the PEGA layer on marine compounds (proteins and phospholipids) adsorption is evidenced by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). It was found that the antifouling efficiency of the PEGA-grafted surfaces increases with both PEGA concentration and PEG chain length.     

Electrosyntheses of poly(2,3-benzofuran) films in boron trifluoride diethyl etherate containing poly(ethylene glycol) oligomers

Visible-light transparent high-quality substrate-supported poly(2,3-benzofuran) (PBF) film has been successfully electrosynthesized by direct anodic oxidation of 2,3-benzofuran on stainless steel sheet in boron trifluoride diethyl etherate (BFEE) containing 10% poly(ethylene glycol) (PEG) with molar mass of 400 (by volume). The oxidation potential of 2,3-benzofuran in this medium was measured to be only 1.0 V vs. SCE, which is lower than that determined in acetonitrile + 0.1 M Bu₄NBF₄ (1.2 V vs. SCE). The PBF films obtained in this media showed good electrochemical behaviors and good thermal stability with conductivity of 10⁻² S cm⁻¹, and the doping level of as-prepared PBF films was determined to be only 8.9%. The structure and morphology of the polymer were investigated by UV-vis, infrared spectroscopy and scanning electron microscopy (SEM), respectively. To the best of our knowledge, this is the first case for the syntheses of PBF films.     

Oriented growth of TS-1 zeolite ultrathin films on poly(ethylene oxide) monolayer templates

Self-assembled monolayers of poly(ethylene oxide) (PEOM) were used as templates to direct the nucleation and subsequent oriented growth of TS-1 zeolite thin films. The resulting TS-1 zeolite thin films exhibited completely oriented crystalline domains with the 010 crystallographic direction parallel to the surface normal with a little deformation in the in-plane direction. Remarkably, the correlation length of the film is as extremely large as 1700 A (1200 A) in the out-of-plane (in-plane) direction. PEOM act as two-dimensional media for the nucleation and growth of highly oriented TS-1 zeolite thin films. This study demonstrates that the highly oriented TS-1 thin films can be achieved by using the inner parts of PEOM as templates.     

Synthesis and characterization of poly(ethylene glycol) methyl ether endcapped poly(ethylene terephthalate)

Linear and branched poly(ethylene terephthalate) (PET) copolymers with polyethylene glycol) (PEG) methyl ether (700 or 2000 g/mol) end groups were synthesized using conventional melt polymerization. DSC analysis demonstrated that low levels of PEG end groups accelerated PET crystallization. The incorporated PEG end groups also decreased the crystallization temperature of PET dramatically, and copolymers with a high content of PEG (>17.6 wt%) were able to crystallize at room temperature. Rheological analysis demonstrated that the presence of PEG end groups effectively decreased the melt viscosities and facilitated melt processing. XPS and ATR-FTIR revealed that the PEG end groups tended to aggregate on the surface, and the surface of compression molded films containing 34.0 wt% PEG were PEG rich (85 wt% PEG). PEG end-capped PET (34.0 wt% PEG) and PET films were immersed into a fibrinogen solution (0.7 mg/mL BSA) for 72 h to investigate the propensity for protein adhesion. XPS demonstrated that the concentration of nitrogen (1.05%) on the surface of PEG endcapped PET film was statistically lower than PET (7.67%). SEM analysis was consistent with XPS results, and revealed the presence of adsorbed protein on the surface of PET films.     

Infrared spectroscopic study of solid films of poly(ethylene glycol) doped with cations

The infrared spectra of solid films, prepared on a silicon plate of poly(ethylene glycol) doped with various cations (Li⁺, Na⁺, K⁺, Ca²⁺ and Ba²⁺), have been measured. The spectral analysis indicates that the films are non-crystalline and essentially amorphous. The polymer chain is significantly disordered by assuming diverse conformational states. The interaction between the ether oxygens of the polymer and the cation, as estimated from the C---O stretching wavenumber, is correlated to the size of the cation; the interaction is stronger for the cation with larger size.     

Surface modification of polyethersulfone membranes by blending triblock copolymers of methoxyl poly(ethylene glycol)-polyurethane-methoxyl poly(ethylene glycol)

The surface of polyethersulfone (PES) membrane was modified by blending triblock copolymers of methoxyl poly(ethylene glycol)-polyurethane-methoxyl poly(ethylene glycol) (mPEG-PU-mPEG), which were synthesized through solution polymerization with mPEG Mns of 500 and 2000, respectively. The PES and PES/mPEG-PU-mPEG blended membranes were prepared through spin coating coupled with liquid-liquid phase separation. FTIR and (1)H NMR analysis confirmed that the triblock copolymers were successfully synthesized. The functional groups and morphologies of the membranes were studied by ATR-FTIR and SEM, respectively. It was found that the triblock copolymers were blended into PES membranes successfully, and the morphologies of the blended membranes were somewhat different from PES membrane. The water contact angles and platelet adhesion were decreased after blending mPEG-PU-mPEG into PES membranes. Meanwhile, the activated partial thromboplastin time (APTT) for the blended membranes increased. The anti-protein-fouling property and permeation property of the blended membranes improved obviously. SEM observation and 3-(4, 5-Dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay proved the surfaces of the blended membranes promoted human hepatocytes adhesion and proliferation better than PES membrane.     

Vibrational analysis of molten poly(ethylene glycol)

The infrared absorption of poly(ethylene glycol) was measured in the molten state. Characteristic bands of the molten state were identified. Normal vibrations and frequency distributions were treated for various conformation models with CH₂CH₂O repeat units. The infrared absorption peaks of the molten state closely correspond to the frequency distribution peaks of the TGT conformation with gauche O? CH₂? CH₂? O groups, although infrared bands due to trans O? CH₂? CH₂? O groups are also observed. Vibrational assignments of the infrared bands and Raman lines were made on the basis of potential energy distributions.     

Crystallization of photo-chain extended poly(ethylene glycol)

Coumarin-functionalized poly(ethylene glycol) (PEG) monols and diols were isothermally crystallized at temperatures between 20 and 35 °C before and after exposure to approximately 110 J cm⁻² of ultra-violet A (λ > 300 nm, UVA) irradiation. Irradiation dimerized the coumarin groups and chain-extended the coumarin-functionalized PEG oligomers. The higher molecular weights reduced the crystal growth rate by as much as 50% compared to the non-irradiated coumarin-functionalized PEG oligomers under ambient crystallization conditions. Hoffman’s kinetic nucleation theory was utilized to evaluate the types of nucleation that occurred for the coumarin-functionalized PEG diols (COU-PEG-COU). Crystallization regimes II and III were observed for the coumarin-modified PEG oligomers before and after exposure to UVA light.