Search results for "specificity"
showing 10 items of 2234 documents
Multitype spatial point patterns with hierarchical interactions.
2001
Multitype spatial point patterns with hierarchical interactions are considered. Here hierarchical interaction means directionality: points on a higher level of hierarchy affect the locations of points on the lower levels, but not vice versa. Such relations are common, for example, in ecological communities. Interacting point patterns are often modeled by Gibbs processes with pairwise interactions. However, these models are inherently symmetric, and the hierarchy can be acknowledged only when interpreting the results. We suggest the following in allowing the inclusion of the hierarchical structure in the model. Instead of regarding the pattern as a realization of a stationary multivariate po…
Lead-time and overdiagnosis estimation in neuroblastoma screening.
2003
In Germany, neuroblastoma is the most frequent extracranial solid childhood tumour. Its properties made it seem an ideal candidate for screening. A German trial assessed the effect of screening at one year of age from 1995-2001 in a nationwide project. We present here the methods developed for the estimation of lead-time and overdiagnosis in this project. Follow up on 1.5 million screened children and 2.1 million control children is currently available until June 2002. Ascertainment of control cohort cases and false negative cases is complete up to this date. A method for determining an empirical lead-time distribution and overdiagnosis estimate from comparing the age specific incidences in…
Structure–activity relationship of sphingomyelin analogs with sphingomyelinase from Bacillus cereus
2012
AbstractThe aim of this study was to examine how structural properties of different sphingomyelin (SM) analogs affected their substrate properties with sphingomyelinase (SMase) from Bacillus cereus. Using molecular docking and dynamics simulations (for SMase–SM complex), we then attempted to explain the relationship between SM structure and enzyme activity. With both micellar and monolayer substrates, 3O-methylated SM was found not to be degraded by the SMase. 2N-methylated SM was a substrate, but was degraded at about half the rate of its 2NH–SM control. PhytoPSM was readily hydrolyzed by the enzyme. PSM lacking one methyl in the phosphocholine head group was a good substrate, but PSM lack…
Palladium-catalyzed Suzuki-Miyaura reaction involving a secondary sp3 carbon: studies of stereochemistry and scope of the reaction.
2007
Palladium-catalyzed C--C bond formation involving secondary sp3-hybridized carbon is described. These reactions occur with secondary 1-bromoethyl arylsulfoxides and different arylboronic acids, to produce the corresponding arylated sulfoxides in moderate to high yields and with complete stereospecificity. Despite the presence of beta hydrogens in the substrate, the competitive beta-hydride elimination is not a significant side reaction when coordinating solvents are used. The reported cross-coupling involves secondary C(sp3)--C(sp2) bond formation: this is the first time that a mechanistic study has been carried out with such substrates. The reaction proceeds with inversion of configuration…
Differential Enantioselectivity of Murine GlutathioneS-Transferase Isoenzymes in the Glutathione Conjugation ofTrans-3,4-dihydroxy-1,2-oxy- 1,2,3,4-t…
1998
Abstract The kinetics of the glutathione (GSH) conjugation of (+)- and (−)-enantiomers ofanti- as well assyn-3,4-dihydroxy-1,2-oxy-1,2,3,4-tetrahydrobenzo[c]phenanthrene (B[c]PDE) catalyzed by murine GSHS-transferase (GST) isoenzymes has been investigated. Murine GSTs exhibited significant differences in their enantioselectivity toward B[c]PDE stereoisomers. For example, while pi class isoenzyme mGSTP1-1 was virtually inactive toward stereoisomers with 1Sconfiguration [(−)-syn-and (+)-anti-B[c]PDE], these stereoisomers were good substrates for alpha class isoenzyme mGSTA1-2. When GST activity was measured as a function of varying B[c]PDE concentration (10–320 μM) at a fixed saturating conce…
Palladium-Catalyzed Skeletal Rearrangement of Spirotricyclic Olefins: A Facile One-Pot Strategy for the Synthesis of a Novel Motif with Cyclopentene …
2013
The first utilization of acyclic cyclopropane bearing spirocyclic olefines for the generation of stereospecific complex fused ring systems with an achiral catalyst is reported.
Solanum incanum and S. heteracanthum as sources of biologically active steroid glycosides: Confirmation of their synonymy
2012
A new spirostanol saponin (1), along with four known saponins, dioscin (2), protodioscin (3), methyl-protodioscin (4), and indioside D (5), and one known steroid glycoalkaloid solamargine (6) were isolated from the two synonymous species, Solanum incanum and S. heteracanthum. The structure of the new saponin was established as (23S,25R)-spirost-5-en-3β,23-diol 3-O-{β-D-xylopyranosyl-(1→2)-O-α-L-rhamnopyranosyl-(1→4)-[O-α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside}, by using a combination of 1D and 2D NMR techniques including (1)H, (13)C, COSY, TOCSY, NOESY, HSQC and HMBC experiments and by mass spectrometry. The compounds 1, 3, 4 and 5 were evaluated for cytotoxicity against five cancer c…
Stereoselective synthesis and determination of the cytotoxic properties of spicigerolide and three of its stereoisomers.
2003
Stereoselective syntheses of the naturally occurring, cytotoxic lactone spicigerolide and three nonnatural stereoisomers thereof are described. The commercially available sugar l-rhamnose was in all cases the chiral starting material. Key steps in each of these syntheses were asymmetric Brown allylations and ring-closing metatheses. The cytotoxic activities of the four lactones against a range of tumoral lines were then determined.
Structural Basis and Enzymatic Mechanism of the Biosynthesis of C9- from C10-Monoterpenoid Indole Alkaloids
2009
Cutting carbons: The three-dimensional structure of polyneuridine aldehyde esterase (PNAE) gives insight into the enzymatic mechanism of the biosynthesis of C(9)- from C(10)-monoterpenoid indole alkaloids (see scheme). PNAE is a very substrate-specific serine esterase. It harbors the catalytic triad S87-D216-H244, and is a new member of the alpha/beta-fold hydrolase superfamily. Its novel function leads to the diversification of alkaloid structures.
Detection of Single Oxygen Molecules with Fluorescence-Labeled Hemocyanins
2005
This study introduces a method to detect individual oxygen molecules by fluorescence microscopy of single hemocyanins. These respiratory proteins from a tarantula bind oxygen with high affinity. A spectrometric signature of the oxygenated protein is transferred to an attached fluorescence label, which can be detected at the single-molecule level. This technique opens new perspectives for the development of small and sensitive oxygen sensors as well as for the investigation of cooperative oxygen binding in respiratory proteins.