Bioinspired Adaptive Microdrugs Enhance the Chemotherapy of Malignant Glioma: Beyond Their Nanodrugs.

Solid nanoparticle-mediated drug delivery systems are usually confined to nanoscale due to the enhanced permeability and retention effect. However, they remain a great challenge for malignant glioma chemotherapy because of poor drug delivery efficiency and insufficient tumor penetration resulting from the blood-brain barrier/blood-brain tumor barrier (BBB/BBTB). Inspired by biological microparticles (e.g., cells) with excellent adaptive deformation, it is demonstrated that the adaptive microdrugs (even up to 3.0 µm in size) are more efficient than their nanodrugs (less than 200 nm in size) to cross BBB/BBTB and penetrate into tumor tissues, achieving highly efficient chemotherapy of malignant glioma. The distinct delivery of the adaptive microdrugs is mainly attributed to the enhanced interfacial binding and endocytosis via adaptive deformation. As expected, the obtained adaptive microdrugs exhibit enhanced accumulation, deep penetration, and cellular internalization into tumor tissues in comparison with nanodrugs, significantly improving the survival rate of glioblastoma mice. It is believed that the bioinspired adaptive microdrugs enable them to efficiently cross physiological barriers and deeply penetrate tumor tissues for drug delivery, providing an avenue for the treatment of solid tumors.

Janus particle-engineered structural lipiodol droplets for arterial embolization.

Embolization (utilizing embolic materials to block blood vessels) has been considered one of the most promising strategies for clinical disease treatments. However, the existing embolic materials have poor embolization effectiveness, posing a great challenge to highly efficient embolization. In this study, we construct Janus particle-engineered structural lipiodol droplets by programming the self-assembly of Janus particles at the lipiodol-water interface. As a result, we achieve highly efficient renal embolization in rabbits. The obtained structural lipiodol droplets exhibit excellent mechanical stability and viscoelasticity, enabling them to closely pack together to efficiently embolize the feeding artery. They also feature good viscoelastic deformation capacities and can travel distally to embolize finer vasculatures down to 40 µm. After 14 days post-embolization, the Janus particle-engineered structural lipiodol droplets achieve efficient embolization without evidence of recanalization or non-target embolization, exhibiting embolization effectiveness superior to the clinical lipiodol-based emulsion. Our strategy provides an alternative approach to large-scale fabricate embolic materials for highly efficient embolization and exhibits good potential for clinical applications.

Fruit-Derived Extracellular-Vesicle-Engineered Structural Droplet Drugs for Enhanced Glioblastoma Chemotherapy.

Existing solid-nanoparticle-based drug delivery systems remain a great challenge for glioblastoma chemotherapy due to their poor capacities in crossing the blood-brain barrier/blood-brain tumor barrier (BBB/BBTB). Herein, fruit-derived extracellular-vesicle (EV)-engineered structural droplet drugs (ESDDs) are demonstrated by programming the self-assembly of fruit-derived EVs at the DOX@squalene-PBS interface, greatly enhancing the antitumor efficacy against glioblastoma. The ESDDs experience a flexible delivery via deformation-amplified macropinocytosis and membrane fusion, enabling them to highly efficiently cross the BBB/BBTB and deeply penetrate glioblastoma tissues. As expected, the ESDDs exhibit approximately 2.5-fold intracellular uptake, 2.2-fold transcytosis, and fivefold membrane fusion higher than cRGD-modified EVs (REs), allowing highly efficient accumulation, deep penetration, and cellular internalization into the glioblastoma tissues, and thereby significantly extending the survival time of glioblastoma mice.

Three Polyoxovanadates-Based Organic-Inorganic Hybrids: Structural Variation, Bifunctional Electrocatalytic Activities, and Computational Studies.

Three bimetallic organic-inorganic hybrids based on the [V2O6]2- building unit, [Cu(pty)(V2O6)]·H2O (1), [Cu(pty)(V2O6)] (2), [Cu(tpy)(V2O6)] (3), (pty = 4'-(4″-pyridyl)-2,2':6',2″-terpyridine, tpy = 2,2':6',2″-terpyridine), were synthesized via a one-pot method. Hybrid 1 has a 1D straight chain architecture with [V2O6]2- clusters and Cu-pty complexes; hybrids 2 and 3 possess a 2D sheet structure including 10-membered rings assembled from four [Cu(pty)]2+ motifs and six [V2O6]2- clusters in 2, and two [Cu(tpy)]2+ units and eight [V2O6]2- clusters in 3. Noteworthy, hybrids 1-3 can be employed as bifunctional electrocatalysts for electroreduction of nitrite and electrooxidation of ascorbic acid. Additionally, theoretical calculations including the molecular electrostatic potential and the frontier molecular orbital were performed to estimate the electronic structure of hybrids 1-3. The natural bond orbital analysis was also calculated to interpret the electron charge distribution.

A series of organic-inorganic hybrid compounds formed by [P2W18O62]6- and several types of transition metal complexes.

Five new organic-inorganic hybrid compounds based on [P2W18O62]6- (abbreviated as {P2W18}) and several types of transition metal complexes (TMCs) have been synthesized and characterized by IR, UV-Vis, XRD, cyclic voltammetry measurements and single crystal X-ray diffraction analysis. [Cu(phen)2][Cu(phen)(H2O)3][Cu(phen)2(H2O)][P2W18O62]·8H2O (1) (phen = 1,10-phenanthroline) is a {P2W18} bi-supported complex of phen, while [Cu(2,2'-bpy)(H2O)2]2[Cu(2,2'-bpy)2][P2W18O62]·3.5H2O (2) (2,2'-bpy = 2,2'-bipyridine) is a 1-D chain structure formed by {P2W18} and copper complexes of 2,2'-bpy. [Ag(2,2'-bpy)2]5[HP2W18O62]·H2O (3), [Ag(2,2'-bpy)(H2O)]2[Ag(2,2'-bpy)]2[Ag2(2,2'-bpy)3][P2W18O62] (4), and [Ag(2,2'-bpy)(H2O)]3[Ag2(2,2'-bpy)3][Ag(2,2'-bpy)][P2W18O62]·H2O (5) are constructed from {P2W18} and silver complexes of 2,2'-bpy. Compounds 4 and 5 are novel dimers of {P2W18} joined by silver complexes, while compound 3 contains two different kinds of silver complexes, forming a novel supramolecular structure. Each of the five compounds is formed by {P2W18} and more than one type of TMC. The formation mechanism of these compounds has been carefully discussed. In addition, we also synthesized two supramolecular structures based on {P2W18} and organic moieties: [H6P2W18O62](phen)5.5 (6) and [H6P2W18O62](phen)3·43H2O (7). The catalytic properties of these compounds were also tested.

Crystal structure of a binuclear nickel(II) complex constructed of 1H-imidazo[4,5-f][1,10]phenanthroline and doubly deprotonated benzene-1,3,5-tri-carb-oxy-lic acid.

The title complex, [Ni2(C9H4O6)2(C13H8N4)2(H2O)4]·2H2O, bis-(µ-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ(2) O (1):O (1'))bis-[di-aqua(1H-imidazo[4,5-f][1,10]phenanthroline-κ(2) N (7),N (8))nickel(II)] di-hydrate, was obtained under solvothermal conditions by the reaction of benzene-1,3,5-tricarboxylic acid (H3BTC) with Ni(NO3)2 in the presence of 1H-imidazo[4,5-f][1,10]phenanthroline (IP). The crystal has triclinic (P-1) symmetry with a centrosymmetric binuclear nickel(II) cluster. The Ni(II) atom is coordinated by two N atoms from a chelating 1H-imidazo[4,5-f][1,10]phenanthroline ligand, two carboxyl-ate O atoms from two 5-carb-oxy-benzene-1,3-di-carboxyl-ate ligands and two water mol-ecules in a slightly distorted octa-hedral geometry. Two carboxyl-ate groups bridge two Ni(II) cations, forming the binuclear complex. Extensive N-H⋯O, O-H⋯O and O-H⋯N hydrogen bonding is present in the crystal structure, forming a three-dimensional supermolecular framework. Weak π-π stacking is observed between parallel HBTC(2-) and IP ring systems, the face-to-face separation being 3.695 (2) Å.

Two unprecedented porous anionic frameworks: organoammonium templating effects and structural diversification.

Two unprecedented 3D porous anionic metal-organic frameworks, [Me2NH2]2[Cd2(bpdc)3].4dma 1 and [Me2NH2]2[Cd2(NH2bdc)3].4dma 2 (dma = N,N'-dimethylacetamide, bpdc = 4,4'-biphenyldicarboxylate, NH(2)bdc = 2-amino-1,4-benzenedicarboxylate) have been solvothermally synthesized with a dimethylammonium cations template. Both 1 and 2 are constructed from low-symmetry SBUs. 1 has a chiral framework with helical nanotube-like channels, and 2 has a MOF-5-like motif. The fluorescence, N2 adsorption and ion-exchange properties for 1 have been examined.

Combination of POMs and deliberately designed macrocations: a rational approach for synthesis of POM-pillared metal-organic framework.

Two POM-pillared 3D porous compounds, [Cu(I)Cu(II)(Cu(II)fcz)(2)(H(2)O)(5)(PMo(VI)(10)Mo(V)(2)O(40))].6H(2)O () and [Cu(I)(2)(Cu(II)fcz)(2)(H(2)O)(2)(PMo(VI)(8)V(V)(3)V(IV)(3)O(42))].6H(2)O () (Hfcz = fluconazole, (1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-1-yl)methyl]benzyl alcohol) have been constructed based on different polyanions, (Cufcz)(2)(2+) macrocations and copper cations by the hydrothermal method. The (Cufcz)(2)(2+) macrocations link Cu cations to generate a 2D wavelike cationic sheet. Then the POM anions act as pillars to the cationic sheet to form different POM-pillared 3D frameworks. In compound 2 , the polyanion exhibits a rare coordination mode and acts as a penta-dentate ligand, which acts as to pillars to the cationic sheet to form an unprecedented 3D (3,4,5,6)-connected open framework with (3.6.7)(3(2).6.7(3))(3(3).4.6(2).7(3).8)(3(4).4(2).6(2).7(6).8)(3(2).6(2).7(6).8(4).10) topology. In compound , polyanions covalently link cationic sheets to extend to an unusual 3D (3,4,6)-connected framework with the (5(2).6)(5(2).6(2).7.9)(5(4).6(4).7(4).9(3)) topology. To the best of our knowledge, it is the first time that POM-pillared 3D metal-organic frameworks have been realized by combining POMs with deliberately designed macrocations and transition-metal ions, using a rational approach for synthesis of POM-based open metal-organic frameworks. In addition, the electrochemical behaviors of compounds 1 and 2 have been investigated.

A 3D chiral nanoporous coordination framework consisting of homochiral nanotubes assembled from octuple helices.

A 3D chiral nanoporous coordination framework consisting of homochiral nanotubes assembled from octuple helices with a 19.4 A by 22.4 A aperture is formed by the parallel alignment of eight infinite helical chains.

A novel cadmium(II) coordination polymer with biphenyl-3,3',4,4'-tetracarboxylic acid and 4,4'-bipyridine.

A novel cadmium(II) coordination polymer, poly[[[bis(4,4'-bipyridine)cadmium(II)]-mu(3)-4,4'-dicarboxybiphenyl-3,3'-dicarboxylato] 0.35-hydrate], {[Cd(C(16)H(8)O(8))(C(10)H(8)N(2))(2)].0.35H(2)O}(n), was obtained by reaction of Cd(CH(3)COO)(2).3H(2)O, 4,4'-bipyridine (4,4'-bpy) and biphenyl-3,3',4,4'-tetracarboxylic acid (H(4)L) under hydrothermal conditions. Each Cd(II) atom lies at the centre of a distorted octahedron, coordinated by four O atoms from three H(2)L(2-) ligands and N atoms from two monodentate 4,4'-bpy ligands. Each H(2)L(2-) ligand coordinates to three Cd(II) atoms through two carboxylate groups, one acting as a bridging bidentate ligand and the other in a chelating bidentate fashion. Two Cd atoms, two H(2)L(2-) anions and four 4,4'-bpy ligands form a ring dimer node, which links into an extended broad zonal one-dimensional chain along the c axis.

A novel copper(II) coordination polymer with 2,2'-bipyridyl-3,3'-dicarboxylic acid.

A novel copper(II) coordination polymer, poly[[[aquacopper(II)]-mu3-2,2'-bipyridyl-3,3'-dicarboxylato-kappa4N,N':O:O'] dihydrate], {[Cu(C12H6N2O4)(H2O)].2H2O}n, was obtained by the reaction of CuCl2.2H2O and 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2L) in water. In the molecule, each Cu(II) atom is five-coordinated and lies at the centre of a square-pyramidal basal plane, bridged by three L ligands to form a two-dimensional (4,4)-network. Each L moiety acts as a bridging tetradentate ligand, coordinating to three Cu(II) atoms through its two aromatic N atoms and two O atoms of the two carboxyl groups. The two-dimensional square-grid sheets superimpose in an off-set fashion through the inorganic water layer.

A new system in organooxotin cluster chemistry incorporating inorganic and organic spacers between two ladders each containing five tin atoms.

Hydrolysis of dibenzyltin dichloride in ethanol has been found to give an unprecedented carbonate anion (CO(3) (2-))-bridged double-ladder organooxotin cluster, [(R(2)SnO)(3)(R(2)SnOH)(2)(CO(3))](2) (1, R = C(6)H(5)CH(2)), with five tin atoms in each ladder. With the aim of obtaining organooxotin clusters with large cavities suitable for host-guest chemistry, we used 1,1'-ferrocenedicarboxylic acid (H(2)L(a)) and hexanedioic acid (H(2)L(b)) to replace the carbonate anions (CO(3) (2-)), and thereby clusters [(R(2)SnO)(3)(R(2)SnOH)(2)L(a)](2) (2) and [(R(2)SnO)(3)(R(2)SnOH)(2)L(b)](2) (3) were obtained. When 1 was treated with benzoic acid (HL(c)) in different stoichiometric ratios (1:4, 1:10), ladder cluster (R(2)SnO)(3)(R(2)SnOH)(2)(L(c))(2) (4) and drum cluster [RSn(O)L(c)](6) (5) were obtained. Through the hydrolysis of Cy(2)SnCl(2) (Cy = C(6)H(11)) and (C(6)H(5)CH(2))(2)SnCl(2), two interesting ethanolate-modified clusters [Cy(2)(C(2)H(5)O)SnOSn(C(2)H(5)O)Cy(2)](2) (6) and [(R(2)SnO)(3)(R(2)SnOH)(R(2)SnOC(2)H(5))(CO(3))](2) (7) were obtained. All the tin atoms in these ladder clusters are five-coordinate surrounded by two alkyl groups and three O atoms, and have distorted trigonal-bipyramidal coordination environments with two carbon atoms and one O atom in the equatorial positions and two O atoms in the axial positions. The structures of all these compounds have been established by single-crystal X-ray diffraction analyses.