Chih-Chia Cheng

A new supramolecular sulfonated polyimide for use in proton exchange membranes for fuel cells

Uracil-terminated telechelic sulfonated polyimides (SPI-U) were transformed into noncovalent network membranes through biocomplementary hydrogen bonding recognition in the presence of an adenine-based crosslinking agent. SPI-U membrane exhibited dramatically improved methanol permeability, oxidative stability, proton conductivity, and selectivity relative to those of the standard SPI.

A New Supramolecular Hole Injection/Transport Material on Conducting Polymer for Application in Light-Emitting Diodes

A new DNA-mimetic π-conjugated polymer poly(triphenylamine-carbazole) (PTC-U) has been prepared which exhibits high thermal stability, non-corrosion, excellent hole injection and electron-blocking abilities in the solid state owing to the uracil induced physical cross-linking. In addition, a trilayer device with PTC-U as a hole injection/transport layer is approximately 1.6 times higher than that of the commercial product PEDOT:PSS-based devices.

A new supramolecular POSS electroluminescent material

A new polyhedral oligomeric silsesquioxane (POSS) core star-like supramolecular blue-light electroluminescent material, 4-uracilbutyl-1-methylpyrene ether (U-PY)/octakis[dimethyl(N-(6-acetamidopyridin-2 yl))siloxy] silsesquioxane (ODAP-POSS) has been synthesized. This U-PY/ODAP-POSS contains eight pyrene chromophore arms formed through complementary uracil-diamidopyridine (U-DAP) pairs and exhibits high quantum efficiencies and good solution processing properties. The photoluminescence spectra of U-PY/ODAP-POSS (50/50) reveal that the color is stable after heating the sample at 150 °C for 1 h, in contrast, the pyrene/ODAP-POSS (50/50) shows significant thermal quenching. An electroluminescence (EL) device based on U-PY/ODAP-POSS exhibits higher maximum brightness and higher luminance efficiency relative to that of the U-PY. In addition, U-PY/ODAP-POSS also behaves as an effective dopant that enhances energy transfer from itself to MEH-PPV. The U-PY/ODAP-POSS-doped MEH-PPV blends exhibit high luminance efficiency, 1.45 times greater than MEH-PPV.

Self-supporting Polymer from a POSS Derivative

A new polyhedral oligomeric silsesquioxane macromer, octakis[N-(6-aminopyridin-2-yl)undecanamide-10-dimethyl-siloxy]silsesquioxane (POSS-C11-Py), containing eight diaminopyridine arms, is able to self-assemble to form a physically crosslinked polymer-like structure with good mechanical properties (tensile strength = 46.1 MPa, tensile modulus = 0.58 GPa, elongation = 49.3%) through quadruple hydrogen bonding interactions between these arms. POSS-C11-Py is the first organic/inorganic supermolecule possessing polymer-like mechanical properties as a result of self-complementary interactions, providing a potential route toward the design and fabrication of polymer-like supramolecular materials.

Supramolecular structures of uracil-functionalized PEG with multi-diamidopyridine POSS through complementary hydrogen bonding interactions

In this study, we synthesized (i) a multi-diamidopyridine-functionalized polyhedral oligomeric silsesquioxane (MD-POSS) through nucleophilic substitution and click 1,3-cycloaddition reactions and (ii) both mono- and bis-uracil (U)-functionalized poly(ethylene glycol) derivatives (U–PEG and U–PEG–U, respectively) through Michael additions of U to acryloyl-functionalized PEG oligomers. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) revealed that supramolecular structures self-assembled from mixtures of MD-POSS and U–PEG and from MD-POSS and U–PEG–U. Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy confirmed the presence of multiple hydrogen bonding interactions between the diaminopyridine groups of MD-POSS and the U groups of U–PEG and U–PEG–U. Because of these strong reversible intermolecular multiple hydrogen bonds, the POSS-based polymer-like supramolecular materials exhibited improved thermal properties upon increasing the MD-POSS content.

Bioinspired hole-conducting polymers for application in organic light-emitting diodes

A novel uracil-functionalized poly(3-thiophene) as a hole-injecting/transporting layer in an organic light-emitting device is able to form physical crosslinkages resulting in high thermal stability, non-corrosion, excellent hole injection/transport and electron-blocking capabilities in the solid state, and it achieves up to 10 times higher performance than that of conventional poly(3-thiophene)s under similar experimental conditions.

A new supramolecular film formed from a silsesquioxane derivative for application in proton exchange membranes

A new polyhedral oligomeric silsesquioxane ionomer (HCl-doped POSS-C11-Py) has been investigated. This new ionomer is able to self-assemble through macromers by quadruple hydrogen bonding interactions into a physically crosslinked polymer-like material that can be easily fabricated into films with micro-phase separation. This HCl-doped POSS-C11-Py membrane exhibits higher proton conductivity than a typical Nafion® membrane at high temperature, which is extremely rare for a non-sulfonic acid system. This newly developed material may provide an alternative route toward design and fabrication of a new type of proton exchange membranes.

A new benzoxazine containing uracil, complementary functionality

A new benzoxazine, uracil containing benzoxazine (UBz), has been successfully synthesized. The FTIR and DSC measurement of the poly(UBz)/poly(BA-a) blends indicated that hydrogen bonding interactions between uracil groups would result in a decrease in the exothermic peak temperature. In addition, the PL measurement confirmed that the poly(UBz)/poly(BA-a) blend possessed complementary behavior.

Reversibly thermoswitchable two-dimensional periodic gratings prepared from tethered poly(N-isopropylacrylamide) on silicon surfaces.

In this study we used atom transfer radical polymerization to graft poly(N-isopropylacrylamide) (PNIPAAm) onto flat Si substrates. We then applied very large-scale integration and reactive ion etching sequentially to generate 200-nm-scale hole arrays of tethered PNIPAAm as two-dimensional periodic concave gratings (2DPCGs) on the Si surfaces. The hole array structures of tethered PNIPAAm could be created and erased reversibly at 25 and 40 °C, respectively, leading to significant changes in the effective refractive index (neff). The values of neff of the 2DPCGs were related to the depth of their holes generated after etching for various times, resulting in a color change from blue to red that could be observed by the naked eye at incident angles of 10-20°. Moreover, we used effective-medium theory to calculate the filling factors of air inside the 2DPCGs to verify the structural changes of the tethered PNIPAAm. Such designed 2DPCGs of thermorespective hydrogel films have potential applications in temperature-responsive optical devices [e.g., as antireflection structured surfaces (ARSs)] that operate at both visible and near-infrared wavelengths.

Bioinspired supramolecular fibers for mercury ion adsorption

A novel photo-cross-linkable nanofiber based on a uracil-functionalized polymer, poly[1-(4-vinylbenzyl uracil)] (PVBU), was prepared using the electrospinning technique. This PVBU nanofiber can be converted into a covalent network nanofiber through exposure to UV light at a wavelength of 254 nm. This PVBU nanofiber is able to distinguish and selectively remove mercury ions (Hg2+) from other metal ions in aqueous solution. The maximum Hg2+ adsorption capacity of the PVBU nanofiber is 543.9 mg g−1, which is significantly higher than that of cyclic imide derivatives. The improved adsorption of Hg2+ allows a detection limit of less than 1 ppm, which has rarely been achieved for Hg2+ sensing. Furthermore, the PVBU fiber can be reused for 10 consecutive cycles using 1.0 M HCl treatment. This new material has significant potential for the simultaneous detection and separation of Hg2+ in environmental and industrial fields.