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71.
A new type of chiral discotic liquid crystal is described. It is based on a triphenylene core but carries only one asymmetric side chain per mesogen. This system displays a columnar liquid-crystalline mesophase with a helical superstructure and a pitch of 3·0 nm over a temperature range of 227 K. Upon cooling it forms a glassy state. By broadband dielectric and 2H NMR spectroscopy two motional processes are detected. The axial rotation of the discs around the column axis exhibits non-Arrhenius behaviour and is directly related to the glass transition. The second process is ascribed to localized side chain motions involving the ester linkages. 相似文献
72.
Biology‐Oriented Synthesis of a Withanolide‐Inspired Compound Collection Reveals Novel Modulators of Hedgehog Signaling
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Dr. Jakub Švenda Dipl.‐Biochem. Michael Sheremet M. Sc. Lea Kremer Lukáš Maier Dr. Jonathan O. Bauer Prof. Dr. Carsten Strohmann Dr. Slava Ziegler Dr. Kamal Kumar Prof. Dr. Herbert Waldmann 《Angewandte Chemie (International ed. in English)》2015,54(19):5596-5602
Biology‐oriented synthesis employs the structural information encoded in complex natural products to guide the synthesis of compound collections enriched in bioactivity. The trans‐hydrindane dehydro‐δ‐lactone motif defines the characteristic scaffold of the steroid‐like withanolides, a plant‐derived natural product class with a diverse pattern of bioactivity. A withanolide‐inspired compound collection was synthesized by making use of three key intermediates that contain this characteristic framework derivatized with different reactive functional groups. Biological evaluation of the compound collection in cell‐based assays that monitored biological signal‐transduction processes revealed a novel class of Hedgehog signaling inhibitors that target the protein Smoothened. 相似文献
73.
Flow goods (like electricity) are sold through auctions in a dynamic framework. An important design question is the frequency of such auctions. We use a simple dynamic auction model in continuous time to answer this question. We focus on the relationship between the persistency of bidders’ valuations and the optimal choice of frequency. If the seller focuses on the equilibrium in which bidders follow a repeated static Nash strategy, then the frequency of auctions should typically increase when persistency declines. However, accounting for the fact that bidders can follow different equilibria that are collusive in nature, the comparative statics are reversed, forcing the seller to reduce the frequency when bidders’ valuations are less persistent. The argument builds on the fact that high frequency auctions are more conducive to collusion among bidders. 相似文献
74.
Iwan Zimmermann Reinhard K. Kremer Mats Johnsson 《Journal of solid state chemistry》2011,184(11):3080-3084
The new compound Co3Te2O2(PO4)2(OH)4 was synthesized using hydrothermal techniques. It crystallizes in the monoclinic space group C2/m with the unit cell a=19.4317(10) Å, b=6.0249(3) Å, c=4.7788(2) Å, β=103.139(5)°. The crystal structure is an open framework having chains of edge sharing [Co(1)O6] octahedra. Other building blocks are [TeO3(OH)2], [PO4] and [Co(2)O2(OH)4] connected mainly via corner sharing. The –OH groups protrude into channels in the structure. The magnetic susceptibility measured from 2 to 300 K shows two broad anomalies at around 21 K and 4 K, respectively. The peak at ∼20 K is ascribed to a two-dimensional antiferromagnetic ordering of linear [Co(1)O6] chains coupled by interchain interaction via [PO4] groups in the Co(1) sheets. The second transition at 4 K is ascribed to a second antiferromagnetic ordering of the moments of the Co(2) entities via super–super exchange involving [PO4] and [TeO3(OH)2] groups. This assignment is strongly supported by low-temperature heat capacity measurements indicating an entropy removal within the high-temperature transition of about twice the magnitude of the low-temperature transition. 相似文献
75.
L. S. Kudin V. B. Motalov M. F. Butman S. N. Nakonechnyi K. B. Kremer 《Russian Journal of General Chemistry》2011,81(1):33-40
Molecular and ionic sublimation of gadolinium and terbium tribromides in Knudsen and Langmuire modes was studied by the method of high-temperature mass-spectrometry. On the basis of obtained enthalpies of sublimation and ion-molecule reactions the enthalpies of formation of LnBr3 and Ln2Br6 molecules and LnBr 4 ? and Ln2Br 7 ? negative ions were determined. For the first time the electron work function for crystals of the studied tribromides was calculated. 相似文献
76.
Background
Pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) are highly toxic and widespread in every environmental compartment. Some of metabolic products such as amino/nitro containing chlorinated aromatic compounds can be determined by gas chromatography coupled with electron capture detector (GC-ECD). However, it is difficult to identify some of chlorophenolic and chloroquinolic intermediates produced from PCNB and HCB by the above mentioned technique. Therefore, for analysis of these compounds and their metabolites, we have developed a high performance liquid chromatography (HPLC) based method.Results
The extraction of PCNB and HCB from soil and minimal salt medium was carried out with ethyl acetate and hexane respectively with good recoveries (98% for PCNB and 97% for HCB). The validation of the proposed extraction and HPLC method was done by analysis of PCNB and HCB biodegradation and their metabolites identification from anaerobic enriched soil samples.Conclusion
A rapid, sensitive and simple HPLC based analytical method was developed for the analysis of PCNB, HCB and their possible intermediates. 相似文献77.
Halverson JD Lee WB Grest GS Grosberg AY Kremer K 《The Journal of chemical physics》2011,134(20):204905
Molecular dynamics simulations were conducted to investigate the dynamic properties of melts of nonconcatenated ring polymers and compared to melts of linear polymers. The longest rings were composed of N = 1600 monomers per chain which corresponds to roughly 57 entanglement lengths for comparable linear polymers. The ring melts were found to diffuse faster than their linear counterparts, with both architectures approximately obeying a D ~ N(-2.4) scaling law for large N. The mean-square displacement of the center-of-mass of the rings follows a sub-diffusive behavior for times and distances beyond the ring extension [linear span]R(g)(2)[linear span], neither compatible with the Rouse nor the reptation model. The rings relax stress much faster than linear polymers, and the zero-shear viscosity was found to vary as η(0) ~ N(1.4 ± 0.2) which is much weaker than the N(3.4) behavior of linear chains, not matching any commonly known model for polymer dynamics when compared to the observed mean-square displacements. These findings are discussed in view of the conformational properties of the rings presented in the preceding paper [J. D. Halverson, W. Lee, G. S. Grest, A. Y. Grosberg, and K. Kremer, J. Chem. Phys. 134, 204904 (2011)]. 相似文献
78.
79.
Locatelli M Epifano F Genovese S Carlucci G Koncić MZ Kosalec I Kremer D 《Natural product communications》2011,6(9):1275-1280
The anthraquinone profile, antioxidant and antimicrobial activities as well as the total phenol and total flavonoid contents were determined in methanol extracts of the barks of Rhamnus catharticus L. and R. orbiculatus Bornm. The most abundant anthraquinone derivatives in R. catharticus were physcion (67.8%) and emodin (26.2%), while R. orbiculatus contained mostly physcion (81.3%) and chrysophanol (14.6%). R. catharticus displayed better activity in the beta-carotene-linoleic acid assay, as well as chelating activity, whereas its activity in the reducing power assay was significantly lower than that of R. orbiculatus. Both methanol extracts showed antimicrobial activity against all microbial species tested (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Candida albicans, Aspergillus niger, Microsporum gypseum) with MIC values either equal to or lower than 2.50 mg/mL. R. catharticus and R. orbiculatus contained several anthranoid aglycones and their bark extracts demonstrated notable antioxidant and antimicrobial properties. The results obtained indicate the medicinal potential of these two species. 相似文献
80.
S. Decoster C. J. Glover B. Johannessen R. Giulian D. J. Sprouster P. Kluth L. L. Araujo Z. S. Hussain C. Schnohr H. Salama F. Kremer K. Temst A. Vantomme M. C. Ridgway 《Journal of synchrotron radiation》2013,20(3):426-432
Lift‐off protocols for thin films for improved extended X‐ray absorption fine structure (EXAFS) measurements are presented. Using wet chemical etching of the substrate or the interlayer between the thin film and the substrate, stand‐alone high‐quality micrometer‐thin films are obtained. Protocols for the single‐crystalline semiconductors GeSi, InGaAs, InGaP, InP and GaAs, the amorphous semiconductors GaAs, GeSi and InP and the dielectric materials SiO2 and Si3N4 are presented. The removal of the substrate and the ability to stack the thin films yield benefits for EXAFS experiments in transmission as well as in fluorescence mode. Several cases are presented where this improved sample preparation procedure results in higher‐quality EXAFS data compared with conventional sample preparation methods. This lift‐off procedure can also be advantageous for other experimental techniques (e.g. small‐angle X‐ray scattering) that benefit from removing undesired contributions from the substrate. 相似文献