Rh-Catalyzed Decarbonylative Cross-Coupling between o-Carboranes and Twisted Amides: A Regioselective,Additive-Free,and Concise Late-Stage Carboranylation

The convenient cross-coupling of sp² or sp³ carbons with a specific boron vertex on carborane cage represents significant synthetic values and insurmountable challenges. In this work, we report an Rh-catalyzed reaction between o-carborane and N-acyl-glutarimides to construct various B_cage−C bonds. Under the optimized condition, the removable imine directing group (DG) leads to B(3)− or B(3,6)−C couplings, while the pyridyl DG leads to B(3,5)−Ar coupling. In particular, an unexpected rearrangement of amide reagent is observed in pyridyl directed B(4)−C(sp³) formation. This scalable protocol has many advantages, including easy access, the use of cheap and widely available coupling agents, no requirement of an external ligand, base or oxidant, high efficiency, and a broad substrate scope. Leveraging the Rh^I dimer and twisted amides, this method enables straightforward access to diversely substituted and therapeutically important carborane derivatives at boron site, and provides a highly valuable vista for carborane-based drug screening.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

Asymmetric Michael Addition of Aldimino Esters with Chalcones Catalyzed by Silver/Xing‐Phos: Mechanism‐Oriented Divergent Synthesis of Chiral Pyrrolines

The mechanism‐oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide‐derived nonbiarylatropisomer/silver (silver/Xing‐Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis‐Δ(1)‐pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing‐Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)‐pyrrolines, in which an epimerization of the cis‐Δ(1)‐pyrrolines to the trans‐isomers during was revealed.     

Non-recurrence of exp(z)/z

In this paper, we consider the dynamics of the map z→exp(z)/z on the punctured plane C*=C\{0}. We show that for almost every point z ∈ C*, the ω-limit set of z is equal to {0, ∞}. In particular, the map is not recurrent.     

Adsorption of thorium(IV) on magnetic multi-walled carbon nanotubes

The influences of pH, contact time, solid-liquid ratio, temperature and C60(C(COOH)2)n on Th(IV) adsorption onto the magnetic multi-walled carbon nanotubes(MMWCNTs) were studied by batch technique. The dynamic process showed that the adsorption of Th(IV) onto MMWCNTs could reach equilibrium in 40 h and matched the pseudo-second-order kinetics model. The adsorption of Th(IV) onto MMWCNTs was significantly dependent on pH values, the adsorption ratio increased markedly at pH 3.0–5.0, and then maintained a steady state as pH values increased. At low pH, different C60(C(COOH)2)n content could enhance the adsorption content of Th(IV) onto MMWCNTs, but restrained it at higher pH. Through simulating the adsorption isotherms by Langmuir, Freundlich and Dubini-Radushkevich models, it could be seen respectively that the adsorption pattern of Th(IV) onto MMWCNTs was mainly surface complexation, and that the adsorption process was endothermic and irreversible.     

Evaluation of simulated reservoirs by using the oblique-incidence reflectivity difference technique

正Dear Editors,The evaluation of the oil-gas resources’potential depends on the characterization of reservoirs.The geometry of the pore-crack structures and the compositions of the pore walls have influence on hydrocarbon production about capillarity and permeability[1].Besides,it has been known that the adsorption phenomenon in micro-structure plays a significant role in oil-gas reservoirs.Some techniques have been applied to characterize conventional and unconventional reservoirs,     

Modeling fatigue of ascending stair evacuation with modified fine discrete floor field cellular automata

Fatigue even increases the complexity of the pedestrian dynamics which is regarded as a kind of nonlinear system, and might have a significant negative impact on the crowd evacuation. However, it has never been investigated completely and properly. Thus, the fine discrete floor field cellular automata model is modified by integrating the fatigue function to explore the influence of fatigue on the crowd ascending evacuation. The simulation fits well with the empirical data and the observations quantitatively and qualitatively, indicating the model captures the main features of evacuation considering fatigue impact. As a prediction, without merging streams, compared with the case of walking in constant speed, when fatigue is considered, it takes 71.4% longer for all persons to enter the stairs and 87.2% longer to evacuate. With merging streams, fatigue has little impact on the inflow, while it makes the total evacuation time 84.2% longer.     

Diastereoselective Synthesis of Polysubstituted Piperidines through Visible-Light-Driven Silylative Cyclization of Aza-1,6-Dienes: Experimental and DFT Studies

A visible-light-driven radical silylative cyclization of aza-1,6-dienes featuring an acrylonitrile or acrylate moiety and an electron-neutral olefin was developed, which allows for stereoselective synthesis of densely functionalized piperidines in a highly atom-economical manner. Depending on the substitution pattern of the electron-neutral olefin, poor-to-excellent diastereoselectivity was observed. It was suggested that the 6-exo-trig cyclization was initiated by a chemoselective addition of silyl radical toward electron-deficient olefin and the geometry of the remaining olefin is closely associated with the cis-stereoselectivity. DFT calculations supported that a transition state with a cyano group locating at the axial position of the forming piperidine ring might be involved, in which either the increase of 1,3-diaxial repulsion or the lack of hydrogen bonding interaction will diminish diastereoselectivity.