Molecularly informed field theory for estimating critical micelle concentrations of intrinsically disordered protein surfactants.

The critical micelle concentration (CMC) is a crucial parameter in understanding the self-assembly behavior of surfactants. In this study, we combine simulation and experiment to demonstrate the predictive capability of molecularly informed field theories in estimating the CMC of biologically based protein surfactants. Our simulation approach combines the relative entropy coarse-graining of small-scale atomistic simulations with large-scale field-theoretic simulations, allowing us to efficiently compute the free energy of micelle formation necessary for the CMC calculation while preserving chemistry-specific information about the underlying surfactant building blocks. We apply this methodology to a unique intrinsically disordered protein platform capable of a wide variety of tailored sequences that enable tunable micelle self-assembly. The computational predictions of the CMC closely match experimental measurements, demonstrating the potential of molecularly informed field theories as a valuable tool to investigate self-assembly in bio-based macromolecules systematically.

Cortical Thickness in bilingual and monolingual children: Relationships to language use and language skill.

There is a growing body of evidence based on adult neuroimaging that suggests that the brain adapts to bilingual experiences to support language proficiency. The Adolescent Brain Cognitive Development (ABCD) Study is a useful source of data for evaluating this claim during childhood, as it involves data from a large sample of American children. Using the baseline ABCD Study data collected at ages nine and ten, the goal of this study was to identify differences in cortical thickness between bilinguals and monolinguals and to evaluate how variability in English vocabulary and English use within bilinguals might explain these group differences. We identified bilingual participants as children who spoke a non-English language and were exposed to the non-English language at home. We then identified a matched sample of English monolingual participants based on age, sex, pubertal status, parent education, household income, non-verbal IQ, and handedness. Bilinguals had thinner cortex than monolinguals in widespread cortical regions. Within bilinguals, more English use was associated with greater frontal and parietal cortical thickness; greater English vocabulary was associated with greater frontal and temporal cortical thickness. These findings replicate and extend previous research with bilingual children and highlight unexplained cortical thickness differences between bilinguals and monolinguals.

Subcortical and cerebellar volume differences in bilingual and monolingual children: An ABCD study.

Research suggests that bilingual children experience an extension or delay in the closing of the sensitive/critical period of language development due to multiple language exposure. Moreover, bilingual experience may impact the development of subcortical regions, although these conclusions are drawn from research with adults, as there is a scarcity of research during late childhood and early adolescence. The current study included 1215 bilingual and 5894 monolingual children from the ABCD Study to examine the relationship between subcortical volume and English vocabulary in heritage Spanish bilingual and English monolingual children, as well as volumetric differences between the language groups. We also examined the unique effects of language usage in bilingual children's subcortical volumes. In general, bilingual children had less cerebellar volume and greater volume in the putamen, thalamus, and globus pallidus than monolingual children. English vocabulary was positively related to volume in the cerebellum, thalamus, caudate, putamen, nucleus accumbens, and right pallidum in all children. Moreover, the positive relationship between vocabulary and volume in the nucleus accumbens was stronger for monolingual adolescents than bilingual adolescents. The results are somewhat in line with existing literature on the dynamic volume adaptation of subcortical brain regions due to bilingual development and experience. Future research is needed to further explore these regions longitudinally across development to examine structural changes in bilingual brains.

Enhanced photoreduction efficiency of Cr(VI) driven by visible light in a new Zr-based metal-organic framework modified by hydroxyl groups.

While metal-organic framework (MOF) photocatalysts have demonstrated a unique Cr(VI) photoreduction capability in recent decades, their performance is still insufficient for practical applications because of their low Cr(VI) uptake and poor visible light response. To cope with these drawbacks, a new OH-modified Zr-based MOF, termed HCMUE-1, was successfully prepared via a solvothermal method in this work. The complete characterization of HCMUE-1 was performed through various techniques, including powder X-ray diffraction (PXRD), Raman spectroscopy, Fourier transform infrared (FT-IR), thermogravimetric analysis and differential scanning calorimetry (TGA-DSC), scanning electron microscopy combined with energy-dispersive X-ray (SEM-EDX), and X-ray photoelectron spectroscopy (XPS). The obtained data exhibited the excellent Cr(VI) photoreduction efficiency of HCMUE-1, reaching up to 98% after 90 min and almost 100% after 120 min under visible light illumination in a low acidic medium. Noteworthily, HCMUE-1 retained the same Cr(VI) removal rate for at least seven cycles without considerable loss. Further experimental investigations demonstrated that the structural stability and surface morphology of HCMUE-1 were retained after photoreduction. Moreover, the photocatalytic reduction mechanism of Cr(VI) to Cr(III) was interpreted through a series of systematic experimental measurements. These results indicate that HCMUE-1 possesses potential as an efficient photocatalyst for reducing toxic Cr(VI) species from wastewater in real-life conditions.

Cortical Thickness Is Related to Variability in Heritage Bilingual Language Proficiency.

Research suggests that bilingual experience is associated with gray matter changes, such that initial language gains are associated with expansion and language expertise is associated with renormalization. Previous studies on language proficiency development primarily focused on between-subjects, quasiexperimental comparisons of monolinguals and bilinguals. This study proposes a new paradigm to examine language expertise and cortical thickness within heritage bilinguals (n = 215), as well as between bilinguals and monolinguals (n = 145), using data combined from eight previous magnetic resonance imaging studies. In general, results highlight variability within bilinguals, finding relationships between cortical thickness and English proficiency that are relatively consistent within monolinguals, but inconsistent within bilinguals. In all participants, higher levels of proficiency in English-monolinguals' only language and bilinguals' second but stronger language-were negatively related to cortical thickness. In bilinguals, higher proficiency in the weaker, albeit first learned, language was positively related to cortical thickness. Moreover, there was an interaction between language group and English proficiency in predicting cortical thickness, such that the relationship between proficiency and thickness was stronger in monolinguals than in bilinguals. Findings also demonstrate that the regions associated with language expertise differ between bilinguals and monolinguals. Future directions for cognitive-developmental neuroscience research in bilinguals are suggested, particularly the longitudinal examination of cortical changes in relation to bilingual experiences.

Influence of ZIF-9 and ZIF-12 structure on the formation of a series of new Co/N-doped porous carbon composites as anode electrodes for high-performance lithium-ion batteries.

A series of new Co/N-doped porous carbon composites, denoted as Co/CZIF-9 and Co/CZIF-12, containing Co nanoparticles encapsulated in nitrogen-doped carbon matrices were prepared by annealing Co-based zeolite imidazolate framework materials, ZIF-9 and ZIF-12, as the efficient precursors at different temperatures. The structural features of the as-synthesized composites at 900 °C were determined by analytical methods with high reliability. Consequently, Co/CZIF-12_900 exhibits a high first specific discharge capacity of 971.0 mA h g-1 at a current density of 0.1 A g-1. Notably, the specific discharge/charge capacity of Co/CZIF-12_900 reaches about 508.8 mA h g-1 at 0.1 A g-1 after 100 cycles. The outstanding behaviors can be accounted for by the efficient incorporation of hetero-nitrogen doping and the Co nanoparticles within the layered structure of porous carbon, enhancing electrical conductivity and structural stability and limiting volume change during the intercalation/deintercalation of Li+ ions. These findings suggest that the Co/CZIF-12_900 material could be employed as a promising anode electrode for energy storage products.

Factors predicting secondary school language course enrollment and performance among U.S. heritage speakers of Spanish.

Introduction: While a growing body of research indicates that Spanish language courses can promote Spanish maintenance and lead to overall improved educational outcomes among heritage speakers, there is little empirical or longitudinal evidence of factors that shape their enrollment in Spanish language courses at the secondary level. To address this issue, the current study takes a large-scale, longitudinal approach to investigate rates of enrollment in secondary school (6th-12th grade) Spanish and other non-English language courses, as well as factors that predict heritage speakers' enrollment and performance in non-English language courses. Method: We analyzed subsample data from the Miami School Readiness Project (MSRP), a large-scale, longitudinal study consisting of 17,341 heritage speakers of Spanish (47% female, 95.4% Hispanic/Latino, 82.8% received free/reduced-price lunch, and 18.3% with a disability) who were followed from 4 years old until the end of high school. Results: In general, Heritage speakers enrolled in Spanish language courses at a higher rate than other non-English language courses (52.2 and 25.3%, respectively). Enrollment patterns varied across different type of languages and grade level. Student-level factors including disability status, poverty status, early behavioral problems, and prior academic achievement significantly predicted students' enrollment in Spanish and performance in non-English language courses. Discussion: Findings shed light on the long-term patterns of language study of this growing segment of the US school population with implications for future research and school policies that seek to improve heritage language learning and maintenance as well as equitable access to language education for language-minority students.

Engineering of appropriate pore size combined with sulfonic functionalization in a Zr-MOF with reo topology for the ultra-high removal of cationic malachite green dye from an aqueous medium.

A Zr-based metal-organic framework with reo topology, denoted as Reo-MOF-1, was fabricated through a solvothermal method capable of efficiently removing the cationic MG dye from an aqueous medium. The effect of pH solution, adsorbent content, adsorption isotherm, and kinetics on the MG capture was observed to determine the optimal conditions. Accordingly, the maximum adsorption capacity of MG over H+⊂Reo-MOF-1 reaches the value of 2532.1 mg g-1 at neutral pH, which is much greater than the published materials. Moreover, the results of the MG process on H+⊂Reo-MOF-1 fit with the Langmuir isotherm and pseudo second order kinetic model. Hence, MG removal is a chemical adsorption process. Remarkably, H+⊂Reo-MOF-1 can maintain the uptake for MG at about 94% over eight cycles. The MG adsorption mechanism is interpreted via the incorporated analyses and experiments. In detail, Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, powder X-ray diffraction (PXRD), and thermogravimetric analysis (TGA-DSC) of MG⊂Reo-MOF-1 in comparison with H+⊂Reo-MOF-1 indicate that the electrostatic attraction and π-π stacking interaction are found via the interaction between the cationic MG ions and SO3 - moieties within MOF as well as the π electron clouds in the benzene ring of the adsorbent and adsorbate, resulting in significant improvement the MG adsorption uptake. These data prove that acidified Reo-MOF-1 possesses promising application as an effective absorbent of toxic dye in practical conditions.

Enhancing the remarkable adsorption of Pb2+ in a series of sulfonic-functionalized Zr-based MOFs: a combined theoretical and experimental study for elucidating the adsorption mechanism.

A series of Zr-based metal-organic frameworks was prepared via the solvothermal route using sulfonic-rich linkers for the efficient capture of Pb2+ ions from aqueous medium. The factors affecting adsorption such as the solution pH, adsorbent dosage, contact time, adsorption isotherms, and mechanism were studied. Consequently, the maximum adsorption capacity of Pb2+ on the acidified VNU-23 was determined to be 617.3 mg g-1, which is much higher than that of previously reported adsorbents and MOF materials. Furthermore, the adsorption isotherms and kinetics of the Pb2+ ion are in good accordance with the Langmuir and pseudo-second-order kinetic model, suggesting that the uptake of Pb2+ is a chemisorption process. The reusability experiments demonstrated the facile recovery of the H+⊂VNU-23 material through immersion in an HNO3 solution (pH = 3), where its Pb2+ adsorption efficiency still remained at about 90% of the initial uptake over seven cycles. Remarkably, the adsorption mechanism was elucidated through a combined theoretical and experimental investigation. Accordingly, the Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy connected to energy-dispersive X-ray mapping (SEM-EDX-mapping), and X-ray photoelectron spectroscopy (XPS) analysis of the Pb⊂VNU-23 sample and comparison with H+⊂VNU-23 confirmed that the electrostatic interaction occurs via the interaction between the SO3- moieties in the framework and the Pb2+ ion, leading to the formation of a Pb-O bond. In addition, the density functional theory (DFT) calculations showed the effective affinity of the MOF adsorbent toward the Pb2+ ion via the strong driving force mentioned in the experimental studies. Thus, these findings illustrate that H+⊂VNU-23 can be employed as a potential adsorbent to eliminate Pb2+ ions from wastewater.

Early bilingualism predicts enhanced later foreign language learning in secondary school.

Foreign language learning is generally not required in the United States, despite its link to various cognitive and social benefits later in life. Students who speak a home language different from the instructional language of school may experience unique benefits when learning additional languages in school. The present study examined whether students' early language status (monolingual, dual language learner [DLL], or bilingual) in Kindergarten predicts later foreign language course enrollment and performance in middle and high school. A total of 33,247 students (48% female, 59% Latino, 34% Black, 7% White/Asian/other, 82% receiving free/reduced-price lunch) were assessed for school readiness at age 4 and prospectively followed through high school. Regression analyses predicted foreign language course enrollment and performance in middle or high school, with students' demographic, school readiness, and prior academic performance as covariates. Results show early language status significantly predicts later enrollment and performance in foreign language courses, even after controlling for student demographics, school readiness skills, and early academic achievement. Early bilinguals were more likely to take foreign language courses than DLLs, who enrolled in such courses more than monolingual students. The same pattern favoring bilinguals, then DLLs, then monolinguals was found for performance in foreign language courses. Early bilingualism is an important resource for young children that continues to offer benefits throughout schooling. Implications for heritage language maintenance, language learning, and bilingual education are discussed. (PsycInfo Database Record (c) 2021 APA, all rights reserved).

A confinement of N-heterocyclic molecules in a metal-organic framework for enhancing significant proton conductivity.

A series of N-heterocyclic⊂VNU-23 materials have been prepared via the impregnation procedure of N-heterocyclic molecules into VNU-23. Their structural characterizations, PXRD, FT-IR, Raman, TGA, 1H-NMR, SEM-EDX, and EA, confirmed that N-heterocyclic molecules presented within the pores of parent VNU-23, leading to a remarkable enhancement in proton conductivity. Accordingly, the composite with the highest loading of imidazole, Im13.5⊂VNU-23, displays a maximum proton conductivity value of 1.58 × 10-2 S cm-1 (85% RH and 70 °C), which is ∼4476-fold higher than H+⊂VNU-23 under the same conditions. Remarkably, the proton conductivity of Im13.5⊂VNU-23 exceeds the values at 85% RH for several of the reported high-performing MOF materials. Furthermore, Im13.5⊂VNU-23 can retain a stable proton conductivity for more than 96 h, as evidenced by FT-IR and PXRD analyses. These results prove that this hybrid material possesses potential applications as a commercial proton exchange membrane fuel cell.

A new approach for ultra-high adsorption of cationic methylene blue in a Zr-sulfonic-based metal-organic framework.

A series of Zr-sulfonic-based metal-organic frameworks have been synthesized by the solvothermal method, namely VNU-17 and VNU-23. Particularly, VNU-17 and VNU-23 adopt the sulfonate group (SO3 -) moieties densely packed within their structure, which can efficiently uptake MB+ from wastewater. The maximum adsorption capacity for MB+ onto VNU-23 is up to 1992 mg g-1 at pH = 7, which is more than five times that of activated carbon and possesses the highest value among all the reported MOF materials. In addition, VNU-23 retains the adsorption uptake of MB for at least five cycles. The adsorption isotherms and kinetic studies reveal that MB+ dye adsorption onto VNU-23 fits a Langmuir isotherm and the pseudo second order kinetic model. Furthermore, the ultra-high adsorption capacity of VNU-23 for MB dye can be accounted for by the suitable pore/channel size together with electrostatic attraction and π-π interactions. These results indicate that VNU-23 can be utilized as a promising candidate for removing MB+ from an aqueous medium.

A new iron-based metal-organic framework with enhancing catalysis activity for benzene hydroxylation.

A new Fe-based metal-organic framework (MOF), termed Fe-TBAPy Fe2(OH)2(TBAPy)·4.4H2O, was solvothermally synthesized. Structural analysis revealed that Fe-TBAPy is built from [Fe(OH)(CO2)2]∞ rod-shaped SBUs (SBUs = secondary building units) and 1,3,6,8-tetrakis(p-benzoate)pyrene (TBAPy4-) linker to form the frz topological structure highlighted by 7 Å channels and 3.4 Å narrow pores sandwiching between the pyrene cores of TBAPy4-. Consequently, Fe-TBAPy was used as a recyclable heterogeneous catalyst for benzene hydroxylation. Remarkably, the catalysis reaction resulted in high phenol yield and selectivity of 64.5% and 92.9%, respectively, which are higher than that of the other Fe-based MOFs and comparable with those of the best-performing heterogeneous catalysts for benzene hydroxylation. This finding demonstrated the potential for the design of MOFs with enhancing catalysis activity for benzene hydroxylation.

Combining Linker Design and Linker-Exchange Strategies for the Synthesis of a Stable Large-Pore Zr-Based Metal-Organic Framework.

A Zr(IV)-based metal-organic framework (MOF), termed reo-MOF-1 [Zr6O8(H2O)8(SNDC)4], composed of 4-sulfonaphthalene-2,6-dicarboxylate (HSNDC2-) linkers and Zr6O8(H2O)8(CO2)8 clusters was synthesized by solvothermal synthesis. Structural analysis revealed that reo-MOF-1 adopts the reo topology highlighted with large cuboctahedral cages (23 Å). This structure is similar to that found in DUT-52 (fcu topology), however, reo-MOF-1 lacks the body-centered packing of the 12-connected Zr6O4(OH)4(CO2)12 clusters, which is attributed to the subtle, but crucial influence in the bulkiness of functional groups on the linkers. The control experiments, where the ratio of H3SNDC/naphthalene-2,6-dicarboxylate linkers was varied, also support our finding that the bulky functionalities play a key role for defect-controlled synthesis. The reo-MOF-1A framework was obtained by linker exchange to yield a chemically and thermally stable material despite its large pores. Remarkably, reo-MOF-1A exhibits permanent porosity (Brunauer-Emmett-Teller and Langmuir surface areas of 2104 and 2203 m2 g-1, respectively). Owing to these remarkable structural features, reo-MOF-1A significantly enhances the yield in Brønsted acid-catalyzed reactions.