Ionic Radius Dependent Kinetic Behavior for the Self-Assemblyand Chiral Amplification of Lanthanide Tetrahedral Cages

Comprehensive Summary Understanding the kinetic process during the self-assembly and chiral amplification of metal-organic polyhedra(MOPs)is critical for the rational preparation of chiral MOPs.Herein,we report the ionic radius dependent kinetic processes for the self-assembly and chiral amplification of Ln4L4-type(Ln,Lanthanides;L,ligand)lanthanide tetrahedral cages.The chiral Eu4(LR)4 tetrahedral cage is structurally characterized by nuclear magnetic resonance(NMR),electrospray ionization time-of-flight mass spectrometry(ESI-TOF-MS),and single crystal X-ray diffraction.Kinetic study on the stereo-controlled self-assembly of circularly polarized luminescence(CPL)-active Ln4(LR)4(Ln=LaIII,PrIII and EuIII)tetrahedra manifests that the larger ionic radius of Ln leads to faster assembly rates.Mixed-ligand cage assembly experiments with chiral LR/S,achiral Lac and Ln(1:3:4 molar ratio)reveal that the self-assembly and chiral amplification occur synchronously for the LaIII and PrIII cages,while two distinct steps,i.e.,first self-assembly and then chiral amplification,are observed for the EuIII cage.Such distinct kinetic behavior is attributed to different ligands exchange rates among the mixed-ligand Ln4L4 cages.This work provides fundamental guidance for fabrication and property-optimization of chiral lanthanide-based molecular materials.

Short-term efficacy of microwave ablation in the treatment of liver cancer and its effect on immune function

BACKGROUND Hepatectomy is the first choice for treating liver cancer.However,inflammatory factors,released in response to pain stimulation,may suppress perioperative immune function and affect the prognosis of patients undergoing hepatectomies.AIM To determine the short-term efficacy of microwave ablation in the treatment of liver cancer and its effect on immune function.METHODS Clinical data from patients with liver cancer admitted to Suzhou Ninth People’s Hospital from January 2020 to December 2023 were retrospectively analyzed.Thirty-five patients underwent laparoscopic hepatectomy for liver cancer(liver cancer resection group)and 35 patients underwent medical image-guided microwave ablation(liver cancer ablation group).The short-term efficacy,complications,liver function,and immune function indices before and after treatment were compared between the two groups.RESULTS One month after treatment,19 patients experienced complete remission(CR),8 patients experienced partial remission(PR),6 patients experienced stable disease(SD),and 2 patients experienced disease progression(PD)in the liver cancer resection group.In the liver cancer ablation group,21 patients experienced CR,9 patients experienced PR,3 patients experienced SD,and 2 patients experienced PD.No significant differences in efficacy and complications were detected between the liver cancer ablation and liver cancer resection groups(P>0.05).After treatment,total bilirubin(41.24±7.35 vs 49.18±8.64μmol/L,P<0.001),alanine aminotransferase(30.85±6.23 vs 42.32±7.56 U/L,P<0.001),CD4+(43.95±5.72 vs 35.27±5.56,P<0.001),CD8+(20.38±3.91 vs 22.75±4.62,P<0.001),and CD4+/CD8+(2.16±0.39 vs 1.55±0.32,P<0.001)were significantly different between the liver cancer ablation and liver cancer resection groups.CONCLUSION The short-term efficacy and safety of microwave ablation and laparoscopic surgery for the treatment of liver cancer are similar,but liver function recovers quickly after microwave ablation,and microwave ablation may enhance immune function.

Coordination-Assembled Lanthanide-Organic Ln3L3 Sandwiches or Ln4L4 Tetrahedron: Structural Transformation and Luminescence Modulation

Photo-functional supramolecular lanthanides assemblies have shown great potential in the materials and biomedical fields.Two new tri(tridentate) ligands (L3 and L4) highlighting small variation of the connection position to the central tridentate linkers have been designed,which leads to the emergent formation of either Ln3L3-type sandwich structures or Ln4L4-type tetrahedral cages.Moreover,nonlinear enhancement of lanthanide luminescence based on the modulation of inter-ligand charge-transfer states has been revealed on the mix-ligand Ln3L3 sandwiches.Our results provide important guidance for structure-design and photoluminescence optimization of supramolecular lanthanide-organic assemblies.