Characterization and drug solubilization of arginine-based ionic liquids - Impact of counterions and stoichiometry.

Ionic liquids (ILs) exhibit very diverse physicochemical properties, such as non-volatility, stability, and miscibility, which render them excellent candidate excipients for multi-purpose use. Six novel arginine (Arg)-based ILs were obtained using a one-step ultrasound method. Salt formation was confirmed by Fourier-transform infrared (FTIR), Raman, and nuclear magnetic resonance (NMR) spectroscopies. Moreover, the effects of anions and molar ratio on the molecular states and thermal properties of Arg-ILs were investigated. In addition, the solubilization of drugs with different pKa and LogP values was attempted using Arg-ILs consisting of asparagine, proline, octanoic acid, and malic acid, respectively, and a comparative study was performed. Furthermore, the interaction mode between the drugs and ILs was determined by FTIR and Raman spectroscopy. Presumably, partial interaction between the component of ILs and drugs such as ofloxacin and valsartan occurred, whereas flurbiprofen and isosorbide mononitrate were dispersed in the viscous IL. The development of strategies for the application of ILs as solubilizers or carriers of active pharmaceutical ingredients is an extremely promising and wide avenue of research.

Cognitive and neural mechanisms of voluntary versus forced language switching in Chinese-English bilinguals: an fMRI study.

The ecological validity of bilingual code-switching has garnered increasing attention in recent years. Contrary to traditional studies that have focused on forced language switching, emerging theories posit that voluntary switching may not incur such a cost. To test these claims and understand differences between forced and voluntary switching, the present study conducted a systematic comparison through both behavioral and neural perspectives. Utilizing fMRI alongside picture-naming tasks, our findings diverge from prior work. Voluntary language switching not only demonstrated switching costs at the behavioral level but also significantly activated brain regions associated with inhibitory control. Direct comparisons of voluntary and forced language switching revealed no significant behavioral differences in switching costs, and both shared several common brain regions that were activated. On the other hand, a nuanced difference between the two types of language switching was revealed by whole-brain analysis: voluntary switching engaged fewer language control regions than forced switching. These findings offer a comprehensive view of the neural and behavioral dynamics involved in bilingual language switching, challenging prior claims that voluntary switching imposes no behavioral or neural costs, and thus providing behavioral and neuroimaging evidence for the involvement of inhibitory control in voluntary language switching.

[Ultrasonic Composite Iron-carbon Activated Persulfate for Treating Organic Wastewater].

A coupling system of ultrasonic composite iron-carbon activated persulfate (US/PS/Fe-C) was built to treat a triphenylmethane derivative, crystal violet (CV). The results revealed that US/PS/Fe-C ternary system had a good coupling effect. The structure and surface morphology of commercial Fe-C and self-made Fe-C catalysts were analyzed using an X-ray diffractometer (XRD) and scanning electron microscope (SEM), respectively. Finally, commercial Fe-C was used to study the effects of different factors on the CV of US/PS/Fe-C ternary coupling degradation, and the optimum conditions were as follows:PDS concentration 2 mmol·L-1, iron-carbon catalyst 1 g·L-1, pH without adjustment, and the removal rate of 15 mg·L-1 CV reached 90% after 30 min. To explore the effects of anions and cations on the system, it was observed that Mg2+ and NO3- had almost no effect on the treatment of the system, and Mn2+, Cl-, and CO32- had a certain effect on the treatment of the system, whereas Fe2+ could promote the reaction at low concentration and inhibit the reaction at high concentration. By adding different quenchants, it was concluded that there were four types of active substances:1O2, SO4-·,·O2-, and·OH.

Physicochemical Properties and Transdermal Absorption of a Flurbiprofen and Lidocaine Complex in the Non-Crystalline Form.

Amorphous drug formulations exploiting drug-drug interactions have been extensively studied. This study aims to develop a transdermal system containing an amorphous complex of the nonsteroidal anti-inflammatory drug (NSAID) flurbiprofen (FLU) and lidocaine (LDC) for alleviating chronic pain. The high-viscosity complex between FLU and LDC (Complex) was obtained by heating in ethanol. For the complex, attenuated total reflection-Fourier transform infrared spectroscopy showed a shift in the carboxy-group-derived peak of FLU, and differential scanning calorimetry indicated the endothermic peaks associated with the melting of FLU and LDC disappeared. 13C dipolar decoupling and 15N cross-polarization magic-angle spinning nuclear magnetic resonance measurement suggested the interaction between the carboxyl group of FLU and the secondary amine of LDC. The interaction between the aromatic rings of FLU and LDC contributed to the molecular complex formation. The solubility of FLU from the complex was about 100 times greater than FLU alone. The skin permeation flux of FLU from the complex through the hairless mouse skin was 3.8 times higher than FLU alone in hypromellose gel. Thus, adding LDC to the formulation can be an effective method for enhancing the skin permeation of NSAIDs, which can prove useful for treating chronic pain and inflammatory diseases.

Promoting Activity of Terpenes on Skin Permeation of Famotidine.

Famotidine (FMT) is a competitive histamine-2 (H2) receptor antagonist that inhibits gastric acid secretion for the treatment of Gastroesophageal reflux disease. To study the promoting effect and mechanism of terpenes, including l-menthol, borneol, and geraniol, as chemical enhancers, FMT was used as a model drug. Attenuated total reflectance-Fourier transform IR spectroscopy (ATR-FTIR) and differential scanning calorimetry (DSC) were used to explore the effects of terpenes on the skin. Hairless mouse skin was mounted on Franz-type diffusion cell, and skin permeation experiment of FMT hydrogel was carried out. The results suggested that the thermodynamic activity influenced the permeability of the drug, and the main mechanism of terpenes to enhance skin permeation of the drug was based on increasing the fluidity of the intercellular lipids. Moreover, it was revealed that l-menthol simultaneously relaxed the packing structure and lamellar structure, whereas geraniol had a great influence on the lamellar structure only. Collectively, all terpenes had a promoting effect on skin permeation of FMT, indicating their potential as chemical enhancers to change the microstructure of stratum corneum and improve the permeation of FMT through the skin, and it has great potential to be used in transdermal formulations of FMT.

Iron species activating chlorite: Neglected selective oxidation for water treatment.

Chlorite (ClO2 -) is the by-product of the water treatment process carried out using chlorine dioxide (ClO2) as an effective disinfectant and oxidant; however, the reactivation of ClO2 - has commonly been overlooked. Herein, it was unprecedentedly found that ClO2 - could be activated by iron species (Feb: Fe0, FeII, or FeIII), which contributed to the synchronous removal of ClO2 - and selective oxidative treatment of organic contaminants. However, the above-mentioned activation process presented intensive H+-dependent reactivity. The introduction of Feb significantly shortened the autocatalysis process via the accumulation of Cl- or ClO- during the protonation of ClO2 - driven by ultrasonic field. Furthermore, it was found that the interdependent high-valent-Fe-oxo and ClO2, after identification, were the dominant active species for accelerating the oxidation process. Accordingly, the unified mechanisms based on coordination catalysis ([Fe N (H2O) a (ClO x m-) b ] n +-P) were putative, and this process was thus used to account for the pollutant removal by the Feb-activated protonated ClO2 -. This study pioneers the activation of ClO2 - for water treatment and provides a novel strategy for "waste treating waste". Derivatively, this activation process further provides the preparation methods for sulfones and ClO2, including the oriented oxidation of sulfoxides to sulfones and the production of ClO2 for on-site use.

How infants' utterances grow: A probabilistic account of early language development.

Why are children's first utterances short and ungrammatical, with some obvious constructions missing? What determines the lengthening of children's early utterances over time? The literature is replete with references to a one-word, a two-word, and a later multiword stage in language development, but with little empirical evidence, and with little account for how and why utterances grow. To address these questions, we analyze speech samples from 25 children between the ages of 14 and 43 months; we construct distributions of their utterances of lengths one to five by age. Our novel findings are that multiword utterances of different lengths appear early in acquisition and increase together until they reach relatively stable proportions similar to those found in parents' input. To explain such patterns, we develop a probabilistic computational model, VIRTUAL, that posits an interaction between a) varying, increasing resources from various developmental domains and b) target utterance lengths mirroring the input. VIRTUAL successfully accounts for most of the empirical patterns, suggesting a probabilistic and dynamic process that is nonetheless compatible with apparent distinct milestones in development. We provide a new, systematic way of showing how developmental cascade theories could work in language development. Our findings and model also suggest insights into syntactic, semantic, and cognitive development.

A tuff interlayer in deep potash-bearing salt rocks and its implication for potash mineralization in the Simao Basin, southwestern China.

The lithology and genesis of a dark grey clastic interlayer first encountered within the deepest potassium-rich salt body in the Simao Basin, southwestern China, were analysed. Analyses of the petrography, mineralogy, and element geochemistry of the layer revealed that (1) the layer contains quartz crystals with gulf corrosion edges and explosion cracks and angular volcanic ash-sized glasses; (2) the main mineral components of the crystal fragments are chlorite, illite, biotite, quartz, anhydrite, gypsum, magnesite, pyrite, molybdenite, clinopyroxene, and zircon; (3) the rare earth element patterns, Zr/TiO2 and Nb/Y diagrams as well as boron content all indicate a volcanic origin for the layer. Based on these observations, the layer is suggested to be an altered tuff associated with various volcanic fragments dominated by chlorite and formed after alteration of a parent tuff in an alkaline, salty, and low-temperature water body. Discovery of the layer indicates that the potash-bearing salt rocks could have taken in volcanic materials during these volcanic activities and provides the possibility of reliable zircon U‒Pb dating to determine the absolute age of the host rock, which is fundamental in studying the genetic mechanism of this deeply buried salt body.

Genetic Model of Mud-Clast Conglomerates in Salt Rocks and Their Significance for Salt Mineralization in Mohei Area, Simao Basin, China: A Case Study of Well L-2.

The Simao Basin is one of the most important Mesozoic salt basins in China, and the salt rocks generally contain mud-clast conglomerates. The characteristics of mud-clast conglomerates can provide effective information indicating the evolution process of the salt deposits. A combined analysis of trace elements and clay minerals was performed to characterize the genetic model of mud-clast conglomerates in the salt rocks. The results show that the sedimentary materials are felsic rocks from the Upper Crust. Ternary plot diagrams show that the tectonic settings are between the continental margin and the continental island arc. The clay minerals in the samples mainly contain illite and illite-smectite mixed layers. A dry and hot climate prevailed during the deposition of the Mengyejing Formation, and the warm-humid climate that also occurred is interspersed in some periods. Evaporation makes the water bodies shallower, and the concentrated brine starts to precipitate salt under the arid and hot climate conditions. Redox proxies indicate that most of the samples were deposited in relatively oxic conditions. The Sr/Ba ratios (average of 0.5) and paleosalinity (average of ∼35‰) during the depositional period indicate an increase in terrigenous freshwater input and carry of clasts into the evaporation basin. Furthermore, the freshwater supply enhances the hydrodynamics; as a result, the detritus that deposited in the early stage is broken into mud-clast conglomerates and co-deposited with the salt rocks. The results provide a geochemical basis for further study of mud-clast conglomerates in the Simao Basin and supply recommendations for the origin of salt deposits in similar basins around the world.

Magnetically separable Fe-base deposited on different carbon sources for ultrasound/persulfate-like heterogeneous activation: Optimized synthesis and field driving process.

The eco-friendly composite materials, micro-nano Fe-base/glucose-derived hydro-chars (Feb/HCs), were prepared, whose magnetic separation can be achieved in both preparation and water treatment stages. The performances of Feb/HCs after N2 heat-treatment to activate persulfate, chlorite, hydrogen peroxide, etc., in ultrasound field, obtained great improvement by extracting "O". For comparison, other different sized and magnetic iron-carbon based composites based on different carbon sources of activated carbons, cornstalk-derived bio-chars, and glucose-derived pyrolytic carbons were prepared and applied to systematically compare the performance of activation. The Feb/HCs with optimizing preparation were utilized as activators to well treat different structures (triphenylmethane-, azo-, and xanthene-) contaminants. The detected p-Benzoquinone and 2-chloro-p-Benzoquinone could be considered as transitional and characteristic intermediates from carbocyclic compounds to chain compounds. The degradation mechanisms were evoked by pH and absorption to trigger via free/non-free radicals processes: high valence iron-oxo species, sulfate radicals, hydroxyl radicals, Cl-based substances, etc. The findings contrastively provided the potential applications of magnetically separable iron-carbon based composites for heterogeneous activation in environmental remediation.

A novel co-catalyzed system between persulfate and chlorite by sonolysis for removing triphenylmethane derivative.

Triphenylmethane (tpm) derivatives (e.g. tpmCV) have threatened the safety of the aquatic environment due to the potential toxicity and carcinogenicity. In this study, the novel ultrasonic/persulfate/chlorite (US/S2O82-/ClO2-) oxidation process was developed for the effective removal of tpmCV in wastewater. The apparent non-integer kinetics (n around 1.20) of tpmCV degradation under different factors (R2Adj > 0.990) were investigated, respectively. Inhibiting effects of anions were greater than those of cations (except Fe(II/III)). The adding of micromolecule organic acids could regulate degradation towards positive direction. The double response surface methodology (RSM) was designed to optimize tpmCV removal process, and the acoustic-piezoelectric interaction was simulated to determine the propagation process of acoustic wave in the reactor. The possible degradation pathway was explored to mainly include carbonylation, carboxylation, and demethylation. The estimated effective-mean temperature at the bubble-water interface was calculated from 721 to 566 K after introducing the ClO2-, however, the adsorption or partitioning capacity of tpmCV in the reactive zone was widened from 0.0218 to 0.0982. The proposed co-catalysis of US/S2O82-/ClO2- was based on the determined active species mainly including ClO2, SO4⋅-, and ⋅OH. Compared with other US-based processes, the operating cost (3.97 $/m3) of US/S2O82-/ClO2- with the EE/O value (16.8 kWh/m3) was relatively reduced.

Ultrasonic role to activate persulfate/chlorite with foamed zero-valent-iron: Sonochemical applications and induced mechanisms.

The novel system, consisting of composite oxidants (persulfate/chlorite, S2O82-/ClO2-) and stationary phase activator (zero-valent-iron foam, Fe0f) driven by ultrasonic (US) field, was applied to treat the triphenylmethane derivative effectively even at low temperature (≈ 289 K). By comparisons of sub-systems, the US roles to S2O82-, ClO2-, and Fe0f were seriatim analyzed. US made the reaction order of multi-component system tend to within 1 (leading to de-order reaction), and widened pH activating range of the Fe0f by sonicate-polishing during the process of ClO2- co-activating S2O82-. US and Fe0f were affected by fluid eddy on activating S2O82-/ClO2-. The Fe0f had slight effect on the temperature of US bubble-water interface but the addition of ClO2- lowered it. The partitioning capacity of the above US reactive zone increased during the reaction. US and ClO2- could enrich the kinds of degradation intermediates. The contributions of free radicals (ClOx-based radicals, sulfate radicals (SO4-), and hydroxyl radicals (OH)) and non-free radicals (ClO2, and O = FeIV/V from ionic Fe under "-O-O-" of S2O82- and cyclic adjustment reaction of ClO2-) processes by sonochemical induction were equally important by corresponding detection means. Especially, real-time and online high-resolution mass spectrum by self-developing further confirmed the chain transfers of different free radicals due to US role. The findings expanded the application of sono-persulfate-based systems and improved understanding on activation mechanism.

Modeling Bilingual Lexical Processing Through Code-Switching Speech: A Network Science Approach.

The study of code-switching (CS) speech has produced a wealth of knowledge in the understanding of bilingual language processing and representation. Here, we approach this issue by using a novel network science approach to map bilingual spontaneous CS speech. In Study 1, we constructed semantic networks on CS speech corpora and conducted community detections to depict the semantic organizations of the bilingual lexicon. The results suggest that the semantic organizations of the two lexicons in CS speech are largely distinct, with a small portion of overlap such that the semantic network community dominated by each language still contains words from the other language. In Study 2, we explored the effect of clustering coefficients on language choice during CS speech, by comparing clustering coefficients of words that were code-switched with their translation equivalents (TEs) in the other language. The results indicate that words where the language is switched have lower clustering coefficients than their TEs in the other language. Taken together, we show that network science is a valuable tool for understanding the overall map of bilingual lexicons as well as the detailed interconnections and organizations between the two languages.

Synergistic photocatalytic activity of a combination of carbon nanotubes-graphene-nickel foam nanocomposites enhanced by dielectric barrier discharge plasma technology for water purification.

Degradation activity of plasma catalysis between dielectric barrier discharge (DBD) and carbon nanotubes-graphene-nickel foam (CNTs-G-Nif) has been studied in treatment of dye wastewater. CNTs-G-Nif was prepared through a two-step chemical vapor deposition (CVD) approach. The composite has been characterized by different techniques such as X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman spectroscopy. SEM results showed that the Nif as the growth substrate was evenly wrapped by G and then CNTs were successfully grown on G as the support. The growth mechanism of composite was proposed. The possible coupled catalytic mechanism between DBD and CNTs-G-Nif were addressed. In addition, the modification on G-Nif was found by SEM during the discharge process in liquid phase. And the modification mechanism of DBD plasma (DBDP) acting on composites was discussed. Finally, by means of analyses of ultraviolet-visible (UV-Vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS), the general degradation pathway and stepwise degradation pathways of alizarin green (AG) were proposed in detail.

Aquaculture drug degradation in persulfate by PANI-based microparticles controlled via ultrasonic field: Forced motion of "burning hot micromotors".

The triphenylmethane derivative malachite green (tpmMaG) despite repeated prohibitions but is frequently detected in aquatic environment and draws emerging attention because of the potential poisonous effects. The polyaniline/persulfate with ultrasound catalysis (US/PANI-PS) was developed for tpmMaG removal. The effects of 12 factors and the optimization by response surface methodology (RSM) for tpmFG removal were evaluated based on the pseudo-first-kinetics (kobs). From free radical inhibition, the ratios of active species in US/PANI-PS (δ11 = 0.355, δ12 = 0.593) were close to that in US-PS (δ21 = 0.346, δ22 = 0.586) and different to that in PANI-PS and PS systems. A possible degradation pathway (hydroxylation, N-demethylation, deamination, and open-benzene ring) was explored by gas chromatography-mass spectrometer (GC/MS) and high performance liquid chromatography-mass spectrometer (HPLC-MS). The designed reactor involving the US-driven PANI was simulated by acoustic-piezoelectric interaction. From cavitation calculations, the estimated effective-mean temperature at bubble-water interface had little increasing (from 704 K to 711 K) after adding the PANI, however, the adsorption capacity of tpmMaG in reactive zone decreased from 0.0891 µM to 0.0787 µM. The mechanism (PANI hot turbo-micromotors) with US/PANI-PS was proposed. The tpmMaG was removed with a low treatment cost of 2.81 $⋅m-3 (the EE/O value 18.29 kWh⋅m-3) by US/PANI-PS, presenting a cost-effective treating process. The reusability tests and characterizations (contact angle, X-ray diffraction (XRD), and scanning electron microscope (SEM)) further confirmed the stability of PANI.

Corrigendum: Modeling Bilingual Lexical Processing Through Code-Switching Speech: A Network Science Approach.

[This corrects the article DOI: 10.3389/fpsyg.2021.662409.].

Integrated remediation for organic-contaminated site by forcing running-water to modify alkali-heat/persulfate via oxidation process transfer.

As organic pollution of soil and groundwater increases, the effective and economical remediation of contaminated sites has drawn growing attention. In this study, running-water (RW) was designed to modify alkali-heat/persulfate (MAH/PS) for integrated remediation of an actual organic-contaminated site. The degradation efficiency mainly reached 60%-99% for Benz[a]anthracene, Benzo[a]pyrene and total petroleum hydrocarbons (TPHs). MAH/PS was more effective in degrading Benzene and 1,2-Dichloroethane with simple molecular configurations. The pollutant degradation efficiencies decreased with increasing site depth and increased with increasing pollutant concentrations. Migration with RW enhanced site remediation. By monitoring the groundwater after remediation, it was found that residual TPHs presented anomalous diffusion; SO42- ranged from 8.00 to 237.00 mg L-1 to 8.00-290.00 mg L-1 and pH presented alkalescence (7.00-8.20). Mathematical models were established to describe the reaction process including the solubility equilibrium of calcium hydroxide, temperature equilibrium, and reaction kinetics. Moreover, MAH/PS provided a cost-saving approach for site remediation.

Mechanism and dynamic study of reactive red X-3B dye degradation by ultrasonic-assisted ozone oxidation process.

The effectiveness of ozone combined with ultrasound techniques in degrading reactive red X-3B is evaluated. A comparison among ozone (O3), ultrasonic (US), ozone/ultrasonic (O3/US) for degradation of reactive red X-3B has been performed. Results show that O3/US system was the most effective and the optimally synergetic factor reaches to 1.42 in O3/US system. The cavitation of ultrasound plays an important role during the degradation process. It is found that 99.2% of dye is degraded within 6min of reaction at the initial concentration of 100mg·L-1, pH of 6.52, ozone flux of 40L·h-1 and ultrasonic intensity of 200W·L-1. Ozonation reactions in conjunction with sonolysis indicate that the decomposition followed pseudo-first-order reaction kinetics but the degradation efficiencies are affected by operating conditions, particularly initial pH and ultrasonic intensity. A kinetic model is established based on the reaction corresponding to operational parameters. In addition, the main reaction intermediates, such as p-benzoquinone, catechol, hydroquinone, phthalic anhydride and phthalic acid, are separated and identified using GC/MS and a possible degradation pathway is proposed during the O3/US process.

Degradation of Reactive Yellow X-RG by O3/Fenton system: response surface approach, reaction mechanism, and degradation pathway.

O3/Fenton for the treatment of effluent containing Reactive Yellow X-RG is investigated. The response surface methodology is applied to study the main and interactive effects of the parameters. With the initial dye concentration being controlled at 300 mg L-1, the optimized conditions for wastewater treatment are 3.68, 29.19 and 18.49 mg min-1 for initial pH, mole ratio of [H2O2]/[Fe2+] and ozone dosage, respectively. The regression quadratic model well describing the degradation efficiency of O3/Fenton process is developed and validated by the analysis of variances, respectively. In addition, a possible pathway for Reactive Yellow X-RG degradation is proposed by detecting the temporal evolution of intermediates in the solution, with the use of some techniques including ultraviolet spectrophotometric method (UV-Vis), Fourier transform infrared spectroscopy (FT-IR) and gas chromatography-mass spectrometry (GC/MS). Meanwhile, every reaction step is given to explain the degradation mechanisms.

Facile and Mild Strategy to Construct Mesoporous CeO2-CuO Nanorods with Enhanced Catalytic Activity toward CO Oxidation.

CeO2-CuO nanorods with mesoporous structure were synthesized by a facile and mild strategy, which involves an interfacial reaction between Ce2(SO4)3 precursor and NaOH ethanol solution at room temperature to obtain mesoporous CeO2 nanorods, followed by a solvothermal treatment of as-prepared CeO2 and Cu(CH3COO)2. Upon solvothermal treatment, CuO species is highly dispersed onto the CeO2 nanorod surface to form CeO2-CuO composites, which still maintain the mesoporous feature. A preliminary CO catalytic oxidation study demonstrated that the CeO2-CuO samples exhibited strikingly high catalytic activity, and a high CO conversion rate was observed without obvious loss in activity even after thermal treatment at a high temperature of 500 °C. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H2-TPR) analysis revealed that there is a strong interaction between CeO2 and CuO. Moreover, it was found that the introduction of CuO species into CeO2 generates oxygen vacancies, which is highly likely to be responsible for high catalytic activity toward CO oxidation of the mesoporous CeO2-CuO nanorods.