Biomedical subjects

Jacqueline M Veauthier

Publications and source records attributed to Jacqueline M Veauthier.

9 recordsLinked to original sources

PubMed2006

Observation of internal electron transfer in bulky allyl ytterbium complexes with substituted terpyridine ligands.

A series of new bulky allyl terpyridyl-ytterbium complexes have been synthesized to determine the effect of allyl ligands on the internal charge-transfer process that exists in these materials. Compared to the pentamethylcyclopentadienyl-ytterbocene compound Cp*2Yb(tpyCN) (nu(C(triple bond)N) = 2172 cm(-1)), the symmetrically substituted allyl complex [1,3-(SiMe3)2C3H3]2Yb(tpyCN) possesses a markedly lowered C(triple bond)N frequency of 2130 cm(-1). Furthermore, the electronic nature of these bulky allyl complexes can be tuned, as demonstrated by the C(triple bond)N frequency of the asymmetric derivatives [1-(SiMe3)C3H4]2Yb(tpyCN) and [1-(SiPh3)-3-(SiMe3)C3H3]2Yb(tpyCN) (2171 and 2164 cm(-1), respectively). The differences in these frequencies can be attributed to differences in the ligands' steric and electronic character. Single-crystal X-ray characterization of [1,3-(SiMe3)2C3H3]2Yb(tpy) reveals that the allyl moiety possesses shorter Yb-C and Yb-N bond distances than the Cp* analogue. The magnetic susceptibility data for [1,3-(SiMe3)2C3H3]2Yb(tpy) departs dramatically from the Curie law, with a room-temperature magnetic moment of 2.95 mu(B).

Journal Article↗

PubMed2006

Ytterbocene charge-transfer molecular wire complexes.

A systematic study of the novel charge-transfer [(f)14-(pi)0-(f)14 --> (f)13-(pi)2-(f)13] electronic state found in 2:1 metal-to-ligand adducts of the type [(Cp)2Yb](BL)[Yb(Cp)2] [BL = tetra(2-pyridyl)pyrazine (tppz) (1), 6',6' '-bis(2-pyridyl)-2,2':4',4'':2'',2'''-quaterpyridine (qtp) (2), 1,4-di(terpyridyl)-benzene (dtb) (3), Cp = (C5Me5)] has been conducted with the aim of determining the effects of increased Yb-Yb separation on the magnetic and electronic properties of these materials. The neutral [(f)13-(pi)2-(f)13], cationic [(f)13-(pi)1-(f)13] and dicationic [(f)13-(pi)0-(f)13] states of these complexes were studied by cyclic voltammetry, UV-vis-NIR electronic absorption spectroscopy, NMR, X-ray crystallography, and magnetic susceptibility measurements. The spectroscopic and magnetic data for the neutral bimetallic complexes is consistent with an [(f)13(pi)2(f)13] ground-state electronic configuration in which each ytterbocene fragment donates one electron to give a singlet dianionic bridging ligand with two paramagnetic Yb(III) centers. The voltammetric data demonstrate that the electronic interaction in the neutral molecular wires 1-3, as manifested in the separation between successive metal reduction waves, is large compared to analogous transition metal systems. Electronic spectra for the neutral and monocationic bimetallic species are dominated by pi-pi and pi-pi transitions, masking the f-f bands that are expected to best reflect the electronic metal-metal interactions. However, these metal-localized transitions are observed when the electrons are removed from the bridging ligand via chemical oxidation to yield the dicationic species, and they suggest very little electronic interaction between metal centers in the absence of pi electrons on the bridging ligands. Analysis of the magnetic data reveals that the qtp complex displays antiferromagnetic coupling of the type Yb(alpha)(alphabeta)Yb(beta) at approximately 13 K.

Journal Article↗

PubMed2006

4f-5f heterotrimetallic complexes exhibiting electrochemical and magnetic communication.

Novel 4f-5f complexes of U(IV) and Th(IV) with Yb have been prepared using a terpyridyl-functionalized ketimide linking group. These 4f-5f heterotrimetallic complexes (C5Me5)2An[-N=C(CH2C6H5)(tpyYb(C5Me5)2)]2 (where An = Th, U) exist in Yb(II/III) valence equilibria and exhibit rich electrochemical behavior consistent with electronic coupling between the actinide and Yb(II/III)tpy*- moieties. The magnetic response of the uranium complex, studied qualitatively using a subtraction method, is indicative of a coupled magnetic state between the U(IV) and Yb(III)tpy*- groups at low temperatures. Both the electrochemical and magnetic data are in agreement and are consistent with differences in participation of the actinide valence orbitals in the ketimide bonding.

Journal Article↗

PubMed2005

Calix[4]pyrrole Schiff base macrocycles: novel binucleating ligands for Cu(I) and Cu(II).

New bimetallic copper(I) and copper(II) complexes of dipyrromethane-derived Schiff base macrocycles are reported. Two different structural motifs were identified, providing support for the notion that ligands of this type can support a variety of coordination modes. In the case of the Cu(I) complexes, the metal centers were found to have a distorted tetrahedral geometry and be coordinated to two imine nitrogens on each side of the ligand, with the exact structure depending on the choice of Schiff base macrocycle. In contrast to what is seen for Cu(I), with Cu(II) as the coordinated cation the Cu(II) metal centers assumed distorted square planar geometries, and both pyrrole N-Cu and imine N-Cu interactions were confirmed by single-crystal X-ray diffraction analysis. This structural analysis revealed a copper-copper distance of 3.47 A, while SQUID magnetic susceptibility data provided evidence for antiferromagnetic coupling between the two metal centers.

Copper↗

PubMed2005

Ligand substituent effect observed for ytterbocene 4'-cyano-2,2':6',2' '-terpyridine.

A new N-heterocyclic complex of ytterbocene (Cp(2)Yb(II), Cp = C(5)Me(5)) has been prepared by the addition of 4'-cyano-2,2':6',2' '-terpyridine (tpyCN) to Cp(2)Yb(II)(OEt(2)) in toluene to give a dark blue species designated as Cp(2)Yb(tpyCN). The effect of the electron-withdrawing group (-CN) on the redox potentials of the charge-transfer form of this complex [in which an electron is transferred from the f(14) metal center to the lowest unoccupied (pi) molecular orbital of the tpyCN ligand to give a 4f(13)-pi(1) electronic configuration] has been quantified by cyclic voltammetry. The tpyCN ligand stabilizes this configuration by 60 mV more than that in the unsubstituted tpy ligand complex and by 110 mV more than that in the unsubstituted bpy ligand complex. Magnetic susceptibility measurements corroborate the enhanced stabilization of the 4f(13)-pi(1) configuration by the substituted terpyridyl ligand complex. Furthermore, the temperature dependence of the magnetic data is most consistent with a thermally induced valence tautomeric equilibrium between this paramagnetic 4f(13)-pi(1) form that dominates near room temperature and the diamagnetic 4f(14)-pi(0) form that dominates at low temperature. Differing coordination modes for the tpyCN ligand to the ytterbocene center have also been confirmed by isolation and X-ray crystallographic characterization of complexes binding through either the cyano nitrogen of tpyCN or the three terpyridyl nitrogen atoms of tpyCN.

Journal Article↗

PubMed2005

A Schiff base expanded porphyrin macrocycle that acts as a versatile binucleating ligand for late first-row transition metals.

The coordination chemistry of the Schiff base polypyrrolic octaaza macrocycle 1 toward late first-row transition metals was investigated. Binuclear complexes with the divalent cations Ni(II), Cu(II), and Zn(II) and with the monovalent cation Cu(I) were prepared and characterized. Air oxidation of the Cu(I) ions in the latter complex to their divalent oxidation state resulted in a change in the coordination mode relative to the macrocycle.

Copper↗

PubMed2004

Octaethylporphyrin and expanded porphyrin complexes containing coordinated BF2 groups.

In contrast to octaethylporphyrin, which forms a very labile bis-BF(2) complex, treatment of the hexa- and octapyrrolic expanded porphyrins amethyrin and [32]octaphyrin with BF(3).Et(2) under standard reaction and work-up conditions gives rise to stable, non-labile mono- and bis-BF(2) complexes; these were readily characterised by, inter alia, X-ray diffraction analyses.

Boron Compounds↗

PubMed2004

Calix[4]pyrrole Schiff base macrocycles. Novel binucleating ligands for mu-oxo iron complexes.

New bimetallic mu-oxo diferric complexes of several previously reported calix[4]pyrrole Schiff base macrocycles are described. The synthesis of a new member of this class of macrocycles is also reported; it was prepared via an acid-catalyzed condensation between 1,9-bisformyl-5,5-dipropyldipyrromethane and o-phenylenediamine. Reactions of the free base macrocycles or their bis-HCl salts with Fe(II) mesitylene, followed by air oxidation, gave the binuclear mu-oxo bis-Fe(III) compounds 6-10 in moderate yield. X-ray crystallography data reveal two different coordination environments for the Fe-O-Fe subunit in 6-10 that it is suggested can be controlled by altering the reaction conditions. Structural properties of these metalated pyrrolic macrocycles are also compared to those of mu-oxo diferric porphyrins and mu-oxo diferric texaphyrin. Complexes 6-10 exhibit two distinct types of M-N bonds that are similar in length to the bonds observed in metallotexaphyrin complexes. However, the electronics of the present systems are very different from those of texaphyrins and porphyrins in that no delocalized bonding patterns are observed within the ligands as a whole.

Benzene Derivatives↗

PubMed2004

Anesthetic requirement is increased in redheads.

BACKGROUND: Age and body temperature alter inhalational anesthetic requirement; however, no human genotype is associated with inhalational anesthetic requirement. There is an anecdotal impression that anesthetic requirement is increased in redheads. Furthermore, red hair results from distinct mutations of the melanocortin-1 receptor. Therefore, the authors tested the hypothesis that the requirement for the volatile anesthetic desflurane is greater in natural redheaded than in dark-haired women. METHODS: The authors studied healthy women with bright red (n = 10) or dark (n = 10) hair. Blood was sampled for subsequent analyses of melanocortin-1 receptor alleles. Anesthesia was induced with sevoflurane and maintained with desflurane randomly set at an end-tidal concentration between 5.5 and 7.5%. After an equilibration period, a noxious electrical stimulation (100 Hz, 70 mA) was transmitted through bilateral intradermal needles. If the volunteer moved in response to stimulation, desflurane was increased by 0.5%; otherwise, it was decreased by 0.5%. This was continued until volunteers "crossed over" from movement to nonmovement (or vice versa) four times. Individual logistic regression curves were used to determine desflurane requirement (P50). Desflurane requirements in the two groups were compared using Mann-Whitney nonparametric two-sample test; P < 0.05 was considered statistically significant. RESULTS: The desflurane requirement in redheads (6.2 vol% [95% CI, 5.9-6.5]) was significantly greater than in dark-haired women (5.2 vol% [4.9-5.5]; P = 0.0004). Nine of 10 redheads were either homozygous or compound heterozygotes for mutations on the melanocortin-1 receptor gene. CONCLUSIONS: Red hair seems to be a distinct phenotype linked to anesthetic requirement in humans that can also be traced to a specific genotype.

Adult↗