Polyanionic Ligand Platforms for Methyl- and Dimethylaluminum Arrays.

Trimethylaluminum finds widespread applications in chemical and materials synthesis, most prominently in its partially hydrolyzed form of methylalumoxane (MAO), which is used as a cocatalyst in the polymerization of olefins. This work investigates the sequential reactions of trimethylaluminum with hexaprotic phosphazenes (RNH)PN (=XH) equipped with substituents R of varied steric bulk including tert-butyl (1H), cyclohexyl (2H), isopropyl (3H), isobutyl (4H), ethyl (5H), propyl (6H), methyl (7H), and benzyl (8H). Similar to MAO, the resulting complexes of polyanionic phosphazenates [XH ] accommodate multinuclear arrays of [AlMe] and [AlMe].

Improving communication of patient issues on transfer out of intensive care.

The written medical handover document is frequently poor in quality and highly variable which raises concerns about patient safety. Intensive care unit (ICU) patients have complex medical and social issues which increases the risk of errors during ongoing hospital treatment. Our project team of four doctors and two nurses aimed to improve the documentation of patient problems as they leave the ICU.

Fairy Liquid® consumption: squeaky clean or deadly serious?

Fairy Liquid® is a detergent used daily throughout the United Kingdom. Currently, Toxbase suggests ingestion only causes nausea, vomiting and diarrhoea; however, we report a patient who developed multi-organ failure following a large ingestion and subsequent aspiration of Fairy Liquid.

The synthesis of, and characterization of the dynamic processes occurring in Pd(II) chelate complexes of 2-pyridyldiphenylphosphine.

Pd(II) complexes in which 2-pyridyldiphenylphosphine (Ph(2)Ppy) chelates the Pd(II) centre have been prepared and characterized by multinuclear NMR spectroscopy and by X-ray crystallographic analysis. trans-[Pd(kappa(1)-Ph(2)Ppy)(2)Cl(2)] is transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]Cl by the addition of a few drops of methanol to dichloromethane solutions, and into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)Cl]X by addition of AgX or TlX, (X = BF(4)(-), CF(3)SO(3)(-) or MeSO(3)(-)). [Pd(kappa(1)-Ph(2)Ppy)(2)(p-benzoquinone)] can be transformed into [Pd(kappa(2)-Ph(2)Ppy)(kappa(1)-Ph(2)Ppy)(MeSO(3))][MeSO(3)] by the addition of two equivalents of MeSO(3)H.

Applying rapid serial visual presentation to adolescent sexual offenders: attentional bias as a measure of deviant sexual interest?

Attentional bias toward child images is assessed among adolescent sexual offenders and nonsexual offenders using the rapid serial visual presentation (RSVP) method, which measures the effects of "attentional blink." Twenty adolescent sexual offenders against children and 26 nonsexual offenders are asked to identify a child or animal image and then a second image in streams of 10 images. A stronger attentional blink effect is expected for offenders against children after viewing child rather than animal images.

In situ recrystallisation of a coordination polymer with hemilabile linkers.

The variable coordination pattern of a hemilabile phosphazene ligand equipped with six pendent olefin groups facilitates the in situ recrystallisation of a silver(I) complex from an amorphous precipitate into a 1D coordination polymer and its subsequent isomerisation to a 3D coordination network.

Precursors for MOCVD and ALD of rare earth oxides-complexes of the early lanthanides with a donor-functionalized alkoxide ligand.

Complexes of the early lanthanides with the donor-functionalized alkoxide ligand mmp (Hmmp = HOCMe(2)CH(2)OMe, 1-methoxy-2-methylpropan-2-ol) are excellent precursors for Metal Organic Chemical Vapor Deposition (MOCVD) and Atomic Layer Deposition (ALD) of lanthanide oxides; however, their coordination chemistry, which is the subject of this paper, is rather complex. Precursors for MOCVD and ALD of lanthanide oxides are prepared by the reaction of [Ln{N(SiMe(3))(2)}(3)] with 3 equiv of the alcohol Hmmp in toluene in the presence of 1 equiv of tetraglyme and are indefinitely stable in solution. Reaction of [Ln{N(SiMe(3))(2)}(3)] with 3 equiv of Hmmp in the absence of stabilizing Lewis bases gives complex condensed products with empirical formula [{Ln(mmp)(3-n)}(2)O(n)].

Inorganic-cored photoactive assemblies: synthesis, structure, and photochemical investigations on stannoxane-supported multifluorene compounds.

Organostannoxanes were used as inert supports for the preparation of multichromophore assemblies. The synthesis involves a single-step procedure and allows the preparation of compounds in which the number of chromophore units can be varied from one to six. Thus, the reactions of LCOOH (1-fluorenecarboxylic acid) or L'COOH (9-fluorenecarboxylic acid) with various organostannoxane precursors afforded the fluorenyl derivatives [Ph(3)SnO(2)CL] (1), [Ph(3)SnO(2)CL'] (2), [{nBu(3)SnO(2)CL''}(n)] (3), [{nBu(3)SnO(2)CL'}(n)] (4), [{tBu(2)Sn(OH)O(2)CL}(2)] (5), [{tBu(2)Sn(OH)O(2)CL'}(2)] (6), [{[nBu(2)SnO(2)CL](2)O}(2)] (7) [{[nBu(2)SnO(2)CL'](2)O}(2)] (8), [{nBuSn(O)O(2)CL}(6)] (9), and [{nBuSn(O)O(2)CL'}(6)] (10).

The mechanism of the hydroalkoxycarbonylation of ethene and alkene-CO copolymerization catalyzed by Pd(II)-diphosphine cations.

All the intermediates in the "carboalkoxy" pathway, and their interconversions giving complete catalytic cycles, for palladium-diphosphine-catalyzed hydroalkoxycarbonylation of alkenes, and for alkene-CO copolymerization, have been demonstrated using (31)P{(1)H} and (13)C{(1)H} NMR spectroscopy. The propagation and termination steps of the "hydride" cycles and the crossover between the hydride and carboalkoxy cycles have also been demonstrated, providing the first examples of both cycles, and of chain crossover, being delineated for the same catalyst. Comparison of the propagation and termination steps in the pathways affords new insight into the selectivity-determining steps.

Alternating hydrophilic and hydrophobic pockets in the channel structures of organostannoxane prismanes: preferential confinement of guest molecules.

A hydroxyl-rich hexameric organooxotin prismane has been prepared by reaction of n-BuSn(O)OH with 9-hydroxy-9-fluorenecarboxylic acid. The supramolecular structure of this cage shows channels with hydrophobic and hydrophilic segments, which selectively entrap guest molecules.

Organostannoxane-supported multiferrocenyl assemblies: synthesis, novel supramolecular structures, and electrochemistry.

Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R2SnO (R = Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph2Sn[OC(O)Fc]2}2] (1), [{[nBu2SnOC(O)Fc]2O}2] (2), [nBu2Sn{OC(O)Fc}2] (3), [{tBu2Sn(OH)OC(O)Fc}2] (4), and [tBu2Sn{OC(O)Fc}2] (5) (Fc = eta(5)C5H4-Fe-eta(5)C5H5).

Synthesis, structure, and stereochemistry of trinuclear metal complexes formed from the phosphorus-based achiral tripodal ligand {P(S)[N(Me)N=CHC6H4-o-OH]3} (LH3): luminescent properties of L2Cd3 x 2H2O.

Neutral trinuclear metal complexes L2Cd3 x 2H2O, L2Mn3 x MeOH, and L2Zn3 x MeOH were isolated in the reaction between the phosphorus-centered achiral tris(hydrazone) P(S)[N(Me)N=CHC6H(4)-o-OH]3 (LH3) and the corresponding divalent metal ions. The trinuclear complexes contain two equivalent terminal metal ions (M(t)) and a central metal ion (M(c)). The ligand encapsulates M(t) in a facial N3O3 coordination environment.

A luminescent linear trinuclear magnesium complex assembled from a phosphorus-based tris-hydrazone ligand.

A novel linear trinuclear magnesium complex (P(S)[N(CH3)N=CHC6H4-o-O]3)2Mg3 was prepared by the reaction of P(S)[N(CH3))N=CHC6H4-o-OH]3 with MgCl2 x 6H2O in the presence of triethylamine. The trinuclear magnesium complex is fluorescent in solution as well as in the solid-state.

Application of thiol-olefin co-oxygenation methodology to a new synthesis of the 1,2,4-trioxane pharmacophore.

[reaction: see text] Thiol-olefin co-oxygenation (TOCO) of substituted allylic alcohols generates alpha-hydroxyperoxides that can be condensed in situ with various ketones to afford a series of functionalized 1,2,4-trioxanes in good yields. Manipulation of the phenylsulfenyl group in 4a allows for convenient modification to the spiro-trioxane substituents, and we describe, for the first time, the preparation of a new class of antimalarial prodrug.

From the tetra(amino) phosphonium cation, [P(NHPh)4]+, to the tetra(imino) phosphate trianion, [P(NPh)4]3-, two-faced ligands that bind anions and cations.

The tetraanilino phosphonium cation, [P(N(H)Ph)4]+, 1+, is sequentially deprotonated by Bu(n)Li in thf. The deprotonation reaction of the chloride derivative, Cl, was monitored by (31)P NMR, which revealed the successive formation of the neutral [P(N(H)Ph)3(NPh)], 2, the monoanionic [P(N(H)Ph)2(NPh)2]-, 3-, the dianionic [P(N(H)Ph)(NPh)3]2-, 4(2-), and finally the trianionic species [P(NPh)(4)](3-), (3-). Considering the isoelectronic relationship of oxo, =O, and imino groups, =NR, as well as hydroxy, -OH, and amino groups, -N(H)R, the neutral complex corresponds to phosphoric acid, H3PO4, whereas the anions 3-, 4(2-) and 5(3-) are analogues of dihydrogen phosphate, H2PO4-, monohydrogenphosphate, HPO4(2-), and orthophosphate ions, PO4(3-), respectively.

Reactions of some cyclopentenones with selected cysteine derivatives and biological activities of the product thioethers.

The conjugate addition reaction between glutathione, N-Boc-cysteine methyl ester, N-acetyl cysteine methyl ester and N-acetyl cysteine and several substituted cyclopentenones is described. The reversibility of this process was demonstrated by thio-adduct metathesis on treatment of the adduct with a different cysteinyl derivative. The levels at which these compounds inhibit the function of nuclear factor kappa B (NF-kappaB) and potentiate heat shock factor (HSF) are reported and the possible relevance of these studies concerning the antiviral and anti-inflammatory activities of the cyclopentenone prostanoids is discussed.

Cyclotriphosphazene hydrazides as efficient multisite coordination ligands. eta(3)-fac-non-geminal-N(3) coordination of spiro-N(3)P(3)[O(2)C(12)H(8)][N(Me)NH(2)](4) (L) in L(2)CoCl(3) and L(2)M(NO(3))(2) (M = Ni, Zn, Cd).

The cyclophosphazene tetrahydrazide spiro-N(3)P(3)[O(2)C(12)H(8)][N(Me)NH(2)](4) (L) functions as a multisite coordination ligand and affords L(2)CoCl(3).2CH(3)OH (4), L(2)Ni(NO(3))(2).2CHCl(3).

Isoquine and related amodiaquine analogues: a new generation of improved 4-aminoquinoline antimalarials.

Amodiaquine (AQ) (2) is a 4-aminoquinoline antimalarial that can cause adverse side effects including agranulocytosis and liver damage. The observed drug toxicity is believed to involve the formation of an electrophilic metabolite, amodiaquine quinoneimine (AQQI), which can bind to cellular macromolecules and initiate hypersensitivity reactions. We proposed that interchange of the 3' hydroxyl and the 4' Mannich side-chain function of amodiaquine would provide a new series of analogues that cannot form toxic quinoneimine metabolites via cytochrome P450-mediated metabolism.

A phosphorus supported multisite coordinating tris hydrazone P(S)[N(Me)N=CH-C6H4-o-OH]3 as an efficient ligand for the assembly of trinuclear metal complexes: synthesis, structure, and magnetism.

A phosphorus supported multisite coordinating ligand P(S)[N(Me)N=CH-C(6)H(4)-o-OH](3) (2) was prepared by the condensation of the phosphorus tris hydrazide P(S)[N(Me)NH(2)](3) (1) with o-hydroxybenzaldehyde. The reaction of 2 with M(OAc)(2).xH(2)O (M = Mn, Co, Ni, x = 4; M = Zn, x = 2) afforded neutral trinuclear complexes [P(S)[N(Me)N=CH-C(6)H(4)-o-O](3)](2)M(3) [M = Mn (3), Co (4), Ni (5), and Zn (6)].

Preparation, X-ray structure and reactivity of a stable glycosyl iodide.

Highly selective reaction of methyl tetra-O-pivaloyl-beta-D-glucopyranuronate 2 with iodotrimethylsilane or (Me3Si)2 and I2 affords, in excellent yield, the 'disarmed' glycosyl iodide 1 which has good stability at 20 degrees C and excellent stability at 0 degrees C; the X-ray crystal structure of 1 is described, along with a comparison of its utility as a glycosyl donor to that of the corresponding bromide.

Implications for treatment of sexual offenders of the Ward and Hudson model of relapse.

A group of 59 child abusers were classified as having either an "avoidant" (n = 15) or an "approach" (n = 44) goal regarding deviant sexual activity with children. Level of distorted beliefs about sexual activity with children (cognitive distortions) and distorted beliefs about their own victims (victim blaming attitudes) in both groups were measured before and after treatment. Results indicate that there was an overall reduction in the level of these distorted beliefs at the posttreatment stage in the approach group.

Polymeric anionic networks using dibromine as a crosslinker; the preparation and crystal structure of [(C4H9)4N]2[Pt2Br10].(Br2)7 and [(C4H9)4N]2[PtBr4Cl2].(Br2)6.

The reaction of M[PtX3(CO)] (M+ = [(C4H9)4N]+, X = Br, Cl) with an excess of Br2 gives the new platinum(IV) salts, [(C4H9)4N]2[Pt2Br10].(Br2)7, 1, and [(C4H9)4N]2[PtBr4Cl2].(Br2)6, 2, which, in the solid state, contain strong Br Br interactions resulting in the formation of polymeric networks; they could provide useful solid storage reservoirs for elemental bromine.