Facile Achievement of Complementary Resistive Switching in Block Copolymer Micelle-Based Resistive Memories.

Interest in resistive random access memory (RRAM) has grown rapidly in recent years for realizing ultrahigh density data storage devices. However, sneak currents in these devices can result in misreading of the data, thus limiting the applicability of RRAM. Complementary resistive switching (CRS) memory consisting of two antiserial RRAMs can considerably reduce sneak currents; however, complicated device architectures and manufacturing processes still remain as challenges. Herein, an effective and simple approach for fabricating CRS memory devices using self-assembled block copolymer micelles is reported. Cu ions are selectively placed in the core of polystyrene-block-poly(2-vinylpyridine) spherical micelles, and a hexagonally packed micelle monolayer is prepared through spin-coating. The micelle monolayer can be a symmetrical resistive switching layer, because the micelles and Cu act as dielectric and active metals in memory devices, respectively. The locally enhanced electric field and Joule heating achieved by the structured Cu atoms inside the micelles promote metal ionization and ion migration in a controlled manner, thus allowing for position selectivity during resistive switching. The micelle-based memory device exhibits stable and reliable CRS behavior, with a nonoverlapping and narrow distribution of threshold voltages. Therefore, this approach is promising for fabricating CRS memory devices for high-performance and ultrahigh-density RRAM applications.

Polymeric embolization coil of bilayered polyvinyl alcohol strand for therapeutic vascular occlusion: a feasibility study in canine experimental vascular models.

PURPOSE: To investigate the feasibility of polyvinyl alcohol (PVA) polymer coil as a new endovascular embolic agent and to gauge the related histologic response in a canine vascular model. MATERIALS AND METHODS: PVA polymer coil was fabricated by cross-linking PVA and tantalum particles. Basic properties were then studied in vitro via swelling ratio and bending diameter. Normal renal segmental arteries and wide-necked aneurysms of carotid sidewalls served as canine vascular models. Endovascular PVA coil embolization of normal renal segmental arteries (N = 20) and carotid aneurysms (N = 8) was performed under fluoroscopic guidance in 10 dogs. Degree of occlusion was assessed immediately and at 4 weeks after embolization by conventional and computed tomographic angiography. Histologic features were also graded at acute (day 1, six segmental arteries and four aneurysms) and chronic phases (week 4, 14 segmental arteries and four aneurysms) after embolization to assess inflammation, organization of thrombus, and neointimal proliferation. RESULTS: Swelling ratio declined as concentrations of cross-linking agent increased. Mean bending diameters were 2.05 mm (range, 0.86-6.25 mm) in water at 37 °C and 2.29 mm (range, 0.94-6.38 mm) in canine blood samples at 37 °C. Occlusion of normal renal segmental arteries was sustained (complete occlusion at day 1, n = 20; at week 4, n = 14), whereas immediate outcomes in carotid aneurysms (day 1, complete occlusion, n = 5; residual neck only, n = 3) were not sustained (week 4, complete occlusion, n = 1; minor recanalization, n = 1; major recanalization, n = 2). At week 4, chronic inflammatory cells predominated, with progressive organization of thrombus and fibrocellular ingrowth. All aneurysms bore full neointimal linings on the coil mass in the chronic phase. CONCLUSIONS: Vascular occlusion by PVA polymer coil proved superior in normal renal segmental arteries and feasible in surgically constructed carotid aneurysms (with packing densities ≥ 30%), constituting acceptable radiologic feasibility and histologic response.

Epitaxial relationships between calcium carbonate and inorganic substrates.

The polymorph-selective crystallization of calcium carbonate has been studied in terms of epitaxial relationship between the inorganic substrates and the aragonite/calcite polymorphs with implication in bioinspired mineralization. EpiCalc software was employed to assess the previously published experimental results on two different groups of inorganic substrates: aragonitic carbonate crystals (SrCO3, PbCO3, and BaCO3) and a hexagonal crystal family (α-Al2O3, α-SiO2, and LiNbO3). The maximum size of the overlayer (aragonite or calcite) was calculated for each substrate based on a threshold value of the dimensionless potential to estimate the relative nucleation preference of the polymorphs of calcium carbonate. The results were in good agreement with previous experimental observations, although stereochemical effects between the overlayer and substrate should be separately considered when existed. In assessing the polymorph-selective nucleation, the current method appeared to provide a better tool than the oversimplified mismatch parameters without invoking time-consuming molecular simulation.

Computational analysis of blood clot dissolution using a vibrating catheter tip.

We developed a novel concept of endovascular thrombolysis that employs a vibrating electroactive polymer actuator. In order to predict the efficacy of thrombolysis using the developed vibrating actuator, enzyme (plasminogen activator) perfusion into a clot was analyzed by solving flow fields and species transport equations considering the fluid structure interaction. In vitro thrombolysis experiments were also performed. Computational results showed that plasminogen activator perfusion into a clot was enhanced by actuator vibration at frequencies of 1 and 5 Hz. Plasminogen activator perfusion was affected by the actuator oscillation frequencies and amplitudes that were determined by electromechanical characteristics of a polymer actuator. Computed plasminogen activator perfused volumes were compared with experimentally measured dissolved clot volumes. The computed plasminogen activator perfusion volumes with threshold concentrations of 16% of the initial plasminogen activator concentration agreed well with the in vitro experimental data. This study showed the effectiveness of actuator oscillation on thrombolysis and the validity of the computational plasminogen activator perfusion model for predicting thrombolysis in complex flow fields induced by an oscillating actuator.

Synthesis and Modification of Hydroxyapatite Nanofiber for Poly(Lactic Acid) Composites with Enhanced Mechanical Strength and Bioactivity.

To enhance the bioactivity of poly(lactic acid) (PLA), a potential bone repair material, without the lowering of mechanical strength, hydroxyapatite (HA) was introduced in the form of nanofibers as the filler for application in spinal implant materials. HA nanofibers (HANF) with aspect ratio as high as ~100 were synthesized by controlling the starting pH of the reaction. While the tensile and flexural strength of PLA/HANF composites were enhanced compared with those of PLA resin, and were higher for the composites with HANF of higher aspect ratio. To further strengthen the composites, HANF was grafted with PLA chain to form HANF-g-PLA, which could improve the interface between the HANF and matrix PLA. PLA/HANF-g-PLA composites showed even higher tensile and flexural strength than PLA/HANF composites, apparently due to the better dispersion and interfacial adhesion. The composite containing 10 wt% HANF-g-PLA showed the flexural strength of 124 MPa, which was 25% higher than that of PLA resin. In the bioactivity test using a simulated body fluid solution, the rate and uniformity of the apatite growth were observed to be higher for the composites with HANF, and were even higher for those with HANF-g-PLA. This study suggested the possibility of using the PLA/HANF-g-PLA composite in the field of spinal implant materials.

Mechanical Properties and Bioactivity of Poly(Lactic Acid) Composites Containing Poly(Glycolic Acid) Fiber and Hydroxyapatite Particles.

To enhance the mechanical strength and bioactivity of poly(lactic acid) (PLA) to the level that can be used as a material for spinal implants, poly(glycolic acid) (PGA) fibers and hydroxyapatite (HA) were introduced as fillers to PLA composites. To improve the poor interface between HA and PLA, HA was grafted by PLA to form HA-g-PLA through coupling reactions, and mixed with PLA. The size of the HA particles in the PLA matrix was observed to be reduced from several micrometers to sub-micrometer by grafting PLA onto HA. The tensile and flexural strength of PLA/HA-g-PLA composites were increased compared with those of PLA/HA, apparently due to the better dispersion of HA and stronger interfacial adhesion between the HA and PLA matrix. We also examined the effects of the length and frequency of grafted PLA chains on the tensile strength of the composites. By the addition of unidirectionally aligned PGA fibers, the flexural strength of the composites was greatly improved to a level comparable with human compact bone. In the bioactivity tests, the growth of apatite on the surface was fastest and most uniform in the PLA/PGA fiber/HA-g-PLA composite.

Mechanical Properties and Bioactivity of Polyetheretherketone/Hydroxyapatite/Carbon Fiber Composite Prepared by the Mechanofusion Process.

The main obstacles in the melt-processing of hydroxyapatite (HA) and carbon fiber (CF) reinforced polyetheretherketone (PEEK) composite are the high melting temperature of PEEK, poor dispersion of HA nanofillers, and poor processability due to high filler content. In this study, we prepared PEEK/HA/CF ternary composite using two different non-melt blending methods; suspension blending (SUS) in ethanol and mechanofusion process (MF) in dry condition. We compared the mechanical properties and bioactivity of the composite in a spinal cage application in the orthopedic field. Results showed that the PEEK/HA/CF composite made by the MF method exhibited higher flexural and compressive strengths than the composite prepared by the SUS method due to the enhanced dispersibility of HA nanofiller. On the basis of in vitro cell compatibility and cell attachment tests, PEEK/HA/CF composite by mechanofusion process showed an improvement in in vitro bioactivity and osteo-compatibility.

Radiation-grafted fluoropolymers soaked with imidazolium-based ionic liquids for high-performance ionic polymer-metal composite actuators.

On purpose to develop a polymer actuator with high stability in air-operation as well as large bending displacement, a series of ionic polymer-metal composites (IPMC) was constructed with poly(styrene sulfonate)-grafted fluoropolymers as ionomeric matrix and immidazolium-based ionic liquids (IL) as inner solvent. The prepared IPMC actuators exhibited greatly enhanced bending displacement compared to Nafion-based actuators. The actuators were stable in air-operation, maintaining initial displacement for up to 10(4) cycles or 24 h. Investigating the material parameters and morphology of the IPMCs, high ion exchange capacity of the ionomers resulted in high ion conductivity and robust electrode of IPMC, which synergistically contributed to the high bending performance.

Effect of the Fluorination of Graphene Nanoflake on the Dispersion and Mechanical Properties of Polypropylene Nanocomposites.

In order to investigate the effect of fluorination of graphene nanoflake on the dispersibility in polypropylene (PP) composites, fluorinated graphene oxide (FGO) was prepared by solvo-thermal reaction and applied as a filler of the PP nanocomposite. Due to the weakened inter-particle attraction among the graphene nanoflake and reduced surface energy difference between PP and the filler, PP/FGO composites showed better exfoliation and dispersion state of the filler compared with that of PP/graphene oxide (GO) or PP/reduced graphene oxide (RGO) composites. The improved exfoliation and dispersion of graphene nanoflake resulted in a significant reinforcement on the composites. The Young's modulus and tensile strength of PP composites filled with 2 wt% of FGO increased by 31% and 15%, respectively, compared with those of PP.

Mechanical Properties and Chemical Durability of Nafion/Sulfonated Graphene Oxide/Cerium Oxide Composite Membranes for Fuel-Cell Applications.

To improve both the mechanical and chemical durability of Nafion membranes for polymer electrolyte membrane fuel-cells (PEMFCs), Nafion composite membranes containing sulfonated graphene oxide (SGO) and cerium oxide (CeO2; ceria) were prepared by solution casting. The structure and chemical composition of SGO were investigated by FT-IR and XPS. The effect of the sulfonation, addition of SGO and ceria on the mechanical properties, proton conductivity, and chemical stability were evaluated. The addition of SGO gave rise to an increase in the number of sulfonic acid groups in Nafion, resulting in a higher tensile strength and proton conductivity compared to that of graphene oxide (GO). Although the addition of ceria was found to decrease the tensile strength and proton conductivity, Nafion/SGO/ceria composite membranes exhibited a higher tensile strength and proton conductivity than recast Nafion. Measurement of the weight loss and SEM observations of the composite membranes after immersing in Fenton's reagent indicate an excellent radical scavenging ability of ceria under radical degradation conditions.

In Vitro and In Vivo Biosafety Analysis of Resorbable Polyglycolic Acid-Polylactic Acid Block Copolymer Composites for Spinal Fixation.

Herein, spinal fixation implants were constructed using degradable polymeric materials such as PGA-PLA block copolymers (poly(glycolic acid-b-lactic acid)). These materials were reinforced by blending with HA-g-PLA (hydroxyapatite-graft-poly lactic acid) and PGA fiber before being tested to confirm its biocompatibility via in vitro (MTT assay) and in vivo animal experiments (i.e., skin sensitization, intradermal intracutaneous reaction, and in vivo degradation tests). Every specimen exhibited suitable biocompatibility and biodegradability for use as resorbable spinal fixation materials.

Novel PEEK Copolymer Synthesis and Biosafety - I: Cytotoxicity Evaluation for Clinical Application.

In this research, we synthesized novel polyetheretherketone (PEEK) copolymers and evaluated the biosafety and cytotoxicity of their composites for spinal cage applications in the orthopedic field. The PEEK copolymers and their composites were prepared through a solution polymerization method using diphenyl sulfone as a polymerization solvent. The composite of PEEK copolymer showed good mechanical properties similar to that of natural bone, and also showed good thermal characteristics for the processing of clinical use as spine cage. The results of an in vitro cytotoxicity test did not show any evidence of a toxic effect on the novel PEEK composite. On the basis of these cytotoxicity test results, the PEEK composite also proved its in vitro biosafety for application to an implantable spine cage.

Synthesis of a Carbonaceous Two-Dimensional Material.

Despite tremendous accomplishments achieved in 2D materials, little progress has been made in carbonaceous 2D materials beyond graphene and graphene oxide. Here, we report a 2D material of carbonaceous nanoplates (CANP). The bottom-up synthesis of CANP is green, separation-free, and massive. The nanoplates are 2 to 3 monolayers thick with an average interlayer spacing of 0.57 nm. The synthesis involves viscosity-aided two-dimensional growth of fragmented glucose derivatives and leads to the complete conversion of glucose to the 2D nanoplates. Application tests demonstrate the usefulness of the affordable 2D material.

Improving Dispersion and Barrier Properties of Polyketone/Graphene Nanoplatelet Composites via Noncovalent Functionalization Using Aminopyrene.

A series of polyketone (PK) nanocomposite films with varying content of noncovalently functionalized graphene nanoplatelet with 1-aminopyrene (GNP/APy) is prepared by solution blending with a solvent of hexafluoro-2-propanol. GNP/APy, prepared by a facile method, can effectively induce specific interaction such as hydrogen bonding between the amine functional group of GNP/APy and the carbonyl functional group of the PK matrix. With comparison of GNP and GNP/Py as reference materials, intensive investigation on filler-matrix interaction is achieved. In addition, the dispersion state of the functionalized GNP (f-GNPs; GNP/Py and GNP/APy) in the PK matrix is analyzed by three-dimensional nondestructive X-ray microcomputed tomography, and the increased dispersion state of those fillers results in significant improvement in the water vapor transmission rate (WVTR). The enhancement in WVTR of the PK/GNP/APy nanocomposite film at 1 wt % loading of filler leads to a barrier performance approximately 2 times larger compared to that of PK/GNP nanocomposite film and an approximately 92% reduction in WVTR compared to the case of pristine PK film. We expect that this facile method of graphene functionalization to enhance graphene dispersibility as well as interfacial interaction with the polymer matrix will be widely utilized to expand the potential of graphene materials to barrier film applications.

High-Performance Electroactive Polymer Actuators Based on Ultrathick Ionic Polymer-Metal Composites with Nanodispersed Metal Electrodes.

Ionic polymer-metal composites (IPMCs) have been proposed as biomimetic actuators that are operable at low applied voltages. However, the bending strain and generating force of the IPMC actuators have generally exhibited a trade-off relationship, whereas simultaneous enhancement of both the qualities is required for their practical applications. Herein, a significant improvement in both the strain and force of the IPMC actuators is achieved by a facile approach, exploiting thickness-controlled ion-exchange membranes and nanodispersed metal electrodes. To guarantee a large generating force of the IPMC actuators, ultrathick ion-exchange membranes are prepared by stacking pre-extruded Nafion films. Metal electrodes with a nanodispersed structure are formed on the membranes via alcohol-assisted electroless plating, which allows increased capacitance and facilitated ion transport. The resulting actuators exhibit greatly enhanced electromechanical properties, including an approximately four times larger strain and two times larger force compared to those of actuators having the conventional structure. Moreover, the ability to lift 16 coins (a weight of 124 g) has been successfully demonstrated using ultrathick IPMC actuators, which shows great promise in realizing artificial muscles.

Highly Enhanced Force Generation of Ionic Polymer-Metal Composite Actuators via Thickness Manipulation.

On purpose to enhance the generating force of ionic polymer-metal composite (IPMC) actuators, the thickness of the ion-exchange membrane is manipulated in two different ways. One is grafting poly(styrenesulfonic acid) onto poly(vinylidene fluoride-co-hexafluoropropylene) films with varying thickness, and the other is stacking pre-extruded Nafion films to thicker films by pressing at high temperatures. For both groups of the membranes, ionic properties including ion-exchange capacity and ionic conductivity are maintained similarly inside the groups regardless of the thickness. The actuation tests clearly show the increase in generating force with increasing thickness of the IPMCs prepared. It is due to a larger bending stiffness of thicker IPMCs, which is consistent with the predicted result from the cantilever beam model. The increase in force is more remarkable in Nafion-stacked IPMCs, and a thick IPMC lifts a weight of 100 g, which far exceeds the reported values for IPMCs.

Ionic polymer-metal composite actuators obtained from radiation-grafted cation- and anion-exchange membranes.

Two series of ionic polymer-metal composites (IPMCs), one cationic and one anionic, are designed and prepared from radiation-grafted ion-exchange membranes. Through examination of the properties of the membranes synthesized from the two grafting monomers and the two base polymers, acrylic acid-grafted poly(vinylidene fluoride-co-hexafluoropropylene) and quarternized 4-vinylpyridine-grafted poly(ethylene-co-tetrafluoroethylene) with the appropriate amount of ionic groups are employed for the fabrication of cation and anion IPMCs, respectively. The bending displacement of the cation IPMC is comparable to Nafion-based IPMC under direct- and alternating-current voltage, but back-relaxation is not observed. The actuation performance of the anion IPMC is highly improved over those reported earlier in the literature for the other anion IPMCs.

Development of endovascular vibrating polymer actuator probe for mechanical thrombolysis: in vivo study.

In this study, we propose a new method for the enhancement of intraarterial thrombolysis by use of an endovascular vibrating polymer actuator probe (VPAP), which is fabricated from an ionic polymer metal composite (IPMC) actuator. The endovascular VPAP was fabricated by combining 0.8 × 0.8 × 10 mm3 IPMC samples, 0.22 mm × 50 cm copper wires, and 40 cm of Teflon tube. The purpose of this study was to evaluate the thrombolysis efficiency of an endovascular VPAP in a dog model. Both renal arteries of the enrolled dogs (n = 5) were used in the current study. A distal portion of the renal artery in a mongrel dog was occluded by a blood clot from autologous venous whole blood. Intraarterial thrombolysis was performed by use of a VPAP without the actuation force (control group), by a VPAP-only (VPAP-only group), or with a combination of recombinant tissue plasminogen activator (rtPA) and a VPAP (VPAP + rtPA group). The thrombolysis efficiency was evaluated by the modified Thrombolysis in Myocardial Infarction (TIMI) grading system based on the consensus between two radiologists. The grading scales were compared according to each intraarterial thrombolysis method. The VPAP + rtPA and VPAP-only groups showed a significantly higher thrombolysis efficiency than did the control group (p < 0.05). The VPAP-only group also showed a significantly higher thrombolysis efficiency than did the control group (p < 0.05). The VPAP+ rtPA group showed a significantly higher thrombolysis efficiency than did the VPAP-only group (p < 0.05). The use of an endovascular VPAP was a feasible and useful method for intraarterial thrombolysis, and it enhanced the thrombolysis efficiency when combined with the thrombolytic agent rtPA.

Development of endovascular vibrating polymer actuator probe for mechanical thrombolysis: a phantom study.

In this study, we propose a new method for enhancement of intraarterial thrombolysis using an ionic polymer-metal composite (IPMC) actuator. The purpose of this study was to test the mechanical thrombolysis efficiency of IPMC actuators and evaluate the endovascular vibrating polymer actuator probe for mechanical thrombolysis in a phantom model; 2 × 1 × 15 mm (2 mm in width, 1 mm in thickness, and 15 mm in length) and 0.8 × 0.8 × 10 mm (0.8 mm in width, 0.8 mm in thickness, and 10 mm in length) IPMC actuators were fabricated by stacking five and four Nafion-117 films, respectively. We manufactured the endovascular vibrating polymer actuator probe, for which thrombolysis efficiency was tested in a vascular phantom. The phantom study using 2 × 1 × 15 mm IPMC actuators showed that 5 Hz actuation is the optimal frequency for thrombolysis under both 2 and 3 V, when blood clot was not treated with rtPA, and when exposed to rtPA, IPMC actuators under the optimized condition (3 V, 5 Hz, and 5 min) significantly increased the thrombolysis degree compared with control and other experimental groups (p < 0.05). In addition, 0.8 × 0.8 × 10 mm IPMC actuators also revealed a significantly higher thrombolysis degree under the optimized condition than the control and rtPA only groups (p < 0.05). Finally, the fabricated probe using 0.8 × 0.8 × 10 mm IPMC actuators also incurred higher thrombolysis degree under the optimized condition than the control and rtPA only groups (p < 0.05). A vibrating polymer actuator probe is a feasible device for intravascular thrombolysis, and further study in an animal model is warranted.

Synthesis of gold nanoparticles from gold(I)-alkanethiolate complexes with supramolecular structures through electron beam irradiation in TEM.

Monodisperse gold nanoparticles were prepared via electron beam irradiation of Au(I)-SR (R = -CnH2n+1) polymers with highly ordered supramolecular structures in transmission electron microscopy. The Au(I)-SR polymers were synthesized simply by mixing LiAuCl4 and an excess amount of alkanethiol in tetrahydrofuran. The sizes of the gold nanoparticles were controlled by changing the length of the alkyl group or by adjusting the energy of the electron beam.