Combination of Optimization and Metalated‐Ligand Exchange: An Effective Approach to Functionalize UiO‐66(Zr) MOFs for CO2 Separation

The strategy to functionalize water‐stable metal–organic frameworks (MOFs) in order to improve their CO₂ uptake capacities for efficient CO₂ separation remains limited and challenging. We herein present an effective approach to functionalize a prominent water‐stable MOF, UiO‐66(Zr), by a combination of optimization and metalated‐ligand exchange. In particular, by systematic optimization, we have successfully obtained UiO‐66(Zr) of the highest BET surface area reported so far (1730 m² g^?1). Moreover, it shows a hybrid Type I/IV N₂ isotherm at 77 K and a mesopore size of 3.9 nm for the first time. The UiO‐66 MOF underwent a metalated‐ligand‐exchange (MLE) process to yield a series of new UiO‐66‐type MOFs, among which UiO‐66‐(COONa)₂‐EX and UiO‐66‐(COOLi)₄‐EX MOFs have both enhanced CO₂ working capacity and IAST CO₂/N₂ selectivity. Our approach has thus suggested an alternative design to achieve water‐stable MOFs with high crystallinity and gas uptake for efficient CO₂ separation.     

Four-dimensional investigation of the 2nd order volume autocorrelation technique

The 2nd order volume autocorrelation technique, widely utilized in directly measuring ultra-short light pulses durations, is examined in detail via model calculations that include three-dimensional integration over a large ionization volume, temporal delay and spatial displacement of the two beams of the autocorrelator at the focus. The effects of the inherent displacement to the 2nd order autocorrelation technique are demonstrated for short and long pulses, elucidating the appropriate implementation of the technique in tight focusing conditions. Based on the above investigations, a high accuracy 2nd order volume autocorrelation measurement of the duration of the 5th harmonic of a 50 fs long laser pulse, including the measurement of the carrier wavelength oscillation, is presented.     

A Theoretical design of new inorganic ring systems as potential antitumor agents

Quantum calculations of electronic structures and ring stabilities along the (NCMe)_3?x(NPMe₂)_x and (NCNMe₂)_3?x(NPMe₂)_x predict that the aziridinyl mixed terms (x = 1 and 2) of these two families may be anticancer agents even more efficient than (NCAz)₃(TEM) and (NPAz₂)₃(MYKO 63).     

An answer to the spiro versus ANSA dilemma in cyclophosphazenes : Part IX. The first genuine ANSA derivatives from N3P3Cl6 itself

The reaction of the simplest Lehn's ligand, H₂N---(CH₂)₂---O---(CH₂)₂---NH₂, on N₃P₃Cl₆ in suitable stoichiometric conditions leads quite neatly to the first genuine MONOANSA and DIANSA derivatives.     

Calcul approché des contributions dipolaires et orbitales au couplage J cc à l'aide de fonctions d'onde LCAO-SCF non empiriques

The contributions of the spin-dipolar and orbital terms to the nuclear spin coupling constants in acetylene, ethylene and ethane have been evaluated by systematically using the Mulliken-Ruedenberg approximation for the matrix elements of the corresponding operators. Both contributions are found to be negligeable as compared to the usual contact term.     

Cyclofunctionalization and free-radical-based hydrogen-transfer reactions. An iterative reaction sequence applied to the synthesis of the C(7)-C(16) subunit of zincophorin

The strategy considered herein features an iodocyclofunctionalization/hydrogen-transfer reaction sequence for the elaboration of propionate motifs. Proceeding with excellent yield and diastereoselectivity, the synthetic sequence proposed gives access to the anti-anti dipropionate motif when the reduction step is performed under the control of the exocyclic effect. The tandem sequence is applied successfully to the synthesis of the C(7)-C(16) subunit of zincophorin, and iteration of the process gives the desired anti-anti-anti-anti polypropionate stereopentad. Modifications of the reaction sequence--including phenylselenocyclofunctionalization, carbonate hydrolysis, and chelation-controlled radical reduction reactions--lead to the formation of the anti-syn dipropionate motif with remarkable diastereocontrol.     

Synthesis of BILN 2061, an HCV NS3 protease inhibitor with proven antiviral effect in humans

The synthesis of BILN 2061, an NS3 protease inhibitor with proven antiviral effect in humans, was accomplished in a convergent manner from four building blocks. The procedure described here was suitable for the preparation of multigram quantities of BILN 2061 for preclinical pharmacological evaluation.     

Structure électronique de quelques cyclophosphazènes halogénés de symétrie Dnh

The electronic structure of some D_nh cyclophosphazenes is investigated by the /2 approximation of the method. The results allow a critical analysis of ideas previously developed by Craig et al. and Dewar et al. This work supports the localised model of Dewar and tests the Faraday effect experimentally.