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Here, we comprehensively investigated methanol electrooxidation on Cu-based catalysts, allowing us to build the first microfluidic fuel cell (μFC) equipped with a Cu anode and a metal-free cathode that converts energy from methanol. We applied a simple, fast, small-scale, and surfactant-free strategy for synthesizing Cu-based nanoparticles at room temperature in steady state (ST), under mechanical stirring (MS), or under ultrasonication (US). The morphology evaluation of the Cu-based samples reveals that they have the same nanoparticle (NP) needle-like form. The elemental mapping composition spectra revealed that pure Cu or Cu oxides were obtained for all synthesized materials. In addition to having more Cu 2 O on the surface, sample US had more Cu(OH) 2 than the others, according to X-ray diffractograms and X-ray photoelectron spectroscopy. The sample US is less carbon-contaminated because of the local heating of the sonic bath, which also enhances the cleanliness of the Cu surface. The activity of the Cu NPs was investigated for methanol electrooxidation in an alkaline medium through electrochemical and spectroelectrochemical measurements. The potentiodynamic and potentiostatic experiments showed higher current densities for the NPs synthesized in the US. In situ FTIR experiments revealed that the three synthesized NP materials eletcrooxidize methanol completely to carbonate through formate. Most importantly, all pathways were led without detectable CO, a poisoning molecule not found at high overpotentials. The reaction path using the US electrode experienced an additional round of formate formation and conversion into carbonate (or CO 2 in the thin layer) after 1.0 V (vs. Ag/Ag/Cl), suggesting improved catalysis. The high activity of NPs synthesized in the US is attributed to effective dissociative adsorption of the fuel due to the site's availability and the presence of hydroxyl groups that may fasten the oxidation of adsorbates from the surface. After understanding the surface reaction, we built a mixed-media μFC fed by methanol in alkaline medium and sodium persulfate in acidic medium. The μFC was equipped with Cu NPs synthesized in ultrasonic-bath-modified carbon paper as the anode and metal-free carbon paper as the cathode. Since the onset potential for methanol electrooxidation was 0.45 V and the reduction reaction revealed 0.90 V, the theoretical OCV is 0.45 V, which provides a spontaneous coupled redox reaction to produce power. The μFC displayed 0.56 mA cm -2 of maximum current density and 26 μW cm -2 of peak power density at 100 μL min -1 . This membraneless system optimizes each half-cell individually, making it possible to build fuel cells with noble metal-free anodes and metal-free cathodes.

Photocatalytic fuel cells (PFCs) are considered the next generation of energy converter devices, since they can harvest solar energy through relatively low-cost semiconductor material to convert the chemical energy of renewable fuels and oxidants directly into electricity. Here, we report black TiO 2 nanoparticle (NP) photoanodes for simple single-compartment PFCs and microfluidic photo fuel cells (μPFCs) fed by methanol. We show that Ti 3+ and oxygen vacancy (O V ) defects at the TiO 2 NPs are easily controlled by annealing in a NaBH 4 -containing atmosphere. This optimized noble-metal-free black TiO 2 photoanode shows superior PFC performance for methanol oxidation and O 2 reduction with a maximum power density ( P max ) ∼2000% higher compared to the undoped TiO 2 . At flow conditions, the black TiO 2 photoanode showed a P max ∼90 times higher than the μFC equipped with regular TiO 2 in the dark. The PFC and μPFC operate spontaneously with little activation polarization, and black TiO 2 photoanodes are stable under light irradiation. The improved photoactivity of the black TiO 2 photoanode is a consequence of the self-doping with Ti 3+ /O V defects, which significantly red-shifted the bandgap energy, induced intragap electronic states, and widened both the valence band and conduction band, enhancing the overall absorption of visible light and decreasing the interfacial charge transfer resistance.

Plant-based compounds are an option to explore and perhaps overcome the limitations of current antitumor treatments. Annona coriacea Mart. is a plant with a broad spectrum of biological activities, but its antitumor activity is still unclear. The purpose of our study was to determine the effects of A. coriacea fractions on a panel of cervical cancer cell lines and a normal keratinocyte cell line. The antitumor effect was investigated in vitro by viability assays, cell cycle, apoptosis, migration, and invasion assays. Intracellular signaling was assessed by Western blot, and major compounds were identified by mass spectrometry. All fractions exhibited a cytotoxic effect on cisplatin-resistant cell lines, SiHa and HeLa. C3 and C5 were significantly more cytotoxic and selective than cisplatin in SiHa and Hela cells. However, in CaSki, a cisplatin-sensitive cell line, the compounds did not demonstrate higher cytotoxicity when compared with cisplatin. Alkaloids and acetogenins were the main compounds identified in the fractions. These fractions also markedly decreased cell proliferation with p21 increase and cell cycle arrest in G2/M. These effects were accompanied by an increase of H2AX phosphorylation levels and DNA damage index. In addition, fractions C3 and C5 promoted p62 accumulation and decrease of LC3II, as well as acid vesicle levels, indicating the inhibition of autophagic flow. These findings suggest that A. coriacea fractions may become effective antineoplastic drugs and highlight the autophagy inhibition properties of these fractions in sensitizing cervical cancer cells to treatment.