An ultra-sensitive selective fluorescent sensor based on a 3D zinc-tetracarboxylic framework for the detection and enrichment of trace Cu2+ in aqueous media.

Herein, a novel and fluorescent zinc-organic framework sensor [Zn3(µ3-Hbptc)2(µ2-4,4'-bpy)2(H2O)4]n·2nH2O (1) (H4bptc = 2,3,3',4'-biphenyl tetracarboxylic acid, 4,4'-bpy = 4,4'-bipyridine) is synthesized and characterized, demonstrating its excellent fluorescence performance for Cu2+ detection and the enrichment of Cu2+ in aqueous media. The fluorescence intensity of 1 can be selectively quenched by Cu2+ in a linear range of Cu2+ concentrations of 0-0.7 µM. The limit of detection (LOD) value is as low as 32.4 nM, which is superior to those of most of the fluorescent sensors based on metal-organic frameworks (MOFs). It is also far below the maximum allowable concentration of Cu2+ in drinking water as defined by the U.S. Environmental Protection Agency (EPA) and the World Health Organization (WHO), so it is employed for the detection of Cu2+ in actual water samples. More importantly, the nature of the interaction between the active coordination site (COO-) of 1 and Cu2+ determines the quenching mechanism, that is Cu2+ in the analyte is captured by MOF 1, which has been investigated by ICP, luminescence, UV-vis, XPS, and lifetime studies. Besides, the chemosensor shows regeneration performance without the loss of performance in five consecutive cycles. So MOF 1 is a simple and convenient probe used not only for the rapid detection but also for the enrichment of trace amounts of Cu2+ in aqueous media, and the application can be further extended to a variety of environmental and biological analysis processes.

Luminescent and magnetic bifunctional coordination complex based on a chiral tartaric acid derivative and europium.

A new mononuclear europium complex incorporating the (+)-di-p-toluoyl-D-tartaric acid (D-H2DTTA) ligand, namely, catena-poly[tris{µ2-3-carboxy-2,3-bis[(4-methylphenyl)carbonyloxy]propanoato}tris(methanol)europium(III)], [Eu(C20H17O8)3(CH3OH)3]n, (I), has been synthesized and characterized by IR spectroscopy, elemental analysis, powder X-ray diffraction and single-crystal X-ray diffraction analysis. The structure analysis indicates that complex (I) crystallizes in the trigonal space group R3 and exhibits an infinite one-dimensional chain structure, in which the Eu3+ ion is surrounded by six O atoms from six D-HDTTA- ligands and three O atoms from three coordinated methanol molecules, thus forming a tricapped trigonal prism geometry. The D-H2DTTA ligand is partially deprotonated and adopts a µ1,6-coordination mode via two carboxylate groups to link adjacent Eu3+ ions, affording an infinite one-dimensional propeller-shaped coordination polymer chain along the c axis, with an Eu...Eu distance of 7.622 (1) Å. Moreover, C-H...π interactions lead to the formation of helical chains running along the c axis and the whole structure displays a snowflake pattern in the ab plane. The circular dichroism spectrum confirms the chirality of complex (I). The solid-state photoluminescence properties were also investigated at room temperature and (I) exhibits characteristic red emission bands derived from the Eu3+ ion (CIE 0.63, 0.32), with a reasonably long lifetime of 0.394 ms, indicating effective energy transfer from the ligand to the metal centre. In addition, a magnetic investigation reveals single-ion magnetic behaviour. The spin-orbit coupling parameter (λ) between the ground and excited states is fitted to be 360 (2) cm-1 through Zeeman perturbation. Therefore, complex (I) may be regarded as a chiral optical-magneto bifunctional material.

Three chiral one-dimensional lanthanide-ditoluoyl-tartrate bifunctional polymers exhibiting luminescence and magnetic behaviors.

Since Ln-CPs have excellent optical properties (higher color purity, longer fluorescence lifetime and higher quantum yield) and magnetic properties, it is of great significance to prepare dual magneto-optical materials based on Ln(iii). Herein, we obtained three versatile Ln-CPs, [Ln(HDTTA)3(CH3OH)3] n , derived from reactions of lanthanide salts (Ln = Tb 1, Dy 2, Ho 3) and a chiral and flexible ligand, namely, (+)-di-p-toluoyl-d-tartaric acid (d-H2DTTA) in a methanol-water solution, at room temperature and pressure. The structures of these compounds have been characterized by single crystal and powder X-ray diffraction, infrared spectroscopy, elemental analyses and thermogravimetric analyses. Complexes 1-3 are isomorphic, crystallizing in the chiral trigonal R3 space group with the linkage of Ln3+ ions and featuring 1D propeller chain structures. The circular dichroism spectra confirm that the complexes maintain the chirality from the ligands. Furthermore, the luminescent and magnetic properties have been investigated, relying on intrinsic properties of the lanthanide ions. The photoluminescence measurements indicate that 1, 2 and 3 show strong green, white and blue emission bands with CIE chromaticity coordinates of (0.32, 0.56), (0.29, 0.26) and (0.21, 0.12), respectively. The decay lifetime curve of 1 shows the exponential decay with long lifetime of 1.169 ms and the relative quantum yield for 1 was 19.31%. In addition, the magnetic properties of complexes 1-3 have been investigated by measuring the magnetic susceptibility in the temperature range of 2-300 K. They are all dominated by spin-orbit coupling and ligand field perturbation, and the exchange coupling between Ln3+ ions is almost negligible. Therefore, complexes 1-3 are promising chiral, optical and magnetic multifunctional materials.

[Compositional characteristics and roles of soil mineral substances in depressions between hills in karst region].

Based on the investigation and analysis of seven soil mineral substance variables, nine vegetation factors, four topographical factors, and ten soil physicochemical factors in the 200 m x 40 m dynamic monitoring plots in farmland, forest plantation, secondary forest, and primary forest in the depressions between hills in karst region, and by using traditional statistical analysis, principal component analysis (PCA), and canonical correlation analysis (CCA), this paper studied the compositional characteristics and roles of soil mineral substances as well as the coupling relationships between the mineral substances and the vegetation, topography, and other soil properties. In the depressions, soil mineral substances were mainly composed of SiO2, Al2O3, K2O, and Fe2O3, whose contents were obviously lower than the mean background values of the soils in the world and in the zonal red soils at the same latitudes. The soil CaO and MgO contents were at medium level, while the soil MnO content was very low. The composition of soil mineral substances and their variation degrees varied with the ecosystems, and the soil development degree also varied. There was a positive correlation between vegetation origin and soil origin, suggesting the potential risk of rock desertification. Due to the high landscape heterogeneity of the four ecosystems, PCA didn't show good effect in lowering dimension. In all of the four ecosystems, soil mineral substances were the main affecting factors, and had very close relationships with vegetation, topography, and other soil properties. Especially for SiO2, CaO, and MnO, they mainly affected the vegetation species diversity and the soil organic matter, total nitrogen, and total potassium. This study indicated that soil mineral substances were the one of the factors limiting the soil fertility and vegetation growth in the depressions between hills in karst region. To effectively use the soil mineral resources and rationally apply mineral nutrients would have significances in the restoration and reconstruction of karst degraded ecosystems.