Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F
and the strongly ...electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor
. Here, we report the preparation, use and properties of N-fluoro-N-arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild conditions. Their N-F bond dissociation energies (BDE) are 30-45 kJ mol
lower than the N-F BDE of the reagents of the second generation. This favors clean radical fluorination processes over undesired side reactions. The utility of NFASs is demonstrated by a metal-free radical hydrofluorination of alkenes including an efficient remote C-H fluorination via a 1,5-hydrogen atom transfer. NFASs have the potential to become the reagents of choice in many radical fluorination processes.
Quinacridone (QA) and 2,9-dimethylquinacridone (DQA) are synthetic substances suitable as a hard, abrasion-resistant, self-organizing gliding layer on ice and snow. For sustainable use, a large ...number of parameters must be considered to demonstrate that these non-biogenic substances and their by-products and degradation products are harmless to humans and the environment in the quantities released. For this task, available experimental data are used and supplemented for all tautomers by numerous relevant physical, chemical, toxicological and ecotoxicological estimated values based on various Quantitative Structure Activity Relationship (QSAR) methods. On the one hand, the low solubility of QA and DQA leads to stable gliding layers and thus, low abrasion and uptake by plants, animals and humans. On the other hand, the four hydrogen bond forming functional groups per molecule allow nanoparticle decomposition and enzymatic degradation in natural environments. All available data justify a sustainable use of QA and DQA as a gliding layer. The assessment of the toxicological properties is complemented by an investigation of the size and morphology of DQA particles, as well as field tests indicating excellent performance as a gliding layer on snow.
The growth of silica particles synthesized by the Stöber method was investigated by the co-condensation of pyrene sulfonyl chloride (PySCl) coupled to (3-aminopropyl)triethoxysilane (APTES). Growth ...by monomer addition could be distinguished from growth by aggregation based on the intensity of the pyrene excimer emission of the resulting particles. The influence of the base concentration, water/ethanol ratio, solvent, temperature, and type of silica precursor was studied. At high hydrolysis rates, the growth occurred primarily by aggregation, whereas growth by monomer addition was predominant at low hydrolysis rates. The results were confirmed by evaluating the accessibility of the co-condensed pyrene moieties and by determining the porosity of the particles.
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We report argon adsorption/desorption isotherms of MCM-41 and of SBA-15. The shape of all hysteresis loops we have observed corresponds to type H1. The data have been analyzed quantitatively using ...the multiple equilibria description and applying the notion of metastable thermodynamic equilibrium. It is remarkable and important that for both mesoporous materials the desorption process can be understood according to this description but with a corresponding equilibrium constant. This procedure therefore allows determining the thermodynamic values for the enthalpy and the free enthalpy of cavity desorption and thus to obtain information not available so far. We observed that the MCM-41 adsorption isotherms show first an increase with the characteristic Langmuir shape, followed by the almost instantaneous filling of cavities that ends as soon as all cavities are completely filled. The SBA-15 isotherms show a characteristic Langmuir shape at low relative pressure. The pressure slightly below the inflection point at prel, infl = 0.312 marks the beginning of the growth of a second layer, before an almost instantaneous filling of cavities takes place. It is interesting to observe that the values of the enthalpy and the free enthalpy for cavity filling and cavity desorption differ by about 0.1 kJ/mol for both, MCM-41 and SBA-15. This means that the driving force for developing a hysteresis is small. The hysteresis loop is therefore driven by delicate changes occurring within the cavities, partially or completely filled by the adsorbate. The monolayer coverage and monolayer desorption processes are decoupled from the cavity filling and cavity emptying processes. Knowing thermodynamic parameters for the hysteresis loop ultimately helps to better characterize and understand the experimental observations.
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•Hysteresis in gas sorption isotherms of MCM-41 and of SBA-15 materials is reported.•Data have been analyzed applying the notion of metastable thermodynamic equilibrium.•Description provides information on thermodynamic parameters of the H1 hysteresis.•Values for the enthalpy and the free enthalpy of cavity desorption are obtained.
Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F-2 and the strongly ...electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor (R). Here, we report the preparation, use and properties of N-fluoro-N- arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild conditions. Their N-F bond dissociation energies (BDE) are 30-45 kJ moI(-1) lower than the N-F BDE of the reagents of the second generation. This favors clean radical fluorination processes over undesired side reactions. The utility of NFASs is demonstrated by a metal-free radical hydrofluorination of alkenes including an efficient remote C-H fluorination via a 1,5-hydrogen atom transfer. NFASs have the potential to become the reagents of choice in many radical fluorination processes.
•We present a polynomial algorithm for user-based relocation and vehicle dispatching.•We solve instances with 100,000 requests and 10,000 vehicles in less than 4 min.•We show that spatial relocation ...outperforms temporal relocation.•We analyze the impact of discount strategies on user comfort.
Free-floating car sharing (FFCS) systems are a promising concept to reduce the traffic volume in cities. However, spatial and temporal mismatches of supply and demand require a relocation of rental cars in order to avoid low degrees of utilization. Here, especially user-based relocation strategies seem to be promising to increase utilization in a cost-efficient manner. However, a thorough optimization-based assessment of user-based relocation strategies for FFCS systems is still missing.
In this paper, we introduce an integer program that optimizes the assignment of user-based relocation strategies in FFCS fleets. We develop a graph representation that allows to reformulate the problem as a k-disjoint shortest paths problem and propose an exact algorithm to solve large-size instances. We show that this algorithm can solve real-world instances within a few milliseconds as well as instances with up to 100,000 customers and 10,000 vehicles in a few minutes.
Furthermore, we present a case study based on real-world data and derive managerial insights on user-based relocation strategies. Our results reveal an upper bound on the benefit of user-based relocation strategies and demonstrate that the employment of such strategies can increase the number of fulfilled rental requests by 21%, while increasing the operator’s revenue by 10%.
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•Experimental study of femtosecond laser shock peening.•Increase in the surface hardness is demonstrated.•LIPSS formation and surface oxidation reduce hardness.
In this paper we ...report on the competition in metal surface hardening between the femtosecond shock peening on the one hand, and formation of laser-induced periodic surface structures (LIPSS) and surface oxidation on the other hand. Peening of the stainless steel AISI 316 due to shock loading induced by femtosecond laser ablation was successfully demonstrated. However, for some range of processing parameters, surface erosion due to LIPSS and oxidation seems to dominate over the peening effect. Strategies to increase the peening efficiency are discussed.
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