1. A new trinuclear cluster-based Cd(II) compound: photocatalytic property and nursing application values on the bacterial infection
Yan Hu, Jiao Ni Des Monomers Polym. 2021 May 31;24(1):173-181. doi: 10.1080/15685551.2021.1935010.
A new Cd(II) coordination polymer with the formula of n (1 NH2-H2bdc = 2-aminoterephthalic acid, Hbtz = 1 H-benzotriazole) was produced and then it was structurally characterized through powder X-ray diffraction (PXRD), the analysis of X-ray single-crystal diffraction, along with elemental analysis (EA). The photocatalytic property investigations indicate that compound 1 exhibits good activity for photodegradation of methyl violet (MV) with 60.7% of MV removal in 40 min under room temperature. Furthermore, the assessment of the compound's treatment activity and nursing application values on the bacterial infection was conducted and its corresponding mechanism was also studied. Evaluation of the in vitro hemolysis of the compound was determined by measuring the degree of red blood cell lysis and hemoglobin release. The effect of new compounds on the relative proliferation rate of L-929 cells was measured by MTT assay. The ELISA detection kit showed that the compound could reduce the TNF-α and IL-1β content released into plasma. Next, the inhibitory activity of the compound on the bacterial survival gene expression was also proved with real-time RT-PCR. The hemolysis rate of the new compound to blood is 3.4%, which is less than the standard 5%, which is non-hemolytic reaction. The compound also has no obvious cytotoxicity and has good cell compatibility.
2. Interesting copper(ii)-assisted transformations of 2-acetylpyridine and 2-benzoylpyridine
Alexandros A Kitos, Constantinos G Efthymiou, Manolis J Manos, Anastasios J Tasiopoulos, Vassilios Nastopoulos, Albert Escuer, Spyros P Perlepes Dalton Trans. 2016 Jan 21;45(3):1063-77. doi: 10.1039/c5dt03912f.
The reactions of various copper(ii) sources with 2-acetylpyridine, (py)(me)CO, and 2-benzoylpyridine, (py)(ph)CO, under strongly basic conditions have been studied and novel ligand transformations have been discovered. Reaction of Cu(ClO4)2·6H2O and (py)(me)CO in the presence of NBu4(n)OMe (1 : 1 : 1) in CHCl3 gave a mixture of [Cu2Cl2(HLA)2](ClO4)2 (1) and [Cu2Cl2(LB)2(ClO4)2] (2), where HLA is 3-hydroxy-1,3-di(pyridin-2-yl)-butane-1-one and LB is the zwitterionic-type ligand 3-hydroxy-1-methyl-3-(pyridin-2-yl)-3H-indolizin-4-ium. The ligand HLA is formed through an aldol reaction-type mechanism, while the formation of LB takes place via an intramolecular nucleophilic attack of the remote 2-pyridyl nitrogen atom on the positive carbonyl carbon of HLA, after the transformation of the latter through deprotonation and dehydration.
3. Dinuclear Metallacycles with Single M-X-M Bridges (X = Cl-, Br-; M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II)): Strong Antiferromagnetic Superexchange Interactions
Daniel L Reger, Andrea E Pascui, Elizabeth A Foley, Mark D Smith, Julia Jezierska, Agnieszka Wojciechowska, Sebastian A Stoian, Andrew Ozarowski Inorg Chem. 2017 Mar 6;56(5):2884-2901. doi: 10.1021/acs.inorgchem.6b02933. Epub 2017 Feb 20.
A series of monochloride-bridged, dinuclear metallacycles of the general formula [M2(μ-Cl)(μ-L)2](ClO4)3 have been prepared using the third-generation, ditopic bis(pyrazolyl)methane ligands L = m-bis[bis(1-pyrazolyl)methyl]benzene (Lm), M = Cu(II), Zn(II), and L = m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*), M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II). These complexes were synthesized from the direct reactions of M(ClO4)2·6H2O, MCl2, and the ligand, Lm or Lm*, in the appropriate stoichiometric amounts. Three analogous complexes of the formula [M2(μ-Cl)(μ-L)2](BF4)3, L = Lm, M = Cu(II), and L = Lm*, M = Co(II), Cu(II), were prepared from the reaction of [M2(μ-F)(μ-L)2](BF4)3 and (CH3)3SiCl. The bromide-bridged complex [Cu2(μ-Br)(μ-Lm*)2](ClO4)3 was prepared by the first method. Three acyclic complexes, [Co2(μ-Lm)μ-Cl4], [Co2(μ-Lm*)Cl4], and [Co2(μ-Lm*)Br4], were also prepared. The structures of all [M2(μ-X)(μ-L)2]3+ (X = Cl-, Br-) complexes have two ditopic bis(pyrazolyl)methane ligands bridging two metals in a metallacyclic arrangement. The fifth coordination site of the distorted trigonal bipyramidal metal centers is filled by a bridging halide ligand that has an unusual linear or nearly linear M-X-M angle. The NMR spectra of [Zn2(μ-Cl)(μ-Lm*)2](ClO4)3 and especially [Cd2(μ-Cl)(μ-Lm*)2](ClO4)3 demonstrate that the metallacycle structure is maintained in solution. Solid state magnetic susceptibility data for the copper(II) compounds show very strong antiferromagnetic exchange interactions, with -J values of 536 cm-1 for [Cu2(μ-Cl)(μ-Lm)2](ClO4)3·xCH3CN, 720 cm-1 for [Cu2(μ-Cl)(μ-Lm*)2](ClO4)3, and 945 cm-1 for [Cu2(μ-Br)(μ-Lm*)2](ClO4)3·2CH3CN. Smaller but still substantial antiferromagnetic interactions are observed with other first row transition metals, with -J values of 98 cm-1 for [Ni2(μ-Cl)(μ-Lm*)2](ClO4)3, 55 cm-1 for [Co2(μ-Cl)(μ-Lm*)2](ClO4)3, and 34 cm-1 for [Fe2(μ-Cl)(μ-Lm*)2](ClO4)3. EPR spectra of [Cu2(μ-Cl)(μ-Lm*)2](BF4)3 confirm the dz2 ground state of copper(II). In addition, the sign of the zero-field splitting parameter D was determined to be positive for [Cu2(μ-F)(μ-Lm*)2](BF4)3. Electronic spectra of the copper(II) complexes as well as Mössbauer spectra of the iron(II) complexes were also studied in relation with the EPR spectra and magnetic properties, respectively. Density functional theory calculations were performed using ORCA, and exchange integral values were obtained that parallel but are slightly higher than the experimental values by about 30%.
