All-inorganic open frameworks based on gigantic four-shell Ln@W8@Ln8@(SiW12)6 clusters.

A series of POM-based all-inorganic open frameworks, H9[Ln9W8(µ4-O)12(µ2-O)24(H2O)24](SiW12O40)3·60H2O (1-Ln, Ln = La, Pr and Nd), have been fabricated and structurally characterized for the first time. The unique architectures are constructed from nanoscale four-shell Ln@W8@Ln8@(SiW12)6 clusters. Additionally, the porous nature of the frameworks has also been investigated.

A Rare 3D Porous Inorganic-Organic Hybrid Polyoxometalate Framework Based on a Cubic Polyoxoniobate-Cupric-Complex Cage with a High Water Vapor Adsorption Capacity.

A rare 3D porous inorganic-organic polyoxoniobate framework based on the cubic polyoxoniobate-cupric-complex cage {[Cu(en)2]@{[Cu2(en)2(trz)2]6(Nb68O188)}} (1a), has been successfully synthesized by a hydrothermal method. The cubic cages 1a are connected with 4-(tetrazol-5-yl)pyridine to form a 1D pillar-like chain structure, and every 1D pillar-like chain is further linked with four adjacent pillar-like chains by the [Cu(en)2]2+ complex to form a 3D porous inorganic-organic polyoxoniobate framework with 4-connected CdSO4-type topology. To our knowledge, it is the first time that three different types of organic ligands are simultaneously introduced into one polyoxoniobate. This material also exhibits a high vapor adsorption capacity and good ionic conductivity properties.

A new type of composite MOFs based on high-valent Sb(v)-based units and cuprous-halide clusters.

An unusual high-valent Sb(v)-based unit [SbL2]- (L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) was developed for the first time to combine with various cuprous-halide clusters for the construction of a brand-new class of heterometallic MOFs. This work not only promotes the limited development of Sb-based MOFs, but also provides a practical strategy for developing new types of composite materials.

Inorganic-organic hybrid high-dimensional polyoxotantalates and their structural transformations triggered by water.

The first two inorganic-organic hybrid three-dimensional (3D) polyoxotantalates (POTas) and the first two inorganic-organic hybrid 2D POTas have been obtained. All of these high-dimensional POTas are built from a new-type POTa dimeric cluster {Cu(en)(Ta6O19)}2/{Cu(enMe)(Ta6O19)}2 (en = ethylenediamine, enMe = 1,2-diaminopropane) bridged by copper complexes. Interestingly, extended POTas 1 and 3 can undergo single-crystal to single-crystal structural transformations triggered by water.

Development of a new Lindqvist-like Fe6 cluster secondary building unit for MOFs.

This work demonstrates a new Lindqvist-like [FeIII6(µ6-O)L4Cl6]2- (Fe6, L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol) cluster for the construction of a novel class of Fe-cluster organic frameworks. The novel Fe6 cluster can be used to build not only a homometallic MOF, but also a heterometallic MOF by introducing copper halide clusters to the reaction system. In particular, the heterometallic MOF achieved a skillful combination of Fe6 SBU and cuprous-halide clusters for the first time. Our synthesis strategy opens up an effective avenue to novel Fe-cluster-based MOF materials.

A nested Cu24@Cu72-based copper-organic polyhedral framework for selective adsorption of cationic dyes.

A nested Cu24@Cu72 copper-organic framework, [Cu5(bdc)4(ina)2(H2O)3]·solvent (1, H2bdc = 1,3-benzenedicarboxylic acid and Hina = isonicotinic acid) based on paddlewheel Cu2(COO)4 SBUs, has been synthesized. There are three types of cages with different sizes and shapes: Cu24-cage, Cu60-cage and Cu72-cage. The Cu72-cage, which is the highest-nuclearity Cu-cage reported to date, encapsulates a Cu24-cage to form a double-walled Cu24@Cu72 cage-within-cage structure. Dye adsorption studies reveal that compound 1 can rapidly and selectively adsorb cationic dyes.

A Chromium-Substituted Polyoxoniobate with High Ionic Conductivity.

A rare and novel Cr-substituted polyoxoniobate (PONb), [Cr2.5Nb27.5O66(OH)20(H2O)2]7-, has been synthesized by a combination of hydrothermal and conventional solution methods. The PONb shows an unknown tetrameric structure, which is the largest Cr-containing PONb to date. Interestingly, every two PONb tetramers can be joined together by alkali-metal cations to form a discrete cubelike ionic cluster. The obtained PONb not only enriches the very limited members of the Cr-substituted PONb family but also exhibits high ionic conductivity.

Construction of Two High-Nuclear 3d-4d Heterometallic Cluster Organic Frameworks by Introducing a Bifunctional Tripodal Alcohol as a Structure-Directing Agent.

Two unique heterometallic cluster organic frameworks, [Cd4 MnIII 4 MnII 6 (Tri)4 (CH3 COO)14 (µ4 -O)2 (µ3 -O)2 (H2 O)2 ] Cd(H2 O)2 ⋅9 H2 O (1) and Cu[Cd5 Cu6 (Tri)4 (CH3 COO)9 (H2 O)4 ]2 (CH3 COO)3 ⋅24 H2 O (2) (H3 Tri=2-(hydroxymethyl)-2-(pyridine-4-yl)-1,3-propanediol), have been successfully prepared by employing a bifunctional tripodal alcohol ligand as a structure-directing agent. Crystal structure analyses reveal that 1 represents a rare example of frameworks constructed from Cd-Mn heterometallic chains, and 2 is the first heterometallic MOF based on highest-nuclear Cd-Cu heterometallic cluster building blocks. Furthermore, the magnetic properties and gas adsorption abilities of 1 and 2 were systematically studied.

Recent Advances in Zeolite-like Cluster Organic Frameworks.

During the past decade, research on the design and synthesis of zeolite-like metal-organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal-halide cluster SBUs, 2) ZCOFs based on metal-oxygen cluster SBUs, 3) ZCOFs based on metal-chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed.

All-Inorganic Ionic Porous Material Based on Giant Spherical Polyoxometalates Containing Core-Shell K6 @K36 -Water Cage.

This work demonstrates that the use of high-negative and high-symmetry lacunary polyoxometalates (POMs) for the clustering of alkali metal ions is a feasible strategy not only for the formation of rare high-nuclearity alkali-metal clusters but also for the construction of new-type all-inorganic ionic porous materials. By the strategy, an unprecedented high-nuclearity K-H2 O cluster {K42 (H2 O)60 } with core-shell K6 @K36 configuration is stabilized by 8 C3v -symmetry trivacant POMs [GeW9 O34 ]10- , forming a novel giant ionic alkali-metal-POM composite cluster {K42 Ge8 W72 O272 (H2 O)60 } with more than 100 metal centers. The incorporated 42-nuclearity K-H2 O cluster {K42 (H2 O)60 } exhibits the highest-nuclearity alkali-metal-water cluster known to date in POM chemistry. Further, the giant {K42 Ge8 W72 O272 (H2 O)60 } clusters can be linked by another kind of alkali metal ions Na+ to generate a fascinating three-dimensional all-inorganic ionic porous framework with high chemical stability, proton conductivity, and water vapor adsorption.

Construction of Zeolite-Like Cluster Organic Frameworks from 3 d-4 d/3 d-3 d Heterometallic Supertetrahedral Secondary Building Units: Syntheses, Structures, and Properties.

Two zeolite-like cluster organic frameworks based on Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units have been successfully constructed under solvothermal conditions, namely, Cu[Cd4 Cu6 (L)4 (H2 O)18 ](Ac)9 ⋅DMA⋅3 H2 O (1), and Cu[Mn4 Cu6 (L)4 (Ac)3 (H2 O)12 ](Ac)6 ⋅CH3 CN⋅13 H2 O (2), where H3 L=2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol, Ac=CH3 COO- , DMA=N,N'-dimethylacetamide. Single-crystal X-ray structural analysis reveals that both 1 and 2 exhibit 3-dimensional zeolite-like architectures with similar 4-connected components, but possess definitely different topologies of diamondoid (dia) and uncommon lonsdaleite (lon), respectively. 1 and 2 represent the first cases of zeolite-like cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral secondary building units. Furthermore, the magnetic properties and porous nature of 1 and 2 were also studied.

Cluster Organic Frameworks Constructed from Heterometallic Supertetrahedral Cluster Secondary Building Units.

The two novel cluster organic frameworks based on heterometallic supertetrahedral cluster secondary building units (SBUs) [Cd4Cu6(L)4(Ac)7(H2O)4](Ac)·7H2O (1) and [Mn4Cu6(L)4(Ac)4.5(H2O)9]CuCN(Ac)3.5·H2O (2), where H3L = 2-(hydroxymethyl)-2-(pyridin-4-yl)-1,3-propanediol and Ac = CH3COO-, have been prepared under solvothermal conditions. 1 and 2 are the first cases of cluster organic frameworks containing Cd-Cu/Mn-Cu heterometallic supertetrahedral cluster SBUs. Furthermore, 1 and 2 show an integration of magnetic properties and adsorption properties from both the heterometallic cluster secondary building units and the framework in a porous material.

[Effects of human ERMAP-siRNA on erythroid differentiation of K562 cells induced by Ara-C].

In order to investigate the potential role of human ERMAP gene in erythropoiesis, the ERMAP-dsDNA was designed, ERMAP-shRNA expressing plasmids was constructed, and ERMAP-shRNA/K562 cell was established. Cell morphology, biphenylamine staining, expression of cell surface antigens as well as quantitative level of human ERMAP gene were observed during K562 cells differentiating toward erythroid lineage induced by Ara-C. The results showed that at 72 hours after Ara-C treatment, ERMAP-shRNA/K562 cell size became large with increasing cytoplasm content. The percentage of biphenylamine positive cells increased from 1.17% to 2.04% (p < 0.05), but still lower than that in group K562 + Ara-C. The percentage of CD36(-)/CD235a(+) increased from 8.83% to 11.28%, CD36(+)/CD235a(+) increased from 1.23% to 2.64%, and CD36(+)/CD235a(-) increased from 0.59% to 1.47% respectively, which were all lower than that in group K562 + Ara-C at either time point. At the same time, the level of ERMAP expression increased slowly from 2.52 x 10(-3) to 4.53 x 10(-3), which was also significantly lower than that of group K562 + Ara-C. It is concluded that the ERMAP-shRNA inhibits the Ara-C-induced erythroid differentiation of K562 cells, which further suggests that there is relationship between hERMAP and erythroid differentiation and development.

[Expression of human ermap gene in umbilical cord blood mononuclear cells during differentiation and development towards erythroid lineage].

The aim of study was to explore the potential of human erythroid membrane associated protein (ERMAP) gene in erythroid cell differentiation and development, mononuclear cells (MNCs) were isolated from umbilical cord blood and induced to erythroid cell differentiation by SCF, IL-3 and EPO. The cell morphology was observed by using optical microscopy, the positive rate of cells was counted by biphenylamine staining and the ratios of CD36+/CD235a-, CD36+/CD235a+, CD36-/CD235a+ cells were detected by flow cytometry, the change of human ermap gene expression level was analyzed by using fluorescent quantitative PCR (FQ-PCR). The results showed that the ermap gene expression level increased while MNCs were induced to erythroid lineage after treatment with SCF, IL-3 and EPO. It is concluded that the human ermap gene plays an important role in differentiation and development of erythroid cells.