Mass fabrication of size-controllable hydrogel microarrays by dip-pen nanolithography with viscosity-tunable ink

A method of mass fabricating poly(ethylene glycol) (PEG) hydrogel microarrays is demonstrated. Microarrays of poly(ethylene glycol) dimethacrylate (PEG-DMA) with photoinitiator were patterned by one-dimensional (1-D) parallel dip-pen nanolithography (DPN), and the microarrays were cross-linked to form PEG hydrogels by UV irradiation in N₂ air. As an ink material for DPN printing, solid and liquid phase of PEG-DMA were mixed and prepared to tune viscosity of the ink material by temperature. Thus, the diameter of the microarrays was able to be averagely controlled from 1.7 to 6.2 μm as temperature during printing was increased from 25 °C to 37 °C, respectively. The overall microarrays showed less than 16% coefficient of variation (C.V.). Moreover, small molecules, such as fluorescence dyes, were able to be embedded in the PEG hydrogel microarrays.     

Influence of Mass Ratio of Polyols on Properties of Polycaprolactone-Polyethylene Glycol/Methylene Diphenyl Diisocyanate/Diethylene Glycol Hydrogels

Polyurethane (PU) hydrogels with good hydrophilicity and biocompatibility have been applied as biomedical materials. A series of polyurethane prepolymers based on methylene diphenyl diisocyanate (MDI), polycaprolactone (PCL) and polyethylene glycol (PEG), using diethylene glycol (DEG) as the chain-extender, were synthesized; then the polyurethane hydrogels were obtained from the prepolymers using benzoyl peroxide (BPO) as a cross-linker by free radical polymerization. The influences of the ratio of polyols (PCL and PEG) on the contact angle, swelling ratio and morphology of the polyurethane hydrogel were investigated. The loading capacity and release behavior of chloramphenicol from the PCL-PEG/MDI/DEG hydrogels with different compositions were also studied. The contact angle and swelling degree results showed that the PCL-PEG/MDI/DEG hydrogel with PCL/PEG mass ratio of 3:1 had higher hydrophilicity than that with PCL/PEG mass ratios of 1:1 and 1:3. All PCL-PEG/MDI/DEG hydrogels showed three dimensional porous structures; however, the pore size increased with increasing PEG content. The chloramphenicol release kinetics from PCL-PEG/MDI/DEG hydrogels indicated Fickian diffusion, and the drug release rate increased with increasing PEG content in the PU hydrogels.     

Preparation of PVDF Microfiltration Membranes with Thermo-responsive PNIPAM Hydrogel Composite Particles

Silica-core composite particles with poly(N-isopropylacrylamide) (PNIPAM) hydrogel-shell were prepared by using silica microparticle templates, which were modified with [3-(methacryloxy)propyl]trimethoxysilane (MPS). The thermo-responsive PNIPAM hydrogel microcapsules were prepared by soaking the core–shell composite particles in hydrofluoric acid solution. These hydrophilic PNIPAM hydrogel microcapsules were applied to poly(vinylidene fluoride) (PVDF) microfiltration membranes in order to control the hydrophobicity of membrane surface without sacrificing the permeability. PVDF/PNIPAM hydrogel composite membranes were made by phase inversion and diffusion in the mixed solvents of N-methyl-2-pyrrolidone (NMP) and ethylene glycol monomethyl ether (EGME) with polyethylene glycol 600 (PEG 600) as plasticizer.     

Preparation and Properties of Polyurethane Hydrogels Based on Hexamethylene Diisocyanate/Polycaprolactone-Polyethylene Glycol

Hydrogels are considered an optimum material for controlled release drug systems and tissue engineering scaffolds since they are tri-dimensional networks. In this work hexamethylene diisocyanate (HMDI), polycaprolactone (PCL) and polyethylene glycol (PEG) were used to prepare polyurethane prepolymers using diethylene glycol (DEG) as a chain-extender. Then the prepolymer was used to fabricate the HMDI/PCL-PEG/DEG polyurethane hydrogels by free radical polymerization using benzoyl peroxide (BPO) as a cross-linking agent. The influences of the ratio of polyol on the contact angle, swelling ratio, morphology and cytotoxicity in-vitro of the HMDI/PCL-PEG/DEG polyurethane hydrogel were investigated. The biological behavior of the polyurethane hydrogels was analyzed by studying the cell behavior using the standard biological MTT (3–4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2-H-tetrazolium bromide) test. The Fourier transform infrared (FTIR) spectra results showed that the polyurethane hydrogels were successfully synthesized. The change of the molar the ratio of the polyhydric alcohols (PEG and PCL) played important roles in the swelling degree, the contact angle and the pore size. The HMDI/PCL-PEG/DEG polyurethane hydrogel (PCL/PEG = 1:3) was hydrophilic with many more large pores while the polyurethane hydrogel with PCL/PEG = 3:1 had a dense structure. The fibroblastic cell proliferation improved with decreasing relative PEG content; however, there were insignificant differences (P > 0.05) on all days of observation of the samples with various PEG contents compared with the negative control group. The MTT assays revealed that the cells were able to grow and proliferate quite quickly in the extracts of the HMDI/PCL-PEG/DEG polyurethane hydrogels as well as the extract of the negative control.     

Fabrication of patterned polyaniline microstructure through microcontact printing and electrochemistry

Polyaniline (PANI) microstructures on ITO glass surface were achieved by microcontact printing of self-assembled film and electrochemical polymerization in an aqueous monoaniline solution. The patterned microstructures of PANI were easily transferred to an adhesive tape surface, which could be applied in the area of plastic circuit application. Optical microscope, atomic force microscopy (AFM), lateral force microscopy (LFM) and X-ray photoelectron spectroscopy (XPS) were used to examine the topography and properties of patterned PANI films. Optical microscope and AFM results showed that the PANI microstructure has regular pattern and clear boundary, while LFM and XPS results implied that this microstructure was completely covered by PANI. The data suggested that the interfacial properties of the surface control the rate of electrochemical polymerization, and the polymerization rate on the modified ITO surface is higher than that on the bare ITO area. In our experiments, cyclic voltammetric method, potentiostatic method and chronopotentiometry method were employed to deposited patterned PANI films on octadecyltrichorosilane modified ITO substrate.     

Fabrication and electrochemical properties of free-standing single-walled carbon nanotube film electrodes

An easily manipulative approach was presented to fabricate electrodes using free-standing single-walled carbon nanotube (SWCNT) films grown directly by chemical vapor deposition.Electrochemical properties of the electrodes were investigated.In comparison with the post-deposited SWCNT papers,the directly grown SWCNT film electrodes manifested enhanced electrochemical properties and sensitivity of sensors as well as excellent electrocatalytic activities.A transition from macroelectrode to nanoelectrode behaviours was observed with the increase of scan rate.The heat treatment of the SWCNT film electrodes increased the current signals of electrochemical analyser and background current,because the heat-treatment of the SWCNTs in air could create more oxide defects on the walls of the SWCNTs and make the surfaces of SWCNTs more hydrophilic.The excellent electrochemical properties of the directly grown and heat-treated free-standing SWCNT film electrodes show the potentials in biological and electrocatalytic applications.     

Preparation and Characterization of P(MAA-g-EG) Nanospheres for Protein Delivery Applications

Novel complexation hydrogel nanospheres of poly(methacrylic acid-grafted-poly(ethylene glycol)) (P(MAA-g-EG)) were prepared by dispersion polymerization to be used for protein delivery applications. Polymerization was conducted in solvents such as deionized water, ethanol/water, sodium hydroxide, hydrochloric acid, and acetic acid solutions. When polymerizing in deionized water we produced nanospheres without agglomeration. Photon correlation spectroscopy studies revealed that the nanospheres possessed a narrow particle size distribution and the size was inversely proportional to the concentration of poly(ethylene glycol) incorporated in the monomer mixture. These nanospheres exhibited pH-sensitivity comparable to that encountered in hydrogel films with the same composition. The composition of the nanospheres was investigated by transmission Fourier transform infrared spectroscopy. The comparison between hydrogel films and nanospheres with the same monomer composition revealed that nanospheres possessed similar spectral characteristics than hydrogel films prepared by the same techniques. These nanospheres could be used for calcitonin release under physiological conditions.     

Microporated PEG Spheres for Fluorescent Analyte Detection

Poly(ethylene glycol) (PEG) hydrogels have been used to encapsulate fluorescently labeled molecules in order to detect a variety of analytes. The hydrogels are designed with a mesh size that will retain the sensing elements while allowing for efficient diffusion of small analytes. Some sensing assays, however, require a conformational change or binding of large macromolecules, which may be sterically prohibited in a dense polymer matrix. A process of hydrogel microporation has been developed to create cavities within PEG microspheres to contain the assay components in solution. This arrangement provides improved motility for large sensing elements, while limiting leaching and increasing sensor lifetime. Three hydrogel compositions, 100% PEG, 50% PEG, and microporated 100% PEG, were used to create pH-sensitive microspheres that were tested for response time and stability. In order to assess motility, a second, more complex sensor, namely a FITC-dextran/TRITC-Con A glucose-specific assay was encapsulated within the microspheres.     

Preparation and Properties of Polyurethane Hydrogels Based on Methylene Diphenyl Diisocyanate/Polycaprolactone-Polyethylene Glycol

Polyurethane (PU) hydrogel is an important biomedical material for drug controlled release systems, wound dressings and medical bandages. Three series of polyurethane prepolymers based on methylene diphenyl diisocyanate (MDI), polycaprolactone (PCL) and polyethylene glycol (PEG), using diethylene glycol (DEG), N-methyldiethanolamine (MDEA) or dimethylolpropionic acid (DMPA), as the chain-extender, were prepared. Then the polyurethane hydrogels were obtained from the prepolymers, using benzoyl peroxide (BPO) as a cross-linking agent, by free radical polymerization. The influences of the types of chain-extenders and polyols on the contact angle, swelling ratio and morphology of the polyurethane hydrogels were investigated. The effect of the variety of the chain-extenders in the PU hydrogel on the drug release behavior was also studied. The FT-IR results showed that the PU hydrogels were successfully synthesized. The introduction of PEG improved the hydrophilicity of the PU hydrogels. The MDI/PCL-PEG/DEG hydrogel was hydrophobic, and there were small micropores on its surface; while the MDI/PCL-PEG/DMPA and MDI/PCL-PEG/MDEA hydrogels had high hydrophilicity and a micropouous structure on their surface due to the existence of carboxyl and tertiary amino functional groups. The change of chain-extenders had no significant effect on the cumulative drug release of chloramphenicol from the PU hydrogels. However, the introduction of PEG increased the drug release rate. The chloramphenicol release kinetics from the MDI/PCL-PEG hydrogels indicated non-Fickian diffusion.     

Two-dimensional nanopatterning by PDMS relief structures of polymeric colloidal crystals

A new constructive method of fabricating a nanoparticle self-assembly on the patterned surface of a poly(dimethylsiloxane) (PDMS) relief nanostructure was demonstrated. Patterned PDMS templates with close-packed microwells were fabricated by molding against a self-assembled monolayer of polystyrene spheres. Alkanethiol-functionalized gold nanoparticles with an average particle size of 2.5 nm were selectively deposited onto a hydrophobic self-assembled monolayer printed on the substrate by the micro-contact printing (μCP) of the prepared PDMS microwell, in which the patterned gold nanoparticles consisted of close-packed hexagons with an average diameter of 370 nm. In addition, two-dimensional colloidal crystals derived from PMMA microspheres with a diameter of 380 nm and a negative surface charge were successfully formed on the hemispherical microwells by electrostatic force using positively charged PAH-coated PDMS as a template to produce multidimensional nanostructures.     

MAPLE deposition of biomaterial multilayers

Double layers of polyethylene glycol (PEG) and 3-(3,4-dihydroxyphenyl)-2-methyl-l-alanine (m-DOPA) thin films were obtained by matrix assisted pulsed laser evaporation (MAPLE) technique, by depositing a first layer of m-DOPA on Si substrate and a second layer of PEG on top of it. The films were characterized by low angle X-ray diffraction (LAXRD), X-ray reflectivity (XRR), atomic force microscopy (AFM), and micro-Raman spectroscopy. From these analyses it resulted that PEG was deposited without any relevant damage both in terms of chemical structure and molecular weight. Furthermore, PEG chains were mostly in the extended conformation, although PEG micelles appeared.     

聚乙二醇/二氧化钛一维光子晶体的制备及其性质研究

采用旋涂法制备了多层聚乙二醇/二氧化钛(PEG/TiO₂)一维光子晶体膜,通过控制旋涂时间、旋涂速度和聚乙二醇溶液质量浓度,制备出具有不同光子禁带的PEG/TiO₂一维光子晶体膜。制备的PEG/TiO₂膜对有机溶剂二甲亚砜(DMSO)和强碱溶液有双重响应。     

Effects of poly(ethylene glycol) on electrical conductivity of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) film

A series of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) composite thin films with prescribed concentrations of poly(ethylene glycol) were prepared. The PEDOT–PSS pristine film and PEDOT–PSS/PEG films were studied using four-probe method, photoelectron spectroscopy and atomic force microscopy. The electrical conductivity of PEDOT–PSS/PEG hybrid films was found to be enhanced compared to the PEDOT–PSS pristine film, depending on the PEG concentration and molecular weight. XPS analysis and AFM results showed that PEG induces the phase separation between the PEDOT–PSS conducting particles and the excessive PSSNa shell. Simultaneously PEG may form hydrogen bond with sulfonic groups of PSSH, and hence weaken the electrostatic interactions between PEDOT cationic chains and PSS anionic chains. These resulted in the creation of a better conduction pathway among PEDOT–PSS particles, attributed to the improvement of conductivity.     

Stabilization of the anatase phase in TiO2(Fe, PEG) nanostructured coatings

Multilayered TiO₂(Fe³⁺, PEG) films were deposited on glass and SiO₂/glass substrates by sol-gel dipping method. The influence of Fe³⁺ and PEG(polyethylene glycol) concentrations, the number of layers, the thermal treatment time and the temperature on the optical and microstructural properties of the TiO₂ films were studied.As-deposited TiO₂(Fe³⁺, PEG) films were very porous, but after the thermal treatment at 500 °C, the PEG decomposed and burned out to porosity decreasing. Homogeneous nanostructured films were obtained, where the amorphous and the anatase phases coexist. XRD analysis showed that no rutile phase is observed in the films deposited on SiO₂/glass as compared with those deposited directly on glass and that the presence of the anatase phase in the films without PEG is more evident in the three-layers film. The XRD intensity of the main peak of anatase from 25° decreases with the increase of PEG concentration.The optical gap of the TiO₂(Fe³⁺, PEG) films is found in 2.52-2.56 eV range and does not essentially depend on the PEG content.     

High fluence deposition of polyethylene glycol films at 1064 nm by matrix assisted pulsed laser evaporation (MAPLE)

Matrix assisted pulsed laser evaporation (MAPLE) has been applied for deposition of thin polyethylene glycol (PEG) films with infrared laser light at 1064 nm. We have irradiated frozen targets (of 1 wt.% PEG dissolved in water) and measured the deposition rate in situ with a quartz crystal microbalance. The laser fluence needed to produce PEG films turned out to be unexpectedly high with a threshold of 9 J/cm², and the deposition rate was much lower than that with laser light at 355 nm. Results from matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis demonstrate that the chemistry, molecular weight and polydispersity of the PEG films were identical to the starting material. Studies of the film surface with scanning electron microscopy (SEM) indicate that the Si-substrate is covered by a relatively homogenous PEG film with few bare spots.     

Preparation and characterization of branched polymers as postoperative anti-adhesion barriers

Homopolymers and copolymers synthesized from biocompatible monomers with polyethylene glycol (PEG) and polycaprolactone side chains, were applied to separate healing tissues and prevent postsurgical adhesions. The results of the contact angle and the ESCA spectra reveal the presence of more PEG segments on the surface of the PEMC1 film than the P(EM)₃(EMC4)₁ film. The effects of the molecular structures on the surface properties, including the wetting properties and the anti-tissue adhesion behaviors, of the films were examined. Fluorescent polymer was fixed on the surface of the film to form the marking dot. The in vivo degradation behaviors of the surface-marked films were investigated non-invasively by monitoring the location of the fluorescent signal. The degradation behaviors of various films observed in the animal study were consistent with those observed by in vivo imaging. Proper arrangement of PEG segments on the polymer side chain helped to keep a large proportion of PEG segments close to the surface of the film. Such an arrangement represents an effective means of preventing postoperative tissue adhesion.     

Micro-patterning of NdFeB and SmCo magnet films for integration into micro-electro-mechanical-systems

The integration of high-performance RE-TM (NdFeB and SmCo) hard magnetic films into micro-electro-mechanical-systems (MEMS) requires their patterning at the micron scale. In this paper we report on the applicability of standard micro-fabrication steps (film deposition onto topographically patterned substrates, wet etching and planarization) to the patterning of 5-8 μm thick RE-TM films. While NdFeB comprehensively fills micron-scaled trenches in patterned substrates, SmCo deposits are characterized by poor filling of the trench corners, which poses a problem for further processing by planarization. The magnetic hysteresis loops of both the NdFeB and SmCo patterned films are comparable to those of non-patterned films prepared under the same deposition/annealing conditions. A micron-scaled multipole magnetic field pattern is directly produced by the unidirectional magnetization of the patterned films. NdFeB and SmCo show similar behavior when wet etched in an amorphous state: etch rates of approximately 1.25 μm/min and vertical side walls which may be attributed to a large lateral over-etch of typically 20 μm. Chemical-mechanical-planarization (CMP) produced material removal rates of 0.5-3 μm/min for amorphous NdFeB. Ar ion etching of such films followed by the deposition of a Ta layer prior to film crystallization prevented degradation in magnetic properties compared to non-patterned films.     

Structural role of polyethylene glycol in the formation of anatase nanocrystalline titania at low temperature

Anatase nanocrystalline TiO₂ thin films were obtained by a sol–gel dip‐coating method, in which the nanocrystallization is effected by a simple hot water treatment of the deposited films at temperatures below 90 °C under atmospheric pressure for 1 h. The dip‐coating sol was prepared by reacting titanium tetra‐n‐butoxide [Ti(OⁿBu)₄] with polyethylene glycol (PEG) in ethanol. Films obtained from a sol that do not contain PEG show no sign of crystallization, demonstrating the importance of PEG in the crystallization process. Raman studies of reaction dynamics show that PEG undergoes a nucleophilic substitution reaction replacing butoxy groups in Ti(OⁿBu)₄. Stoichiometric reactions of Ti(OⁿBu)₄ with PEG in polar and nonpolar solvents were performed, and they yielded different titanium–PEG hybrid polymers, which were isolated and characterized by various spectroscopic techniques such as IR, Raman, solid‐state NMR and MALDI‐TOF‐MS. NMR studies evidenced the location and the way in which PEG is bonded with titanium atoms in the titanium–PEG hybrid polymers. On the basis of these studies, we have proposed structures for these polymers. It is demonstrated that the structure of the obtained polymers plays an important role in the formation of anatase TiO₂ nanoparticles in hot water at temperatures below 90 °C under atmospheric pressure. Copyright © 2009 John Wiley & Sons, Ltd.     

In vitro studies of PEG thin films with different molecular weights deposited by MAPLE

In this work, polyethylene glycol (PEG) films were produced by Matrix Assisted Pulsed Laser Evaporation (MAPLE). The possibility to tailor the properties of the films by means of polymer molecular weight was explored. The films of PEG of average molecular weights 400 Da, 1450 Da, and 10000 Da (PEG₄₀₀, PEG₁₄₅₀, and PEG₁₀₀₀₀) were investigated in vitro, in media similar with those inside the body (phosphate buffer saline PBS with pH 7.4 and blood). The mass of the polymer did not change during this treatment, but the polymer molecular weight was found to strongly influence the films properties and their behavior in vitro. Thus, immersion in PBS induced swelling of the PEG films, which was more pronounced for PEG polymers of higher molecular weight. Prior to immersion in PBS, the PEG films of higher molecular weight were more hydrophilic, the water contact angles decreasing from ～66 grd for PEG₄₀₀ to ～41 grd for PEG₁₄₅₀ and to ～15 grd for PEG₁₀₀₀₀. The same trend was observed during immersion of the PEG films in PBS. Before immersion in PBS, the refractive index of the films increased from ～1.43 for PEG₄₀₀ to ～1.48 for PEG₁₄₅₀ and to ～1.68 for PEG₁₀₀₀₀. During immersion in PBS the refractive index decreased gradually, but remained higher for the PEG molecules of higher mass. Finally, blood compatibility tests showed that the PEG films of higher molecular weight were most compatible with blood.     

阳极缓冲层修饰对聚合物太阳能电池性能的影响

为提高聚合物太阳能电池的能量转换效率,将聚乙二醇(PEG)掺入PEDOT∶PSS阳极缓冲层,研究了阳极缓冲层修饰对聚合物太阳能电池性能的影响。首先研究了聚乙二醇对PEDOT∶PSS薄膜电导率的影响,发现PEG会与PEDOT和PSS相互作用,使得PEDOT链重新排布,有利于电荷载流子的传输,从而显著改善了PEDOT∶PSS薄膜的电导率,当PEDOT∶PSS中掺入体积分数为2%~4%的PEG时,可得到较大的电导率。然后,以PEG修饰的PEDOT∶PSS薄膜作为阳极缓冲层制备了聚合物太阳能电池,研究了PEG的掺入对聚合物太阳能电池性能的影响。实验发现,PEG改善的PEDOT∶PSS电导率有利于提高电池的短路电流密度和填充因子,从而改善了器件光伏性能。当PEDOT∶PSS中掺入体积分数为2%的PEG时,聚合物太阳能电池的能量转换效率最高,比未掺杂的器件提高了24.4%。