RESUMEN

Colorless, transparent, and mechanically robust aramid polymers are synthesized from two diamine monomers with strong electron-withdrawing groups, using low-temperature solution condensation with diacid chloride. The aramids dissolved very well in the liquid acrylamide monomers. When N,N-dimethylacrylamide (DMA) is used as a reactive diluent, films with the desired features are produced from the hybrid aramid-DMA resins via ultraviolet (UV) curing. The hybrid films are colorless and transparent in the visible region and showed an increase in the glass transition temperature, tensile strength, and elastic modulus in proportion to the aramid content. Laminated glass is manufactured using the hybrid resin as an interlayer, which exhibits very strong adhesion between the two sheets of glass, is not easily broken by an external impact, and do not scatter fragments. Moreover, the laminated glass do not distort images and functioned very effectively in UV blocking, soundproofing, and suppressing changes in the ambient temperature. Heat treatment further improves the light transmittance and impact resistance of the laminated glass. Laminated glass specimens with various fluorescence colors are also manufactured. Aramid-reinforced films prepared using N,N-diethylacrylamide as a reactive diluent underwent thermally induced phase separation in a wet state, providing smart glass with a privacy protection function.

RESUMEN

In this study, various diamine monomers were used to synthesize aramid polymer films via a low-temperature solution condensation reaction with diacid chloride. For diamines with relatively high basicity, the reaction system became opaque because amine salt formation inhibited polymer synthesis. Meanwhile, low-basicity diamines with strong electron-withdrawing groups, such as CF3 and sulfone, were smoothly polymerized without amine salt formation to provide highly viscous solutions. The acid byproduct HCl generated during polymerization was removed by adding propylene oxide to the reaction vessel and converting the acid into highly volatile inert substances. The resulting solutions were used as varnishes without any additional purification, and polymer films with an excellent appearance were easily obtained through a conventional casting and convection drying process. The films neither tore nor broke when pulled or bent by hand; furthermore, even when heated up to 400 °C, they did not decompose or melt. Moreover, polymers prepared from 2,2-bis(trifluoromethyl)benzidine (TFMB) and bis(4-aminophenyl)sulfone (pAPS) did not exhibit glass transition until decomposition. The prepared polymer films showed a high elastic modulus of more than 4.1 GPa and a high tensile strength of more than 52 MPa. In particular, TFMB-, pAPS-, and 2,2-bis(4-aminophenyl)hexafluoropropane-based polymer films were colorless and transparent, with very high light transmittances of 95%, 96%, and 91%, respectively, at 420 nm and low yellow indexes of 2.4, 1.9, and 4.3, respectively.

RESUMEN

The Sonogashira coupling reaction was used to synthesize a fluorenone derivative, with an extended conjugated structure to which fluorene is connected via acetylene linkage. This compound exhibited diverse fluorescence (FL) colors in the visible region depending on the polarity of the matrix solvents used. The solvatochromic FL presented as sky blue, green, and yellow in hexane, THF, and DMF, respectively. Fluorene moiety and fluorenone moiety acted as an electron donor (D) and as an electron acceptor (A), respectively, leading to an excited state intramolecular charge transfer based on the D-π-A electronic structure. In particular, this derivative showed a remarkable FL quenching in alcohol and chloroform, probably due to vibronic coupling through hydrogen bonding with these solvents. This idea was supported by the fact that the two solvents are characterized by very high hydrogen bond donor acidities compared to other solvents used in this study. This derivative also responded to the presence of very small amounts of water at several mg/mL levels in organic solvents, resulting in remarkable FL quenching.

RESUMEN

In this study, we synthesized three novel acrylic monomers with a cinnamate group. We then mixed each monomer with 2-hydroxyethyl methacrylate (HEMA) to prepare soft contact lenses through bulk polymerization. Fourier transform infrared (FT-IR) and UV spectral analyses confirmed that the cinnamate group in the polymer undergoes a photodimerization reaction via UV irradiation. After UV curing, the present lenses stably maintained their shapes even in a water-swollen state and showed significantly improved mechanical properties compared to conventional lenses manufactured using a cross-linking agent. These lenses showed slightly lower water contact angles than the conventional lenses, although the water content was slightly reduced. The present photodimerization cross-linking method was found to be useful in reducing the tearability of soft lenses.

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In this study, a chalcone-branched polyimide (CB-PI) was synthesized by the Steglich esterification reaction for selective recognition of the toxic peptide melittin (MEL). MEL was immobilized on a nanopatterned poly(dimethylsiloxane) (PDMS) mold using a conventional surface modification technique to increase binding sites. A stripe-nanopatterned thin CB-PI film was formed on a quartz crystal (QC) substrate by simultaneously performing microcontact printing and ultraviolet (UV) light dimerization using a MEL-immobilized mold. The surface morphology changes and dimensions of the molecularly imprinted polymer (MIP) films with stripe nanopatterns (S-MIP) were analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The sensing signals (Δf and Qe) of the S-MIP sensor were investigated upon adsorption in a 100-µL dilute plasma solution containing 30 µg/mL MEL, and its reproducibility, reuse, stability, and durability were investigated. The S-MIP sensor showed high sensitivity (5.49 mL/mg) and coefficient of determination (R2 = 0.999), and the detection limit (LOD) and the quantification limit (LOQ) were determined as 0.3 and 1.1 µg/mL, respectively. In addition, the selectivity coefficients (k*) calculated from the selectivity tests were 2.7-5.7, 2.1-4.3, and 2.8-4.6 for bovine serum albumin (BSA), immunoglobulin G (IgG), and apamin (APA), respectively. Our results indicate that the nanopatterned MIP sensors based on CB-PI demonstrate great potential as a sensing tool for the quantitative analysis of biomolecules.

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RESUMEN

Conjugated polyelectrolytes (CPEs) are emerging as promising materials in the sensor field because they enable high-sensitivity detection of various substances in aqueous media. However, most CPE-based sensors have serious problems in real-world application because the sensor system is operated only when the CPE is dissolved in aqueous media. Here, the fabrication and performance of a water-swellable (WS) CPE-based sensor driven in the solid state are demonstrated. The WS CPE films are prepared by immersing a water-soluble CPE film in cationic surfactants of different alkyl chain lengths in a chloroform solution. The prepared film exhibits rapid, limited water swellability despite the absence of chemical crosslinking. The water swellability of the film enables the highly sensitive and selective detection of Cu2+ in water. The fluorescence quenching constant and the detection limit of the film are 7.24 × 106 L mol-1 and 4.38 nM (0.278 ppb), respectively. Moreover, the film is reusable via a facile treatment. Furthermore, various fluorescent patterns introduced by different surfactants are successfully fabricated by a simple stamping method. By integrating the patterns, Cu2+ detection in a wide concentration range (nM-mM) can be achieved.

RESUMEN

Spontaneously sp2-carbonized polyamides (PA1, PA2) were prepared via Knoevenagel-type side reactions of malonyl moieties under mild conditions in the polycondensation of dicarbonyl chloride and diamine. Both polymers were soluble in water and emissive in the visible region, and the fluorescence (FL) intensity and the maximum wavelength were highly dependent on the excitation wavelength and the pH. Their chemical structures and FL origin were clarified by performing various spectroscopic analyses. π*-π transition was assumed to be allowed in an enol form based on the conjugated structure formed by the side reaction; this was responsible for its pH dependency and high FL quantum efficiency. In particular, PA2, which comprises the tertiary amide linkage, showed quick endocytosis, low cytotoxicity, excellent biocompatibility, and exclusively stained lysosomes with the lowest intracellular pH. These results will help in understanding the origin of the FL emission of carbonized nanomaterials and exploring more advanced functions in the field of bioimaging.

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RESUMEN

Noncovalent chemistry may offer diversity in the functions and applications for artificial polymers by allowing various ordered-disordered phase transitions in a precisely controlled manner. To verify this notion from a fundamental perspective, we examined an achiral poly(phenylacetylene) derivative with an α-helical structure as a helical-spring polymer for revealing phase changes through control of intramolecular hydrogen bonding with the chiral solvent and temperature. When an amine capable of hydrogen bonding was used as the chiral solvent, either an irreversible helix-helix or a reversible helix-coil phase change occurred in an optically dissymmetric manner according to the amount of the chiral solvent added and ambient temperature. Considering the hydrogen-bonding strength values of the solvent mixture and the thermodynamic parameters, we could predict if the optical-dissymmetry phase changes would occur and, if so, how they occur. Our results were similar to those see for the denaturation of proteins, induced by solvent and temperature, based on helix-coil phase transition.

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The piezochromic fluorescence (FL) of a distyrylpyrazine derivative, 2,3-diisocyano-5,6-distyrylpyrazine (DSP), was investigated in this study. Depending on the recrystallization method, DSP afforded two different crystals with green and orange FL emission. The orange color FL emission crystal (O-form) was easily converted to the green color FL emission one (G-form) by manual grinding. The G-form was also converted to a slightly different orange color FL emission crystal (RO-form) by a weak UV irradiation. When the RO-form was ground again, the G-form was regenerated. The FL colors changed between the G- and RO-forms over several ten times by repeated mechanical grinding and UV irradiation. The FL, UV-visible, 1H-NMR and XRD results showed that the O (or RO)-to-G transformation induced by mechanical stress results from the change of degree of molecular stacking from dense molecular stacking structure to relatively loose molecular stacking structure, whereas the G-to-RO reconversion by UV irradiation results from return to dense molecular stacking structure again due to lattice movement (lattice slipping) allowed by photocycloaddition in solid-state.

RESUMEN

A substituted poly(phenylacetylene) derivative (PPAHB ) with two hydroxymethyl groups at the meta position of the side phenyl ring was examined as a conformation-switchable helical spring polymer that responds to solvent and heat stimuli in a precisely controlled manner. Intramolecular hydrogen bonds, which cause the helical structure of the polymer, were broken and re-formed by adjusting the hydrogen-bonding strength values (pKHB ) of various combinations of solvents or by varying the temperature. In this process, a reversible conformational change from cis-cisoid to cis-transoid, accompanied by a phase transition in the form of a helix-coil transformation occurred, with the polymer exhibiting critical changes of color fading and recovery in specific environments. These results demonstrate that PPAHB can be used as either a pKHB indicator or a thermometer. The color changes of the polymer solution are described in detail based on spectroscopic analyses and thermodynamic considerations.

RESUMEN

A conformation-variable conjugated polyelectrolyte responding to oppositely charged biomolecules was examined as an imaging agent for the detection of latent fingerprints (LFPs). Sulfonated poly(diphenylacetylene) (SPDPA) produces high-resolution fluorescence (FL) LFP images by simple wetting of the target objects with the polymer solution without any additional treatment. SPDPA readily interacts with LFP sweat components (especially amino acids) via electrostatic interactions, leading to significantly enhanced FL images in a "turn-on" mode. The FL emission enhancement was examined in a model reaction between SPDPA and an amino acid standard. Visualization with SPDPA is effective on various surfaces, including both rough (paper) and smooth (glass and plastic) ones. Moreover, SPDPA readily interacts with extremely thin sweat LFPs, especially on smooth glass surfaces.

RESUMEN

Conjugated-polymer nanofibers with a thermodynamically stable, coarsened, disordered structure in an amorphous glassy state were fabricated via a freeze-drying method using a poly(diphenylacetylene) derivative. The nanofibers were extremely emissive, with a fluorescence (FL) quantum yield of approximately 0.34, which was much higher than that of both the cast film (0.02) and the solution (0.21). Similarly, the amplitude-weighted average FL lifetime of the nanofibers was 0.74 ns, which was much longer than that of the film (0.29 ns) and the solution (0.57 ns). This unusual and enhanced FL-emission behavior was attributed to the abruptly quenched chain structure that was created by the freeze-drying process. The polymer chains in the nanofibers remained frozen-in and the side phenyl rings were retained in a relaxed state. The metastable chains did not undergo vibrational relaxation and collisional quenching to generate the radiative emission decay effectively.

RESUMEN

A highly emissive, optically active poly(diphenylacetylene) derivative, NpSi*-PDPA, was synthesized by introducing a bulky chiral pendant group into the polymer chain. NpSi*-PDPA exists in a glassy state having a highly disordered and amorphous structure. Hence, the fractional free volume is quite high, i.e., 0.29. NpSi*-PDPA emits a green light in solution and a yellow light in film. This polymer is quite emissive, as the photoluminescence (PL) quantum yield is 56.1% in solution and 6.2% in film, and the PL lifetime is relatively long, 1.71 ns in solution and 1.05 ns in film. NpSi*-PDPA shows the strongest circular dichroism (CD) signal at 384 nm, with a magnitude of circular polarization (gCD) of 0.90 × 10-3 and an optical rotation of 110° (4.30 × 10-3 g mL-1, in CHCl3). The CD intensity is significantly increased by annealing at 80 °C, reaching an equilibrium at gCD of 7.10 × 10-3 after 72 h.

RESUMEN

A novel surface modifier, ethylenediamine tetraacetic acid tetrasodium salt (EDTNa), was incorporated on the surface of TiO2, and the resulting electrodes were applied to the photoanode of dye-sensitized solar cells (DSSCs). The DSSC with EDTNa-incorporated photoelectrode showed an increase in short-circuit current (JSC) and open-circuit voltage (VOC), resulting in a 16.5% enhancement in power conversion efficiency, compared to that of reference cell without EDTNa. It was found that the presence of the bulky ethylenediamine tetraacetate moieties increases lifetime of electrons injected from dye molecules to TiO2, resulting from an effective prevention of direct contact between electrolyte ions and the TiO2 surface. This improvement of lifetime induced the enhancement in J, and VOC.

RESUMEN

When aqueous conjugated-polyelectrolyte colloidal solutions containing an adequate amount of surfactant with an appropriate hydrophile-lipophile balance were sprayed onto latent fingerprints (LFPs), the polymer nanoparticles were readily transferred to the LFPs to reveal highly distinguishable fluorescent images, while the LFPs themselves remained intact.

RESUMEN

This paper reports a unique fluorescence (FL) response and diverse applications of conjugated polyelectrolyte (CPE) through nonelectrostatic interaction with appropriate (bio)surfactants in an immiscible two-phase system. A sulfonated microporous conjugated polymer (SMCP) with a conformation-variable intramolecular stacked structure was used as the CPE film. Despite the extremely high hydrophilicity, the SMCP film responded significantly to the hydrophobic circumstances, either physicochemically or electronically, in the presence of water-in-oil (w/o)-type nonionic surfactants with appropriate hydrophile-lipophile balance (HLB) values. The polymer film became fully wet with hydrophobic solvents due to the addition of small amounts of (bio)surfactant to reveal remarkable FL emission enhancement and chromism. Microcontact and inkjet printing using the SMCP film (or SMCP-adsorbed paper) and the surfactant solution as substrate and ink, respectively, provided high-resolution FL images due to the distinctive surfactant-induced FL change (SIFC) characteristic. Moreover, the additional electrostatic interaction of SMCP film with oppositely charged surfactants further enhanced the FL emission. Our findings will help comprehensive understanding of the nonelectrostatic SIFC mechanism of CPEs and development of novel SIFC-active materials.

RESUMEN

Novel thermoresponsive sensor systems consisting of a molecular rotor (MR) and paraffin wax (PW) were developed for various thermometric and biometric identification applications. Polydiphenylacetylenes (PDPAs) coupled with long alkyl chains were used as MRs, and PWs of hydrocarbons having 16-20 carbons were utilized as phase-change materials. The PDPAs were successfully dissolved in the molten PWs and did not act as an impurity that prevents phase transition of the PWs. These PDPA-in-PW hybrids had almost the same enthalpies and phase-transition temperatures as the corresponding pure PWs. The hybrids exhibited highly reversible fluorescence (FL) changes at the critical temperatures during phase transition of the PWs. These hybrids were impregnated into common filter paper in the molten state by absorption or were encapsulated into urea resin to enhance their mechanical integrity and cyclic stability during repeated use. The wax papers could be utilized in highly advanced applications including FL image writing/erasing, an array-type thermo-indicator, and fingerprint/palmprint identification. The present findings should facilitate the development of novel fluorescent sensor systems for biometric identification and are potentially applicable for biological and biomedical thermometry.

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To improve the operation lifetime of organic solar cell, two different diphenylacetylene polymers were tested as UV blocking layer. One of them showed either stronger UV absorption or a relatively intense fluorescence emission in the visible region which is well overlapped with the absorption of P3HT in the OSC. The diphenylacetylene polymer film significantly improved the operation lifetime of the OSC by efficiently absorbing the UV light, while reducing the UV-light energy loss to a minimum by converting the UV light to visible light through a down-conversion process.

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The surface of TiO2 photoelectrodes coated on F-doped SnO2 (FTO) was modified by soaking it in a TiCl4:AlCl3 mixed aqueous solution with various molar ratios, and then calcining to produce the TiCl4:AlCl3-treated TiO2 photoelectrode (Ti:Al-TiO2/FTO). The highest power conversion efficiency (PCE) was obtained from dye-sensitized solar cells (DSSC) with Ti:Al(5:5)-TiO2/FTO, which was prepared from the mixed solution with the molar ratio of 5:5 (TiCi4:AlCl3). PCE of DSSC with Ti:Al (5:5)-TiO2/FTO was improved by ca. 19.6%, compared to that of the reference device with Ti:Al (10:0)-TiO2/FTO (i.e., TiO2-coated TiO2/FTO) due to an enhancement in both short-circuit photocurrent (J(sc)) and open-circuit voltage (V(oc)). A series of measurements such as UV-visible absorption, electrochemical impedance, open circuit voltage decay and dark current revealed that the increase in J(sc) was attributed to the improvement of electron collection efficiency by a prolonged electron lifetime, and the suppression of the charge recombination between injected electrons and I3(-) ions was found to increase the V(oc) value of the device with Ti:Al(5:5)-TiO2/FTO.

RESUMEN

An anionic conjugated polyelectrolyte based on polydiphenylacetylene showed a significant fluorescence turn-on response to positively-charged proteins through a conformational relaxation of its intramolecular stack structure.

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