Electrochemical Response of 3D-Printed Free-Standing Reduced Graphene Oxide Electrode for Sodium Ion Batteries Using a Three-Electrode Glass Cell.

Graphene and its derivatives have been widely used to develop novel materials with applications in energy storage. Among them, reduced graphene oxide has shown great potential for more efficient storage of Na ions and is a current target in the design of electrodes for environmentally friendly Na ion batteries. The search for more sustainable and versatile manufacturing processes also motivates research into additive manufacturing electrodes. Here, the electrochemical responses of porous 3D-printed free-standing log-type structures fabricated using direct ink writing (DIW) with a graphene oxide (GO) gel ink are investigated after thermal reduction in a three-electrode cell configuration. The structures delivered capacities in the range of 50-80 mAh g-1 and showed high stability for more than 100 cycles. The reaction with the electrolyte/solvent system, which caused an initial capacity drop, was evidenced by the nucleation of various Na carbonates and Na2O. The incorporation of Na into the filaments of the structure was verified with transmission electron microscopy and Raman spectroscopy. This work is a proof of concept that structured reduced GO electrodes for Na ion batteries can be achieved from a simple, aqueous GO ink through DIW and that there is scope for improving their performance and capacity.

Detection of suspected carcinogen azo dyes in textiles using thermogravimetric analysis.

Textiles that are in direct contact with human skin are problematic due to the possibility of transferring the dyes or their aromatic amine metabolites through direct contact. 18 samples of women underwear panties of different colors and fabrics materials were examined for their content of azo dyes using thermogravimetric-gas chromatography-mass spectrometry (TGA-GCMS) technique. The nature of fabrics (cotton, nylon, and polyesters) was identified based on their unique thermogravimetric analyses (TGA) pattern. Aromatic amines produced from thermal degradation of the samples were identified using NIST mass spectra data base. Aniline was found in all samples regardless of their color or fabric composition. Black cotton textiles were characterized by the presence of diaminobenzene, red cotton sample showed the presence of 4-amino-3-nitrobenzene-1-sulfonic acid, blue cotton sample showed the presence of chlorobenzenediamine and chloroaniline, and purple cotton textiles showed the presence of 4-nitroaniline. All four purple nylon samples contained nitroaniline and biphenylamine, the three red nylon samples contained nitroaniline and methyldihydro-thiadiazole, the two pink samples showed the presence of chloro-2-(trifluoromethyl) anilinechloro- benzenediamine, the purple polyethylene sample show the presence of diphenyldiazene, and the brown polyester sample showed the presence of 2-amino-1,4-phenylene) dimethanol.[Formula: see text].

New Insights on the Conversion Reaction Mechanism in Metal Oxide Electrodes for Sodium-Ion Batteries.

Due to the abundance and low cost of exchanged metal, sodium-ion batteries have attracted increasing research attention for the massive energy storage associated with renewable energy sources. Nickel oxide (NiO) thin films have been prepared by magnetron sputtering (MS) deposition under an oblique angle configuration (OAD) and used as electrodes for Na-ion batteries. A systematic chemical, structural and electrochemical analysis of this electrode has been carried out. The electrochemical characterization by galvanostatic charge-discharge cycling and cyclic voltammetry has revealed a certain loss of performance after the initial cycling of the battery. The conversion reaction of NiO with sodium ions during the discharge process to generate sodium oxide and Ni metal has been confirmed by X-ray photoelectron spectra (XPS) and micro-Raman analysis. Likewise, it has been determined that the charging process is not totally reversible, causing a reduction in battery capacity.

Sol-Gel Synthesis of Nanocrystalline Mesoporous Li4Ti5O12 Thin-Films as Anodes for Li-Ion Microbatteries.

The development of anodes based on Li4Ti5O12 (LTO) for lithium ion batteries has become very important in recent years on the basis that it allows a long service life (stability in charge-discharge cycling) and safety improvements. The processing of this material in the form of thin film allows for greater control of its characteristics and an improvement of its disadvantages, namely reduced electrical conductivity and low diffusion of lithium ions. In this work, we try to limit these disadvantages through the synthesis of a mesostructured carbon-doped Li4Ti5O12 thin-film with a pure spinel phase using a combination of a block-copolymer template and in situ synthesis of Li-Ti double alkoxide. Structural and electrochemical characterization has been carried out to determine the best conditions (temperature, time, atmosphere) for the thermal treatment of the material to reach a compromise between crystallinity and porosity distribution (pore size, pore volume, and interconnectivity).

Blend Hybrid Solid Electrolytes Based on LiTFSI Doped Silica-Polyethylene Oxide for Lithium-Ion Batteries.

Organic/inorganic hybrid membranes that are based on GTT (GPTMS-TMES-TPTE) system while using 3-Glycidoxypropyl-trimethoxysilane (GPTMS), Trimethyletoxisilane (TMES), and Trimethylolpropane triglycidyl ether (TPTE) as precursors have been obtained while using a combination of organic polymerization and sol-gel synthesis to be used as electrolytes in Li-ion batteries. Self-supported materials and thin-films solid hybrid electrolytes that were doped with Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared. The hybrid network is based on highly cross-linked structures with high ionic conductivity. The dependency of the crosslinked hybrid structure and polymerization grade on ionic conductivity is studied. Ionic conductivity depends on triepoxy precursor (TPTE) and the accessibility of Li ions in the organic network, reaching a maximum ionic conductivity of 1.3 × 10-4 and 1.4 × 10-3 S cm-1 at room temperature and 60 °C, respectively. A wide electrochemical stability window in the range of 1.5-5 V facilitates its use as solid electrolytes in next-generation of Li-ion batteries.

Consolidated Melting Gel Coatings on AZ31 Magnesium Alloy with Excellent Corrosion Resistance in NaCl Solutions: An Interface Study.

Magnesium alloys, with a density two-thirds that of aluminum, are very attractive for the industry. However, these alloys are extremely susceptible to corrosion in the presence of aggressive electrolytes such as NaCl solutions. Here, we designed hybrid coatings obtained by the consolidation of organically modified polysilsesquioxanes called "melting gels" for the corrosion protection of AZ31 magnesium alloy in NaCl solutions. The main focus was to study the interaction between coatings and substrate and the influence of the coating thickness on the final properties. Micro-scratch tests, adhesion by tape tests, confocal Raman microscopy, SEM-EDS, and ToF-SIMS indicate good adhesion of coatings based on the interaction of melting gels and substrate. These measurements indicate the presence of the Si-O-Mg bonds between the substrate and coatings. Electrochemical results show very low current densities (10-13 A cm-2) without any breakdown potential and impedance values of 1010 Ω cm2.

The Neural Basis of Speech Perception through Lipreading and Manual Cues: Evidence from Deaf Native Users of Cued Speech.

We present here the first neuroimaging data for perception of Cued Speech (CS) by deaf adults who are native users of CS. CS is a visual mode of communicating a spoken language through a set of manual cues which accompany lipreading and disambiguate it. With CS, sublexical units of the oral language are conveyed clearly and completely through the visual modality without requiring hearing. The comparison of neural processing of CS in deaf individuals with processing of audiovisual (AV) speech in normally hearing individuals represents a unique opportunity to explore the similarities and differences in neural processing of an oral language delivered in a visuo-manual vs. an AV modality. The study included deaf adult participants who were early CS users and native hearing users of French who process speech audiovisually. Words were presented in an event-related fMRI design. Three conditions were presented to each group of participants. The deaf participants saw CS words (manual + lipread), words presented as manual cues alone, and words presented to be lipread without manual cues. The hearing group saw AV spoken words, audio-alone and lipread-alone. Three findings are highlighted. First, the middle and superior temporal gyrus (excluding Heschl's gyrus) and left inferior frontal gyrus pars triangularis constituted a common, amodal neural basis for AV and CS perception. Second, integration was inferred in posterior parts of superior temporal sulcus for audio and lipread information in AV speech, but in the occipito-temporal junction, including MT/V5, for the manual cues and lipreading in CS. Third, the perception of manual cues showed a much greater overlap with the regions activated by CS (manual + lipreading) than lipreading alone did. This supports the notion that manual cues play a larger role than lipreading for CS processing. The present study contributes to a better understanding of the role of manual cues as support of visual speech perception in the framework of the multimodal nature of human communication.

29Si NMR and SAXS investigation of the hybrid organic-inorganic glasses obtained by consolidation of the melting gels.

This study is focused on structural characterization of hybrid glasses obtained by consolidation of melting gels. The melting gels were prepared in molar ratios of methyltriethoxysilane (MTES) and dimethyldiethoxysilane (DMDES) of 75%MTES-25%DMDES and 65%MTES-35%DMDES. Following consolidation, the hybrid glasses were characterized using Raman, 29Si and 13C Nuclear Magnetic Resonance (NMR) spectroscopies, synchrotron Small Angle X-Ray Scattering (SAXS) and scanning electron microscopy (SEM). Raman spectroscopy revealed the presence of Si-C bonds in the hybrid glasses and 8-membered ring structures in the Si-O-Si network. Qualitative NMR spectroscopy identified the main molecular species, while quantitative NMR data showed that the ratio of trimers (T) to dimers (D) varied between 4.6 and 3.8. Two-dimensional 29Si NMR data were used to identify two distinct types of T3 environments. SAXS data showed that the glasses are homogeneous across the nm to micrometer length scales. The scattering cross section was one thousand times lower than what is expected when phase separation occurs. The SEM images show a uniform surface without defects, in agreement with the SAXS results, which further supports that the hybrid glasses are nonporous.

Choosing the best molecular precursor to prepare Li4Ti5O12 by the sol-gel method using (1)H NMR: evidence of [Ti3(OEt)13](-) in solution.

(1)H NMR spectroscopy at 400 MHz in toluene-d8 of evaporated mixtures of lithium ethoxide and titanium(iv) isopropoxide in ethanol, used to prepare the spinel Li4Ti5O12 by the sol-gel method, may help clarify why the atomic ratio 5Li : 5Ti and not 4Li : 5Ti is the right choice to obtain the pure phase when performing hydrolysis at room temperature. The mixtures xLiOEt/yTi(OPr(i))4 in ethanol undergo alcohol exchange at room temperature, and the evaporated residues contain double lithium-titanium ethoxide [LiTi3(OEt)13] rather than simple mixtures of single metal alkoxides; this is of great relevance to truly understanding the chemistry and structural changes in the sol-gel process. Detailed inspection of the (1)H and (13)C VT NMR spectra of mixtures with different Li/Ti atomic ratios unequivocally shows the formation of [LiTi3(OEt)13] in a solution at low temperature. The methylene signals of free lithium ethoxide and Li[Ti3(OEt)13] coalesce at 20 °C when the atomic ratio is 5 : 5; however, the same coalescence is only observed above 60 °C when the atomic ratio is 4 : 5. We suggest that the highest chemical equivalence observed by (1)H NMR spectroscopy achieved through chemical exchange of ethoxide groups involves the highest microscopic structural homogeneity of the sol precursor and will lead to the best gel after hydrolysis. Variable temperature (1)H NMR spectra at 400 MHz of variable molar ratios of LiOEt/Ti(OPr(i))4 are discussed to understand the structural features of the sol precursor. While the precursor with the atomic ratio 5Li : 5Ti shows no signal of free LiOEt at 20 °C, both 4Li : 5Ti and 7Li : 5Ti show free LiOEt at 20 °C in their (1)H NMR spectra, indicating that the molar ratio 5Li : 5Ti gives the maximum rate of chemical exchange. DFT calculations have been performed to support the structure of the anion [Ti3(OEt)13](-) at room temperature.

Accurate Mass GC/LC-Quadrupole Time of Flight Mass Spectrometry Analysis of Fatty Acids and Triacylglycerols of Spicy Fruits from the Apiaceae Family.

The triacylglycerol (TAG) structure and the regio-stereospecific distribution of fatty acids (FA) of seed oils from most of the Apiaceae family are not well documented. The TAG structure ultimately determines the final physical properties of the oils and the position of FAs in the TAG molecule affects the digestion; absorption and metabolism; and physical and technological properties of TAGs. Fixed oils from the fruits of dill (Anethum graveolens), caraway (Carum carvi), cumin (Cuminum cyminum), coriander (Coriandrum sativum), anise (Pimpinella anisum), carrot (Daucus carota), celery (Apium graveolens), fennel (Foeniculum vulgare), and Khella (Ammi visnaga), all from the Apiaceae family, were extracted at room temperature in chloroform/methanol (2:1 v/v) using percolators. Crude lipids were fractionated by solid phase extraction to separate neutral triacylglycerols (TAGs) from other lipids components. Neutral TAGs were subjected to transesterification process to convert them to their corresponding fatty acids methyl esters (FAMES) using 1% boron trifluoride (BF3) in methanol. FAMES were analyzed by gas chromatography-quadrupole time of flight (GC-QTOF) mass spectrometry. Triglycerides were analyzed using high performance liquid chromatography-quadrupole time of flight (LC-QTOF) mass spectrometry. Petroselinic acid was the major fatty acid in all samples ranging from 57% of the total fatty acids in caraway up to 82% in fennel. All samples contained palmitic (16:0), palmitoleic (C16:1n-9), stearic (C18:0), petroselinic (C18:1n-12), linoleic (C18:2n-6), linolinic (18:3n-3), and arachidic (C20:0) acids. TAG were analyzed using LC-QTOF for accurate mass identification and mass spectrometry/mass spectrometry (MS/MS) techniques for regiospesific elucidation of the identified TAGs. Five major TAGs were detected in all samples but with different relative concentrations in all of the tested samples. Several other TAGs were detected as minor components and were present in some samples and absence in the others. Regiospecific analysis showed a non-random fatty acids distribution. Petroselinic acid was predominantly located at the sn-1 and sn-3 positions.

Antifungal ellagitannin isolated from Euphorbia antisyphilitica Zucc.

OBJECTIVE: To study antifungal activity of a new ellagitannin isolated from the plant residues of Euphorbia antisyphilitica (E. antisyphilitica) Zucc in the wax extraction process. METHODS: An extract was prepared from dehydrated and pulverized residues and fractionated by liquid chromatography on Amberilte XAD-16, until obtained an ellagitannin-rich ethanolic fraction which was treated by rotaevaporation to recover the ellagitannin as fine powder. An aqueous solution was prepared and treated through ionic exchange liquid chromatography (Q XL) and gel permeation chromatography (G 25). The ellagitannin-rich fraction was thermogravimetrically evaluated (TGA and DTA) to test the thermo-stability of ellagic acid (monomeric unit). Then ellagitannin powder was analyzed by infrared spectrospcopy to determinate the functional groups and, also mass spectroscopy was used to determine the molecular ion. RESULTS: The principal functional groups of ellagitannin were determined, the molecular weight was 860.7 g/mol; and an effective antifungal activity against phytopathogenic fungi was demonstrated. CONCLUSIONS: It can be concluded that the new ellagitannin (860.7 g/mol) isolated from E. antisyphilitica Zucc is an effective antifungal agent against Alternaria alternata, Fusarium oxyzporum, Colletotrichum gloeosporoides and Rhizoctnia solani.

Early experience of Cued Speech enhances speechreading performance in deaf.

It is known that deaf individuals usually outperform normal hearing subjects in speechreading; however, the underlying reasons remain unclear. In the present study, speechreading performance was assessed in normal hearing participants (NH), deaf participants who had been exposed to the Cued Speech (CS) system early and intensively, and deaf participants exposed to oral language without Cued Speech (NCS). Results show a gradation in performance with highest performance in CS, then in NCS, and finally NH participants. Moreover, error analysis suggests that speechreading processing is more accurate in the CS group than in the other groups. Given that early and intensive CS has been shown to promote development of accurate phonological processing, we propose that the higher speechreading results in Cued Speech users are linked to a better capacity in phonological decoding of visual articulators.

Is there an alternative cerebral network associated with enhanced phonological processing in deaf speech-users? An exceptional case.

Most people born deaf and exposed to oral language show scant evidence of sensitivity to the phonology of speech when processing written language. In this respect they differ from hearing people. However, occasionally, a prelingually deaf person can achieve good processing of written language in terms of phonological sensitivity and awareness, and in this respect appears exceptional. We report the pattern of event-related fMRI activation in such a deaf reader while performing a rhyme-judgment on written words with similar spelling endings that do not provide rhyme clues. The left inferior frontal gyrus pars opercularis and the left inferior parietal lobe showed greater activation for this task than for a letter-string identity matching task. This participant was special in this regard, showing significantly greater activation in these regions than a group of hearing participants with a similar level of phonological and reading skill. In addition, SR showed activation in the left mid-fusiform gyrus; a region which did not show task-specific activation in the other respondents. The pattern of activation in this exceptional deaf reader was also unique compared with three deaf readers who showed limited phonological processing. We discuss the possibility that this pattern of activation may be critical in relation to phonological decoding of the written word in good deaf readers whose phonological reading skills are indistinguishable from those of hearing readers.

Phonological processing in relation to reading: an fMRI study in deaf readers.

Without special education, early deprivation of auditory speech input, hinders the development of phonological representations and may alter the neural mechanisms of reading. By using fMRI during lexical and rhyming decision tasks, we compared in hearing and pre-lingually deaf subjects the neural activity in functional regions of interest (ROIs) engaged in reading. The results show in deaf readers significantly higher activation in the ROIs relevant to the grapho-phonological route, but also in the posterior medial frontal cortex (pMFC) and the right inferior frontal gyrus (IFG). These adjustments may be interpreted within the dual route model of reading as an alternative strategy, which gives priority to rule-based letter-to-sound conversion. Activation in the right IFG would account for compensation mechanisms based on phonological recoding and inner speech while activation in the posterior medial frontal cortex (pMFC) may relate to the cognitive effort called for by the alternative strategy. Our data suggest that the neural mechanisms of reading are shaped by the auditory experience of speech.