Convenient ultrasonic preparation of a water stable cluster-based Cadmium(II) coordination material and highly sensitive fluorescent sensing for biomarkers DPA and 5-HT.

In recent years, a new type of micro-porous material, namely metal organic framework material, has received more and more attention from many basic and industrial fields because these materials possess unique advantages. In this work, through the powerful sonochemical preparation method, a three-dimensional cluster-based CdII-MOFs, {[Cd(abtz)2(H2O)2]·(ClO4)2·H2O}n (1, abtz = 1-(4-aminobenzyl)-1H-1,2,4-triazole) can be quickly synthesized in the facile ultrasonic method. Powder X-ray diffraction (PXRD) measurement confirms that these bulky samples 1 (synthesized on different ultrasonic powers and ultrasonic time conditions) were pure. In addition, ultrasonic chemical time and irradiation power did not change the structure of composites materials 1. SEM and morphological changes of 1 in the ultrasonic synthesis are also determined. Moreover, 1 exhibits good stability, the structure of 1 can be maintained not just in various solvents, and in aqueous environments with pH values from 2 to 12. Photo-luminescent experiment also reveals that complex 1 has the excellent application prospect as highly sensitive sensing material for the biomarker DPA (2,6-pyridine dicarboxylic acid) and 5-HT (5-hydroxytryptamine) through the photo-luminescence "turn-on" and "turn-off" effect, respectively. Further photo-luminescent measurements also show that different ultrasonic powers and ultrasonic time can effectively induce fluorescent sensing enhancement for biomarkers DPA and 5-HT based on the water stable clustered-based cadmium(II) coordination framework.

Sonochemical synthesis of a multi-responsive regenerable water-stable zinc(II) fluorescent probe for highly selective, sensitive and real-time sensing of benzaldehyde, ferric ion and PH.

In this work, a novel water-stable coordination polymer with {44} network topology {[Zn(L)2(NO3)2]}n (1) (L = 4,4'-Bis(triazol-1-ylmethyl)biphenyl) has been synthesized through the hydrothermal and sonochemical approaches. 1 has been characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy, UV-vis absorption spectrum and scanning electron microscopy (SEM). PXRD patterns of the as-synthesized samples 1 have confirmed the purity of the bulky samples. In the sonochemical preparation approaches, different ultrasound irradiation power and ultrasound time were also used in order to investigate the impact factor for morphology and size of nano-structured 1. Photo-luminescence studies have revealed that 1 can efficiently distinguish Fe3+ from Fe2+ and other metal ions. On the other hand, 1 also can exhibit a highly sensitive, excellently selective and real-time detection of benzaldehyde and pH through photo-luminescence quenching process. As for 1, density functional theory (DFT) and time-dependent DFT (TDDFT) theory has been applied to calculate these spectroscopic data, the result agree with the experimental results for detection of benzaldehyde. Photo-luminescent recyclability results indicated 1 can be reused at least five times in the detection process. To the best of our knowledge, this is the first example of a multi-responsive regenerable luminescent sensor for highly selective, sensitive and real-time sensing of Fe3+ over Fe2+, benzaldehyde and pH values.

Solvo-thermal synthesis of a unique alkaline earth-transition Ba-Cd micro-porous coordination framework as hetero-metallic luminescent sensor for Cu2+ and real-time detection of benzaldehyde.

In this work a unique hetero-metallic alkaline earth-transition Ba-Cd luminescent micro-porous metal-organic framework {[BaCd(µ6-tp)1.5(µ2-Cl)(H2O) (DMF)2]·0.75H2O}n (H2tp=terephthalic acid) (1) has been prepared under solvo-thermal conditions. In 1 infinite 1D {Ba-X-Cd} (X=O, Cl) inorganic chains are linked via these full de-pronated tp2- ligands forming a unique 3D I1O2 type micro-porous coordination framework. PXRD patterns of 1 have been determined confirming pure phases of 1. Luminescence investigations suggested that 1 exhibits highly selective and sensitive sensing for trace amounts of benzaldehyde in ethanol, which provides a facile method for real-time detection of benzaldehyde. Meanwhile 1 also exhibits highly selective and sensitive sensing for Cu2+ over other cations with high quenching efficiency Ksv value 1.15×104L·mol-1. As far as we know, 1 represents the first example of alkaline earth-transition hetero-metallic Ba-Cd micro-porous coordination framework as bi-functional luminescent probes for Cu2+ and benzaldehyde.

Heterometallic Alkaline Earth-Lanthanide Ba(II)-La(III) Microporous Metal-Organic Framework as Bifunctional Luminescent Probes of Al(3+) and MnO4(.).

In this work a rigid asymmetrical tricarboxylate ligand p-terphenyl-3,4″,5-tricarboxylic acid (H3L) has been employed, and a unique heterometallic alkaline earth-lanthanide microporous luminescent metal-organic framework (MOF) {[Ba3La0.5(µ3-L)2.5(H2O)3(DMF)]·(3DMF)}n (1·3DMF) (DMF = dimethylformamide) has been isolated under solvothermal conditions. Single-crystal X-ray structural analysis demonstrates that 2D inorganic Ba-O-La connectivity can be observed in 1, which are further bridged via rigid terphenyl backbones of L(3-), forming a unique I(2)O(1)-type microporous luminescent framework. A 1D microporous channel with dimensionality of 9.151(3) Å × 10.098(1) Å can be observed along the crystallographic a axis. PXRD patterns have been investigated indicating pure phases of 1. The luminescence explorations demonstrated that 1 exhibits highly selective and sensitive sensing for Al(3+) over other cations with high quenching efficiency Ksv value of 1.445 × 10(4) L·mol(-1) and low detection limit (1.11 µM (S/N = 3)). Meanwhile 1 also exhibits highly selective and sensitive sensing for MnO4(-) over other anions with quenching efficiency Ksv = 7.73 × 10(3) L·mol(-1) and low detection limit (0.28 µM (S/N = 3)). It is noted that, when different concentrations of MnO4(-) solutions (0.5 to 100 µM) were dropped into the suspension of 1, the bright blue luminescence of the suspension observed under UV light can gradually change into pink color, indicating visually luminescent sensing, which makes the detection process of MnO4(-) more convenient in practical. The result also reveals that 1 represents the first example of bifunctional heterometallic alkaline earth-lanthanide MOF-based luminescent probes for selectively detecting Al(3+) and MnO4(-) in the water solutions.

Synthesis, characterization and biological activity of lanthanum(III) complexes containing 2-methylene-1,10-phenanthroline units bridged by aliphatic diamines.

Two novel lanthanum(III) complexes containing 2-methylene-1,10-phenanthroline units bridged by aliphatic diamines were synthesized and characterized by elemental analysis, IR, NMR, thermal analysis and conductance measurements. They have been assayed for anticancer activity in vitro against HL-60 (human leukocytoma) cells, PC-3MIE8 (human prostate carcinoma) cells, BGC-823 (human stomach carcinoma) cells, MDA-MB-435 (human galactophore carcinoma) cells, Bel-7402 (human liver carcinoma) cells, and Hela (human cervix carcinoma) cells. The results show that the two complexes exhibit good cytotoxic activities against different cell lines in general, especially more effective than cisplatin against Bel-7402, BGC-823 and MDA-MB-435 cell lines. DNA-binding studies indicate that, besides the intercalation, the complexes bind to DNA by the other interaction(s), which might be responsible for the production of more compact DNA, coinciding with more A-like feature of DNA as suggested by CD spectra.