Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Artematrovirenolides A—D and Artematrolides S—Z,Sesquiterpenoid Dimers with Cytotoxicity against Three Hepatoma Cell Lines from Artemisia atrovirens

Inspired by the intriguing structures and remarkable activities of sesquiterpenoid dimers,12 new sesquiterpenoid dimers,artematrovirenolides A—D(1—4)and artematrolides S—Z(8—12),were isolated from the EtOAc fraction of Artemisia atrovirens through a bioactivity-guided approach.Their structures were elucidated by comprehensive spectroscopic data and absolute configuration was assigned based on single crystal X-ray diffraction data and ECD calculations.Structurally,all compounds are presumably formed via[4+2]cycloaddition involving three connecting model.Compounds 1—4 are four novel hetero-dimeric[4+2]Diels-Alder adducts dimerized from a rotundane-type unit and a guaiane-type monomer,and compounds 5—12 are eight new homo-dimeric[4+2]adducts derived from two guaianolide moieties.A putative biosynthetic pathway for compounds 1—4 was also proposed.Compounds 4,6,7,and 10 demonstrated moderate cytotoxicity against HepG2,SMMC-7721,and Huh7 cell lines with IC50 values ranging from 9.3 to 62.3μmol/L.Interestingly,compounds 5 and 11 manifested cytotoxicity with IC50 values of 13.6 and 12.8(HepG2),18.5 and 13.1(SMMC-7721),and 16.5 and 19.4μmol/L(Huh7),respectively,which were equivalent to the positive control,sorafenib.This investigation suggests that compounds 5 and 11 might be considered as potent antihepatoma candidates and deserve further structural modification and mechanism study.     

Application of advanced nuclear analytical techniques for the electrocatalyst's characterization: Paving the path for mechanistic investigations

As the application of electrocatalyst continues to expand, envisaging the hidden mechanisms occurring at various length scale affecting the catalytic efficiency became important. To enhance the stability of electrocatalyst and reduce the cost, it is of paramount importance to reveal the active site's dynamics (using in situ techniques for getting the real-time information) which directly affect the reactions such as oxygen evolution reaction, hydrogen evolution reaction, and so on. Since such reactions are crucial for many engineering and scientific applications, in situ characterization techniques are required, which could capture such reactions happening at a different length and time scale. This article analyzes the recent progress made in the field of electrocatalyst's characterization using in situ neutron techniques. The article also paves the future path and has delineated the future challenges involved in multiscale correlative techniques (e.g., neutron techniques in the combination of synchrotron or microscopic techniques) used for getting the multiscale (atomic to micrometer range) mechanistic information about the electrocatalyst's working and degradation.     

Practical effects of pressure-transmitting media on neutron diffraction experiments using Paris–Edinburgh presses

ABSTRACT

To understand the practical effects of pressure-transmitting media (PTM) on neutron diffraction using Paris–Edinburgh presses, diffraction patterns of MgO were collected to approximately 20?GPa using PTMs of Pb, AgCl, 4:1 methanol–ethanol (ME) mixture with and without heating, N₂, and Ar. Hydrostaticity in the sample chamber estimated from the MgO 220 peak width improves in the order of Pb, AgCl, Ar, ME mixture, N₂, and the heated ME mixture. Unlike previous results using diamond anvil cells, the unheated ME mixture is superior to Ar even after freezing, probably due to the cup on the anvil face. Considering these results and the sizable coherent scattering of Ne, which would show good hydrostaticity, we conclude that the ME mixture (preferably the heated one) is the best PTM in neutron experiments up to 20?GPa, while Ar can be substituted when a sample is reactive to alcohols.     

Developments of nano-polycrystalline diamond anvil cells for neutron diffraction experiments

ABSTRACT

A new high pressure cell for neutron diffraction experiments using nano-polycrystalline anvils is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to ～82?GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of Fe₃O₄ at ambient conditions using this cell and discuss the current limitation and future developments.     

Heterotrimetallic Mixed-Valent Molecular Precursors Containing Periodic Table Neighbors: Assignment of Metal Positions and Oxidation States

A known trinuclear structure was used to design the heterobimetallic mixed-valent, mixed-ligand molecule [Co^II(hfac)₃−Na−Co^III(acac)₃] ( 1 ). This was used as a template structure to develop heterotrimetallic molecules [Co^II(hfac)₃−Na−Fe^III(acac)₃] ( 2 ) and [Ni^II(hfac)₃−Na−Co^III(acac)₃] ( 3 ) via isovalent site-specific substitution at either of the cobalt positions. Diffraction methods, synchrotron resonant diffraction, and multiple-wavelength anomalous diffraction were applied beyond simple structural investigation to provide an unambiguous assignment of the positions and oxidation states for the periodic table neighbors in the heterometallic assemblies. Molecules of 2 and 3 are true heterotrimetallic rather than a statistical mixture of two heterobimetallic counterparts. Trinuclear platform 1 exhibits flexibility in accommodating a variety of di- and trivalent metals, which can be further utilized in the design of molecular precursors for the NaMM′O₄ functional oxide materials.     

New soft porous frameworks based on lambda-zirconium phosphate and aliphatic dicarboxylates: Synthesis and structural characterization

New dicarboxylate-functionalized pillared materials with a general formula of λ-ZrPO₄(OH)_1-x(OOC(CH₂)_nCOO)_x/2(dmso) (n=6, 8 and 10) have been prepared by post-synthesis modification of the inorganic layers of λ-zirconium phosphate (λ-ZrP), where the superficial Chloride monovalent anionic ligands of λ-layer are partially exchanged with the divalent anionic ligands of a series of long-chain aliphatic dicarboxylic acids, namely octanedioic acid, decanedioic acid and dodecanedioic acid. The synthesized materials are characterized by X-ray diffractometry, FT-IR spectrophotometry, elemental and thermogravimetric analyses. The X-ray diffraction patterns show that the obtained solid phases are pure. Furthermore, the interlayer distance of λ-ZrP systematically increases from 1.02 to 1.59 nm as a result of the incorporation of the mentioned acids inside the interlayer gallery.     

Rational Topological Design for Fluorescence Enhancement upon Aggregation of Distyrylfuran Derivatives

A series of 2,5‐distyrylfuran derivatives bearing pentafluorophenyl‐ and cyanovinyl units have been synthesized for aggregation‐induced emission (AIE). The effect of the type and extent of the supramolecular connections on the AIE of the furan derivatives were examined and correlated with their X‐ray crystal structures. It was found that the simultaneous presence of cyano and perfluorophenyl units strongly enhances the fluorescence upon aggregation. Single‐crystal X‐ray diffraction analysis confirmed that C?H???F, F???F, C?H???nitrile, Ar???Ar_F (Ar=aryl, Ar_F=fluoroaryl), and nitrile???Ar_F intra‐ and intermolecular interactions drive the topology of the molecule and that solid‐state supramolecular contacts favor AIE of the furan derivatives.     

Pressure induced lattice anomalies in pnictides

Hydrostatic pressure Raman and synchrotron XRD measurements at room temperature have been carried out on a series of NdFeAsO_1−xF_y (Nd1111) oxypnictides in order to investigate pressure-induced lattice modifications. The synchrotron XRD data indicate that there is an increased deviation of the lattice constants from smooth pressure dependence in the superconducting compound, in close agreement with the results from SmFeAsO_1−xF_x (Sm1111), although the effect is less pronounced in Nd1111. As in Sm1111 the hydrostatic pressure Raman measurements show that the A_1g mode of the rare earth atom deviates from the linear pressure dependence. Anomalous pressure dependence and a hysteresis is observed in the phonon width of the phonon modes. The calculated Grüneisen parameter for the Nd phonon is very similar to the corresponding value for SmFeAsO_1−xF_x compound and it does not vary with substitution. For the As mode it has a lower value indicating a stiffer phonon with the increased ion size. In connection with the XRD measurements the Raman data show a sudden increase of the pressure-induced lattice anomalies close to doping where the compounds become superconducting.     

Conventional vs. Microwave- or Mechanically-Assisted Synthesis of Dihomooxacalix[4]arene Phthalimides: NMR,X-ray and Photophysical Analysis §

Direct O-alkylation of p-tert-butyldihomooxacalix[4]arene (1) with N-(bromopropyl)- or N-(bromoethyl)phthalimides and K₂CO₃ in acetonitrile was conducted under conventional heating (reflux) and using microwave irradiation and ball milling methodologies. The reactions afforded mono- and mainly distal di-substituted derivatives in the cone conformation, in a total of eight compounds. They were isolated by column chromatography, and their conformations and the substitution patterns were established by NMR spectroscopy (¹H, ¹³C, COSY and NOESY experiments). The X-ray structures of four dihomooxacalix[4]arene phthalimide derivatives (2a, 3a, 3b and 5a) are reported, as well as their photophysical properties. The microwave (MW)-assisted alkylations drastically reduced the reaction times (from days to less than 45 min) and produced higher yields of both 1,3-di-substituted phthalimides (3a and 6a) with higher selectivity. Ball milling did not reveal to be a good method for this kind of reaction.