Zeeman effect of chlorine nuclear quadrupole resonance and hydrogen bonding in 2,6-, 2,5- and 3,5-dichlorophenols

The Zeeman effect of chlorine nuclear quadrupole resonance in polycrystalline samples of 2,6-, 2,5 and 3,5-dichlorophenol has been investigated at room temperature in order to study the effect of hydrogen bonding on the electric field gradient asymmetry parameter n. While the two n.q.r. lines in 3,5-dichlorophenol gave an asymmetry parameter of 10%, those in 2,6- and 2,5-dichlorophenol gave different values of n for the two chlorines. The chlorine atom which is ortho to the OH group and involved in hydrogen bonding (i.e., corresponding to the low frequency line) gave an asymmetry parameter of 0.21 in 2,6-dichlorophenol and 0.17 in 2,5-dichlorophenol while the other chlorine (i.e., corresponding to the high frequency line) gave a lower value of 0.12 in 2,6-dichlorophenol and 0.11 in 2,5-dichlorophenol. These values of n are discussed in terms of hydrogen bonding and bond parameters.

A note on Gittins indexes for pharmaceutical research

The Bernoulli/exponential target process is considered. Such processes have been found useful in modelling the search for active compounds in pharmaceutical research. An inequality is presented which improves a result of Gittins (1989), thus providing a better approximation to the Gittins indices which define the optimal search policy.

Shared common variants in prostate cancer and blood lipids

Background Epidemiological and clinical studies suggest comorbidity between prostate cancer (PCA) and cardiovascular disease (CVD) risk factors. However, the relationship between these two phenotypes is still not well understood. Here we sought to identify shared genetic loci between PCA and CVD risk factors. Methods We applied a genetic epidemiology method based on conjunction false discovery rate (FDR) that combines summary statistics from different genome-wide association studies (GWAS), and allows identification of genetic overlap between two phenotypes. We evaluated summary statistics from large, multi-centre GWA studies of PCA (n = 50 000) and CVD risk factors (n = 200 000) [triglycerides (TG), low-density lipoprotein (LDL) cholesterol and high-density lipoprotein (HDL) cholesterol, systolic blood pressure, body mass index, waist-hip ratio and type 2 diabetes (T2D)]. Enrichment of single nucleotide polymorphisms (SNPs) associated with PCA and CVD risk factors was assessed with conditional quantile-quantile plots and the Anderson-Darling test. Moreover, we pinpointed shared loci using conjunction FDR. Results We found the strongest enrichment of P-values in PCA was conditional on LDL and conditional on TG. In contrast, we found only weak enrichment conditional on HDL or conditional on the other traits investigated. Conjunction FDR identified altogether 17 loci; 10 loci were associated with PCA and LDL, 3 loci were associated with PCA and TG and additionally 4 loci were associated with PCA, LDL and TG jointly (conjunction FDR < 0.01). For T2D, we detected one locus adjacent to HNF1B. Conclusions We found polygenic overlap between PCA predisposition and blood lipids, in particular LDL and TG, and identified 17 pleiotropic gene loci between PCA and LDL, and PCA and TG, respectively. These findings provide novel pathobiological insights and may have implications for trials using targeting lipid-lowering agents in a prevention or cancer setting.

Studies in Nonlinear Optical Materials: Structure of 3-Menthyl 2-[Bis(dimethylarnino)methylene]-3-oxobutyrate Hemihydrate

C 19Ha4N203.~xH 2 O, Mr= 347.5, monoclinic, C2, a = 15.473 (3), b = 6.963 (2), c = 20.708 (4) ]1, //=108.2(2) ° , V=2119(2)A 3, Z=4, Ox= 1.089 Mg m -3, ,~(Cu Ktx) = 1.5418 ]1, p = 0.523 mm -~, F(000) = 760.0, T= 293 K, R = 0.068 for 1967 unique reflections. The C=C bond length is 1-447 (6)]1, significantly longer than in ethylene, 1.336 (2)]1. The crystal structure is stabilized by O-H...O hydrogen bonding. Explanation for the observed low second-harmonic-generation efficiency (0.5 times that of urea) is provided.

Push-pull ethylenes: the structures of 3-(2-imidazolidinylidene)-2,4-pentanedione (I), C8H12N2O2, and 3-(1,3-dimethyl-2-imidazolidinylidene)-2,4-pentanedione trihydrate (II), C10H16N2O2.3H2O

(I): Mr= 168, triclinic, P1, Z=2, a= 5.596 (2), b = 6.938 (3), c = 10.852 (4) A, ~t= 75.64 (3), fl= 93.44 (3), ),= 95.47 (3) °, V= 406.0A 3, Din= 1.35 (by flotation using carbon tetrachloride and n-hexane), D x= 1.374 Mg m -3, g(Mo Kct, 2 = 0.7107 A) = 1.08 cm -l, _F(000) = 180, T= 293 K. (II): Mr= 250, triclinic, P1, Z= 2, a = 7.731(2), b=8.580(2), c=11.033(3)A, a= 97-66 (2), fl= 98.86 (2), y= 101.78 (2) °, V= 697.5 A 3, D m = 1.18 (by flotation using KI solution), Dx= 1.190Mgm -3, g(MoKa, 2=0.7107A)= 1.02 cm -1, F(000) = 272, T= 293 K. Both structures were solved by direct methods and refined to R = 4.4% for 901 reflexions for (I) and 5.7% for 2001 reflexions for (II). The C=C bond distances are 1.451 (3) A in (I) and 1.468 (3)A in (II), quite significantly longer than the C=C bond in ethylene [1.336 (2).~; Bartell, Roth, Hollowell, Kuchitsu & Young (1965). J. Chem. Phys. 42, 2683-2686]. The twist angle about the C=C bond in (II) is 72.9 (5) ° but molecule (I) is essentially planar, the twist angle being only 4.9 (5) ° .

Dynamics of plant populations in Heteropogon contortus (black speargrass) pastures on a granite landscape in southern Queensland. 3. Dynamics of Aristida spp. populations

The dynamics of the unpalatable Aristida spp. (wiregrasses) were measured in a subset of treatments contained within an extensive grazing study conducted between 1990 and 1996 in H. contortus pasture in southern Queensland. This paper reports the results from these treatments which included 2 land classes (silver-leaved and narrowleaved ironbark), 3 stocking rates (0.3, 0.6 and 0.9 beasts/ha) in both native pasture and legumeoversown native pasture, all in the absence of fire. Changes in plant density and basal area of Aristida spp. reflected differences in both the survival and size of existing plants together with a large seedling recruitment in 1991. Two different taxa of Aristida spp. were distinguished; however, there were no clear differences in the response of these 2 taxa to the treatments. Grazing had the greatest impact on population dynamics through reducing basal area as stocking rate increased. Neither landscape position nor legume oversowing had a major impact on Aristida spp. The results suggest that populations of Aristida spp. will be highest under light grazing and that seedling recruitment may be episodic

Studies in Nonlinear Optical Materials: Structure of Methyl 2-(4-Ethyl-5-methyl- 2-thioxo-2,3-dihydro-l,3-thiazol- 3-yl) propionate

CIoH15NO282, Mr=245"0, orthorhombic, P21212 ~, a = 6.639 (2), b = 8.205 (2), c = 22.528(6)A, V= I227.2(6)A 3, z=4, Dm= 1.315, Dx= 1.326gem -3, MoKa, 2=0.7107A, 12= 3.63 cm -1, F(000) = 520, T= 293 K, R = 0.037 for 1115 significant reflections. The second-harmonicgeneration (SHG) efficiency of this compound is only 1/10th of the urea standard. The observed low second-order nonlinear response may be attributed to the unfavourable packing of the molecules in the crystal lattice.

A high yield synthesis of (±)-5,8-dimethoxy-2-α-hydroxyethyl-3,4-dihydronaphthalene, a key intermediate in anthracyclinone synthesis

The dimethoxytetralol gives on Vilsmeier reaction the dihydronaphthaldehyde (yield,92%), which on Grignard reaction with MeMgI affords the title compound (yield,�100%), the reactions constituting a high yield synthesis of this important anthracyclinone intermediate.

Structure of 7-methyl-1(2)a,1(6)a,3(4)a-trihomocubane-1(6)a,3(4)a-dione,star-c12h12o2- a case of enantiomeric and rotational disorder

M r = 188.22, monoclinic, P21/n, a = 6.219 (2), b= 10.508 (2), c=7.339 (1)A, t= 107.64 (2) °, V= 457 ,/k 3, Z = 2, D m - - 1.360 (3), D x = 1.366 (2)Mgm -3, ~,(MoKa) = 0.7107/~, #= 0.053 mm -I, F(000) = 200, T= 293 K. Final R = 5.8% for 614 significant reflections. The molecule, which does not possess a centre of symmetry, occupies a crystallographic centre of symmetry because of the statistical enantiomeric and rotational disorder. Latticeenergy calculations, based on van der Waals attractive and repulsive potentials, clearly show minima at the observed disordered positions.

Host range, symptom expression and RNA 3 sequence analyses of six Australian strains of Cucumber mosaic virus

We have characterised six Australian Cucumber mosaic virus (CMV) strains belonging to different subgroups, determined by the sequence of their complete RNA 3 and by their host range and the symptoms they cause on species in the Solanaceae, Cucurbitaceae and on sweet corn. These data allowed classification of strains into the known three CMV subgroups and identification of plant species able to differentiate the Australian strains by symptoms and host range. Western Australian strains 237 and Twa and Queensland strains 207 and 242 are closely related members of CMV subgroup IA, which cause similar severe symptoms on Nicotiana species. Strains 207 and 237 (subgroup IA) were the only strains tested which systemically infected sweet corn. Strain 243 caused the most severe symptoms of all strains on Nicotiana species, tomato and capsicum and appears to be the first confirmed subgroup IB strain reported in Australia. Based on pair-wise distance analysis and phylogeny of RNA 3, as well as mild disease symptoms on Nicotiana species, CMV 241 was assigned to subgroup II, as the previously described Q-CMV and LY-CMV.

Stabilization of the Alleged 'Bishomoaromatic' Bicyclo[3.2.l]octa-2,6-dienyl Anion by Counterion Interactions and by Hyperconjugation

Hyperconjugation and inductive effects, rather than homoaromaticity, are responsible for the stabilization of the title anion in the gas phase; interaction of the double bond with the Li+ gegenion in the endo geometry contributes additionally in solution.

Structure of 5-Bromo-2',3'-O-isopropylideneuridine, C12H15BrN206

Mr= 363.17, orthorhombic, P21212 ~, a= 5.251(4), b=14.962(5), c=19.112(5)A, U= 1501.41/k 3, Z=4, Dx=1.61Mgm -3, /t(CuKa)= 3.02 mm -1, 2(Cu Ka)= 1.5418/~, final R = 7.0% for 1091 reflections with Fo> 2e(Fo). The glycosidic torsion angle ZCN is 13"1 (12) °. The ribose has a C (3')-exo,C (4)-endo twist geometry. The dioxolane ring assumes an envelope conformation with 0(3') displaced by 0.453 (10)/k from the plane of the other four atoms. The conformation about the C(4')-C(5') bond is gauche-gauche. The structure is stabilized by two hydrogen bonds between screw-axis-related molecules. The crystal packing and the conformation of the molecule are very similar to those found in the structure of 2',3'-O-isopropylideneuridine which lacks the Br atom at the 5-position.

Structure of 2',3'-O-Isopropylidene-5'-O-tosyluridine, C19H22N 2Oas

M r = 438.45, trigonal, P32, a = b = 13.385 (4), c = 9.900 (5) A,, V = 1536.0 A 3, Z = 3, D x = 1.42, D m = 1.42 Mg m -3, 2(Cu Ka) = 1.5418 A,,g(CuKa) = .800mm -], T=290K, F(000)=690, R=6.0% for 1222 unique reflections with F o>_2o(Fo). This is the first 2',3'-O-isopropylidene pyrimidine nucleoside with the base in a syn orientation with respect to the ribose [Xcy= 116.0(7)°]. The ribose has a C(3')-endo conformation with the phase angle of pseudorotation P = 16.36 (2) °. The dioxolane ring assumes an envelope conformation with 0(2') displaced from the best four-atom plane by 0.50 (1) k. The crystal structure is possibly stabilized by a bifurcated hydrogen bond between N(3) and the 0(2) and 0(4) atoms of screw-related molecules.