13C chemical shift tensors in MOF α-Mg3(HCOO)6: Which component is more sensitive to host-guest interaction?

Metal–organic frameworks (MOFs) are a class of important porous materials with many current and potential applications. Their applications almost always involve the interaction between host framework and guest species. Therefore, understanding of host–guest interaction in MOF systems is fundamentally important. Solid-state NMR spectroscopy is an excellent technique for investigating host–guest interaction as it provides information complementary to that obtained from X-ray diffraction. In this work, using MOF α-Mg₃(HCOO)₆ as an example, we demonstrated that ¹³C chemical shift tensor of organic linker can be utilized to probe the host–guest interaction in MOFs. Obtaining ¹³C chemical shift tensor components (δ₁₁, δ₂₂, and δ₃₃, where δ₁₁ ≥ δ₂₂ ≥ δ₃₃) in this MOF is particularly challenging as there are six coordinatively equivalent but crystallographically non-equivalent carbons in the unit cell with very similar local coordination environment. Two-dimensional magic-angle-turning experiments were employed to measure the ¹³C chemical shift tensors of each individual crystallographically non-equivalent carbon in three microporous α-Mg₃(HCOO)₆ samples with different guest species. The results indicate that the δ₂₂ component (with its direction approximately being co-planar with the formate anion and perpendicular to the C−H bond) is more sensitive to the adsorbate molecules inside the MOF channel due to the weak C−H···O hydrogen bonding or the ring current effect of benzene. The ¹³C isotropic chemical shift, on the other hand, seems much less sensitive to the subtle changes in the local environment around formate linker induced by adsorption. The approach described in this study may be used in future studies on host–guest interaction within MOFs.     

High effects of smoke suppression and char formation of Ni?Mo/Mg(OH)2 for polypropylene

The Ni? Mo/Mg(OH)₂ (NMM) hybrid as an efficient flame retardancy and smoke suppression composite for polypropylene (PP) was synthesized through Ni? Mo co‐precipitation on the surface of Mg(OH)₂ (MH) hexagonal nanosheets. Compared to PP/MH, PP/NMM exhibited excellent smoke suppressing and flame retardancy on the heat release rate, total heat release, smoke production rate, total smoke production, CO production rate and total CO production with the same loading. The reduced hazard of PP/NMM was mainly attributed to the high physical barrier effect of compact char residues on heat, smoke and combustible gas. The mechanism study indicated that multiwalled carbon nanotubes (MWCNTs) generated from the catalytic carbonization of PP by the Ni? Mo compound could play the role of “rebar” to strengthen the char residues, avoid the generation of cracks and form highly compact char layer. Furthermore, MgO could facilitate the production of MWCNTs through changing the pyrolysis process of PP and increasing the reaction time between pyrolysis gas and Ni? Mo compound. Hence, the new Ni? Mo/MH catalyst hybrid may explore the potential for solving the tough problem of the flammability and heavy smoke of the polyolefins system.     

Gas-Sensing Activity of Amorphous Copper Oxide Porous Nanosheets

In this paper, the gas-sensing properties of copper oxide porous nanosheets in amorphous and highly crystalline states were comparatively investigated on the premise of almost the same specific surface area, morphology and size. Unexpectedly, the results show that amorphous copper oxide porous nanosheets have much better gas sensing properties than highly crystalline copper oxide to a serious of volatile organic compounds, and the lowest detection limit (LOD) of the amorphous copper oxide porous nanosheets to methanal is even up to 10 ppb. By contrast, the LOD of the highly crystalline copper oxide porous nanosheets to methanal is 95 ppb. Experiments prove that the oxygen vacancies contained in the amorphous copper oxide porous nanosheets play a key role in improving gas sensitivity, which greatly improve the chemical activity of the materials, especially for the adsorption of molecules containing oxygen-groups such as methanal and oxygen.     

Color tuning of up-conversion emission in ytterbium,erbium, aluminum tri-doped zinc oxide crystal by adjusting aluminum concentration

Ytterbium, erbium, aluminum tri-doped zinc oxide crystal was synthesized, which can turn color from red to green up-conversion luminescence through adjusting aluminum content. When the aluminum concentration reached 4?mol%, the color of up-conversion emission first turn from red to green. Meanwhile, the ratio of red to green emission reduced from 25.32 to 0.26, and the coordinates of chromaticity coordinate calculation changes from (0.5749, 0.3378) to (0.2190, 0.7169) with aluminum concentration range from 0 to 4?mol%. The up-conversion emission peaks at 521, 542, and 660?nm of sample originate from the transitions of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2, and ⁴F_9/2 → ⁴I_15/2 of erbium ions, respectively. X-ray diffraction patterns perform the better crystallization degree with increasing aluminum concentration. The scanning electron microscopy images show the porous and lamellar structures with different aluminum concentrations. A convenient but effective design to obtain ytterbium, erbium, aluminum tri-doped zinc oxide up-conversion luminescence is reported, which can turn color from red to green.     

Rotational viscosity of a liquid crystal mixture: a fully atomistic molecular dynamics study

Fully atomistic molecular dynamics (MD) simulations at 293, 303 and 313~K have been performed for the four-component liquid crystal mixture, E7, using the software package Material Studio. Order parameters and orientational time correlation functions (TCFs) were calculated from MD trajectories. The rotational viscosity coefficients (RVCs) of the mixture were calculated using the Nemtsov--Zakharov and Fialkowski methods based on statistical-mechanical approaches. Temperature dependences of RVC and density were discussed in detail. Reasonable agreement between the simulated and experimental values was found.     

Synthesis, Characterization, DNA-Binding and Antiproliferative Activity of Nd(III) Complexes With N-(Nitrogen Heterocyclic) Norcantharidin Acylamide Acid

Three novel complexes [Nd(L)(NO₃)(H₂O)₂]·NO₃·2H₂O (HL¹ = N-pyrimidine norcantharidin acylamide acid, C₁₂H₁₃N₃O₄; HL² = N-pyridine norcantharidin acylamide acid, C₁₃H₁₄N₂O₄; HL³ = N-phenyl norcantharidin acylamide acid, C₁₄H₁₅NO₄) were synthesized. HL¹, HL² and HL³ are the ligand of complex(1), complex(2) and complex(3), respectively. Their structures were characterized by elemental analysis, conductivity measurement, infrared spectra and thermogravimetric analysis. The DNA-binding properties of the complexes have been investigated by fluorescence spectroscopy and viscosity measurements. The results suggest that the complexes can bind to DNA by partial intercalation. The liner Stern-Volmer quenching constant K_sq values are 3.3(±0.21)(1), 1.7(±0.19)(2) and 0.9(±0.04)(3), respectively. Complex (1) and (2) have been found to cleave pBR322 plasmid DNA at physiological pH and temperature. The test of antiproliferation activity indicates that complex(1) has strong antiproliferative ability against the SMMC7721 (IC₅₀ = 131.7 ± 23.4 μmol·L⁻¹) and A549 (IC₅₀ = 128.4 ± 19.9 μmol·L⁻¹) cell lines. The inhibition rates of complex(2) (IC₅₀ = 86.3 ± 11.3 μmol·L⁻¹) are much higher than that of NCTD (IC₅₀ = 115.5 ± 9.5 μmol·L⁻¹) and HL² (111.0 ± 5.7 μmol·L⁻¹) against SMMC7721 cell lines.     

Preparation and ionic conductivity of composite polymer electrolytes based on hyperbranched star polymer

Hyperbranched star polymer HBPS-(PPEGMA) _x was synthesized by atom transfer radical polymerization (ATRP) using hyperbranched polystyrene (HBPS) as macroinitiator and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as monomer. The structure of the prepared hyperbranched star polymer was characterized by ¹H NMR, ATR-FTIR, and GPC. Polymer electrolytes based on HBPS-(PPEGMA) _x , lithium salt, and/or nano-TiO₂ were prepared. The influences of lithium salt concentration and type, nano-TiO₂ content, and size on ionic conductivity of the obtained polymer electrolytes were investigated. The results showed that the low crystallinity of the prepared polymer electrolyte was caused by the interaction between lithium salt and polymer. The addition of TiO₂ into HBPS-(PPEGMA) _x /LiTFSI improved the ionic conductivity at low temperature. The prepared composite polymer electrolyte showed the highest ionic conductivity of 9?×?10^?5 S cm^?1 at 30 °C when the content of TiO₂ was 15 wt% and the size of TiO₂ was 20 nm.