Water Radiocatalysis for Selective Aqueous-Phase Methane Carboxylation with Carbon Dioxide into Acetic Acid at Room Temperature.

Methane (CH4) carboxylation with carbon dioxide (CO2) into acetic acid (CH3COOH) is an ideal chemical reaction to utilize both greenhouse gases with 100% atom efficiency but remains a great challenge under mild conditions. Herein, we introduce a concept of water (H2O) radiocatalysis for efficient and selective aqueous-phase CH4 carboxylation with CO2 into CH3COOH at room temperature. H2O radiolysis occurs under γ-ray radiation to produce ·OH radicals and hydrated electrons that efficiently react with CH4 and CO2, respectively, to produce ·CH3 radicals and ·CO2- species facilely coupling to produce CH3COOH. CH3COOH selectivity as high as 96.9 and 96.6% calculated respectively from CH4 and CO2 and a CH3COOH production rate of as high as 121.9 µmol·h-1 are acquired. The water radiocatalysis driven by γ-rays is also applicable to selectively produce organic acids from other hydrocarbons and CO2.

Oral Delivery of Gambogenic Acid by Functional Polydopamine Nanoparticles for Targeted Tumor Therapy.

To enhance the water solubility, oral bioavailability, and tumor targeting of gambogenic acid (GNA), polydopamine nanoparticles (PDA NPs) were prepared to encapsulate and stabilize GNA surface modified by folic acid (FA) and then coated with sodium alginate (GNA@PDA-FA SA NPs) to achieve an antitumor effect by oral administration. GNA@PDA-FA SA NPs exhibited in vitro pH-sensitive release behavior. In vitro cell studies manifested that GNA@PDA-FA NPs had higher cytotoxicity to 4T1 cells compared with raw GNA (IC50 = 2.58 µM vs 7.57 µM). After being modified with FA, GNA@PDA-FA NPs were taken up easily by 4T1 cells. In vivo studies demonstrated that the area under the curve (AUC0→∞) of the plasma drug concentration-time of GNA@PDA-FA SA NPs was 2.97-fold higher than that of raw GNA, along with improving drug distribution in the liver, lung, and kidney tissues. In vivo anti-tumor experiments, GNA@PDA-FA SA NPs significantly inhibited the growth of breast tumors in the 4T1 xenograft breast cancer model via oral administration without obvious toxicity on major organs. Our studies indicated that the GNA@PDA-FA SA NPs modified with FA and coated with SA were a promising drug delivery system for targeting tumor therapy via oral administration.

Preparation, preliminary pharmacokinetics and brain tissue distribution of Tanshinone IIA and Tetramethylpyrazine composite nanoemulsions.

Objective: Tanshinone IIA (TSN) and Tetramethylpyrazine (TMP) were combined in a composite, oil-in-water nanoemulsions (TSN/TMP O/W NEs) was prepared to prolong in vitro and vivo circulation time, and enhance the bioavailability of TSN. Material and methods: Physicochemical characterization of TSN/TMP O/W NEs was characterized systematically. The in vitro dissolution and in vivo pharmacokinetic experiments of TSN/TMP O/W NEs were also evaluated. Result: A formulation was optimized, yielding a 32.5 nm average particle size, an encapsulation efficiency of over 95 %, and were spherical in shape as shown by TEM. TSN/TMP O/W NEs were shown to extend the release and availability in vitro compared to raw compounds. In pharmacokinetic study, the AUC0→∞ and t1/2 of the TSN/TMP O/W NEs were 481.50 mg/L*min and 346.39 min higher than TSN solution, respectively. Brain tissue concentration of TSN was enhanced with TSN/TMP O/W NEs over raw TSN and even TSN O/W NEs. Conclusions: Therefore, nanoemulsions are an effective carrier to increase encapsulation efficiency of drugs, improve bioavailability and brain penetration for TSN - which is further enhanced by pairing with the co-delivery of TMP, providing a promising drug delivery.

TiO2 /Cu2 O Core/Ultrathin Shell Nanorods as Efficient and Stable Photocatalysts for Water Reduction.

P-type Cu2 O has been long considered as an attractive photocatalyst for photocatalytic water reduction, but few successful examples has been reported. Here, we report the synthesis of TiO2 (core)/Cu2 O (ultrathin film shell) nanorods by a redox reaction between Cu(2+) and in-situ generated Ti(3+) when Cu(2+) -exchanged H-titanate nanotubes are calcined in air. Owing to the strong TiO2 -Cu2 O interfacial interaction, TiO2 (core)/Cu2 O (ultrathin film shell) nanorods are highly active and stable in photocatalytic water reduction. The TiO2 core and Cu2 O ultrathin film shell respectively act as the photosensitizer and cocatalyst, and both the photoexcited electrons in the conduction band and the holes in the valence band of TiO2 respectively transfer to the conduction band and valence band of the Cu2 O ultrathin film shell. Our results unambiguously show that Cu2 O itself can act as the highly active and stable cocatalyst for photocatalytic water reduction.

Therapeutic effects of Tanshinone IIA and Tetramethylpyrazine nanoemulsions on cognitive impairment and neuronal damage in Alzheimer's disease rat models.

OBJECTIVES: The aim of this study was to investigate the therapeutic effects and related mechanisms of Tanshinone IIA and Tetramethylpyrazine O/W composite nanoemulsions on Alzheimer's disease (AD) rats. METHODS: The therapeutic effect of TSN/TMP O/W NEs on AD rats was evaluated by behavioral tests, H&E, Nissl, and Immunohistochemistry staining. ELISA and Western blot were used to analyze the mechanism. KEY FINDINGS: The results showed that TSN/TMP O/W NEs could down-regulate the expression of Bax and Caspase-3 proteins, decrease the level of MDA, increase the expression of SOD and GSH-Px, and alleviate cognitive impairment in AD rats. CONCLUSIONS: TSN/TMP O/W NEs can inhibit MAPK/ERK/CREB signaling pathway and effectively alleviate cognitive impairment, oxidative stress injury, and neuronal apoptosis in AD rats.

Classic Famous Prescription Kai-Xin-San Ameliorates Alzheimer's Disease via the Wnt/ß-Catenin Signaling Pathway.

Kai-Xin-San (KXS) is a classic famous prescription composed of Polygalae Radix, Ginseng Radix et Rhizoma, Acori Tatarinowii Rhizoma, and Poria. Clinically, KXS is effective in treating amnesia and regulating cognitive dysfunction of Alzheimer's disease (AD), whereas its mechanism of action is still unclear. In this study, the AD model rats were established by combining intraperitoneal injection of D-galactose (150 mg/kg/day) and intracerebral injection of Aß25-35 (10 µL) to investigate the meliorative effect of KXS on AD and explore its mechanism. After 1-month KXS treatment, Morris water maze test showed that different doses of KXS all improved the cognitive impairment of AD rats. The results of hematoxylin and eosin staining, Nissl staining, and Tunnel staining showed that the neuron injury in the hippocampal CA1 region of the AD rats was markedly improved after KXS treatment. Concurrently, KXS reversed the levels of biochemical indexes of AD rats. Furthermore, the protein expressions of Wnt1 and ß-catenin in KXS groups were remarkably increased, while the expressions of Bax and caspase-3 were significantly decreased. Besides, KXS-medicated serum reduced the levels of tumor necrosis factor-α, interleukin-1ß, and reactive oxygen species and regulated the protein expressions of ß-catenin, glycogen synthase kinase-3ß (GSK-3ß), p-GSK-3ß, Bax, and caspase-3 in Aß25-35-induced pheochromocytoma cells. Most importantly, this effect was attenuated by the Wnt inhibitor IWR-1. Our results suggest that KXS improves cognitive and memory function of AD rats, and its neuroprotective mechanism may be mediated through the Wnt/ß-catenin signaling pathway.

CuOx-TiO2 junction: what is the active component for photocatalytic H2 production?

CuOx based junctions e.g. CuOx-TiO2 have been demonstrated to be very effective in photocatalytic H2 production, but the active component at the junction is less understood. We herein report that an as-prepared CuOx-TiO2 photocatalyst undergoes an in situ restructuring process during photocatalytic H2 production under solar light irradiation to form the active Cu2O-TiO2 interfacial structure on the surface. These results unambiguously demonstrate that Cu2O is the active copper species in CuOx-TiO2 photocatalysts.

Molecular oxygen enhances H2O2 utilization for the photocatalytic conversion of methane to liquid-phase oxygenates.

H2O2 is widely used as an oxidant for photocatalytic methane conversion to value-added chemicals over oxide-based photocatalysts under mild conditions, but suffers from low utilization efficiencies. Herein, we report that O2 is an efficient molecular additive to enhance the utilization efficiency of H2O2 by suppressing H2O2 adsorption on oxides and consequent photogenerated holes-mediated H2O2 dissociation into O2. In photocatalytic methane conversion over an anatase TiO2 nanocrystals predominantly enclosed by the {001} facets (denoted as TiO2{001})-C3N4 composite photocatalyst at room temperature and ambient pressure, O2 additive significantly enhances the utilization efficiency of H2O2 up to 93.3%, giving formic acid and liquid-phase oxygenates selectivities respectively of 69.8% and 97% and a formic acid yield of 486 µmolHCOOH·gcatalyst-1·h-1. Efficient charge separation within TiO2{001}-C3N4 heterojunctions, photogenerated holes-mediated activation of CH4 into ·CH3 radicals on TiO2{001} and photogenerated electrons-mediated activation of H2O2 into ·OOH radicals on C3N4, and preferential dissociative adsorption of methanol on TiO2{001} are responsible for the active and selective photocatalytic conversion of methane to formic acid over TiO2{001}-C3N4 composite photocatalyst.