Biomedical subjects
Publications and source records attributed to A J Blake.
Incorporation of an alkoxide functional group into an N-heterocyclic carbene (NHC) ligand allows the synthesis of the first anionic NHC chelating ligands, which react to give the first neutral, molecular silver(I) alkoxide carbene complex, and a copper(I) derivative containing the first nonmacrocyclic, square planar Cu(I) centres.
The novel bicyclic and tricyclic systems dimethyl (4aS*,6S*)-6-methoxy-7-oxo-4a,5,6,7,8,9-hexahydro-2H-benzocycloheptene-3,4-dicarboxylate, C(16)H(20)O(6), (I), dimethyl (4aS*,6R*)-6-methoxy-7-oxo-4a,5,6,7,8,9-hexahydro-2H-benzocycloheptene-3,4-dicarboxylate, C(16)H(20)O(6), (II), (3aS*,9R*,10aS*,10bR*)-9-methoxy-2-oxa-1,3a,4,6,7,8,9,10,10a,10b-decahydro-3H-cyclohepta[e]indene-1,3,8-trione, C(14)H(16)O(5), (III), and (1S*,2R*,9S*,10aR*)-9-methoxy-8-oxo-1,2,3,5,6,7,8,9,10,10a-decahydrobenzocyclooctene-1,2-dicarboxylic acid, C(15)H(20)O(6), (IV), have been crystallographically characterized, allowing the determination of the relative configuration of the stereogenic centres. The poor quality of the dicarboxylic acid crystals necessitated the use of synchrotron radiation.
In the title compound, [Ag(2)(C(6)H(4)N(2))(4)](BF(4))(2), the Ag(I) cations adopt distorted trigonal-planar coordination geometries. The Ag(I) centres are linked via two bridging 2-cyanopyridine ligands to give a centrosymmetric dinuclear complex in which the Ag(I) coordination environment is completed by monodentate non-bridging 2-cyanopyridine ligands. Bridging Ag...F(BF(2))F...Ag interactions link the dinuclear cations into molecular ladders.
4,4'-Bipyridine N,N'-dioxide (L) acts as a hydrogen-bond acceptor in the compounds ([M(NO3)2(H2O)4].L2) (M = Co, Ni) to form doubly-interpenetrated framework materials with sixfold topological connectivity.
Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.
A new N,O-bidentate pro-ligand (HL), [ML2] (M = Cu, Zn) and [CuL2][BF4] have been synthesised; [CuL2].4DMF and [CuL2][BF4].2CH2Cl2 have been crystallographically and spectroscopically characterised; these data indicate that [CuL2]+ cations are constituted as [Cu2+(L.)(L-)]+ and involve the phenoxyl radical L..
Reaction of the vanadium(V) imide [V(NAr)Cl(3)(THF)] (Ar = 2,6-C(6)H(3)(i)()Pr(2)) with the diamino-pyridine derivative MeC(2-C(5)H(4)N)(CH(2)NHSiMe(2)(t)()Bu)(2) (abbreviated as H(2)N'(2)N(py)) gave modest yields of the vanadium(IV) species [V(NAr)(H(3)N'N' 'N(py))Cl(2)] (1 where H(3)N'N' 'N(py) = MeC(2- C(5)H(4)N)(CH(2)NH(2))(CH(2)NHSiMe(2)(t)()Bu) in which the original H(2)N'(2)N(py) has effectively lost SiMe(2)(t)()Bu (as ClSiMe(2)(t)()Bu) and gained an H atom. Better behaved reactions were found between the heavier Group 5 metal complexes [M(NR)Cl(3)(py)(2)] (M = Nb or Ta, R = (t)()Bu or Ar) and the dilithium salt Li(2)[N(2)N(py)] (where H(2)N(2)N(py) = MeC(2-C(5)H(4)N)(CH(2)NHSiMe(3))(2)), and these yielded the six-coordinate M(V) complexes [M(NR)Cl(N(2)N(py))(py)] (M = Nb, R = (t)()Bu 2; M = Ta, R = (t)()Bu 3 or Ar 4). The compounds 2-4 are fluxional in solution and undergo dynamic exchange processes via the corresponding five-coordinate homologues [M(NR)Cl(N(2)N(py))]. Activation parameters are reported for the complexes 2 and 3. In the case of 2, high vacuum tube sublimation afforded modest quantities of [Nb(N(t)()Bu)Cl(N(2)N(py))] (5). The X-ray crystal structures of the four compounds 1, 2, 3, and 4 are reported.
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In the title complex, [CuCl2(C12H24S6)]n, the CuCl2 unit and the ligand lie on and about inversion centres, respectively. The coordination geometry at CuII is a tetragonally elongated octahedron with the equatorial positions occupied by two chlorides, Cu-Cl 2.2786 (12) A, and two S donors, Cu-S 2.3710 (13) A. The apical positions of the octahedron are defined by two S donors at distances of 2.8261 (14) A from the metal. The macrocyclic ligand adopts a very puckered and distorted conformation. Eight of the 18 torsion angles are less than 90 degrees and all S-donors are oriented exo to the ring.
The title compound, C(9)H(6)O(2), contains two moderate C-H.O hydrogen bonds. That involving the terminal alkyne gives rise to chains along the b axis. The other hydrogen bond occurs over a centre of symmetry, leading to dimers. The combination of the two interactions gives rise to rings, each comprising six molecules, which are part of infinite sheets in the bc plane.
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OBJECTIVE: To determine the factors influencing the consumption or avoidance of milk in women. SUBJECTS/SETTING: One hundred women completed food frequency questionnaires and a milk attitudes questionnaire framed within the Theory of Reasoned Action and performed sensory evaluations of different milk samples. STATISTICAL ANALYSES: Differences among milk types were assessed using 2-way analysis of variance and least-significant-difference mean comparison procedures. Correlation and multiple regression analyses, and standardized partial regression coefficients, were used to determine the contribution of each component of the model in predicting behavior. RESULTS: Mean age of the 100 subjects was 39 years (range = 20-70 years). Milk consumption among subjects was low; 23 subjects indicated that they seldom or never drank milk. Data from the dairy frequency questionnaire showed that the primary milk for 42%, 36%, 27%, and 18% of the milk drinkers was skim, 2%, 1%, and whole, respectively (subjects could indicate more than 1 type of milk consumed). The Theory of Reasoned Action indicated that health and familiarity belief items were most associated with attitudes toward milk consumption. Skim milk had significantly lower scores for taste and texture belief items than 1%, 2%, and whole milk (P < .05), yet more subjects reported that they drank skim milk (42%) than the other milk types. Sensory evaluation demonstrated that subjects linked whole milk significantly more than skim milk (P < .05). CONCLUSIONS/APPLICATIONS: Some people continue to consume skim milk for reasons other than beliefs about taste and texture or actual sensory preference. This study identifies important factors contributing to milk consumption such as beliefs, attitudes, and sensory evaluation, which can be used to develop a specific framework in which to examine other components of milk consumption behavior.
7-(3-[1-(4-Phenylthiosemicarbazono)ethyl]-bicyclo[2.2.1]hept-2- yl)-5-heptenoic acid, C23H31N3-O2S, Mr = 413.7, monoclinic, P2(1)/a, a = 12.9650 (7), b = 11.2081 (6), c = 16.8941 (12) A, beta = 110.452 (5) degrees, V = 2300.2 A3, Z = 4, Dx = 1.194 g cm-3, Mo K alpha, lambda = 0.71073 A, mu = 1.55 cm-1, F(000) = 888, T = 298 K. Final R = 0.0472 with 2778 independent data. EP 092 is a thromboxane receptor antagonist akin to many other analogues of the thromboxane A2 [Wilson & Jones (1985). Adv. Prostaglandin Thromboxane Leukotriene Res. 14, 393-425].
We found no definitive differences in the ability of overweight and normal-weight subjects to accurately estimate food portions. Therefore, our data do not support conclusions by others that overweight subjects are significantly less accurate than the normal-weight subjects in their estimates. However, our overweight sample included only 50% obese and was homogeneous as to education, income, and ethnicity. Nevertheless, we found serious errors in food portion estimation by all subjects. Moreover, our data support the findings of Rapp, which show inaccurate portion estimation even when subjects were actively involved in a diet counseling program. And, in general, our data support researchers who have concluded that inaccurate estimation of portion size is a major problem. If the results hold true across populations, the magnitude of errors could have a profound effect on the accuracy of our food composition data for therapeutic or monitoring purposes and requires creative modification of methods taught for monitoring and reporting food intake.
Of 1042 individuals aged 65 years and over who were successfully interviewed in a community survey of health and physical activity, 35% (n = 356) reported one or more falls in the preceding year. Although the overall ratio of female fallers to male fallers was 2.7:1, this ratio approached unity with advancing age. Mobility was significantly impaired in those reporting falls. Asked to provide a reason for their falls, 53% reported tripping, 8% dizziness and 6% reported blackouts. A further 19% were unable to give a reason. There was no association between falls and the use of diuretics, antihypertensives or tranquilizers, but a significant association between falls and the use of hypnotics and antidepressants was found. Discriminant analysis of selected medical and anthropometric variables indicated that handgrip strength in the dominant hand and reported symptoms of arthritis, giddiness and foot difficulties were most influential in predicting reports of recent falls.
Encouragement of a degree of personal responsibility for the maintenance of health by individuals and communities is being increasingly advocated by planners of health care. With the increasing numbers of people reaching old age it is particularly desirable that individuals be made aware of potential measures that may ensure a reasonably independent old age. In the course of a study to identify the defining characteristics of referred geriatric patients in a teaching hospital, a number of recurring factors emerged that seemed to favour the retention of independence among the subjects studied as controls. These were adequate retirement planning, the timely development of satisfying interests, the prior adoption of a healthy lifestyle, the sensible use of health services and the presence of adequate family and community support systems. Six cases are described to illustrate the presence or absence of such factors, and these are discussed against the background of the respective degrees of responsibility to be expected of the individual and of society in securing and maintaining independence in old age.
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