Ni-based (over MgO and Al2O3) and noble metal-based (Pd and Pt over Al2O3) catalysts were prepared by wet impregnation method and thereafter impregnated in microreactors. The catalytic activity was ...measured at several temperatures, atmospheric pressure and different steam to carbon, S/C, ratios. These conditions were the same for conventional, fixed bed reactor system, and microreactors. Weight hourly space velocity, WHSV, was maintained equal in order to compare the activity results from both reaction systems. For microreactor systems, similar activities of Ni-based catalyst were measured in the steam methane reforming (SMR) activity tests, but not in the case of natural gas steam reforming tests. When noble metal-based catalysts were used in the conventional reaction system no significant activity was measured but all catalysts showed some activity when they were tested in the microreactor systems. The analysis by SEM and TEM revealed a carbon-free surface for Ni-based catalyst as well as carbon filaments growth in case of noble metal-based catalysts.
► Hydrogen production from methane and natural gas steam reforming process was studied. ► Two different reaction systems were used: fixed bed reactor and microreactor systems. ► Ni/MgO catalyst was more selective for WGS reaction than Ni/Al2O3 catalyst. ► Ni/Al2O3 catalyst suffered a quick deactivation in natural gas SR process. ► For Pd/Al2O3 and Pt/Al2O3catalysts a very low activity was measured.
The feasibility of treating the supernatant of a municipal sludge digester supplemented with co-substrates by means of an anammox-based process (ELAN(®)) was tested in Guillarei (NW of Spain). ...Ammonia concentration measured in the supernatant of the sludge digester varied in the range 800-1,500 g N/m(3) due to the fact that the sludge produced in the plant was co-digested with wastes coming from surrounding food industries. Treating this supernatant in the ELAN(®) reactor, nitrogen removal rates up to 1.1 kg N/(m(3) d) were reached in experiments run in a pilot plant reactor operated in batch mode. No nitrite oxidation was registered after several months of operation despite the average dissolved oxygen (DO) concentrations being 1.5 g O2/m(3) and the temperature reaching values as low as 18 °C. By keeping the DO set point at 1-2 g O2/m(3) and tuning the hydraulic retention time, the stability of the process was guaranteed and the presence of co-substrates in the anaerobic digester did not affect negatively the operation of the autotrophic nitrogen removal process. Due to the success of the pilot plant experiment, an upscale of the process to full scale is proposed. Mass balances applied to Guillarei wastewater treatment plant revealed that in the main stream line the average denitrification rate calculated with the data of year 2011 was 226 kg N/d. Since the nitrogen removal efficiency is limited by the amount of readily biodegradable organic matter available to carry out denitrification in the water line, the implementation of an anammox-based process to treat the supernatant seems the best option to improve the effluent quality in terms of nitrogen content. The nitrogen removal rate in the sludge line would be 30 times higher than the one in the water line. The implementation of the process would improve the energetic balance and the nitrogen removal performance of the plant.
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•An untargeted metabolomic method for the non-volatile profile of the Graciano wine was developed.•411 different metabolites in Graciano Vitis vinifera red wine were identified.•15 ...compounds could serve to differentiate Graciano and Tempranillo wines.•An enological database (WinMet) with 2080 compounds was constructed.
The current study presents a method for comprehensive untargeted metabolomic fingerprinting of the non-volatile profile of the Graciano Vitis vinifera wine variety, using liquid chromatography/electrospray ionization time of flight mass spectrometry (LC–ESI-QTOF). Pre-treatment of samples, chromatographic columns, mobile phases, elution gradients and ionization sources, were evaluated for the extraction of the maximum number of metabolites in red wine. Putative compounds were extracted from the raw data using the extraction algorithm, molecular feature extractor (MFE). For the metabolite identification the WinMet database was designed based on electronic databases and literature research and includes only the putative metabolites reported to be present in oenological matrices. The results from WinMet were compared with those in the METLIN database to evaluate how much the databases overlap for performing identifications. The reproducibility of the analysis was assessed using manual processing following replicate injections of Vitis vinifera cv. Graciano wine spiked with external standards. In the present work, 411 different metabolites in Graciano Vitis vinifera red wine were identified, including primary wine metabolites such as sugars (4%), amino acids (23%), biogenic amines (4%), fatty acids (2%), and organic acids (32%) and secondary metabolites such as phenols (27%) and esters (8%). Significant differences between varieties Tempranillo and Graciano were related to the presence of fifteen specific compounds.
A neutrino with energy ∼290 TeV, IceCube-170922A, was detected in coincidence with the BL Lac object TXS 0506+056 during enhanced gamma-ray activity, with chance coincidence being rejected at ∼3 ...level. We monitored the object in the very-high-energy (VHE) band with the Major Atmospheric Gamma-ray Imaging Cherenkov (MAGIC) telescopes for ∼41 hr from 1.3 to 40.4 days after the neutrino detection. Day-timescale variability is clearly resolved. We interpret the quasi-simultaneous neutrino and broadband electromagnetic observations with a novel one-zone lepto-hadronic model, based on interactions of electrons and protons co-accelerated in the jet with external photons originating from a slow-moving plasma sheath surrounding the faster jet spine. We can reproduce the multiwavelength spectra of TXS 0506+056 with neutrino rate and energy compatible with IceCube-170922A, and with plausible values for the jet power of . The steep spectrum observed by MAGIC is concordant with internal γγ absorption above ∼100 GeV entailed by photohadronic production of a ∼290 TeV neutrino, corroborating a genuine connection between the multi-messenger signals. In contrast to previous predictions of predominantly hadronic emission from neutrino sources, the gamma-rays can be mostly ascribed to inverse Compton upscattering of external photons by accelerated electrons. The X-ray and VHE bands provide crucial constraints on the emission from both accelerated electrons and protons. We infer that the maximum energy of protons in the jet comoving frame can be in the range ∼1014 - 1018 eV.
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•Multivariate data analysis of 16 metabolites from three arginine-related metabolic pathways was carried out.•CIT, SAM, SDMA and CNN found to be potential biomarkers for pediatric ...CKD.•CIT, SAM, SDMA and CNN add 18% accuracy for early CKD diagnosis in comparison with CNN-based classification.•4 new biomarkers for preliminary CKD stage establishment prior to nephrologic assessment.
Chronic kidney disease (CKD) is a progressive pathological condition in which renal function deteriorates in time. The first diagnosis of CKD is often carried out in general care attention by general practitioners by means of serum creatinine (CNN) levels. However, it lacks sensitivity and thus, there is a need for new robust biomarkers to allow the detection of kidney damage particularly in early stages. Multivariate data analysis of plasma concentrations obtained from LC-QTOF targeted metabolomics method may reveal metabolites suspicious of being either up-regulated or down-regulated from urea cycle, arginine methylation and arginine-creatine metabolic pathways in CKD pediatrics and controls. The results show that citrulline (CIT), symmetric dimethylarginine (SDMA) and S-adenosylmethionine (SAM) are interesting biomarkers to support diagnosis by CNN: early CKD samples and controls were classified with an increase in classification accuracy of 18% when using these 4 metabolites compared to CNN alone. These metabolites together allow classification of the samples into a definite stage of the disease with an accuracy of 74%, being the 90% of the misclassifications one level above or below the CKD stage set by the nephrologists. Finally, sex-related, age-related and treatment-related effects were studied, to evaluate whether changes in metabolite concentration could be attributable to these factors, and to correct them in case a new equation is developed with these potential biomarkers for the diagnosis and monitoring of pediatric CKD.
The synthesis of polymers with tailored properties for the recognition of macromolecules such as proteins is challenging. In this work, the synthesis of a new polymer format, a linear polymer (LP), ...as the selective recognition element for the globular protein lactoferrin (LF) is proposed as a proof-of-concept study. For the synthesis, a solid-phase strategy using the reversible deactivation radical polymerisation (RDRP) mechanism is proposed. This approach, which is usually used in molecular imprinting, involves the immobilisation of LF on the surface of a solid support, but, unlike classical imprinting, a cross-linker in the polymerisation mixture is not required. Consequently, the copolymer is soluble and flexible, thus overcoming the drawbacks associated with traditional synthetic polymers for macromolecule imprinting. This new polymer format has great potential for replacing natural antibodies in bioassays such as enzyme-linked immunosorbent assays (ELISA), dot blot, western blot, or pull-down. In our case, the linear polymer was used as a recognition element to replace natural antibodies in a LF-selective ELISA. The responses of the linear polymer between LF concentrations of 0.1 nM and 0.25 μM were studied, and a significant difference was observed between the non-specific signals and the signals measured in the presence of the polymeric material. Further, the response versus log concentration curves were fitted to a logistic equation, allowing estimation of the EC50 value: 11.8 ± 1.4 nM. We also confirmed the selective detection of LF using the competitive inhibition of the selective LF-biotin conjugate (LF-Bi) binding to the plastic receptor (LP) for closely related proteins (e.g. those having similar molecular weights or isoelectric points) such as human lysozyme, trypsin, and albumin, which are present in human body fluids. The system presents a cross-reactivity value or selectivity of 1.95% for lysozyme, 0.028% for trypsin, and 0.016% for albumin. The applicability of this method for the determination of urine LF levels in inflammatory and infectious diseases of the human urinary tract is also demonstrated.
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•A linear polymer for the selective recognition of lactoferrin is presented.•The linear polymer works as a plastic antibody in enzyme-linked immunosorbent assays.•Assay performance for lactoferrin was tested in the presence of other proteins.
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•Imprinted nanoparticles for 4-ethylphenol synthesised by solid-phase imprinting.•Imprinted nanoparticles are used as recognition elements in voltammetric sensors.•Gold electrode ...modification was followed by EIS and CV.•MIP nanoparticles favoured 4-ethylphenol determination by DPV.•The MIN-based sensor showed excellent selectivity for the target compound.
A voltammetric sensor based on molecularly imprinted high affinity nanoparticles has been developed for the direct, selective, and label-free detection of 4-ethylphenol (4EP). The poorly functionalised template 4EP, was successfully imprinted by the recently developed method of solid-phase synthesis of molecularly imprinted nanoparticles. These nanoparticles were grafted to the surface of gold electrodes allowing for selective and sensitive detection of 4EP. Each step of the electrode modification process was characterised by cyclic voltammetry and electrochemical impedance spectroscopy. The electrochemical response of the developed sensor was evaluated and a linear range between 0.24 and 5mgL−1 was obtained, together with good repeatability (RSD<10%). The sensor was proven to recognise specifically the target compound over structural analogues, including compounds that belong to the same metabolic pathway such as coumaric acid ethyl ester, coumaric acid and 4-vinylphenol, or other phenolic compounds such as 4-ethylguaiacol or paracetamol.
ABSTRACT
We report a characterization of the multiband flux variability and correlations of the nearby (z = 0.031) blazar Markarian 421 (Mrk 421) using data from Metsähovi, Swift, Fermi-LAT, MAGIC, ...FACT, and other collaborations and instruments from 2014 November till 2016 June. Mrk 421 did not show any prominent flaring activity, but exhibited periods of historically low activity above 1 TeV (F>1 TeV < 1.7 × 10−12 ph cm−2 s−1) and in the 2–10 keV (X-ray) band (F$_{2-10\, \mathrm{keV}}\lt 3.6\times 10^{-11}$ erg cm−2 s−1), during which the Swift-BAT data suggest an additional spectral component beyond the regular synchrotron emission. The highest flux variability occurs in X-rays and very high-energy (E > 0.1 TeV) γ-rays, which, despite the low activity, show a significant positive correlation with no time lag. The HRkeV and HRTeV show the harder-when-brighter trend observed in many blazars, but the trend flattens at the highest fluxes, which suggests a change in the processes dominating the blazar variability. Enlarging our data set with data from years 2007 to 2014, we measured a positive correlation between the optical and the GeV emission over a range of about 60 d centred at time lag zero, and a positive correlation between the optical/GeV and the radio emission over a range of about 60 d centred at a time lag of $43^{+9}_{-6}$ d. This observation is consistent with the radio-bright zone being located about 0.2 parsec downstream from the optical/GeV emission regions of the jet. The flux distributions are better described with a lognormal function in most of the energy bands probed, indicating that the variability in Mrk 421 is likely produced by a multiplicative process.
Unilateral Gamma Knife™ stereotactic radiosurgery on the ventral-intermediate nucleus of the thalamus is a minimally invasive neurosurgical option for refractory tremor. We describe the experience of ...Gamma Knife™ thalamotomy (GKT) in patients with essential tremor (ET) and tremor-dominant Parkinson's disease (PD) at our specialised stereotactic neurosurgery unit.
We reviewed the cases of patients treated with GKT between January 2014 and February 2018 with a minimum of 12 months' follow-up. We analysed clinical and demographic variables, indication, radiation dose, effectiveness (based on subscales of the Fahn-Tolosa-Marin FTM scale and the Movement Disorders Society-Unified Parkinson's Disease Rating Scale MDS-UPDRS motor score), and adverse events.
Thirteen patients were registered, 6 with a diagnosis of tremor-dominant PD, four with refractory ET, and three with ET and PD. Median age was 78 years (range, 62-83), with seven patients aged over 75 years. Four patients were receiving anticoagulants and two had history of stroke. The maximum radiation dose administered was 130 Gy. Mean (standard deviation) follow-up duration was 30.0 (14.5) months. Significant tremor improvement was observed on the FTM subscales: 63.6% at 12 months and 63.5% at the end of follow-up; MDS-UPDRS tremor items showed improvements of 71.3% at 12 months and 60.3% at the end of follow up. Eleven patients reported significant improvements in quality of life, and 3 reported mild and transient adverse effects.
This is the largest series of patients with essential and parkinsonian tremor treated with GKT and followed up in the long term in Spain. GKT can be safe and effective in the long term in patients with refractory tremor, including in elderly patients and those receiving anticoagulants.