Problems, Models and Complexity. Part II: Application to the DLSP

In Part I of this study, we suggest to identify an operations research (OR) problem with the equivalence class of models describing the problem and enhance the standard computer-science theory of computational complexity to be applicable to this situation of an often model-based OR context. The Discrete Lot-sizing and Scheduling Problem (DLSP) is analysed here in detail to demonstrate the difficulties which can arise if these aspects are neglected and to illustrate the new theoretical concept. In addition, a new minimal model is introduced for the DLSP which makes this problem eventually amenable to a rigorous analysis of its computational complexity.     

伽达默尔解释学视域中的黑格尔遗产

西方现代哲学的整个发展历程表明,重要的议题不是不要黑格尔,而恰恰是如何与黑格尔展开有意义的对话。伽达默尔公开表示要继承黑格尔的遗产,他的哲学解释学本质上是一种“新黑格尔主义”。在伽达默尔眼中,形而上学是黑格尔的重要思想遗产,是一个民族文化庙宇中的至圣神。致力于恢复辩证法的名誉,这是伽达默尔解释学的郑重承诺,他赞美黑格尔的辩证法永远是一个令人兴奋的源泉。黑格尔给伽达默尔在科学时代反思科学的界限留下了丰富的思想资源。把黑格尔思想视为一种敌视自由和进步的理论,这是对黑格尔的误解。伽达默尔特别以黑格尔对法国大革命自由思想的继承来作辩护。     

Correlative and Mechanistic QSAR Models in Toxicology

Abstract

An outline is provided on the development and use of correlative and mechanistic approaches to predictive toxicology, with particular emphasis on the experience at the U.S. EPA as applied to assessing the potential hazard posed by new industrial chemicals for which little or no test data are provided under the Toxic Substances Control Act. This information is presented with a historical perspective.     

An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles**

In this paper, we present an unprecedented and general umpolung protocol that allows the functionalization of silyl enol ethers and of 1,3-dicarbonyl compounds with a large range of heteroatom nucleophiles, including carboxylic acids, alcohols, primary and secondary amines, azide, thiols, and also anionic carbamates derived from CO₂. The scope of the reaction also extends to carbon-based nucleophiles. The reaction relies on the use of 1-bromo-3,3-dimethyl-1,3-dihydro-1λ³[d][1,2]iodaoxole, which provides a key α-brominated carbonyl intermediate. The reaction mechanism has been studied experimentally and by DFT, and we propose formation of an unusual enolonium intermediate with a halogen-bonded bromide.     

Comparison of criteria used to access carcinogenicity in CPANN QSAR models versus the knowledge-based expert system Toxtree

The primary goal of this study was to describe and compare the criteria used to assess carcinogenic activity. The statistically-based predictive quantitative structure–activity relationship (QSAR) models based on the counter propagation artificial neural network (CPANN) algorithm, and knowledge-based expert systems based on a decision tree structural alert (SA) approach (Toxtree application), were considered. The integration of the QSAR (CPANN models) and SAR (Toxtree SA application) approach contributed to the mechanistic understanding of the QSAR model considered. The mapping technique inherent to CPANN Kohonen enables us to relate the similarities or dissimilarities within a congeneric set of chemicals with particular SAs for carcinogenicity. The focus of our investigations was the similarities and dissimilarities of the features used in the QSAR and SAR methods. Due to the complexity of the carcinogenic endpoint, the integration of different approaches allows the models to be improved and provides a valuable technique for evaluating the safety of chemicals.     

亚里士多德的哲学元素观及其在化学中的演化

亚里士多德早在两千多年前就总结了古希腊自然哲学家们探索世界万物本原的思想成果,提出了与近代表述极其相近的古代元素概念。只是由于长期无人挖掘和论述,以致被埋没和误解。本文探讨了亚里士多德的哲学元素学说(包括元素概念和元素体系两部分内容)及其对近代化学、尤其是对近代化学元素论和原子论建立和发展的影响。指出了亚里士多德元素观中的“不可分性”概念,一直被近代化学元素论所继承和发展,直至现代科学元素学说建立后才被推翻。     

Superbase‐catalyzed domino 3H‐pyrroles synthesis from ketoximes and acetylene: DFT study vs experiment

Elimination of vinyl alcohol from 5‐vinyloxypyrrolines in the presence of superbases (final step of domino 3H‐pyrroles synthesis from ketoximes and acetylene) is studied computationally at different levels of theory in DMSO solution (PCM). The sequences of transformations starting from nucleophilic addition of hydroxide ion to carbon‐carbon or carbon‐nitrogen double bonds are proposed as possible mechanisms. Unusual reactivity of 2,5‐dimethylphenyl substituted 5‐vinyloxypyrroline is explained within these mechanisms.     

Direct through anionic,cationic, and radical active species: Terminal carbon–halogen bond for “controlled”/living polymerizations of styrene

In this work, we examined the synthesis of novel block (co)polymers by mechanistic transformation through anionic, cationic, and radical living polymerizations using terminal carbon–halogen bond as the dormant species. First, the direct halogenation of growing species in the living anionic polymerization of styrene was examined with CCl₄ to form a carbon–halogen terminal, which can be employed as the dormant species for either living cationic or radical polymerization. The mechanistic transformation was then performed from living anionic polymerization into living cationic or radical polymerization using the obtained polymers as the macroinitiator with the SnCl₄/n‐Bu₄NCl or RuCp^*Cl(PPh₃)/Et₃N initiating system, respectively. Finally, the combination of all the polymerizations allowed the synthesis block copolymers including unprecedented gradient block copolymers composed of styrene and p‐methylstyrene. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 465–473