Magnetoresistance of Manganese-Doped Colloidal Quantum Dot Films

The magnetoresistance of films of manganese-doped colloidal quantum dots of CdSe, ZnO, HgS, and ZnTe is investigated. At low concentration of manganese ions (1% or less), the hyperfine splitting of the Mn²⁺ electron spin resonance is resolved and similar to that of the bulk doped materials, indicating successful doping into the nanocrystals. At high Mn concentration (∼10%), the hyperfine splitting disappears because of interaction between the Mn²⁺ ions. Thin films of Mn:CdSe, Mn:ZnO, and Mn:HgS quantum dots are charged negative by applying an electrochemical potential, and the magnetoresistance is measured down to 2 K and up to 9 T. At low charging level, the magnetoresistance of thin films is positive, exhibits little effect of the manganese dopant, and is instead consistent with predictions from the variable range hopping model and the squeezing of the wave function of the quantum dots. At high charging level, the magnetoresistance becomes linear both for Mn:CdSe and Mn:ZnO, and this is not explained. At high Mn doping and low temperature, the positive magnetoresistance is greatly increased at low fields. This is proposed to be a signature of electron-magnetic polarons on the transport properties of the quantum dot films

Selective Actinide-Catalyzed Tandem Proton-Transfer Esterification of Aldehydes with Alcohols for the Production of Asymmetric Esters

Actinide-catalyzed tandem proton-transfer esterification between aldehydes and alcohols is presented herein for the first time. It represents a novel convenient and external-oxidant-free methodology in the preparation of asymmetric ester compounds. Various kinds of aldehydes and alcohols can be applied to this reaction, affording the corresponding ester product in moderate to high yields. A plausible mechanism was proposed on the basis of the kinetic, stoichiometric, and deuterium-labeling studies

The average value of error system with adaptive feedback in NW small-world network with 0 in-degree nodes.

<p>The average value of error system with adaptive feedback in NW small-world network with 0 in-degree nodes.</p

The value of each cluster's stable state with adaptive feedback in NW small-world network with 0 in-degree nodes.

<p>The value of each cluster's stable state with adaptive feedback in NW small-world network with 0 in-degree nodes.</p

Tempo-Spatially Resolved Scattering Correlation Spectroscopy under Dark-Field Illumination and Its Application to Investigate Dynamic Behaviors of Gold Nanoparticles in Live Cells

In this study, a new tempo-spatially resolved fluctuation spectroscopy under dark-field illumination is described, named dark-field illumination-based scattering correlation spectroscopy (DFSCS). DFSCS is a single-particle method, whose principle is similar to that of fluorescence correlation spectroscopy (FCS). DFSCS correlates the fluctuations of the scattered light from single nanoparticle under dark-field illumination. We developed a theoretical model for translational diffusion of nanoparticles in DFSCS system. The results of computer simulations documented that this model was able to well describe the diffusion behaviors of nanoparticles in uniformly illuminated field. The experimental setup of DFSCS was achieved by introducing a dark-field condenser to the frequently used bright-field microscope and an electron multiplying charge-coupled device (EMCCD) as the array detector. In the optimal condition, a stack of 500 000 frames were collected simultaneously on 64 detection channels for a single measurement with acquisition rate of 0.5 ms per frame. We systematically investigated the effect of certain factors such as particle concentration, viscosity of the solution, and heterogeneity of gold nanoparticles (GNPs) samples on DFSCS measurements. The experiment data confirmed theoretical model proposed. Furthermore, this new method was successfully used for investigating dynamic behaviors of GNPs in live cells. Our preliminary results demonstrate that DFSCS is a practical and affordable tool for ordinary laboratories to investigate the dynamic information of nanoparticles <i>in vitro</i> as well as <i>in vivo</i>

Assessing the Blinking State of Fluorescent Quantum Dots in Free Solution by Combining Fluorescence Correlation Spectroscopy with Ensemble Spectroscopic Methods

The current method for investigating the blinking behavior is to immobilize quantum dots (QDs) in the matrix and then apply a fluorescent technique to monitor the fluorescent trajectories of individual QDs. So far, no method can be used to directly assess the blinking state of ensemble QDs in free solution. In this study, a new method was described to characterize the blinking state of the QDs in free solution by combining single molecule fluorescence correlation spectroscopy (FCS) with ensemble spectroscopic methods. Its principle is based on the observation that the apparent concentration of bright QDs obtained by FCS is less than its actual concentration measured by ensemble spectroscopic method due to the QDs blinking. We proposed a blinking index (<i>K</i>_blink) for characterizing the blinking state of QDs, and <i>K</i>_blink is defined as the ratio of the actual concentration (<i>C</i>_b,actual) measured by the ensemble spectroscopic method to the apparent concentration (<i>C</i>_b,app) of QDs obtained by FCS. The effects of certain factors such as laser intensity, growth process, and ligands on blinking of QDs were investigated. The <i>K</i>_blink data of QDs obtained were successfully used to characterize the blinking state of QDs and explain certain experimental results

The value of each cluster's stable state in BA scale-free network without 0 in-degree nodes.

<p>The value of each cluster's stable state in BA scale-free network without 0 in-degree nodes.</p

Catalytic 1,2-Regioselective Dearomatization of N‑Heteroaromatics via a Hydroboration

The thorium methyl and hydride complex (C₅Me₅)₂ThMe₂ and [(C₅Me₅)₂Th­(H)­(μ-H)]₂ catalyzed highly 1,2-regioselective dearomatization of pyridines via a hydroboration process is reported herein. Twelve different kinds of meta- and para-substituted pyridines are applicable to this reaction, giving the corresponding <i>N</i>-boryl-1,2-dihydropyridine products in high yields. Other N-heteroaromatic compounds, such as benzo-fused N-heterocycles, pyrazines, pyrimidines, 1,3,5-triazine, and benzothiazole, were also found to be hydroborated with high chemoselectivity. Kinetics including isotope effect studies revealed a first-order dependence on the concentration of catalyst, pyridine, and pinacolborane, with release of the dearomatized final product as the rate-determining step. A plausible mechanism is proposed on the basis of stoichiometric reactions and kinetic studies

Small Bright Charged Colloidal Quantum Dots

Using electrochemical charge injection, the fluorescence lifetimes of negatively charged core/shell CdTe/CdSe QDs are measured as a function of core size and shell thickness. It is found that the ensemble negative trion lifetimes reach a maximum (∼4.5 ns) for an intermediate shell thickness. This leads to the smallest particles (∼4.5 nm) with the brightest trion to date. Single dot measurements show that the negative charge suppresses blinking and that the trion can be as bright as the exciton at room temperature. In contrast, the biexciton lifetimes remain short and exhibit only a monotonous increase with shell thickness, showing no correlation with the negative trion decays. The suppression of the Auger process in small negatively charged CdTe/CdSe quantum dots is unprecedented and a significant departure from prior results with ultrathick CdSe/CdS core/shell or dot-in-rod structures. The proposed reason for the optimum shell thickness is that the electron–hole overlap is restricted to the CdTe core while the electron is tuned to have zero kinetic energy in the core for that optimum shell thickness. The different trend of the biexciton lifetime is not explained but tentatively attributed to shorter-lived positive trions at smaller sizes. These results improve our understanding of multiexciton recombination in colloidal quantum dots and may lead to the design of bright charged QDs for more efficient light-emitting devices

Reversible Hydrogen Electrode (RHE) Scale Dependent Surface Pourbaix Diagram at Different pH

In the analysis of electrocatalysis mechanisms and the design of catalysts, the effect of electrochemistry-induced surface coverage is a critical consideration that should not be overlooked. The surface Pourbaix diagram emerges as a fundamental tool in this context, providing essential insights into the surface coverage of adsorbates generated via electrochemical potential-driven water activation. A classic surface Pourbaix diagram considers the pH effects by correcting the free energy of H+ ions by the concentration-dependent term: −kBT ln(10) × pH, which is independent of the reversible hydrogen electrode (RHE) scale. However, this is sometimes inconsistent with the experimentally observed potential-dependent surface coverage at an RHE scale, especially under high-pH conditions. Here, we derived the pH-dependent surface Pourbaix diagram at an RHE scale by considering the energetics computed by density functional theory with the Bayesian Error Estimation Functional with van der Waals corrections (BEEF-vdW), the electric field effects, the derived adsorption-induced dipole moment and polarizability, and the potential of zero-charge. Using Pt(111) as the typical example, we found that the surface coverage predicted by the proposed RHE-dependent surface Pourbaix diagram can significantly minimize the discrepancy between theory and experimental observations, especially under neutral-alkaline, moderate-potential conditions. This work provides a new methodology and establishes guidelines for the precise analysis of the surface coverage prior to the evaluation of the activity of an electrocatalyst