A three-dimensional microporous metal–organic framework assembled from a T-shaped pyridyl dicarboxylate ligand, 4′-(pyridin-4-yl)-[1,1′-biphenyl]-3,5-dicarboxylic acid (H2PBPD), has been successfully synthesized via solvothermal reaction with copper(II) nitrate. Compound 1 was characterized by X-ray single-crystal diffraction, elemental analysis, IR spectroscopy and thermogravimetric analyses. Single-crystal X-ray diffraction analysis indicates that compound 1 is a (3,6)-connected three-dimensional framework with the point symbol {42·6}2{44·62·86·103}. In the framework of this compound, there exist two large metal–ligand cages. Stability tests show that compound 1 keeps its crystal structure after being soaked in several organic solvents or calcined at 250 °C under air atmosphere. The N2 adsorption at 77 K shows that compound 1 is microporous with a BET surface area of 1682 m2 g−1. Compound 1 possesses high adsorption capacities for CO2 (114 cm3 g−1, 273 K) under ambient pressure. The test of CO2 cyclic adsorption and regeneration of 1 shows that it has a stable CO2 adsorption capacity and no obvious weight change after doing this ten times.

The template effect of chiral organic molecules to aluminophosphate open frameworks was investigated by the syntheses of two layered structures, [R-C8H12N]8[H2O]2·[Al8P12O48H4] and [S-C8H12N]8[H2O]2·[Al8P12O48H4] (denoted as AlPO-CJ72-R and -S), with a mirror symmetric feature. The two structures are obtained separately, which is the first instance in inorganic open-framework materials to our knowledge, by α-methylbenzylamine with homochirality. Single-crystal X-ray diffraction analysis reveals that the structure of either AlPO-CJ72-R or AlPO-CJ72-S crystallizes in the chiral triclinic space group P1, and the existence of AAAA-stacked Al2P3O123− layers made up of alternating AlO4 and PO3(O) or PO2(O)(OH) tetrahedra to form a 4 × 6 network. Their structures show self-assembled chiral H-bond chains, the chiralities of which are transferred to adjacent helical T–O (T = Al and P) chains. The frameworks are mirror symmetric to each other. The performance of AlPO-CJ72 regarding proton conductivity was tested. It shows an excellent result up to 3.01 × 10−3 S cm−1 (363 K, 98% RH), which might be attributed to the H-bond chains in the structure.

●Structural transformation of an aluminophosphate and its proton conduction are studied.●The transformation of crystal structure leads to highly mobile proton carriers.●Its proton conductivity is 1.1×10−4 S cm−1 at 150 °C under anhydrous conditions.●The proton conduction mechanism is influenced by the structural transformation.We focused on an imidazolium-templated two-dimensional aluminophosphate (C3N2H5)[Al(HPO4)2(H2O)2] (denoted as AlPO-PC-1) with complex hydrogen bonding network to show inherent proton conductivity under anhydrous conditions. Inherent proton conductivity was studied under a N2 atmosphere (zero-humidity conditions). Notably, the AlPO-PC-1 suffers the ordered-to-disordered structural transformation induced by the increase of temperature, which influences the proton conduction process and conduction mechanism. The resulting material shows a proton conductivity of 1.1×10−4 S cm−1 at 150 °C. At 25–100 °C, the proton conduction is controlled by Grotthuss mechanism. While at 115–150 °C, the transformation of the structure affords highly mobile proton carriers and both vehicle and Grotthuss mechanism contribute to the proton conduction.

A novel metal–organic framework [Cd3(TPT)2(DMF)2]·(H2O)0.5 (1) has been solvothermally synthesized using a new rigid unsymmetrical tricarboxylate ligand p-terphenyl-3,4′′,5-tricarboxylic acid (H3TPT). Single-crystal X-ray diffraction analysis reveals that 1 possesses a three-dimensional (3D) framework with an alb-4,8-C2/c topology constructed by the combination of Cd–carboxylate chains and TPT linkers. The π-electron rich ligand H3TPT enables 1 to have an excellent luminescent property. The micrometer-sized compound 1′ dispersed in ethanol exhibits high efficiency detection for picric acid (PA). The high efficiency, stability and recyclability of 1′ make it a potential chemosensor for nitroaromatic explosives.

A new manganese phosphate |H3N(CH2)2NH3|[Mn2P2O8] (denoted as JIS-14), has been ionothermally synthesized by using eutectic mixtures as the solvent and template-delivery agent, which in situ yields ethylene diammonium cations (en2+) acting as the template. JIS-14 is the first example of manganese phosphate with 4-connected zeolite topology and exhibits a DFT-zeotype framework built up from the strict alternation of MnO4 and PO4 tetrahedra forming 3D 8-ring channels. Protonated en2+ cations locate in the channels compensate the negative charges of the inorganic framework. Magnetic measurements reveal that weak antiferromagnetic interaction exists in JIS-14.

•A new kind of layered aluminophosphate framework with 8-ring channels was synthesized.•Fe and Co substituted layered aluminophosphates were synthesized.•Higher proton conductivity than most of zeolites reported immersed in water at room temperature.A new two-dimensional layered aluminophosphate [C9H14N]8[H2O]4·[Al8P12O48H4] (denoted as AlPO-CJ70) has been synthesized by using N,N-dimethylbenzylamine as the template under solvothermal conditions at 403 K. Single-crystal X-ray diffraction analysis reveals that the structure of AlPO-CJ70 consists of AAAA-stacked Al2P3O123 − layers made of alternating AlO4 and PO4 (PO3(O) and PO2(O)(OH)) tetrahedra, forming 1D 8-ring channels along the [100] direction. The inorganic layer exhibits a new type of 4 × 6 × 8 sheets with the Al/P ratio of 2/3. Protonated N,N-dimethylbenzylamine cations are located between the layers compensating the negative charge of the anionic framework. The existence of guest water and extensive H-bonds in the structure endows AlPO-CJ70 with proton conduction properties, as elucidated by impedance studies of the powder sample.A layered aluminophosphate AlPO-CJ70 constructed by a new type of 4 × 6 × 8 sheets with the stoichiometry of Al2P3O123 − was synthesized under solvothermal conditions, which shows interesting conduction properties when immersed in water.

We report a dual-responsive targeted drug delivery system (DDS) based on smart polymer coated mesoporous silica for laryngeal carcinoma therapy. Thermo/pH-coupling sensitive polymer poly[(N-isopropylacrylamide)-co-(methacrylic acid)] was grafted onto mesoporous silica active as a “valve” to moderate the diffusion of the embedded drugs in and out of the pore channels. The DDS showed a low level of drug leakage at low temperature/high pH values, but the significantly enhanced release at higher temperature/lower pH values, which exhibits an apparent thermo/pH controlled “on–off” drug release pattern. Most importantly, covalent binding of folic acid molecules to the composite allowed it to specifically target Hep2 cells, laryngeal squamous cancer cells with folic acid receptors. These results demonstrated that the composite nanoparticles were thermo/pH-coupling sensitive responsive, implying that the designed biocompatible system could be potentially applied as target release drug nanocarriers for laryngeal carcinoma therapy.

Microwave-assisted hydrothermal synthesis of a Zn-containing aluminophosphate with ERI-zeotype structure, was successfully prepared by using N,N,N,N′,N′,N′-hexamethyl-1,6-hexanediammonium (Me6-diquat-6) as the template. The as-synthesized zeolite possesses high thermal stability, large surface area and weak and medium acid sites, which will be potentially interesting for applications in adsorption and catalysis.

•A novel 3D open-framework manganese diphosphate was synthesized.•Ionothermal synthesis was first use to prepare manganese diphosphate.•Open-framework manganese diphosphate with 12-ring channels was first synthesized.A novel open-framework manganese diphosphate compound, [NH3(CH2)2NH3][MnP2O7], denoted as JIS-13 (Jilin Ionothermal Synthesis-13), has been ionothermally synthesized by using a eutectic mixture of tetramethylammonium chloride and 2-imidazolidone as the solvent and template-delivery agent, which in situ yields ethylene diammonium cations (en2+) as the template. The structure of JIS-13 is determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction (PXRD), inductively coupled plasma (ICP), thermogravimetric (TG), elemental analyses, X-ray photoelectron spectroscopy (XPS) and magnetic measurements. The alternation of MnO5 trigonal bipyramids and P2O7 units linking through their vertices forms the three-dimensional (3-D) open framework of JIS-13, which comprises 12-ring channels along the [100] direction. Protonated en2+ cations act as the templates to compensate the negative charges of the inorganic framework. Magnetic measurements reveal that weak antiferromagnetic interaction exists in JIS-13.Under ionothermal condition, a novel open-framework manganese diphosphate JIS-13 was synthesized by using a eutectic mixture of tetramethylammonium chloride and 2-imidazolidone as the solvent and template-delivery agent, which in situ yields ethylene diammonium cations (en2+) as the template.

•A new open-framework aluminum-iron phosphate with interconnecting 8-ring channels.•(Fe/Al) MOn (n = 4, 5, 6) polyhedra and PO4 tetrahedrons construct the framework.•It shows antiferromagnetic interactions with equal amounts of Fe2+ and Fe3+ ions.A new open-framework aluminum–iron phosphate (C4H12N2)2[Fe2Al5(PO4)8(H2O)] (denoted as FeAPO-CJ51), with mixed-valence iron (II, III) has been hydrothermally synthesized by using piperazine as the template. The three-dimensional framework of FeAPO-CJ51 is constructed by the connection of metal-centered MOn (M = Fe/Al, n = 4, 5, 6) polyhedra and PO4 tetrahedra, which contains interconnecting 8-ring channels along the [010] and [001] directions. Diprotonated piperazine cations locate in the 8-ring channels to compensate the negative charge of the anionic framework. Mössbauer and magnetic susceptibility measurements show that equal amounts of Fe2 + and Fe3 + are present in FeAPO-CJ51, which undergo the long-range antiferromagnetic interactions.Under hydrothermal condition a new open-framework aluminum–iron phosphate constructed by metal-centered (Fe/Al) MOn (n = 4, 5, 6) polyhedra, and PO4 tetrahedrons has been synthesized, which shows antiferromagnetic behavior.

Multifunctional Fe3O4@SiO2–Au@silicalite-1 core–shell magnetic zeolite composites were fabricated by combining a series of sol–gel process and vapor-phase transfer of silicalite-1 zeolite nanocrystal-seeded silica shells. The obtained composite has high magnetization (32.00 emu/g), stably confined and active gold nanoparticles (ca. 15 nm), and a hierarchical silicalite-1 outer shell. The core–shell composite exhibits a high efficiency of magnetic separability, excellent catalytic performance, and reusability for the reduction of 4-nitrophenol with conversion of 98% in 12 min. Moreover, it preserves a good stability after a high-temperature hydrothermal treatment.

A novel metal–organic framework [Cd3(TPT)2(DMF)2]·(H2O)0.5 (1) has been solvothermally synthesized using a new rigid unsymmetrical tricarboxylate ligand p-terphenyl-3,4′′,5-tricarboxylic acid (H3TPT). Single-crystal X-ray diffraction analysis reveals that 1 possesses a three-dimensional (3D) framework with an alb-4,8-C2/c topology constructed by the combination of Cd–carboxylate chains and TPT linkers. The π-electron rich ligand H3TPT enables 1 to have an excellent luminescent property. The micrometer-sized compound 1′ dispersed in ethanol exhibits high efficiency detection for picric acid (PA). The high efficiency, stability and recyclability of 1′ make it a potential chemosensor for nitroaromatic explosives.

The template effect of chiral organic molecules to aluminophosphate open frameworks was investigated by the syntheses of two layered structures, [R-C8H12N]8[H2O]2·[Al8P12O48H4] and [S-C8H12N]8[H2O]2·[Al8P12O48H4] (denoted as AlPO-CJ72-R and -S), with a mirror symmetric feature. The two structures are obtained separately, which is the first instance in inorganic open-framework materials to our knowledge, by α-methylbenzylamine with homochirality. Single-crystal X-ray diffraction analysis reveals that the structure of either AlPO-CJ72-R or AlPO-CJ72-S crystallizes in the chiral triclinic space group P1, and the existence of AAAA-stacked Al2P3O123− layers made up of alternating AlO4 and PO3(O) or PO2(O)(OH) tetrahedra to form a 4 × 6 network. Their structures show self-assembled chiral H-bond chains, the chiralities of which are transferred to adjacent helical T–O (T = Al and P) chains. The frameworks are mirror symmetric to each other. The performance of AlPO-CJ72 regarding proton conductivity was tested. It shows an excellent result up to 3.01 × 10−3 S cm−1 (363 K, 98% RH), which might be attributed to the H-bond chains in the structure.