The development of highly efficient oxygen‐evolving catalysts compatible with powerful proton‐exchange‐membrane‐based electrolyzers in acid environments is of prime importance for sustainable hydrogen production. In this field, understanding the role of electronic structure of catalysts on catalytic activity is essential but still lacking. Herein, a family of pyrochlore oxides R2Ir2O7 (R = rare earth ions) is reported as acidic oxygen‐evolving catalysts with superior‐specific activities. More importantly, it is found that the intrinsic activity of this material significantly increases with the R ionic radius. Electronic structure studies reveal that the increased R ionic radius weakens electron correlations in these iridate oxides. This weakening induces an insulator–metal transition and an enhancement of IrO bond covalency, both of which promote oxygen evolution kinetics. This work demonstrates the importance of engineering the electron correlations to rationalize the catalytic activity toward water oxidation in strongly correlated transition‐metal oxides.
The conjugation of hydrophilic low‐fouling polymers to therapeutic molecules and particles is an effective approach to improving their aqueous stability, solubility, and pharmacokinetics. Recent concerns over the immunogenicity of poly(ethylene glycol) has highlighted the importance of identifying alternative low fouling polymers. Now, a new class of synthetic water‐soluble homo‐fluoropolymers are reported with a sulfoxide side‐chain structure. The incorporation of fluorine enables direct imaging of the homopolymer by 19F MRI, negating the need for additional synthetic steps to attach an imaging moiety. These self‐reporting fluoropolymers show outstanding imaging sensitivity and remarkable hydrophilicity, and as such are a new class of low‐fouling polymer for bioconjugation and in vivo tracking.
Ambimodal reactions involve a single transition state leading to multiple products. In such reactions, transition state theory gives no information about the ratio of products that are formed, and molecular dynamics must be performed to predict this ratio. Understanding the relationship between the transition structure and the product ratio is a long-standing problem in molecular dynamics. We have studied 15 ambimodal pericyclic reactions and investigated the relationship between the TS bond lengths in the saddle points and the product ratios from trajectory simulations. A linear correlation, ln(B:A) = -9.4(Bond 3 - Bond 2), is found with R = 0.92, where A and B refer to the products formed upon formation of bonds 2 and 3, respectively. The correlation shows that the ratio of products formed after the bifurcation is related to the partial bond lengths, and corresponding bond orders, in the transition state.
A promising electrochemiluminescence (ECL) sensing strategy was proposed with dual-stabilizers-capped CdSe quantum dots (QDs) as ECL emitters. The dual-stabilizers-capped CdSe QDs were covalently immobilized onto p-aminobenzoic acid modified glass carbon electrode with ethylenediamine as a link molecule. This strategy can preserve the completely passivated surface states of dual-stabilizers-capped CdSe QDs, so that the sensor demonstrated eye-visible greenish, band gap engineering and monochromatic ECL emission at 546 nm with a fwhm of 35 nm. Moreover, the proposed sensor could accurately quantify dopamine from 10.0 nM to 3.0 μM with a detection limit of 3.0 nM in practical drug, human urine, and cerebrospinal fluid samples without any signal amplification techniques. This strategy is promising for developing ECL sensors with high sensitivity and spectral selectivity.
The interaction of three cyclodextrins (CDs), viz. beta-CD, heptakis (2,6-di-O-methyl)-beta-CD (DM-beta-CD), and 2-hydroxypropyl-beta-CD (HP-beta-CD), with cholesterol was investigated using molecular dynamics (MD) simulations. The free energy along the reaction pathway delineating the inclusion of cholesterol into each CD was computed using the adaptive biasing force method. The association constant and the corresponding association free energy were derived by integrating the potential of mean force (PMF) over a representative ordering parameter. The results show that the free energy profiles possess two local minima corresponding to roughly equally probable binding modes. Among the three CDs, DM-beta-CD exhibits the highest propensity to associate with cholesterol. Ranking for binding cholesterol, viz. DM-beta-CD > HP-beta-CD > beta-CD, agrees nicely with experiment. Partitioning of the PMF into free energy components illuminates that entering of cholesterol into the CD cavity is driven mainly by electrostatic interactions, whereas deeper inclusion results from van der Waals forces and solvation effects. Additional MD simulations were performed to investigate the structural stability of the host-guest complexes near the free energy minima. The present results demonstrate that association of cholesterol and CDs follows two possible binding modes. Although the latter are thermodynamically favorable for all CDs, one of the two inclusion complexes appears to be preferred kinetically in the case of DM-beta-CD.
Antifouling
surfaces are important in a broad range of applications.
An effective approach to antifouling surfaces is to covalently attach
antifouling polymer brushes. This work reports the synthesis of a
new class of antifouling polymer brushes based on highly hydrophilic
sulfoxide polymers by surface-initiated photoinduced electron/energy
transfer-reversible addition-fragmentation chain transfer (PET-RAFT)
polymerization. The sulfoxide polymer brushes are able to effectively
reduce nonspecific adsorption of proteins and cells, demonstrating
remarkable antifouling properties. Given the outstanding antifouling
behavior of the sulfoxide polymers and versatility of surface-initiated
PET-RAFT technology, this work presents a useful and general approach
to engineering various material surfaces with antifouling properties,
for potential biomedical applications in areas such as tissue engineering,
medical implants, and regenerative medicine.
The selectivities in C-H oxidations of a variety of compounds by DMDO have been explored with density functional theory. There is a linear Evans-Polanyi-type correlation for saturated substrates. Activation energies correlate with reaction energies or, equivalently, BDEs (ΔH = 0.91*BDE - 67.8). Unsaturated compounds, such as alkenes, aromatics, and carbonyls, exhibit a different correlation for allylic and benzylic C-H bonds (ΔH = 0.35*BDE - 13.1). Bernasconi's Principle of Non-Perfect Synchronization (NPS) is found to operate here. The origins of this phenomenon were analyzed by a Distortion/Interaction model. Computations indicate early transition states for H-abstractions from allylic and benzylic C-H bonds, but later transition states for the saturated. The reactivities are mainly modulated by the distortion energy and the degree of dissociation of the C-H bond. While the increase in barrier with higher BDE is not unexpected from the Evans-Polanyi relationship, two separate correlations, one for saturated compounds, and one for unsaturated leading to delocalized radicals, were unexpected.
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