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Control on Dimensions and Supramolecular Chirality of Self-Assemblies through Light and Metal Ions
摘要： Precise control over helical chirality and dimensions of molecular self-assemblies, a remaining challenge for both chemists and materials scientists, is the key to manipulate the property and performance of supramolecular materials. Herein, we report that a cholesterol-azopyridine conjugate could self-assemble into organogels with photo-controllable dimensional transition from 2D microbelts to 1D nanotubes and finally to 0D nanoparticles. The E/Z-Photoisomerization of the 4-azopyridine unit is the major driving force for the dimensional transformation. Furthermore, the self-assembled structures were observed to exhibit metal ion-mediated helicity inversion through the metal coordination. These observations were collectively confirmed by several techniques including scanning electron microscopy, atomic force microscope, circular dichroism, and X-ray crystallography. The rational design of building blocks for the construction of dimension and chirality controllable self-assembly systems may lead to versatile applications in smart display, advanced optoelectronic device, and supramolecular asymmetric catalysis.
关键词： photoisomerization,dimensional transition,supramolecular chirality,metal coordination,self-assembly
更新于2025-09-23 15:21:21
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Manipulating Pharmacokinetics of Purification-Free <sup>99m</sup> Tc-Labeled Bivalent Probes for In Vivo Imaging of Saturable Targets
摘要： The accumulation of 99mTc-labeled probes targeting saturable systems of the body is hindered by the presence of a large excess of unlabeled ligands needed to ensure high radiochemical yields in short reaction time. To address the issue, we recently reported a novel concept of a metal coordination-mediated synthesis of a bivalent 99mTc-labeled probe from a monovalent ligand using D-penicillamine (Pen) as a chelating molecule and c(RGDfK) as a model targeting device. The Pen-conjugated c(RGDfK) via a hexanoate linkage (Pen-Hx-c(RGDfK)) provided a bivalent [99mTc]Tc-[(Pen-Hx-c(RGDfK))2 that possessed much higher integrin αvβ3 binding affinity than Pen-Hx-c(RGDfK) and visualized murine tumor without purification. However, high radioactivity levels were observed in the abdominal regions, which necessitated improved pharmacokinetic of the probes for practical applications. In this study, a pharmacokinetic (PK) modifier was introduced to manipulate the pharmacokinetics of the 99mTc-Pen2-based bivalent probe. The Hx linkage in Pen-Hx-c(RGDfK) was replaced with acetyl-D-serine-D-serine-glycine (Ac-ssG) or hexanoyl-D-seiner-D-serine-D-serine (Hx-sss) to prepare Pen-Ac-ssG-c(RGDfK) or Pen-Hx-sss-c(RGDfK). Pen-Ac-ssG-c(RGDfK) impaired the complexation ability of Pen-Hx-c(RGDfK), and a monovalent 99mTc-labeled compound was generated at low ligand concentration. However, Pen-Hx-sss-c(RGDfK) provided the objective bivalent 99mTc-labeled probe in high radiochemical yields at the concentration similar to that of Pen-Hx-c(RGDfK). [99mTc]Tc-[Pen-Hx-sss-c(RGDfK)]2 also possessed stability and integrin αvβ3 binding affinity similar to those of [99mTc]Tc-[Pen-Hx-c(RGDfK)]2. As a result, [99mTc]Tc-[Pen-Hx-sss-c(RGDfK)]2 exhibited the tumor and the abdominal radioactivity levels similar to and significantly lower than those of [99mTc]Tc-[Pen-Hx-c(RGDfK)]2. These findings indicate the incorporation of a tripeptide PK modifier to Pen-Hx-c(RGDfK) preserved the complexation ability and improved the pharmacokinetics of the resulting 99mTc-labeled bivalent probe without impairing the targeting ability. Thus, [Pen-Hx-(PK modifier)-(targeting device)] would constitute a basic formulation for preparing the 99mTc-Pen2-based bivalent probes for imaging saturable systems of the body.
关键词： metal coordination,99mTc,cyclic RGD peptide,bivalent probe,pharmacokinetics
更新于2025-09-23 15:19:57
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Competitive metal-coordination of hexaaminotriphenylene on Cu(111) by intrinsic copper versus extrinsic nickel adatoms
摘要： The interplay between self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution Scanning-Tunneling-Microscopy (STM) and X-ray Photoelectron Spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on competitive metal-coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room temperature deposition of HATP onto pristine Cu(111) self-assembled aggregates were observed by STM, while XPS indicated non-deprotonated amino groups. Annealing up to 200 °C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse π-d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal-organic trimer, where three HATP molecules were coordinated by Cu3 clusters, as corroborated by accompanying Density Functional Theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)-Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by a restricted reversibility of these metal-organic bonds.
关键词： Scanning Tunneling Microscopy,Cu(111),metal-coordination,hexaaminotriphenylene,X-ray Photoelectron Spectroscopy
更新于2025-09-10 09:29:36