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Triplet photosensitizer-nanotube conjugates: Synthesis, characterization and photochemistry of charge stabilizing, palladium porphyrin/carbon nanotube conjugates

The ability of a triplet photosensitizer to generate long-lived charge separated states, in contrast to traditionally used singlet photosensitizers, in covalently functionalized single-walled carbon nanotube hybrids has been investigated. Enriched single-walled carbon nanotubes with two diameters, namely (6,5) and (7,6), were covalently modified to carry a charge-stabilizing triplet photosensitizer derived from a palladium porphyrin. The nanohybrids were fully characterized and the presence of intramolecular interactions between the porphyrin and nanotubes was established from various spectroscopic, imaging, electrochemical and thermochemical studies. Photoluminescence of palladium porphyrin was found to be quantitatively quenched in the presence of covalently appended SWCNTs and this quenching is due to excited state charge separation and has been established by femtosecond transient absorption studies. Owing to the presence of the triplet photosensitizer, the charge separated states lasted over 3 ns, i.e., much longer than those reported earlier for singlet photosensitizer-derived nanotube hybrids. The nanohybrids also exhibited efficient photocatalytic behavior in experiments involving electron pooling of one-electron reduced methyl viologen in the presence of a sacrificial electron donor. Higher yields of photoproducts were achieved from the present donor-acceptor nanohybrids when compared with those of singlet photosensitizer-derived nanohybrids, more so for (6,5) nanotube derived hybrids compared to (7,6) nanotube derived hybrids. The present findings highlight the importance of triplet photosensitizer derived nanohybrids in artificial photosynthesis of charge separation and photocatalytic applicatons.

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

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Enantioselective Pd-catalyzed decarboxylative allylic alkylation of thiopyranones. Access to acyclic, stereogenic alpha-quaternary ketones

A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The alpha- quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening beta- sulfur elimination. In addition, reduction of the carbon-sulfur bonds provides access to elusive acyclic alpha-quaternary ketones. The alkylated products are obtained in up to 92% yield and 94% enantiomeric excess.

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

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Platelet ADP receptor inhibitors

Novel compounds of formulae (I) to (VIII), which more particularly include sulfonylurea derivatives, sulfonylthiourea derivatives, sulfonylguanidine derivatives, sulfonylcyanoguanidine derivatives, thioacylsulfonamide derivatives, and acylsulfonamide derivatives which are effective platelet ADP receptor inhibitors. These derivatives may be used in various pharmaceutical compositions, and are particularly effective for the prevention and/or treatment of cardiovascular diseases, particularly those diseases related to thrombosis. The invention also relates to a method for preventing or treating thrombosis in a mammal comprising the step of administering a therapeutically effective amount of a compound of formulae (I) to (VIII), or a pharmaceutically acceptable salt thereof.

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

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D-A Polymer with a Donor Backbone – Acceptor-side-chain Structure for Organic Solar Cells

We report the design, synthesis, and properties of a novel type of donor (D)-acceptor (A) polymer, poly(3-(([2,2?:5?,2??-terthiophen]-3-yl-5,5?-diyl)methylene)-1-(2-octyldodecyl)indolin-2-one) (PTIBT), with a donor backbone and acceptor side chains (Type II D-A polymer) as donor for organic solar cells (OSCs) as opposed to the conventional D-A polymers having both donor and acceptor units on backbone (Type I D-A polymers). PTIBT having a backbone consisting of thiophene donor units and side chains containing indolin-2-one acceptor units was synthesized very conveniently in three steps. This polymer has a high dielectric constant of 7.70, which is beneficial for the exciton diffusion and dissociation in the active blend layer in an OSC. In addition, PTIBT was found to have a low-lying HOMO energy level of ?5.41 eV and a wide band gap of 1.80 eV in comparison to its counterpart Type I D-A polymer. In organic thin film transistors (OTFTs), PTIBT showed typical p-type semiconductor performance with hole mobilities of up to 1.81¡Á10?2 cm2 V?1 s?1. When PTIBT and ITIC were used as donor and acceptor to form a blend active layer, the best OSC device showed a JSC of 15.19 mAcm?2, a VOC of 0.66 V, and a fill factor of 0.57, resulting in a power conversion efficiency (PCE) of up to 5.72%.

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

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Accessing 2-(hetero)arylmethyl-, -allyl-, and -propargyl-2,1-borazaronaphthalenes: Palladium-catalyzed cross-couplings of 2-(Chloromethyl)-2,1-borazaronaphthalenes

The synthesis of 2-(chloromethyl)-2,1-borazaronaphthalene has provided an opportunity to expand dramatically the functionalization of the azaborines. This azaborinyl building block can serve as the electrophile in palladium-catalyzed cross-coupling reactions to form sp3-sp and sp3-sp2 bonds. The cross-coupling reactions of 2-(chloromethyl)-2,1-borazaronaphthalene with potassium (hetero)aryl- and alkenyltrifluoroborates as well as terminal alkynes provides access to a variety of novel azaborines, allowing a library of pseudobenzylic substituted azaborines to be prepared from one common starting material.

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

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Comprehensive review on tumour active palladium compounds and structure-activity relationships

This article provides a comprehensive review of palladium compounds that have been evaluated for anticancer activity in vivo or in vitro from the era of discovery of cisplatin up to 2015. In total, 847 compounds have been discussed into three categories namely (1) potent palladium compounds, (2) palladium compounds with comparable activity and (3) palladium compounds with insignificant activity. Structure activity relationships are proposed that may aid in the design of new palladium compounds with greater antitumour activity.

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

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Palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines with amines

A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.

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

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Mercaptobenzoic acid-palladium(0) complexes as active catalysts for S-benzylation with benzylic alcohols via (eta3-benzyl)palladium(II) cations in water

Mercaptobenzoic acid-palladium(0) complexes show high catalytic activity for S-benzylation with benzylic alcohols via the (eta3-benzyl) palladium(ii) cation in water. Notably, these palladium(0) complexes could play an important role in formation of active (eta3-benzyl)palladium(ii) cation complexes followed by S-benzylation. Hammett studies on the rate constants of S-benzylation by various substituted alcohols show good correlation between log(kX/kH) and the sigma+ value of the respective substituents. From the slope, negative rho values are obtained, suggesting that there is a build-up of positive charge in the transition state. Water plays an important role in the catalytic system for sp3 C-O bond activation and stabilization of the activated Pd(ii) cation species. The catalytic system can be performed using only 2.5 mol% Pd2(dba) 3 without the phosphine ligand or other additives. This journal is the Partner Organisations 2014.

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

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Palladium Nanoparticle-Catalyzed Stereoretentive Cross-Coupling of Alkenyl Sulfides with Grignard Reagents

Reaction conditions allowing a stereoretentive cross-coupling of alkenyl sulfides with Grignard reagents using ligand-free Pd catalysis are discussed here. The presence of an adequately positioned OH function is a key feature that allows a Mg-promoted Lewis acid activation of the mercaptide leaving group. This easy to implement procedure actually relies on an in situ generation of stable Pd nanoparticles by simply mixing Pd2(dba)3, the Grignard reagent, and the vinyl sulfide cross-coupling partner in THF. The efficiency of this procedure has been demonstrated in a natural product total synthesis context.

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

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Diastereo- and enantioselective construction of oxindole-fused spirotetrahydrofuran scaffolds through palladium-catalyzed asymmetric [3+2] cycloaddition of vinyl cyclopropanes and isatins

A novel asymmetric formal [3+2] cycloaddition of vinyl cyclopropanes and isatins in the presence of Pd2(dba)3 and the chiral imidazoline-phosphine ligand (aS,R,R)-L3 has been developed, affording the corresponding highly functionalized oxindole-fused spirotetrahydrofuran frameworks in good yields along with good diastereo- and high enantioselectivities under mild conditions.

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