Vinsonwinkel3361

As a proof-of-concept, under the effective guidance of local-tumor imaging by PA and whole-body imaging by NIR-II FL, complete tumor eradication was achieved via PDT and PTT combinational therapy. This work provides a novel perspective into conceiving and developing single molecule for efficient versatile biomedical applications.The gold(iii)-catalyzed annulations of alkynes with anthranils were evaluated using DFT calculations. A unified rationale for the Br-migration on α-imino gold(iii)-carbene was proposed, from which an unprecedented "N-donation/abstraction substitution" mechanism was established using the substituted anthranils, while direct C-H nucleophilic attack was involved with the unsubstituted anthranils. The controlling factors guiding the site-selectivity were uncovered. These computational studies provide insight for developing new α-imino gold(iii)-carbene mediated reactions.High entropy oxides (HEOs) are single phase solid solutions consisting of five or more elements in equiatomic or near-equiatomic proportions incorporated into the cationic sub-lattice(s). The uniqueness of the HEOs lies in their extreme chemical complexity enveloped in a single crystallographic structure, which in many cases results in novel functionalities. From the local structure perspective, HEOs consist of an unusually large number of different metal-oxygen-metal couples. Consequently, magnetic correlations in HEOs that inherently depend on the coordination geometry, valence, spin state and type of the metal cations that are hybridized with the bridging oxygen, are naturally affected by an extreme diversity of neighboring ionic configurations. In these conditions, a complex magneto-electronic free-energy landscape in HEOs can be expected, potentially leading to stabilization of unconventional spin-electronic states. This Frontier article provides an overview of the unique magnetic features stemming from the extreme chemical disorder in HEOs along with the possible opportunities for further research and exploration of potential functionalities.The 17O resonances of zirconium-oxo clusters that can be found in porous Zr carboxylate metal-organic frameworks (MOFs) have been investigated by magic-angle spinning (MAS) NMR spectroscopy enhanced by dynamic nuclear polarization (DNP). High-resolution 17O spectra at 0.037% natural abundance could be obtained in 48 hours, thanks to DNP enhancement of the 1H polarization by factors ε(1H) = Swith/Swithout = 28, followed by 1H → 17O cross-polarization, allowing a saving in experimental time by a factor of ca. 800. The distinct 17O sites from the oxo-clusters can be resolved at 18.8 T. Their assignment is supported by density functional theory (DFT) calculations of chemical shifts and quadrupolar parameters. Protonation of 17O sites seems to be leading to large characteristic shifts. Hence, natural abundance 17O NMR spectra of diamagnetic MOFs can thus be used to probe and characterize the local environment of different 17O sites on an atomic scale.Disordered media are ubiquitous in systems where self-propelled particles are present, ranging from biological settings to synthetic systems, like in active microfluidic devices. Here we investigate the behavior of active Brownian particles that have an internal energy depot and move through a landscape with a quenched frictional disorder. We consider the cases of very fast internal relaxation processes and the limit of strong disorder. Analytical calculations of the mean-square displacement in the fast-relaxation approximation is shown to agree well with numerically integrated energy depot dynamics and predict normal dispersion for a bounded drag coefficient and anomalous dispersion for power-law dependence of the drag on spatial coordinates. Furthermore, we show that in the strongly disordered limit the self-propulsion speed can, for practical purposes, be considered a fluctuating quantity. Distributions of self-propulsion speeds are investigated numerically for different parameter choices.Single-atom catalysts (SACs) have attracted much interest for electrochemical CO2 reduction because of their high metal utilization and excellent catalytic activity. However, the practical applications of SACs were restricted by the low production yield. Herein, we developed a facile synthetic strategy for fabricating metal-nitrogen-carbon nanotube (M-N-CNT, M = Ni, Co, Cu, Fe, Mn, Zn, Pt, or Ru) SACs at scale (>1 g) by direct pyrolysis of metal cations, phenanthroline and CNTs at high temperature. The pyrolysis leads to forming coordinated Ni-N active sites anchored on CNTs. The prepared Ni-N-CNT catalyst with a remarkable Ni loading of 2 wt% determined by ICP exhibits the highest activity for CO2-to-CO conversion with a high faradaic efficiency of 94% and excellent stability. Aberration-corrected high-angle annular dark-field transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy confirm the presence of isolated Ni single atoms in Ni-N-CNT, which act as the active centers for CO2 electroreduction while the CNT support offers fast pathways for electron and mass transports. This work laid foundations for future practical applications in CO2 electroreduction, oxygen reduction reactions, water splitting and nitrogen reduction and beyond.A multi-binding site chemosensor, N-(3-methoxy-2-hydroxybenzylidene)-3-hydroxy-2-naphthahydrazone (H3L), with excited-state intramolecular proton transfer (ESIPT) behaviour was prepared and characterized. It possesses no aggregation-induced emission (AIE) characteristics but can detect Cd2+ and Zn2+ ions selectively in the "off-on" mode based on the AIE of their complexes in the media of THF/HEPES and THF/H2O, respectively, which will provide a new strategy for target detection based on AIE. The detection limits of Zn2+ and Cd2+ were 9.85 × 10-9 M and 1.27 × 10-7 M, respectively. The aggregates of the complexes formed in the detection system were confirmed by DLS data and SEM images. The corresponding Zn2+ (1) and Cd2+ (2) complexes were prepared to investigate the response mechanism. Powder X-ray diffraction and single crystal X-ray diffraction proved that complex 1 is the species formed in the detection system. The chemosensor coordinates with the Cd2+ and Zn2+ ions in different formation and coordination modes, leading to the emission position of the aggregates at 560 and 645 nm, respectively, based on which Cd2+ ions were successfully differentiated from Zn2+ ions. Moreover, the detection of Cd2+ and Zn2+ ions was realized qualitatively via test paper and quantitatively in water.Triangulene and its π-extended homologues constitute non-Kekulé polyradical frameworks with high-spin ground states, and are anticipated to be key components of organic spintronic devices. We report a combined in-solution and on-surface synthesis of the hitherto largest triangulene homologue, [7]triangulene (C78H24), consisting of twenty-eight benzenoid rings fused in a triangular fashion. We employ low-temperature scanning tunneling microscopy to confirm the chemical structure of individual molecules adsorbed on a Cu(111) surface. While neutral [7]triangulene in the gas phase is predicted to have an open-shell septet ground state; our scanning tunneling spectroscopy measurements, in combination with density functional theory calculations, reveal chemisorption of [7]triangulene on Cu(111) together with considerable charge transfer, resulting in a closed-shell state. Furthermore, substantial hybridization between the molecular orbitals of [7]triangulene is observed.A series of glycoside-peptide conjugates were prepared by engineering at the N-terminus of the natural peptide gramicidin A. The conjugate containing galactose moiety formed a unimolecular transmembrane channel and mediated ion transport to induce apoptosis of cancer cells. More importantly, it exhibited liver cancer cell-targeting behavior due to the galactose-asialoglycoprotein receptor recognition.Using a model molecule, we show that it is possible to create molecules that show the required properties for use as elements in a molecular circuit or computer two conformations with similar energy but different electric conductivity, and the possibility to switch between those by applying an external electric field.Angiogenesis driven tumor initiation and progression calls for a targeted therapy. Moreover, combined chemotherapy supplements the therapy to act on the cause of concern. In this study, we aimed to develop a targeted crystalsomes approach to delineate tumor cells against normal cells. see more Self-assembled crystalline monodispersed nanosized polyethylene-polyethylene glycol (PE-PEG)-based hollow crystalsomes were modified with pluronylated putrescine (Put-PF) and loaded with doxorubicin (Dox), synergistically in combination with oleanolic acid (OA) to target the glypican-1 (gp-1) receptor on tumor cells. The developed crystalsomes (Put-D + O@NCs) showed increased intracellular accumulation of Dox and OA in a synergistic combination inside the MDA-MB-231 cell lines. The developed crystalsomes marked an enhanced depolarization of the mitochondrial membrane potential and cell cycle arrest leading to apoptosis. Furthermore, the proposed therapy has a greater anti-angiogenesis activity with vascular endothelial growth factor (VEGF) dependent modulation in the proliferation, invasion, migration and tube formation of human endothelial umbilical vein cells (HUVECs) in vitro and in vivo in a BALB/c mouse model. Interestingly, the perseverance of the tumor boundary, inhibiting the expression and activity of the matrix metalloproteinase (MMPs) (>5.2-fold) with suppressed degradation of the extracellular matrix paves the way for significant inhibition of metastases. However, an intravenously administered Put-D + O@NCs showed an improved pharmacokinetic profile and exquisite inhibition of the 4T1 induced tumor with a significantly lower toxicity. In a nutshell, these findings highlight the important role of Put in the gp-1 receptor for specific targeting and synergistic delivery of Dox and OA through crystalsomes as a potential approach for the treatment of metastatic breast cancer using combined chemotherapy.Electroreduction of CO2 to HCOOH with high current densities and efficiencies remains a challenge. Herein, we developed a metallic Bi catalyst with abundant grain boundaries through the electrochemical transformation of BiPO4 nanorods to boost the catalytic performance of the electroreduction of CO2 to HCOOH. The phosphate-derived Bi catalyst (PD-Bi) achieved an FE of 91.9% for HCOOH at a high current density of -600.0 mA cm-2. Mechanistic study revealed that the abundant grain boundaries within PD-Bi promoted the adsorption of CO2 and stabilization of the CO2˙- intermediate, resulting in facilitated CO2 activation and thus enhanced catalytic performance.The introduction of nanoparticles (MNPs) at the surface of cationic poly-porphyrin films, obtained by electrostatic interaction between the bis-porphyrin copolymer and the Preyssler type polyoxometalate P5W30@MNPs, enhances the photocurrent (up to 2.5-3 times greater as a function of the used nanoparticle).A series of rubidium rare earth thiophosphates with the formula Rb4Ln2(P2S6)(PS4)2 (Ln = La, Ce, Pr, Nd, Sm, and Gd) were synthesized using the high temperature molten flux crystal growth method utilizing a RbBr flux. Single crystals of all title compounds, as well as phase pure powders of the La-, Ce-, and Sm-containing compositions, were obtained. Single crystals of the title compounds were characterized by single crystal and powder X-ray diffraction for structure and phase identification. Rb4Ln2(P2S6)(PS4)2 crystallizes in the monoclinic crystal system adopting the P21/n space group for the large rare earths (Ln = La, Ce, Pr) and the C2/c space group for the smaller rare earths (Ln = Nd, Sm, Gd). This Rb4Ln2(P2S6)(PS4)2 series is a rare example of thiophosphates containing both tetrahedral [PVS4]3- and dimeric [PIV2S6]4- thiophosphate units that, in this structural family, link corrugated rare earth sulfide chains into sheets. The band gaps of the materials were determined from UV-Vis data and the fluorescence spectrum of Rb4Ce2(P2S6)(PS4)2 was collected.