Experimental Investigation and RSM Modeling of the Effects of Injection Timing on the Performance and NOx Emissions of a Micro-Cogeneration Unit Fueled with Biodiesel Blends

The (partial or total) substitution of petro-diesel with biodiesel in internal combustion engines (ICEs) could represent a crucial path towards the decarbonization of the energy sector. However, critical aspects are related to the controversial issue of the possible increase in Nitrogen Oxides (NOx) emissions. In such a framework, the proposed study aims at investigating the effects of biodiesel share and injection timing on the performance and NOx emissions of a diesel micro combined heat and power (CHP) system. An experimental campaign has been conducted considering the following operating conditions: (i) a reference standard injection timing (17.2° BTDC), an early injection timing (20.8° BTDC), and a late injection timing (12.2° BTDC); (ii) low (0.90 kW), partial (2.45 kW), and full (3.90 kW) output power load; and (iii) four fuel blends with different biodiesel (B) shares (B0, B15, B30, and B100). Experimental data were also elaborated on thanks to the response surface modelling (RSM) technique, aiming at (i) quantifying the influences of the above-listed variables and their trends on the responses, and (ii) obtaining a set of predictive numerical models that represent the basis for model-based design and optimization procedures. The results show: (i) an overall improvement of the engine performance due to the biodiesel presence in the fuel blend —in particular, B30 and B100 blends have shown peak values in both electrical (29%) and thermal efficiency (42%); (ii) the effective benefits of late SOI strategies on NOx emissions, quantified in an overall average NOx reduction of 27% for the early-to-late injection, and of 16% for the standard-to-late injection strategy. Moreover, it has emerged that the NOx-reduction capabilities of the late injection strategy decrease with higher biodiesel substitution rates; through the discussion of high-prediction-capable, parametric, data-driven models, an extensive RSM analysis has shown how the biodiesel share promotes an increase of NOx whenever it overcomes a calculated threshold that is proportional to the engine load (from about 66.5% to 85.7% of the biodiesel share)

Novel Regioselective Synthesis of 1,3,4,5-Tetrasubstituted Pyrazoles and Biochemical Valuation on F1FO-ATPase and Mitochondrial Permeability Transition Pore Formation

An efficient, eco-compatible, and very cheap method for the construction of fully substituted pyrazoles (Pzs) via eliminative nitrilimine-alkene 1,3-dipolar cycloaddition (ENAC) reaction was developed in excellent yield and high regioselectivity. Enaminones and nitrilimines generated in situ were selected as dipolarophiles and dipoles, respectively. A deep screening of the employed base, solvent, and temperature was carried out to optimize reaction conditions. Recycling tests of ionic liquid were performed, furnishing efficient performance until six cycles. Finally, a plausible mechanism of cycloaddition was proposed. Then, the effect of three different structures of Pzs was evaluated on the F1FO-ATPase activity and mitochondrial permeability transition pore (mPTP) opening. The Pz derivatives’ titration curves of 6a, 6h, and 6o on the F1FO-ATPase showed a reduced activity of 86%, 35%, and 31%, respectively. Enzyme inhibition analysis depicted an uncompetitive mechanism with the typical formation of the tertiary complex enzyme-substrate-inhibitor (ESI). The dissociation constant of the ESI complex (Ki’) in the presence of the 6a had a lower order of magnitude than other Pzs. The pyrazole core might set the specific mechanism of inhibition with the F1FO-ATPase, whereas specific functional groups of Pzs might modulate the binding affinity. The mPTP opening decreased in Pz-treated mitochondria and the Pzs’ inhibitory effect on the mPTP was concentration-dependent with 6a and 6o. Indeed, the mPTP was more efficiently blocked with 0.1 mM 6a than with 1 mM 6a. On the contrary, 1 mM 6o had stronger desensitization of mPTP formation than 0.1 mM 6o. The F1FO-ATPase is a target of Pzs blocking mPTP formation

Inside-out submitochondrial particles affect the mitochondrial permeability transition pore opening under conditions of mitochondrial dysfunction

The inside-out submitochondrial particles (IO-SMPs) showed a strong protective effect against mitochondrial permeability transition pore (mPTP) opening in mitochondria isolated from swine hearts 3 h after explantation. The latter condition was used to emulate situation of mitochondrial damage. We identified that the protective effect of IO-SMPs cannot be attributed to a functional modulation of the enzymatic complexes involved in mPTP formation. Indeed, oxidative phosphorylation and F1FO-ATPase activity were not affected. Conversely, mPTP desensitization might be caused by structural modification. IO-SMP incorporation into the mitochondria can modulate the membrane-bound enzyme complexes' functionality, inducing F1FO-ATPase to be unable to carry out the conformational changes useful for mPTP opening. Thus, the data are a valid starting point for IO-SMP application in the treatment of impaired cardiovascular conditions supported by mPTP opening

Melatonin rescues cell respiration impaired by hypoxia/reoxygenation in aortic endothelial cells and affects the mitochondrial bioenergetics targeting the F1FO-ATPase

Melatonin is evaluated as a potential molecular therapy to counteract mitochondrial dysfunction caused by hypoxia/reoxygenation (H/R) in aortic endothelial cells (pAECs). The mitochondrial permeability transition pore (mPTP) opening undergoes a desensitizing action coupled with a reduction of superoxide anion production in mitochondria treated with melatonin. The effect on mPTP has been attributed to the direct interaction of melatonin with the hydrophilic F1 domain of Ca2+-activated F1FO-ATPase. Mutual exclusion analysis highlights an overlapping binding site between melatonin and the specific F1 inhibitor NBD-Cl. The results are corroborated by melatonin inhibition of ATPase activity of the purified F1 domain in the presence of Ca2+, but not in the presence of natural cofactor Mg2+. Moreover, the impairment of bioenergetics parameters in pAECs metabolism and the increase of oxidative stress arising by H/R injury have been rescued in cells protected by melatonin treatment

Are researchers deliberately bypassing the technology transfer office? An analysis of TTO awareness

Most universities committed to the commercialization of academic research have established technology transfer offices (TTOs). Nonetheless, many researchers bypass these TTOs and take their inventions directly to the marketplace. While TTO bypassing has typically been portrayed as deliberate and undesirable behavior, we argue that it could be unintentional as many researchers may simply be unaware of the TTO’s existence. Taking an information-processing perspective and using data on 3250 researchers in 24 European universities, we examine researcher attributes associated with TTO awareness. Our evidence confirms that only a minority of researchers are aware of the existence of a TTO at their university. TTO awareness is greater among researchers who possess experience as entrepreneurs, closed many research and consulting contracts with industry partners, conduct research in medicine, engineering or life sciences, or occupy postdoctoral positions. Policy implications of these findings are discussed

Mitochondrial bioenergetics analysis on SLC-selected boar spermatozoa during liquid storage

: Semen preservation at 17 °C plays a pivotal role in the porcine breeding industry, though it presents challenges; not all ejaculates retain their quality during storage. Colloidal centrifugation has been developed to improve it since this method eliminates seminal plasma and microorganisms while simultaneously allowing the selection of spermatozoa based on gradient density centrifugation. This study aimed to evaluate whether two different colloid densities (1.026 g/ml - 20 %Porcicoll® and 1.104 g/ml - 80 % Porcicoll®) improve sperm bioenergetics, assessed using Agilent seahorse, along with key semen quality parameters such as viability, mitochondrial activity, oxidative stress and motility analyzed through flow cytometry and the CASA system over time. Fifteen ejaculates were divided into three groups: Control (CTR), 20 % Porcicoll® (P20), and 80 % Porcicoll® (P80). Sperm parameters were analyzed at days 0, 3, and 7 of storage. Results revealed a metabolic shift from mitochondrial oxidative phosphorylation to glycolysis during storage, with a 15 % decrease in ATP production by day 3. P80-treated sperm showed higher ATP production on day 0 compared to P20. Sperm quality parameters such as viability and mitochondrial activity decreased after colloidal centrifugation, possibly because of early capacitation; we also hypothesize that SLC could increase sensitivity to the high glucose levels in the medium. Although Porcicoll® effectively selected metabolically active sperm, the lack of seminal plasma and limitations in media composition negatively affected long-term sperm quality. Further research is necessary to optimize media formulations and assess fertility outcomes of selected sperm for enhanced sperm preservation techniques

A922 Sequential measurement of 1 hour creatinine clearance (1-CRCL) in critically ill patients at risk of acute kidney injury (AKI)

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