A 3D Cross-Linked Metal-Organic Framework (MOF)-Derived Polymer Electrolyte for Dendrite-Free Solid-State Lithium-Ion Batteries.

Lithium metal batteries (LMBs) with high energy density have received widespread attention; however, there are usually issues with lithium dendrite growth and safety. Therefore, there is a demand for solid electrolytes with high mechanical strength, room-temperature ionic conductivity, and good interface performance. Herein, a 3D cross-linked metal-organic framework (MOF)-derived polymer solid electrolyte exhibits good mechanical and ionic conductive properties simultaneously, in which the MOF with optimized pore size and strong imidazole cation sites can restrict the migration of anions, resulting in a uniform Li+ flux and a high lithium-ion transference number (0.54). Moreover, the MOF-derived polymer solid electrolytes with the 3D cross-linked network can promote the rapid movement of Li+ and inhibit the growth of lithium dendrites. Lithium symmetric batteries assembled with the 3D MOF-derived polymer solid electrolytes are subjected to lithium plating/stripping and cycled over 2000 h at a current density of 0.1 mA cm-2 and over 800 h at a current density of 0.2 mA cm-2 . The Li/P-PETEA-MOF/LiFePO4 batteries exhibit excellent long-cycle stability and cycle reversibility.

A simple liposome-based bionic bacterium for tumor treatment by re-education of tumor-associated microphages in combination with chemotherapy.

Re-education of tumor-associated macrophages (TAMs) into M1-like macrophages (Mφ1) has become one of the aims of tumor immunotherapy. Injection of live bacteria has been applied for this purpose; however, an acute innate immune response might be caused in this progress, and therefore a bacteria-based strategy with great security is needed. In this study, the bacterial walls of Staphylococcus aureus were inserted into the bilayer of liposome to construct liposome-based bionic bacteria (Bio-Bac), and doxorubicin (DOX) was encapsulated to form DOX@Bio-Bac. DOX@Bio-Bac re-educated the THP-1-derived TAMs into Mφ1 in vitro, and subsequently inhibited the migration and invasion of CAL27 cells. In a mouse model of hepatocellular carcinoma with lymphatic metastasis, the re-education of TAMs was proved, and an effective inhibition of tumor growth and metastasis in mice was observed. The liposome-based bionic bacteria constructed in this study provide a new strategy for re-education of TAMs, replacing the bacterial therapy reported previously, and a more effective anti-tumor effect can be obtained by combining the chemotherapy drugs with this bionic bacterium.

An Asymmetric Cross-Linked Ionic Copolymer Hybrid Solid Electrolyte with Super Stretchability for Lithium-Ion Batteries.

Composite solid electrolytes are recommended to be the most promissing strategy for solid-state batteries because they combine the advantages of inorganic ceramics and polymers. However, the huge interfacial resistance between the inorganic ceramic and polymer results in low ionic conductivity, which is still the major impediment that limits their applications. Herein, a novel highly elastic and weakly coordinated ionic copolymer hybrid electrolyte with asymmetric structure based on surface-modified Li1.5 Al0.5 Ge1.5 (PO4 )3 by "in situ" polymerization is proposed to improve ionic conductivity and mechanical properties simultaneously. The all-solid hybrids electrolytes exhibit room-temperature ionic conductivity up to 2.61 × 10-4 S cm-1 and lithium-ion transference number of 0.41. The hybrids electrolytes can be repeatedly stretching-releasing-stretching, showing a super stretchability with the elongation at break up to 496%. The Li symmetrical cells assembled with the hybrid electrolytes can continuously operate for 800 h at 0.1 mA cm-2 without discernable dendrites, indicating good interfacial compatibility between the hybrid electrolytes and lithium electrodes. The Li|LiFePO4 batteries assembled with the hybrid electrolytes deliver an initial discharge specific capacity of 165.5 mAh g-1 with an initial coulombic efficiency of 94.8% and 154 mAh g-1 after 100 cycles at 0.1 C, and maintain 95.4% capacity retention after 100 cycles at 0.5 C.

O-carboxymethyl chitosan based pH/hypoxia-responsive micelles relieve hypoxia and induce ROS in tumor microenvironment.

The hypoxia in tumor microenvironment (TME) can upregulate the HIF-1α and PD-L1 expression and cause immunosuppression of tumor. In this study, a carboxymethyl chitosan-based pH/hypoxia-responsive and γ-Fe2O3/isosorbide dinitrate carrying micelle was designed, and it could catalyze endogenous H2O2 to generate oxygen and relieve hypoxia in TME, so as to relieve the overexpression of HIF-1α and PD-L1 in tumor; meanwhile, it could react with H2O2 to release ROS via Fenton reaction and induce cytotoxicity in tumor. Along with these multiple effects, this carboxymethyl chitosan-based micelles could provide a comprehensive strategy for tumor treatment.

Improvement in phenotype homeostasis of macrophages by chitosan nanoparticles and subsequent impacts on liver injury and tumor treatment.

When organic polymer-based drug nanocarriers become concentrated in macrophages, their influence on macrophage polarization has been rarely reported. This study prepared chitosan-based nanoparticles (CNs, 181.5 nm, +14.83 mV) and detected their impacts on macrophage reprogram. RT-PCR results showed in M1-like RAW264.7 cells (Mφ1), CNs decreased CD86 and iNOS expressions by 53.8% and 57.1%, and increased Arg-1 and IL-10 by 642.9% and 102.1%; in M2-like cells (Mφ2), CNs reduced Arg-1 and MR expressions by 70.7% and 93.0%, but increased CD86, iNOS and TNF-α by 290.4%, 86.2% and 728.6%; these results, consistent with cytokine secretions and surface CD86/CD206 expressions, showed CNs polarized Mφ1 and Mφ2 toward opposite type so as to improve the macrophage polarization homeostasis. In CCl4-induced mouse liver injury model, CNs reduced the hepatic Mφ1/Mφ2 ratio from 1.1 (model group) to 0.3, and then reduced the serum AST and ALT level by 42.3% and 39.0%; in mouse model of hepatocellular carcinoma, CNs decreased the number of CD163-positive cells and increased CD86-positive ones in tumor, and subsequently inhibited the tumor growth and metastasis. This study suggests CNs can improve the phenotype homeostasis of macrophages and subsequently promote the treatment of certain diseases such as liver injury and tumor.

Room temperature cupric halides mediated olefin alkoxylation of BODIPYs with methanol: mechanisms and scope.

We disclose an efficient methodology for olefin alkoxylation of fluorescent BODIPYs (boron-dipyrromethene) at the 3,5-styryl group with methanol by cupric halide (chloride or bromide) at room temperature. Mechanistic studies provide evidence for the alkoxylation reaction firstly initiated by a radical cation, that is, halide promotes the oxidizing ability of the Cu(ii) center to an extent that the single electron transfer (SET) from BODIPYs to the cupric ion and results in the production of a BODIPYs radical cation and Cu(i), then the BODIPYs radical cation subsequently reacts with methanol to afford the alkoxylated product. As the dialkoxylated product complexes with cuprous halide and further decreases its reducing ability, which is supported by DFT calculations, only strongly oxidative cupric bromide can mediate tetraalkoxylation and give rise to the tetraalkoxylated product. In addition, the expanded scope studies suggest that this method is also well suited for the alkoxylation of electron-rich conjugated olefins. The active benzyl bromide derivative may be another intermediate in the presence of cupric bromide. Therefore, the reaction is highly dependent on the anions of cupric salts; Cu(OAc)2, CuSO4 and Cu(NO3)2 containing weakly nucleophilic anions show no activity in alkoxylation.

[Effect of percutaneous intervention on adrenomedullin and tumor necrosis factor in the coronary circulation].

OBJECTIVE: To evaluate the effect of percutaneous intervention (PCI) on coronary circulation levels of adrenomedullin (ADM) and tumor necrosis factor alpha (TNF-alpha) in patients with coronary heart disease (CHD). METHODS: Thirty-three CHD patients underwent percutaneous transluminal coronary angioplasty (PTCA) and stenting (altogether 48 stents were implanted). Blood samples were collected from the coronary sinus and femoral artery at the time points of immediately before and after angioplasty, immediately after PTCA or stenting, 10 min after procedures, respectively. RESULTS: The ADM and TNF-alpha levels in the coronary sinus varied little after coronary angiography, but were elevated markedly following PTCA from the basal levels of 36.3+/-1.3 pg/ml to 28.9+/-1.9 pg/ml (P<0.01) and from 11.10+/-0.46 ng/ml to 8.84+/-0.37 ng/ml (P<0.01), respectively. Further increases of ADM and TNF-alpha levels were detected immediately after stent deployment. ADM recovered to basal levels 10 min after completion of the procedures, while TNF-alpha underwent further increase. Before the procedure, ADM and TNF-alpha levels were higher in the coronary sinus than in the femoral artery (28.9+/-1.9 pg/ml vs 22.6+/-0.8 pg/ml, P<0.01; 8.84+/-0.37 ng/ml vs 7. 56+/-0.23 ng/ml, P<0.01, respectively), and their levels in the femoral artery did not undergo significant changes in response to the operations. CONCLUSION: The coronary circulation levels of ADM and TNF-alpha increase after PTCA and stenting but not after coronary angiography in CHD patients, which might be attributed to injuries by the procedures as well as the mechanical stimulation by the stent.