Atomically dispersed Fe-N-C catalysts for the oxygen reduction reaction (ORR) have been synthesized with a template-free method using carbon xerogels (CXG) as a porous matrix. The porosity of the ...CXGs is easily tunable through slight variations in the synthesis procedure. In this work, CXGs are prepared by formaldehyde and resorcinol polymerization, modifying the pH during the process. Materials with a broad range of porous structures are obtained: from non-porous to micro-/meso-/macroporous materials. The porous properties of CXG have a direct effect on Fe-N-CXG activity against ORR in an acidic medium (0.5 M H
SO
). Macropores and wide mesopores are vital to favor the mass transport of reagents to the active sites available in the micropores, while narrower mesopores can generate additional tortuosity. The role of microporosity is investigated by comparing two Fe-N-C catalysts using the same CXG as the matrix but following a different Fe and N doping procedure. In one case, the carbonization of CXG occurs rapidly and simultaneously with Fe and N doping, whereas in the other case it proceeds slowly, under controlled conditions and before the doping process, resulting in the formation of more micropores and active sites and achieving higher activity in a three-electrode cell and a better durability during fuel cell measurements. This work proves the feasibility of the template-free method using CXG as a carbon matrix for Fe-N-C catalysts, with the novelty of the controlled porous properties of the carbon material and its effect on the catalytic activity of the Fe-N-C catalyst. Moreover, the results obtained highlight the importance of the carbon matrix's porous structure in influencing the activity of Fe-N-C catalysts against ORR.
Fe−N−C catalysts are an interesting option for polymer electrolyte fuel cells due to their low cost and high activity towards the oxygen reduction reaction (ORR). Since Fe−N−C active sites are ...preferentially formed in the micropores of the carbon matrix, increasing the microporosity is highly appealing. In this work, carbon xerogels (CXG) were activated by physical and chemical methods to favor the formation of micropores, used as carbon matrices for Fe−N−C catalysts, and investigated for the ORR. The catalysts were characterized by solid‐state techniques to determine chemical composition and pore structure. Physical activation increased microporosity up to 2‐fold leading to catalysts with a larger density of active sites (more than twice iron and nitrogen uptake, pyridinic N and Nx−Fe). This entailed a higher ORR intrinsic activity determined in a 3‐electrode cell (80 mV better half‐wave potential). At the cathode of a fuel cell, the catalysts based on activated carbon materials showed 26 % lower power density ascribed to a more hydrophilic surface, causing a larger extent of flooding of the electrode that counterbalances the higher intrinsic activity. Interestingly, a more stable behavior was observed for the activated catalysts, with up to 2‐fold better relative power density retention after 20‐hour operation.
Activated carbon xerogels were studied as matrix for Fe−N−C catalysts. The increased microporosity lead to catalysts with a larger density of active sites, achieving up to more than twice iron and nitrogen uptake, and consequently, a higher ORR intrinsic activity. Whereas, fuel cell power density is negatively affected by a more hydrophilic character, but stability enhances with activation.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The liver plays a central role in the response to fasting. The hormonal profile in this condition, low insulin, and high concentrations of glucagon in plasma, induce the release of large amounts of ...fatty acids from adipose tissue. Prolonged starvation can therefore induce a dramatic change in the fatty acid oxidative capacity of liver metabolism. Modulation of gene expression by PPARα plays a crucial role in this response. While a major role for PPARα in the liver is to produce ketone bodies as fuel through β-oxidation for peripheral tissues during fast, its participation in the control of CPT1A, the rate-limiting step of the pathway, remains controversial. Using Web-based software (VISTA) combining transcription factor binding site database searches with comparative sequence analyses, we have localized a conserved functional PPAR responsive element downstream of the transcriptional start site of the human CPT1A gene. We have shown that this sequence is fundamental for fatty acids or PGC1-induced transcriptional activation of the CPT1A gene. These results corroborate the hypothesis that PPARα regulates the limiting step in the oxidation of fatty acids in liver mitochondria.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPUK
Platinum group metal-free catalysts have been intensively investigated in the last decades as an alternative to platinum with the aim of lowering the cost of polymer electrolyte fuel cells. In ...particular, iron-nitrogen-carbon (Fe-N-C) has proved to be the most active towards the oxygen reduction reaction. For practical application, a hierarchical pore structure is required, with micropores favouring the creation of active sites and larger pores (meso- and macropores) facilitating the mass transport. In this work, carbon xerogels are investigated to hosting iron and nitrogen species obtained by a template-free method. The introduction of nitrogen in a one-step polymerization of urea with resorcinol and formaldehyde is investigated for the first time in this field by varying the relative content of reactants. The urea/resorcinol ratio greatly influences the pore structure of the Fe-N-C catalyst and the ORR electrocatalytic activity thereof. The ORR activity is favored for a balanced urea/resorcinol ratio where porosity is well developed and relatively high iron and nitrogen contents are incorporated to the carbon xerogel. In acid (0.5 M H2SO4), the onset potential is 0.82 V vs. RHE, with a number of exchanged electrons very close to 4 (i.e. full conversion to water) and low Tafel slope of 71 mV dec−1, for the most active catalyst of the series, possessing the best compromise of iron and nitrogen active sites. Fuel cell tests corroborate that the catalyst with the most developed porous structure shows the best performance.
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•N-doped carbon xerogels serve as carbon matrix for Fe-N-C catalysts.•Urea is introduced during gel polymerization to dope CXG with nitrogen.•A balanced urea amount leads to proper porosity including both micro and mesopores.•Pyridinic nitrogen and Fe concentration rely on N/C ratio.•High content of pyridinic N and Fe are key for enhanced ORR catalytic activity.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPUK, ZAGLJ, ZRSKP
Carnitine palmitoyltransferase I (CPT-I) and II (CPT-II) enzymes are components of the carnitine palmitoyltransferase shuttle system which allows entry of long-chain fatty acids into the ...mitochondrial matrix for subsequent oxidation. This system is tightly regulated by malonyl-CoA levels since this metabolite is a strong reversible inhibitor of the CPT-I enzyme. There are two distinct CPT-I isotypes (CPT-Iα and CPT-Iβ), that exhibit different sensitivity to malonyl-CoA inhibition. Because of its ability to inhibit fatty acid synthase, C75 is able to increase malonyl-CoA intracellular levels. Paradoxically it also activates long-chain fatty acid oxidation. To identify the exact target of C75 within the CPT system, we expressed individually the different components of the system in the yeast
Pichia pastoris. We show here that C75 acts on recombinant CPT-Iα, but also on the other CPT-I isotype (CPT-Iβ) and the malonyl-CoA insensitive component of the CPT system, CPT-II.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Carnitine palmitoyltransferase I (CPTI) catalyzes the conversion of long-chain fatty acyl-CoAs to acylcarnitines in the presence of l-carnitine. To determine the role of the highly conserved ...C-terminal glutamate residue, Glu-590, on catalysis and malonyl-CoA sensitivity, we separately changed the residue to alanine, lysine, glutamine, and aspartate. Substitution of Glu-590 with aspartate, a negatively charged amino acid with only one methyl group less than the glutamate residue in the wild-type enzyme, resulted in complete loss in the activity of the liver isoform of CPTI (L-CPTI). A change of Glu-590 to alanine, glutamine, and lysine caused a significant 9- to 16-fold increase in malonyl-CoA sensitivity but only a partial decrease in catalytic activity. Substitution of Glu-590 with neutral uncharged residues (alanine and glutamine) and/or a basic positively charged residue (lysine) significantly increased L-CPTI malonyl-CoA sensitivity to the level observed with the muscle isoform of the enzyme, suggesting the importance of neutral and/or positive charges in the switch of the kinetic properties of L-CPTI to the muscle isoform of CPTI. Since a conservative substitution of Glu-590 to aspartate but not glutamine resulted in complete loss in activity, we suggest that the longer side chain of glutamate is essential for catalysis and malonyl-CoA sensitivity. This is the first demonstration whereby a single residue mutation in the C-terminal region of the liver isoform of CPTI resulted in a change of its kinetic properties close to that observed with the muscle isoform of the enzyme and provides the rationale for the high malonyl-CoA sensitivity of muscle CPTI compared with the liver isoform of the enzyme.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPUK, ZAGLJ, ZRSKP
Benign prostatic hyperplasia (BPH) is a prevalent disease associated with lower urinary tract symptoms (LUTS). The standard of care for moderate-to-severe LUTS unresponsive to pharmacological ...treatment is the transurethral resection of the prostate (TURP). However, this intervention is not exempt from complications. Prostatic artery embolization (PAE) has been described as a new, effective and safe procedure for the treatment of LUTS secondary to BPH. To date, only one clinical trial has been published on the use of PAE for LUTS, but the study was methodologically flawed in terms of safety monitoring. Therefore, well-designed clinical studies are required to compare the efficacy and safety of both techniques in the treatment of LUTS secondary to BPH.
This was a prospective, randomized, non-inferiority clinical trial comparing efficacy and safety of PAE and TURP in the treatment of BPH-related LUTS. A total of 60 patients diagnosed with BPH with obstructive moderate or severe LUTS refractory to medical therapy and candidates for TURP were randomized to either PAE or TURP. The presence and severity of LUTS were assessed using the validated Spanish version of the International Prostate Symptom Score (IPSS). Primary end points included improvement in maximum urinary flow rate (
) as measured at baseline and 1 year after the intervention. Improvement in IPSS as measured at baseline and after the intervention, reduction in prostate volume, no deterioration or improvement of sexual function (International Index of Erectile Function IIEF), reduction in PSA and PVR, satisfaction of the patient with the operation and adverse events occurring during the study were secondary outcome measures.
The aim of this clinical study was to investigate whether PAE is a valid therapeutic option for LUTS that is not inferior to TURP in terms of efficacy and safety. This study also helped to define the profile of candidates for PAE and analyzed the benefits and complications associated with this new technique.
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