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A novel 3D Zn-based coordination polymer (NH2-LCU-110, LCU names Liaocheng University) with the formula [Zn(L1)(bpea)n (H2L1 ​= ​2-aminoterephthalic acid, bpea ​= ​1,2-bis(4-pyridyl)ethane), was hydrothermally synthesized from a flexible nitrogen-containing carboxylic acid ligand with various coordination modes as main ligands and nitrogen-containing auxiliary ligand with different structures. NH2-LCU-110 demonstrates an interesting 5-fold interpenetrating diamond structure. Luminescence measurements reveal that this complex has obvious emission enhancement and quenching towards Al3+ and Cu2+, respectively. The mixed matrix membranes (MMMs) incorporating NH2-LCU-110 and poly(methyl methacrylate) (PMMA) as well as simple test papers were both prepared for potential application. The MMMs can quickly detect Al3+ and Cu2+ and the original emission could be regenerated by lifting from the analytical solutions, demonstrating its fast response and good selectivity. The sensing mechanism was investigated in details by various measurements and compared with isostructural complex LCU-110 without –NH2 groups. All observations indicate that introduction of Lewis basic –NH2 groups can enhance the intermolecular interactions between the frameworks of coordination polymers and sensing analytes (Al3+ and Cu2+).

Animal models used to evaluate efficacies of immune checkpoint inhibitors are insufficient or inaccurate. We thus examined two xenograft models used for this purpose, with the aim of optimizing them. One method involves the use of peripheral blood mononuclear cells and cell line-derived xenografts (PBMCs-CDX model). For this model, we implanted human lung cancer cells into NOD-scid-IL2Rg−/− (NSI) mice, followed by injection of human PBMCs. The second method involves the use of hematopoietic stem and progenitor cells and CDX (HSPCs-CDX model). For this model, we first reconstituted the human immune system by transferring human CD34+ hematopoietic stem and progenitor cells (HSPCs-derived humanized model) and then transplanted human lung cancer cells. We found that the PBMCs-CDX model was more accurate in evaluating PD-L1/PD-1 targeted immunotherapies. In addition, it took only four weeks with the PBMCs-CDX model for efficacy evaluation, compared to 10–14 weeks with the HSPCs-CDX model. We then further established PBMCs-derived patient-derived xenografts (PDX) models, including an auto-PBMCs-PDX model using cancer and T cells from the same tumor, and applied them to assess the antitumor efficacies of anti-PD-L1 antibodies. We demonstrated that this PBMCs-derived PDX model was an invaluable tool to study the efficacies of PD-L1/PD-1 targeted cancer immunotherapies. Overall, we found our PBMCs-derived models to be excellent preclinical models for studying immune checkpoint inhibitors.

Three new zinc(II) complexes, namely, [Zn2(H2L1)2(OAc)2] (1), [Zn3(H2L1)2(OAc)4] (2) and {[Zn3(H2L2)2(OAc)4]·C2H5OH·DMF} (3) [(H3L1 = Schiff-base derived from salicylaldehyde and 2-amino-2-ethyl-1,3-propanediol and H3L2 = Schiff-base derived from 5-chlorosalicylaldehyde and 2-amino-2-ethyl-1,3-propanediol)], were synthesized and characterized using elemental analyses, infrared spectroscopy and X-ray diffraction. Single crystal structure analysis reveals that complex 1 is five-coordinated distorted square pyramidal configuration. Complexes 2 and 3 exhibit the similar trinuclear structure. And the alkoxy groups in the ligands are play an important role in the formation of supramolecular networks of complexes 1–3. The interaction of the complexes 1–3 with calf thymus (CT) DNA was investigated using UV–visible (UV–Vis), circular dichroism spectra (CD), fluorescence, viscosity and thermal denaturation methods. The intrinsic binding constants for the complexes are found to order of 104 indicating that the complexes are good metallo-intercalators. Complex 1 shows maximum binding affinity (Kb: 7.64 × 104) compared to others. The all complexes can bind to CT-DNA via intercalative mode. The MTT assay show that the cytotoxicity of dinuclear complex 1 is more effective with HeLa cancerous cells. All the experimental results are suggestive that the nuclearity and configuration of zinc complexes have significant influence on their properties.

Two coordination complexes, constructed by 5-(benzimidazol-2-yl) isophthalic acid ligand, namely, [Eu(HL)2(NO3)]n (1) and [Tb(HL)2(NO3)]n (2) (H2L = 5-(benzimidazol-2-yl) isophthalic acid), were obtained under the same reaction conditions and characterized. Complexes 1 and 2 were isostructral, the Ln3+ cations were linked by the carboxylate groups of L ligand to form 1-D coordination chain. And these chains were connected with four adjacent ones through hydrogen bonds to form a three-dimensional supramolecular network structure. The fluorescence properties of complexes 1 and 2 have been studied. The emission bands are located at violent region 418 nm. The fluorescence intensity is apparently affected by different solvents and metal ions. Among which, the nitrobenzene and Cu2+ can quench the fluorescence emission efficiently; however, the addition of Cd2+ enhances the fluorescence intensity. The variable temperature susceptibility of complexes 1 and 2 were also studied.

As an emerging class of crystalline materials, porous coordination polymers (PCPs) with regular and flexible nanopores have become particularly promising for adsorption applications. Here, we report a new method to synthesize PCPs with varied flexibility by shifting the position of the methyl group, the shortest alkyl chain, around the coordination sites of T-shaped ligands of H2NL1 (5-(2′-methyl-imidazol-1-yl)-isophthalic acid) and H2NL2 (5-(4′-methyl- imidazol-1-yl)-isophthalic acid). The two generated PCPs (NTU-40 and NTU-41) showed a significant change in gate opening pressure (P/P0: 0.25 to 0.0001) under the stimulus of N2 at 77 K. In addition, the square window (5 × 5 A2) of the one-dimensional (1D) zigzag channel was divided into two small triangular and straight channels in NTU-41. More importantly, the synergistic effect of structural flexibility, channel type and the micro-pores enabled highly efficient CO2/CH4 and C2H4/CH4 separation under both equilibrium state and dynamic conditions, as well as having good potential for challenging C2H4/C2H6 separation.

Three new luminescent transition coordination polymers, namely, {[Cd(L)(4,4-bpy)]·DMF·H2O}n (1), {[Cd2(L)2(bpe)2]·3DMF·2.5H2O}n (2), and {[Cd(L)(bibp)]·2DMF}n (3), (H2L = 4,4′-[benzene-1,3-diylbis(methanediylsulfanediyl)]dibenzoic acid, 4,4-bpy = 4,4-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene, and bibp = 4,4′-bis(benzoimidazo-1-ly)biphenyl), were solvothermally synthesized using Cd2+ ions and S-containing dicarboxylate acid in the presence of different N coligands. These complexes were fully characterized via elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermal gravimetric analysis (TGA). Complexes 1–3 consist of 2-D structures through the connectivity of similar 1-D Cd-L chains by different N coligands. With an increase in the size of the N coligands, these complexes show structural changes from 2D → 3D with 3-fold interpenetration of complexes 1 and 2 to the 2-D packing modes of complex 3. The luminescence properties of these three complexes were studied in detail. The results reveal that each complex exhibits selectivity and sensitivity towards Fe3+ and Cr2O72− ions, and complex 2 demonstrates the lowest detection limit towards both ions.

Two one-dimensional (1-D) cobalt(II) compounds, namely, {[Co(L1)(2,2′-bipy)]·0.5DMF}n (1) and {[Co(bimb)(H2O)4]·(L2)·2DMF}n (2) (H2L1 = 2,2′-[benzene-1,4-diylbis(methanediylsulfanediyl)]dibenzoic acid, H2L2 = 2,2′-(1,4-phenylenebis(methylene))bis(sulfanediyl)dinicotinic acid, 2,2′-bipy = 2,2′-bipyridine, bimb = 1,4-bis(benzoimidazo-1-ly)benzene), have been synthesized using cobalt(II) salts with long flexible carboxylic acids and N-containing ligands. Compounds 1 and 2 were systematically characterized by elemental analysis, infrared spectroscopy, and single crystal X-ray diffraction analysis. Both compounds display 1-D chain structures with two types of well-separated six-coordinated cobalt(II) ions possessing the same coordination sphere CoO4N2 but different coordination geometries: distorted trigonal prism and octahedron, respectively, which lead to different magnetic properties. Compound 1 exhibits more significant frequency-dependent signals and larger field-induced slow relaxation magnetization than compound 2. High frequency electron paramagnetic resonance (HF-EPR) studies further demonstrated the large anisotropy of both compounds with D values of −56.2 and +57.5 cm−1, respectively.

The functional groups and flexibility of organic building blocks were crucial for regulating the structure and luminescence as well as detecting activity of MOFs. Three Complexes of a flexible carboxylate ligand with –CH2-O- groups, namely, [Cd3(L)2(DMF)4]n (1), {[Cd3(L)2(bpea)3(H2O)4]∙2H2O∙4DMF}n (2), and [Cd3(L)2(bpy)]n (3) (H3L = 3,5-bis[(3-carboxyphenyl)oxy]benzoic acid, bpea = bis(pyridyl)ethane, and bpy = 4,4′-bipyridine), were synthesized under solventhermal conditions. Both complexes 1 and 2 exhibit interesting 2-D trilayer structures with (3,6)- and (3,4,6)-connected topology, respectively. Complex 3 displays 3-D complicated framework, in which Cd2+ ions are connected by the carboxylate groups of L3− ligands into 3-D motifs and further linked by bpy ligands. The flexible carboxylate ligand adopts three different coordination modes with the aromatic rings forming diverse dihedral angles. Luminescence measurements reveal that both the frameworks and the solvents play an important role on the sensing activities. Three complexes can selectively and sensitively detect Fe3+ and Cr2O72− in DMF through luminescence quenching (turn-off) with the latter two showing high water stability and sensing activities toward Fe3+ and Cr(VI) (Cr2O72− and CrO42−). The detection limits are in the range of 0.21–2.05 μM, comparable or superior to those of previous luminescence sensors. Specially, complex 3 could also detect Pb2+ in H2O with detection limit of 1.43 μM (0.30 ppm). The building units, the structures, the sensing media all have an effect on the sensing activities. Possible quenching mechanisms for detection of these ions were carefully investigated and proposed based on luminescence inner filter effect (IFE) and weak interactions between the target ions and frameworks. Moreover, the recoveries of 96.7–103.4% for the detection of above ions in tap water samples are achieved, suggesting practical application.

// Zhiwu Jiang 1, 2, 3 , Di Wu 1, 2 , Wei Ye 1, 2 , Jianyu Weng 4 , Peilong Lai 4 , Pengcheng Shi 5 , Xutao Guo 5 , Guohua Huang 6 , Qiuhua Deng 6 , Yanlai Tang 7 , Hongyu Zhao 8 , Shuzhong Cui 9 , Simiao Lin 1, 2 , Suna Wang 1, 2 , Baiheng Li 1, 2 , Qiting Wu 1, 2 , Yangqiu Li 10 , Pentao Liu 11 , Duanqing Pei 1, 2 , Xin Du 4 , Yao Yao 1, 2, 3 and Peng Li 1, 2, 3 1 Key Laboratory of Regenerative Biology, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, Guangzhou 510530, China 2 Guangdong Provincial Key Laboratory of Stem Cell and Regenerative Medicine, South China Institute for Stem Cell Biology and Regenerative Medicine, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, Guangzhou 510530, China 3 Department of Abdominal Surgery, Affiliated Cancer Hospital and Institute of Guangzhou Medical University of Guangzhou Medical University, Guangzhou Medical University, Guangzhou, Guangdong 510095, China 4 Department of Hematology, Guangdong Provincial People’s Hospital, Guangzhou 510500, China 5 Department of Hematology, Nanfang Hospital, Guangzhou 510500, China 6 Department of Respiratory Medicine, Nanfang Hospital, Southern Medical University, Guangzhou 510515, China 7 Department of Hematology, The First Affiliated Hospital, Sun Yat-sen University, Guangzhou 510500, China 8 The First Affiliated Hospital, University of Zhengzhou, Zhengzhou 450000, China 9 Affiliated Caner Hospital and Institute of Guangzhou Medical University, Guangzhou 510095, China 10 Department of Hematology, Medical College, Jinan University, Guangzhou 510632, China 11 Wellcome Trust Sanger Institute, Hinxton, Cambridge CB10 1HH, England, UK Correspondence to: Peng Li, email: li_peng@gibh.ac.cn Yao Yao, email: yao_yao@gibh.ac.cn Keywords: B-ALL; microenvironment; growth factors; drug screening; kinase inhibitors Abbreviations: B-ALL: B Acute lymphoblastic leukemia; OP9TA: OP9-derived adipocytes; CDK: cyclin-dependent kinase; FBS: fetal bovine serum; NSI: NOD/SCID/IL2Rg −/− mice Received: June 21, 2017 Accepted: October 28, 2017 Published: November 15, 2017 ABSTRACT Functional screening for compounds represents a major hurdle in the development of rational therapeutics for B-acute lymphoblastic leukemia (B-ALL). In addition, using cell lines as valid models for evaluating responses to novel drug therapies raises serious concerns, as cell lines are prone to genotypic/phenotypic drift and loss of heterogeneity in vitro . Here, we reported that OP9 cells, not OP9-derived adipocytes (OP9TA), support the growth of primary B-ALL cells in vitro . To identify the factors from OP9 cells that support the growth of primary B-ALL cells, we performed RNA-Seq to analyze the gene expression profiles of OP9 and OP9TA cells. We thus developed a defined, serum/feeder-free condition (FI76V) that can support the expansion of a range of clinically distinct primary B-ALL cells that still maintain their leukemia-initiating ability. We demonstrated the suitability of high-throughput drug screening based on our B-ALL cultured conditions. Upon screening 378 kinase inhibitors, we identified a cluster of 17 kinase inhibitors that can efficiently kill B-ALL cells in vitro . Importantly, we demonstrated the synergistic cytotoxicity of dinaciclib/BTG226 to B-ALL cells. Taken together, we developed a defined condition for the ex vivo expansion of primary B-ALL cells that is suitable for high-throughput screening of novel compounds.

Chimeric antigen receptor (CAR) T-cell immunotherapies have shown unprecedented success in treating leukemia but limited clinical efficacy in solid tumors. Here, we generated 1928zT2 and m28zT2, targeting CD19 and mesothelin, respectively, by introducing the Toll/interleukin-1 receptor domain of Toll-like receptor 2 (TLR2) to 1928z and m28z. T cells expressing 1928zT2 or m28zT2 showed improved expansion, persistency and effector function against CD19+ leukemia or mesothelin+ solid tumors respectively in vitro and in vivo. In a patient with relapsed B-cell acute lymphoblastic leukemia, a single dose of 5 × 104/kg 1928zT2 T cells resulted in robust expansion and leukemia eradication and led to complete remission. Hence, our results demonstrate that TLR2 signaling can contribute to the efficacy of CAR T cells. Further clinical trials are warranted to establish the safety and efficacy of this approach.

Two helical Eu(III) metal-organic frameworks, namely, {[Eu(L)(DMF)(H2O)]·0.5DMF}n (1) and [Eu(L)(DEF)(H2O)]n (2) (H3L=3,5-bis(2-carboxylphenoxy)benzoic acid, DMF=N,N-dimethylformamide, DEF=N,N-diethylformamide), have been solvothermally synthesized in different solvents, respectively. Both complexes possess helical structures through the connectivity of Eu atoms and phenolic-oxygen containing branches of the flexible multicarboxylate ligand. Based on different helices, these two complexes exhibited hexagonal and tetragonal channels, respectively. Both complexes possess (3,6)-connected (4.62)2(42.610.83) topology but with different long Schlafli symbol. The solvent plays an important role in the formation of the final frameworks. Both complexes can sensitively and selectively detect nitrobenzene and Cu2+ ions.

Immunodeficient mice engrafted with either normal or cancerous human cells are widely used in basic and translational research. In particular, NOD/SCID/IL2rg−/− mice can support the growth of various types of human cancer cells. However, the hairs of these mice interfere with the observation and imaging of engrafted tissues. Therefore, novel hairless strains exhibiting comparable immunodeficiency would be beneficial. Recently, the CRISPR/Cas9 system has been used for efficient multiplexed genome editing. In the present study, we generated a novel strain of nude NOD/SCID/IL2rg−/− (NSIN) mice by knocking out Foxn1 from NOD/SCID/IL2rg−/− (NSI) mice using the CRISPR/Cas9 system. The NSIN mice were deficient in B, T, and NK cells and not only showed impaired T cell reconstitution and thymus regeneration after allogeneic bone marrow nucleated cell transplantation but also exhibited improved capacity to graft both leukemic and solid tumor cells compared with NSI, NOG, and NDG mice. Moreover, the NSIN mice facilitated the monitoring and in vivo imaging of both leukemia and solid tumors. Therefore, our NSIN mice provide a new platform for xenograft mouse models in basic and translational research.

Two 2-D Zn(II) compounds, namely, [Zn(HL1)(bpy)]n (1) and {[Zn(HL2)(bpe)]·0.5bpe}n (2) (H3L1 = 5-(2′-carboxyl phenoxy)isophtalic acid, H3L2 = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4′-bipyridine, bpe = 4,4′-vinylenedipyridine), have been solvothermally synthesized from two flexible phenolic carboxylic acid ligands. Both compounds exhibit 2-D layered structures with 4-conneted 44 and 3- connected 63 topology, respectively. PXRD indicated that these compounds were stable in the basic conditions with pH range of 7–11 and their fluorescence intensities are strongly correlated with the pH value. The protonated carboxylic groups may have influences on the resulting fluorescence intensities. The possible proton transfer mechanism was discussed for such pH sensors in details through FTIR and ICP measurements. In addition, the analytical efficiency and accuracy in practical applications of these sensors were performed on the real lake water.

Four novel coordination polymers with distinct different structures, {[CdL(H2O)]·0.5H2O}n (1), {[ZnL(H2O)]·H2O}n (2), {[CoL(H2O)2]·2H2O}n (3), and {[NiL(H2O)2]·2H2O}n (4) (L = 5-(1-H-imidazole-1-yl)isophthalate) have been synthesized by the reaction of different transition metal cations with a rigid bi-functional ligand L. 1 possesses three-dimensional (3D) network framework, in which Cd(II) center is six coordinated by four L ligands and one aqua molecule. In compound 2, Zn(II) center adopts tetrahedral geometry and coordinated by three L ligands and one aqua molecule. 2 displays a [-AB-(H2O)n-AB-(H2O)n-] fashion 3D supramolecular network, in which A and B are two types of 2D covalent coordination layers. 3 and 4 are isostructural, metal center is six coordinated by three L ligands and two aqua molecules, and the 2D coordination layers construct the 3D supramolecular network with 1D rectangular channels via O H⋯O hydrogen bonds. The structural variation depends on the nature of metal cations. Solid-state luminescent for compounds 1–2 and magnetic properties for compounds 3–4 have been investigated.

Two cobalt(ii) compounds, namely, {[Co(HL)(bpy)(H2O)2]·DMF}n (1), and {[Co(HL)(bpe)]·0.5bpe}n (2) (H3L = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4'-bipyridine, bpe = 4,4'-vinylenedipyridine), have been synthesized using cobalt(ii) transition metal salt with phenolic carboxylic acid and different N-donor ligands. The compounds were fully characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). Both compounds exhibit 2-D (4,4)-sql networks but with a wavelike and a double layered arrangement, respectively. Remarkably, these two compounds not only exhibit field-induced single-ion relaxation magnetization but also exceptional catalytic activities of benzylic C-H oxidation (conv. 90.3-99%; sele. 98.1-99%).

In the design and construction of porous materials, these with exceptional structure and composition are often highly expected, as they may offer unique nanopore space for desired applications. Here, a new family of quasi-3D and a 3D porous coordination polymers (PCPs) (termed

The efficient transformation of carbon dioxide into useful chemical feedstock is of great significance, attracting intense research interest. The widely studied porous-coordinated polymers possess large pores to adsorb guest molecules and further allow the contact and to transfer the substrate molecule within their microenvironment. Here we present the synthesis of a silver-based metal-organic frameworks (MOFs) material with a three-dimensional structure by incorporating a tetraphenyl-ethylene moiety as the four-point connected node via the solvothermal method. This polymer exhibits as an efficient heterogeneous catalyst for the carboxylative cyclization of CO2 to &alpha, methylene cyclic carbonates in excellent yields. Moreover, the introduction of silver (Ag (I)) chains in this framework shows the specific alkynophilicity to activate C&equiv, C bonds in propargylic alcohols to greatly accelerate the efficient conversion, and the large pores in the catalyst exhibit a size-selective catalytic performance.

The ability to fabricate perfusable, small-diameter vasculature is a foundational step toward generating human tissues/organs for clinical applications. Currently, it is highly challenging to generate vasculature integrated with smooth muscle and endothelium that replicates the complexity and functionality of natural vessels. Here, a novel method for directly printing self-standing, small-diameter vasculature with smooth muscle and endothelium is presented through combining tailored mussel-inspired bioink and unique “fugitive-migration” tactics, and its effectiveness and advantages over other methods (i.e., traditional alginate/calcium hydrogel, post-perfusion of endothelial cells) are demonstrated. The biologically inspired, catechol-functionalized, gelatin methacrylate (GelMA/C) undergoes rapid oxidative crosslinking in situ to form an elastic hydrogel, which can be engineered with controllable mechanical strength, high cell/tissue adhesion, and excellent bio-functionalization. The results demonstrate the bioprinted vascular construct possessed numerous favorable, biomimetic characteristics such as proper biomechanics, higher tissue affinity, vascularized tissue manufacturing ability, beneficial perfusability and permeability, excellent vasculoactivity, and in vivo autonomous connection (~2 weeks) as well as vascular remodeling (~6 weeks). The advanced achievements in creating biomimetic, functional vasculature illustrate significant potential toward generating a complicated vascularized tissue/organ for clinical transplantation.

Dinuclear metal clusters as metalloenzymes execute efficient catalytic activities in biological systems. Enlightened by this, a dinuclear {CoII2} cluster was selected to survey its ORR (Oxygen Reduction Reaction) catalytic activities. The crystalline {CoII2} possesses defined structure and potential catalytic active centers of {CoN4O2} sites, which was identified by X-ray single crystal diffraction, Raman and XPS. The appropriate supramolecular porosity combining abundant pyridinic-N and triazole-N sites of {CoII2} catalyst synergistically benefit the ORR performance. As a result, this non-noble metal catalyst presents a nice ORR electrocatalytic activity and abides by a nearly 4-electron reduction pathway. Thus, this unpyrolyzed crystalline catalyst clearly provide precise active sites and the whole defined structural information, which can help researcher to design and fabricate efficient ORR catalysts to improve their activities. Considering the visible crystal structure, a single cobalt center-mediated catalytic mechanism was also proposed to elucidate the ORR process.

A novel three-dimensional coordination polymer, namely, poly[[diaquabis(μ-4,4'-bipyridine)bis{μ

Herein, a series of Fe-based catalysts have been designed and prepared by grinding a mixture of MIL-88d and melamine, and then the mixture was followed by pyrolysis. An unusual Fe/Fe

In the field of catalysis, material scientists pay much attention to tuning the activity and chemoselectivity of metal nanoparticles. Herein, we design and successfully synthesize a series of Co NPs which show high performance on hydrogenation of nitroarenes with both activity and chemoselectivity. Co

A flexible-ligand-based metal-organic cage containing functional amide and secondary amino groups as guest-interacted sites has been synthesized. The synergistic effect between the size-defined cavity and self-adaptive backbone endows the cage excellent properties for the selective recognition of specific natural guests over other similar molecules via fluorescent response.

Reaction of the flexible phenolic carboxylate ligand 2-(3,5-dicarboxylbenzyloxy)benzoic acid (H3 L) with nickel salts in the presence of 1,2-bis(pyridin-4-yl)ethylene (bpe) leads to the generation of a mixture of the two complexes under solvolthermal conditions, namely poly[[aqua[μ-1,2-bis(pyridin-4-yl)ethylene-κ2 N:N′]{μ-5-[(2-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato-κ3 O 1,O 1′:O 3}nickel(II)] dimethylformamide hemisolvate monohydrate], {[Ni(C16H10O7)(C12H10N2)(H2O)]·0.5C3H7NO·H2O} n or {[Ni(HL)(bpe)(H2O)]·0.5DMF·H2O} n , 1, and poly[[diaquatris[μ-1,2-bis(pyridin-4-yl)ethylene-κ2 N:N′]bis{μ-5-[(2-carboxyphenoxy)methyl]benzene-1,3-dicarboxylato-κ2 O 1:O 5}nickel(II)] dimethylformamide disolvate hexahydrate], {[Ni2(C16H10O7)2(C12H10N2)3(H2O)2]·2C3H7NO·6H2O} n or {[Ni2(HL)2(bpe)3(H2O)2]·2DMF·6H2O} n , 2. In complex 1, the NiII centres are connected by the carboxylate and bpe ligands to form two-dimensional (2D) 4-connected (4,4) layers, which are extended into a 2D+2D→3D (3D is three-dimensional) supramolecular framework. In complex 2, bpe ligands connect to NiII centres to form 2D layers with Ni6(bpe)6 metallmacrocycles. Interestingly, 2D+2D→3D inclined polycatenation was observed between these layers. The final 5-connected 3D self-penetrating structure was generated through further connection of Ni–carboxylate chains with these inclined motifs. Both complexes were fully characterized by single-crystal analysis, powder X-ray diffraction analysis, FT–IR spectra, elemental analyses, thermal analysis and UV–Vis spectra. Notably, an interesting metal/ligand-induced crystal-to-crystal transformation was observed between the two complexes.

Background Gastric cancer (GC) is a common cancer in Asia and currently lacks a targeted therapy approach. Mesothelin (MSLN) has been reported to be expressed in GC tissue and could be targeted by chimeric antigen receptor (CAR) T cells. Mesothelin targeting CAR-T has been reported in mesothelioma, lung cancer, breast cancer, and pancreas cancer. However, the feasibility of using anti-MSLN CAR T cells to treat GC remains to be studied. Methods We verified MSLN expression in primary human GC tissues and GC cell lines and then redirected T cells with a CAR containing the MSLN scFv (single-chain variable fragment), CD3ζ, CD28, and DAP10 intracellular signaling domain (M28z10) to target MSLN. We evaluated the function of these CAR T cells in vitro in terms of cytotoxicity, cytokine secretion, and surface phenotype changes when they encountered MSLN+ GC cells. We also established four different xenograft GC mouse models to assess in vivo antitumor activity. Results M28z10 T cells exhibited strong cytotoxicity and cytokine-secreting ability against GC cells in vitro. In addition, cell surface phenotyping suggested significant activation of M28z10 T cells upon target cell stimulation. M28z10 T cells induced GC regression in different xenograft mouse models and prolonged the survival of these mice compared with GFP-transduced T cells in the intraperitoneal and pulmonary metastatic GC models. Importantly, peritumoral delivery strategy can lead to improved CAR-T cells infiltration into tumor tissue and significantly suppress the growth of GC in a subcutaneous GC model. Conclusion These results demonstrate that M28z10 T cells possess strong antitumor activity and represent a promising therapeutic approach to GC.

Through reaction of La(NO3)3 with a flexible carboxylic acid ligand named 3,5-bis[(2-carboxyphenyl)oxy]benzoic acid (H3L) under solvothermal condition, the complex with the formula of [La(L)(DMF)2] (1) was obtained. One-dimensional chain of the complex was generated through the connection of binuclear units of La2(COO)4 across the flexible acid ligands. Luminescence results showed that different pollutants (Fe3+, acetone and benzothiophene organic compounds) could quench the luminescence of the blue emission of the complex in DMF with much low detection limit. Among several 2-substituted benzothiophene compounds, 2,2′-dithiobisbenzothiazole (DM) has a strongest binding constant of 10.8 ​× ​104 ​M−1 and lowest detection limit of 0.332 ​μM (0.110 ​ppm). All quenching effect was found within 15 ​s. The sensing mechanism was investigated through a series of experiments and theoretical calculation. Complex 1 could be employed as a multi-responsive chemsensor for detection of different pollutants with high sensitivity and fast response.

Two coordination polymers [Cu(H2L)(bpyBr)]n (1) and [Ni(H2L)(bpy)(H2O)2]n (2) (H4L ​= ​5,5’-(butane-1,4-diylbis (oxy)) diisophthalic acid, bpyBr ​= ​4,4′-dibromo −2, 2′-bipyridyl, bpy ​= ​4, 4′-bipyridyl) were synthesized at lower temperature and weaker acidity condition. Crystal structure studies revealed that both compounds exhibited 2-D coordination layer with uncoordinated protonated –COOH groups, which can promote the acidity of compounds, form hydrogen bonds and benefit to proton conducting behavior. So, their proton conductivities have been evaluated through incorporating with Nafion to form composite membrane. AC impedance spectra studies suggested that compounds 1–2 can promote the proton conductivity of the composite membrane about 15.97% and 24.61% higher than that of pure Nafion membrane, respectively. The higher proton conductivity of 2/Nafion should be attributed to the continuous hydrogen bonding chains in the crystal structure.

Two novel dinuclear clusters, [Ni(pmmat)·ClO4]2 (1) and [Co(pmmat)·ClO4]2 (2) (Hpmmat = 3,5-bis[(2-pyridyl-2-methoxyl-methyl)-amino]-1,2,4-triazole), have been constructed from a rare multidentate chelating ligand. The formation of Hpmmat ligand involves the in situ addition reaction of C=N groups and CH3OH solvents in the presence of Ni2+/Co2+ ions as Lewis-acid catalysts and coordination agents. Compounds 1 and 2 are similar structures that have a dinuclear cluster (M2) (M = Ni and Co) aggregation. Moreover, the magnetic properties of them have been also investigated.

Two types of lanthanide coordination polymers, namely, [Ln(PA)(NO3)(DMA)3] n (Ln=Gd (1), Dy (2), Eu (3), Tb (4)) (type I), and {[Ln2(PA)3(DMF)4]·2DMF} (Ln=Eu (5), Tb (6)) (type II) (PA=Pamoic acid, DMA=dimethylacetamide, DMF=N,N-dimethylformamide), have been synthesized by the reaction of Ln(NO3)3·6H2O with pamoic acid through layer diffusion method. These complexes were characterized by single crystal X-ray diffraction, infrared spectroscopy (IR), thermogravimetric analysis (TGA), fluorescence and magnetic measurements. Solvents and lanthanide atoms in the reaction play an important role in controlling different structures. Type I demonstrated 1-D linear chain structure connected by Ln atoms and PA ligands. Type II exhibited non-interpenetrating 3-D 6-connected 43612 nets based on binuclear [Ln2(CO2)6(DMF)4] cores. Magnetic properties of complexes 1–4 were investigated in details. Complex 1 shows significant magnetocaloric effect with–ΔSm=20.37 J kg–1 K–1 at 3.0 K and 7 T. Complex 2 exhibits slow relaxation of the magnetization. Complexes 3–6 exhibit both ligand- and metal-centered fluorescent properties. Complex 6 demonstrates fluorescent sensing of DMF and Cu2+ ion.

Two isostructural (3,6)-connected porous coordination polymers topologically featuring both self- and interpenetration have been successfully synthesized. The porous material shows a reversible crystalline-to-amorphous transition associated with the removal and recapture of guest molecules. Particularly, the porous material demonstrates selective detection of nitrobenzene through fluorescence quenching.

A microporous Tm-MOF {[Tm2L2(ox)(H2O)2]·4H2O}n (Tm-MOF, L ​= ​2-(pyridin-4-yl)-2H-imidazole-4, 5-dicarboxylate dianion; ox ​= ​oxalate dianion) with hydrogen bonds between the guest water molecules and host framework has been obtained. The CV and AC impendence studies suggested there was remarkable proton conducting behavior within Tm-MOF crystals, which was influenced by external voltage. The proton conducting mechanism was explored through dynamic simulation calculation. It was suggested that proton transferred between L ligand and water molecules through hydrogen bonds. And L ligand can isomerize to excited state stimulated by external voltage, which was essential and ensured the continuity of proton transfer. This simulated proton conduction process was verified by the fact that the low proton conductivity at 0 ​V vs. Ag-AgCl increased dramatically while open-circuit voltage increased to 1.6 ​V vs. Ag-AgCl. The UV absorption peak red shifting under higher voltage and the Ea value of 0.22eV lower than 0.4eV also confirmed the result of dynamic simulation.

Based on a flexible ether-oxygen tricarboxylate ligand, H3L ​= ​3,5-bis[(3-carboxylphenyl)oxy]benzoic acid, one novel 2-D La-CP with the formula of {[La(L)(H2O)3]·H2O}n has been solventhermally synthesized. The 2-D bilayer structure of La-CP is constructed by carboxylate-bridged Lan(CO2)n layers connected by M-shaped tricarboxylate ligands arranged below and above, respectively. The La-CP exhibits blue luminescence and demonstrates multi-responsive luminescence sensing activities toward Fe3+, Cr(VI) and benzothiazoles (BTs) through luminescence quenching. It could be repeated after at least five cycling runs. The fast response, high sensitivity and selectivity makes it a potential multi-functional chemosensor.

In order to face emergency situation of the rail vehicle air conditioning system, a cool storage device was designed. The device was made up of phase change paraffin and heat exchanger. For the purpose of optimum system design, the mathematic model of phase change and heat transfer in process of cool discharging was established, numerical simulation was finished. Discharging rate of cool and cooling capacity of the device was analyzed. According to the calculation results, the wind speed and air temperature had the greatest influence on the cooling effect, while the thermal conductivity had little effect on it.

Chimeric antigen receptor (CAR) T cell immunotherapies have shown remarkable efficacy in treating multiple types of hematological malignancies but are not sufficiently effective at treating solid tumors. NKG2D is a strong activating receptor for NK cells and a co-stimulatory receptor for T cells. NKG2D signal transduction depends on DNAX-activating protein 10 (DAP10). Here, we introduced the cytoplasmic domain of DAP10 into the second-generation CARs M28z and G28z to generate M28z10 and G28z10, which target mesothelin (MSLN) and glypican 3 (GPC3), respectively. T cells expressing M28z10 or G28z10 showed enhanced and prolonged effector function against MSLN+ lung cancer or GPC3+ hepatocellular carcinoma cell lines in culture and secreted elevated levels of cytokines, including IL-2, IFN-γ, granzyme B, and GM-CSF. In addition, M28z10 CAR-T cells showed greater anti-tumor activity than those expressing M28z in both A549 cell line xenografts and human lung cancer patient-derived xenografts (PDX). Similarly, G28z10 exhibited higher efficacy in causing tumor regression than did G28z in hepatocellular carcinoma PDX. Therefore, our results show that DAP10 signaling contributes to the function of CAR-T cells in both lung cancer and hepatocellular carcinoma and can enhance the efficacy of CAR-T cells.

Three new luminescent transition coordination polymers, namely, {[Cd(L)(4,4-bpy)]·DMF·H2O}n (1), {[Cd2(L)2(bpe)2]·3DMF·2.5H2O}n (2), and {[Cd(L)(bibp)]·2DMF}n (3), (H2L = 4,4'-[benzene-1,3-diylbis(methanediylsulfanediyl)]dibenzoic acid, 4,4-bpy = 4,4-bipyridine, bpe = 1,2-bis(4-pyridyl)ethylene, and bibp = 4,4'-bis(benzoimidazo-1-ly)biphenyl), were solvothermally synthesized using Cd2+ ions and S-containing dicarboxylate acid in the presence of different N coligands. These complexes were fully characterized via elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermal gravimetric analysis (TGA). Complexes 1-3 consist of 2-D structures through the connectivity of similar 1-D Cd-L chains by different N coligands. With an increase in the size of the N coligands, these complexes show structural changes from 2D → 3D with 3-fold interpenetration of complexes 1 and 2 to the 2-D packing modes of complex 3. The luminescence properties of these three complexes were studied in detail. The results reveal that each complex exhibits selectivity and sensitivity towards Fe3+ and Cr2O72- ions, and complex 2 demonstrates the lowest detection limit towards both ions.

Four new homobinuclear lanthanide(III) complexes of multidentate 3-methyloxysalicylaldoxime (MeOsaloxH2), [Ln2(MeOsaloxH)4(PhCOO)2(CH3OH)2] (Ln = Pr, 1; Nd, 2; Sm, 3) and [Gd2(MeOsaloxH)4(CH3COO)2(H2O)2]·2H2O (4), have been synthesized and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction. In these complexes, the two LnIII ions are bridged by two phenolate oxygens from two η1:η2:η1:μ2-[MeOsaloxH]- ligands and two carboxylate groups to form a [Ln2O2(RCOO)2] binuclear structure (R = Ph, 1-3; CH3, 4). The noncovalent interactions (hydrogen bonds and weak C-H···O interactions) led to two types of three-dimensional supramolecular architectures. Magnetic and luminescence properties of these complexes have also been studied.

Seven new copper(II) coordination networks combining flexible 3,3′,5,5′-tetramethyl-4,4′-bipyrazole (bpz) and diverse dicarboxylates, [Cu(bpz)0.5(adip)]n (1), [Cu2(bpz)4(sub)2]n (2), [Cu4(bpz)1.5(aze)·H2O]n (3), [Cu2(bpz)(pta)2(H2O)·H2O]n (4), [Cu2(bpz)(ipa)]n (5), [Cu2(bpz)(o-pda)2·H2O]n (6), and [Cu2(μ3-OH)(bpz)(p-pda)1.5·H2O]n (7) (H2adip = adipic acid, H2sub = suberic acid, H2aze = azelaic acid, H2pta = phthalic acid, H2ipa = isophthalic acid, H2o-pda = o-phenylenediacetic acid, H2p-pda = p-phenylenediacetic acid), have been obtained under solvothermal conditions and structurally verified by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, powder X-ray diffraction (PXRD), infrared spectroscopy (IR), UV-vis spectroscopy and thermogravimetric analyses (TGA). Single crystal X-ray diffraction analysis revealed that both 1 and 6 are 6-connected pcu networks (point symbol: {412·63}) based on paddle-wheel [Cu2(COO)4] secondary building units (SBU). Complexes 2 and 4 are 2D 44-sql networks based on a single metal ion node and a binuclear [Cu2(COO)4(H2O)] SBU, respectively, while complex 3 features an extremely rare 3D 5-connected hxg-d-5-C2/c (point symbol: {42·67·8}) network. Complex 5 shows a 1D tape structure built from bpz sealed 1D helical Cu2(ipa) chains along the b axis, and 7 is a 3D 8-connected hex (point symbol: {36·418·53·6}) network based on a centrosymmetric [Cu4(μ3-OH)2(COO)4] SBU. A thorough structural comparison of these coordination networks suggests that the coordination fashions, conformations of dicarboxylates along with the different inorganic Cu(II) SBUs simultaneously play a significant role in constructing the diverse networks. Variable-temperature magnetic susceptibility data denote that 4 and 7 display antiferromagnetic interactions in binuclear [Cu2(COO)4(H2O)] and [Cu4(μ3-OH)2(COO)4] SBUs. Moreover, the thermal stability and UV-vis spectra of 1–7 are discussed in detail.

Three new ZnII–ditetrazolate coordination polymers (CPs), namely [Zn(m-pdtz)(4,4′-bipy)(H2O)]n (1), [Zn2Cl2(m-pdtz)(4,4′-bipy)]n (2) and [Zn2(OH)2(m-pdtz)]n (3) (4,4′-bipy = 4,4′-bipyridine, m-H2pdtz = 5,5′-1,3-phenylene-ditetrazole), have been constructed by an in situ ditetrazolate-ligand synthesis system. The formation of m-pdtz2- ligand involves the Sharpless [2 + 3] cycloaddition reaction between isophthalonitrile (IPN) and NaN3 in the presence of Zn2+ ions as Lewis-acid catalysts under hydro/solvothermal conditions. Single-crystal structural analyses reveal that compound 1 exhibits a new 6-connected 3D structural topology constructed from dimeric {Zn2} clusters as secondary building units (SBUs), compound 2 represents a 2D sql structural feature built from rhombic tetrameric {Zn4} rings as SBUs, while compound 3 displays a new (4,6)-connected 3D structural topology constructed from rod-shaped 1D Zn-chains as SBUs. Regarding these three CPs, we have performed a thorough investigation on their crystal structure, topology, and fluorescence property.

Four coordination complexes based on two amino-alcohol derived Schiff base ligands, namely, [Cu(H2L1)(Cl)]·CH3OH (1), [Cu4(HL2)2(H2L2)2(H2O)(C2H5OH)]·2(ClO4)·2(C2H5OH) (2), [Ni2(H2L1)2(OAc)2(C2H5OH)2]2 (3) and [Ni4(HL2)3(μ3-O)(H2O)3]·9H2O (4) (H3L1 = {2-ethyl-2-((2-hydroxybenzylideneamino)propane-1,3-diol), and H3L2 = 2-ethyl-2-((2-hydroxy-3-methoxybenzylideneamino)propane-1,3-diol)}), were synthesized and characterized. Alkoxo and phenoxo groups of the Schiff base ligands bridge the metal atoms in diverse modes, leading to interesting mononuclear (1), dinuclear (3), and tetranuclear (2 and 4) complexes, respectively. The in vitro cytotoxic effect of these complexes on cancerous cell lines, including the human lung carcinoma cell line (A549), human colon carcinoma cell lines (HCT-116), human promyelocytic leukemia cells (HL-60) and the chronic myelogenous leukemia cell line (K-562) showed that all these complexes exhibited substantial cytotoxic activity. Their interactions with calf thymus DNA (CT-DNA) and bovine serum albumin (BSA) were also investigated using UV-visible, fluorescence and synchronous fluorescence spectroscopic methods. All complexes could quench the intrinsic fluorescence of BSA in a static quenching process. Variable temperature magnetic properties of these complexes were investigated in details. The nuclearity and metal centers play an important role in the properties of the complexes.

One novel coordination polymer, [Zn2(L)(bpp)(Cl)2]n (1) (H2L=9,10-di-(1H-tetrazole-5-yl) anthracene, bpp=1,3-bis(4-pyridyl) propane), has been constructed by in situ ligands synthesis system. The formation of ditetrazole-based ligand H2L involves the in situ Sharpless [2+3] cycloaddition reaction between 9,10-dicyanoanthracene (DCA) and NaN3 in the presence of Zn2+ ions as Lewis-acid catalysts under solvothermal conditions. At the same time, the bpp ligand is introduced to adjust the structure of 1. Compound 1 exhibits an 8-connected three-dimensional (3D) bcu (body centered cubic) topology constructed from rhombic tetrameric {Zn4} rings as secondary building units (SBUs). Moreover, the luminescent properties of 1 have been also investigated.

Background Multiple iterations of chimeric antigen receptors (CARs) have been developed, mainly focusing on intracellular signaling modules. However, the effect of non-signaling extracellular modules on the expansion and therapeutic efficacy of CARs remains largely undefined. Methods We generated two versions of CAR vectors, with or without a hinge domain, targeting CD19, mesothelin, PSCA, MUC1, and HER2, respectively. Then, we systematically compared the effect of the hinge domains on the growth kinetics, cytokine production, and cytotoxicity of CAR T cells in vitro and in vivo. Results During in vitro culture period, the percentages and absolute numbers of T cells expressing the CARs containing a hinge domain continuously increased, mainly through the promotion of CD4+ CAR T cell expansion, regardless of the single-chain variable fragment (scFv). In vitro migration assay showed that the hinges enhanced CAR T cells migratory capacity. The T cells expressing anti-CD19 CARs with or without a hinge had similar antitumor capacities in vivo, whereas the T cells expressing anti-mesothelin CARs containing a hinge domain showed enhanced antitumor activities. Conclusions Hence, our results demonstrate that a hinge contributes to CAR T cell expansion and is capable of increasing the antitumor efficacy of some specific CAR T cells. Our results suggest potential novel strategies in CAR vector design. Electronic supplementary material The online version of this article (doi:10.1186/s13045-017-0437-8) contains supplementary material, which is available to authorized users.

Two Fe-based porous MOFs have been constructed from dimeric Fe-clusters and rod-shaped heterobimetallic Fe/Na-chains as SBUs, respectively. Notably, both of them exhibit highly selective CO2 uptake over CH4 and N2 owing to abundant multiple active sites.

In recent years, immunotherapies, such as those involving chimeric antigen receptor (CAR) T cells, have become increasingly promising approaches to non-small-cell lung cancer (NSCLC) treatment. In this study, we explored the antitumor potential of prostate stem cell antigen (PSCA)-redirected CAR T and mucin 1 (MUC1)-redirected CAR T cells in tumor models of NSCLC. First, we generated patient-derived xenograft (PDX) mouse models of human NSCLC that maintained the antigenic profiles of primary tumors. Next, we demonstrated the expression of PSCA and MUC1 in NSCLC, followed by the generation and confirmation of the specificity and efficacy of PSCA- and MUC1-targeting CAR T cells against NSCLC cell lines in vitro. Finally, we demonstrated that PSCA-targeting CAR T cells could efficiently suppress NSCLC tumor growth in PDX mice and synergistically eliminate PSCA+MUC1+ tumors when combined with MUC1-targeting CAR T cells. Taken together, our studies demonstrate that PSCA and MUC1 are both promising CAR T cell targets in NSCLC and that the combinatorial targeting of these antigens could further enhance the antitumor efficacy of CAR T cells.

Three zinc compounds assembled from a bithiophene dicarboxylic acid H2DMTDC and different N-donor co-ligands, [Zn(DMTDC)(bpt)(H2O)]n (1), {[Zn(DMTDC)(5,5’dmbpy)]·0.5DMF·1.5H2O}n (2) and {[Zn(DMTDC)(1,3-bimb)]·2DMF·H2O}n (3) (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, bpt = 4-amino-3,5-bis(4-pyridyl)1,2,4-triazole, 5,5’-dmbpy = 5,5’-dimethyl-2,2’-bipyridyl, 1,3-bimb = 1,3-bis(imidazol-1ylmethyl)benzene), were solvothermally synthesized and characterized. Compounds 1 and 2 are one-dimensional linear and zigzag chains with different supramolecular structures. In 1, adjacent chains form zipper-like structures through N-H···N interactions. In 2, however, chains in adjacent layers are stacked in an unusual unparallel level through C-H···O interactions. Compound 3 features a highly corrugated two-dimensional (4,4) layer and the layers are penetrated by each other to give 3D polycatenations. Right and left-handed helical Zn-bimb chains are arranged alternately within and between the layers, leading to mesomeric property of the whole network. Thermal stability and the decomposed products of all compounds were investigated. Luminescent properties of the ligands and compounds in the solid state at room temperature have also been explored. Moreover, the luminescence intensities of the compounds in different solvents are largely dependent on the solvent.

A new cobalt(II)–organic framework, [Co{sub 2}(L)(py){sub 2}(DMSO)]{sub n}• 0.5nDMF• 2nDMSO (1) [H{sub 4}L=5,5'-((naphthalene-2,6-dicarbonyl)bis(azanediyl))diisophthalic acid, py=pyridine, DMSO=dimethyl sulfoxide, DMF=N,N-dimethylformamide], has been solvothermally synthesized and characterized by elemental analysis, IR, TGA, PXRD and single-crystal X-ray crystallography. The structural analysis reveals that complex 1 is a 3D framework built from nanosized acylamide-containing tetracarboxylate ligands (L{sup 4−}) and dinuclear [Co{sub 2}(CO{sub 2}){sub 4}] secondary building units (SBUs), exhibiting a uninodal (4,4)-connected crb topology with the Schlafli symbol of (4• 6{sup 5}). The desolvated complex (1a) displays higher adsorption capability for CO{sub 2} than N{sub 2}, which may be due to the relatively strong binding affinity between the CO{sub 2} molecules and acylamide groups in the framework. The magnetic investigation shows that the dominant antiferromagnetic interaction is observed in complex 1. - Graphical abstract: A new 3D Co(II)–organic framework with nanosized acylamide-containing tetracarboxylate ligand was solvothermally synthesized and structurally characterized, its thermal stability, gas adsorption and magnetic property were studied. - Highlights: • A new 3D Co(II)–organic framework with nanosized acylamide-containing tetracarboxylate ligand has been solvothermally synthesized and characterized. • Complex 1 exhibits a uninodal (4,4)-connected crb topology. • The thermal stability, gas adsorption and magnetic property were studied.