Separation and purification of five alkaloids from Aconitum duclouxii by counter‐current chromatography

C₁₉‐diterpenoid alkaloids are the main components of Aconitum duclouxii Levl. The process of separation and purification of these compounds in previous studies was tedious and time consuming, requiring multiple chromatographic steps, thus resulted in low recovery and high cost. In the present work, five C₁₉‐diterpenoid alkaloids, namely, benzoylaconine ( 1 ), N‐deethylaconitine ( 2 ), aconitine ( 3 ), deoxyaconitine ( 4 ), and ducloudine A ( 5 ), were efficiently prepared from A. duclouxii Levl (Aconitum L.) by ethyl acetate extraction followed with counter‐current chromatography. In the process of separation, the critical conditions of counter‐current chromatography were optimized. The two‐phase solvent system composed of n‐hexane/ethyl acetate/methanol/water/NH₃·H₂O (25%) (1:1:1:1:0.1, v/v) was selected and 148.2 mg of 1 , 24.1 mg of 2 , 250.6 mg of 3 , 73.9 mg of 4, and 31.4 mg of 5 were obtained from 1 g total Aconitum alkaloids extract, respectively, in a single run within 4 h. Their purities were found to be 98.4, 97.2, 98.2, 96.8, and 96.6%, respectively, by ultra‐high performance liquid chromatography analysis. The presented separation and purification method was simple, fast, and efficient, and the obtained highly pure alkaloids are suitable for biochemical and toxicological investigation.     

A three‐dimensional cadmium(II) coordination polymer with unequal homochiral double‐stranded concentric helical chains

A homochiral helical three‐dimensional coordination polymer, poly[[(μ₂‐acetato‐κ³O,O′:O)(hydroxido‐κO)(μ₄‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁵N¹,O:N²:N⁴:N⁵)(μ₃‐5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ido‐κ⁴N¹,O:N²:N⁴:N⁵)dicadmium(II)] 0.75‐hydrate], {[Cd₂(C₇H₅N₆O)₂(CH₃COO)(OH)]·0.75H₂O}_n, was synthesized by the reaction of cadmium acetate, N‐(1H‐tetrazol‐5‐yl)isonicotinamide (H‐NTIA), ethanol and H₂O under hydrothermal conditions. The asymmetric unit contains two crystallographically independent Cd^II cations, two deprotonated 5‐nicotinamido‐1H‐1,2,3,4‐tetrazol‐1‐ide (NTIA⁻) ligands, one acetate anion, one hydroxide anion and three independent partially occupied water sites. The two Cd^II cations, with six‐coordinated octahedral and seven‐coordinated pentagonal bipyramidal geometries are located on general sites. The tetrazole group of one symmetry‐independent NTIA⁻ ligand links one of the independent Cd^II cations into 6₁ helical chains, while the other NTIA⁻ ligand links the other independent Cd^II cations into similar but unequal 6₁ helical chains. These chains, with a pitch of 24.937 (5) Å, intertwine into a double‐stranded helix. Each of the double‐stranded 6₁ helices is further connected to six adjacent helical chains through an acetate μ₂‐O atom and the tetrazole group of the NTIA⁻ ligand into a three‐dimensional framework. The helical channel is occupied by the isonicotinamide groups of NTIA⁻ ligands and two helices are connected to each other through the pyridine N and carbonyl O atoms of isonicotinamide groups. In addition, N—H...O and O—H...N hydrogen bonds exist in the complex.     

A two‐dimensional layered CdII coordination polymer with a three‐dimensional supramolecular architecture incorporating mixed multidentate N‐ and O‐donor ligands

The combination of N‐heterocyclic and multicarboxylate ligands is a good choice for the construction of metal–organic frameworks. In the title coordination polymer, poly[bis{μ₂‐1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole‐κ²N³:N⁴}(μ₄‐butanedioato‐κ⁴O¹:O^1′:O⁴:O^4′)(μ₂‐butanedioato‐κ²O¹:O⁴)dicadmium], [Cd(C₄H₄O₄)(C₉H₈N₆)]_n, each Cd^II ion exhibits an irregular octahedral CdO₄N₂ coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) ligands. Cd^II ions are connected by two kinds of crystallographically independent succinate ligands to generate a two‐dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three‐dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.     

A New Fluorescence Turn-On Probe for Aluminum(III) with High Selectivity and Sensitivity,and its Application to Bioimaging

The development of novel selective probes with high sensitivity for the detection of Al³⁺ is widely considered an important research goal due to the importance of such probes in medicine, living systems and the environment. Here, we describe a new fluorescent probe, N′-(4-diethylamino-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (1), for Al³⁺. Probe 1 was evaluated in a solution of acetonitrile/water (1:1 v/v). Compared with previously reported probes for Al³⁺, probe 1 can be synthesized easily and in high yield. A Job plot confirmed that probe 1 is able to complex Al³⁺ in a 1:1 ratio, and the binding constant was determined to be 4.25×10⁸ m⁻¹. Moreover, the detection limit was as low as 6.7×10⁻⁹ m, suggesting that probe 1 has a high sensitivity. Common coexistent metal ions, such as K⁺, Co²⁺, Ca²⁺, Ba²⁺, Ni²⁺, Pb²⁺, Hg²⁺, Ce²⁺, Zn²⁺, Cd²⁺, Fe³⁺, showed little or no interference in the detection of Al³⁺ in solution, demonstrating the high selectivity of the probe. Finally, the ability of probe 1 to act as a fluorescent probe for Al³⁺ in living systems was evaluated in Gram-negative bacteria, Escherichia coli, and confocal laser scanning microscopy confirmed its utility. The results of this study suggest that 1 has appropriate properties to be developed for application as a fluorescent probe of Al³⁺ for use in biological studies.     

Solvothermal Syntheses,Crystal Structures,and Luminescent Properties of Two New Cadmium(II) Coordination Polymers Based on Rigid / Flexible Dicarboxylate and N,N′‐Bis(4‐pyridyl)‐1,4,5,8‐naphthalenetetracarboxydiimide

In order to investigate the effect of the organic ligands on the structures of coordination polymers, two new cadmium(II) coordination polymers based on the different dicarboxylate ligands, namely [Cd₂(bpdc)₂(DPNDI)₂] · 3H₂O · NMF ( 1 ) and [Cd(obb)(DPNDI)] ( 2 ) [H₂bpdc = biphenyl‐4,4′‐dicarboxylate, H₂obb = 4,4′‐oxybis(benzoic acid), DPNDI = N,N′‐bis(4‐pyridyl)‐1,4,5,8‐naphthalene tetracarboxydiimide, and NMF = N‐methylformamide), were synthesized under solvothermal condition and further characterized. Complex 1 shows a twofold interpenetrated pcu topology. Complex 2 possesses a two‐dimensional (2D) layer structure with –ABCD– stacking sequence. Furthermore, the luminescent properties of complexes 1 and 2 are investigated.     

Syntheses,Structures, and Magnetic Properties of Two Cobalt(II) Metal‐Organic Frameworks Based on Y‐shaped 3,5,4′‐Azobenzenetricarboxylic Acid and Different N‐donor Ligands

Two metal‐organic frameworks, [Co₂(ABTC)(bimh)(OH)] · 2H₂O ( 1 ) and [Co₃(ABTC)₂(dimb)₄]_n ( 2 ) [H₃ABTC = 3,4′,5‐azobenzenetricarboxylic acid, bimh = 1,1′‐(1,4‐hexanediy)bis(imidazole), dimb = 1,4‐bis(1H‐imidazol‐1‐yl)benzene], were prepared under solvothermal conditions and structurally characterized. Complex 1 demonstrates a complicated 3D (3,8)‐connected tfz‐d net with (4³)₂(4⁶.6¹⁷.8⁵) topology. The framework of 2 can be classified as a rare 3D (3,6,6)‐connected net with the Schäfli symbol of (4.6²)₂(4².6¹⁰.8³)(4⁴.6¹⁰.8), and exhibits an intriguing self‐penetrating motif. Meanwhile, the thermal stabilities and magnetic properties for 1 and 2 were also probed.     

A Convenient Synthesis of Pyridophenanthroline Derivatives under Catalyst Free Conditions

A three‐component reaction between an aromatic aldehyde, quinolin‐6‐amine or quinolin‐5‐amine, and tert‐butyl 2,4‐dioxopiperidine‐1‐carboxylate in reflux EtOH gave pyrido phenanthroline derivatives in high yields under catalyst free conditions. The rare C‐H…F hydrogen bond is found in the crystal structure of 6h .     

Two Uranyl Complexes with Pyromellitic Acid. A Heterometallic Complex with U=O–CuII Interaction

Two uranyl complexes based on pyromellitic acid were hydrothermally synthesized, and their X‐ray single‐crystal diffraction structures were determined. Complex [UO₂(Hbtec)]^–(Himd)⁺ · H₂O ( 1 ) (H₄btec = pyromellitic acid, imd = imidazole), is an ionic complex, which shows a typical (4, 4) topological structure in the space. A heterometallic complex, UO₂Cu(btec)(phen) ( 2 ) (phen = 1,10‐phenanthroline) results from the reaction of uranyl nitrate and copper(II) bromide with pyromellitic acid. The structure of complex 2 revealed that the chains of UO₇ and CuO₃N₂ units were connected to each other through the carboxyl groups and U=O–Cu interactions to create a two‐dimensional framework.     

Syntheses,Structures, and Luminescent Properties of d10 Coordination Polymers with 2‐(4‐Carboxyphenyl)‐imidazo[4, 5‐f]‐1, 10‐phenanthroline and 1, 3‐Benzenedicarboxylate Derivatives

Four Zn^II/Cd^II coordination polymers (CPs) based on 2‐(4‐carboxy‐phenyl)imidazo[4, 5‐f]‐1, 10‐phenanthroline (HNCP) and different derivatives of 5‐R‐1, 3‐benzenedicarboxylate (5‐R‐1, 3‐BDC) (R = NO₂, H, OH), [Zn(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 1 ), [Cd(HNCP)(5‐NO₂‐1, 3‐BDC)]_n ( 2 ), [Zn(HNCP)(1, 3‐BDC)(H₂O)₂]_n ( 3 ), and {[Zn(HNCP)(5‐OH‐1, 3‐BDC)(H₂O) · H₂O}_n ( 4 ) were synthesized under hydrothermal conditions. Compounds 1 – 4 were determined by elemental analyses, IR spectroscopy, and single‐crystal and powder X‐ray diffraction. Compounds 1 and 2 are isomorphous, presenting a 4‐connected uninodal (4, 4)‐sql 2D framework with threefold interpenetration, which are further extended into the three‐dimensional (3D) supramolecular architecture through π ··· π stacking interactions between the aryl rings of 5‐NO₂‐1, 3‐BDC. Compared to compound 1 , 3 is obtained by using different reaction temperatures and metal‐ligand ratios, generating a 3D framework with –ABAB– fashion via π ··· π stacking interactions. Compound 4 is a 1D chain, which is further extended into a 3D supramolecular net by hydrogen bonds and π ··· π stacking interactions. The thermogravimetric and fluorescence properties of 1 – 4 were also explored.