The precise asymmetric photochemical transformation of organic compounds containing multiple reactive sites presents significant progress in synthetic chemistry. Herein, we report an unprecedented visible-light-induced cascade transformation of tropolone cyclic triene derivatives by using chiral photoactive metal-organic cages (cPMOCs) as enzyme-mimicking multipocket photocatalysts. The cage-confined photocatalysis promotes three successive elementary steps, .
View Article and Find Full Text PDFAchieving high guest loading and multiguest-binding capacity holds crucial significance for advancement in separation, catalysis, and drug delivery with synthetic receptors; however, it remains a challenging bottleneck in characterization of high-stoichiometry guest-binding events. Herein, we describe a large-sized coordination cage (MOC-70-ZnPd) possessing 12 peripheral pockets capable of accommodating multiple guests and a high-resolution electrospray ionization mass spectrometry (HR-ESI-MS)-based method to understand the solution host-guest chemistry. A diverse range of bulky guests, varying from drug molecules to rigid fullerenes as well as flexible host molecules of crown ethers and calixarenes, could be loaded into open pockets with high capacities.
View Article and Find Full Text PDFThe structural dynamics of artificial assemblies, in aspects such as molecular recognition and structural transformation, provide us with a blueprint to achieve bioinspired applications. Here, we describe the assembly of redox-switchable chiral metal-organic cages Λ/Δ-[Pd(CoL)] and Λ/Δ-[Pd(CoL)]. These isomeric cages demonstrate an on-off chirality logic gate controlled by their chemical and stereostructural dynamics tunable through redox transitions between the labile Co-state and static Co-state with a distinct Cotton effect.
View Article and Find Full Text PDFPrevious laboratory-scale studies have consistently shown that carbon-based conductive materials can notably improve the anaerobic digestion of food waste, typically employing reactors with regular capacity of 1-20 L. Furthermore, incorporating riboflavin-loaded conductive materials can further address the imbalance between fermentation and methanogenesis in anaerobic systems. However, there have been few reports on pilot-scale investigation.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
September 2024
A macrocyclic compound, hemicucurbit[6]uril (HemiQ[6]), is employed as the carbon source to produce a novel sort of carbon quantum dots (CQDs) with blue fluorescence in aqueous solution. The CQDs are fully identified by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Nuclear Magnetic Resonance (NMR), zeta potential, ultraviolet/visible (UV-vis) and photoluminescence spectroscopy (PL). The nanomaterial is developed for the analysis of Pb in the light of the Resonance Rayleigh scattering (RRS) changes with the increasing Pb concentration.
View Article and Find Full Text PDFObjective: The aim of this study is to investigate the clinical value of radiomics based on non-enhanced head CT in the prediction of hemorrhage transformation in acute ischemic stroke (AIS).
Materials And Methods: A total of 140 patients diagnosed with AIS from January 2015 to August 2022 were enrolled. Radiomic features from infarcted areas on non-enhanced CT images were extracted using ITK-SNAP.
A series of isostructural supramolecular cages with a rhombic dodecahedron shape have been assembled with distinct metal-coordination lability (M Pd -MOC-16, M=Ru , Fe , Ni , Zn ). The chirality transfer between metal centers generally imposes homochirality on individual cages to enable solvent-dependent spontaneous resolution of Δ /Λ -M Pd enantiomers; however, their distinguishable stereochemical dynamics manifests differential chiral phenomena governed by the cage stability following the order Ru Pd >Ni Pd >Fe Pd >Zn Pd . The highly labile Zn centers endow the Zn Pd cage with conformational flexibility and deformation, enabling intrigue chiral-Δ /Λ -Zn Pd to meso-Δ Λ -Zn Pd transition induced by anions.
View Article and Find Full Text PDFMolecular recognition lies at the heart of biological functions, which inspires lasting research in artificial host syntheses to mimic biomolecules that can recognize, process, and transport molecules with the highest level of complexity; nonetheless, the design principle and quantifying methodology of artificial hosts for multiple guests (≥4) remain a formidable task. Herein, we report two rhombic dodecahedral cages [(Zn/Fe)Pd-MOC-16], which embrace 12 adaptive pockets for multiguest binding with distinct conformational dynamics inherent in metal-center lability and are able to capture 4-24 guests to manifest a surprising complexity of binding scenarios. The exceptional high-order and hierarchical encapsulation phenomena suggest a wide host-guest dynamic-fit, enabling conformational adjustment and adaptation beyond the duality of induced-fit and conformational selection in protein interactions.
View Article and Find Full Text PDFIntegration of clinical imaging and collaborative multimodal therapies into a single nanomaterial for multipurpose diagnosis and treatment is of great interest to theranostic nanomedicine. Here, we report a rational design of a discrete Os-based metal-organic nanocage Pd(OsL) (MOC-43) as a versatile theranostic nanoplatform to meet the following demands simultaneously: (1) synergistic treatments of radio-, chemo-, and X-ray-induced photodynamic therapies (X-PDT) for breast cancer, (2) NIR imaging for cancer cell tracking and tumor-targeting, and (3) anticancer drug transport through a host-guest strategy. The nanoscale MOC-43 incorporates high-Z Os-element to interact with X-ray irradiation for dual radiosensitization and photosensitization, showing efficient energy transfer to endogenous oxygen in cancer cells to enhance X-PDT efficacy.
View Article and Find Full Text PDFIntroduction: The primary factor for cardiovascular disease and upcoming cardiovascular events is atherosclerosis. Recently, carotid plaque texture, as observed on ultrasonography, is varied and difficult to classify with the human eye due to substantial inter-observer variability. High-resolution magnetic resonance (MR) plaque imaging offers naturally superior soft tissue contrasts to computed tomography (CT) and ultrasonography, and combining different contrast weightings may provide more useful information.
View Article and Find Full Text PDFComput Methods Programs Biomed
April 2023
Background: Automated segmentation techniques for cardiac magnetic resonance imaging (MRI) are beneficial for evaluating cardiac functional parameters in clinical diagnosis. However, due to the characteristics of unclear image boundaries and anisotropic resolution anisotropy produced by cardiac magnetic resonance imaging technology, most of the existing methods still have the problems of intra-class uncertainty and inter-class uncertainty. However, due to the irregularity of the anatomical shape of the heart and the inhomogeneity of tissue density, the boundaries of its anatomical structures become uncertain and discontinuous.
View Article and Find Full Text PDFBackground And Objective: In today's society, people's work pressure, coupled with irregular diet, lack of exercise and other bad lifestyle, resulting in frequent cardiovascular diseases. Medical imaging has made great progress in modern society, among which the role of MRI in cardiovascular field is self-evident. Based on this research background, how to process cardiac MRI quickly and accurately by computer has been extensively discussed.
View Article and Find Full Text PDFComput Math Methods Med
October 2022
Supramolecular cage chemistry is of lasting interest because, as artificial blueprints of natural enzymes, the self-assembled cage structures not only provide substrate-hosting biomimetic environments but also can integrate active sites in the confined nanospaces for function synergism. Herein, we demonstrate a vertex-directed organic-clip chelation assembly strategy to construct a metal-organic cage FeL (MOC-63) incorporating 12 imidazole proton donor-acceptor motifs and four redox-active Fe centers in an octahedral coordination nanospace. Different from regular supramolecular cages assembled with coordination metal vertices, MOC-63 comprises six ditopic organic-clip ligands as vertices and four tris-chelating Fe(N∩N) moieties as faces, thus improving its acid, base, and redox robustness by virtue of cage-stabilized dynamics in solution.
View Article and Find Full Text PDFA novel Rh(iii)-catalyzed olefination reaction of oxazoles to generate diverse oxazole skeleton derivatives has been realized by directly using oxazole as the directing group. The reaction could tolerate many functional groups, affording complex oxazole derivatives with long chain alkenyls in moderate to good yields, which might find applications in the construction of diverse compounds.
View Article and Find Full Text PDFObjective: The present study aimed to investigate the effect of functional mitral regurgitation (FMR) on recurrence of paroxysmal atrial fibrillation (PAF) in patients undergoing radiofrequency catheter ablation.
Methods: This prospective cohort study comprised 107 patients with PAF. The patients were divided into the FMR and non-FMR groups.
Purpose: Previous studies have indicated that platelet indices are related to the pathogenesis of cardiovascular diseases (CVD). However, it is unclear which platelet-related indicators are associated with CVD events in patients with chronic kidney disease (CKD) without dialysis.
Methods: We performed a single-center prospective cohort study involved 1391 CKD patients to explore the relationship between platelet indices and CVD events in CKD patients.
Spectrochim Acta A Mol Biomol Spectrosc
February 2020
The chem-sensors, based on the triazole-CH-anthracene-functionalized multifarene[2,2] were successfully synthesized, which could efficiently and rapidly detect 2,4,6-trinitrophenol (TNP). The high specificities of the proposed macrocyclic sensors were achieved by selective response for TNP in the existence of other competing phenolic compounds, and the limits of detection in ∼10 mol/L range were produced to confirm the high sensitivities of the chem-sensors, which could be attributed to the mechanism of electron and resonance energy transfer processes in the complexes with the supramolecular interactions. H NMR titration analysis revealed the actual binding position should be the triazole rings of sensors with the hydroxyl group on TNP to offer a hydrogen bonding.
View Article and Find Full Text PDFBackground: The Cavernous Angioma in Posterior Sagittal Sinus is exceedingly rare.
Methods: We report for the case of a 10-year-old male patient who was diagnosed with Cavernous Angioma in Posterior Sagittal Sinus.
Results: Our case is the second reported case of Cavernous Angioma in Posterior Sagittal Sinus in the world.
Spectrochim Acta A Mol Biomol Spectrosc
July 2019
Fluorescent chemosensors based on a new macrocyclic compound, multifarene[2,2], with modification by triazole-linked pyrene or anthracene were synthesized. These macrocyclic sensors exhibited high affinity and selectivity toward Ag over other metal ions, with ratiometric or enhanced response of their fluorescence emissions depending upon the substituent species for coordination to Ag, and an unexpected response to a concentration threshold of the metal cations was discovered. The experimental evidences of fluorescence spectra, H NMR titration, IR spectra, and high-resolution mass spectra suggested the coordination behaviors of the sensors with Ag, that is, the 1:1 complexes were formed with moderate association constants of about 10 L·mol, and the sulfur atoms on macrocyclic ligand should affinite to the metal cations.
View Article and Find Full Text PDFBackground: To determine whether uric acid (UA) and intracranial and extracranial atherosclerosis stenosis of elderly patients suffering from ischaemic stroke are inter-related.
Methods: Elderly patients with ischaemic stroke underwent computed tomography angiography (CTA) were enrolled between October 2015 and December 2017. We collected clinical assessment, image data, and laboratory tests, and divided patients into four groups: (1) intracranial stenosis atherosclerosis (ICAS) group, (2) combined intracranial and extracranial atherosclerosis stenosis (COAS) group, (3) extracranial carotid stenosis atherosclerosis (ECAS) group, and (4) non-cerebral stenosis atherosclerosis (NCAS) group.