Hitherto-Unexplored Photodynamic Therapy of Ag2S and Enhanced Regulation Based on Polydopamine In Vitro and Vivo

Given their superior penetration depths, photosensitizers with longer absorption wavelengths present broader application prospects in photodynamic therapy (PDT). Herein, Ag₂S quantum dots were discovered, for the first time, to be capable of killing tumor cells through the photodynamic route by near-infrared light irradiation, which means relatively less excitation of the probe compared with traditional photosensitizers absorbing short wavelengths. On modification with polydopamine (PDA), PDA-Ag₂S was obtained, which showed outstanding capacity for inducing reactive oxygen species (increased by 1.69 times). With the addition of PDA, Ag₂S had more opportunities to react with surrounding O₂, which was demonstrated by typical triplet electron spin resonance (ESR) analysis. Furthermore, the PDT effects of Ag₂S and PDA-Ag₂S achieved at longer wavelengths were almost identical to the effects produced at 660 nm, which was proved by studies in vitro. PDA-Ag₂S showed distinctly better therapeutic effects than Ag₂S in experiments in vivo, which further validated the enhanced regulatory effect of PDA. Altogether, a new photosensitizer with longer absorption wavelength was developed by using the hitherto-unexplored photodynamic function of Ag₂S quantum dots, which extended and enhanced the regulatory effect originating from PDA.     

On s-hamiltonian line graphs of claw-free graphs

For an integer $s\ge 0$, a graph $G$ is $s$-hamiltonian if for any vertex subset $S?V\left(G\right)$ with $\left|S\right|\le s$, $G?S$ is hamiltonian, and $G$ is $s$-hamiltonian connected if for any vertex subset $S?V\left(G\right)$ with $\left|S\right|\le s$, $G?S$ is hamiltonian connected. Thomassen in 1984 conjectured that every 4-connected line graph is hamiltonian (see Thomassen, 1986), and Ku?zel and Xiong in 2004 conjectured that every 4-connected line graph is hamiltonian connected (see Ryjá?ek and Vrána, 2011). In Broersma and Veldman (1987), Broersma and Veldman raised the characterization problem of $s$-hamiltonian line graphs. In Lai and Shao (2013), it is conjectured that for $s\ge 2$, a line graph $L\left(G\right)$ is $s$-hamiltonian if and only if $L\left(G\right)$ is $(s+2)$-connected. In this paper we prove the following.(i) For an integer $s\ge 2$, the line graph $L\left(G\right)$ of a claw-free graph $G$ is $s$-hamiltonian if and only if $L\left(G\right)$ is $(s+2)$-connected.(ii) The line graph $L\left(G\right)$ of a claw-free graph $G$ is 1-hamiltonian connected if and only if $L\left(G\right)$ is 4-connected.     

Nickel/Photoredox-Catalyzed Asymmetric Reductive Cross-Coupling of Racemic α-Chloro Esters with Aryl Iodides

A unique nickel/organic photoredox co-catalyzed asymmetric reductive cross-coupling between α-chloro esters and aryl iodides is developed. This cross-electrophile coupling reaction employs an organic reductant (Hantzsch ester), whereas most reductive cross-coupling reactions use stoichiometric metals. A diverse array of valuable α-aryl esters is formed under these conditions with high enantioselectivities (up to 94 %) and good yields (up to 88 %). α-Aryl esters represent an important family of nonsteroidal anti-inflammatory drugs. This novel synergistic strategy expands the scope of Ni-catalyzed reductive asymmetric cross-coupling reactions.     

Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

Fabricating Dual-Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear-complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

The coupled-cluster formalism – a mathematical perspective

ABSTRACT

The Coupled-Cluster (CC) theory is one of the most successful high precision methods used to solve the stationary Schrödinger equation. In this article, we address the mathematical foundation of this theory with focus on the advances made in the past decade. Rather than solely relying on spectral gap assumptions (non-degeneracy of the ground state), we highlight the importance of coercivity assumptions – Gårding type inequalities – for the local uniqueness of the CC solution. Based on local strong monotonicity, different sufficient conditions for a local unique solution are suggested. One of the criteria assumes the relative smallness of the total cluster amplitudes (after possibly removing the single amplitudes) compared to the Gårding constants. In the extended CC theory the Lagrange multipliers are wave function parameters and, by means of the bivariational principle, we here derive a connection between the exact cluster amplitudes and the Lagrange multipliers. This relation might prove useful when determining the quality of a CC solution. Furthermore, the use of an Aubin–Nitsche duality type method in different CC approaches is discussed and contrasted with the bivariational principle.     

Highly Proton-Conductive Zinc Metal-Organic Framework Based On Nickel(II) Porphyrinylphosphonate

The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10⁻³ S cm⁻¹ at 75 °C and 80 % relative humidity).