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HDAC inhibition is emerging as a new strategy for cancer therapy. We previously reported that Nhydroxy-3-{4-[2-(2-methyl-1H-indol-3-yl)-ethylsulfamoyl]-phenyl}-acrylamide (9) demonstrated potent histone deacetylases (HDAC) inhibition and anti-inflammatory effects. This continuous study provides detailed structureactivity relationship (SAR) of novel indol-3-ethylsulfamoylphenylacrylamides as anti-cancer agents. These compounds are endowed with potent HDAC inhibitory activity, almost 2.5 folds to 42 folds better than suberanilohydroxamic acid (SAHA). Compounds 8, 10, 11 and 17 exhibited significant inhibitory effects on various cancer cell lines with GI50 values in the range of 0.02 to 0.35 muM which are 10-50 folds better than SAHA. In-vivo nude mice model indicated the anti-angiogenic potential of these acrylamides. This study has indicated the potential of 3-{4-[2-(1-Ethyl-2-methyl-1H-indol-3-yl)-ethyl-N-tert-butoxycarbonylsulfamoyl]-phenyl}-N-hydroxy-acrylamide (11, mean GI50 = 0.04 muM) as a lead molecule for further development as anti-cancer agent.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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In this work, by conjugating 2-cyanoacrylic acid (CA), 4-(benzo[c][1,2,5]thiadiazol-7-yl)benzoic acid (BTBA), 4-(7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)benzoic acid (EBTBA), and 4-((7-ethynylbenzo[c][1,2,5]thiadiazol-4-yl)ethynyl)benzoic acid (EBTEBA) to a binary electron-donor diphenylamine-phenanthrocarbazole (DPA-PC), we systematically investigate the impacts of electron-acceptors upon energy level, energy gap, light-harvesting ability, photovoltaic parameter, and cell stability of donor-acceptor dyes in photoelectrochemical cells. In conjunction with an ionic liquid composite electrolyte, the DPA-PC dye with EBTEBA as electron-acceptor yields a high power conversion efficiency of 8% and an outstanding stability after a 1000 h aging test under the soaking of full sunlight at 60C in a dye-sensitized solar cell. Femtosecond fluorescence up-conversion measurements have suggested that energy relaxation and electron injection both occur to dye molecules in the nonequilibrium excited states. Moreover, the time constants of injecting electrons from dye molecules in the excited states to titania are very dispersive for over 1 order of magnitude, mainly owing to the broad energy distribution of excited states. (Chemical Equation Presented).

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The use of sulfones as electron-withdrawing groups in substrates for palladium-catalyzed decarboxylative allylation was explored. A previously published trifluoromethanesulfonyl-based substrate was highly reactive and selective under mild conditions, but the substrate scope was not readily expanded. Instead, 3,5-bis(trifluoromethyl)phenyl sulfones were employed, thereby simultaneously retaining most of the electron deficiency and providing facile synthetic access. Optimization of the catalytic conditions to maximize the product distribution to a synthetically useful level of the allylation product over the protonation side product proved extremely challenging, with inconsistent and irreproducible results afforded with Pd2(dba)3 as the palladium source. A variety of substrates were subjected to the optimized catalytic conditions of PdCp(1-cinnamyl) and Xantphos in tetrahydrofuran at 50 C for 30 min. These conditions were applicable to all substrates with the exception of the alpha,alpha-dimethyl allyl ester, which required more forcing conditions and afforded four products: the allylation and protonation products, as expected, along with a cyclopropylation product and an unprecedented pseudodimeric product. The mechanism for the formation of these unusual side products is considered.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The use of Pd-, Rh(II)- and Ru(II)-based catalysts has been explored in the transition metal-catalysed intramolecular carbenoid C?H insertion of alpha-diazoesters leading to pyrrolidines. Although the outcome of the reaction was highly substrate-dependent, in general, it was possible to control the chemoselectivity of the process towards pyrrolidines by adequate catalyst selection. The Pd(0)-catalysts were as efficient as [Rh(Ph3CCO2)2]2 in promoting the C(sp3)?H insertion of ortho-substituted anilines. In contrast, for anilines bearing meta- and para-substituents, the Rh(II)-catalyst provided the best chemoselectivities and reaction yields. On the other hand, [Ru(p-cymene)Cl2]2 was the most efficient catalyst for the insertion reaction of the N-benzyl-N-phenyl and N,N-dibenzyl alpha-diazoesters, while the C(sp3)?H insertion of the N-benzylsulfonamide substrate was only promoted by [Rh(Ph3CCO2)2]2. According to density functional theory (DFT) calculations, the mechanism involved in the Pd(0)- and Ru(II)-catalysed C(sp3)?H insertions differs considerably from that typically proposed for the Rh(II)-catalysed transformation. Whereas the Pd(0)-catalysed reaction involves a Pd-mediated 1,5-H migration from the C(sp3)?H bond to the carbenoid carbon atom leading to the formal oxidation of the transition metal, a Ru(II)-promoted Mannich type reaction involving a zwitterionic intermediate seems to be operative in the Ru(II)-catalysed transformation. (Figure presented.).

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The bisphosphomide, 1,3-{Ph2PC(O)}2C 6H4 (1), was prepared by the reaction of isophthaloyl chloride with diphenylphosphine in the presence of triethylamine. The corresponding bromo-derivative, 2-Br-1,3-{Ph2PC(O)}2C 6H3 (2), was obtained by the reaction of 2-bromoisophthaloyl chloride with diphenylphosphine. The reaction of 1 with elemental sulfur or selenium yielded the bis(chalcogenides), 1,3-{Ph 2P(S)C(O)}2C6H4 (3) and {1,3-Ph 2P(Se)C(O)}2C6H4 (4). The reaction between 1 and [Ru(eta6-p-cymene)Cl2]2 and [Pd(eta3-C3H5)Cl]2 in 1:1 stoichiometry yielded the corresponding binuclear complexes, [Ru 2(eta6-p-cymene)2Cl4{1,3-{Ph 2PC(O)}2(C6H4)}] (5) and [Pd 2(eta3-C3H5)2Cl 2{1,3-{Ph2PC(O)}2(C6H4)}] (6). The reaction of 1 with AgClO4 followed by the addition of [Pd(COD)Cl2] at room temperature resulted in the formation of a pincer complex [PdCl{2,6-{Ph2PC(O)}2(C6H 3)}] (9), via transmetallation. Pincer complex formation through C-H activation requires drastic conditions and yields are generally moderate. The oxidative addition reaction between 2 and [Ni(COD)2] gave a pincer complex [NiBr{2,6-{Ph2PC(O)}2(C6H 3)}] (8), whereas the 2:1 reaction of 2 with [Pd2(dba) 3] yielded the palladium analogue [PdBr{2,6-{Ph2PC(O)} 2(C6H3)}] (9) in quantitative yield. The reaction between 1 and CuX in a 1:1 molar ratio produced binuclear complexes, [Cu2(mu-X)2{1,3-{Ph2PC(O)}2(C 6H4)}2] (10, X = Cl; 11, X = Br; 12, X = I), whereas the reaction between 1 and [Cu(NCCH3)4]BF 4 led to the isolation of a spirocyclic complex, [Cu(CH 3CN)2{1,3-{Ph2PC(O)}2(C 6H4)}]BF4 (13). The silver complexes [Ag 2(mu-ClO4)2{1,3-{Ph2PC(O)} 2(C6H4)}2] (14), [Ag 2(mu-OTf)2{1,3-{Ph2PC(O)}2(C 6H4)}2] (15) and [Ag2X 2{1,3-{Ph2PC(O)}2(C6H4)}] (16, X = ClO4; 17, X = OTf) were obtained by treating 1 with AgClO4 or AgOTf in 1:1 or 1:2 molar ratios. The reactions of 1 with [AuCl(SMe2)] in 1:1 and 1:2 molar ratios afforded mono- and binuclear complexes, [AuCl{1,3-{Ph2PC(O)}2(C6H 4)}2] (18) and [Au2Cl2{1,3-{Ph 2PC(O)}2(C6H4)}AuCl] (19), in good yield. The structures of complexes 5, 7-10, 12 and 14a were confirmed by single-crystal X-ray diffraction studies. DFT calculations were performed in order to gain additional insights into the structure and bonding of the pincer complexes. An additional analysis of the orbital interactions in the case of palladium complex 9 is also included. The in situ generated rhodium complex of bisphosphomide 1 showed moderate to good selectivity in the hydroformylation of hex-1-ene and styrene derivatives.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladium-catalyzed primary and secondary sp3 C-H bond arylation is reported. The method using diarylhyperiodonium salts as arylation reagents shows good functional group tolerance and proceeds under mild reaction conditions. The KIE experiments show that the C-H bond activation is the rate-determining step.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The present invention provides a compound of the following formula, salts, racemates, diastereomers, enantiomers, esters, carbamates, phosphates, sulfates, deuterated forms and prodrugs thereof. Also provided is the use of these compounds as antibacterials, compositions comprising them and processes for their manufacture.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Poly(butyl acrylate) (PBA) side chain equipped isoindigo-bithiophene (II2T) conjugated polymers have been designed and synthesized for stretchable electronic applications. The PBA segment possesses low glass transition temperature and high softness, offering a great opportunity to improve the mechanical property of semiconducting polymer thin films that typically contain lots of rigid conjugated rings. Polymers with 0, 5, 10, 20 and 100% of PBA side chains, named PII2T, PII2T-PBA5, PII2T-PBA10, PII2T-PBA20, and PII2T-PBA100, were explored, and their polymer properties, surface morphology, electrical characteristics, and strain-dependent performance were investigated systematically. The series polymers showed a charge carrier mobility of 0.06-0.8 cm2 V-1 s-1 with an on/off current ratio over 105 dependent on different amounts of PBA chains as probed using a top-contact transistor device. Moreover, we can still achieve a mobility higher than 0.2 cm2 V-1 s-1 even if 10% of PBA side chains were added (i.e., PII2T-PBA10). Such PII2T-PBA polymers, more attractive, exhibited superior thin film ductility with a low tensile modulus down to 0.12 GPa (PII2T-PBA20) due to the soft PBA side chain. The more PBA segment was incroporated, the lower modulus was reached. The mobility performance, at the same time, remained approximately 0.08 cm2 V-1 s-1 based on PII2T-PBA10 films even under a 60% strain and could be simultaneously operated over 400 stretching/releasing cycles without significant electrical degradations. The above results suggest that the rational design of soft PBA side chains provides a great potential for next-generation soft and wearable electronic applications.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A facile Ni-catalyzed semihydrogenation of internal alkynes to (E)-alkenes using the cheap and easily handled hypophosphorous acid as a hydrogen donor was described. This reaction is featured by high reaction efficiency to produce the corresponding (E)-alkenes selectively.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A series of indolo[2,3-b]quinoxaline derivatives were efficiently synthesized from 2,3-dibromoquinoxaline by two pathways. A one-pot approach using Pd-catalyzed two-fold C-N coupling and C-H activation reactions gave indolo[2,3-b]quinoxaline derivatives in good yields, but with limited substrate scope. In addition, a two-step approach to indolo[2,3-b]quinoxalines was developed which is based on Pd-catalyzed Suzuki coupling reactions and subsequent annulation by Pd-catalyzed two-fold C-N coupling with aromatic and aliphatic amines. The electrochemical and photochemical properties of indolo[2,3-b]quinoxaline derivatives were investigated. These studies show that 6-(4-methoxyphenyl)-6H-indolo[2,3-b]quinoxaline showed the highest HOMO energy level and lowest band gap. This journal is the Partner Organisations 2014.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method