Thick Poly Research Articles

Diffusivity, permeability and solubility of H2, Ar, N2, and CO2 in poly(tetrafluoroethylene) between room temperature and 180 °C

The transport parameters of hydrogen, argon, nitrogen and carbon dioxide through a 0.1 mm thick poly(tetrafluoroethylene) (PTFE) membrane are investigated. The pre-exponential factors and activation energies for the diffusivity and permeability as well as the heat of solutions for these gases are reported based on a considerable number of experiments conducted between room temperature and 180 °C.

Adhesion promotion of thick polyphosphate-poly(allylamine) films onto polyolefin substrates by plasma polymers

The adhesion of thick poly(allylamine)-polyphosphate layers (1 μm) deposited by the wet-chemical layer-by-layer (LbL) technique onto polyethylene or polystyrene (each 100 μm) was very low. To promote the adhesion of these LbL deposited layers, the polyolefin substrates were oxidized at the surface by short exposure to the oxygen plasma (2 or 5 s) and subsequently coated with an interlayer of plasma-deposited poly(allylamine) or poly(allyl alcohol) (100 nm). The plasma polymer interlayers have improved strongly the adhesion between polyolefin substrates and polyphosphate coatings. Such phosphate coatings are interesting for life sciences (nucleotide formation) but also for fire retardancy in combination with N-rich compounds such as melamine. The intention was to prefer chemical hydrogen bonds for adhesion promoting because of their high binding energy. Therefore the introduced oxygen-containing groups at the polyolefin surface could interact with the OH or NH2 groups of the adhesion-promoting plasma polymer interlayer. These groups were also able to interact strongly with the poly(allylamine)-polyphosphate topcoating. The coated polyolefins were investigated using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy, thermogravimetric analyses and atomic force spectroscopy, and 90° peel test.

High-Resolution, Large-Area Fabrication of Compliant Electrodes via Laser Ablation for Robust, Stretchable Dielectric Elastomer Actuators and Sensors.

A key element in stretchable actuators, sensors, and systems based on elastomer materials are compliant electrodes. While there exist many methodologies for fabricating electrodes on dielectric elastomers, very few succeed in achieving high-resolution patterning over large areas. We present a novel approach for the production of mechanically robust, high-resolution compliant electrodes for stretchable silicone elastomer actuators and sensors. Cast, 2-50 μm thick poly(dimethylsiloxane) (PDMS)-carbon composite layers are patterned by laser ablation and subsequently bonded to a PDMS membrane by oxygen plasma activation. The technique affords great design flexibility and high resolution and readily scales to large-area arrays of devices. We validate our methodology by producing arrays of actuators and sensors on up to A4-size substrates, reporting on microscale dielectric elastomer actuators (DEA) generating area strains of over 25%, and interdigitated capacitive touch sensors with high sensitivity yet insensitivity to substrate stretching. We demonstrate the ability to cofabricate highly integrated multifunctional transducers using the same process flow, showing the methodology's promise in realizing sophisticated and reliable complex stretchable devices with fine features over large areas.

Structure and optical properties of thin poly(p-xylylene) – Silver nanocomposite films prepared by low-temperature vapor deposition polymerization

In this study, variable-temperature grazing-incidence X-ray diffraction, transmission electron and scanning force microscopy were employed to address the semicrystalline structure and surface morphology of thin poly(p-xylylene) – silver nanocomposite films with Ag concentrations up to 12 vol.%. It was observed that the dominant crystalline modification of poly(p-xylylene) in the studied films is α-form, which is in contrast to thick poly(p-xylylene) films deposited at liquid nitrogen temperature where β-form prevails. The films exhibit planar texture that can be further enhanced on annealing. The optical properties of the films were studied by UV–vis and IR-spectroscopy. It was found that the samples display surface plasmon resonance, with the peak wavelength in the range of 435–445 nm. The peak positions undergo a redshift upon a long-term storage under ambient conditions. The IR-spectroscopy reveals the bands, which can be assigned to the vibrations of oxygen-containing groups, with intensity increasing with silver content.

A Surface Tailoring Method of Ultrathin Polymer Gate Dielectrics for Organic Transistors: Improved Device Performance and the Thermal Stability Thereof

Tailoring the surface of the dielectric layer is of critical importance to form a good interface with the following channel layer for organic thin film transistors (OTFTs). Here, a simple surface treatment method is applied onto an ultrathin (<15 nm) organosilicon‐based dielectric layer via the initiated chemical vapor deposition (iCVD) to make it compatible with organic semiconductors without degrading its insulating property. A molecular‐thin oxide capping layer is formed on a 15 nm thick poly(1,3,5‐trimetyl‐1,3,5‐trivinyl cyclotrisiloxane) (pV3D3) by a brief oxygen plasma treatment. The capping layer greatly enhances the thermal stability of the dielectrics, without degrading the original mechanical flexibility and insulating performance of the dielectrics. Moreover, the surface silanol functionalities formed by the plasma treatment can also be utilized for the surface modification with silane compounds. The surface‐modified dielectrics are applied to fabricate low‐voltage operating (<5 V) pentacene‐based OTFTs. The highest field‐effect mobility of the device with the surface‐treated 15 nm thick pV3D3 is 0.59 cm2 V−1 s−1, which is improved up to two times compared to the TFT with the pristine pV3D3. It is believed that the simple surface treatment method can widely extend the applicability of the highly robust, ultrathin, and flexible pV3D3 gate dielectrics to design the surface of the dielectrics to match well various kinds of organic semiconductors.

A soft, stretchable and conductive biointerface for cell mechanobiology.

In mechanobiology the study of cell response to mechanical stimuli is fundamental, and the involved processes (i.e., mechanotransduction) need to be investigated by interfacing (mechanically and electrically) with the cells in dynamic and non-invasive natural-like conditions. In this work, we present a novel soft, stretchable and conductive biointerface that allows both cell mechanical stimulation and dynamic impedance recording. The biointerface stretchability and conductivity, jointly to the biocompatibility and transparency needed to perform cell culture studies, were obtained by exploiting the formation of wrinkles on the surface of a 90 nm thick conductive layer of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) on a pre-stretched 130 μm thick poly(dimethylsiloxane) (PDMS) substrate. Cell adhesion and proliferation of SH-SY5Y human neuroblastoma cells were evaluated, and cell differentiation on the corrugated surface was assessed. We demonstrate how the biointerface remains conductive when applying uniaxial strain up to 10%, and when cell culturing is performed. Finally, a reduction of about 30% of the relative impedance variation signal was measured, with respect to the control, as a result of the mechanical stimulation of cells.

Promoted water transport across graphene oxide–poly(amide) thin film composite membranes and their antibacterial activity

Hybrid composite membranes have great potential for desalination applications since water transport can be favorably promoted by selective diffusion at the interface between matrix and reinforcement materials. In this paper, graphene oxide nano-sheets were successfully incorporated across 200nm thick poly(amide) films by interfacial polymerization to form novel thin-film composite membranes. The impact of the graphene oxide on the morphology, chemistry, and surface charge of the ultra-thin poly(amide) layer, and the ability to desalinate seawater was investigated. The graphene oxide nano-sheets were found to be well dispersed across the composite membranes, leading to a lower membrane surface energy and an enhanced hydrophilicity. The iso-electric point of the samples, key to surface charge repulsion during desalination, was found to be consistently shifted to higher pH values with an increasing graphene oxide content. Compared to a pristine poly(amide) membrane, the pure water flux across the composite membranes with 0.12wt.% of graphene oxide was also found to increase by up to 80% from 0.122 to 0.219L·μm·m−2·h−1·bar−1 without significantly affecting salt selectivity. Furthermore, the inhibitory effects of the composite membrane on microbial growth were evaluated and the novel composite membranes exhibited superior anti-microbial activity and may act as a potential anti-fouling membrane material.

A living thick nanofibrous implant bifunctionalized with active growth factor and stem cells for bone regeneration.

New-generation implants focus on robust, durable, and rapid tissue regeneration to shorten recovery times and decrease risks of postoperative complications for patients. Herein, we describe a new-generation thick nanofibrous implant functionalized with active containers of growth factors and stem cells for regenerative nanomedicine. A thick electrospun poly(ε-caprolactone) nanofibrous implant (from 700 μm to 1 cm thick) was functionalized with chitosan and bone morphogenetic protein BMP-7 as growth factor using layer-by-layer technology, producing fish scale-like chitosan/BMP-7 nanoreservoirs. This extracellular matrix-mimicking scaffold enabled in vitro colonization and bone regeneration by human primary osteoblasts, as shown by expression of osteocalcin, osteopontin, and bone sialoprotein (BSPII), 21 days after seeding. In vivo implantation in mouse calvaria defects showed significantly more newly mineralized extracellular matrix in the functionalized implant compared to a bare scaffold after 30 days’ implantation, as shown by histological scanning electron microscopy/energy dispersive X-ray microscopy study and calcein injection. We have as well bifunctionalized our BMP-7 therapeutic implant by adding human mesenchymal stem cells (hMSCs). The activity of this BMP-7-functionalized implant was again further enhanced by the addition of hMSCs to the implant (living materials), in vivo, as demonstrated by the analysis of new bone formation and calcification after 30 days’ implantation in mice with calvaria defects. Therefore, implants functionalized with BMP-7 nanocontainers associated with hMSCs can act as an accelerator of in vivo bone mineralization and regeneration.

Au Foil Activation Measurement and Simulation of the Concrete Neutron Shielding Ability for the Proposed New SANRAD Facility

The purpose of this study was to measure the effective neutron shielding characteristics of the new shielding material designed and manufactured to be used for the construction of the new SANRAD facility at Necsa, South Africa, through Au foil activation as well as MCNP simulations. The shielding capability of the high density shielding material was investigated in the worst case region (the neutron beam axis) of the experimental chamber for two operational modes.The everyday operational mode includes the 15cm thick poly crystalline Bismuth filter at room temperature (assumed) to filter gamma-rays and some neutron spectrum energies. The second mode, dynamic imaging, will be conducted without the Bi-filter. The objective was achieved through a foil activation measurement at the current SANRAD facility and MCNP calculations.Several Au foilswere imbedded at different thicknesses(two at each position) of shielding material up to 80cm thick to track the attenuation of the neutron beam over distance within the shielding material. The neutron flux and subsequently the associated dose rates were calculated from the activation levels of the Au foils. The concrete shielding material was found to provide adequate shielding for all energies of neutrons emerging from beam port no-2 of the SAFARI-1 research reactorwithin a thickness of 40cm of concrete.

Ion-transfer voltammetry of perfluoroalkanesulfonates and perfluoroalkanecarboxylates: picomolar detection limit and high lipophilicity.

Here we report on ion-transfer voltammetry of perfluoroalkanesulfonates and perfluoroalkanecarboxylates at the interface between a plasticized polymer membrane and water to enable the ultrasensitive detection of these persistent environmental contaminants with adverse health effects. The ion-transfer cyclic voltammograms of the perfluoroalkyl oxoanions are obtained by using a ∼1 μm thick poly(vinyl chloride) membrane plasticized with 2-nitrophenyl octyl ether. The cyclic voltammograms are numerically analyzed to determine formal ion-transfer potentials as a measure of ion lipophilicity. The fragmental analysis of the formal potentials reveals that the 10(4) times higher lipophilicity of a perfluoroalkanesulfonate in comparison to the alkanesulfonate with the same chain length is due to the inductive effect of perfluorination on lowering the electron density of the adjacent sulfonate group, thereby weakening its hydration. The fragmental analysis also demonstrates that the lipophilicities of perfluoroalkyl and alkyl groups with the same length are nearly identical and vary with the length. Advantageously, the high lipophilicity of perfluorooctanesulfonate allows for its stripping voltammetric detection at 50 pM in the presence of 1 mM aqueous supporting electrolytes, a ∼10(7) times higher concentration. Significantly, this detection limit for perfluorooctanesulfonate is unprecedentedly low for electrochemical sensors and is lower than its minimum reporting level in drinking water set by the U.S. Environmental Protection Agency. In comparison, the voltammetric detection of perfluoroalkanecarboxylates is compromised not only by the lower lipophilicity of the carboxylate group but also by its oxidative decarboxylation at the underlying poly(3-octylthiophene)-modified gold electrode during voltammetric ion-to-electron transduction.

Characteristics of Each Bonded Layer of a Polymer-Based Magnetic Tape Using Rule-of-Mixtures and Dynamic Mechanical Analysis

A rule-of-mixtures approach is used with dynamic mechanical analysis (DMA) to determine the viscoelastic characteristics of individual layers of a fourth-generation advanced magnetic tape used for archival storage. Such tapes are comprised of three layers: a 0.92 µm thick poly(ester-urethane)-based front coat that binds the magnetic particles together, a 5.00 µm thick poly(ethylene naphthalate) substrate, and a protective 0.64 µm thick back coat with cellulose nitrate as a constituent. The storage modulus, loss modulus, and loss tangent determined for each layer are discussed in terms of their influence on magnetic tape properties and characteristics.

Large-scale and environmentally friendly synthesis of pH-responsive oil-repellent polymer brush surfaces under ambient conditions.

Contrary to conventional ATRP, aqueous A(R)GET-ATRP at ambient temperature without deoxygenating reaction solutions is an extremely facile method to create polymer brushes. Using these techniques, extremely thick poly[2-(dimethylamino)ethyl methacrylate] polymer brushes can be prepared (∼700 nm), or reaction solutions can be low chemical-content, consisting of 99% v/v water. Based on these techniques, we have also developed an easy and inexpensive method, referred to as "paint on"-ATRP, that directly pastes reaction solutions onto various large-scale real-life substrates open to the air. The resulting brush surfaces possess excellent oil-repellent properties, which can be activated or deactivated in response to solution pH.

Volume polarization holographic recording in thick photopolymer for optical memory.

Based on a vector wave theory of volume holograms, dependence of holographic reconstruction on the polarization states of the writing and reading beams is discussed. It is found that under paraxial approximation the circular polarization holograms provide a better distinction of the reading beams. Characteristics of recording polarization holograms in thick phenanthrenequinone-doped poly(methyl methacrylate) (PQ/PMMA) photopolymer are experimentally investigated. It is found that the circular polarization holographic recording possesses better dynamic range and material sensitivity, and a uniform spatial frequency response over a wide range. The performance is comparable to that of the intensity holographic recording in PQ/PMMA. Based on theoretical analyses and the material properties, a polarization multiplexing holographic memory using circularly polarization recording configuration for increasing storage capacity has been designed and experimentally demonstrated.

High-frequency (20 to 40 MHz) acoustic response of liquid-filled nanocapsules

Liquid-core nanoparticles are promising candidates for targeted ultrasound-controlled therapy, but their acoustic detection remains challenging. High-frequency (20 to 40 MHz) tone burst sequences were implemented with a programmable ultrasound biomicroscope to characterize acoustic response from perfluorooctyl bromide-core nanoparticles with thick poly(lactide-coglycolide) (PLGA) shells. Radio-frequency signals were acquired from flowing solutions of nanoparticles with two different shell-thickness-to-particle-radius ratios, solid PLGA nanoparticles, and latex nanobeads (linear controls). Normalized fundamental (20 MHz) and second-harmonic power spectral density (PSD) increased with particle concentration and was highest for the thinnest shelled particles. The second- harmonic PSD was detectable from the nanoparticles for peak rarefactional pressures (PRP) from 0.97 to 2.01 MPa at 23 cycles and for tone bursts from 11 to 23 cycles at 2.01 MPa. Their second-harmonic¿to¿fundamental ratio increased as a function of PRP and number of cycles. Within the same PRP and cycle ranges, the second-harmonic¿to¿fundamental ratios from matched concentration solutions of latex nanobeads and solid PLGA nanoparticles was more weakly detectable but also increased with PRP and number of cycles. Nanoparticles were detectable under flow conditions in vitro using the contrast agent mode of a high-frequency commercial scanner. These results characterize linear acoustic response from the nanoparticles (20 to 40 MHz) and demonstrate potential for their highfrequency detection.

Tissue Scaffold Engineering by Micro-Stamping

ABSTRACTA hand operated benchtop stamping press was developed to conduct research on microscale hole fabrication in polymer membranes for applications as scaffolds in tissue engineering. A biocompatible and biodegradable polymer, poly(ε-caprolactone), was selected for micropunching. Membranes between 30 μm and 50 μm thick were fabricated by hot melt extrusion, but could not be stamped with a 200 μm circular punch at room temperature, regardless of die clearance due to excessive strain to fracture. This problem was overcome by cooling the membrane and die sets with liquid nitrogen to take advantage of induced brittle behavior below the polymer’s glass transition temperature. While cooled, 203 μm hole patterns were successfully punched in 33 μm thick poly(ε-caprolactone) membranes with 11% die clearance, achieving 71% porosity.

Voltammetric microwell array for oxidized guanosine in intact ds-DNA.

Oxidative stress in humans causes damage to biomolecules by generating reactive oxygen species (ROS). DNA can be oxidatively damaged by ROS, which may lead to carcinogenesis. Here we report a microfluidic electrochemical array designed to rapidly detect oxidation in intact DNA in replicate measurements. Sensor arrays were fabricated by wet-chemistry patterning of gold compact discs. The eight-sensor array is incorporated into a 60 μL microfluidic channel connected to a pump and sample valve. The array features 7 nm thick osmium bipyridyl poly(vinylpyridine) chloride [Os(bpy)2(PVP)10Cl](+) films assembled layer-by-layer with polyions onto the gold sensors. 8-Hydroxy-7,8-hydro-2'-deoxyguanosine (8-oxodG) is selectively oxidized by [Os(bpy)2(PVP)10Cl](+) in intact ds-DNA to provide catalytic square wave voltammograms (SWV). The device is easy-to-use, fast, inexpensive, reusable, and can detect one 8-oxodG per 6600 nucleobases. The mass detection limit is 150-fold lower than a previously reported dip-and-read voltammetric sensor for oxidized DNA. Fast assays (<1 min) and moderate sample consumption (15 pmol DNA) suggest potential for research and clinical applications. Practical use is illustrated by detecting DNA oxidation from cigarette smoke and ash extracts in dispersions with NADPH and Cu(2+).

Patterned Enzymatic Degradation of Poly(ε-caprolactone) by High-Affinity Microcontact Printing and Polymer Pen Lithography

This paper reports deposition of Candida antarctica Lipase B (CALB) on relatively thick poly(ε-caprolactone) (PCL) films (300-500 nm) to create well-defined patterns using two different writing techniques: high-affinity microcontact (HA-μCL) and polymer pen (PPL) lithography. For both, an aqueous CALB ink is absorbed onto a polydimethylsiloxane (PDMS) writing implement (PDMS stamp or a PDMS pen tip), which is transferred to a spun-cast PCL film. HA-μCL experiments demonstrated the importance of applied pressure to obtain high-resolution patterns since uniform contact is needed between raised 20 μm parallel line regions of the PDMS stamp and the surface. AFM imaging shows pattern formation evolves gradually over incubation time only in areas stamped with CALB cutting through spherulites without apparent influence by grain boundaries. Strong binding of CALB to PCL is postulated as the mechanism by which lateral diffusion is limited. PPL enables formation of an arbitrary image by appropriate programming of the robot. The PDMS pen tips were coated with an aqueous CALB solution and then brought into contact with the PCL film to transfer CALB onto the surface. By repeating the ink transfer step multiple times where pen tips are brought into contact with the PCL film at a different locations, a pattern of dots is formed. After printing, patterns were developed at 37 °C and 95% RH. Over a 7-day period, CALB progressively etched the PCL down to the silicon wafer on which it was spun (350 nm) giving round holes with diameters about 10 μm. AFM images show the formation of steep PCL walls indicating CALB degraded the PCL film in areas to which it was applied. This work demonstrates that high-resolution patterns can be achieved without immobilizing the enzyme on the surface of polymeric stamps that limits the depth of features obtained as well as the throughput of the process.

Zirconium-Cation-Immobilized Core/Shell (Fe3O4@Polymer) Microspheres as an IMAC Material for the Selective Enrichment of Phosphopeptides

Immobilized metal affinity chromatography (IMAC) is a widely employed method for the enrichment of phosphopeptides from complex proteolytic digests prior to mass spectrometric analysis. In this work, a novel IMAC material, zirconium-phosphate (Zr4+-PO3)-modified magnetic Fe3O4/GMA-co-EDMA (core/shell) (Zr4+-Fe3O4@polymer) microspheres, has been synthesized in a facile manner and used for the selective capture of phosphopeptides from protein tryptic digests for mass spectrometry analysis. The enrichment conditions were optimized using a protein digest solution of β-casein. By virtue of a thick and biocompatible poly(GMA-co-EDMA) shell, high tolerance of contaminants (salt, nonphosphopeptide) was demonstrated for the use of Zr4+-Fe3O4@polymer microspheres for the highly selective enrichment of phosphopeptides from a protein tryptic solution that contained a high concentration of NaCl (6.2 M) or urea (8 M) and a high ratio of nonphosphoprotein (BSA) to phosphoprotein (α-casein) (1:500). The performance of the Zr4+-Fe3O4@polymer microspheres was further successfully examined by the phosphoproteome analysis of mouse liver lysate.

Surface grafted glycopolymer brushes to enhance selective adhesion of HepG2 cells

This work demonstrates the application of carbohydrate based methacrylate polymer brush, poly(2-lactobionamidoethyl methacrylate), for the purpose of cell adhesion studies. The first part of the work illustrates the effects of the structure of the aminosilane based ATRP initiator layer on the polymerization kinetics of 2-lactobionamidoethyl methacrylate) (LAMA) monomer on thermally oxidized silicon wafer. Both monolayer and multilayered aminosilane precursor layers have been prepared followed by reaction with 2-bromoisobutyrylbromide to form the ATRP initiator layer. It is inferred from the kinetic studies that the rate of termination is low on a multilayered initiator layer compared to a disordered monolayer structure. However both initiator types results in similar graft densities. Furthermore, it is shown that thick comb-like poly(LAMA) brushes can be constructed by initiating a second ATRP process on a previously formed poly(LAMA) brushes. The morphology of human hepatocellular carcinoma cancer cells (HepG2) on the comb-like poly(LAMA) brush layer has been studied. The fluorescent images of the HepG2 cells on the glycopolymer brush surface display distinct protrusions that extend outside of the cell periphery. On the other hand the cells on bare glass substrate display spheroid morphology. Further analysis using ToF-SIMS imaging shows that the HepG2 cells on glycopolymer surfaces is enriched with protein fragment along the cell periphery which is absent in the case of cells on bare glass substrate. It is suggested that the interaction of the galactose units of the polymer brush with the asialoglycoprotein receptor (ASGPR) of HepG2 cells has resulted in the protein enrichment along the cell periphery.

Visualization procedures for proteins and peptides on flat-bed monoliths and their effects on matrix-assisted laser-desorption/ionization time-of-flight mass spectrometric detection

The present study concerns the application of visualization methods, i.e. coomassie-brilliant-blue-R staining (CBB-R), silver-nitrate staining, and fluorescamine labeling, and subsequent MALDI-MS analysis of intact proteins and peptides on the surface of flat-bed monoliths, intended for spatial two-dimensional chromatographic separations. The use of 100-μm thick macroporous poly(butyl methacrylate-co-ethylene dimethacrylate) flat-bed monoliths renders a fixation step obsolete, so that CBB-R and silver-nitrate staining and destaining could be achieved in 10–15min as opposed to up to 24h, as is typical on 2D-PAGE gels. The detection limits remained comparable. The compatibility of the monolithic layer with subsequent MALDI-MS analysis of individual proteins and peptide spots was investigated with regards to mass accuracy, mass precision, resolution, and signal intensity. When comparing results from MALDI-MS analysis of proteins and peptides on a flat-bed monolith to results obtained directly on stainless-steel target plates, significant losses in mass precision, signal intensity, and an increased variation in resolution were observed. In addition, a loss in signal intensity up to two orders of magnitude was observed when using monolithic layers. After CCB-R and silver-nitrate staining and destaining to disrupt the protein–dye complexes no MALDI spectra with significant S/N ratios could be achieved. After fluorescamine labeling heterogeneous signals were observed, which resulted from a distribution in the number of fluorescence-labeled lysine groups and from the presence of labeled derivatives that had undergone condensation reactions.