Despite their potential applications in host–guest chemistry, there are only five reported structures of poly-[n]-catenanes self-assembled by elusive M12L8 icosahedral nanocages. This small number of structures of M12L8 poly-[n]-catenanes is because self-assembly of large metal–organic cages (MOCs) with large windows allowing catenation by means of mechanical bonds is very challenging. Structural reports of M12L8 poly-[n]-catenanes are needed to increase our knowledge about the self-assembly and genesis of such materials. Poly-[n]-catenane (1·p-CT) self-assembly of interlocked M12L8 icosahedral cages (M = Zn(II) and L = 2,4,6-tris-(4-pyridyl)benzene (TPB)) including a new aromatic guest (p-chlorotoluene ( p-CT)) is reported by single-crystal XRD. Despite the huge internal M12L8 voids (> 2500 Å3), p-CT is ordered, allowing a clear visualization of the relative host–guest positions. DFT calculations have been used to compute the electrostatic potential of the TPB ligand, and various aromatic guests (i.e., o-dichlorobenzene ( o-DCB), p-chloroanisole ( p-CA), and nitrobenzene (NBz)) included (ordered) within the M12L8 cages were determined by single-crystal XRD. The computed maps of electrostatic potential (MEPs) allow for the rationalization of the guest’s inclusion seen in the 3D X-ray structures. Although more crystallographic X-ray structures and DFT analysis are needed to gain insights of guest inclusion in the large voids of M12L8 poly-[n]-catenanes, the reported combined experimental/DFT structural analyses approach can be exploited to use isostructural M12L8 poly-[n]-catenanes as hosts for molecular separation and could find applications in the crystalline sponge method developed by Fujita and co-workers. We also demonstrate, exploiting the instant synthesis method, in solution (i.e., o-DCB), and in the solid-state by neat grinding (i.e., without solvent), that the isostructural M12L8 poly-[n]-catenane self-assembled with 2,4,6-tris-(4-pyridyl)pyridine (TPP) ligand and ZnX2 (where X = Cl, Br, and I) can be kinetically synthesized as crystalline (yields ≈ 60%) and amorphous phases (yields ≈ 70%) in short time and large quantities. Despite the change in the aromatic nature at the center of the rigid exo-tridentate pyridine-based ligand (TPP vs TPB), the kinetic control gives the poly-[n]-catenanes selectively. The dynamic behavior of the TPP amorphous phases upon the uptake of aromatic guest molecules can be used in molecular separation applications like benzene derivatives.
Robust atomic-to-meso-scale chirality is now observed in the one-dimensional form of tellurium. This enables a large and counter-intuitive circular-polarization dependent second harmonic generation response above 0.2 which is not present...
Hybrid perovskites have attracted enormous attention in the next generation resistive switching (RS) memristor for the artificial synapses, owing to their ambipolar charge transport, long diffusion length, and tunable visible bandgap. However, the variable switch, limited reproducibility, and poor endurance are the obstacles to the practical application of the perovskite memristors. Herein, we reported a multilevel RS nonvolatile memory based on a 3D trigonal HC(NH2)2PbI3 (α‐FAPbI3) perovskite layer modified by 1‐cyanobutyl‐3‐methylimidazolium chloride ([CNBmim]Cl) and sandwiched between ITO and Au electrodes (Au/[CNBmim]Cl/α‐FAPbI3/SnO2/ITO). In contrast to the bare memristor with failure switching from low resistance state (LRS) to high resistance state (HRS), the memristor device based on the α‐FAPbI3 modified with [CNBmim]Cl (Target device) shows the retention time over 104 s with On/Off ratio (>102) and endurance up to 550 cycles. The stable RS cycle benefits from the accelerated electrons de‐trapping from the reduced defects and fast charge separation in the interface of α‐FAPbI3/electrode, leading to the rupture of conductive filaments and transition of LRS to HRS. As a two‐terminal analog synaptic device, the target device can realize random handwritten digit recognition with an impressive accuracy of 89.3% on the condition of low learning phases (500 training cycles).
The ability to reconfigure spin structure and spin-photon interactions by an external electric field is a prerequisite for seamless integration of optospintronics into modern electronics. In this study, the use of electric field on the tuning of circular photo galvanic effect in a quasi-2D oxyhalide perovskite Bi 4 NbO 8 Cl is reported. The electrical transport measurements are applied to study the switching characteristics of the microsheet devices. The electric field is used to tune the nanoscale devices and an optical orientation approach is applied to understand the field-tuned spin-polarized band structures. It is found that the circular photogalvanic current can be erased and re-created by poling, indicating the electric-field-based control over spin structure. The study enriches the basic understanding of the symmetry-regulated optoelectronic response in ferroelectrics with spin-orbit coupling.
BackgroundObservational studies suggest that ulceration is considered to be a negative prognostic factor for cutaneous melanoma. However, the impact of ulceration over different subgroups (e.g. AJCC Stage, thickness level) are controversial and its true causal effect on survival is lack of studies in the view of treating ulceration as an exposure.ObjectiveTo explore the true causal effect of ulceration on melanoma’s survival by adopting a combination of methods to discover proper adjustment set and confirming its correctness through a variety of means.MethodsA minimal sufficient adjustment set (MSAS) was found using directed acyclic graphs (DAG) to adjust the effect of causality. Sensitivity analysis was conducted to diagnose potential confounders in addition to MSAS. Cox models were built to analyze the causality in-depth and the model was validated using a novel method. Lastly, stratified effects of ulceration were examined to illustrate its impact within subgroups.ResultsHazard ratio (HR) of ulceration after adjustment by MSAS variables was 1.99 (95% CI=1.88-2.09). The sensitivity analysis of propensity score matching and E-value both demonstrated that variables other than MSAS do not have great influence on ulceration and MSS relationship. The HR of ulceration in AJCC Stage, thickness level, invasion level and tumor extension were all monotonically decreased from 5.76 to 1.57, 4.03 to 1.78, 2.75 to 1.78 and 2.65 to 1.71 respectively.ConclusionUlceration in all subgroups were shown to have a significantly negative impact on MSS and its magnitude of effect was monotonically decreased as the disease progressed. The true effect of ulceration can be adjusted by MSAS and its correctness was validated through a variety of approaches.
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