New mu-opioid receptor agonists with phenoxyacetic acid moiety

New muq-opioid receptor (MOR) agonists containing 4-hydroxypiperidine, piperidine and piperazine moieties were synthesized and evaluated to find a peripheral opioid analgesic. Among the synthesized compounds, 12-[1-[3-(N,N-dimethylcarbamoyl)-3,3-diphenylpropyl]-4-hydroxypiperidin-4-yl]phenoxy]acetic acid (8: SS620) having phenoxyacetic acid and 4-hydroxypiperidine moieties showed the highest agonist potency on the MOR in an isolated guinea-pig ileum preparation, and it also had selectivity to the human MOR expressed in Chinese hamster ovary (CHO)-K1 cells compared with the same types of delta- and kappa-opioid receptors (DOR and KOR). In addition, compound 8 showed a 10 times more potent MOR agonist activity than loperamide. Furthermore, compound 8 showed a peripheral analgesic activity in vivo screening on rat.     

Beta-replacement reaction of serine-O-carbonate derivatives with thiols catalyzed by a pyridoxal model having an ionophore side-chain

Serine-O-carbonate derivatives, including peptides having a serine-O-carbonate residue at the N-terminal position, are catalytically transformed into S-substituted cysteine derivatives employing the pyridoxal model having an ionophore function in the presence of Li+; this is the first artificial model mimicking cystathionine Beta-synthase.     

Controllable photopatterning and photochemical properties of novel copolymer containing dianthracene langmuir–blodgett films

A new series of copolymer poly(N‐hexadecylmeth acrylamide‐co‐bis(anthracen‐9‐ylmethyl) 2‐allylmalonate) [poly(HDMA‐co‐DAnMAMA)]s containing swallow‐tailed double anthracenyl groups and long alkyl group are designed and synthesized. The main route of the photochemical reaction of the p(HDMA‐DAnMAMA)copolymer Langmuir–Blodgett (LB) films is dimerization reaction between the anthracenyl groups under the irradiation of both 365 and 248 nm for limiting irradiation time, resulting to a fine negative‐tone pattern. On the other hand, the anthracenyl groups act just as photodecomposition group under 248 nm for longer irradiation time, resulting to a fine positive‐tone pattern. Consequently, positive‐tone and negative‐tone pattern are obtained by choosing not only a suitable irradiation light wavelength, but the irradiation time at 248 nm. Moreover, it is found that the exposed and unexposed regions of copolymer LB films irradiated at 248 nm have solubility differentiation in gold etchant (I₂/NH₄I/C₂H₅OH/H₂O), that is to say, the gold photopatterns with the maximal resolution of the used mask can be obtained easily without any development process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 139–147, 2012     

R3Al-R'3SiOTf: novel and powerful reagent system for stereospecific alkylation-silylation reactions of epoxides

[reaction: see text] A novel and powerful reagent system R(3)Al-R'(3)SiOTf for the one-pot alkylation-silylation reaction of epoxides was discovered, and the reactions of various epoxides with the new reagent system have been demonstrated to occur stereospecifically giving rise to the corresponding alkylation-silylation products in excellent yields.     

Influences of Acid on Molecular Forms of Fluorescein and Photoinduced Electron Transfer in Fluorescein‐Dispersing Sol–Gel Titania Films

Fluorescein‐dispersing titania gel films were prepared by the acid‐catalyzed sol–gel reaction using a titanium alkoxide solution containing fluorescein. The molecular forms of fluorescein in the films, depending on its acid–base equilibria, and the complex formation and photoinduced electron transfer process between the dye and titania surface were investigated by fluorescence and photoelectric measurements. The titanium species were coordinated to the carboxylate and phenolate‐like groups of the fluorescein species. The quantum efficiencies of the fluorescence quenching and photoelectric conversion were higher upon excitation of the dianion species interacting with the titania, i.e. the dye–titania complex. This result indicated that the dianion form was the most favorable for formation of the dye–titania complex exhibiting the highest electron transfer efficiency. Using nitric acid as the catalyst, the titania surface bonded to the fluorescein instead of the adsorbed nitrate ion during the steam treatment. The dye–titania complex formation played an important role in the electron injection from the dye to the titania conduction band.     

Mechanochromic Delayed Fluorescence Switching in Propeller‐Shaped Carbazole–Isophthalonitrile Luminogens with Stimuli‐Responsive Intramolecular Charge‐Transfer Excited States

Herein, the universal design of high‐efficiency stimuli‐responsive luminous materials endowed with mechanochromic luminescence (MCL) and thermally activated delayed fluorescence (TADF) functions is reported. The origin of the unique stimuli‐triggered TADF switching for a series of carbazole–isophthalonitrile‐based donor–acceptor (D–A) luminogens is demonstrated based on systematic photophysical and X‐ray analysis, coupled with theoretical calculations. It was revealed that a tiny alteration of the intramolecular D–A twisting in the excited‐state structures governed by the solid morphologies is responsible for this dynamic TADF switching behavior. This concept is applicable to the fabrication of bicolor emissive organic light‐emitting diodes using a single TADF emitter.     

The origin of open circuit voltage of porphyrin-sensitised TiO(2) solar cells

Electron lifetime and diffusion coefficient measurements in highly efficient porphyrin-sensitised TiO(2) solar cells showed reduced electron lifetime, and consequently, lower photo-induced electron density under illumination compared to commonly used ruthenium dye (N719)-sensitised solar cells, which is proposed to be the origin of the generally lower open circuit voltage.     

Alkyl-functionalized organic dyes for efficient molecular photovoltaics

We designed and synthesized new alkyl-functionalized organic dyes, MK-1 and MK-2, for dye-sensitized solar cells (DSSCs). Based on the MK-2 dye, a high performance of efficiency (eta, 7.7%; short-circuit current density Jsc = 14.0 mA cm-2, open-circuit voltage Voc = 0.74 V, and fill factor FF = 0.74) was achieved under AM 1.5 G irradiation (100 mW cm-2). Remarkably, the relatively higher Voc for DSSCs based on MK-1 and MK-2 dyes, which have long alkyl chains, were observed among the organic dyes caused by the increasing of the electron lifetime in the conduction band of TiO2. Our molecular design of alkyl-functionalized dyes strongly suggests the promising performance of molecular photovoltaics based on organic dyes.     

Proton transport properties of poly(aspartic acid) with different average molecular weights

We synthesized seven partially protonated poly(aspartic acids)/sodium polyaspartates (P-Asp) with different average molecular weights to study their proton transport properties. The number-average degree of polymerization (DP) for each P-Asp was 30 (P-Asp30), 115 (P-Asp115), 140 (P-Asp140), 160 (P-Asp160), 185 (P-Asp185), 205 (P-Asp205), and 250 (P-Asp250). The proton conductivity depended on the number-average DP. The maximum and minimum proton conductivities under a relative humidity of 70% and 298 K were 1.7 · 10^?3 S cm^?1 (P-Asp140) and 4.6 · 10^?4 S cm^?1 (P-Asp250), respectively. Differential thermogravimetric analysis (TG-DTA) was carried out for each P-Asp. The results were classified into two categories. One exhibited two endothermic peaks between t = (270 and 300) °C, the other exhibited only one peak. The P-Asp group with two endothermic peaks exhibited high proton conductivity. The high proton conductivity is related to the stability of the polymer. The number-average molecular weight also contributed to the stability of the polymer.