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Robert J Baker

Publications and source records attributed to Robert J Baker.

At least 19 recordsLinked to original sources
PubMed2006

Complexes of a gallium heterocycle with transition metal dicyclopentadienyl and cyclopentadienylcarbonyl fragments, and with a dialkylmanganese compound.

The reactivity of several transition metal half sandwich complexes towards an anionic gallium(I) heterocyclic complex, [K(tmeda)][Ga{[N(Ar)C(H)]2}](Ar = C6H3Pri2-2,6), has been investigated. This has led to the anionic half sandwich complexes, [K(tmeda)][(C5H4R)M(CO)n[Ga{[N(Ar)C(H)]2}]](M = V, R = H, n= 3; M = Mn, R = Me, n= 2; M = Co, R = H, n= 1), which crystallographic studies show to form dimers (M = Mn and Co) or a polymer (M = V) through bridging potassium cations. The metal-gallium bond lengths in all complexes are very short which, combined with some spectroscopic evidence, is suggestive of M-Ga pi-bonding. Density functional theory studies of models of all complexes indicate that the level of back-bonding in these complexes is, however, minimal and of a similar order to that seen in analogous complexes incorporating neutral N-heterocyclic carbene ligands. Reactions of the metallocenes, [M(C5H4Me)2](M = V or Cr), with the digallane4, [Ga{[N(Ar)C(H)]2}]2, have afforded the neutral complexes, [M(C5H4Me)2[Ga{[N(Ar)C(H)]2}]], which are thought to be formed via an initial oxidative insertion of the transition metal centre into the Ga-Ga bond of the digallane. X-Ray crystallography shows the complexes to be monomeric. One (M = V) reacts with one equivalent of [K(tmeda)][Ga{[N(Ar)C(H)]2}] to give the crystallographically characterised, anionic bis(gallyl)-complex, [K(tmeda)][V(C5H4Me)2[Ga{[N(Ar)C(H)]2}]2]. For comparison, the reaction of [K(tmeda)][Ga{[N(Ar)C(H)]2}] with [Mn{CH(SiMe3)2}2] was carried out and gave the monomeric, anionic complex, [K(tmeda)][Mn{CH(SiMe3)2}2[Ga{[N(Ar)C(H)]2}]].

Journal Article↗
PubMed2006

Molecular systematics of Vampyressine bats (Phyllostomidae: Stenodermatinae) with comparison of direct and indirect surveys of mitochondrial DNA variation.

Approximately 29 species in seven genera (Chiroderma, Mesophylla, Platyrrhinus, Uroderma, Vampyressa, Vampyriscus, and Vampyrodes) compose the Subtribe Vampyressina, a group of New World leaf-nosed bats (Phyllostomidae) specialized in fruit-eating. A recent study of restriction-site variability within the mitochondrial ND3-ND4 gene region contrasts with other molecular data, including sequence data from other mitochondrial genes, by suggesting that the monotypic genus Ectophylla (E. alba) also is member of the group and is related closely to Mesophylla. In this study, we address possible explanations for why the restriction-site data appear to contradict other molecular data by performing phylogenetic analysis of DNA sequence variation (direct survey) in the ND3-ND4 region and cytochrome b gene and by re-assessing ND3-ND4 restriction-site variability in the known sequences (indirect survey). Results from analysis of sequence data reject the Ectophylla-Mesophylla hypothesis (P<0.001) and suggest four primary lineages within Vampyressina: (1) Mesophylla-Vampyressa; (2) Chiroderma-Vampyriscus; (3) Platyrrhinus-Vampyrodes; and (4) Uroderma. We also find no support for the Ectophylla-Mesophylla hypothesis in our re-analysis of ND3-ND4 restriction-site variability, and suggest the differences between molecular studies have a methodological basis.

Animals↗
PubMed2006

Musculoskeletal injuries in sports.

A large number of adolescents participate in various sports. Not withstanding the methodologic problems with epidemiologic data, a large percentage of athletes sustain musculoskeletal injuries. In most instances, the athlete first presents to his or her primary care physician, who must perform the initial assessment and decide on further management. Many injuries can be managed by the primary care physician. It is important to recognize the unique characteristics of adolescent growth and development that have implications for the diagnosis and management of musculoskeletal injuries.

Acute Disease↗
PubMed2006

Variation in mitochondrial DNA control region haplotypes in populations of the bank vole, Clethrionomys glareolus, living in the Chernobyl environment, Ukraine.

Bank vole, Clethrionomys glareolus, specimens have been annually sampled from the radioactive Chernobyl, Ukraine, environment and nonradioactive reference sites since 1997. Exposed voles continually exhibit increased mitochondrial DNA haplotype (h) and nucleotide diversity (ND), observed in the hypervariable control region (1997-1999). Increased maternal mutation rates, source-sink relationships, or both are proposed as hypotheses for these differences. Samples from additional years (2000 and 2001) have been incorporated into this temporal study. To evaluate the hypothesis that an increased mutation rate is associated with increased h, DNA sequences were examined in a phylogenetic context for novel substitutions not observed in haplotypes from bank voles from outside Ukraine or in other species of Clethrionomys. Such novel substitutions might result from in situ mutation events and, if largely restricted to samples from radioactive environments, support an increased maternal mutation rate in these areas. The only unique substitution meeting this criterion was found in an uncontaminated reference site. All other substitutions are found in other haplotypes of the bank vole or in other species. Increased maternal mutation rates do not appear to explain trends in h and ND observed in northern Ukraine. Studies examining ecological dynamics will clarify the reasons behind, and significance of, increased levels of h in contaminated areas.

Animals↗
PubMed2005

The reactivity of gallium-(I), -(II) and -(III) heterocycles towards Group 15 substrates: attempts to prepare gallium-terminal pnictinidene complexes.

The reactivity of a series of Ga(I), Ga(II) and Ga(III) heterocyclic compounds towards a number of Group 15 substrates has been investigated with a view to prepare examples of gallium-terminal pnictinidene complexes. Although no examples of such complexes were isolated, a number of novel complexes have been prepared. The reactions of the gallium(I) N-heterocyclic carbene analogue, [K(tmeda)][:Ga{[N(Ar)C(H)](2)}] (Ar = 2,6-diisopropylphenyl) with cyclo-(PPh)(5) and PhN[double bond, length as m-dash]NPh led to the unusual anionic spirocyclic complexes, [{kappa(2)P,P'-(PhP)(4)}Ga{[N(Ar)C(H)](2)}](-) and [{kappa(2)N,C-PhNN(H)(C(6)H(4))}Ga{[N(Ar)C(H)](2)}](-), via formal reductions of the Group 15 substrate. The reaction of the digallane(4), [Ga{[N(Ar)C(H)](2)}](2), with (Me(3)Si)N(3) afforded the paramagnetic, dimeric imido-gallane complex, [{[N(Ar)C(H) ](2)}Ga{mu-N(SiMe(3))}](2), via a Ga-Ga bond insertion process. In addition, the new gallium(III) phosphide, [GaI{P(H)Mes*}{[N(Ar)C(H)](2) }], Mes* = C(6)H(2)Bu(t)(3)-2,4,6; was prepared and treated with diazabicycloundecane (DBU) to give [Ga(DBU){P(H)Mes*}{[N(Ar)C(H)](2)}], presumably via a gallium-terminal phosphinidene intermediate, [Ga{[double bond, length as m-dash]PMes*}{[N(Ar)C(H)](2) }]. The possible mechanisms of all reactions are discussed, all new complexes have been crystallographically characterised and all paramagnetic complexes have been studied by ENDOR and/or EPR spectroscopy.

Journal Article↗
PubMed2005

Oxidation reactions of an anionic gallium(I) N-heterocyclic carbene analogue with group 16 compounds.

The reactivity of an anionic gallium(I) heterocycle, [K(tmeda)][:Ga([N(Ar)C(H)]2)], Ar = C6H3Pr(i)2-2,6, towards sources of elemental chalcogens and diorgano-dichalcogenides has been investigated and comparisons drawn with the reactivity of the valence isoelectronic N-heterocyclic carbene class of ligand. The reactions of the heterocycle with N2O or (Te)PEt3 yielded the dimeric, dianionic gallium(III) complexes, [K(L)]2[(mu-E)Ga([N(Ar)C(H)]2)]2, E = O, L = tmeda; E = Te, L = THF. Treatment of [K(tmeda)][:Ga([N(Ar)C(H)]2)] with the diphenyl dichalcogenides, PhEEPh, E = Se or Te, gave the one dimensional polymer, [K[(PhSe)2Ga([N(Ar)C(H)]2)]]infinity and the monomeric complex, [K(OEt2)3][(PhTe)2Ga([N(Ar)C(H)]2)], respectively. The X-ray crystal structures of the four complexes are reported.

Journal Article↗
PubMed2005

An EPR and ENDOR investigation of a series of diazabutadiene-group 13 complexes.

Paramagnetic diazabutadienegallium(II or III) complexes, [(Ar-DAB)2Ga] and [{(Ar-DAB*)GaX}2] (X = Br or I; Ar-DAB = {N(Ar)C(H)}2, Ar = 2,6-diisopropylphenyl), have been prepared by reactions of an anionic gallium N-heterocyclic carbene analogue, [K(tmeda)][:Ga(Ar-DAB)], with either "GaI" or [MoBr2(CO)2(PPh3)2]. A related InIII complex, [(Ar-DAB*)InCl2(thf)], has also been prepared. These compounds were characterised by X-ray crystallography and EPR/ENDOR spectroscopy. The EPR spectra of all metal(III) complexes incorporating the Ar-DAB ligand, [(Ar-DAB(.))MX(2)(thf)(n)] (M = Al, Ga or In; X = Cl or I; n = 0 or 1) and [(Ar-DAB)2Ga], confirmed that the unpaired spin density is primarily ligand centred, with weak hyperfine couplings to Al (a = 2.85 G), Ga (a = 17-25 G) or In (a = 26.1 G) nuclei. Changing the N substituents of the diazabutadiene ligand to tert-butyl groups in the gallium complex, [(tBu-DAB*)GaI2] (tBu-DAB={N(tBu)C(H)}2), changes the unpaired electron spin distribution producing 1H and 14N couplings of 1.4 G and 8.62 G, while the aryl-substituted complex, [(Ar-DAB*)GaI2], produces couplings of about 5.0 G. These variations were also manifested in the gallium couplings, namely aGa approximately 1.4 G for [(tBu-DAB*)GaI2] and aGa approximately 25 G for [(Ar-DAB*)GaI2]. The EPR spectra of the gallium(II) and indium(II) diradical complexes, [{(Ar-DAB*)GaBr}2], [{(Ar-DAB*)GaI}2], [{(tBu-DAB*)GaI}2] and [{(Ar-DAB*)InCl}2], revealed doublet ground states, indicating that the Ga-Ga and In-In bonds prevent dipole-dipole coupling of the two unpaired electrons. The EPR spectrum of the previously reported complex, [(Ar-BIAN*)GaI2] (Ar-BIAN = bis(2,6-diisopropylphenylimino)acenaphthene) is also described. The hyperfine tensors for the imine protons, and the aryl and tert-butyl protons were obtained by ENDOR spectroscopy. In [(Ar-DAB*)GaI2], gallium hyperfine and quadrupolar couplings were detected for the first time.

Journal Article↗
PubMed2005

Reactions of a gallium(II)-diazabutadiene dimer, [{{[(H)C(Bu(t))N]2}GaI}2], with [ME(SiMe3)2] (M = Li or Na; E = N, P, or As): structural, EPR, and ENDOR characterization of paramagnetic gallium(III) pnictide complexes.

The reactions of the paramagnetic gallium(II) complex [{(Bu(t)-DAB)GaI}2] (Bu(t)-DAB = {(Bu(t))NC(H)}2) with the alkali metal pnictides [ME(SiMe3)2] (M = Li or Na; E = N, P, or As) have been carried out under a range of stoichiometries. The 1:2 reactions have led to a series of paramagnetic gallium(III)-pnictide complexes, [(Bu(t)-DAB)Ga{E(SiMe3)2}I] (E = N, P, or As), while two of the 1:4 reactions afforded [(Bu(t)-DAB)Ga{E(SiMe3)2}2] (E = P or As). In contrast, treatment of [{(Bu(t)-DAB)GaI}2] with 4 equiv of [NaN(SiMe3)2] resulted in a novel gallium heterocycle coupling reaction and the formation of the diradical species [(Bu(t)-DAB)Ga{N(SiMe3)2}{[CC(H)N2(Bu(t))2]Ga[N(SiMe3)2]CH3}]. The mechanism of this unusual reaction has been explored, and evidence suggests it involves an intramolecular transmethylation reaction. The X-ray crystal structures of all prepared complexes are reported, and all have been characterized by EPR and ENDOR spectroscopies. The observed spin Hamiltonian parameters provide a detailed picture of the distribution of the unpaired spin density over the molecular frameworks of the complexes.

Journal Article↗
PubMed2005

"GaI": a versatile reagent for the synthetic chemist.

The current renaissance in main group chemistry has been fuelled by the remarkable array of fundamentally interesting yet synthetically applicable low oxidation state p-block compounds that have appeared over the last decade. Their syntheses generally require the ready availability of low oxidation state element halide precursors. In the case of gallium this is provided by the simple to prepare reagent, "GaI", which since it was first reported in 1990, has been utilised in areas as varied as organic synthesis and gallium cluster construction. This article tracks the history of this extraordinary material and highlights its synthetic diversity; hopefully allowing the reader to envisage its application to aspects of their own research fields.

Journal Article↗
PubMed2005

Evidence for the first oxidative insertion of a transition metal into a digallane(4): synthesis, structural characterisation and EPR studies of [Cp2Zr(III){Ga[N(Ar)C(H)]2}2][Li(THF)4], Ar = C6H3Pr(i)2-2,6.

Treatment of "ZrCp2" with the digallane(4), [{Ga[N(Ar)C(H)]2}2], Ar = C6H3Pri2-2,6, in the presence of excess Bu(n)Li leads to the first example of a gallyl-Group 4 complex, [Cp2Zr{Ga[N(Ar)C(H)]2}2][Li(THF)4], via an unprecedented oxidative insertion reaction; the paramagnetic complex has been characterised by X-ray crystallography and EPR spectroscopy.

Journal Article↗
PubMed2005

Lower back pain in the athlete: common conditions and treatment.

Athletes younger than 12 years of age commonly have pathology related to the lower back pain. Spondylolysis is the most common condition in these athletes. Other conditions, including lumbar Scheuermann's disease,scoliosis, disc herniation, fractures, and muscular stains, can occur. Most of the mature general population experiences low back at some time in life. Athletes may be at increased risk, but outcomes are good. The majority of low back pain in mature athletes is mechanical in nature. Herniated discs,spinal stenosis, sacoilitis, and sacral stress fractures can also cause low back pain in these athletes. Low back conditions mentioned above may be treated with rest, specific exercise programs, and medication. Surgery is indicated for severe spinal stenosis, pain with evidence of neurological compromise,and some painful deformities. Newer treatments for back pain are emerging,but few controlled clinical trials are available.

Athletic Injuries↗
PubMed2005

The hand in sports: an update on the clinical anatomy and physical examination.

The hand plays an important role in the athlete's ability to compete, and there is a tendency to misdiagnose and undertreat these injuries. Thus,a detailed anatomic understanding and a timely and accurate diagnosis through a thorough physical examination are critical to guide the treatment and return of normal function of the hand.

Athletic Injuries↗
PubMed2005

MysTR: an endogenous retrovirus family in mammals that is undergoing recent amplifications to unprecedented copy numbers.

A large percentage of the repetitive elements in mammalian genomes are retroelements, which have been moved primarily by LINE-1 retrotransposons and endogenous retroviruses. Although LINE-1 elements have remained active throughout the mammalian radiation, specific groups of endogenous retroviruses generally remain active for comparatively shorter periods of time. Identification of an unusual extinction of LINE-1 activity in a group of South American rodents has opened a window for examination of the interplay in mammalian genomes between these ubiquitous retroelements. In the course of a search for any type of repetitive sequences whose copy numbers have substantially changed in Oryzomys palustris, a species that has lost LINE-1 activity, versus Sigmodon hispidus, a closely related species retaining LINE-1 activity, we have identified an endogenous retrovirus family differentially amplified in these two species. Analysis of three full-length, recently transposed copies, called mysTR elements, revealed gag, pro, and pol coding regions containing stop codons which may have accumulated either before or after retrotransposition. Isolation of related sequences in S. hispidus and the LINE-1 active outgroup species, Peromyscus maniculatus, by PCR of a pro-pol region has allowed determination of copy numbers in each species. Unusually high copy numbers of approximately 10,000 in O. palustris versus 1,000 in S. hispidus and 4,500 in the more distantly related P. maniculatus leave open the question of whether there is a connection between endogenous retrovirus activity and LINE-1 inactivity. Nevertheless, these independent expansions of mysTR represent recent amplifications of this endogenous retrovirus family to unprecedented levels.

Animals↗
PubMed2005

Management of sport-related concussion in young athletes.

Sport-related head injuries are a common clinical problem. Most head injuries in young athletes are mild traumatic brain injuries or concussions. The highest number of sport-related concussions has been reported in American football. In addition to the well described physical and psychosocial growth, there is ongoing neurocognitive development of the brain during childhood and through adolescence. This developmental process has direct implications in the assessment and management of head injuries in young athletes. Research on the management and long-term outcome following brain injuries in young athletes is limited. Traditionally, the assessment of concussion has been based on clinical history and physical and neurological examination. Increasingly, neuropsychological testing, especially computerised testing, is providing objective measures for the initial assessment and follow-up of young athletes following brain injuries. Numerous guidelines have been published for grading and return to play criteria following concussion; however, none of these have been prospectively validated by research and none are specifically applicable to children and adolescents.

Acute Disease↗
PubMed2004

Reconstruction of radioactive plume characteristics along Chernobyl's Western Trace.

Using data obtained from 435 radiation sampling stations in the Red Forest, 1.5 km W if the Chernobyl Nuclear Complex, we reconstructed the deposition pathway of the first plume released by the accident, Chernobyl's Western Trace. The dimensions and deposition rates of the plume remain sharply defined 15 years after the accident. Assuming a uniform particle distribution within the original cloud, we derived estimates of plume dimensions by applying geometric transformations to the coordinates at each sample point. Our derived estimates for the radioactive cloud accounted for 87% of the variation of radioactivity in this region. Results show a highly integrated bell-shaped cross-section of the cloud of radiation, approximately 660 m wide and 290 m high, traveling at a bearing of 264 degrees from reactor IV. Particle sizes within Chernobyl's Western Trace were within the most dangerous range for inhaled aerosols (2-5 microm). Therefore, reconstruction of the dispersion of such particles is critical for understanding the aftermath of nuclear and biological aerosol releases.

Aerosols↗
PubMed2004

Clinical effects and P-glycoprotein inhibition in patients with acute myeloid leukemia treated with zosuquidar trihydrochloride, daunorubicin and cytarabine.

BACKGROUND AND OBJECTIVES: P-glycoprotein (P-gp) is a major cause of multidrug resistance (MDR) in acute myelogenous leukemia (AML) and is thought to contribute to the failure of chemotherapy. Zosuquidar trihydochloride (Z.3HCL) is a potent and selective inhibitor of P-gp which rapidly and effectively inhibits drug efflux. DESIGN AND METHODS: The aim of this study was to evaluate the clinical effects of Z.3HCL and determine its influence on P-gp activity. Sixteen AML patients were entered into a phase 1 dose ranging clinical trial of Z.3HCL, co-administered intravenously with daunorubicin and cytosine arabinoside (ARA-C). Clinical outcomes, toxicity abd adverse events were assessed. P-gp function was analyzed by flow cytometry. In vitro cytotoxicity was studied using the MTT assay. RESULTS: Eleven patients achieved a complete remission and one a partial remission with a median survival of 559 (range 38-906) days. Non-hematologic grade 3 and 4 toxicities were seen in 4 patients. Z.3HCL infusion was associated with rapid inhibition of Rh123 efflux in CD56+ cells in 16/16 patients and in CD33+ cells from 6/10 patients. The median inhibition was 95% for CD56+ cells and 85.25% for CD33+ cells was significantly elevated in 6/16 patients. The median IC50, using a MTT assay for daunorubicin, decreased significantly between Z.3HCL modulated and unmodulated cells (n=11,153 and 247 ng/mL respectively, p=0.01). INTERPRETATION AND CONCLUSIONS: The modulator Z.3HCL is a specific inhibitor of P-gp efflux and can be given safely to patients with AML in combination with induction doses of conventional cytotoxic drugs.

ATP Binding Cassette Transporter, Subfamily B, Mem↗