Organic ligands regulate the environmental impacts of metal-organic frameworks on nitrogen-fixing bacterium Azotobacter vinelandii.

Metal-organic frameworks (MOFs) are rapidly developed materials with fantastic properties and wide applications. The increasing studies highlighted the potential threats of MOF materials to the environment. Comparing to the limited species of metal elements, the organic ligands have much higher diversity, but the influence of organic ligands on the environmental impacts of MOFs has not been revealed. Herein, we synthesized three Cu-MOFs with different organic ligands, namely Cu-BDC (1,4-terephthalic acid), Cu-IM (imidazole) and Cu-TATB (2,4,6-tris(4-carboxyphenyl)- 1,3,5-triazine), and evaluated their environmental toxicity to the nitrogen-fixing bacterium Azotobacter vinelandii. Cu-BDC inhibited the bacterial growth at lower concentrations than Cu-IM and Cu-TATB. The transcriptomes suggested the changes of membrane components by Cu-MOFs, consistent with the membrane leakage and cell wall damages. Cu-MOFs inhibited the nitrogen fixation activity through energy metabolism disturbance according to Gene Ontology functional annotation of ATP binding, Ca2+Mg2+-ATPase activity and ATP content. Only Cu-IM lowered the nitrogen fixation related nif genes, and affected the ribosome, purine metabolism and oxidative phosphorylation pathways. Otherwise, Cu-BDC and Cu-TATB mainly affected the flagellar assemblies and bacterial chemotaxis pathways. Our results collectively indicated that organic ligands regulated the environmental toxicity of MOFs through different metabolism pathways.

Stimulating effects of reduced graphene oxide on the growth and nitrogen fixation activity of nitrogen-fixing bacterium Azotobacter chroococcum.

Graphene has found important applications in various areas and hundred tons of graphene materials are annually produced. It is crucial to investigate both the negative and positive environmental effects of graphene materials to ensure the safe applications and develop environmental applications. In this study, we reported the stimulating effects of reduced graphene oxide (RGO) to nitrogen-fixing bacterium Azotobacter chroococcum. RGO stimulated the cell growth of A. chroococcum at 0.010-0.500 mg/mL according to the growth curves and the colony-forming unit (CFU) increases. RGO wrapped over the A. chroococcum cells without inducing ultrastructural changes. RGO decreased the leakage of cell membrane, but slight oxidative stress was observed in A. chroococcum. RGO promoted the nitrogen fixation activity of A. chroococcum at 0.5 mg/mL according to both isotope dilution method and acetylene reduction activity measurements. Consequently, the increases of soil nitrogen contents were evidenced, in particular about 30% increase of organic nitrogen occurred at 0.5 mg/mL of RGO. In addition, RGO might possibly benefit the plant growth through enhancing the indoleacetic acid production of A. chroococcum. These results highlighted the positive environmental effects of graphene materials to nitrogen-fixing bacteria in nitrogen cycle.

Toxicity and activity inhibition of metal-organic framework MOF-199 to nitrogen-fixing bacterium Azotobacter vinelandii.

Metal-organic framework (MOF) materials with fantastic properties have found important applications in various areas. Learning the lessons from plastics and microplastics, it is urgent to investigate the environmental impacts of emerging materials to avoid potential pollution. However, the environmental toxicity and risks of MOF materials are seldom reported. Herein, we studied the toxicity and activity inhibition of MOF-199 to nitrogen-fixing bacterium Azotobacter vinelandii. MOF-199 significantly suppressed the growth of A. vinelandii and led to cell death at 40 mg/L. MOF-199 penetrated the cell wall and induced the shrinking of bacterial cells. MOF-199 reduced the nitrogen fixation activity of A. vinelandii at 40 mg/L by decreasing the gene nifH levels and inhibiting the Ca2+Mg2+-ATPase activity, which was further confirmed by the changes in oxidative phosphorylation related genes. Complete growth inhibition and activity loss of A. vinelandii occurred at 60 mg/L of MOF-199. The toxicological mechanism of MOF-199 to A. vinelandii was assigned to the oxidative stress, which occurred at 20 mg/L and higher. Both Cu2+ release and particulates themselves contributed to the toxicity of MOF-199 to A. vinelandii. These findings highlighted the environmental hazards and risks of MOF materials to nitrogen-fixing bacteria and nitrogen fixation in the biogeochemical cycle.

Biocompatible zinc gallogermanate persistent luminescent nanoparticles for fast tumor drainage lymph node imaging in vivo.

Tumor drainage lymph node identification and dissection are crucial for the oncological surgery to prevent/delay the recurrence. However, commercial imaging reagents distinguish the lymph nodes by staining them dark, which would be seriously interfered by blood and surrounding tissues. In this study, we reported the Cr3+/Pr3+-doped zinc gallogermanate persistent luminescent nanoparticles (PLNPs) for fast tumor drainage lymph node imaging with high contrast. PLNPs were synthesized by citrate sol-gel method and dispersed in Tween 80 for in vivo applications. PLNPs were well dispersed in water with hydrodynamic radii of 5 nm and emitted strong persistent luminescence at 696 nm upon the irradiation of UV light. The advantage of afterglow imaging over fluorescent imaging of PLNPs was first established after subcutaneous injection to mice with much higher contrast and less interference of autofluorescence. PLNPs quickly migrated to sentinel lymph nodes after the interdermal injection to extremity of mice. The tumor drainage lymph node imaging was achieved within 5 min upon the intratumoral injection to H460 tumor bearing mice and the signal to noise ratio was 462. Due to the lack of targeting moieties, the intravenous injected PLNPs mainly accumulated in liver. There were no statistical changes in serum biochemistry and abnormal histopathological characteristic, indicating the low toxicity of PLNPs. These findings highlighted the great potential of PLNPs as high-performance imaging reagent for lymph node identification.