Synthesis of fluorinated aminium cations coupled with carborane anions for use as strong one-electron oxidants.

Synthesis of a series of hydrocarbon-soluble triarylamines bearing F, CF, and Br substituents showing quasi-reversible redox events in the 0.59-1.32 V range is reported.

The prostaglandin EP4 receptor is a master regulator of the expression of PGE receptors following inflammatory activation in human monocytic cells.

Prostaglandin E (PGE) is responsible for inflammatory symptoms. However, PGE also suppresses pro-inflammatory cytokine production. There are at least 4 subtypes of PGE receptors, EP1-EP4, but it is unclear which of these specifically control cytokine production.

Comparison of the electronic properties of diarylamido-based PNZ pincer ligands: redox activity at the ligand and donor ability toward the metal.

This paper presents the synthesis and characterization of a series of pincer ligands and their Ni, Pd, Pt, and Rh complexes. The ligands under examination are based on a diarylamine which is modified either by two phosphino (-PR2) substituents in the ortho-positions (PNP ligands) or by a combination of a phosphino and an iminyl (-CH═NX) substituent (PNN ligands). The ligands can be broken down into three groups: (a) C2v-symmetric PNP ligands with identical side -PR2 donors, (b) Cs-symmetric PNP' ligands with different -PR2 side donors, and (c) PNN ligands containing a -P(i)Pr2 side donor.

Zirconium-mediated synthesis of arsaalkene compounds from arsines and isocyanides.

An atom-economical synthesis of arsaalkenes via a net coupling of aryl arsines with aryl or alkyl isocyanides at zirconium is presented. Reaction of zirconium arsenido complexes (N3N)ZrAsHAr [N3N = N(CH2CH2NSiMe3)3(3-); Ar = Ph, (2) Mes (3)] with aryl and alkyl isocyanides yields arsaalkene products of the general form (N3N)Zr[NRC(H)═As(Ar)]. Two examples (5: R = Mes, Ar = Ph; 6: R = CH2Ph, Ar = Mes) were structurally characterized.

Eicosapentaenoic acid suppression of systemic inflammatory responses and inverse up-regulation of 15-deoxyΔ(12,14) prostaglandin J2 production.

Background And Purpose: Eicosapentaenoic acid (EPA) has been shown to suppress immune cell responses, such as cytokine production and downstream PG production in vitro. Studies in vivo, however, have used EPA as a minor constituent of fish oil with variable results. We investigated the effects of EPA on systemic inflammatory responses as pure EPA has not been evaluated on immune/inflammatory responses in vivo.

Characterisation of the prostaglandin E2-ethanolamide suppression of tumour necrosis factor-α production in human monocytic cells.

Background And Purpose: Prostaglandin ethanolamides or prostamides are naturally occurring neutral lipid derivatives of prostaglandins that have been shown to be synthesised in vivo following COX-facilitated oxygenation of arachidonoyl ethanolamine (anandamide). Although the actions of prostaglandins have been extensively studied, little is known about the physiological or pathophysiological effects of prostamides. Since prostaglandin E2 has potent immunosuppressive/immunomodulating actions, the aim of the present study was to determine whether the derivative, prostaglandin E2 ethanolamide (PGE2-EA), could modulate the production of the pro-inflammatory cytokine tumour necrosis factor-α in human blood and human monocytic cells and indicate whether this action involved the same receptor systems/signals as PGE2.

7beta-hydroxy-epiandrosterone modulation of 15-deoxy-delta12,14-prostaglandin J2, prostaglandin D2 and prostaglandin E2 production from human mononuclear cells.

7beta-hydroxy-epiandrosterone (7beta-OH-EPIA) has been shown to be cytoprotective in various organs including the brain. It has also been shown that prostaglandin D2 (PGD2) and its spontaneous metabolite 15-deoxy-Delta12,14-prostaglandin J2 (15d-PGJ2) are also cytoprotective. It is possible that these prostaglandins derived from circulating mononuclear cells may mediate the actions of 7beta-OH-EPIA.

Mechanistic variety in zirconium-catalyzed bond-forming reaction of arsines.

Triamidoamine-supported zirconium complexes have been demonstrated to catalyze a range of bond-forming events utilizing arsines. Three different mechanisms have been observed in these reactions. In the first mechanism, triamidoamine-supported zirconium complexes of the general type (N3N)ZrX (N3N =N(CH2CH2NSiMe3)33-; X = monoanionic ligand) catalyzed the dehydrogenative dimerization of diphenylarsine.

Age-related changes in smooth pursuit initiation.

Quantitative analysis of eye movements is a useful tool for examining the behavioural effects of ageing. Although the effect of ageing on saccadic eye movement has been examined in some detail, the effect of ageing on a second class of eye movement, smooth pursuit (SP), has received less attention. We examined the initiation of SP in a group of fifteen healthy older people (mean age 72 years) and compared their performance with that of ten young controls (mean age 21 years).