Short-Chained Platinum Complex Catalyzed Hydrosilylation under Thermomorphic Conditions: Heterogeneous Phase Separation at Ice Temperature.

Homogeneous catalysts PtCl2[5,5'-bis-(n-ClCF2(CF2)3CH2OCH2)-2,2'-bpy] (2A) and PtCl2[5,5'-bis-(n-HCF2(CF2)3CH2OCH2)-2,2'-bpy] (2B), which contained short fluorous chains, were synthesized and used in catalysis of hydrosilylation of alkynes. In these reactions the thermomorphic mode was effectively used to recover these catalysts from the reaction mixture up to eight cycles by taking advantage of heterogeneous phase separation at ice temperature. This kind of catalysis had previously been observed in fluorous catalysts of platinum containing about 50% F-content, but in this work the percentage of F-content is decreased to only about 30%, by which we termed them as "very light fluorous". Our new type of catalyst with limited number of F-content is considered as the important discovery in the fluorous technology field as the reduced number of fluorine atoms will help to be able to comply the EPA 8-carbon rule. The metal leaching after the reaction has been examined by ICP-MS, and the testing results show the leaching of residual metal to be minimal. Additionally, comparing these results to our previous work, fluorous chain assisted selectivity has been observed when different fluorous chain lengths of the catalysts are used. It has been found that there exists fluorous chain assisted better selectivity towards ß-(E) form in the Pt-catalyzed hydrosilylation of non-symmetric terminal alkyne when the Pt catalyst contains short fluorous chain (i.e., 4 Cs). Phenyl acetylenes showed the opposite regioselectivity due to pi-pi interaction while using the same catalyst via Markovnikov's addition to form terminal vinyl silane, which is then a major product for Pt-catalyzed hydrosilylation of terminal aryl acetylene with triethylsilane. Finally, the kinetic studies indicate that the insertion of alkyne into the Pt-H bond is the rate-determining step.

Synthesis and In Vitro Photocytotoxicity of 9-/13-Lipophilic Substituted Berberine Derivatives as Potential Anticancer Agents.

The objective of this study was to synthesize the 9-/13-position substituted berberine derivatives and evaluate their cytotoxic and photocytotoxic effects against three human cancer cell lines. Among all the synthesized compounds, 9-O-dodecyl- (5e), 13-dodecyl- (6e), and 13-O-dodecyl-berberine (7e) exhibited stronger growth inhibition against three human cancer cell lines, (HepG2, HT-29 and BFTC905), in comparison with structurally related berberine (1). These three compounds also showed the photocytotoxicity in human cancer cells in a concentration-dependent and light dose-dependent manner. Through flow cytometry analysis, we found out a lipophilic group at the 9-/13-position of berberine may have facilitated its penetration into test cells and hence enhanced its photocytotoxicity on the human liver cancer cell HepG2. Further, in cell cycle analysis, 5e, 6e, and 7e induced HepG2 cells to arrest at the S phase and caused apoptosis upon irradiation. In addition, photodynamic treatment of berberine derivatives 5e, 6e, and 7e again showed a significant photocytotoxic effects on HepG2 cells, induced remarkable cell apoptosis, greatly increased intracellular ROS level, and the loss of mitochondrial membrane potential. These results over and again confirmed that berberine derivatives 5e, 6e, and 7e greatly enhanced photocytotoxicity. Taken together, the test data led us to conclude that berberine derivatives with a dodecyl group at the 9-/13-position could be great candidates for the anti-liver cancer medicines developments.

The selective synthesis of N-arylbenzene-1,2-diamines or 1-arylbenzimidazoles by irradiating 4-methoxy-4'-substituted-azobenzenes in different solvents.

The solvent-controllable photoreaction of 4-methoxyazobenzenes to afford 1-aryl-1H-benzimidazoles or N-arylbenzene-1,2-diamines has been studied. The irradiation of 4-methoxyazobenzenes in DMF containing 0.5 M hydrochloric acid provided N 2-aryl-4-methoxybenzene-1,2-diamines as the major product, while irradiation in acetal containing 0.16 M hydrochloric acid led to 1-aryl-6-methoxy-2-methyl-1H-benzimidazoles as the major product. A possible reaction mechanism explaining the selectivity was also discussed.

Pentiptycene-derived light-driven molecular brakes: substituent effects of the brake component.

Five pentiptycene-derived stilbene systems (1 R; R = H, OM, NO, Pr, and Bu) have been prepared and investigated as light-driven molecular brakes that have different-sized brake components (1 H<1 OM<1 NO<1 Pr<1 Bu). At room temperature (298 K), rotation of the pentiptycene rotor is fast (k(rot)=10(8)-10(9)  s(-1)) with little interaction with the brake component in the trans form ((E)-1 R), which corresponds to the brake-off state. When the brake is turned on by photoisomerization to the cis form ((Z)-1 R), the pentiptycene rotation can be arrested on the NMR spectroscopic timescale at temperatures that depend on the brake component. In the cases of (Z)-1 NO, (Z)-1 Pr, and (Z)-1 Bu, the rotation is nearly blocked (k(rot)=2-6 s(-1)) at 298 K. It is also demonstrated that the rotation is slower in [D(6)]DMSO than in CD(2)Cl(2). A linear relationship between the free energies of the rotational barrier and the steric parameter A values is present only for (Z)-1 H, (Z)-1 OM, and (Z)-1 NO, and it levels off on going from (Z)-1 NO to (Z)-1 Pr and (Z)-1 Bu. DFT calculations provide insights into the substituent effects in the rotational ground and transition states. The molar reversibility of the E-Z photoswitching is up to 46%, and both the E and Z isomers are stable under the irradiation conditions.

A pentiptycene-derived light-driven molecular brake.

A room-temperature light-driven molecular brake (1), consisting of a pentiptycene rotator, a 3,5-dinitrophenyl brake, and a photoisomerizable ethenyl spacer, is reported. The rotation rates of the rotator differ by about 9 orders of magnitude between the brake-on (cis-1) and brake-off (trans-1) states.

Electronic properties of star-shaped oligofluorenes containing an isotruxene core: interplay of para and ortho conjugation effects in phenylene-based pi systems.

The synthesis, photophysics, cyclic voltammetry, spectroelectrochemistry, and electrogenerated chemiluminescence (ECL) properties of a series of unsymmetrical star-shaped oligophenylenes IT1-IT4 are reported. The electronic couplings among the three oligofluorene arms in IT1-IT4 are strong due to the para-ortho branched isotruxene core. The ortho conjugation effect results in band splitting in the absorption spectra for both the neutral and the radical ionic form with a stronger effect for the latter. However, such an ortho conjugation effect becomes weaker as the oligofluorene arms are longer. The same fluorescence maxima displayed by IT2-IT4 suggest that the exciton coherence size (or the bound electron-hole pair) is no larger than 16 phenylene rings. The little chain-length dependence of the first reduction and oxidation potentials for IT1-IT4 suggests that the reversible electron-transfer processes of the neutral species are mainly associated with the isotruxene core. The ECL of IT1-IT4 is from the singlet excited state, but the spectra are red shifted with respect to the fluorescence spectra of dilute solutions due to the reabsorption effect. Our results also reveal that the meta conjugation interactions in the previously reported C 3-symmetrical truxene-oligofluorene analogs T1-T4 (Kanibolotsky, A. L.; Berridge, R.; Skabara, P. J.; Perepichka, I. F.; Bradley, D. D. C.; Koeberg, M. J. Am. Chem. Soc. 2004, 126, 13695-13702) are rather weak.

Novel photoreaction of N-alkyl(p-methoxyphenyl)arylamines assisted by protic acids.

A novel photochemical transformation from N-alkyl(p-methoxyphenyl)arylamines (1a-1f) to 1,2,4-trihydro(4aH)-carbazol-3-ones (2a-2f) is reported with the assistance of protonation at the dihydrocarbazole intermediate followed by sequential formal [1,5]hydrogen, [1,3]hydrogen shifts and proton assisted hydrolysis.

Site-selective hydrogen-bonding-induced fluorescence quenching of highly solvatofluorochromic GFP-like chromophores.

The unconstrained green fluorescence protein (GFP)-like chromophore m-DMABDI displays a high solvatofluorochromicity in aprotic solvents, but the fluorescence is quenched in protic solvents. According to the site-specific intramolecularly hydrogen-bonded analogs 1OH and 2OH, the hydrogen bonding to the carbonyl oxygen is more important than that to the imino nitrogen of the imidazolinone group in the fluorescence quenching.

Excimer and intramolecular charge transfer chemiluminescence from electrogenerated ion radicals of donor-acceptor stilbenoids.

Electrongenerated chemiluminescence (ECL) of a series of intramolecular charge transfer (ICT) donor acceptor stilbenoid systems (2-9) bearing N,N-dimethylamino group as donor and pyridine, thiophene, quinoline or aryl groups as acceptors are studied. Most of the compounds (3-9) show ICT ECL through direct annihilation of the radical ions. For the weaker ICT compound (2), excimer ECL is observed instead.