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71.
Prof. Dr. Peter Comba Dr. Nina Dovalil Prof. Dr. Lawrence R. Gahan Prof. Dr. Gebhard Haberhauer Prof. Dr. Graeme R. Hanson Dr. Christopher J. Noble Dr. Björn Seibold Dr. Prabha Vadivelu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2578-2590
Two synthetic derivatives of the naturally occurring cyclic pseudooctapeptides patellamide A–F and ascidiacyclamide, that is, H4pat2, H4pat3, as well as their CuII complexes are described. These cyclic peptide derivatives differ from the naturally occurring macrocycles by the variation of the incorporated heterocyclic donor groups and the configuration of the amino acids connecting the heterocycles. The exchange of the oxazoline and thiazole groups by dimethylimidazoles or methyloxazoles leads to more rigid macrocycles, and the changes in the configuration of the side chains leads to significant differences in the folding of the cyclic peptides. These variations allow a detailed study of the various possible structural changes on the chemistry of the CuII complexes formed. The coordination of CuII with these macrocyclic species was monitored by high‐resolution electrospray mass spectrometry (ESI‐MS), spectrophotometric (UV/Vis) and circular dichroic (CD) titrations, and electron paramagnetic resonance (EPR) spectroscopy. Density functional theory (DFT) calculations and molecular mechanics (MM) simulations have been used to model the structures of the CuII complexes and provide a detailed understanding of their geometric preferences and conformational flexibility. This is related to the CuII coordination chemistry and the reactivity of the dinuclear CuII complexes towards CO2 fixation. The variation observed between the natural and various synthetic peptide systems enables conclusions about structure–reactivity correlations, and our results also provide information on why nature might have chosen oxazolines and thiazoles as incorporated heterocycles. 相似文献
72.
Edward N.C. Tong Christophe Mues Lyn C. Thomas 《European Journal of Operational Research》2012,218(1):132-139
Mixture cure models were originally proposed in medical statistics to model long-term survival of cancer patients in terms of two distinct subpopulations - those that are cured of the event of interest and will never relapse, along with those that are uncured and are susceptible to the event. In the present paper, we introduce mixture cure models to the area of credit scoring, where, similarly to the medical setting, a large proportion of the dataset may not experience the event of interest during the loan term, i.e. default. We estimate a mixture cure model predicting (time to) default on a UK personal loan portfolio, and compare its performance to the Cox proportional hazards method and standard logistic regression. Results for credit scoring at an account level and prediction of the number of defaults at a portfolio level are presented; model performance is evaluated through cross validation on discrimination and calibration measures. Discrimination performance for all three approaches was found to be high and competitive. Calibration performance for the survival approaches was found to be superior to logistic regression for intermediate time intervals and useful for fixed 12 month time horizon estimates, reinforcing the flexibility of survival analysis as both a risk ranking tool and for providing robust estimates of probability of default over time. Furthermore, the mixture cure model’s ability to distinguish between two subpopulations can offer additional insights by estimating the parameters that determine susceptibility to default in addition to parameters that influence time to default of a borrower. 相似文献
73.
Lee J. Silverberg Carlos Pacheco Debashish Sahu Peter Scholl Hany F. Sobhi Joshua T. Bachert Kaitlyn Bandholz Ryan V. Bendinsky Heather G. Bradley Baylee K. Colburn David J. Coyle Jonathon R. Dahl Megan Felty Ryan F. Fox Kyanna M. Gonzalez Jasra M. Islam Stacy E. Koperna Quentin J. Moyer Duncan J. Noble Melissa E. Ramirez Ziwei Yang 《Journal of heterocyclic chemistry》2020,57(4):1797-1805
A series of 11 novel 3-aryl-2-phenyl-2,3-dihydro-4H-1,3-benzothiazin-4-ones was prepared at room temperature by T3P-mediated cyclization of N-aryl-C-phenyl imines with thiosalicylic acid. This provides simple and ready access to N-aryl compounds in this family, which have been generally difficult to prepare. 相似文献
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Start-up companies are considered an important factor in the success of a nation’s economy. We are interested in the decisions for long-term survival of these firms when they have considerable cash restrictions. In this paper we analyse several inventory control models to manage inventory purchasing and return policies. The Markov decision models are formulated for both established companies that look at maximising average profit and start-up companies that look at maximising their long-term survival probability. We contrast both objectives, and present properties of the policies and the survival probabilities. We find that start-up companies may need to be riskier if the return price is very low, but there is a period where a start-up firm becomes more cautious than an established company and there is a point, as it accumulates capital, where it starts behaving as an established firm. We compare the various models and give conditions under which their policies are equivalent. 相似文献
76.
An experimental investigation (LDA technique) of coherent structures in the turbulent plane near wake behind a pair of square cylinders in side-by-side arrangement is presented with particular emphasis put on the use of 2D invariant structural measures. 相似文献
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A NaOH-poisoned γ-alumina membrane with 4-nm diameter pores was used to separate CH3OH from a H2/CH3OH mixture. Between 373 and 473 K, CH3OH condensed in the pores for certain pressure ranges, and was preferentially removed through the pores. Separation factors as high as 600 for CH3OH over H2 were obtained. Capillary condensation was observed at CH3OH pressures (0.60 ± 0.05 Psat) much lower than those predicted by the Kelvin equation. Causes for the deviations are indicated. 相似文献