Separation of hexane isomers by introducing“triangular-like and quadrilateral-like channels”in a bcu-type metal-organic framework

The separation of hexane isomers is of vital importance to produce high quality gasoline in the petrochemical industry.However,the similar vapor pressure and boiling point of hexane isomers bring great difficulties and challenges in the separation process.Sieving effect,which allowing smaller molecules pass through and preventing others,should be a powerful strategy to solve this problem by making good use of porous materials.Therefore,physical separation by metal-organic framework(MOF)materials appears and becomes a burgeoning separation technique in industry.Due to the weak interaction between hexane isomers with absorbents,it puts forward higher requirements for the accurate design of MOF materials with optimal pore system.To address this issue,a novel MOF[Zn_(9)(tba)_(9)(dabco)_(3)]·12DMA-6MeOH(abbreviation:Zn_(9)(tba)_(9)(dabco)_(3);H_(2)tba=4-(1H-tetrazol-5-yl)-benzoic acid;dabco=1,4-diazabicyclo[2.2.2]octane;DMA=N,N-dimethylacetamide)with bcu network has been designed and synthesized by reticular chemistry strategy.Benefiting from the pre-designed topology and suitable linear ligand H_(2)tba and dabco,the structure of Zn_(9)(tba)_(9)(dabco)_(3)exhibits two types of channels with triangular-like and quadrilateral-like geometry.Zn_(9)(tba)_(9)(dabco)_(3)with appropriate channel size and shape displays potential selective adsorption capacity of vapor-phase hexane isomers through sieving effect.Moreover,outstanding gas adsorptive separation properties of Zn_(9)(tba)_(9)(dabco)_(3)could also be speculated by theoretical ideal adsorbed solution theory(IAST),suggesting Zn_(9)(tba)_(9)(dabco)_(3)can be regarded as a potential adsorbent material for purification natural gas_Breakthrough experiments show that Zn_(9)(tba)_(9)(dabco)_(3)is capable of discriminating all four hexane isomers at 298 K,and the corresponding research octane number(RON)of the eluted mixture closes to 95,which is higher than the standard for industrially refined hexane blends(about 83).We speculate that sieving effect and diffusion are a synergetic contributory factor in their elution dynamics,which may be ascribed to temperature-dependent interaction between pore aperture and each isomer.This work presents a typical example for design of efficient MOF absorbents by reticular chemistry strategy.

Optical evodiamine derivatives:Asymmetric synthesis and antitumor activity

Evodiamine and its derivatives have an asymmetric center at the C13 b position.Herein,isomers of evodiamine derivatives 2 and 3 were obtained by straightforward asymmetric total synthesis.Their inhibitory activities toward topoisomerases Ⅰ and Ⅱ and their cytotoxicities in cancer cell lines were evaluated.All the four isomers exhibited good to excellent antitumor potency and the（S）-isomers were generally more active than the（R）-isomers.The binding modes of（S）-2 with topoisomerases Ⅰ and Ⅱ were also clarified by molecular docking.