A Zn-coordination polymer for the quantitative and selective colorimetric detection of residual tetracycline in aqueous solution and urine.

A one-step solvothermal synthesis provides a functional crystalline one-dimensional Zn-coordination polymer (Zn-CP) with excellent stability in aqueous solution over a wide range of temperature and pH. Zn-CP is a rapid, highly sensitive and selective sensor for detecting tetracycline (TC). Quantitative TC detection is based on the ratio of fluorescence intensities I530/I420, with a limit of detection (LOD) of 5.51 nM in aqueous solution and 47.17 nM in human urine. The characteristics of colorimetric TC sensing by Zn-CP are highly favorable for application because the color of Zn-CP changes in the visible part of the spectrum from blue-purple to yellow-green upon addition of TC. Conversion of these colors into an RGB signal is simply achieved with an app for the smart phone and provides LODs of 8.04 nM and 0.13 µM TC in water and urine, respectively. Our suggested sensing mechanisms assume that the fluorescence intensity of Zn-CP@TC at 530 nm is enhanced by energy transfer of Zn-CP to TC, while the fluorescence of Zn-CP at 420 nm is quenched by photoinduced electron transfer (PET) from TC to the organic ligand in Zn-CP. These fluorescence properties make Zn-CP a convenient, low-cost, rapid and green detection device for monitoring TC under physiological conditions and in aqueous media.

Structures from MnX2 and proline: isomorphous racemic compounds and a series of chiral non-isomorphous chain polymers.

Reactions of manganese(II) chloride, bromide and iodide with proline as an enantiopure and racemic ligand result in six crystalline solids for which diffraction experiments have been performed at 100 K. For two of these compounds, crystal structures at ambient temperature had been reported previously. The most surprising outcome of our systematic comparison lies in the role of chirality: with enantiopure proline three different coordination polymers have been obtained, whereas racemic proline yields isomorphous mononuclear complexes under the same reaction conditions.

Unexpected proline coordination in the copper chain polymer [Cu(µ-Cl)2(µ-DL-proline-κ²O:O')]¹∞.

In catena-poly[copper(II)-di-µ-chlorido-µ-proline-κ(2)O:O'], [CuCl2(C5H9NO2)]n, two symmetry-independent metal cations adopt distorted octahedral coordination, typical for d(9) Jahn-Teller systems. Each chloride bridge is involved in both a short and a very long interaction with a Cu(II) centre. The centrosymmetric crystal structure contains homochiral chains of opposite handedness which extend along the shortest lattice parameter (i.e. a). The O:O'-bridging coordination mode of proline, although a common motif for such complexes in general, is remarkable for Cu(II); the vast majority of amino acid derivatives of this cation are characterized by N,O-chelation.

One- and two-dimensional polymers from proline and calcium bromide.

Reactions of calcium bromide with enantiopure and racemic proline in aqueous solution lead to two solids in which the zwitterionic amino acid acts as a bridging ligand between neighbouring cations. Depending on the chirality of the amino acid, topologically very different products are obtained. With racemic proline, bromide acts as a simple uncoordinated counter-anion for the cationic heterochiral chains in catena-poly[[aquacalcium(II)]-µ-aqua-µ3-DL-proline-µ2-DL-proline], {[Ca(C5H9NO2)2(H2O)2]Br2}n. In agreement with chemical intuition, only carboxylate and aqua O atoms coordinate the alkaline earth cation in a low-symmetry arrangement. In contrast, L-proline affords the two-dimensional network poly[dibromidobis(µ2-L-proline)calcium(II)], [CaBr2(C5H9NO2)2]n, with an unexpected CaBr2 unit in a more regular coordination sphere.

Aluminium alkyl complexes supported by [OSSO] type bisphenolato ligands: synthesis, characterization and living polymerization of rac-lactide.

Aluminium alkyl complexes [(OSSO)AlR](1-3: R = Me, Et) were isolated in good yields from the protonolysis reaction of AlR3 with the corresponding tetradentate 1,omega-dithiaalkanediyl-bridged bisphenols (1,4-dithiabutanediyl-bis(6-tert-butyl-4-methylphenol), etbmpH2; ortho-xylylenedithio-bis(6-tert-butyl-4-methylphenol), xytbmpH2). The monomeric structures of all three complexes were confirmed by X-ray diffraction studies. Complexes 1 and 2 have an isotypic packing arrangement. The aluminium center is coordinated by the etbmp ligand and one alkyl group with distorted trigonal bipyramidal geometry. Complex 3 shows Cs symmetry with square pyramidal geometry around the metal center. Substitution reaction of complex 1 with trityl alcohol gave the monomeric alkoxide complex [(etbmp)Al(OCPh3)] 4, which has a similar trigonal bipyramidal geometry around the aluminium atom as complex 1. In the presence of isopropanol, complexes 1-3 initiated the living ring-opening polymerization of rac-lactide (PDI = 1.03-1.06, Mw/Mn). The ligand structure influenced the tacticity of the obtained polymer, with complex 3 giving heterotactic-enriched polylactides.