Metallomimetic C-F Activation Catalysis by Simple Phosphines.

Delivering metallomimetic reactivity from simple p-block compounds is highly desirable in the search to replace expensive, scarce precious metals by cheap and abundant elements in catalysis. This contribution demonstrates that metallomimetic catalysis, involving facile redox cycling between the P(III) and P(V) oxidation states, is possible using only simple, cheap, and readily available trialkylphosphines without the need to enforce unusual geometries at phosphorus or use external oxidizing/reducing agents. Hydrodefluorination and aminodefluorination of a range of fluoroarenes was realized with good to very good yields under mild conditions.

Light triggers a network switch between circadian morning and evening oscillators controlling behaviour during daily temperature cycles.

Proper timing of rhythmic locomotor behavior is the consequence of integrating environmental conditions and internal time dictated by the circadian clock. Rhythmic environmental input like daily light and temperature changes (called Zeitgeber) reset the molecular clock and entrain it to the environmental time zone the organism lives in. Furthermore, depending on the absolute temperature or light intensity, flies exhibit their main locomotor activity at different times of day, i.

The cell cycle-related genes RHAMM, AURKA, TPX2, PLK1, and PLK4 are associated with the poor prognosis of breast cancer patients.

Breast cancer is the third most common type of cancer diagnosed. Cell cycle is a complex but highly organized and controlled process, in which normal cells sense mitogenic growth signals that instruct them to enter and progress through their cell cycle. This process culminates in cell division generating two daughter cells with identical amounts of genetic material.

African lates perches (Teleostei, Latidae, Lates): Paraphyly of Nile perch and recent colonization of Lake Tanganyika.

Lates perches of the genus Lates (Latidae) are large piscivorous fishes, with a strikingly disjunct distribution range in coastal areas and estuaries of the Indo-Pacific region and in some large African freshwater systems. Previous phylogenetic hypotheses based on osteological and ontogenetic data suggested paraphyly of the African representatives, or even the small Lake Tanganyika species assemblage, with respect to the remaining Lates species. Based on a multilocus phylogeny, however, we show that extant African lates perches are monophyletic.

Isoprene polymerization mediated by vanadium-[ONNO] complexes.

A series of vanadium complexes bearing dianionic tetradentate amine-bisphenolate [ONNO] ligands, V([double bond, length as m-dash]O)X[ONNO(Me)] (X = Cl (1); O(i)Pr (2)), VCl2[ONNO(Me)] (3) and V(O(i)Pr)2[ONNO(R)] (R = Me (4), (t)Bu (5), Cl (6)), displaying various electronic and steric properties have been prepared. The molecular structures of two of these complexes, namely V[ONNO(R)](O(i)Pr)2 with R = (t)Bu (5) or Cl (6), are reported. Activated with dialkylmagnesium, all complexes lead to modest isoprene homo-polymerization activities at 50 °C.

Novel aspects of the transamination reaction between Ti(NMe2)4 and primary amines.

A detailed study of the transamination reaction between Ti(NMe2)4 and primary amines RNH2 is reported Alkylamines (1-adamantylamine, t-butylamine) and triphenylsilylamine yield dimers of the type [Ti(μ-NR)(NMe2)2]2 (R = 1-adamantyl (1), (t)Bu (2), SiPh3 (3)). The experimental conditions and the nature of the amine are important issues that determine the scope and yield of the reaction. When reacted under the same conditions, aniline PhNH2 does not yield the expected dimer, but instead the trimer [Ti3(μ(2)-NPh)3(μ(3)-NPh)(NMe2)4(NHMe2)] (5) and tetramer [Ti4(μ-NPh)5(NMe2)6] (6) complexes were characterized.

Tight encapsulation of a "naked" chloride in an imidotitanium hexanuclear host.

Treating the imidotitanium dimer [Ti(μ-NAr)(NMe2)2]2 (Ar = 2,6-(i)Pr2C6H3) with excess Me3SiCl affords the hexanuclear complex [{Ti(═NAr)Cl2}6(Cl)](-)[Q](+). The self-assembled hexameric cage arrangement encapsulates a chloride ion guest that provides evidence of new host-guest chemistry in this area, while the cationic part is composed of mixtures of the Q(+) cations Me2NHSiMe3(+) and Me2N(SiMe3)2(+).

Callous and unemotional traits and social cognitive processes in a sample of community-based aggressive youth.

Psychopathic traits are associated with violent, aggressive behaviors and recidivism in adulthood. To increase positive treatment outcomes, it is arguably beneficial to identify and treat psychopathy as early as possible. Furthermore, because research shows that the effectiveness of behavior modification is likely to be affected by the social information-processing patterns of aggressive children, it is important to understand the relationship between conduct-disordered traits and social cognitions.

Imido-bridged homo- and heterobimetallic complexes.

Transamination reactions of primary amines with group 4 and 5 amido precursors M(NMe(2))(4) have been studied to prepare homo- and heterobimetallic complexes [(Me(2)N)(2)M(1)(μ-NR(1))(μ-NR(2))M(2)(NMe(2))(2)(NHMe(2))(x)] (x = 0, 1) with two identical or distinct bridging imido ligands.

Synthesis and structure of early transition metal NHC complexes.

The synthesis and structure of several new early transition metal (Ti, Zr, Hf, and V) NHC complexes supported by one or two IMes ligands is described. Reaction of M(NMe2)4 with IMes.HCl gives compounds VCl2(NMe2)(IMes)2 (2), and MCl2(NMe2)2(IMes) (M = V (3), Zr (4), Hf (5)).

Odontology or philologic: medical disputation about the teeth.

The dissertation, here rendered, was published at the gymnasium of Hof in 1669. It is remarkable that the respondent, who was probably also its author, declared in the title page that he intends to do his task "following the custom of the blessed Hebrews and any other conventions of true Israelites" and cites in the following text repeated proverbs of Rabbis. Therefore, we suppose him to have been a Jew converted to the Christian faith.

Reaction of p-toluenesulfonylamide and M(NMe2)4 (M = Ti, V): generation of electron-deficient imido complexes of early transition metals.

p-Toluenesulfonamide (p-TsNH2) was successfully employed as an imido ligand precursor in the synthesis of highly air- and moisture-sensitive titanium(IV) and vanadium(IV) complexes. Reaction of M(NMe2)4 (M = Ti, V) with TsNH2 in toluene afforded [M(micro-NTs)(NMe2)2]2 dimer complexes (M = Ti (1), V (2)). By contrast, the reaction carried out in dichloromethane led to [Ti[micro-N,O-NTs]Cl(NMe2)(NHMe2)2]2 (3) and [Ti[micro-N,O-NTs]Cl2(NHMe2)2]n (4) through solvent activation.

Vanadium(V) complexes of a chelating dianionic [ONNO]-type amine bis(phenolate) ligand: synthesis and solid state and solution structures.

The reaction between VO(OR)(3) (R = (i)()Pr, (t)()Bu, CH(2)CF(3)) and the chelating dianionic bis(phenoxy)amine ligand [ONNO]H(2) affords a mixture of two isomers (A and B in a ratio A:B approximately 3:1) formulated as VO(OR)[ONNO] (1a-c) (R = (i)()Pr (1a), (t)Bu (1b), CH(2)CF(3) (1c)). Multinuclear and NOESY NMR spectroscopy experiments were able to determine the structure in solution of the complexes. Both isomers have the symmetry-related phenolate groups in a trans configuration, the difference arising from the different configuration of the oxo and alkoxo ligands being located either cis (in isomer A) or trans (in isomer B) to the tripodal amino nitrogen donor atom and the (dimethylamino)ethyl sidearm respectively for the oxo and the alkoxo ligands.

Biographical sketches of some dental practitioners in Germany at the end of the eighteenth century.

These biographies include those of well-qualified surgeons as well as those with limited theoretical knowledge. Some enjoyed a very comfortable living, were highly literate, producing weighty tomes whilst others were grossly ignorant and could barely scrape a living. They all practised at a time of great change, in both medical care and in society itself.

Germany between 1780 and 1810.

A study of the relationships between the nobility, townsfolk, artisans and those living in rural areas, as well as the legislation that binds them together, are important for the understanding of dental treatments needed and/or requested by all of these groups. Education, literacy, citizenship, religious tolerance (or the lack of it) are also analysed in this chapter which provides a relevant background to the subsequent studies on German dental practice.

Synthesis and crystal structure of unprecedented phosphine adducts of d(1)-aryl imido-vanadium(IV) complexes.

The reaction of the imido precursor [V(NAr)Cl(2)](n)() (1) (Ar = 2,6-i-Pr(2)C(6)H(3)) with 3 equiv of PMe(2)Ph yields the monomeric complex [V(=NAr)Cl(2)(PMe(2)Ph)(2)] (2). Reacting 1 with 1.5 equiv of dmpe or 1 equiv of dppm affords the dimeric complexes [V(=NAr)Cl(2)(dmpe)](2)(mu-P,P'-dmpe) (3) and [V(=NAr)Cl(2)(dppm)](2) (4), respectively.

Reactivity of vanadocene with a nitrile -C identical to N bond activated by a tris(fluorophenyl)borane as Lewis acid: formation of borane adducts of vanada(IV)azirine complexes--EPR evidence for an intramolecular C-F...V interaction.

Reaction of vanadocene [V(Cp)2] with "activated" nitrile R1CN.L (L: Lewis acid), obtained by the reaction of borane adducts (L = BR3; R = C6F5, 2,6-F2C6H3, 3,4,5-F3C6H2) with nitriles (CH3CN, F3CC6H4CN), yields the borane adduct of vanada(IV)azirine complexes [V(Cp)2(eta 2-R1C = N.L)].

Synthesis and structure of a series of new d(1)-Aryl imido-vanadium(IV) complexes stabilized by n-donor ligands.

A family of new coordination vanadium(IV) compounds supported by a terminal or bridged aryl imido ligand are reported. Reaction of V(NMe(2))(4) with anilines ArNH(2), where Ar = 2,6-i-Pr(2)-C(6)H(3), 2,6-Me(2)-C(6)H(3), Ph, 2,6-Cl(2)-C(6)H(3), and C(6)F(5), afforded the diamagnetic imido-bridged complexes [V(NAr)(NMe(2))(2)](2) (1a-e). Chlorination of 1a-e with trimethylchlorosilane afforded complexes 2a-e formulated as [V(=NAr)Cl(2)(NHMe(2))(x)()](n)().

Continuous venovenous hemofiltration improves arterial oxygenation in endotoxin-induced lung injury in pigs.

Background: Hypoxemia is common in septic acute lung failure. Therapy is mainly supportive, and most trials using specific inhibitors of key inflammatory mediators (ie., tumor necrosis factor alpha, interleukin 1) have failed to prove beneficial.

Red cell antibodies in frequently transfused patients with myelodysplastic syndrome.

Therapy for myelodysplastic syndrome (MDS) is often restricted to lifelong support with red blood cell units (RBCU). A variety of immune phenomena associated with antibody production have been reported in MDS patients. Therefore, we hypothesized that red cell antibodies are more frequent in patients with MDS compared to other regularly transfused patients.

[Cp2V] migration along an octatetrayne chain: from the monometallic complex (Cp2V(2-4eta-tBuC triple bond C2-C triple bond CC triple bond CtBu)] to the dimetallic complex.

The oxidative addition of one equivalent of [Cp2V] (4) to the tetrayne ligand tBuC triple bond CC triple bond CC triple bond CC triple bond CtBu (5) gives the monometallic complex [Cp2V(3-4eta-tBuC triple bond C-C2-C triple bond CC triple bond CtBu)] (7). Compound 7 reacts further with a second equivalent of [Cp2V] to give the dimetallic complex [(Cp2V)2(1-2eta:7-8eta-tBuC2-C triple bond CC triple bond C-C2tBu)] (8), which involves a shift of the first coordinated [Cp2V] unit from the internal C3-C4 to the external C1-C2 positions on the alkynyl ligand. Compound 8 is also directly obtained by the addition of two equivalents of [Cp2V] to 5.

Synthesis and reactivity studies of model complexes for molybdopterin-dependent enzymes.

The molybdenum cofactor (Moco)-containing enzymes are divided into three classes that are named after prototypical members of each family, viz. sulfite oxidase, DMSO reductase and xanthine oxidase. Functional or structural models have been prepared for these three prototypical enzymes: (i) The complex [MoO2(mnt)2]2- (mnt2- = 1,2-dicyanoethylenedithiolate) has been found to be able to oxidize hydrogen sulfite to HSO4- and is thus a functional model of sulfite oxidase.

Controlled airway pressure therapy, nitric oxide inhalation, prone position, and extracorporeal membrane oxygenation (ECMO) as components of an integrated approach to ARDS.

Background: Recent years have seen the introduction of innovative additive therapies for acute respiratory distress syndrome. However, because there are no reliable predictors of response to a particular therapy, potential responders to a specific therapeutic intervention may be lost. Therefore, the authors evaluated the effect of a combined therapeutic approach on the survival of patients with acute respiratory distress syndrome, when treated according to a strict algorithm.