Fabrication of a porous polyacrylonitrile nanofiber adsorbent for removing radioactive 60Co.

A Co2+ adsorbent was prepared using electrospun porous polyacrylonitrile (PAN) nanofibers, featuring easy recovery for reuse compared with a nanoparticle-based adsorbent. As an efficient ligand for Co2+, ethylenediaminetetraacetic acid (EDTA) was introduced on the surface of porous PAN nanofibers with the aid of a branched polyethyleneimine (PEI) linker to obtain an adsorbent with carboxylic acid groups. On the adsorbent surface, the carboxylic acid and amine groups from EDTA could adsorb Co2+ via ion exchange and chelation, and amine groups from PEI that remained after EDTA functionalization played a role in coordinating Co2+. The amine and carboxylic acid groups were simultaneously involved in the adsorption on the surface, making it possible to remove Co2+ over a wide pH range. An investigation of the adsorption isotherms and kinetics of the nanofibrous adsorbent indicated that monolayer chemisorption was achieved with a maximum Co2+ adsorption capacity of 8.32 mg/g. In addition, radioactive 60Co was efficiently removed by the adsorbent with a removal extent of more than 98%. Considering the easy separation from Co2+ solution and regeneration of the nanofibrous adsorbent and its availability in a wide pH range, the adsorbent has great advantages in practical applications.

Cesium ion adsorption and desorption on electrospun mesoporous silica nanofibers immobilized with Prussian blue.

To fabricate an efficient Cs ion adsorbent and prevent unexpected loss of Prussian blue (PB) colloidal particles during use, PB was immobilized on the surface of electrospun mesoporous silica nanofibers (MSFs) via a newly developed method of double exposure to Fe (III) ions. To introduce PB on MSFs, the MSFs were functionalized with ethylenediamine moiety to bind to Fe (III) ions, which would firmly anchor PB. MSFs were pretreated with Fe (III) ions and exposed to K4 [Fe(II) (CN)6] to form PB. We found that this process did not provide a sufficient PB amount on the MSFs. To increase the PB amount, after initial PB formation, the MSFs were treated with Fe (III) ions again so that the unreacted K4 [Fe(II) (CN)6] remaining on the MSFs could become PB. An investigation of the adsorption isotherms and kinetics of the nanofibrous adsorbent indicated that monolayer chemisorption had occurred. The maximum Cs ion adsorption capacity using the method of double exposure to Fe (III) ions was determined to be 14.66 mg/g, which was higher by a factor of 2.24 than the case that was not prepared by this method. Cs ions were selectively adsorbed over other cations and could be removed in both acidic and basic conditions, presumably because of the robust MSFs.

In situ fabrication of silver/polyimide composite films with enhanced heat dissipation.

In this study, silver/polyimide (Ag/PI) composite films with enhanced heat dissipation properties were prepared. Ag was formed in situ by reducing AgNO3 at various locations according to the reduction method. Two different types of soluble PIs capable of solution processing were used, namely Matrimid and hydroxy polyimide (HPI). Unlike Matrimid with bulky substituents, HPI with polar hydroxy groups formed ion-dipole interactions with Ag ions to form Ag particles with uniform size distribution. The location and distribution of Ag particles affect the heat emission characteristics of the composite films, resulting in better heat dissipation properties with the thermally and photochemically reduced Ag/HPI films having more Ag particles distributed inside of the films than the chemically reduced films.

The Combined Effects of Sr(II) and Poly(Acrylic Acid) on the Morphology of Calcite.

Biomineralization of calcium carbonate has interesting characteristics of intricate morphology formation with controlled crystal polymorphs. In particular, modification of calcite morphology with diverse additives has been the focus of many biomimetic and bioinspired studies. The possible role of strontium ions in enhancing the morphology-modifying ability of macromolecules was investigated. In the present study, concentrations of strontium ions were comparable to that in seawater, and anionic poly(acrylic acid) and cationic poly(ethylene imine) were used as model macromolecules. When strontium ions were combined with anionic poly(acrylic acid), new types of calcite surfaces, most likely {hk0}, appeared to drastically change the morphology of the crystals, which was not observed with cationic poly(ethylene imine). This behavior of strontium ions was quite similar to that of magnesium ions, which is intriguing because both ions are available from seawater to be utilized during biomineralization.

Colorless and Transparent Copolyimides and Their Nanocomposites: Thermo-Optical Properties, Morphologies, and Gas Permeabilities.

A series of linear aromatic copolyimides (Co-PIs) were synthesized by reacting 4,4'-biphthalic anhydride (BPA) with various molar contents of 2,2'-bis(trifluoromethyl)benzidine (TFB) and p-xylylenediamine (p-XDA) in N,N'-dimethylacetamide (DMAc). Co-PI films were fabricated by solution casting and thermal imidization with poly(amic acid) (PAA) on glass plates. The thermo-optical properties and gas permeabilities of Co-PI films composed of various molar ratios of p-XDA (0.2⁻1.0 relative to BPA) were investigated. Thermal properties were observed to deteriorate with increasing p-XDA concentration. However, oxygen-transmission rates (O2TRs) and optical transparencies improved with increasing p-XDA concentration. Co-PI hybrids with a 1:0.2:0.8 molar ratio of BPA:TFB:p-XDA and organically modified hectorite (STN) were prepared by the in situ intercalation method. The morphologies and the thermo-optical and gas permeation properties of the hybrids were examined as functions of STN loading (5⁻50 wt %). XRD and TEM revealed substantial increases in clay particle agglomeration in the Co-PI hybrid films as the clay loading was increased from 5 to 50 wt %. The coefficient of thermal expansion (CTE) and the O2TR of a Co-PI hybrid film were observed to improve with increasing STN concentration; however, its optical transparency decreased gradually with increasing STN concentration.

Solvent-Free Processable and Photo-Patternable Hybrid Gate Dielectric for Flexible Top-Gate Organic Field-Effect Transistors.

We report a novel solvent-free and direct photopatternable poly[(mercaptopropyl)methyl-siloxane] (PMMS) hybrid dielectric for flexible top-gate organic field-effect transistors (OFETs) utilizing a photoactivated thiol-ene reaction under UV irradiation of 254 nm to induce cross-linking, even in air and at low temperatures. In particular, a solvent-free PMMS-f dielectric film, for which an optimal cross-linking density is shown by a well-organized molar ratio between thiol and vinyl in the thiol-ene reaction, exhibited a high dielectric constant (5.4 @ 100 Hz) and a low leakage current (<1 nA mm-2 @ 2 MV cm-1). The excellent dielectric characteristics of the solvent-free PMMS-hybrid dielectrics, along with their other unique characteristics of a direct photopatternability for which UV-nanoimprint lithography is used and a high surface energy of 45.6 mJ m-2, allowed the successful application of the dielectrics to flexible solvent-free top-gate OFETs with a high reliability against the radius of curvature (9.5, 7.0, and 5.5 mm) and repetitive bending cycles at the radius of curvature of 5.5 mm. This will eventually enable the proposed dielectric design to be used in a variety of applications such as flexible displays and soft organic sensors including chemical and tactile capability.

Tuning the sphere-to-rod transition in the self-assembly of thermoresponsive polymer hybrids.

Nano-scale drug delivery systems have undergone extensive development, and control of size and structure is critical for regulation of their biological responses and therapeutic efficacy. Amphiphilic polymers that form self-assembled structures in aqueous media have been investigated and used for the diagnosis and therapy of various diseases, including cancer. Here, we report the design and fabrication of thermoresponsive polymeric micelles from alginate conjugated with poly(N-isopropylacrylamide) (PNIPAAm). Alginate-PNIPAAm hybrids formed self-aggregated structures in response to temperature changes near body temperature. A structural transition from micellar spheres to rods of alginate-PNIPAAm hybrids was observed depending on the molecular weight of PNIPAAm and the polymer concentration. Additionally, hydrogels with nanofibrous structures were formed by simply increasing the polymer concentration. This approach to controlling the structure of polymer micelles from nanoparticles to fibrous hydrogels may be useful in applications in drug delivery and tissue engineering.

Finely Formed, Kinetically Modulated Wrinkle Structures in UV-Crosslinkable Liquid Prepolymers.

Special characteristics of wrinkles such as a scattering source and a high surface area are finding use in high-tech applications. UV-crosslinkable prepolymers are occasionally used for fabricating wrinkled films. Wavelength of the wrinkles formed from the prepolymers is several tens and hundreds of micrometers. Here, a UV-crosslinkable liquid prepolymer is synthesized to spontaneously form wrinkle structures in the order of several micrometers. Double layers with a very thin hard skin and a soft and contractible foundation are formed at the same time, by ensuring that all the absorbance wavelengths of the photoinitiator are shorter than the minimum wavelength at which the prepolymer is transparent. The rate of photo-crosslinking reaction, R(p), is also found to affect the thickness of the skin and foundation layers at the early UV-curing stage. The first-order apparent rate constant, k(app), is between ≈0.20 and ≈0.69 s(-1) for the wrinkle formation. This wrinkle structures can be simply modulated by changing R(p).

Chemically tunable ultrathin silsesquiazane interlayer for n-type and p-type organic transistors on flexible plastic.

In organic field-effect transistors (OFETs), surface modification of the gate-dielectric is a critical technique for enhancing the electrical properties of the device. Here, we report a simple and versatile method for fabricating an ultrathin cross-linked interlayer (thickness ∼3 nm) on an oxide gate dielectric by using polymeric silsesquiazane (SSQZ). The fabricated siloxane film exhibited an ultrasmooth surface with minimal hydroxyl groups; the properties of the surface were chemically tuned by introducing phenyl and phenyl/fluorine pendent groups into the SSQZ. The growth characteristics of two semiconductors-pentacene (p-type) and N,N'-ditridecyl-3,4,9,10-perylene tetracarboxylic diimide (PTCDI-C13, n-type)-on this ultrathin film were systematically investigated according to the type of pendent groups in the SSQZ-treated gate dielectric. Pentacene films on phenyl/fluorine groups exhibited large grains and excellent crystalline homogeneity. By contrast, PTCDI-C13 films exhibited greater crystalline order and perfectness when deposited on phenyl groups rather than on phenyl/fluorine groups. These microstructural characteristics of the organic semiconductors, as well as the dipole moment of the pendent groups, determined the electrical properties of FETs based on pentacene or PTCDI-C13. Importantly, compared to FETs in which the gate dielectric was treated with a silane-coupling agent (a commonly used surface treatment), the FETs fabricated using the tunable SSQZ treatment showed much higher field-effect mobilities. Finally, surface treatment with an ultrathin SSQZ layer was also utilized to fabricate flexible OFETs on a plastic substrate. This was facilitated by the facile SSQZ deposition process and the compatibility of SSQZ with the plastic substrate.

Doxorubicin-loaded alginate-g-poly(N-isopropylacrylamide) micelles for cancer imaging and therapy.

Chemotherapy is a widely adopted method for the treatment of cancer. However, its use is often limited due to side effects produced by anti-cancer drugs. Therefore, various drug carriers, including polymeric micelles, have been investigated to find a method to overcome this limitation. In this study, alginate-based, self-assembled polymeric micelles were designed and prepared using alginate-g-poly(N-isopropylacrylamide) (PNIPAAm). Amino-PNIPAAm was chemically introduced to the alginate backbone via carbodiimide chemistry. The resulting polymer was dissolved in distilled water at room temperature and formed self-assembled micelles at 37 °C. Characteristics of alginate-g-PNIPAAm micelles were dependent on the molecular weight of PNIPAAm, the degree of substitution, and the polymer concentration. Doxorubicin (DOX), a model anti-cancer drug, was efficiently encapsulated in alginate-g-PNIPAAm micelles, and sustained release of DOX from the micelles was achieved at 37 °C in vitro. These micelles accumulated at the tumor site of a tumor-bearing mouse model as a result of the enhanced permeability and retention effect. Interestingly, DOX-loaded alginate-g-PNIPAAm micelles showed excellent anti-cancer therapeutic efficacy in a mouse model without any significant side effects. This approach to designing and tailoring natural polymer-based systems to fabricate nanoparticles at human body temperature may provide a useful means for cancer imaging and therapy.

The height of cell-adhesive nanoposts generated by block copolymer/surfactant complex systems influences the preosteoblast phenotype.

In tissue engineering, the nanoscale topography of the substrate is important, because transplanted cells can recognize and respond to topographical patterns, allowing control of gene expression and tissue formation. In this study, we hypothesized that the height of cell-adhesive nanoposts could regulate cell phenotype. Nano-patterned surfaces were generated via self-assembly of polystyrene-b-poly(ethylene oxide)/dodecylbenzenesulfonic acid (PS-b-PEO/DBSA) complex systems. The height of PS nanoposts, which are considered to be cell-adhesion domains, was varied from 11 to 43 nm, while nanopost size and the center-to-center distance between nanoposts were kept constant. Adhesion, growth, and differentiation of mouse preosteoblasts (MC3T3-E1) cultured on the nano-patterned surfaces were significantly influenced by nanopost height. This approach therefore holds great promise for the design of biomedical devices, as well as tissue engineering scaffolds.

Fabrication of sub-20 nm nanopore arrays in membranes with embedded metal electrodes at wafer scales.

We introduce a method to fabricate solid-state nanopores with sub-20 nm diameter in membranes with embedded metal electrodes across a 200 mm wafer using CMOS compatible semiconductor processes. Multi-layer (metal-dielectric) structures embedded in membranes were demonstrated to have high uniformity (± 0.5 nm) across the wafer. Arrays of nanopores were fabricated with an average size of 18 ± 2 nm in diameter using a Reactive Ion Etching (RIE) method in lieu of TEM drilling. Shorts between the membrane-embedded metals were occasionally created after pore formation, but the RIE based pores had a much better yield (99%) of unshorted electrodes compared to TEM drilled pores (<10%). A double-stranded DNA of length 1 kbp was translocated through the multi-layer structure RIE-based nanopore demonstrating that the pores were open. The ionic current through the pore can be modulated with a gain of 3 using embedded electrodes functioning as a gate in 0.1 mM KCl aqueous solution. This fabrication approach can potentially pave the way to manufacturable nanopore arrays with the ability to electrically control the movement of single or double-stranded DNA inside the pore with embedded electrodes.

Superamphiphilic Janus fabric.

Janus fabrics with superamphiphilicity were fabricated via electrospinning of polyacrylonitrile (PAN). PAN nanofibrous mats were formed on an aluminum foil substrate and then thermally treated to cause hydrolysis. An identical PAN solution was subsequently electrospun onto the hydrolyzed PAN layer, followed by peeling off of the bicomposite film from the collector substrate to produce a free-standing Janus fabric. On one side, the electrospun PAN mat exhibited superhydrophobic properties, with a water contact angle of 151.2°, whereas the initially superhydrophobic PAN sheet on the opposite side of the fabric was converted to a superhydrophilic surface (water contact angle of 0°) through hydrolysis of the surface functional groups induced by the thermal treatment. The resulting Janus fabrics exhibited both superhydrophobicity, repelling water on the one side, and superhydrophilicity, absorbing water on the other side. The organic solvent resistance of the PAN nanofibrous sheets was remarkably improved by incorporation of a tetraethyl orthosilicate. This facile and simple technique introduces a new route for the design and development of functional smart, robust fabrics from an inexpensive, commercially available polymer.

Short term effects by acupuncture to SP3 on the autonomic blood flow control.

OBJECTIVES: In this study, we investigated the short term effects of acupuncture on autonomic control of blood flow in healthy subjects. We also studied whether deqi (obtaining qi) sensations are correlated with these autonomic hemodynamic changes. METHODS: The experiment had a randomized, crossover design. Five healthy volunteers (age: 18-26 years) participated in this study. Acupuncture (2 Hz rotations for 10 seconds to 20 mm deep) was applied either to the acupuncture point SP3 or KI2 for 5 minutes. Non-invasively obtained continuous hemodynamic measurements of ultrasound Dopplerography were recorded at the radial artery before, during and after acupuncture stimulation. Cardiovascular autonomic tone was also recorded using power spectral analysis of heart rate variability. After acupuncture stimulation, the participants completed the acupuncture perception scales to measure the degree of deqi or pain they had experienced. RESULTS: Acupuncture stimulation to the acupuncture point SP3, when compared to the acupuncture point KI2, decreased the maximum systolic velocity. It also decreased low frequency component and increased high frequency component of heart rate variability, indicating that the decrease in systolic blood flow velocity was due to the increased parasympathetic response. Interestingly, warm, radiating and energetic feeling, which are related to deqi, had close correlations with the decrease in blood flow velocity. DISCUSSION: Acupuncture stimulation to the acupuncture point SP3 modulates the autonomic cardiovascular responses by enhancing parasympathetic function, and this may help to understand the therapeutic effects of acupuncture.

Heterogeneous nuclear ribonuclear protein C is increased in the celecoxib-induced growth inhibition of human oral squamous cell carcinoma.

Celecoxib is a selective inhibitor of cyclooxygenase-2 (COX-2) that is a critical factor in carcinogenesis, but precise mechanism of its action remains to be elucidated. Here we evaluated the inhibitory effect of celecoxib on cell growth of human oral squamous cell carcinoma (OSCC) YD-10(B), which was established to be used as in vitro OSCC model, and identified celecoxib-regulated protein by proteomics techniques. Celecoxib (IC(50)=37 microM) inhibited the growth of YD-10(B) cells with the decrease of COX-2 protein expression. Its inhibition could be linked in the arrest of G(1) phase with increased levels of p(27) protein, a specific CDK inhibitor. Using proteomics, the 10- to 20-fold increase of heterogeneous nuclear ribonuclear protein C (hnRNP C), which has been suggested to be related with the translation of p(27) mRNA, was observed in celecoxib-treated YD-10(B) cells. In summary, celecoxib has a potential to induce the protein expression of hnRNP C and its increase subsequently induce the translation of p(27) mRNA, which trigger the inhibition of cell growth via p(27)-regulated cell cycle arrest in YD-10(B) cells. In addition, YD-10(B) cells could be useful to study the pathological mechanism of OSCC.

Fluorinated polymers: liquid crystalline properties and applications in lithography.

Fluorinated polymers form an interesting class of materials with a wealth of unique properties including self-assembly, remarkably low surface energies, low absorbance to 157 nm UV light, and solubility in supercritical carbon dioxide. As a result many fluorinated polymers are of use in advanced technology applications. We review some of our work on the synthesis and characterization of block copolymers with fluorinated side chains, with special emphasis on surfaces formed using these polymers. The use of fluorinated polymers as photoresists for 157 nm lithography, with the possibility for processing in environmentally friendly supercritical carbon dioxide is also discussed.