User-demand fast-curable ocular glues enforced by multilength tunable networks.

Achieving fast and secure wound closure without ocular foreign body sensation is highly desired in ophthalmologic surgery. Sutureless approaches using tissue adhesives are gaining popularity, but their practical use is limited by the difficulty in controlling adhesion time and satisfying safety standards without compromising adhesive performance. Herein, we report user-demand hydrogel-forming ocular glues based on multilength photo-crosslinkable hyaluronic acid (HA), achieving firm tissue adhesion under wet and dynamic conditions and possessing cornea-like optical transparency. The HA-based photocurable glue (HA photoglue) quickly seals wounds upon nontoxic low-energy light exposure (320-500 nm, < 5 s, < 1 J cm-2), and its mechanical and adhesive properties are improved by introducing short and long crosslinkable moieties into HA through one-step synthesis, forming multilength networks. Furthermore, the HA photoglue provides stable sealing in wet environments like ocular mucous surface, a clear vision with a light transmittance of more than 95% over the entire visible range, and a lubricating surface with minimal ocular sensation (generating less than 10% frictional force than suture groups). In a rabbit corneal incision model, the HA photoglue showed improved wound healing efficacy based on histological evaluation compared to control groups.

Acid-Treated Water-Soluble Chitosan Suitable for Microneedle-Assisted Intracutaneous Drug Delivery.

Chitosan has been widely used as a nature-derived polymeric biomaterial due to its high biocompatibility and abundance. However, poor solubility in aqueous solutions of neutral pH and multiple fabrication steps for the molding process limit its application to microneedle technology as a drug delivery carrier. Here, we present a facile method to prepare water-soluble chitosan and its application for sustained transdermal drug delivery. The water-soluble chitosan was prepared by acid hydrolysis using trifluoroacetic acid followed by dialysis in 0.1 M NaCl solutions. We successfully fabricated bullet-shaped microneedle (MN) arrays by the single molding process with neutral aqueous chitosan solutions (pH 6.0). The chitosan MN showed sufficient mechanical properties for skin insertion and, interestingly, exhibited slow dissolving behavior in wet conditions, possibly resulting from a physical crosslinking of chitosan chains. Chitosan MN patches loading rhodamine B, a model hydrophilic drug, showed prolonged release kinetics in the course of the dissolving process for more than 72 h and they were found to be biocompatible to use. Since the water-soluble chitosan can be used for MN fabrication in the mild conditions (neutral pH and 25 °C) required for the loading of bioactive agents such as proteins and achieve a prolonged release, this biocompatible chitosan MN would be suitable for sustained transdermal drug delivery of a diverse range of drugs.

High temperature polyimide containing anthracene moiety and its structure, interface, and nonvolatile memory behavior.

A high temperature polyimide bearing anthracene moieties, poly(3,3'-di(9-anthracenemethoxy)-4,4'-biphenylene hexafluoroisopropylidenediphthalimide) (6F-HAB-AM PI) was synthesized. The polymer exhibits excellent thermal stability up to around 410 °C. This polymer is amorphous but orients preferentially in the plane of nanoscale thin films. In device fabrications of its nanoscale thin films with metal top and bottom electrodes, no diffusion of the metal atoms or ions between the polymer and electrodes was found; however, the aluminum bottom electrode had somewhat undergone oxide layer (about 1.2 nm thick) formation at the surface during the post polymer layer formation process, which was confirmed to have no significant influence on the device performance. The polymer thin film exhibited excellent unipolar and bipolar switching behaviors over a very small voltage range, less than ±2 V. Further, the PI films show repeatable writing, reading, and erasing ability with long reliability and high ON/OFF current ratio (up to 10(7)) in air ambient conditions as well as even at temperatures up to 200 °C.

Electrical memory characteristics of a nondoped pi-conjugated polymer bearing carbazole moieties.

Poly[bis(9H-carbazole-9-ethyl)dipropargylmalonate] (PCzDPM) is a novel pi-conjugated polymer bearing carbazole moieties that has been synthesized by polymerization of bis(9H-carbazole-9-ethyl)dipropargylmalonate with the aid of molybdenum chloride solution as the catalyst. This polymer is thermally stable up to 255 degrees C under a nitrogen atmosphere and 230 degrees C in air ambient; its glass-transition temperature is 147 or 128 degrees C, depending on the polymer chain conformation (helical or planar structure). The charge-transport characteristics of PCzDPM in nanometer-scaled thin films were studied as a function of temperature and film thickness. PCzDPM films with a thickness of 15-30 nm were found to exhibit very stable dynamic random access memory (DRAM) characteristics without polarity. Furthermore, the polymer films retain DRAM characteristics up to 180 degrees C. The ON-state current is dominated by Ohmic conduction, and the OFF-state current appears to undergo a transition from Ohmic to space-charge-limited conduction with a shallow-trap distribution. The ON/OFF switching of the devices is mainly governed by filament formation. The filament formation mechanism for the switching process is supported by the metallic properties of the PCzDPM film, which result in the temperature dependence of the ON-state current. In addition, the structure of this pi-conjugated polymer was found to vary with its thermal history; this change in structure can affect filament formation in the polymer film.

The biocompatibility of self-assembled brush polymers bearing glycine derivatives.

We have synthesized brush polymers with various glycine derivatives as the end groups of their long alkyl bristles. The polymers are thermally stable up to 170-210 degrees C and form good quality films through conventional spin- or dip-coating and subsequent drying. Interestingly, the thin films of these brush polymers exhibit different molecular multi-layer structures that arise through the efficient self-assembly of the bristles with glycine derivative end groups. These brush polymer films have hydrophilic surfaces and exhibit some water sorption. The extent of the water sorption by these films depends upon the nature of the glycine derivatives in the bristle end. These films not only repel fibrinogen molecules and platelets from their surfaces, but also have high resistance to bacterial adherence. Moreover, the films were found to provide conducive surface environments for the successful anchoring and growth of HEp-2 cells, and to exhibit excellent biocompatibility in mice. These brush polymers have potential uses in biomedical applications including medical devices, especially blood contacting devices such as catheters, stents, blood vessels, and biosensors, due to their enhanced biocompatibility and the reduced possibility of post-operative infection.

Programmable permanent data storage characteristics of nanoscale thin films of a thermally stable aromatic polyimide.

We have synthesized a new thermally and dimensionally stable polyimide, poly(4,4'-amino(4-hydroxyphenyl)diphenylene hexafluoroisopropylidenediphthalimide) (6F-HTPA PI). 6F-HTPA PI is soluble in organic solvents and is thus easily processed with conventional solution coating techniques to produce good quality nanoscale thin films. Devices fabricated with nanoscale thin PI films with thicknesses less than 77 nm exhibit excellent unipolar write-once-read-many-times (WORM) memory behavior with a high ON/OFF current ratio of up to 10(6), a long retention time and low power consumption, less than +/-3.0 V. Furthermore, these WORM characteristics were found to persist even at high temperatures up to 150 degrees C. The WORM memory behavior was found to be governed by trap-limited space-charge limited conduction and local filament formation. The conduction processes are dominated by hole injection. Thus the hydroxytriphenylamine moieties of the PI polymer might play a key role as hole trapping sites in the observed WORM memory behavior. The properties of 6F-HTPA PI make it a promising material for high-density and very stable programmable permanent data storage devices with low power consumption.

Nonvolatile unipolar and bipolar bistable memory characteristics of a high temperature polyimide bearing diphenylaminobenzylidenylimine moieties.

This study reports the synthesis and properties (in particular, the electrical switching characteristics) of a new high-performance polyimide (PI), poly(3,3'-di(4-(diphenylamino)benzylidenyliminoethoxy)-4,4'-biphenylene hexafluoroisopropylidenediphthalimide) (6F-HAB-TPAIE PI). This PI polymer bears diphenylaminobenzylidenylimine moieties as side groups and is dimensionally stable up to 280 degrees C and thermally stable up to 440 degrees C. In devices fabricated with the PI polymer as an active memory layer, the active PI polymer was found to operate at less than +/-2 V in electrically bistable unipolar and bipolar switching modes by controlling the compliance current. The PI polymer layer exhibits repeatable writing-reading-erasing capability with high reliability in ambient air conditions as well as at high temperatures up to 130 degrees C. This PI polymer also exhibits a high ON/OFF current ratio up to 10(9). The observed nonvolatile memory behaviors are due to Schottky emission and local filament formation. This study has demonstrated that this thermally, dimensionally stable PI polymer is a promising material for mass production at low cost for high-performance, programmable, nonvolatile memory devices that can be operated with low power consumption in unipolar and bipolar switching modes.

Programmable digital memory devices based on nanoscale thin films of a thermally dimensionally stable polyimide.

We have fabricated electrically programmable memory devices with thermally and dimensionally stable poly(N-(N',N'-diphenyl-N'-1,4-phenyl)-N,N-4,4'-diphenylene hexafluoroisopropylidene-diphthalimide) (6F-2TPA PI) films and investigated their switching characteristics and reliability. 6F-2TPA PI films were found to reveal a conductivity of 1.0 x 10(-13)-1.0 x 10(-14) S cm(-1). The 6F-2TPA PI films exhibit versatile memory characteristics that depend on the film thickness. All the PI films are initially present in the OFF state. The PI films with a thickness of >15 to <100 nm exhibit excellent write-once-read-many-times (WORM) (i.e. fuse-type) memory characteristics with and without polarity depending on the thickness. The WORM memory devices are electrically stable, even in air ambient, for a very long time. The devices' ON/OFF current ratio is high, up to 10(10). Therefore, these WORM memory devices can provide an efficient, low-cost means of permanent data storage. On the other hand, the 100 nm thick PI films exhibit excellent dynamic random access memory (DRAM) characteristics with polarity. The ON/OFF current ratio of the DRAM devices is as high as 10(11). The observed electrical switching behaviors were found to be governed by trap-limited space-charge-limited conduction and local filament formation and further dependent on the differences between the highest occupied molecular orbital and the lowest unoccupied molecular orbital energy levels of the PI film and the work functions of the top and bottom electrodes as well as the PI film thickness. In summary, the excellent memory properties of 6F-2TPA PI make it a promising candidate material for the low-cost mass production of high density and very stable digital nonvolatile WORM and volatile DRAM memory devices.