Theoretical investigation of different reactivities of Fe(IV)O and Ru(IV)O complexes with the same ligand topology

<p>The structures and mechanisms for hydrogen abstraction from isopropylbenzene for four high-valence complexes, <i>cis</i>-β-[Fe^IV(O)(BQCN)]²⁺ (<b>Fe-2b</b> and <b>Fe-2b-2</b>) and <i>cis</i>-β-[Ru^IV(O)(BQCN)]²⁺ (<b>Ru-2b</b> and <b>Ru-2b-2</b>) (BQCN = N,N′-dimethyl-N,N′-bis(8-quinolyl)-cyclohexanediamine), were investigated using density functional theory. Of the two iron complexes, <b>Fe-2b-2</b> has more exposed FeO units than <b>Fe-2b</b>, with iron being further out of the equatorial plane because of the steric interaction of the same ligand topologies with the iron-oxo group <i>trans</i> to a quinolyl or amine nitrogen. The contribution of BQCN to <b>Fe-2b</b> is higher than the contribution to <b>Fe-2b-2</b> as shown by the density-of-states spectra. The iron isomers can abstract hydrogen from isopropylbenzene via two-state reactivity patterns, whereas the ruthenium isomers react with isopropylbenzene via a single-state mechanism. In the gas phase, the relative reactivity exhibits the trend <b>Fe-2b</b> > <b>Fe-2b-2</b>, whereas with the addition of the ZPE correction and the SMD model, the relative reactivity follows <b>Fe-2b-2</b> > <b>Fe-2b</b>. For the ruthenium complexes, the relative reactivity follows the trend <b>Ru-2b-2</b> > <b>Ru-2b</b> in both the gas phase and solvent. Thus, the same ligand topologies with the metal-oxo group <i>trans</i> to a different nitrogen affect the reactivities of the iron and ruthenium complexes.</p

Theoretical investigation of different reactivities of Fe(IV)O and Ru(IV)O complexes with the same ligand topology

<p>The structures and mechanisms for hydrogen abstraction from isopropylbenzene for four high-valence complexes, <i>cis</i>-β-[Fe^IV(O)(BQCN)]²⁺ (<b>Fe-2b</b> and <b>Fe-2b-2</b>) and <i>cis</i>-β-[Ru^IV(O)(BQCN)]²⁺ (<b>Ru-2b</b> and <b>Ru-2b-2</b>) (BQCN = N,N′-dimethyl-N,N′-bis(8-quinolyl)-cyclohexanediamine), were investigated using density functional theory. Of the two iron complexes, <b>Fe-2b-2</b> has more exposed FeO units than <b>Fe-2b</b>, with iron being further out of the equatorial plane because of the steric interaction of the same ligand topologies with the iron-oxo group <i>trans</i> to a quinolyl or amine nitrogen. The contribution of BQCN to <b>Fe-2b</b> is higher than the contribution to <b>Fe-2b-2</b> as shown by the density-of-states spectra. The iron isomers can abstract hydrogen from isopropylbenzene via two-state reactivity patterns, whereas the ruthenium isomers react with isopropylbenzene via a single-state mechanism. In the gas phase, the relative reactivity exhibits the trend <b>Fe-2b</b> > <b>Fe-2b-2</b>, whereas with the addition of the ZPE correction and the SMD model, the relative reactivity follows <b>Fe-2b-2</b> > <b>Fe-2b</b>. For the ruthenium complexes, the relative reactivity follows the trend <b>Ru-2b-2</b> > <b>Ru-2b</b> in both the gas phase and solvent. Thus, the same ligand topologies with the metal-oxo group <i>trans</i> to a different nitrogen affect the reactivities of the iron and ruthenium complexes.</p

Plasma-treated Ce/TiO₂–SiO₂ catalyst for the NH₃-SCR of NO<i>_x</i>

<p>Ce/TiO₂–SiO₂ catalysts with different Ti/Si molar ratios are prepared by the incipient impregnation method and their NH₃-SCR activities are evaluated at 100–500°C on a fixed reactor. The Ce/TiO₂–SiO₂ (3/1) catalyst, modified by non-thermal plasma (NTP) treatment and then activated by thermal treatment at 500°C for 4 h, exhibits best performance. Comprehensive deNO<i>_x</i> performance of the catalyst is evidently improved and its efficiency reaches up to 99.21% at 350°C. NO conversion efficiency of the treated catalyst doped with K remains about 90.23% at 300°C and the catalyst also shows improved activity at lower temperatures. Various characterization methods show that the activity enhancement is correlated only with NTP treatment, as it increases the number of Ce³⁺ species, which generates more chemisorbed oxygen, leads to improved dispersion of Brønsted and Lewis acidic sites and finally has an inherent etching effect.</p

Sorafenib-Encapsulated Liposomes to Activate Hypoxia-Sensitive Tirapazamine for Synergistic Chemotherapy of Hepatocellular Carcinoma

Combination therapy with the synergistic effect is an effective way in cancer chemotherapy. Herein, an antiangiogenic sorafenib (SOR) and hypoxia-activated prodrug tirapazamine (TPZ)-coencapsulated liposome (LipTPZ/SOR) is prepared for chemotherapy of hepatocellular carcinoma (HCC). SOR is a multi-target tyrosine kinase inhibitor that can inhibit tumor cell proliferation and angiogenesis. The antiangiogenesis effect of SOR can reduce oxygen supply and aggravate tumor hypoxia, which is able to activate hypoxia-sensitive prodrug TPZ, exhibiting the synergistic antitumor effect. LipTPZ/SOR at different molar ratios of TPZ and SOR can significantly inhibit the proliferation of hepatocellular carcinoma cells. The mole ratio of TPZ and SOR was optimized to 2:1, which exhibited the best synergetic antitumor effect. The synergistic antitumor mechanism of SOR and TPZ was also investigated in vivo. After treated with SOR, the number of vessels was decreased, and the degree of hypoxia was aggravated in tumor tissues. What is more, in the presence of SOR, TPZ could be activated to inhibit tumor growth. The combination of TPZ and SOR exhibited an excellent synergistic antitumor effect. This research not only provides an innovative strategy to aggravate tumor hypoxia to promote TPZ activation but also paints a blueprint about a new nanochemotherapy regimen for the synergistic chemotherapy of HCC, which has excellent biosafety and bright clinical application prospects

Joint trajectory group membership probability of IADL score and CES-D score (%).

<p>Joint trajectory group membership probability of IADL score and CES-D score (%).</p

A Booster for Radiofrequency Ablation: Advanced Adjuvant Therapy via <i>In Situ</i> Nanovaccine Synergized with Anti-programmed Death Ligand 1 Immunotherapy for Systemically Constraining Hepatocellular Carcinoma

Radiofrequency ablation (RFA) is one of the most common minimally invasive techniques for treating hepatocellular carcinoma (HCC), which could destroy tumors through hyperthermia and generate massive tumor-associated antigens (TAAs). However, residual malignant tissues or small satellite lesions are hard to eliminate, generally resulting in metastases and recurrence. Herein, an advanced in situ nanovaccine formed by layered double hydroxides carrying cGAMP (STING agonist) (LDHs-cGAMP) and adsorbed TAAs was designed to potentiate the RFA-induced antitumor immune response. As-prepared LDHs-cGAMP could effectively enter cancerous or immune cells, inducing a stronger type I interferon (IFN-I) response. After further adsorption of TAAs, nanovaccine generated sustained immune stimulation and efficiently promoted activation of dendritic cells (DCs). Notably, infiltrations of cytotoxic lymphocytes (CTLs) and activated DCs in tumor and lymph nodes were significantly enhanced after nanovaccine treatment, which distinctly inhibited primary, distant, and metastasis of liver cancer. Furthermore, such a nanovaccine strategy greatly changed the tumor immune microenvironment and promoted the response efficiency of anti-programmed death ligand 1 (αPD-L1) immunotherapy, significantly arresting the poorly immunogenic hepa1–6 liver cancer progression. These findings demonstrate the potential of nanovaccine as a booster for RFA in liver cancer therapy and provide a promising in situ cancer vaccination strategy

Trajectories of CES-D score over time.

<p>Bar represented the SD for CES-D score in each group in every visit.</p

Logistic regression for adverse CESD group membership.

*<p>With group 1 as reference.</p>#<p>With none condition as reference.</p

Trajectories of IADL score over time.

<p>Bar represented the SD for IADL score in each group in every visit.</p

Percentages of the sample assigned to each trajectory group and average posterior probability for trajectory assignment.

<p>Percentages of the sample assigned to each trajectory group and average posterior probability for trajectory assignment.</p