Behavioural abnormalities of the hyposulphataemic Nas1 knock-out mouse

We recently generated a sodium sulphate cotransporter knock-out mouse (Nas1-/-) which has increased urinary sulphate excretion and hyposulphataemia. To examine the consequences of disturbed sulphate homeostasis in the modulation of mouse behavioural characteristics, Nas1-/- mice were compared with Nas1+/- and Nas1+/+ littermates in a series of behavioural tests. The Nas1-/- mice displayed significantly (P < 0.001) decreased marble burying behaviour (4.33 +/- 0.82 buried) when compared to Nas1+/+ (7.86 +/- 0.44) and Nas1+/- (8.40 +/- 0.37) animals, suggesting that Nas1-/- mice may have decreased object-induced anxiety. The Nas1-/- mice also displayed decreased locomotor activity by moving less distance (1.53 +/- 0.27 m, P < 0.05) in an open-field test when compared to Nas1+/+ (2.31 +/- 0.24 m) and Nas1+/- (2.15 +/- 0.19 m) mice. The three genotypes displayed similar spatiotemporal and ethological behaviours in the elevated-plus maze and open-field test, with the exception of a decreased defecation frequency by the Nas1-/- mice (40% reduction, P < 0.01). There were no significant differences between Nas1-/- and Nas1+/+ mice in a rotarod performance test of motor coordination and in the forced swim test assessing (anti-)depressant-like behaviours. This is the first study to demonstrate behavioural abnormalities in the hyposulphataemic Nas1-/- mice. (C) 2004 Elsevier B.V. All rights reserved.

Cyanocobalt(III) complexes of penta- and tetradentate-coordinated macrocyclic hexaamines

The pendent-arm macrocyclic hexaamine trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L) may coordinate in tetra-, penta- or hexadentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo-octahedral cobalt(III) complexes of L, namely sodium trans-cyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine)cobalt(III) triperchlorate, Na[Co(CN)(C13H30N6)](ClO4)(3) or Na{trans-[CoL(CN)]}(ClO4)(3), (I), where L is coordinated as a pentadentate ligand, and trans-dicyano(trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) cobalt (III) trans-dicyano (trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diaminium)cobalt(III) tetraperchlorate tetrahydrate, [Co(CN)(2)(Cl4H32N6)][Co(CN)(2)(Cl4H30N6)](ClO4)(4)&BULL;-4H(2)O or trans-[CoL(CN)(2)]trans-[Co(H2L)(CN)(2)] (ClO4)(4)&BULL;-4H(2)O, (II), where the ligand binds in a tetradentate mode, with the remaining coordination sites being filled by C-bound cyano ligands. In (I), the secondary amine Co-N bond lengths lie within the range 1.944 (3)-1.969 (3) &ANGS;, while the trans influence of the cyano ligand lengthens the Co-N bond length of the coordinated primary amine [Co-N = 1.986 (3) &ANGS;]. The Co-CN bond length is 1.899 (3) &ANGS;. The complex cations in (11) are each located on centres of symmetry. The Co-N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)-1.982 (3) &ANGS;]. The two independent Co-CN bond lengths are similar [1.918 (4) and 1.926 (4) &ANGS;] but significantly longer than in the structure of (1), again a consequence of the trans influence of each cyano ligand.

Binary games with many players

We examine a problem with n players each facing the same binary choice. One choice is superior to the other. The simple assumption of competition - that an individual's payoff falls with a rise in the number of players making the same choice, guarantees the existence of a unique symmetric equilibrium (involving mixed strategies). As n increases, there are two opposing effects. First, events in the middle of the distribution - where a player finds itself having made the same choice as many others - become more likely, but the payoffs in these events fall. In opposition, events in the tails of the distribution - where a player finds itself having made the same choice as few others - become less likely, but the payoffs in these events remain high. We provide a sufficient condition (strong competition) under which an increase in the number of players leads to a reduction in the equilibrium probability that the superior choice is made.

Immobilisation of electroactive macrocyclic complexes within titania films

The 4-carboxyphenyl-appended macrocyclic ligand trans-6,13-dimethyl-6-((4-carboxybenzyl)amino)-1,4,8,11-tetraazacyclotetradecane-6-amine (HL10) has been synthesised and complexed with Co-III. The mononuclear complexes [Co(HL10)(CN)](2+) and [CoL10(OH)](+) have been prepared and the crystal structures of their perchlorate salts are presented, where the ligand is bound in a pentadentate mode in each case while the 4-carboxybenzyl-substituted pendent amine remains free from the metal. The cyano-bridged dinuclear complex [CoL10-mu-NC-Fe(CN)(5)](2-) was also prepared and chemisorbed on titania-coated ITO conducting glass. The adsorbed complex is electrochemically active and cyclic voltammetry of the modified ITO working electrode in both water and MeCN solution was undertaken with simultaneous optical spectroscopy. This experiment demonstrates that reversible electrochemical oxidation of the Fe-II centre is coupled with rapid changes in the optical absorbance of the film.

N-methylation of diamino-substituted macrocyclic complexes: Intermolecular reactions

Two N-based isomeric copper(II) complexes of the macrocycle trans-6,13-dimethyl-6,13-bis(dimethylamino)1,4,8,11-tetraazacyclotetradecane (L(3)) have been synthesized and characterised spectroscopically and structurally: alpha-[CuL(3)(OH2)(2)]Cl-2, monoclinic, space group C2/m, a = 12.908(4), b = 12.433(2), c = 7.330(2) Angstrom, beta = 105.87(2)degrees, Z = 2; beta-[CuL(3)(OClO3)(2)]. 2H(2)O, monoclinic, space group P2(1)/c, a = 9.708(3), b = 9.686(3), c = 14.202(4) Angstrom, beta = 106.17(1)degrees, Z = 2. The two isomers exhibit very similar co-ordination spheres but significantly different visible electronic maxima. This difference is attributed to an intramolecular N ... H contact between the pendant dimethylamino group and an adjacent secondary amine H atom.

On the structure, electrochemistry, and spectroscopy of the (N,N'-bis(2'-(dimethylamino)ethyl)-N,N'-dimethylpropane-1,3-diamine)copper(II) ion

The synthesis, spectroscopy, and electrochemistry of the acyclic tertiary tetraamine copper(II) complex [CuL(1)](ClO4)(2) (L(1) = N,N-bis(2'-(dimethylamino)ethyl)-N,N'-dimethylpropane-1,3-diamine) is reported. The X-ray crystal structure of [CuL(1)(OClO3)(2)] reveals a tetragonally elongated CuN4O2 coordination sphere, exhibiting relatively long Cu-N bond lengths for a Cu-II tetraamine, and a small tetrahedral distortion of the CuN4 plane. The [CuL(1)](2+) ion displays a single, reversible, one-electron reduction at -0.06 V vs Ag/AgCl. The results presented herein illustrate the inherent difficulties associated with the separation and characterization of Cu-II complexes of tertiary tetraamines, and some previously incorrect assertions and unexplained observations of other workers are discussed.

Paramagnetism of caesium titanium alum

Caesium titanium alum, CsTi(SO4)(2) . 12H(2)O, is a beta alum and exhibits a large trigonal field and a dynamic Jahn-Teller effect. Exact calculations of the linear (2)T(2)xe Jahn-Teller coupling show that in the strict S-6 Site symmetry the ground multiplet consists of a Kramers doublet 2 Gamma(6) with magnetic splitting factors g(parallel to)=1.1 and g perpendicular to=0, a Gamma(4) Gamma(5) doublet at similar to 60 cm(-1) with g(parallel to)=2.51 and g(perpendicular to)=0.06 and another Gamma(4) Gamma(5) doublet at similar to 270 cm(-1) with g(parallel to)=1.67 and g(perpendicular to)=1.83. The controversial g values observed below 4.2 K, g(parallel to)=1.25 and g(perpendicular to)=1.14, are shown to arise from low symmetry distortions. These distortions couple the vibronic levels and induce into the ground state the off-diagonal axial Zeeman interaction that exists between the first excited and the ground vibronic levels. (C) 1997 American Institute of Physics.

Nitrogen- and carbon-based isomerism in the copper(II) complexes of 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine

A number of N- and C-based diastereomeric copper(II) complexes of the pendant-arm macrocyclic hexaamines trans- and cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L-1 and L-2) have been isolated and characterised. The crystal structures of the complexes RRSS-[CuL1(OH2)(2)][ClO4](2), SSRR-[Cu(H2L1)(OClO3)(2)]-[ClO4](2) . 2H(2)O RSRS-[CuL1(OClO3)]ClO4, RSRS-[CuL2(OClO3)]ClO4 and RRSS-[Cu(H2L2)(OClO3)(2)][ClO4](2) have been determined. Some unusual structural and spectroscopic variations are found across this series of diastereomers. The protonation constants of the pendant primary amines are dependent on the relative dispositions of the adjacent macrocyclic secondary amine H atoms, which is indicative of intramolecular hydrogen-bonding interactions.

Structural and electron self-exchange rate variations in isomeric (hexaamine)cobalt(III/II) complexes

The syntheses and characterisation of the new macrocyclic hexaamine trans-(5(S),7(S),12(R),14(R)-tetramethyl)-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L-6) and its Co-III complex are reported. The X-ray crystal structural analyses of [CoL6]Cl-2(ClO4) [monoclinic, space group C2/c, a = 16.468(3) Angstrom, b = 9.7156(7) Angstrom, c = 15.070(3) Angstrom, beta = 119.431(8)degrees, Z = 4] and the closely related cis-diamino-substituted macrocyclic complex [CoL2](ClO4)(3) . 2H(2)O (L-2 = cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) [orthorhombic, space group Pna2(1), a = 16.8220(8) Angstrom, b = 10.416(2) Angstrom, c = 14.219(3) Angstrom, Z = 4] reveal significant variations in the observed Co-N bond lengths and coordination geometries, which may be attributed to the trans or cis disposition of the pendent primary amines. The Co-III/II self-exchange electron transfer rate constants for these and other closely related hexaamines have been determined, and variations of some 2 orders of magnitude are found between pairs of trans and cis isomeric Co-III complexes.

Tris(ethylenediamine-N,N')zinc(II) dinitrate

The Zn-II atom in [Zn(C2H8N2)(3)](NO3)(2) has a distorted octahedral geometry of D-3 symmetry With three ethylenediamine bidentate Ligands completing the coordination.

Relationship between limb movement speed and associated contraction of the trunk muscles

Rapid shoulder movement is preceded by contraction of the abdominal muscles to prepare the body for the expected disturbance to postural equilibrium and spinal stability provoked by the reactive forces resulting from the movement. The magnitude of the reactive forces is proportional to the inertia of the limb. The aim of the study was to investigate if changes in the reaction time latency of the abdominal muscles was associated with variation in the magnitude of the reactive forces resulting from variation in limb speed. Fifteen participants performed shoulder flexion at three different speeds (fast, natural and slow). The onset of EMG of the abdominal muscles, erector spinae and anterior deltoid (AD) was recorded using a combination of fine-wire and surface electrodes. Mean and peak velocity was recorded for each limb movement speed for five participants. The onset of transversus abdominis (TrA) EMG preceded the onset of AD in only the fast movement condition. No significant difference in reaction time latency was recorded between the fast and natural speed conditions for all muscles. The reaction time of each of the abdominal muscles relative to AD was significantly delayed with the slow movement compared to the other two speeds. The results indicate that the reaction time latency of the trunk muscles is influenced by limb inertia only with limb movement below a threshold velocity.

Molybdenum carbonyl complexes of pendant-arm polyazamacrocycles

Molybdenum hexacarbonyl reacted with the pendant-arm macrocycles 10-methyl-1,4,8, 12-tetraazacyclopentadecane-10-amine (L-1) and trans-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6, 13-diamine (L-2) in the absence of air to form complexes fac-[MoL1(CO)(3)] and [Mo2L2(CO)(8)] respectively. The mononuclear complex has the macrocycle bound in a tridentate manner, including the pendant primary amine, whereas the dinuclear complex exhibits a bridging bis(didentate) co-ordination mode, again involving the pendant primary amines. Structures have been defined by crystal structure analyses. The preferential binding of the pendant primary amines rather than additional secondary amines parallels similar behaviour observed earlier with some mercury(II) and rhodium(III) complexes, and points to the important general role of this pendant, despite being fused directly to the macrocyclic ring, in metal-ion binding.

Calcium potassium tris(oxalato-O-1, O-2)-chromate(III) pentahydrate

The Cr-III atom in CaK[Cr(C2O4)(3)].5H(2)O, has a regular octahedral geometry with three oxalato groups completing the coordination, Both the calcium and potassium cations are coordinated to the O atom of the oxalate group.