We investigated the gelation of a hydrophilic polymer with metal-coordination units (HPMC) and metal ions (Pd or Au). Gelation proceeded by addition of an HPMC solution in -methyl-2-pyrrolidone (NMP) to a metal ion aqueous solution. An increase in the composition ratio of the metal-coordination units from 10 mol% to 34 mol% (HPMC-34) increased the cross-linking rate with Au. Cross-linking immediately occurred after dropwise addition of an HPMC-34 solution to the Au solution, generating the separation between the phases of HPMC-34 and Au. The cross-linking of Au proceeded from the surface to the inside of the HPMC-34 droplets, affording spherical gels. In contrast, a decrease in the ratio of metal-coordination units from 10 mol% to 4 mol% (HPMC-4) decreased the Pd cross-linking rate. The cross-linking occurred gradually and the gels extended to the bottom of the vessel, forming fibrous gels. On the basis of the mechanism for the formation of gels with different morphologies, the gelation of HPMC-34 and Au provided nanosheets via gelation at the interface between the Au solution and the HPMC-34 solution. The gelation of HPMC-4 and Pd afforded nanofibers by a facile method, i.e., dropwise addition of the HPMC-4 solution to the Pd solution. These results demonstrated that changing the composition ratio of the metal-coordination units in HPMC can control the gelation behavior, resulting in different types of nanomaterials.
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http://dx.doi.org/10.3390/gels8070435 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Department of Chemistry, Graduate School of Sciences, Tokyo Metropolitan University, Hachioji, 192-0397, Japan.
Stable neutral metal radicaloid complexes have been synthesized from a modified tetrapyrrolic pigment, bilatriene, with iridium(I) and rhodium(I) cyclooctadiene (COD) synthons. The bilatriene skeleton contains α-linked conjugated pyrrole units, whereas an N-confused analogue used in this work possesses β-linked pyrrole moieties at the terminal, demonstrating a unique metal binding capability. Unprecedentedly, the metal-COD cations are accommodated at the outer nitrogen sites, which induced the formation of open-shell metal-radicaloid species.
View Article and Find Full Text PDFInt J Mol Sci
October 2024
Laboratory for Chemical and Biological Crystallography, Division of Physical Chemistry, Ruđer Bošković Institute, Bijenička Cesta 54, 10000 Zagreb, Croatia.
Herein, the presented results show that previously studied DNA/RNA-interacting bis-imidazole-calix[4]arene systems can, in aqueous solutions, efficiently bind a series of biorelevant transition metal cations by coordination with the two imidazole arms at the small rim of their macrocyclic basket. The SCXRD and NMR results structurally characterised the complexes formed by referent bis-imidazole-calix[4]arene with Cu and Zn. In solid-state (crystal), the bis-anilino derivative/Cu complex, only upon exposure to the air, undergoes intramolecular dehydrogenative coupling of two neighbouring aniline units, yielding an azo bridge at the large rim of the calix[4]arene basket.
View Article and Find Full Text PDFSmall
December 2024
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China.
In nature, active Mn -ligand complexes produced by laccase catalyzed oxidation can act as the low-molecular mass, diffusible redox mediators to oxidize the phenolic substrates overcoming the limitations of natural enzymes. Learning from the metal-ligand coordination of natural functional units, high-valence Mn metal-organic framework (Mn MOF) is constructed to simulate the catalysis in natural mediator system. Benefiting from the characteristics of nanoscale size, rich metal coordination unsaturated sites, and mixed valence state dominated by Mn(III), Nano Mn(III)-TP exhibits superior laccase-mimicking activity, whose V (maximal reaction rate) is much higher than that of natural laccase.
View Article and Find Full Text PDFChemistry
December 2024
Department of Chemistry, University of Guelph, Guelph, ON, N1G 2W1, Canada.
A new paramagnetic ligand, 4-(2'-4-(2''-furyl)-pyrimidyl)-1,2,3,5-dithiadiazolyl (furylpymDTDA) and three transition metal coordination complexes, M(hfac)(furylpymDTDA) M=Mn, Co, Ni; hfac=1,1,1,5,5,5-hexafluoroacetylacetonato-), are reported. The solid-state structures are influenced by the geometry of the coordination sphere of the M(II) centers: trigonal (Mn) vs. octahedral (Co and Ni).
View Article and Find Full Text PDFJ Chem Inf Model
September 2024
Center for Biosystems Dynamics Research, RIKEN, 1-7-22 Suehiro-cho, Tsurumi-ku, Yokohama, Kanagawa 230-0045, Japan.
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