A Highly Efficient Sulfur Host Enabled by Nitrogen/Oxygen Dual-Doped Honeycomb-Like Carbon for Advanced Lithium-Sulfur Batteries.

High energy density and long cycle life of lithium-sulfur (Li-S) batteries suffer from the shuttle/expansion effect. Sufficient sulfur storage space, local fixation of polysulfides, and outstanding electrical conductivity are crucial for a robust cathode host. Herein, a modified template method is proposed to synthesize a highly regular and uniform nitrogen/oxygen dual-doped honeycomb-like carbon as sulfur host (N/O-HC-S). The unique structure not only offers physical entrapment for polysulfides (LiPSs) but also provides chemical adsorption and catalytic conversion sites of polysulfides. In addition, this structure offers enough space for loading sulfur, and a regular space of nanometer size can effectively prevent sulfur particles from accumulating. As expected, the as-prepared N/O-HC900-S with high areal sulfur loading (7.4 mg cm-2 ) shows a high areal specific capacity of 7.35 mAh cm-2 at 0.2 C. Theoretical calculations also reveal that the strong chemical immobilization and catalytic conversion of LiPSs attributed to the spin density and charge distribution of carbon atoms will be influenced by the neighbor nitrogen/oxygen dopants. This structure that provides cooperative chemical adsorption, high lithium ions flux, and catalytic conversion for LiPSs can offer a new strategy for constructing a polysulfide confinement structure to achieve robust Li-S batteries.

Hyaluronic Acid-Modified Nanoparticles Self-Assembled from Linoleic Acid-Conjugated Chitosan for the Codelivery of miR34a and Doxorubicin in Resistant Breast Cancer.

In this study, a chitosan-based, self-assembled nanosystem that codelivered microRNA34a (miR34a) and doxorubicin (Dox) with hyaluronic acid (HA) modification (named CCmDH NPs) was developed to reverse the resistance of breast cancer (BCa) cells to Dox. The CCmDH NPs had a diameter of 180 ± 8.3 nm and a ζ potential of 16.5 mV with a slow-release effect for 96 h. The codelivery system could protect miR34a from nuclease and serum degradation and transport miR34a and Dox into drug-resistant MCF-7/A cells. In addition, the CCmDH NPs could inhibit proliferation and promote apoptosis by regulating the protein expression of B-cell lymphoma-2 (Bcl-2) and poly(ADP-ribose) polymerase (PARP) and inhibit invasion, metastasis, and adhesion by regulating E-cadherin, N-cadherin, MMP2, CD44, and Snail molecules. The CCmDH NPs induced a 73.7% tumor reduction in xenograft tumor growth in nude mice in vivo. This study provides evidence for the anticancer activity of CCmDH NPs carrying Dox and miR34a in BCa, especially metastatic Dox-resistant BCa models.

Spontaneous vesicle formation and vesicle-to-α-gel transition in aqueous mixtures of sodium monododecylphosphate and guanidinium salts.

Monoalkyl phosphates (MAPs) are one kind of important single-chain weak acid/salt type surfactants, but the understanding of their aggregation behavior in water is very limited due to their insolubility at room temperature. In the current work, the effect of guanidinium salts (GuSalts) on the solubility of sodium monododecylphosphate (SDP), a typical MAP, in water was determined at 25.0 °C, and the aggregation behavior of SDP in the GuSalt/water mixtures was investigated. The solubility of SDP is significantly improved by GuSalts including GuCl, GuSO4, GuSO3, GuPO4, and GuCO3 at 25.0 °C, resulting in an isotropic phase. SDP vesicles are spontaneously formed in the isotropic phase, with a critical vesicle concentration of ∼1.0 mM independent of the type of GuSalts. A "bridging dimer" mechanism is proposed to explain the formation of SDP vesicles. The SDP vesicles have a unilamellar structure with a size of ∼80 nm and an alkyl interdigitated degree of ∼25%, and exhibit size-selective permeability. Interestingly, a temperature-induced reversible transition between vesicles and α-gels was observed for the SDP/GuSalt/H2O systems when the SDP content is higher than 20 mM. The α-gels obtained are composed of vesicles and bilayer sheets, showing similar viscoelasticity to conventional gels, although their water content is as high as ∼98 wt%. The microviscosity of SDP vesicle membranes (ca. 35.79-49.34 mPa s at 25.0 °C) and the transition temperature between vesicles and α-gels (ca. 21.0-22.8 °C) are all dependent of the type of GuSalts. This work deepens the understanding of the aggregation behavior of MAPs and also provides valuable information for their practical applications.

Vesicle formation of single-chain amphiphilic 4-dodecylbenzene sulfonic acid in water and micelle-to-vesicle transition induced by wet-dry cycles.

Simple single-chain amphiphiles (SCAs) can form vesicular structures in their single-component aqueous solutions, which has attracted great attention, but the understanding of their aggregation behavior is still limited. In this work, the aggregation behavior of 4-dodecylbenzene sulfonic acid (DBSA), a typical simple SCA, in water was investigated. The structure and properties of the aggregates formed were determined. In particular, the effect of wet-dry cycles on the structures of aggregates was examined. The mechanisms of aggregate formation and structural transition were discussed. It was found that the increase of DBSA concentration can drive the occurrence of a micelle-to-vesicle transition, showing a critical micelle concentration and critical vesicle concentration of ∼0.53 and 2.14 mM, respectively. The vesicles formed coexist with micelles in solution, with a unilamellar structure and ∼80 nm size, and exhibit size-selective permeability. In addition, the vesicles show remarkable stability upon long-term storage, exposure to high temperature, and freeze-thaw cycles. The H-bonding interaction between DBSA species and the interdigitated structure of alkyl chains in bilayers play a key role in the formation and stability of DBSA vesicles. Interestingly, it was found that the wet-dry cycle can induce a micelle-to-vesicle transition and an obvious increase in the size of the original vesicles, accompanied by the formation of some multilamellar vesicles. This work provides a better understanding of the aggregation behavior of simple SCAs in their single-component aqueous solutions.