Treadmill Exercise Reverses the Adverse Effects of Intermittent Fasting on Behavior and Cortical Spreading Depression in Young Rats.

Intermittent fasting (IF) and physical exercise (PE) have beneficial psychological and physiological effects, improving memory and anxiety-like behavior. However, the impact of this combination on brain electrophysiological patterns is unknown. We aimed to evaluate the behavior and parameters of a brain excitability-related phenomenon named cortical spreading depression (CSD) in young rats (31-87 days of life) submitted to IF and treadmill PE for eight weeks. Sixty-four male and female Wistar rats aged 24 days were randomized into control, IF, PE, and IF+PE groups. Behavioral tests (open field (OF), object recognition, and elevated plus maze (EPM)) were performed, and the CSD propagation features were recorded. IF caused behavioral responses indicative of anxiety (lower number of entries and time spent in the OF center and EPM open arms). IF also reduced the discrimination index for object recognition memory tests and increased the propagation velocity of CSD. PE rats displayed more entries into the OF center and lowered CSD propagation speed. Data suggest that IF worsens anxiety-like behavior and memory and accelerates CSD in young rats. In contrast, PE reverted the unfavorable effects of IF. The brain effects of IF and PE at younger ages are recommended for study.

Correction: Insight at the atomic scale of corrosion inhibition: DFT study of 8-hydroxyquinoline on oxidized aluminum surfaces.

Correction for 'Insight at the atomic scale of corrosion inhibition: DFT study of 8-hydroxyquinoline on oxidized aluminum surfaces' by Fatah Chiter et al., Phys. Chem. Chem. Phys., 2023, https://doi.org/10.1039/d2cp04626a.

Insight at the atomic scale of corrosion inhibition: DFT study of 8-hydroxyquinoline on oxidized aluminum surfaces.

8-Hydroxyquinoline (8-HQ) is a promising organic molecule for the corrosion protection of aluminum and its alloys in the replacement of chromate salts. On the aluminum surface, the presence of an oxide layer naturally formed can influence the inhibition efficiency which depends on molecule-surface interactions. In the present study, we performed quantum chemical calculations on native 8-HQ, tautomer and 8-Q (deprotonated, H-abstracted or radical) molecules, adsorbed on an oxidized aluminum surface (γ-Al2O3(111)/Al(111)). All species have the ability to interact strongly with the oxidized aluminum surface and can form stable and dense organic films. The bonding strength of different species of 8-HQ on oxidized aluminum surfaces is more favorable for 8-Q and tautomer species than for the native 8-HQ molecule. On the surface, the native 8-HQ molecule is physisorbed, forming H-bonds, in contrast to the tautomer and 8-Q species that show the predominance of chemisorption modes, involving both H-bonds and covalent bonds at the molecule/substrate interface. The dispersion energy significantly contributes to the adsorption mechanism and increases with increasing molecular surface coverage, due to attractive molecule-molecule interactions. Regardless of surface coverage and considered reaction mechanisms, the 8-Q species is able to enhance the stability of all aluminum sites, and thus to slow down the anodic reaction. In contrast, the native molecule and the tautomeric form have no significant effect or even weakened the stability of aluminum surface atoms.

Leucine on Silica: A Combined Experimental and Modeling Study of a System Relevant for Origins of Life, and the Role of Water Coadsorption.

Leucine on silica constitutes an interesting system from the point of view of origins of life studies since leucine coadsorbed on SiO2 together with glutamic acid can give rise to rather long linear polypeptides upon activation. It is also an ideal system to test methods of molecular characterization of biomolecules deposited on mineral surfaces since it combines a small-scale model of peptides and proteins, which are among the most important components of biodevices, with one of the most widely used inorganic materials. We have deposited l-leucine on a high surface fumed silica in the submonolayer range and characterized it by a multipronged approach including macroscopic information (thermogravimetry, X-ray diffraction), in situ spectroscopic methods (IR, multinuclear solid-state NMR including single-pulse and CP-MAS, 2-D HETCOR), and molecular modeling by density functional theory (DFT), including calculation of NMR parameters. Specific information can be obtained on the adsorption and interaction mechanism. Leucine is rather strongly adsorbed without any covalent bonds, through the formation of a specific lattice of H-bonds that often involve coadsorbed water molecules. Its state is indeed strongly dependent on the drying procedure: insufficient drying results in liquid-like surroundings for the leucine functional groups, while vacuum drying only retains a limited number of waters (of the order of 5 per leucine molecule). The most stable models have zwitterionic leucine interacting directly with surface silanols through their ammonium group, while the carboxylate interacts through bridging waters. Experimental NMR chemical shifts are satisfactorily predicted for these models, and leucine can be viewed as a probe for specific groups of surface sites known as silanol nests.

Aneurisma da artéria isquiática persistente: relato de caso de tratamento endovascular / Persistent sciatic artery aneurysm: case report of endovascular treatment

A persistência da artéria isquiática é uma anomalia vascular congênita rara cuja principal complicação é a dilatação aneurismática. O quadro clínico pode incluir sintomas decorrentes da dilatação arterial e da isquemia, causada por trombose ou embolização distal. O tratamento dessa afecção rara conta com opções diversas que abrangem desde a ligadura do aneurisma até a correção endovascular. O presente relato descreve o caso de uma paciente do sexo feminino com queixa de tumoração pulsátil na região glútea. Foi encaminhada ao serviço de referência e realizou angiotomografia, que evidenciou persistência completa da artéria isquiática bilateralmente, com dilatação aneurismática à esquerda. A paciente foi submetida a tratamento endovascular do aneurisma, através de punção contralateral, com implante de dois stents revestidos com manutenção da perviedade distal da artéria. A manutenção da perviedade é particularmente importante nos casos da forma completa dessa variação anatômica. A paciente cursou com boa evolução

A persistent sciatic artery is a rare congenital vascular anomaly. The most common complication is aneurysm. Clinical presentation may include symptoms resulting from arterial dilatation and ischemia caused by thrombosis or embolization. There are diverse options for treatment of this rare condition, ranging from ligature of the aneurism to endovascular repair. This report describes the case of a female patient complaining of a pulsating mass in the left buttock. She was referred to a Vascular Service where an angiotomography showed complete bilateral persistence of the sciatic artery, with an aneurysm of the left sciatic artery. The aneurysm was treated with endovascular techniques, via a contralateral approach, with placement of two stent grafts and preservation of distal patency. Patency is particularly important in cases of this anatomical variation in which the persistent sciatic artery is complete. This patient recovered well

Co-Binding of Pharmaceutical Compounds at Mineral Surfaces: Molecular Investigations of Dimer Formation at Goethite/Water Interfaces.

The emergence of antibiotic and anti-inflammatory agents in aquatic and terrestrial systems is becoming a serious threat to human and animal health worldwide. Because pharmaceutical compounds rarely exist individually in nature, interactions between various compounds can have unforeseen effects on their binding to mineral surfaces. This work demonstrates this important possibility for the case of two typical antibiotic and anti-inflammatory agents (nalidixic acid (NA) and niflumic acid (NFA)) bound at goethite (α-FeOOH) used as a model mineral surface. Our multidisciplinary study, which makes use of batch sorption experiments, vibration spectroscopy and periodic density functional theory calculations, reveals enhanced binding of the otherwise weakly bound NFA caused by unforeseen intermolecular interactions with mineral-bound NA. This enhancement is ascribed to the formation of a NFA-NA dimer whose energetically favored formation (-0.5 eV compared to free molecules) is predominantly driven by van der Waals interactions. A parallel set of efforts also showed that no cobinding occurred with sulfamethoxazole (SMX) because of the lack of molecular interactions with coexisting contaminants. As such, this article raises the importance of recognizing drug cobinding, and lack of cobinding, for predicting and developing policies on the fate of complex mixtures of antibiotics and anti-inflammatory agents in nature.

Tuning the Surface Chirality of Adsorbed Gly-Pro Dipeptide/Cu(110) by Changing Its Chemical Form via Electrospray Deposition.

By changing the ultrahigh vacuum (UHV) deposition method, classical sublimation versus electrospray ionization, one can tune the chemistry of a chiral dipeptide molecule (Gly-Pro, GP), when adsorbed on a Cu(110) surface, from anionic to zwitterionic. This chemical shift will influence the adsorption mode of the dipeptide, either in a three-point fashion in the case of anionic GP molecules with a strong interaction among the copper surface, both O atoms of the carboxylate moiety, and the nitrogen atoms, or in the case of zwitterions GP, the adsorption mode relies on the sole interaction of one carboxylate oxygen atom. These different anchoring modes strongly modify the expression of surface 2D chirality and the supramolecular assemblies with two very distinct unit cells.

Near-ambient XPS characterization of interfacial copper species in ceria-supported copper catalysts.

Catalysts based on combinations of copper and cerium oxides are interesting alternatives to noble metal ones for processes involved in the production/purification of hydrogen produced from hydrocarbons or biomass like the water-gas shift or the preferential oxidation of CO reactions. Active sites for such processes have been proposed to correspond to reduced species formed at the interface between both oxides. The present work provides direct evidence of reduced copper species located at the interface and observed during the course of near-ambient XPS experiments performed over samples of copper oxide supported on ceria nanospheres and nanocubes subjected to interaction with CO at different temperatures. The analysis of XPS results is based on DFT+U calculations employed as a complementary method for the analysis of redox properties of the catalysts and core-level shifts produced upon such redox changes. Differences observed in interfacial redox properties as a function of the ceria support morphology appear to be most useful to explain catalytic properties of this type of system for mentioned processes.

In situ investigation of dissociation and migration phenomena at the Pt/electrolyte interface of an electrochemical cell.

The development of efficient energy conversion systems requires precise engineering of electrochemical interfaces and thus asks for in situ techniques to probe the structure and the composition of the dynamic electrode/electrolyte interfacial region. This work demonstrates the potential of the near ambient pressure X-ray photoelectron spectroscopy (NAPXPS) for in situ studies of processes occurring at the interface between a metal electrode and a liquid electrolyte. By using a model membrane-electrode assembly of a high temperature phosphoric acid-imbibed proton exchange membrane fuel cell, and combining NAPXPS measurements with the density functional theory, it was possible to monitor such fundamental processes as dissociation and migration of the phosphoric acid within a nanostructured Pt electrode under polarization.

The amorphous silica-liquid water interface studied by ab initio molecular dynamics (AIMD): local organization in global disorder.

The structural organization of water at a model of amorphous silica-liquid water interface is investigated by ab initio molecular dynamics (AIMD) simulations at room temperature. The amorphous surface is constructed with isolated, H-bonded vicinal and geminal silanols. In the absence of water, the silanols have orientations that depend on the local surface topology (i.e. presence of concave and convex zones). However, in the presence of liquid water, only the strong inter-silanol H-bonds are maintained, whereas the weaker ones are replaced by H-bonds formed with interfacial water molecules. All silanols are found to act as H-bond donors to water. The vicinal silanols are simultaneously found to be H-bond acceptors from water. The geminal pairs are also characterized by the formation of water H-bonded rings, which could provide special pathways for proton transfer(s) at the interface. The first water layer above the surface is overall rather disordered, with three main domains of orientations of the water molecules. We discuss the similarities and differences in the structural organization of the interfacial water layer at the surface of the amorphous silica and at the surface of the crystalline (0 0 0 1) quartz surface.

Peptides from the variable region of specific antibodies are shared among lung cancer patients.

Late diagnosis of lung cancer is still the main reason for high mortality rates in lung cancer. Lung cancer is a heterogeneous disease which induces an immune response to different tumor antigens. Several methods for searching autoantibodies have been described that are based on known purified antigen panels. The aim of our study is to find evidence that parts of the antigen-binding-domain of antibodies are shared among lung cancer patients. This was investigated by a novel approach based on sequencing antigen-binding-fragments (Fab) of immunoglobulins using proteomic techniques without the need of previously known antigen panels. From serum of 93 participants of the NELSON trial IgG was isolated and subsequently digested into Fab and Fc. Fab was purified from the digested mixture by SDS-PAGE. The Fab containing gel-bands were excised, tryptic digested and measured on a nano-LC-Orbitrap-Mass-spectrometry system. Multivariate analysis of the mass spectrometry data by linear canonical discriminant analysis combined with stepwise logistic regression resulted in a 12-antibody-peptide model which was able to distinguish lung cancer patients from controls in a high risk population with a sensitivity of 84% and specificity of 90%. With our Fab-purification combined Orbitrap-mass-spectrometry approach, we found peptides from the variable-parts of antibodies which are shared among lung cancer patients.

Aluminium in biological environments: a computational approach.

The increased availability of aluminium in biological environments, due to human intervention in the last century, raises concerns on the effects that this so far "excluded from biology" metal might have on living organisms. Consequently, the bioinorganic chemistry of aluminium has emerged as a very active field of research. This review will focus on our contributions to this field, based on computational studies that can yield an understanding of the aluminum biochemistry at a molecular level. Aluminium can interact and be stabilized in biological environments by complexing with both low molecular mass chelants and high molecular mass peptides. The speciation of the metal is, nonetheless, dictated by the hydrolytic species dominant in each case and which vary according to the pH condition of the medium. In blood, citrate and serum transferrin are identified as the main low molecular mass and high molecular mass molecules interacting with aluminium. The complexation of aluminium to citrate and the subsequent changes exerted on the deprotonation pathways of its tritable groups will be discussed along with the mechanisms for the intake and release of aluminium in serum transferrin at two pH conditions, physiological neutral and endosomatic acidic. Aluminium can substitute other metals, in particular magnesium, in protein buried sites and trigger conformational disorder and alteration of the protonation states of the protein's sidechains. A detailed account of the interaction of aluminium with proteic sidechains will be given. Finally, it will be described how alumnium can exert oxidative stress by stabilizing superoxide radicals either as mononuclear aluminium or clustered in boehmite. The possibility of promotion of Fenton reaction, and production of hydroxyl radicals will also be discussed.

Diaminoethane adsorption and water substitution on hydrated TiO2: a thermochemical study based on first-principles calculations.

Epoxy-amines are used as structural adhesives deposited on Ti. The amine adhesion to a Ti surface depends highly on the surface state (oxidation, hydroxylation). Amines may adsorb above preadsorbed water molecules or substitute them to bind directly to surface Ti(4+) Lewis acid sites. The adsorption of a model amine molecule, diaminoethane (DAE), on a model surface, hydrated TiO2-anatase (101) surface, is investigated using Density Functional Theory including Dispersive forces (DFT-D) calculations. DAE adsorption and water substitution by DAE are exothermic processes and turn nearly isoenergetic at high coverage with adsorption-substitution energies around -0.3 eV (including dispersion forces and ZPE). Complementary ab initio molecular dynamics studies also suggest that the formation of an amine-water interaction induces water desorption from the surface at room temperature, a preliminary step towards the amine-Ti bond formation. An atomistic thermodynamic approach is developed to evaluate the interfacial free energy balance of both processes (adsorption and substitution). The main contributions to the energetic balance are dispersive interactions between molecules and the surface on the exergonic side, translational and rotational entropic contributions on the endergonic one. The substitution process is stabilized by 0.55 eV versus the adsorption one when free solvation, rotational and vibrational energies are considered. The main contribution to this free energy gain is due to water solvation. The calculations suggest that in toluene solvent with a water concentration of 10(-4) M or less, a full DAE layer replaces a preadsorbed water layer for a threshold concentration of DAE ≥ 0.1 M.

Unraveling the self-assembly of the (S)-glutamic acid "flower" structure on Ag(100).

(S)-Glutamic acid adsorbed on Ag(100) organizes in different self-assembled structures depending on surface temperature [Smerieri, M.; Vattuone, L.; Kravchuk, T.; Costa, D.; Savio, L. (S)-Glutamic Acid on Ag(100): Self-Assembly in the Nonzwitterionic Form. Langmuir2011, 27, 2393-2404]. In particular, two of these structures, referred to as "square" and "flower" geometries, are found to coexist on the surface upon deposition at T = 350 K. The former assembly was fully resolved at the atomic level in the work of Smerieri et al. [Smerieri, M.; Vattuone, L.; Costa, D.; Tielens, F.; Savio, L. Self-Assembly of (S)-Glutamic Acid on Ag(100): A Combined LT-STM and Ab Initio Investigation. Langmuir2010, 26, 7208-7215], in which we proved that the driving force for adsorption is the van der Waals interactions between the molecules and the Ag surface, that is, that molecules are in a physisorbed state. In this paper, we complete our work by presenting the characterization of the "flower" structure. In contrast to the case of the "square" assembly, a strong chemical bond between glutamic acid radicals and the surface is at the basis of the "flowers" geometry. Whereas the chemisorbed central GLU tetramer interacts strongly with the surface, the physisorbed surrounding GLU molecules conserve some degree of freedom in the layer which counterbalances the weak adsorption energy. The "flower" and the "square" assemblies have similar dispersion energy and H-bond interaction energy; as a consequence of the different chemical state of the GLU molecules, however, such contributions have a very different relative weight in the stabilization of the two structures.

Understanding small biomolecule-biomaterial interactions: a review of fundamental theoretical and experimental approaches for biomolecule interactions with inorganic surfaces.

Interactions between biomolecules and inorganic surfaces play an important role in natural environments and in industry, including a wide variety of conditions: marine environment, ship hulls (fouling), water treatment, heat exchange, membrane separation, soils, mineral particles at the earth's surface, hospitals (hygiene), art and buildings (degradation and biocorrosion), paper industry (fouling) and more. To better control the first steps leading to adsorption of a biomolecule on an inorganic surface, it is mandatory to understand the adsorption mechanisms of biomolecules of several sizes at the atomic scale, that is, the nature of the chemical interaction between the biomolecule and the surface and the resulting biomolecule conformations once adsorbed at the surface. This remains a challenging and unsolved problem. Here, we review the state of art in experimental and theoretical approaches. We focus on metallic biomaterial surfaces such as TiO(2) and stainless steel, mentioning some remarkable results on hydroxyapatite. Experimental techniques include atomic force microscopy, surface plasmon resonance, quartz crystal microbalance, X-ray photoelectron spectroscopy, fluorescence microscopy, polarization modulation infrared reflection absorption spectroscopy, sum frequency generation and time of flight secondary ion mass spectroscopy. Theoretical models range from detailed quantum mechanical representations to classical forcefield-based approaches.

CO adsorption on amorphous silica-alumina: electrostatic or Brønsted acidity probe?

The adsorption of CO on amorphous silica-alumina (ASA) was calculated by DFT. CO appears as a probe of the electrostatic field induced by the whole surface, at the origin of a so-called vibrational Stark effect responsible for the CO frequency shifts. Brønsted acidity of the ASA sites does not directly correlate CO frequency shifts.

Mass spectrometry analyses of κ and λ fractions result in increased number of complementarity-determining region identifications.

Sera from lung cancer patients contain antibodies against tumor-associated antigens. Specific amino acid sequences of the complementarity-determining regions (CDRs) in the antigen-binding fragment (Fab) of these antibodies have potential as lung cancer biomarkers. Detection and identification of CDRs by mass spectrometry can significantly be improved by reduction of the complexity of the immunoglobulin molecule. Our aim was to molecular dissect IgG into κ and λ fragments to reduce the complexity and thereby identify substantially more CDRs than by just total Fab isolation. We purified Fab, Fab-κ, Fab-λ, κ and λ light chains from serum from 10 stage I lung adenocarcinoma patients and 10 matched controls from the current and former smokers. After purification, the immunoglobulin fragments were enzymatically digested and measured by high-resolution mass spectrometry. Finally, we compared the number of CDRs identified in these immunoglobulin fragments with that in the Fab fragments. Twice as many CDRs were identified when Fab-κ, Fab-λ, κ and λ (3330) were combined than in the Fab fraction (1663) alone. The number of CDRs and κ:λ ratio was statistically similar in both cases and controls. Molecular dissection of IgG identifies significantly more CDRs, which increases the likelihood of finding lung cancer-related CDR sequences.

Label-free peptide profiling of Orbitrap™ full mass spectra.

BACKGROUND: We developed a new version of the open source software package Peptrix that can yet compare large numbers of Orbitrap™ LC-MS data. The peptide profiling results for Peptrix on MS1 spectra were compared with those obtained from a small selection of open source and commercial software packages: msInspect, Sieve™ and Progenesis™. The properties compared in these packages were speed, total number of detected masses, redundancy of masses, reproducibility in numbers and CV of intensity, overlap of masses, and differences in peptide peak intensities. Reproducibility measurements were taken for the different MS1 software applications by measuring in triplicate a complex peptide mixture of immunoglobulin on the Orbitrap™ mass spectrometer. Values of peptide masses detected from the high intensity peaks of the MS1 spectra by peptide profiling were verified with values of the MS2 fragmented and sequenced masses that resulted in protein identifications with a significant score. FINDINGS: Peptrix finds about the same number of peptide features as the other packages, but peptide masses are in some cases approximately 5 to 10 times less redundant present in the peptide profile matrix. The Peptrix profile matrix displays the largest overlap when comparing the number of masses in a pair between two software applications. The overlap of peptide masses between software packages of low intensity peaks in the spectra is remarkably low with about 50% of the detected masses in the individual packages. Peptrix does not differ from the other packages in detecting 96% of the masses that relate to highly abundant sequenced proteins. MS1 peak intensities vary between the applications in a non linear way as they are not processed using the same method. CONCLUSIONS: Peptrix is capable of peptide profiling using Orbitrap™ files and finding differential expressed peptides in body fluid and tissue samples. The number of peptide masses detected in Orbitrap™ files can be increased by using more MS1 peptide profiling applications, including Peptrix, since it appears from the comparison of Peptrix with the other applications that all software packages have likely a high false negative rate of low intensity peptide peaks (missing peptides).