Crown ether-like discrete clusters for sodium binding and gas adsorption.

Hexanuclear polyoxomolybdenum-based discrete supermolecules Nax[MoV6O6(µ2-O)9(Htrz)6-x(trz)x]·nH2O (x = 0, n = 15, 1; x = 1, n = 12, 2; x = 2, n = 10, 3; x = 2, n = 49, 4; Htrz = 1H-1,2,3-triazole) have been prepared and fully characterized with different amounts of sodium cations inside and outside the intrinsic holes. Structural analyses demonstrate that they all exist a triangular channel constructed by six molybdenum-oxygen groups with inner diameters of 2.86 (1), 2.48 (2), and 3.04 (3/4) Å, respectively. Zero, one, or two univalent enthetic guest Na+ have been hosted around the structural centers, which reflect the expansion and contraction effects at microscopic level. Water-soluble species can serve as crown ether-like metallacycles before and after the sodium binding. Diverse nanoscale pores are further formed through intermolecular accumulations with hydrogen bonding. Gas adsorption studies indicate that 2-4 can selectively adsorb CO2 and O2 but have little or even no affinities toward H2, N2, and CH4. Theoretical calculations corroborate the roles of Na+ and auxiliary ligand with different states in bond distances, molecular orbitals, electrostatic potentials, and lattice energies in these discrete clusters. The binding orders of sodium cations in 2-4 are similar with the classical crown ethers, where 2 is the strongest one with 2.226(4)av Å for sodium cation bonded to six O atoms.

Binuclear, tetranuclear and hexadecanuclear thio-oxomolybdenum(V/IV) glycolates with selective adsorptions of gases.

By adjusting the pH values of the solutions, binuclear, tetranuclear and hexadecanuclear glycolato thio- and oxomolybdenum(V/IV) complexes [MoV2O2(µ2-O)(µ2-S)(Hglyc)2(Hpz)2]·H2O (1, H2glyc = glycolic acid, Hpz = pyrazole), (Hdpa)[MoV2O2(µ2-S)2(Hglyc)(glyc)(H2O)] (2, dpa = 2,2'-dipyridylamine), (Hdpa)4[MoV4O4(µ3-O)2(µ2-S)2(glyc)2(S2O3)2] (3) and Na2[MoIV4MoV12O12(µ2-O)6(µ2-OH)2(µ3-O)12(glyc)4(Hpz)4(pz)8]·28H2O (4) have been obtained successfully. Here the glycolates existed in varying aggregates with different degrees of protonation and deprotonation in 1-4. The stable formations of 1 and 2 are attributed to strong hydrogen bonds formed between the molecules. In particular, the asymmetric unit in 2 is a tetramer linked by hydrogen bonding [2.574(9) Å] between α-hydroxy and α-alkoxy groups for further construction of unsaturated penta-coordination environments. Moreover, deprotonated glycolates act as bridging ligands to form tetra- and hexadecanuclear compounds 3 and 4, respectively. The smallest unit in 4 exhibits mixed valences of 4+ and 5+ simultaneously, where its gas adsorption experiments manifest that 4 is obviously beneficial for O2 and CO2 compared with no adsorption of N2, CH4 and H2 at different pressures.

Isolated molybdenum-based microporous POMs for selective adsorption of gases.

Dodecanuclear, icosanuclear and octanuclear porous MOF-like POM materials [MoV12O12(µ2-O)4(µ3-O)12(Htrz)4(trz)4]·nH2O (n = 22, 1; n = 92, 2; Htrz = 1H-1,2,3-triazole), [MoV8O8(µ2-O)12(Htrz)8]½·[MoV12O12(µ2-O)4(µ3-O)12(Htrz)4(trz)4]·44H2O (3), and [MoV8O8(µ2-O)12(Htrz)8]·62H2O (4) have been obtained and well characterized. Higher Mo12 agglomerates have been fabricated in acidic solution, while isolated Mo8 species formed in weak alkaline conditions. Fortuitously, their additive 3 is precipitated in a neutral environment. Structural analyses indicate that there are diversiform pores present in 1-4, which are formed by polyoxometalates (POMs) themselves and intermolecular accumulations, or even induced by free disordered water molecules. Obvious downfield shifts have been found in the solid 13C NMR spectra for the coordinated 1,2,3-triazoles in 1 and 2. In particular, isolated single species of polyoxometalate-based porous framework POMOF 4 can be identified in the solution 13C NMR spectrum and further supported by solid and solution UV-vis spectroscopy. Moreover, gas adsorption tests indicate that 1 is the most promising CO2 adsorbent of these four materials, compared with other common gases O2, H2, CH4 and N2 under different pressures. The peculiarities of this sort of POMOFs, as well as the relationships and interactions with gases, have been discussed.

Efficacy and survival-associated factors with gefitinib combined with cisplatin and gemcitabine for advanced non- small cell lung cancer.

OBJECTIVE: To analyze the efficacy and survival associated factors of gefitinib combined with cisplatin and gemcitabine for advanced non-small cell lung cancer. MATERIALS AND METHODS: A total of 57 patients with advanced non-small cell lung cancer (NSCLC), who received platinum-based chemotherapy regimens for more than 1 cycle, were treated with gefitinib combined with cisplatin and gemcitabine until disease progression. Efficacy, survival time and adverse reactions were observed. The Kaplan-Meier method was adopted for analysis of survival and Cox regression for associated influencing factors. RESULTS: The patients were followed up until October 31, 2013, and the median follow-up time was 19 months. Of 57 patients, there were 4 (7.0%) with complete remission (CR), 8 (14.0%) with partial remission, 31 (54.4%) with stable disease, and 14 (24.6%) with disease progression. The remission rate was 21.1% and the disease control rate was 75.4%. The median progression-free survival (PFS) time and the median overall survival time were 10 months and 15.2 months. The one-year, two-year and three- year survival rates were 47.4%, 23.3% and 10.0%. Gender and pathological types were the independent risk factors influencing PFS time (P=0.028, P=0.009). Tumor pathological type and early efficacy were independent factors for the prognosis (P=0.018, P=0.000). Adverse reactions were mostly rashes of I~II degree and diarrhea and slightly increasing level of aminopherase. The skin adverse event incidence of III degree or above was 1.8% (1/57) and brain metastasis was foudn in 31.6% (18/57). CONCLUSIONS: Gefitinib combined with cisplatin andgemcitabine, is effective for patients with IIIb~IV NSCLC who received multiple cycles of chemotherapy.