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Reactive oxygen species play numerous roles in a number of pathological processes. Monitoring H2O2 is a powerful tool for imaging and therapy of diseases wherein oxidative stress is involved. In particular, we report a specific application of functional microspheres as sensors of H2O2. Reactive oxygen species responsive delivery systems were developed to detect in vitro peroxides thanks to the presence of a boronic ester which is readily cleaved with H2O2. This ROS-sensitive cleavable linker underwent a 1,6-elimination to disrupt fluorescence resonance energy transfer by coupled near-infrared fluorophores such as Cy5.5/Cy7. This technology would allow real-time monitoring of therapeutic regimes (and their success), as well as optical detection of inflammation.

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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 general Pd-catalyzed intermolecular reductive Heck reaction of both terminal and internal unactivated aliphatic alkenes has been first developed. This method affords gamma- and delta-arylated alkyl carboxylic acid derivatives in high yields with complete anti-Markovnikov selectivity. Notably, the coupling process is stereoretentive for the alkyl chain. Mechanistically, alkyl palladacycle intermediates stabilized by directing group and ligand, hydride species multigenerated from PS/TFA reductant, are two key factors that successfully promote the reaction and regioselectivity.

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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 aim of the present review is to report the state of the art of an emerging family of molecules, namely 4-substituted spirobifluorenes (SBFs). Their syntheses, physico-chemical and photophysical properties and applications as hosts in Phosphorescent Organic Light-Emitting diodes (PhOLEDs) are described through a structure-property relationship approach. Although substitution at position 2 of a SBF core has been widely developed, substitution at position 4 is very recent (less than 10 years) and stills need to be explored.

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

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We have demonstrated that the gel-like mesophase of Cetyltrimethylammonium bromide (CTAB) can be synthesized by judicial adjustment of water to surfactant molar ratio (W0), without using any additional salts, gelating agents or co-surfactants. Gel formation was found to be highly dependent on the water to surfactant molar ratio (W0), with the lowest value of W0 (41.5) resulting in rapid gel formation. Environmental scanning electron microscope (ESEM) analysis revealed that the gel was comprised of interconnected cylindrical structures. The presence of hydrogen bonding in the gel-like mesophase was confirmed by Fourier Transform Infrared spectroscopy (FTIR) analysis. Rheology measurements revealed that all the gel samples were highly viscoelastic in nature. Furthermore, Au and Ag containing CTAB gels were explored as precursors for the preparation of spherical Gold (Au) and Silver (Ag) nanoparticles using Sodium borohydride (NaBH4) as reducing agent. The effects of NaBH4 concentration on the particle size and morphology of the Au and Ag nanoparticles have also been studied.

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

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Site-selective introduction of a sulfur group into aromatic compounds is essential and useful in organic, material, and pharmaceutical chemistry. A palladium/norbornene-catalyzed chemoselective ortho thiolation of aryl halides was reported. The selectivity of reductive elimination for C(Ar)-SR bond formation was well controlled by tuning the ancillary ligand in the aryl-NBE palladacycle Pd(IV) intermediate. The reaction showcased good substrate scope: both S-alkyl and S-aryl thiosulfonates were compatible.

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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 palladium-catalyzed remote 1,n-arylamination (from 1,3- to 1,11-arylamination) of unactivated terminal alkenes with aryl iodides and arylamines has been realized. This three-component reaction proceeded via Pd-catalyzed Heck arylation, alkene isomerization, and aza-Michael addition, exhibiting good regio- and chemoselectivity, and wide substrate scope. Preliminary mechanistic studies indicated that the in situ generated ortho/para-quinone methide intermediates served as the driving force for the alkene isomerization and promoted the rearomatization upon nucleophilic amination.

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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 Bronsted acid accelerated Pd-catalyzed asymmetric allylic alkylation of azlactones with simple allylic alcohols under mild reaction conditions has been realized, which provides a direct and readily scalable approach for the synthesis of all-carbon quaternary allylic amino acid derivatives in excellent yields and good enantioselectivities. (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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A series of new N-aryl substituted phenyl acetamide analogs of 3-methyl-[1,2,4] triazolo[3,4-a] phthalazines were synthesized starting from commercially available, in-expensive phthalic anhydride in good yields (65-75 %) via Suzuki Coupling. These compounds were tested for inhibition activity against HCT 116 cancer cell line by using MIT assay. Among the library of compounds, N-(3-methoxyphenyl)-2-(4-(3-methyl-[1,2,4]triazolo[3,4-a]phthalazin-6-yl)phenyl) acetamide followed by 2-(4-(3-methyl-[1,2,4]triazolo[3,4-a]phthalazin-6-yl)phenyl)-N-(m-tolyl) acetamide and N-(3-chlorophenyl)-2-(4-(3-methyl-[1,2,4]triazolo[3,4-a]phthalazin-6-yl)phenyl) acetamide were found to be active compounds with IC50 of 70 to and 90 mug mL-1. Further, the compounds were also screened for their antimicrobial activities.

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

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To shed light on the influence of reaction parameters on palladium-catalyzed tandem allylic alkylation in the presence of Fei-Phos (a chiral trans-1,2-diaminocyclohexane-derived phosphine ligand), the effect of different phosphine ligands, inorganic or organic bases, Br°nsted acids, and other additives on the asymmetric palladium-catalysed alkylation of catechol with allylic diacetate was investigated. In this reaction, 2-vinyl-2,3-dihydro-benzo[1,4]dioxin products with promising enantioselectivity were achieved in good yields. In addition, a novel palladium-catalyzed three-component and one-pot allylic substitution/cyclization/reduction reaction assisted by methylphenylsilane was reported with good selectivity.

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

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Arenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sonogashira coupling reactions. In this work, reactions were carried out in DMSO under very mild conditions (without copper or phosphanes), and gave rise to arylated alkynes in good to excellent yields (25 examples, average yield 83 %). o-Benzenedisulfonimide could be recovered from all the reactions in yields of >80 %, so it could be recycled for the preparation of other diazonium salts. Mechanistic insights revealed the fundamental roles of DMSO and the anion of o-benzenedisulfonimide in the formation of the catalyst, and also the importance of DMSO in the catalytic cycle. The Sonogashira coupling between are diazonium o-benzenedisulfonimides and terminal alkynes is a powerful method for the formation of arylated alkynes. No copper, phosphanes, bases, or co-catalysts are needed. Mechanistic insights highlighted the fundamental roles of DMSO and o-benzenedisulfonimide in the formation of the catalyst, and also the important role of DMSO in the catalytic cycle. Copyright

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