Modeling and Thermodynamic Studies of γ-Valerolactone Production from Bio-derived Methyl Levulinate.

The exploitation of biomass to reduce the dependency on fossil fuels represents a challenge that needs to be solved as soon as possible. Nowadays, one of the most fashionable processes is γ-valerolactone (GVL) production from bio-derived methyl levulinate (ML). Deep understanding of the thermodynamic aspects involved in this process is key for a successful outcome, but detailed studies are missing in the existing literature. A thermodynamic study of the reaction of γ-valerolactone (GVL) production from bio-derived methyl levulinate (ML) is performed by the Gibbs free energy minimization method. The effect of various reaction conditions (temperature, concentration, flow rate) and the implication of possible intermediates and byproducts are assessed. Conversion and selectivity are calculated from the simulation of the ML hydrogenation using isopropanol as the hydrogen donor under continuous flow conditions. Significant increases in GVL selectivity can be achieved under dry conditions, keeping the high conversion. Comparison between theoretical and experimental results from a previous article discloses the effect of using 5%RuTiO2 catalysts, which increases the selectivity from 3-40% to 41-98%. Enthalpy and Gibbs free energy of the reactions at issue are also calculated from models using Barin equations according to Aspen Physical Property System parameters.

Integrative Genomic and Transcriptomic Profiling Reveals a Differential Molecular Signature in Uterine Leiomyoma versus Leiomyosarcoma.

The absence of standardized molecular profiling to differentiate uterine leiomyosarcomas versus leiomyomas represents a current diagnostic challenge. In this study, we aimed to search for a differential molecular signature for these myometrial tumors based on artificial intelligence. For this purpose, differential exome and transcriptome-wide research was performed on histologically confirmed leiomyomas (n = 52) and leiomyosarcomas (n = 44) to elucidate differences between and within these two entities. We identified a significantly higher tumor mutation burden in leiomyosarcomas vs. leiomyomas in terms of somatic single-nucleotide variants (171,863 vs. 81,152), indels (9491 vs. 4098), and copy number variants (8390 vs. 5376). Further, we discovered alterations in specific copy number variant regions that affect the expression of some tumor suppressor genes. A transcriptomic analysis revealed 489 differentially expressed genes between these two conditions, as well as structural rearrangements targeting ATRX and RAD51B. These results allowed us to develop a machine learning approach based on 19 differentially expressed genes that differentiate both tumor types with high sensitivity and specificity. Our findings provide a novel molecular signature for the diagnosis of leiomyoma and leiomyosarcoma, which could be helpful to complement the current morphological and immunohistochemical diagnosis and may lay the foundation for the future evaluation of malignancy risk.

Highly Active Co3O4-Based Catalysts for Total Oxidation of Light C1-C3 Alkanes Prepared by a Simple Soft Chemistry Method: Effect of the Heat-Treatment Temperature and Mixture of Alkanes.

In the present work, a simple soft chemistry method was employed to prepare cobalt mixed oxide (Co3O4) materials, which have shown remarkably high activity in the heterogeneously catalyzed total oxidation of low reactive VOCs such as the light alkanes propane, ethane, and methane. The optimal heat-treatment temperature of the catalysts was shown to depend on the reactivity of the alkane studied. The catalytic activity of the Co3O4 catalysts was found to be as high as that of the most effective catalysts based on noble metals. The physicochemical properties, from either the bulk (using XRD, TPR, TPD-O2, and TEM) or the surface (using XPS), of the catalysts were investigated to correlate the properties with the catalytic performance in the total oxidation of VOCs. The presence of S1 low-coordinated oxygen species at the near surface of the Co3O4-based catalysts appeared to be linked with the higher reducibility of the catalysts and, consequently, with the higher catalytic activity, not only per mass of catalyst but also per surface area (enhanced areal rate). The co-presence of propane and methane in the feed at low reaction temperatures did not negatively affect the propane reactivity. However, the co-presence of propane and methane in the feed at higher reaction temperatures negatively affected the methane reactivity.

A Predictive Processing Account of Card Sorting: Fast Proactive and Reactive Frontoparietal Cortical Dynamics during Inference and Learning of Perceptual Categories.

For decades, a common assumption in cognitive neuroscience has been that prefrontal executive control is mainly engaged during target detection [Posner, M. I., & Petersen, S. E. The attention system of the human brain. Annual Review of Neuroscience, 13, 25-42, 1990]. More recently, predictive processing theories of frontal function under the Bayesian brain hypothesis emphasize a key role of proactive control for anticipatory action selection (i.e., planning as active inference). Here, we review evidence of fast and widespread EEG and magnetoencephalographic fronto-temporo-parietal cortical activations elicited by feedback cues and target cards in the Wisconsin Card Sorting Test. This evidence is best interpreted when considering negative and positive feedback as predictive cues (i.e., sensory outcomes) for proactively updating beliefs about unknown perceptual categories. Such predictive cues inform posterior beliefs about high-level hidden categories governing subsequent response selection at target onset. Quite remarkably, these new views concur with Don Stuss' early findings concerning two broad classes of P300 cortical responses evoked by feedback cues and target cards in a computerized Wisconsin Card Sorting Test analogue. Stuss' discussion of those P300 responses-in terms of the resolution of uncertainty about response (policy) selection as well as the participants' expectancies for future perceptual or motor activities and their timing-was prescient of current predictive processing and active (Bayesian) inference theories. From these new premises, a domain-general frontoparietal cortical network is rapidly engaged during two temporarily distinct stages of inference and learning of perceptual categories that underwrite goal-directed card sorting behavior, and they each engage prefrontal executive functions in fundamentally distinct ways.

Mechanochemical Preparation of Magnetically Separable Fe and Cu-Based Bimetallic Nanocatalysts for Vanillin Production.

A highly sustainable method for the preparation of supported iron oxide and copper nanoparticles (NPs) on a biomass-derived carbon by solvent-free mechanochemical process is reported. In-situ mechanochemically obtained extracts from orange peel could behave as a green reducing agent, allowing the formation of Cu metal nanoparticles as well as generating a magnetic phase (magnetite) in the systems via partial Fe3+ reduction. At the same time, orange peel residues also served as template and carbon source, adding oxygen functionalities, which were found to benefit the catalytic performance of mechanochemically synthesized nanomaterials. The series of magnetic Cu-Fe@OP were tested in the oxidation of trans-ferulic acid towards vanillin, remarkably revealing a maximum vanillin yield of 82% for the sample treated at 200 °C.

Fast fronto-parietal cortical dynamics of conflict detection and context updating in a flanker task.

Recent research has found that the traditional target P3 consists of a family of P3-like positivities that can be functionally and topographically dissociated from one another. The current study examined target N2 and P3-like subcomponents indexing conflict detection and context updating at low- and high-order levels in the neural hierarchy during cognitive control. Electroencephalographic signals were recorded from 45 young adults while they completed a hybrid go/nogo flanker task, and Residue Iteration Decomposition (RIDE) was applied to functionally dissociate these peaks. Analyses showed a stimulus-locked frontal N2 revealing early detection and fast perceptual categorization of nogo, congruent and incongruent trials, resulting in frontal P3-like activity elicited by nogo trials in the latency-variable RIDE cluster, and by incongruent trials in the response-locked cluster. The congruent trials did not elicit frontal P3-like activity. These findings suggest that behavioral incongruency effects are related to intermediate and later stages of motor response re-programming.

(Ag)Pd-Fe3O4 Nanocomposites as Novel Catalysts for Methane Partial Oxidation at Low Temperature.

Nanostructured composite materials based on noble mono-(Pd) or bi-metallic (Ag/Pd) particles supported on mixed iron oxides (II/III) with bulk magnetite structure (Fe3O4) have been developed in order to assess their potential for heterogeneous catalysis applications in methane partial oxidation. Advancing the direct transformation of methane into value-added chemicals is consensually accepted as the key to ensuring sustainable development in the forthcoming future. On the one hand, nanosized Fe3O4 particles with spherical morphology were synthesized by an aqueous-based reflux method employing different Fe (II)/Fe (III) molar ratios (2 or 4) and reflux temperatures (80, 95 or 110 °C). The solids obtained from a Fe (II)/Fe (III) nominal molar ratio of 4 showed higher specific surface areas which were also found to increase on lowering the reflux temperature. The starting 80 m2 g-1 was enhanced up to 140 m2 g-1 for the resulting optimized Fe3O4-based solid consisting of nanoparticles with a 15 nm average diameter. On the other hand, Pd or Pd-Ag were incorporated post-synthesis, by impregnation on the highest surface Fe3O4 nanostructured substrate, using 1-3 wt.% metal load range and maintaining a constant Pd:Ag ratio of 8:2 in the bimetallic sample. The prepared nanocomposite materials were investigated by different physicochemical techniques, such as X-ray diffraction, thermogravimetry (TG) in air or H2, as well as several compositions and structural aspects using field emission scanning and scanning transmission electron microscopy techniques coupled to energy-dispersive X-ray spectroscopy (EDS). Finally, the catalytic results from a preliminary reactivity study confirmed the potential of magnetite-supported (Ag)Pd catalysts for CH4 partial oxidation into formaldehyde, with low reaction rates, methane conversion starting at 200 °C, far below temperatures reported in the literature up to now; and very high selectivity to formaldehyde, above 95%, for Fe3O4 samples with 3 wt.% metal, either Pd or Pd-Ag.

Peritoneal Surface Disease Severity Score (PSDSS), AGO-score and TIAN model in patients with platinum-sensitive recurrent ovarian cancer treated by cytoreductive surgery plus HIPEC.

In patients with platinum sensitive recurrent ovarian cancer selected for a secondary cytoreduction, the use of prognostic scores allows predicting the possibilities of a new complete cytoreduction. The aim of this work is to evaluate the usefulness of PSDSSov, the AGO-score and the TIAN-model as prognostic tools in these patients. Sixty four patients with recurrent platinum sensitive ovarian cancer treated by cytoreduction and HIPEC were analyzed between January 2008 and December 2016. Since 2012, the data needed to calculate the PSDSS, AGO-score and TIAN model were collected prospectively. Fifty patients (78%) received systemic chemotherapy before cytoreduction and HIPEC. In 57 patients (89%) a CC-0 was achieved. Patients with PSDSSov I-II and TIAN model of "low risk" had a DFS at 1 and 5 years of 71% and 57%, respectively, without reaching the median of DFS. PSDSSov is a useful prognostic tool and can be used in decision making in patients with peritoneal carcinomatosis due to recurrent platinum-sensitive ovarian cancer. Its combination with the Tian model makes it possible to identify patients with an especially favorable prognosis.

Dynamic low frequency EEG phase synchronization patterns during proactive control of task switching.

Cognitive flexibility is critical for humans living in complex societies with ever-growing multitasking demands. Yet the low-frequency neural dynamics of distinct task-specific and domain-general mechanisms sub-serving mental flexibility are still ill-defined. Here we estimated phase electroencephalogram synchronization by using inter-trial phase coherence (ITPC) at the source space while twenty six young participants were intermittently cued to switch or repeat their perceptual categorization rule of Gabor gratings varying in color and thickness (switch task). Therefore, the aim of this study was to examine whether a proactive control is associated with connectivity only in the frontoparietal theta network, or also involves distinct neural connectivity within the delta band, as distinct neural signatures while preparing to switch or repeat a task set, respectively. To this end, we focused the analysis on late-latencies (from 500 to 800 msec post-cue onset), since they are known to be associated with top-down cognitive control processes. We confirmed that proactive control during a task switch was associated with frontoparietal theta connectivity. But importantly, we also found a distinct role of delta band oscillatory synchronization in proactive control, engaging more posterior frontotemporal regions as opposed to frontoparietal theta connectivity. Additionally, we built a regression model by using the ITPC results in delta and theta bands as predictors, and the behavioral accuracy in the switch task as the criterion, obtaining significant results for both frequency bands. All these findings support the existence of distinct proactive cognitive control processes related to functionally distinct though highly complementary theta and delta frontoparietal and temporoparietal oscillatory networks at late-latency temporal scales.

Water adsorption on the Fe3O4(111) surface: dissociation and network formation.

We monitored adsorption of water on a well-defined Fe3O4(111) film surface at different temperatures as a function of coverage using infrared reflection-absorption spectroscopy, temperature programmed desorption, and single crystal adsorption calorimetry. Additionally, density functional theory was employed using a Fe3O4(111)-(2 × 2) slab model to generate 15 energy minimum structures for various coverages. Corresponding vibrational properties of the adsorbed water species were also computed. The results show that water molecules readily dissociate on regular surface Fetet1-O ion pairs to form "monomers", i.e., terminal Fe-OH and surface OH groups. Further water molecules adsorb on the hydroxyl covered surface non-dissociatively and form "dimers" and larger oligomers, which ultimately assemble into an ordered (2 × 2) hydrogen-bonded network structure with increasing coverage prior to the formation of a solid water film.

Functional Dissociation of Latency-Variable, Stimulus- and Response-Locked Target P3 Sub-components in Task-Switching.

Cognitive control warrants efficient task performance in dynamic and changing environments through adjustments in executive attention, stimulus and response selection. The well-known P300 component of the human event-related potential (ERP) has long been proposed to index "context-updating"-critical for cognitive control-in simple target detection tasks. However, task switching ERP studies have revealed both target P3 (300-350 ms) and later sustained P3-like potentials (400-1,200 ms) to first targets ensuing transition cues, although it remains unclear whether these target P3-like potentials also reflect context updating operations. To address this question, we applied novel single-trial EEG analyses-residue iteration decomposition (RIDE)-in order to disentangle target P3 sub-components in a sample of 22 young adults while they either repeated or switched (updated) task rules. The rationale was to revise the context updating hypothesis of P300 elicitation in the light of new evidence suggesting that "the context" consists of not only the sensory units of stimulation, but also associated motor units, and intermediate low- and high-order sensorimotor units, all of which may need to be dynamically updated on a trial by trial basis. The results showed functionally distinct target P3-like potentials in stimulus-locked, response-locked, and intermediate RIDE component clusters overlying parietal and frontal regions, implying multiple functionally distinct, though temporarily overlapping context updating operations. These findings support a reformulated version of the context updating hypothesis, and reveal a rich family of distinct target P3-like sub-components during the reactive control of target detection in task-switching, plausibly indexing the complex and dynamic workings of frontoparietal cortical networks subserving cognitive control.

An information theory account of late frontoparietal ERP positivities in cognitive control.

ERP research on task switching has revealed distinct transient and sustained positive waveforms (latency circa 300-900 ms) while shifting task rules or stimulus-response (S-R) mappings. However, it remains unclear whether such switch-related positivities show similar scalp topography and index context-updating mechanisms akin to those posed for domain-general (i.e., classic P300) positivities in many task domains. To examine this question, ERPs were recorded from 31 young adults (18-30 years) while they were intermittently cued to switch or repeat their perceptual categorization of Gabor gratings varying in color and thickness (switch task), or else they performed two visually identical control tasks (go/no-go and oddball). Our task cueing paradigm examined two temporarily distinct stages of proactive rule updating and reactive rule execution. A simple information theory model helped us gauge cognitive demands under distinct temporal and task contexts in terms of low-level S-R pathways and higher-order rule updating operations. Task demands modulated domain-general (indexed by classic oddball P3) and switch positivities-indexed by both a cue-locked late positive complex and a sustained positivity ensuing task transitions. Topographic scalp analyses confirmed subtle yet significant split-second changes in the configuration of neural sources for both domain-general P3s and switch positivities as a function of both the temporal and task context. These findings partly meet predictions from information estimates, and are compatible with a family of P3-like potentials indexing functionally distinct neural operations within a common frontoparietal "multiple demand" system during the preparation and execution of simple task rules.

Cooperative Formation of Long-Range Ordering in Water Ad-layers on Fe3 O4 (111) Surfaces.

The initial stages of water adsorption on magnetite Fe3 O4 (111) surface and the atomic structure of the water/oxide interface remain controversial. Herein, we provide experimental results obtained by infrared reflection-absorption spectroscopy (IRAS) and temperature-programmed desorption (TPD), corroborated by density functional theory (DFT) calculations showing that water readily dissociates on Fetet sites to form two hydroxo species. These act as an anchor for water molecules to form a dimer complex which self-assembles into an ordered (2×2) structure. Water ad-layer ordering is rationalized in terms of a cooperative effect induced by a hydrogen-bonding network.

Multisubject Decomposition of Event-related Positivities in Cognitive Control: Tackling Age-related Changes in Reactive Control.

Age-related neurocognitive effects have been observed at different levels ranging from reduced amplitudes of even-related potentials and brain oscillations, to topography changes of brain activity. However, their association remains incompletely understood. We investigated time-frequency and time-course effects in functional networks underlying the P300 and their involvement in reactive control. Electroencephalographic (EEG) data of three different age groups (30 young: 18-26 years, 30 mid-aged: 49-58 years, 30 elderly: 65-75 years) was measured while they performed a cued colour/thickness switching task. Neural data was analysed concerning the targets. To consider restart, mixing, and switching processes, the targets´ position after a cue (first or third target) as well as their context in the single-task (distractor cue) or the mixed-task block (switch- or repeat cue) was analysed. P300 EEG data was decomposed by means of group-independent component and time-frequency analyses focusing on theta and beta oscillations. RTs generally slowed down with age (main effect group), and effects were specifically strong in targets after a switching cue (larger Cohens d). Peaking at around 300 ms, we detected five functionally independent networks reflecting the multicomponent process underlying task-switching. These networks differed in terms of their topography (parietal and frontal), their involvement in task processes (switch-specific, mixing-, restart-, and single-task processes) and in terms of frequency effects. All were affected by age, as indicated by amplitude changes of the target-P300 and power reductions most consistently shown in beta oscillations. Most extensive age-related changes were observed in one parietal network sensitive to mixing and restart processes. Changes included a topography shift, P300 and beta amplitudes, and were ongoing in the elderly group.

Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection-absorption spectroscopy and temperature programmed desorption study.

Atomistic-level understanding of the interaction of α,ß-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C[double bond, length as m-dash]C vs. C[double bond, length as m-dash]O bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection-absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the C[double bond, length as m-dash]C and C[double bond, length as m-dash]O bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported.

Contextually sensitive power changes across multiple frequency bands underpin cognitive control.

Flexible control of cognition bestows a remarkable adaptability to a broad range of contexts. While cognitive control is known to rely on frontoparietal neural architecture to achieve this flexibility, the neural mechanisms that allow such adaptability to context are poorly understood. In the current study, we quantified contextual demands on the cognitive control system via a priori estimation of information across three tasks varying in difficulty (oddball, go/nogo, and switch tasks) and compared neural responses across these different contexts. We report evidence of the involvement of multiple frequency bands during preparation and implementation of cognitive control. Specifically, a common frontoparietal delta and a central alpha process corresponded to rule implementation and motor response respectively. Interestingly, we found evidence of a frontal theta signature that was sensitive to increasing amounts of information and a posterior parietal alpha process only seen during anticipatory rule updating. Importantly, these neural signatures of context processing match proposed frontal hierarchies of control and together provide novel evidence of a complex interplay of multiple frequency bands underpinning flexible, contextually sensitive cognition.

Spectators Control Selectivity in Surface Chemistry: Acrolein Partial Hydrogenation Over Pd.

We present a mechanistic study on selective hydrogenation of acrolein over model Pd surfaces--both single crystal Pd(111) and Pd nanoparticles supported on a model oxide support. We show for the first time that selective hydrogenation of the C═O bond in acrolein to form an unsaturated alcohol is possible over Pd(111) with nearly 100% selectivity. However, this process requires a very distinct modification of the Pd(111) surface with an overlayer of oxopropyl spectator species that are formed from acrolein during the initial stages of reaction and turn the metal surface selective toward propenol formation. By applying pulsed multimolecular beam experiments and in situ infrared reflection-absorption spectroscopy, we identified the chemical nature of the spectator and the reactive surface intermediate (propenoxy species) and experimentally followed the simultaneous evolution of the reactive intermediate on the surface and formation of the product in the gas phase.