Self-Assembled Aza-Boron-Dipyrromethene-Based H2S Prodrug for Synergistic Ferroptosis-Enabled Gas and Sonodynamic Tumor Therapies.

Glioblastoma multiforme (GBM) is the most aggressive and lethal subtype of gliomas of the central nervous system. The efficacy of sonodynamic therapy (SDT) against GBM is significantly reduced by the expression of apoptosis-inhibitory proteins in GBM cells. In this study, an intelligent nanoplatform (denoted as Aza-BD@PC NPs) based on the aza-boron-dipyrromethene dye and phenyl chlorothionocarbonate-modified DSPE-PEG molecules is developed for synergistic ferroptosis-enabled gas therapy (GT) and SDT of GBM. Once internalized by GBM cells, Aza-BD@PC NPs showed effective cysteine (Cys) consumption and Cys-triggered hydrogen sulfide (H2S) release for ferroptosis-enabled GT, thereby disrupting homeostasis in the intracellular environment, affecting GBM cell metabolism, and inhibiting GBM cell proliferation. Additionally, the released Aza-BD generated abundant singlet oxygen (1O2) under ultrasound irradiation for favorable SDT. In vivo and in vitro evaluations demonstrated that the combined functions of Cys consumption, H2S production, and 1O2 production induced significant death of GBM cells and markedly inhibited tumor growth, with an impressive inhibition rate of up to 97.5%. Collectively, this study constructed a cascade nanoreactor with satisfactory Cys depletion performance, excellent H2S release capability, and prominent reactive oxygen species production ability under ultrasound irradiation for the synergistic ferroptosis-enabled GT and SDT of gliomas.

Nanosonosensitizers-engineered injectable thermogel for augmented chemo-sonodynamic therapy of melanoma and infected wound healing.

Easy recurrence and bacteria infected-wound healing after surgery excision pose severe challenges to clinical melanoma therapy. Herein, an injectable CuO2 nanodots-engineered thermosensitive chitosan hydrogel (CuO2-BSO@Gel) for enhanced melanoma chemo-sonodynamic therapy and improved infected wound healing was rationally constructed by facilely integrating the CuO2 nanodots and L-Buthionine-(S, R)-sulfoximine (BSO) with thermoresponsive hydrogel. Favored by the Fenton catalytic activity of Cu2+, the CuO2 nanodots can achieve enhanced chemodynamic therapy (CDT) by self-supplying H2O2 under acidic tumor microenvironment. Simultaneously, the CuO2 nanodots with a narrow bandgap (2.29 â€‹eV) were proven to be the efficient sonosensitizers, and the corresponding quantum yield of singlet oxygen (1O2) could be boosted by the O2 generation during Fenton-like reactions. Additionally, combining with the glutathione (GSH) depletion of loaded BSO, intracellular oxidative stress induced by SDT and CDT was further amplified, leading to the specific ferroptosis. Importantly, this multifunctional hydrogel significantly promoted the proliferation of normal skin cells and accelerated the bacteria-infected wound healing by the effective chemo-sonodynamic antibacterial activity and the enhanced angiogenesis. Thus, the engineered thermogel features the distinct chemo-sonodynamic performance, desirable biocompatibility and bioactivity, providing a competitive strategy for eradicating melanoma and infected wound healing.

Highly Porous Organic Polymers for Hydrogen Fuel Storage.

Hydrogen (H2) is one of the best candidates to replace current petroleum energy resources due to its rich abundance and clean combustion. However, the storage of H2 presents a major challenge. There are two methods for storing H2 fuel, chemical and physical, both of which have some advantages and disadvantages. In physical storage, highly porous organic polymers are of particular interest, since they are low cost, easy to scale up, metal-free, and environmentally friendly. In this review, highly porous polymers for H2 fuel storage are examined from five perspectives: (a) brief comparison of H2 storage in highly porous polymers and other storage media; (b) theoretical considerations of the physical storage of H2 molecules in porous polymers; (c) H2 storage in different classes of highly porous organic polymers; (d) characterization of microporosity in these polymers; and (e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.

Computationally designed families of flat, tubular, and cage molecules assembled with "starbenzene" building blocks through hydrogen-bridge bonds.

Using density functional calculations, we demonstrate that the planarity of the nonclassical planar tetracoordinate carbon (ptC) arrangement can be utilized to construct new families of flat, tubular, and cage molecules which are geometrically akin to graphenes, carbon nanotubes, and fullerenes but have fundamentally different chemical bonds. These molecules are assembled with a single type of hexagonal blocks called starbenzene (D(6h) C(6)Be(6)H(6)) through hydrogen-bridge bonds that have an average bonding energy of 25.4-33.1 kcal mol(-1). Starbenzene is an aromatic molecule with six pi electrons, but its carbon atoms prefer ptC arrangements rather than the planar trigonal sp(2) arrangements like those in benzene. Various stability assessments indicate their excellent stabilities for experimental realization. For example, one starbenzene unit in an infinite two-dimensional molecular sheet lies on average 154.1 kcal mol(-1) below three isolated linear C(2)Be(2)H(2) (global minimum) monomers. This value is close to the energy lowering of 157.4 kcal mol(-1) of benzene relative to three acetylene molecules. The ptC bonding in starbenzene can be extended to give new series of starlike monocyclic aromatic molecules (D(4h) C(4)Be(4)H(4)(2-), D(5h) C(5)Be(5)H(5)(-), D(6h) C(6)Be(6)H(6), D(7h) C(7)Be(7)H(7)(+), D(8h) C(8)Be(8)H(8)(2-), and D(9h) C(9)Be(9)H(9)(-)), known as starenes. The starene isomers with classical trigonal carbon sp(2) bonding are all less stable than the corresponding starlike starenes. Similarly, lithiated C(5)Be(5)H(5) can be assembled into a C(60)-like molecule. The chemical bonding involved in the title molecules includes aromaticity, ptC arrangements, hydrogen-bridge bonds, ionic bonds, and covalent bonds, which, along with their unique geometric features, may result in new applications.

Ti-substituted boranes as hydrogen storage materials: a computational quest for the ideal combination of stable electronic structure and optimal hydrogen uptake.

Based on the Wade-Mingos n+1 rule for the closo-boranes (B(n)H(n) (2-)), a family of Ti-substituted closo-boranes has been designed computationally. Due to the isolobal relation of Ti to a BH(2-) group, these Ti-substituted boranes have n+1 pairs of skeletal electrons to fulfill the bonding requirement for such stable cages. The reported representatives, B(4)H(4)Ti(2)H(2) in particular, not only have stable electronic structures but also superior capability to adsorb hydrogen. The optimal binding energies and high gravimetric densities of hydrogen storage indicate their potential to store hydrogen for practical applications. Simultaneously achieving electronic stability and optimal hydrogen uptake may provide a way of overcoming the issue of aggregation in designing transition-metal-decorated hydrogen storage materials. This study invites experimental realization of novel boranes and provides new ideas for searching for hydrogen storage materials.

Propagation and refraction of chemical waves generated by local periodic forcing in a reaction-diffusion model.

We study wave propagation, interaction, and transmission across the boundary between two chemical media in a model of an oscillatory reaction-diffusion medium subjected to local periodic forcing. The forced waves can be either outwardly (OP) or inwardly propagating (IP), depending on the dispersion of the medium. Competition among forced waves, spontaneous spiral waves, and bulk oscillations is studied for both cases. We demonstrate development of a negatively refracted wave train when forced waves traverse the boundary between the OP medium and the IP medium.