Search

Herein, we present different functionalized meta-stable photoacids in ion-sensors to tune the equilibrium response time. As a proof of concept, two new meta-stable photoacids were synthesized, one contains an ether group and the other has an ester functional group. These functionalized meta-stable photoacids were elucidated in solution of ethanol and in ion-sensing films via pH and kinetic studies. In comparison from our previous work, the response time was reduced from hours to minutes by utilizing an ether functional group in the meta-stable photoacid.

Controlled release of odorous molecules is the key to digital scent technology which will add another dimension to electronics. Photorelease is a cold mechanism that promises better temporal and spatial control than thermal release. Herein we report a novel material composed of an acid-sensitive polymer carrying a fragrant aldehyde and a reversible metastable-state photoacid. It releases the fragrant molecule under visible light, and stops releasing it after the light is turned off. A metastable-state photoacid with a fast reverse-reaction rate was developed to quickly stop the release after irradiation. Both the carrier polymer and the photoacid can be reused after all the fragrant molecules have been released. The material combines the advantages of visible-light activity, fast on/off rate, easy preparation, and recyclability, and thus is promising for digital scent technology.

Presented here is a sensing membrane consisting of a modified merocyanine photoacid polymer and a calcium ionophore in plasticized poly(vinyl chloride). This membrane is shown to actively exchange protons with calcium ions when switched ON after illumination at 470 nm, and the exchange can be followed by UV-vis spectroscopy. The sensing membrane shows no response in the ON state when calcium ions are absent. The limit of detection of the sensor is 5.0 × 10(-4) M with an upper detection limit of 1.0 M. Thus, we demonstrate for the first time the use of a visible light activated, lipophilic photoacid polymer in an ion-sensing membrane for calcium ions, which highly discriminates potassium, sodium, and magnesium ions.

Composites of polyaniline in its emeraldine base form (PANI-EB) and photo-acid generators (PAG) show an increase in conductivity upon photo-irradiation due to the protonation of PANI-EB. Such materials may be utilized to fabricate conducting patterns by photo-irradiation. However, the conductivity obtained by direct irradiation of PANI-EB/PAG composites was normally quite low (

Herein we report the formation of the second-ring Diels–Alder adduct together with the central-ring adduct in a reaction of pentacene and tetracyanoethylene at room temperature. DFT calculations showed that the difference between the free energy of the two isomers is about 3.9 kcal/mol. Photo- and thermal-induced isomerization between the central-ring adduct and the second-ring adduct were studied in solution and in polymer films. In solution, the less-stable second-ring adduct can be converted into the more-stable central-ring adduct either thermally or photochemically, but the reverse transformation does not occur. In a polymer matrix, isomerization can be photochemically induced in both directions at different wavelengths, which results in a photoswitchable system. Formation of pentacene in the photochemical experiments was also observed, which supports an isomerization process involving a photo-retro-Diels–Alder reaction.

Composites of the emeraldine base form of polyaniline (PANI-EB) and photo-acid generators (PAGs) increase their conductivities upon photo-irradiation due to protonation of PANI-EB. Such materials may be utilized to fabricate conducting patterns by photo-irradiation. However, the conductivity obtained by direct irradiation of PANI-EB/PAG composites was normally quite low, and conductivity above 10−3 S cm−1 often required post-treatment with HCl. In this work, poly(vinyl alcohol) (PVA), which can form a hydrogen bonding network, was added to PANI-EB/PAG. Results showed that PVA enhanced film quality, conductivity and reproducibility. Photo-induced conductivity of 10−2 S cm−1 was obtained when the ratio of PANI-EB/PVA/PAG was 1:1:0.6. A novel PAG, bis(p-hydroxyphenyl)phenylsulfoniumtriflate [(PhOH)2PhS+ OTf−], which can form hydrogen bonds with PANI was synthesized and mixed with PANI-EB. A composite of PANI-EB and the PAG with a ratio of 1:0.5 achieved a conductivity of 10−1 S cm−1 after irradiation. However, the initial conductivity before irradiation was as high as 10−5 S cm−1 due to relatively high acidity of the PAG.

Photo-retro-Diels-Alder (PrDA) reactions of a variety of Diels-Alder (DA) adducts were studied. Experimental results showed that the photoreactivity (quantum yield) depends on the electron-donating ability of the diene component and the electron-withdrawing ability of the dienophile component. The mechanism was studied by trapping the reaction intermediate, O(2) quenching, time-resolved absorption, and fluorescence spectroscopy. All the results support a mechanism that involves a charge-separated intermediate generated from a singlet excited state. The PrDA reaction may find applications in photoresponsive materials, photolithography, drug delivery, and mechanistic research.

A photoacid that possesses a metastable acidic state induced by visible light is studied. Previous work showed that this photoacid can reversibly produce a large pH change capable of controlling chemical reactions, altering material properties, and killing bacteria. In this work, we studied the relaxation kinetics of the metastable acidic state in different solvents including water, ethanol, and DMSO. In all of these solvents, the kinetic data can be fitted well to a second-order rate equation, which indicates that protonation is involved in the rate-limiting step. The rate constants in water, ethanol, and DMSO are 73, 1.6, and 0.034 M(-1) s(-1), respectively. The slow relaxation in DMSO allowed us to fully characterize the structure of the metastable acidic state using proton NMR. We also measured the quantum yield of the photoreaction, which is as high as 0.37.

A new photoacid that reversibly changes from a weak to a strong acid under visible light was designed and synthesized. Irradiation generated a metastable state with high CH acidity due to high stability of a trifluoromethyl-phenyl-tricyano-furan (CF3 PhTCF) carbanion. This long-lived metastable state allows a large proton concentration to be reversibly produced with moderate light intensity. Reversible pH change of about one unit was demonstrated by using a 0.1 mM solution of the photoacid in 95 % ethanol. The quantum yield was calculated to be as high as 0.24. Kinetics of the reverse process can be fitted well to a second-order-rate equation with k=9.78×10(2) M(-1) s(-1) . Response to visible light, high quantum yield, good reversibility, large photoinduced proton concentration under moderate light intensity, and good compatibility with organic media make this photoacid a promising material for macroscopic control of proton-transfer processes in organic systems.

Conducting polymers are potentially useful materials in sensor applications. Polyaniline is one of the most promising of these materials due to high conductivity and plasma frequencies as high as the midinfrared. The application of this material is still limited because of low conductivity. In this paper, we chemically prepared a composite of co-doped polyaniline with hydrochloric and HMSA (methanesulfonic acid) in aqueous solution with both colloidal and nano-graphite. Solutions of the composite material were prepared in m-cresol and NMP (1-mthyle-2-pyrolidinone), which are common organic solvents. This approach resulted in material with conductivity higher than either intrinsic polyaniline or graphite alone. The solution of the composite was spin coated on suitable substrates. The thicknesses of the films were measured using atomic force microscope (AFM). Fourier transform infrared spectra (FTIR) and micro-Raman spectra were collected to confirm the composition and determine the infrared thickness. Surface plasmon resonances for grating patterns of this composite material were calculated using experimental determined infrared (IR) ellipsometry data. The goal is to identify a material which has potential application for surface plasmons resonance sensing with high sensitivity and selectivity in IR range.

Novel organic photoCORMs based on micelle-encapsulated unsaturated cyclic α-diketones were designed and synthesized. These photoCORMs can be activated by visible light, have potentially low toxicity, allow the delivery of carbon monoxide to be monitored by fluorescence imaging techniques, and thus are useful tools for the study of the biological function of CO.