Di-isopropyl ether assisted crystallization of organic-inorganic perovskites for efficient and reproducible perovskite solar cells.

Organic-inorganic perovskite solar cells have emerged as a promising photovoltaic technology because of their advantages such as low cost, high efficiency, and solution processability. The performance of perovskite solar cells is highly dependent on the crystallinity and morphology of the perovskite films. Herein, we report a simple, one-step anti-solvent deposition process using di-isopropyl ether as a dripping solvent to obtain extremely uniform and highly crystalline CH3NH3PbI3 perovskite films. Compared to toluene, chlorobenzene, chloroform, or diethyl ether, di-isopropyl ether has proven to be a more suitable solvent for an anti-solvent deposition process. The perovskite solar cells fabricated by the anti-solvent deposition process using di-isopropyl ether treatment exhibit an average power conversion efficiency (PCE) of 17.67 ± 0.54% and the highest PCE of 19.07%. Moreover, the higher boiling point of di-isopropyl ether makes the anti-solvent deposition process more tolerant to elevated ambient temperature, which can be carried out at ambient temperatures up to 40 °C. Our results demonstrate that di-isopropyl ether is an excellent dripping solvent in the anti-solvent deposition process for efficient and reproducible perovskite solar cells.

Fullerene-based amino acid ester chlorides self-assembled as spherical nano-vesicles for drug delayed release.

Fullerenes with novel structures find numerous potential applications, particularly in the fields of biology and pharmaceutics. Among various fullerene derivatives, those exhibiting amphiphilic character and capable of self-assembly into vesicles are particularly interesting, being suitable for delayed drug release. Herein, we report the synthesis and self-assembly of biocompatible hollow nanovesicles with bilayer shells from amphiphilic functionalized fullerenes C60R5Cl (R=methyl ester of 4-aminobutyric/glutamic acid or phenylalanine). The thus prepared vesicles exhibit sizes of 80-135nm (depending on R) and can be used as delayed-release carriers of anti-cancer drugs such as 5-fluorouracil, cyclophosphamide, and cisplatin, with the time of 5-fluorouracil release from drug-containing vesicles exceeding that of non-encapsulated forms by a factor of three. We further reveal the effect of R on the loading amount and release rate/amount of vesicle-encapsulated drugs, demonstrating a potential pharmaceutical application of the prepared nanovesicles depending on the nature of R.

A spin-canted Ni(II)4-based metal-organic framework with gas sorption properties and high adsorptive selectivity for light hydrocarbons.

The reaction of nickel(II) nitrate with isonicotinic acid and 2,6-dimethyl-pyridine-3,5-dicarboxylic acid affords a novel, tetranuclear nickel(II)-based metal-organic framework that exhibits spin-canted antiferromagnetism with a canted angle of 1.65° and high adsorptive selectivity for light hydrocarbons.

A boracite metal-organic framework displaying selective gas sorption and guest-dependent spin-crossover behaviour.

A metal-organic framework, [{Fe(NCS)2}3(TPB)4]·x(guest) [·x(guest), TPB = 1,3,5-tris(4-pyridyl)benzene], shows selective gas adsorption and guest-dependent spin-crossover behaviour.

Four coordination polymers based on identical eight-connected heptanuclear clusters: spin canting, spin glass, antiferromagnetism, and gas adsorption.

Four 3D coordination polymers, [Co7(OH)4(H2O)2(ina)4(ip)3]·10H2O (1·10H2O, ina = isonicotinate, ip = isophthalate), [Ni7(OH)4(H2O)2(ina)4(ip)3]·10H2O (2·10H2O), [Co7(OH)4(H2O)2(ina)4(pip)3]·5H2O (3·5H2O, pip = 5-phenyl-isophthalate), and [Ni7(OH)4(H2O)2(ina)4(pip)3]·5H2O (4·5H2O), respectively, were hydrothermally synthesized. They crystallized in the orthorhombic space group Pba2 for 1·10H2O and 2·10H2O and monoclinic space group P2/n for 3·5H2O and 4·5H2O, respectively, and were constructed with the identical 8-connected heptanuclear {M7(OH)4} (M = Co(II) or Ni(II)) clusters, possessing uninodal hexagonal primitive net with the point symbol {3(6)·4(18)·5(3)·6}. The four coordination polymers showed dominant antiferromangetic properties, in which 1·10H2O shows spin-canted behavior and 2·10H2O exhibits the coexistence of spin canting and spin glass. Meanwhile, the activated polymers 1 and 2 possessed permanent porosity, displaying relatively large H2 uptake capacity (77 K, 1 atm) of 114 and 133 cm(3) g(-1), and CO2 uptake capacity (273 K, 1 atm) of 65.8 and 73.3 cm(3) g(-1), for 1 and 2, respectively.

[Progress in the study of acid-sensitive micelles for the targeting drug delivery system].

As a novel targeting drug delivery system, acid-sensitive micelles have many advantages, such as increasing solubility of lipophilic drugs, acid-sensitive release, high drug loading, etc. They can load drugs though non-covalent encapsulation and covalent conjugation methods. In tumor tissues, drugs are released quickly from the depolymerized micelles with lipophilic copolymer protonation or lypohydrophilic copolymer hydrolysis and covalent conjugated drugs are released when the acid-sensitive covalent linkage breaks. This review mainly advances acid-sensitive micelles for the tumor targeting drug delivery systems from drug-loaded methods and release mechanisms.

Assembly of an undeca-nuclear nickel substituted POM through polycarboxylate ligand.

An undeca-nuclear nickel substituted POM, namely [Ni(H(2)O)(6)][Ni(11)(PW(9)O(34))(2)(IDA)(3)(en)(2)(Hen)(2)(OH)(6)]·(H(2)O)(7)·(H(2)en)(2) (1) (en = 1,2-ethylenediamine, H(2)IDA = iminodiacetic acid), was synthesized through hydrothermal reaction of Na(6)PW(9)O(34), en, H(2)IDA and NiCl(2)·6H(2)O. Single-crystal structure reveals that 1 can be viewed as Ni(6)PW(9) and Ni(5)PW(9) units linked by a µ(3)-O bridge and two IDA(2-) ligands. Magnetic investigation indicates the presence of dominantly ferrimagnetic interactions within the Ni(11) core. Electrochemistry study shows that 1 displays a stable and reproducible voltammetric graph.

Microwave-assisted synthesis of a ferrimagnetic dodecanuclear iron(III) complex with a Fe4(OH)4 cubane core.

The microwave-assisted reaction of Fe(ClO(4))(2) with NaN(3), NaO(2)CPh, and 1,3-di(2-pyridyl)-1,3-propanedione gave a ferrimagnetic dodecanuclear iron(III) complex that shows magnetization relaxation behavior.

Temperature-dependent in situ ligand cyclization via C═C coupling and formation of a spin-crossover iron(II) coordination polymer.

The reaction of N(1),N(2)-bis(pyridin-4-ylmethylene)ethane-1,2-diamine (L) with Fe(NCS)(2) under various temperatures gave rise to three iron(II) coordination polymers, namely, one-dimensional [Fe(L')(NCS)(2)] (1), two-dimensional [Fe(L)(2)(NCS)(2)]·H(2)O (2), and one-dimensional [Fe(L)(2)(NCS)(2)]·2CH(2)Cl(2)·4MeOH (3). The formation of 1 involved an in situ C═C coupling reaction, L to L' [L' = 5,6-di(pyridin-4-yl)-1,2,3,4-tetrahydropyrazine], which was catalyzed by cyanide ions decomposed from thiocyanates; the manganese(II) (1a) and zinc(II) (1b) analogues of 1 were also synthesized for comparison. Magnetic studies showed that complex 1 underwent a pressure-dependent one-step incomplete spin transition whereas complexes 2 and 3 were paramagnetic in the whole temperature range.

An iron(II) incomplete spin-crossover compound: pressure effects and Mössbauer spectroscopy study.

A one-dimensional iron(II) spin-crossover compound [Fe(3py-im)(2)(NCS)(2)].7H(2)O (1) (3py-im = 2,4,5-tris(4-pyridly)-imidazole) has been solvothermally synthesized and structurally characterized. Compound 1 crystallizes in the monoclinic space group P2/c with a = 11.9078(2), b = 9.9474(1), c = 17.7290(3) and beta = 102.361(2) degrees at 105 K. Studies on the variable-temperature magnetic susceptibilities and Mössbauer spectra suggest that compound undergoes incomplete spin transition behaviour. Pressure effects on the transition behaviour have also been investigated, the thermal-induced spin transition becomes more gradual and the critical temperature shifts towards slightly higher temperature range when external pressure increases. However, the spin transition can not be completed by applying external pressure even as high as 0.79 GPa.

Poly[tris-(2,5-dimethyl-benzene-1,4--dicarboxyl-ato)bis-(pyridine)trizinc(II)].

The asymmetric unit of the title polymeric compound, [Zn(3)(C(10)H(8)O(4))(3)(C(5)H(5)N)(2)](n) or [Zn(3)(dmbdc)(3)(py)(2)](n) (dmbdc = 2,5-dimethyl-benzene-dicarboxyl-ate; py = pyridine) contains two Zn(II) ions, one of which is located on an inversion centre, one and a half 2,5-dimethyl-benzene-dicarboxyl-ate ligands and one pyridine ligand. Each ZnO(6) octa-hedron is sandwiched between two ZnO(4)N square-pyramids, forming a trinuclear zinc secondary building unit (SBU); each SBU is further linked by six 2,5-dimethyl-benzene-dicarboxyl-ate ligands with six adjacent trinuclear zinc SBU's, forming a two-dimensional layer structure with a (3,6) net. One of the three zinc ions is octa-hedrally coordinated and the other two are square-pyramidally coordinated. The coordination modes for 2,5-dimethyl-benzene-dicarboxyl-ates are bis-(bidentate) or bidentate-tridentate.

Tetra-aqua-tetra-kis{µ(3)-3,3'-[(E,E)-ethane-1,2-diylbis(nitrilo-methyl-idyne)]benzene-1,2-diolato}octa-zinc(II) N,N-dimethyl-formamide hexa-solvate.

The asymmetric unit of the title compound [Zn(8)(C(16)H(12)N(2)O(4))(4)(H(2)O)(4)]·6C(3)H(7)NO, consists of eight Zn(II) cations, four tetra-valent anionic ligands, L(4-) (L(4-) = 3,3'-(1E,1'E)-(ethane-1,2-diylbis(azan-1-yl-1-yl-idene))bis-(methan-1-yl-1-yl-idene)dibenzene-1,2-bis-(olate), four coordinated water mol-ecules and six N,N-dimethyl-formamide solvate mol-ecules. The coordination complex comprises an octa-nuclear Zn(II) unit with its Zn(II) centers coordinated in two discrete distorted square-pyramidal geometries. Four Zn(II) atoms each coordinate to two nitro-gen atoms and two phenolate oxygen atoms from an individual L(4-) ligand and one coordinated water mol-ecule. The other four Zn(II) atoms each bind to five phenolate oxygen atoms from three different L(4-) ligands. In the crystal structure, the Zn(II) complex unit, coordinated water mol-ecules and dimethyl-formamide solvate mol-ecules are linked via O-H⋯O and C-H⋯O hydrogen bonds. Mol-ecules are connected by additional inter-molecular O-H⋯O and C-H⋯O hydrogen bonds, forming an extensive three dimensional framework.

Pressure effects and Mössbauer spectroscopic studies on a 3D mixed-valence iron spin-crossover complex with NiAs topology.

A three-dimensional mixed-valence iron complex with NiAs-type topology, [(Fe(III)(3)O)Fe(II)(TA)(6)(H(2)O)(3)].(ClO(4))(2)(NO(3))(EtOH)(H(2)O)(2) (1, HTA = tetrazole-1H-acetic acid), shows spin-crossover behavior that was characterized via variable-temperature crystal structures, Mössbauer spectra and magnetic susceptibilities, the pressure effects on the transition behavior were also studied.

Preparation and optical properties of ThO(2) and Eu-doped ThO(2) nanotubes by the sol-gel method combined with porous anodic aluminum oxide template.

In this paper, we report the synthesis of thorium oxide and Eu-doped thorium oxide nanotubes for the first time using the sol-gel method in porous anodic aluminum oxide template. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were applied to characterize the morphology and structure of the as-prepared nanotubes. It has been demonstrated that Eu(3+) ions were homogeneously doped into the ThO(2) crystal lattice. The optical properties resulting from Eu-doped products were investigated by means of photoluminescence spectroscopy. Strong visible light emissions were observed at low doping concentration, and the luminescent intensity decreased at high doping concentration. The luminescent centers were concluded to be the Eu(3+) ions in the cubic (O(h)) sites rather than the C(3v) sites, which accounted well for the decrease of luminescent intensity at high doping concentration.

[Development of gas chromatographic method for chiral analysis of acrylic ketone alcohol and acrylic ketone acetate].

A gas chromatographic method was developed to directly determine the enantiomers of acrylic ketone alcohol and acrylic ketone acetate. Two pairs of enantiomers were nearly baseline-separated by using Model HP-5890 Gas Chromatograph with flame ionization detector and WCOT CD-Chiral-DEX CB (30 m x 0.25 mm i.d.) column. The optimum conditions were the split ratio of 30:1 for the sample injected, the flow rates of 3.7 mL/min for the carrier gas (nitrogen), 60 mL/min for the hydrogen, and 250 mL/min for the oxygen, and temperatures of 148 degrees C for the column, 230 degrees C for the injector, and 230 degrees C for the detector. The linearity and reproducibility were satisfactory. The regression coefficients were over 0.9965. The RSDs obtained were less than 1.25%. The method was further used to trace the reactants and products, and to evaluate the enzyme catalyst activity and selectivity under different conditions. The results show that the method developed is very successful.