Xiaowei Song

A dual responsive targeted drug delivery system based on smart polymer coated mesoporous silica for laryngeal carcinoma treatment

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.

A Gallogermanate Zeolite with Eleven‐Membered‐Ring Channels

Zeolites are crystalline microporous materials composed of corner-sharing TO4 (T= Si, Al, P, etc.) tetrahedra, and widely applied in the fields of catalysis, ion-exchange, adsorption, and separation. So far, 206 types of zeolite frameworks have been identified by the Structure Commission of the International Zeolite Association (IZA-SC). The importance and increasing number of applications for zeolites drives the development of new zeolite materials. Germanate-based zeolites are of particular interest because of their rich structural diversity favored by the larger T O distances and the smaller T-O-Tangles of Ge atoms compared with those of Si atoms in silicate zeolites. Such geometric factors have an important effect on the formation of small rings, such as double four-membered rings (D4Rs), which are believed to be beneficial for the formation of structures with very low framework density (FD), proposed by Brunner and Meier. Notably, a series of D4R-containing germanosilicate zeolites with extra-large pores has been successfully synthesized, such as ITQ-33 (18 10 10 ring), ITQ-43 (28 12 12 ring), ITQ-44 (IRR, 18 12 12 ring), and ITQ-37 (-ITV) with 30-membered-ring windows. In addition, several novel germanate-based zeolites built of small rings that incorporate trivalent elements, such as B, Al, and Ga, have been discovered. Notably, the gallogermanate zeolite GeGaO-CJ63 (JST) is constructed exclusively from 3-membered-ring units, and has a structure that features a pair of chiral cages induced by chiral metal-complex templates. The pore characteristics of zeolites such as pore dimension and pore size may fundamentally affect the shapeselective property with regards to molecular sieving and hydrocarbon transformations, which can lead to new or improved separation and catalytic processes. Compared with even-numbered pore openings, odd-numbered pore openings are much less frequently observed in existing zeolites. Until now, the largest odd-numbered channel openings are 15-membered-ring openings, which are found in germanosilicate ITQ-40. To the best of our knowledge, there is no zeolite that possesses pore openings bordered by eleven tetrahedrally coordinated atoms. Herein, we present the synthesis and characterization of a gallogermanate zeolite j (Ni(C3H10N2)3)36Ni4.7 j [Ga81.4Ge206.6O576] (denoted GaGeOJU64, C3H10N2= 1,2-PDA= 1,2-diaminopropane). It exhibits a novel four-connected zeolite structure that possesses a three-dimensional intersecting 11-membered-ring channel system. The structure features novel [3.4.6.11] cavities that exist as pairs of enantiomers either containing or being surrounded by chiral metal complexes used as the templates. GaGeO-JU64 has the lowest framework density (FD= 9.9 T/ 1000 ) ever achieved in oxide zeolites. GaGeO-JU64 was prepared by the hydrothermal reaction of a mixture of GeO2, Ga(NO3)3, Ni(CH3COO)2·4H2O, 1,2PDA, and H2O in a molar ratio of 1.00:0.39:0.24:19.17:36.76 at 180 8C for 8 days in a Teflon-lined stainless steel autoclave. Themetal complex cation [Ni(1,2-PDA)3] 2+ was formed in the above reaction. The obtained pink cubic crystals were washed by deionized water and dried in air. The phase purity was confirmed by the agreement between the experimental powder X-ray diffraction (XRD) pattern and the simulated one based on structure analysis (see the Supporting Information, Figure S1). The XRD patterns of the GaGeO-JU64 sample recorded at different temperatures are shown in Figure S2 in the Supporting Information. GaGeO-JU64 crystallizes in the R 3 space group (No. 148) with a= 30.0117(12) , and c= 37.301(3) . Its framework is built from TO4 (T=Ge, Ga) tetrahedra, forming the anionic [T288O576]n 81.4n open framework, in which 288 T sites are occupied by both 206.6 Ge and 81.4 Ga atoms. Ga and Ge atoms are difficult to distinguish from each other by X-ray diffraction (See the Experimental Section). The negative charges of the framework of GaGeO-JU64 are compensated by 36 [Ni(1,2-PDA)3] 2+ cations in the void and 4.7 Ni cations trapped in the double six-membered rings (D6Rs). The ratio of Ge/Ga/Ni is about 5:2:1, which is in agreement with energy-dispersive X-ray (EDX) analysis results. The asymmetric unit contains 16 unique T atom positions and 4 unique Ni positions. The T O distances are in the range of 1.724(8)–1.799(7) , and the average T O bond length of 1.76 lies between the ideal Ge O bond length (1.74 ) and Ga O bond length (1.82 ). All T-O-Tangles are in the range of 119.3(5)–131.8(5)8, which is reasonable for both Ge-O-Ga and Ge-O-Ge angles. The framework of GaGeO-JU64 can be described as the combination of different characteristic building units including single six-membered rings, double six-membered rings (D6Rs), and spiro-5 units. The six-membered rings and D6Rs are connected to each other alternately by spiro-5 units to form a layer containing 11-membered-ring windows (Figure 1a). Further connection of these layers by spiro-5 units results in the three-dimensional structure with intersecting 11membered-ring channels along three directions (Figure 1b). The 11-membered-ring channels have free diameters of 5.1 7.0 , 5.2 7.0 , 5.2 7.2 , and 5.3 6.8 2 (calculated from the atomic coordinates and van der Waals diameters of [*] Y. Xu, Dr. Y. Li, Dr. Y. Han, Dr. X. Song, Prof. J. Yu State Key Laboraty of Inorganic Synthesis and Preparative Chemistry College of Chemistry, Jilin University Changchun 130012 (P. R. China) E-mail: jihong@jlu.edu.cn

|(C4NH12)4|[M4Al12P16O64] (M = Co, Zn): new heteroatom-containing aluminophosphate molecular sieves with two intersecting 8-ring channels.

Two novel heteroatom-containing aluminophosphate molecular sieves, |(C(4)NH(12))(4)|[M(4)Al(12)P(16)O(64)] (denoted MAPO-CJ69, M = Co and Zn), have been solvothermally synthesized using diethylamine as the structure-directing agent. The framework of MAPO-CJ69 exhibits a new zeolite topology which is constructed by strict alternation of metal-centered (Al/M)O(4) tetrahedra and PO(4) tetrahedra to form a three-dimensional anionic [M(4)Al(12)(PO(4))(16)](4-) framework. The structure contains two intersecting 8-ring channels along the [010] and [001] directions, and the protonated diethylamine cations reside in the 8-ring channels to achieve charge neutrality. The structure of MAPO-CJ69 is composed of the 4-4- secondary building unit (SBU), which has been found in some known zeolites, such as AFR, SFO, ZON, OWE, etc. The structural relationships between these zeolites have been discussed.

Fabrication and Catalytic Performance of Highly Stable Multifunctional Core–Shell Zeolite Composites

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.

Preparation of superhydrophobic materials for oil/water separation and oil absorption using PMHS–TEOS-derived xerogel and polystyrene

Fabrication of suerhydrophobic materials towards oil/water separation and oil absorption has been receiving great attention nowadays, due to the significant increase of industrial oily wastewater and frequent accident of oil spill. In most previous studies, the usage of expensive precursors restricted the wide applications of prepared superhydrophobic materials. In this work, superhydrophobic filter paper, fabric and polyester sponges were fabricated by dip-coating the mixed solution of polystyrene and xerogels, which were prepared with tetraethoxysilane and polymethylhydrosiloxane, based on previous work. The as-fabricated fabric can effectively separate oil and water mixtures and possesses excellent reusability; more significantly, the materials maintained its good hydrophobic and excellent oil/water separation capacity even after ten cycles. Interestingly enough, the stability was provided, as a result, the fabric still exhibited superhydrophobic after 100 abrasion times and showed high repellency towards many liquids with different pH values. Additionally, the coated polyester sponges can quickly absorb various oil and organic liquid, which will offer a practical application for the treatment of seawater or oily wastewater. By contrast, this experiment process is simple and avoided using costly fluoro-chemicals or complicated fabrication process.

Syntheses and Characterizations of Transition-Metal-Substituted Aluminophosphate Molecular Sieves |(C3N2H5)8|[M8Al16P24O96] (M = Co, Mn, Zn) with Zeotype LAU Topology

Three transitional-metal-substituted aluminophosphate molecular sieves, |(C3N2H5)8|[M8Al16P24O96] (denoted MAPO-LAU, M = Co, Mn, Zn), have been synthesized under solvothermal conditions in the presence of imidazole as the structure-directing agent. Their structures are determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction, inductively coupled plasma, thermogravimetric, and diffuse reflectance spectroscopy (UV-vis) analyses. The structure of MAPO-LAU is based on the strict alternation of MO4/AlO4 tetrahedra and PO4 tetrahedra through vertex oxygen atoms. Their frameworks are analogous to the zeotype LAU structure in which 33% of the aluminum sites are replaced by transitional-metal ions. The protonated imidazole cations resided in the 10-ring channels. These compounds show photoluminescent properties due to the existence of imidazole molecules in the structures. Magnetic measurements reveal that there is very weak antiferromagnetic interaction among the metal centers of MnAPO-LAU.

Ionothermal synthesis and magnetic study of a new manganese( ii ) phosphite with an unprecedented Mn/P ratio

A new layered manganese(II) phosphite, |NH4|4[Mn4(PO3H)6] (JIS-10), has been synthesised via the ionothermal method by using 1-pentyl-3-methylimidazolium bromide ([Pmim]Br) as the solvent. JIS-10 is the first manganese phosphite with a Mn/P ratio of 2/3, whose layered framework is built by the alternate connection of Mn2O9 dimers and PO3H pseudo-tetrahedra. JIS-10 represents an antiferromagnetic dimer system with S = 5/2 for each Mn2+ ion.

Ionothermal synthesis of a new three-dimensional manganese(II) phosphate with DFT-zeotype structure

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.

Synthesis, structure and gas adsorption properties of a stable microporous Cu-based metal–organic framework assembled from a T-shaped pyridyl dicarboxylate ligand

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.

Microwave-assisted synthesis of a thermally stable Zn-containing aluminophosphate with ERI-zeotype structure templated by diquaternary alkylammonium

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.