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991.
A distribution is conditionally specified when its model constraintsare expressed conditionally. For example, Besag's (1974) spatialmodel was specified conditioned on the neighbouring states,and pseudolikelihood is intended to approximate the likelihoodusing conditional likelihoods. There are three issues of interest:existence, uniqueness and computation of a joint distribution.In the literature, most results and proofs are for discreteprobabilities; here we exclusively study distributions withcontinuous state space. We examine all three issues using thedependence functions derived from decomposition of the conditionaldensities. We show that certain dependence functions of thejoint density are shared with its conditional densities. Therefore,two conditional densities involving the same set of variablesare compatible if their overlapping dependence functions areidentical. We prove that the joint density is unique when theset of dependence functions is both compatible and complete.In addition, a joint density, apart from a constant, can becomputed from the dependence functions in closed form. Sinceall of the results are expressed in terms of dependence functions,we consider our approach to be dependence-based, whereas methodsin the literature are generally density-based. Applicationsof the dependence-based formulation are discussed. 相似文献
992.
Tarun K. Panda 《Inorganica chimica acta》2008,361(8):2236-2242
The Lewis acid-base reaction of 2,6-bis[1,3-di-tert-butylimidazolin-2-imino)methyl]pyridine (TLtBu) and LnCl3 in THF leads to the corresponding neutral lanthanide complexes of type [(TLtBu)LnCl3], Ln = Y (1a), Er (1b), Lu (1c). The yttrium and lutetium complexes have been characterized by X-ray diffraction analysis. The solid state structures reveal that the bulky TLtBu ligand causes steric crowding around the lanthanide atoms by coordinating to the metal center in a tridentate fashion. In addition, remote C-H?Ln interactions (H?Ln ca. 2.7 Å) involving one of the tBu methyl groups are observed in both cases. A DFT (density functional theory) calculation on 1a was able to reproduce this interaction, which was additionally characterized by means of an H?Y compliance constant and by employing the AIM (atoms in molecules) theory. 相似文献
993.
Ten asymmetric isomers exist for [Co(pema)(ampy)Cl]2+ (pema=N-(2-aminomethylpyridyl)ethylenediamine, ampy=2-aminomethylpyridine) which involve unsymmetrical triamine and diamine ligands. Four of these have been synthesized, two facial (f3, f2′) and two mer (m3 and m4) isomers. Ab initio energy calculations for the [Co(pema)(ampy)Cl]2+ and [Co(pema)(ampy)OH]2+ systems show that the isomers containing a C-H?π interaction are the more stable forms. The f3 is the most stable isomer in the chloro system and the m3 form in the hydroxo system. The structures are deduced from the 2D NMR spectra and confirmed by the X-ray crystal structure determinations for the four chloro isomers. 相似文献
994.
Mosher MJ Lange LA Howard BV Lee ET Best LG Fabsitz RR Maccluer JW North KE 《Genes & nutrition》2008,3(2):87-97
Low plasma levels of high-density lipoprotein cholesterol (HDL-C) are identified as a risk factor for cardiovascular disease (CVD). Sexual dimorphism, however, is widely reported in both HDL-C and CVD, with the underlying explanations of these sexual differences not fully understood. HDL-C is a complex trait influenced by both genes and dietary factors. Here we examine evidence for a sex-specific effect of APOE and the macronutrient carbohydrate on HDL-C, triglycerides (TG) and apoprotein A-1 (ApoA-1) in a sample of 326 male and 423 female participants of the Strong Heart Family Study (SHFS). Using general estimating equations in SAS to account for kinship correlations, stratifying by sex, and adjusting for age, body mass index (BMI) and SHS center, we examine the relationship between APOE genotype and carbohydrate intake on circulating levels of HDL-C, TG, and ApoA-1 through a series of carbohydrate-by-sex interactions and stratified analyses. APOE-by-carbohydrate intake shows significant sex-specific effects. All males had similar decreases in HDL-C levels associated with increased carbohydrate intake. However, only those females with APOE-4 alleles showed significantly lower HDL-C levels as their percent of carbohydrate intake increased, while no association was noted between carbohydrate intake and HDL-C in those females without an APOE-4 allele. These findings demonstrate the importance of understanding sex differences in gene-by-nutrient interaction when examining the complex architecture of HDL-C variation. 相似文献
995.
The interaction and association between chitosan and hemoglobin (Hb) are studied by UV-vis and fluorescence spectroscopies, viscometry, circular dichroism, dynamic and static light scattering. Chitosan can obviously associate with Hb to form protein-chitosan complexes, which affects microstructure of Hb. The distance between the first association site of chitosan with 214-tryptophan residue in Hb is about 5.473 nm. The intrinsic UV-vis absorption and fluorescence intensities of Hb increase with an increase of chitosan concentration. The alpha-helix in Hb is drawn and changed into beta-sheet. 相似文献
996.
Copper(II) complexes with sparfloxacin and nitrogen-donor heterocyclic ligands: Structure-activity relationship 总被引:1,自引:0,他引:1
Efthimiadou EK Katsarou ME Karaliota A Psomas G 《Journal of inorganic biochemistry》2008,102(4):910-920
Three novel neutral mononuclear copper(II) complexes of the third-generation quinolone antibacterial drug sparfloxacin in the presence of a nitrogen donor heterocyclic ligand 2,2'-bipyridine, 1,10-phenanthroline or 2,2'-dipyridylamine have been prepared and characterized physicochemically and spectroscopically. The resultant complexes are of the type Cu(sparfloxacinato)(N-donor)Cl. Copper(II) is pentacoordinate having a distorted square pyramidal geometry. Molecular modeling calculations have been performed in order to propose the lowest energy model structure of the complexes. The interaction of the complexes with calf-thymus DNA has been investigated with diverse spectroscopic techniques and has shown that the complexes can bind to calf-thymus DNA by the intercalative mode. The antimicrobial activity of the complexes has been tested on three different microorganisms. The Cu(sparfloxacinato)(N-donor)Cl complexes are among the most active ones against Escherichia coli, Pseudomonas aeruginosa and Staphylococcus aureus, when compared to the other corresponding copper-quinolone complexes studied by our group and their antimicrobial activity is increased in the order bipyam相似文献
997.
Henoumont C Henrotte V Laurent S Vander Elst L Muller RN 《Journal of inorganic biochemistry》2008,102(4):721-730
A novel gadolinium complex, derived from Gd-DTPA (DTPA: diethylenetriaminepentaacetic acid) and sulfaphenazole, intended to be a potential MRI contrast agent and to interact with human serum albumin (HSA), was synthesized and characterized. Its relaxometric properties were evaluated in water, and its binding to HSA was investigated by three techniques: proton relaxation rate analysis, NMR diffusometry, and electrospray mass spectrometry. The complex has a higher relaxivity than the parent compound (r(1)=7.8s(-1)mM(-1) at 310K and 0.47T and 7.7s(-1)mM(-1) at 310K and 1.41T), a fast water exchange, and a very good stability versus zinc(II) transmetallation. All techniques agree with a high affinity of the complex for HSA, and competition experiments indicate that this contrast agent competes with ibuprofen for HSA. 相似文献
998.
A new ligand, N,N′-dibenzylethane-1,2-diamine (L) and its four transition metal(II) complexes, ML2(OAc)2 · 2H2O (M = Cu, Ni, Zn, Co), have been synthesized and characterized by elemental analysis, mass spectra, molar conductivity, NMR and IR. Moreover, the crystals structure of Cu(II) and Ni(II) complexes characterized by single crystal X-ray diffraction showed that the complexes have a similar molecular structure. Ni(II) has an regular octahedral coordination environment complexes, but typical Jahn Teller effect influenced Cu(II) in an elongated octahedral environment. The interaction between complexes and calf thymus DNA were studied by UV and fluorescence spectra measure, which showed that the binding mode of complexes with DNA is intercalation. Under physiological pH condition, the effects of Cu(OAc)2L2 · 2H2O and Ni(OAc)2L2 · 2H2O on human serum albumin were examined by fluorescence. The results of spectroscopic measurements suggested that the hydrophobic interaction is the predominant intermolecular force. The enthalpy change ΔH0 and the entropy change ΔS0 of Cu(OAc)2L2 · 2H2O and Ni(OAc)2L2 · 2H2O were calculated to be −11.533 kJ mol−1 and 46.339 J mol−1 K−1, −11.026 kJ mol−1 and 46.396 J mol−1 K−1, respectively, according to the Scatchard’s equation. The quenching mechanism and the number of binding site (n ≈ 1) were also obtained from fluorescence titration data. 相似文献
999.
Analysis of T-RFLP data using analysis of variance and ordination methods: a comparative study 总被引:4,自引:0,他引:4
The analysis of T-RFLP data has developed considerably over the last decade, but there remains a lack of consensus about which statistical analyses offer the best means for finding trends in these data. In this study, we empirically tested and theoretically compared ten diverse T-RFLP datasets derived from soil microbial communities using the more common ordination methods in the literature: principal component analysis (PCA), nonmetric multidimensional scaling (NMS) with Sørensen, Jaccard and Euclidean distance measures, correspondence analysis (CA), detrended correspondence analysis (DCA) and a technique new to T-RFLP data analysis, the Additive Main Effects and Multiplicative Interaction (AMMI) model. Our objectives were i) to determine the distribution of variation in T-RFLP datasets using analysis of variance (ANOVA), ii) to determine the more robust and informative multivariate ordination methods for analyzing T-RFLP data, and iii) to compare the methods based on theoretical considerations. For the 10 datasets examined in this study, ANOVA revealed that the variation from Environment main effects was always small, variation from T-RFs main effects was large, and variation from T-RF × Environment (T × E) interactions was intermediate. Larger variation due to T × E indicated larger differences in microbial communities between environments/treatments and thus demonstrated the utility of ANOVA to provide an objective assessment of community dissimilarity. The comparison of statistical methods typically yielded similar empirical results. AMMI, T-RF-centered PCA, and DCA were the most robust methods in terms of producing ordinations that consistently reached a consensus with other methods. In datasets with high sample heterogeneity, NMS analyses with Sørensen and Jaccard distance were the most sensitive for recovery of complex gradients. The theoretical comparison showed that some methods hold distinct advantages for T-RFLP analysis, such as estimations of variation captured, realistic or minimal assumptions about the data, reduced weight placed on rare T-RFs, and uniqueness of solutions. Our results lead us to recommend that method selection be guided by T-RFLP dataset complexity and the outlined theoretical criteria. Finally, we recommend using binary or relativized peak height data with soil-based T-RFLP data for ordination-based exploratory microbial analyses. 相似文献
1000.
Cation–π interactions are known to be important contributors to protein stability and ligand–protein interactions. In this study, we have analyzed the influence of cation–π interactions in single chain ‘all-alpha’ proteins. We observed 135 cation–π interactions in a data set of 75 proteins. No significant correlation was observed between the total number of amino acid residues and number of cation–π interactions. These interactions are mainly formed by long-range contacts and there is preference of Arg over Lys in these interactions. Arg–Phe interactions are predominant among the various pairs analyzed. Despite the scarcity of interactions involving Trp, the average energy for Trp–cation interactions, was quite high. This information implies that the cation–π interactions involving Trp, maybe of high relevance to the proteins. Secondary structure analysis reveals that cation–π interactions are formed preferrably between residues, in which at least one of them, is in the secondary structure of alpha-helical segments. Among the various types of folds of ‘all-alpha’ proteins considered for the analysis, proteins belonging to alpha–alpha superhelix fold have the highest number of cation–π interaction forming residues. 相似文献