A Small-Molecule Organic Cathode with Extended Conjugation toward Enhancing Na+ Migration Kinetics for Advanced Sodium-Ion Batteries.

Organic cathode materials show excellent prospects for sodium-ion batteries (SIBs) owing to their high theoretical capacity. However, the high solubility and low electrical conductivity of organic compounds result in inferior cycle stability and rate performance. Herein, an extended conjugated organic small molecule is reported that combines electroactive quinone with piperazine by the structural designability of organic materials, 2,3,7,8-tetraamino-5,10-dihydrophenazine-1,4,6,9-tetraone (TDT). Through intermolecular condensation reaction, many redox-active groups C═O and extended conjugated structures are introduced without sacrificing the specific capacity, which ensures the high capacity of the electrode and enhances rate performance. The abundant NH2 groups can form intermolecular hydrogen bonds with the C═O groups to enhance the intermolecular interactions, resulting in lower solubility and higher stability. The TDT cathode delivers a high initial capacity of 293 mAh g-1 at 500 mA g-1 and maintains 90 mAh g-1 at an extremely high current density of 70 A g-1. The TDT || Na-intercalated hard carbon (Na-HC) full cells provide an average capacity of 210 mAh g-1 during 100 cycles at 500 mA g-1 and deliver a capacity of 120 mAh g-1 at 8 A g-1.

Advanced Polymers in Cathodes and Electrolytes for Lithium-Sulfur Batteries: Progress and Prospects.

Lithium-sulfur (Li-S) batteries, which store energy through reversible redox reactions with multiple electron transfers, are seen as one of the promising energy storage systems of the future due to their outstanding advantages. However, the shuttle effect, volume expansion, low conductivity of sulfur cathodes, and uncontrollable dendrite phenomenon of the lithium anodes have hindered the further application of Li-S batteries. In order to solve the problems and clarify the electrochemical reaction mechanism, various types of materials, such as metal compounds and carbon materials, are used in Li-S batteries. Polymers, as a class of inexpensive, lightweight, and electrochemically stable materials, enable the construction of low-cost, high-specific capacity Li-S batteries. Moreover, polymers can be multifunctionalized by obtaining rich structures through molecular design, allowing them to be applied not only in cathodes, but also in binders and solid-state electrolytes to optimize electrochemical performance from multiple perspectives. The most widely used areas related to polymer applications in Li-S batteries, including cathodes and electrolytes, are selected for a comprehensive overview, and the relevant mechanisms of polymer action in different components are discussed. Finally, the prospects for the practical application of polymers in Li-S batteries are presented in terms of advanced characterization and mechanistic analysis.

Advanced Nanostructured Materials for Electrocatalysis in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are considered as among the most promising electrochemical energy storage devices due to their high theoretical energy density and low cost. However, the inherently complex electrochemical mechanism in Li-S batteries leads to problems such as slow internal reaction kinetics and a severe shuttle effect, which seriously affect the practical application of batteries. Therefore, accelerating the internal electrochemical reactions of Li-S batteries is the key to realize their large-scale applications. This article reviews significant efforts to address the above problems, mainly the catalysis of electrochemical reactions by specific nanostructured materials. Through the rational design of homogeneous and heterogeneous catalysts (including but not limited to strategies such as single atoms, heterostructures, metal compounds, and small-molecule solvents), the chemical reactivity of Li-S batteries has been effectively improved. Here, the application of nanomaterials in the field of electrocatalysis for Li-S batteries is introduced in detail, and the advancement of nanostructures in Li-S batteries is emphasized.

Activating peroxymonosulfate using carbon from cyanobacteria as support for zero-valent iron.

In the present study, the cyanobacterial char (ACC) prepared from Chaohu cyanobacteria was used as a nanoscale carrier for zero-valent iron (NZVI) to synthesize a highly efficient activation material designated as cyanobacterial char-supported nanoscale zero-valent iron (NZVI@ACC), which was subsequently used for activating peroxymonosulfate (PMS) to degrade the orange II (OII) dye. The XRD and XPS results revealed that NZVI was anchored onto the ACC through coordination bonding, forming a stable structure. The SEM and TEM observations revealed that the NZVI was embedded in the sheet structure of the ACC. The NZVI@ACC had a larger specific surface area (42.249 m2/g) and also magnetism, due to which its components could be separated through an externally applied magnetic field. Using this NZVI@ACC/PMS system, the rate of degradation of OII (100 mg/L) reached 98.32% within 14 min. The OII degradation reaction using the NZVI@ACC/PMS system followed first-order kinetics. The activation energy of this degradation reaction was 17.34 kJ/(mol·K). Quenching and EPR experiments revealed that various free radicals (SO4·-, ·OH) were produced, with SO4·- playing the major role in the reaction. The theoretical calculations revealed that SO4·- attacked the 12 (N) of OII, thereby destroying and degrading both azo and hydrogenated azo structures of OII. The presence of halogen ions in the actual dye-containing wastewater samples inhibited the OII degradation by the NZVI@ACC system to different degrees, and the inhibition effect followed the order I- > Br- > Cl-.

Low-frequency vibrational spectroscopy: a new tool for revealing crystalline magnetic structures in iron phosphate crystals.

In this report, the strong-dependence of low-frequency (terahertz) vibrational dynamics on weak and long-range forces in crystals is leveraged to determine the bulk magnetic configuration of iron phosphate - a promising material for cathodes in lithium ion batteries. We demonstrate that terahertz time-domain spectroscopy - coupled with quantum mechanical simulations - can discern between various spin configurations in FePO4. Furthermore, the results of this work unambiguously show that the well-accepted space group symmetry for FePO4 is incorrect, and the low-frequency spectroscopic measurements provide a clearer picture of the correct structure over the gold-standard of X-ray diffraction. This work opens the door for characterizing, predicting, and interpreting crystalline magnetic ordering using low-frequency vibrational spectroscopy.

Sulfur-Rich Polymers Based Cathode with Epoxy/Ally Dual-Sulfur-Fixing Mechanism for High Stability Lithium-Sulfur Battery.

Lithium-sulfur (Li-S) batteries have attracted a great deal of attention for the next-generation energy storage devices due to their inherently high theoretical energy density, high natural abundance, and low cost. However, the dissolution of polysulfides in electrolytes and their undesirable shuttle behavior lead to poor cycling performance, which obstructs practical application. Herein, we report a dual-sulfur-fixing mechanism of epoxy/allyl compound/sulfur system to prepare poly(sulfur-random-4-vinyl-1,2-epoxycyclohexane) (SVE) copolymers as powerful cathode materials. Benefiting from the stable C-S bond and a uniform distribution of ultrafine Li2S/S8 in the SVE-based polymer matrix, the SVE electrodes exerted an embedding effect to reduce polysulfides migration. The thiosulfate/polythionate protective layer derived from the terminal hydroxyl group of SVE also ensured the cycle stability of SVE electrodes during cycling. As a result, optimized SVE electrodes deliver a high reversible specific capacity of 1248 mA h g-1 at rates of 0.1 C, together with a stable cycling performance of no capacity decay per cycle over more than 400 cycles. This work provides an effective strategy for the practical application of organosulfur polymers Li-S batteries and inspires the exploration of the reaction mechanism of epoxy/allyl compound/sulfur system.

Paracrine-endocrine FGF chimeras as potent therapeutics for metabolic diseases.

BACKGROUND: The development of a clinically useful fibroblast growth factor 21 (FGF21) hormone has been impeded by its inherent instability and weak FGF receptor (FGFR) binding affinity. There is an urgent need for innovative approaches to overcome these limitations. METHODS: We devised a structure-based chimerisation strategy in which we substituted the thermally labile and low receptor affinity core of FGF21 with an HS binding deficient endocrinised core derived from a stable and high receptor affinity paracrine FGF1 (FGF1ΔHBS). The thermal stability, receptor binding ability, heparan sulfate and ßKlotho coreceptor dependency of the chimera were measured using a thermal shift assay, SPR, SEC-MALS and cell-based studies. The half-life, tissue distribution, glucose lowering activity and adipose tissue remodeling were analyzed in normal and diabetic mice and monkeys. FINDINGS: The melting temperature of the engineered chimera (FGF1ΔHBS-FGF21C-tail) increased by ∼22 °C relative to wild-type FGF21 (FGF21WT), and resulted in a ∼5-fold increase in half-life in vivo. The chimera also acquired an ability to bind the FGFR1c isoform - the principal receptor that mediates the metabolic actions of FGF21 - and consequently was dramatically more effective than FGF21WT in correcting hyperglycemia and in ameliorating insulin resistance in db/db mice. Our chimeric FGF21 also exerted a significant beneficial effect on glycemic control in spontaneous diabetic cynomolgus monkeys. INTERPRETATION: Our study describes a structure-based chimerisation approach that effectively mitigates both the intrinsically weak receptor binding affinities and short half-lives of endocrine FGFs, and advance the development of the FGF21 hormone into a potentially useful drug for Type 2 diabetes.

Impact of drug loading in mesoporous silica-amorphous formulations on the physical stability of drugs with high recrystallization tendency.

In this study, a method is described to determine the monolayer loading capacity (MLC) of the drugs naproxen and ibuprofen, both having high recrystallization tendencies, in mesoporous silica (MS), a well known carrier that is able to stabilize the amorphous form of a drug. The stabilization has been suggested to be due to direct absorption of the drug molecules onto the MS surface, i.e. the drug monolayer. In addition, drug that is not in direct contact with MS surface can fill the pores up to its pore filling capacity (PFC) and is potentially stabilized by confinement due to the pore size being smaller than a crystal nuclei. For drugs with high recrystallization tendencies, any drug outside the pores crystallizes due to its poor physical stability. The drug monolayer does not contribute to the glass transition temperature (Tg ) in the DSC, however, the confined amorphous drug above MLC has a Tg and the heat capacity (ΔC p) over the Tg increases with an increasing fraction of confined amorphous drug. Hence, several drug loading values above the MLC were investigated towards the presence of a Tg and ΔC p using differential scanning calorimetry (DSC). A linear correlation between the amount of confined amorphous drug and its ΔC p was identified for the mixtures between the MLC and PFC. By subsequent extrapolation to zero ΔC p the experimental MLC could be determined. Using theoretical density functional theory (DFT) and ab initio Molecular Dynamics (AIMD), the binding energies for the monolayer suggested that the monolayer in fact is thermodynamically more favorable than the crystalline form, whereas the confined amorphous form is thermodynamically less favorable. Consequently, a physical stability study showed that the confined amorphous drugs above the MLC were thermodynamically unstable and consequently flowing out of the pores in order to crystallize, whereas the monolayer remained physically stable.

Characterising glass transition temperatures and glass dynamics in mesoporous silica-based amorphous drugs.

In this study the glass transition temperatures (Tgα and Tgß) in mesoporous silica-based amorphous drugs were characterized. For this purpose, mesoporous silica Parteck SLC (MPS) was loaded with the drugs ibuprofen and carvedilol, either below, at, or above the monomolecular drug loading capacities, i.e. the concentration at which the entire MPS surface is covered with a monolayer of drug molecules. The resulting amorphous forms were analysed using X-ray powder diffraction and the thermal behaviour was characterised with differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The drug monolayer did not contribute to the thermal signal in DSC. Using DMA however, it could be shown that the monolayer indeed exhibited a very weak Tgα, and that the temperature range of this transition did not differ from that of the quench cooled amorphous drugs. Theoretical ab initio molecular dynamics simulations revealed that the nature of hydrogen bonding geometry of the functional groups interacting with the MPS surface were similar to that of the respective crystalline drugs, which results in restricted molecular motions for those functional groups. On the other hand, the non-interacting parts of the molecules exhibited molecular motions similar to what is observed in pure amorphous drugs. As a result of the interactions of the monolayer with the MPS surface, the monomolecular drug layer did not reveal a Tgß. However, a Tgß was found at any drug-MPS ratios above the monomolecular drug loading capacity as a result of the excess drug which forms a "true" amorphous phase. Overall, this study demonstrated that drug molecules forming an amorphous monolayer on the surfaces of a mesoporous silica particle, even though they are restricted in their mobility, exhibit a Tgα, but lack a Tgß, whereas any excess drug confined in the MPS pores showed similar properties as the pure amorphous drug. These findings will help to increase the overall understanding of drug loaded MS systems, including their physical stability as well as release properties.

Correlation between saturated fatty acid chain-length and intermolecular forces determined with terahertz spectroscopy.

We measured crystalline (C-form) saturated fatty acids with even carbon numbers ranging from 12 to 20 using temperature dependent terahertz time-domain spectroscopy (THz-TDS). Absorption features between 0.5 and 3 THz were identified at temperatures from 96 K to 293 K, and a systematic red-shift was obvserved with the increasing carbon chain length. The origins of these absorption bands were uncovered using state-of-the-art ab initio density functional theory (DFT) calculations. Similar vibrational motions in the absorption bands of the different materials highlight the unique role that THz-TDS has for probing weak non-covalent interactions in these materials. Our results showcase the utility of the terahertz region, which is beyond the scope of related vibrational techniques, providing direct evidence of the effect of chain length on the intermolecular interactions of these molecules.

Naringenin: a potential immunomodulator for inhibiting lung fibrosis and metastasis.

Patients with idiopathic pulmonary fibrosis have a high incidence of lung cancer and a worse prognosis for clinical treatment. A few molecules with antifibrosis properties have been shown promoting cancer progression in clinical trials. The objective of this study was to determine whether there is a similar tendency in mice as in human beings and whether these mice models may be used to find new therapeutic agents with antifibrotic properties but not cancer-promoting properties. We used bleomycin to induce pulmonary fibrosis in mice with or without naringenin treatment and measured the immune-associated lymphocytes and their secreted cytokines using flow cytometry and ELISA from lung tissue. Both passive and spontaneous metastatic models in bleomycin-treated C57BL/6 and BALB/c mice were used to test the hypothesis that mice with pulmonary fibrosis could have an increased risk of lung cancer and associated cancer progression. Here, we show that mice with lung fibrosis challenged using tumors show an increased incidence of lung metastasis and shorter life spans compared with the mice without lung fibrosis. A fibrotic environment in the lung results in increased abundance of transforming growth factor-beta1 and CD4(+)CD25(+)Foxp3(+) regulatory T cells and a decreased proportion of activated effector T cells. This grave immunosuppressive environment favors tumor localization and growth. Naringenin significantly reduces lung metastases in mice with pulmonary fibrosis and increases their survival by improving the immunosuppressive environment through down-regulating transforming growth factor-beta1 and reducing regulatory T cells. Naringenin could be an ideal therapeutic agent in the treatment of both cancer and fibrosis.

[The primary evaluation of Sal-Ammoniac extract on the therapy action in mice bearing Lewis lung cancer].

OBJECTIVE: To evaluate the therapy action of Sal-Ammoniac extract on Lewis lung cancer and its toxicity to immunity. METHODS: The proliferation and cell cycle of Lewis lung cancer cells were determined by MTT assay and flow cytometry respectively. The antitumor effect of Sal-Ammoniac extract was observed by tumor injected subcutaneously in mice and its toxicity to immunity was examined by clearance rate of charcoal particles and delayed type hypersensitivity. RESULTS: Sal-Ammoniac extract could inhibit the proliferation of Lewis lung cancer cells with S cell cycle arrest in a dose-dependent manner in vitro. Sal-Ammoniac extract solution injected in tumor for eight days had 46.7% inhibition on Lewis lung cancer, if taken orally had only 15.7% inhibition on Lewis lung cancer in mice. Sal-Ammoniac extract solution injected subcutaneously or taken orally had no effect on the clearance rate of charcoal particles and delayed type hypersensitivity in mice. CONCLUSION: The antitumor action of Sal-Ammoniac extract has relation to its recipe and has no influence on immunity.