Synthesis and catalytic performance of wood cellulose nanofibers grafted with polylactic acid in rare-earth complexes based on tetrazole carboxylic acids.

Stannous octanoate [Sn(Oct)2] and 4-dimethylamino pyridine (DMAP) were used to catalyze the synthesis of amphiphilic cellulose-based graft copolymers, but the acute toxicity of tin ions and DMAP prompts the need for the application of less harmful catalysts. Herein, green catalyst complexes 1-3 [M(H0.5L)2(H2O)5]·2(H2O) (M = Sm, 1; M = Nd, 2; M = Eu, 3; H2L = 4-(3-(tetrazol-5-yl)pyridin-5-yl)benzoic acid) were synthesized, and their properties were systematically investigated. Single-crystal X-ray diffraction showed that the complexes possessed a zero-dimensional structure, while the thermogravimetry and scanning electron microscopy results confirmed their stability after heating at 110 °C for 10 h. Using complexes 1-3 and DMAP as the catalysts, CNFs were grafted with l-lactide via homogeneous ring-opening polymerization to form wood cellulose nanofibers grafted with l-lactide (WGLAs), and the effects of the ratio of wood cellulose nanofibers (WCNFs) to l-lactide ([AGU]/[LA]) and catalyst dosage were studied. The polymerization followed the coordination-insertion mechanism. Under comparable reaction conditions, the grafting ratio of WGLA-1 reached 84.7 %, and the grafting ratio of complex 1 was found to be higher than those achieved using DMAP. WGLAs demonstrated good thermal stability without cytotoxicity, and the residual catalysts in the WGLAs exhibited fluorescence characteristics. Overall, amphiphilic cellulose-based materials with fluorescence emission offered a promising modification strategy to prepare high-performance polymer composites for agriculture and biomedical application.

Two 6/10-connected Cu12S6 cluster-based organic frameworks: crystal structure and proton conduction.

Nowadays, although the exploration of proton conductive materials has ranged from traditional sulfonated polymers to novel crystalline solid materials such as MOFs, COFs, and HOFs, research on crystalline cluster-based organic framework materials is very limited. Here, a pair of homologues Cu(i)-based organic framework containing a Cu12S6 cluster, [Cu12(MES)6(H2O)3]n (1) and {[Cu12(MPS)6(H2O)4]·6H2O}n (2) (H2MES = 2-mercaptoethanesulfonate acid and H2MPS = 2-mercaptoethanesulfonate acid), were hydrothermally synthesized under the same conditions and fully investigated for their proton conduction. Their structures were characterized by means of single-crystal X-ray diffraction, elemental analysis, thermogravimetric analyses, and PXRD measurements. The two MOFs show significant structural differences in the topological fashions. MOF 1 has a three-dimensional network and can be simplified into two topology types: a 10-connected gpu structure with a Schläfli symbol (312·426·57) and a 3,12-connected new topology with a point symbol {3·42}2{310·418·519·614·74·9}. MOF 2 also has a three-dimensional framework and topology as a 6-connected pcu primitive cubic network with a Schläfli symbol {412·63}. The two MOFs show different proton conduction parameters, but both indicate temperature-dependent proton conductive features. Intriguingly, the two MOFs exhibit high water stability and their proton conductivities are 3.63 × 10-5 and 2.75 × 10-5 S cm-1 under 333 K and 98% RH, respectively. The suggested mechanism for the synthesis for 1 and 2, and their proton conductivity performance comparison has been discussed in detail. In addition, Hirshfeld surface and fingerprint analysis on the two MOFs were computed to compare contacts between the molecules, which is essential for analyzing the relationships between their hydrogen bonds and proton conductivity properties.

Synthesis of Mn-MOFs loaded zinc phosphate composite for water-based acrylic coatings with durable anticorrosion performance on mild steel.

A new metal-organic framework (MOF) compound [Mn2(2,2'-bca)2(H2O)2] n (Mn-MOFs) was successfully synthesized by solvothermal method, and Mn-MOFs@Zn material was prepared by loading zinc phosphate onto Mn-MOFs by ball milling, then Mn-MOFs@Zn was added to the water-based acrylic paint to prepare Mn-MOFs@Zn@acrylic coating. The AC impedance test results showed Mn-MOFs@Zn@acrylic coating has higher corrosion inhibition performance and stability to mild steel when compared with blank coating. The impedance modulus of the blank coating in the low frequency region decreased by 90%, and the R ct showed a trend of first increasing and then decreasing over time, the maximum R ct was only 303.8 Ω, which was only Mn-MOFs@Zn@acrylic coating one-seventh of the R ct value. The artificial scratch experiment showed that the Mn-MOFs@Zn@acrylic coating only slightly corrodes at the scratches, because Mn-MOFs@Zn material made the coating a self-repairing function and improved the durable anticorrosion performance of the acrylic coating.

Novel 2-pyridinecarboxaldehyde thiosemicarbazones Ga(III) complexes with a high antiproliferative activity by promoting apoptosis and inhibiting cell cycle.

Two types of 2-pyridinecarboxaldehyde thiosemicarbazones Ga(III) complexes, which are 2:1 and 1:1 ligand/Ga(III) complexes, were synthesized and determined by X-ray single crystal diffraction. The antiproliferative activity of these Ga(III) complexes have been examined to illuminate the structure-activity relationships essential to form Ga(III) complexes with remarkable anticancer activity. In addition, Ga(III) complexes where the metal/ligand ratio was 1:1 (C4) had observably higher antiproliferative activity than 1:2 (C3). Ga(III) complexes caused a marked increase of caspase-3 and 9 activity in NCI-H460 cells compared to the metal free ligand. Caspase activation was somewhat mediated by the release of Cyt C from mitochondria after incubation with selected agents. Both types of Ga(III) complexes showed more effective in inhibition of the G1/S transition than the ligand alone.

A sixfold interpenetrated microporous MOF constructed from heterometallic tetranuclear cluster exhibiting selective gas adsorption.

A sixfold interpenetrated microporous MOF has been constructed from a heterometallic tetranuclear cluster. The framework contains two types of 1D micro-channels along different directions. Moreover, this compound exhibits high selective gas sorption for H(2) over N(2).

Reversible shuttle action upon dehydration and rehydration processes in cationic coordinatively-bonded (4,4) square-grid nets threaded by supramolecular bonded anions, {[Cu(II)(4,4'-bpy)2(H2O)][Cu(II)(2-pySO3)3](NO3)}·H2O.

{[Cu(II)(4,4'-bpy)(2)(H(2)O)][Cu(II)(2-pySO(3))(3)](NO(3))}·H(2)O, obtained serendipitously by the reaction of the constituents in water, consists of parallel coordinatively bonded cationic (4,4) corrugated square-grids polymer of {[Cu(II)(4,4'-bpy)(2)(H(2)O)](2+)}(n) threaded by π-π and H-bonded supramolecular chains of [Cu(II)(2-pySO(3))(3)](-) through the open squares. A single-crystal to single-crystal transformation takes place upon removal of the noncoordinated water by controlled heating. The resulting structure exhibits a rearrangement of the coordination of the copper atoms in the grids, where the Cu-H(2)O bond is elongated from 2.250(3) to 2.628(3) Å while the Cu-NO(3) is shortened from 3.122(3) to 2.796(1) Å. This process is reversible as demonstrated by the single crystal structure after rehydration with corresponding bond distances of 2.224(3) and 3.152(3) Å. Such a cooperative effect may be associated with the Jahn-Teller distortion of the copper(II) ion accompanying the shuttle action of the hydrogen-bonded water and nitrate moiety.

Crystalline-state guest-exchange and gas-adsorption phenomenon for a "soft" supramolecular porous framework stacking by a rigid linear coordination polymer.

A 1D rigid, linear coordination polymer, (4,4'-bipyridine)(2-pyridylsulfonate)copper, has been applied for the controlled-assembly of a new porous host that generates 1D channels by an interdigitated packing through the recognition of hydrogen bonding and pi-pi stacking interactions. The porous structure is architecturally robust when it reversibly uptakes water molecules and exchanges guest small molecules (MeOH, i-PrOH) from solution as determined by single-crystal-to-single-crystal transformation studies. Moreover, the open-channel solid displays irreversible benzene and toluene vapor sorption behaviors attributed to a widening of the channel cross-section that fetters the larger guest molecules, resulting from the dynamic, "soft" supramolecular framework.