A Novel Fluorescence Sensor for Iodide Detection Based on the 1,3-Diaryl Pyrazole Unit with AIE and Mechanochromic Fluorescence Behavior.

A D-A type of luminophore, TPA-CDP, was designed and synthesized by using triphenylamine (TPA) as D (electron donor), 1,3-diaryl pyrazole with cyano groups (CDP) as A (electron acceptor) and employing a cyanovinyl segment as a recognition group. Firstly, TPA-CDP demonstrates effective fluorescence quenching as a sensor for I- by the nucleophilic addition reaction of the cyanovinyl segment with a high level of sensitivity, selectivity and a low determination limit of 4.43 µM. Interestingly, TPA-CDP exhibited an AIE phenomenon with the fw value reaching 50%. In addition, TPA-CDP displayed distinct mechanochromic fluorescence behavior with 70 nm red shift, which was observed over four repeated cycles. Furthermore, the mechanochromic fluorescence behavior of TPA-CDP, as observed in powder XRD experiments, was found to be associated with the morphological transition from a crystalline state to an amorphous state. These results confirm the significant potential of CDP as a powerful electron-deficient component in the creation of D-A-type mechanochromic fluorescence materials and biosensors for detecting I-.

Mapping the evolution of regional brain network efficiency and its association with cognitive abilities during the first twenty-eight months of life.

Human brain undergoes rapid growth during the first few years of life. While previous research has employed graph theory to study early brain development, it has mostly focused on the topological attributes of the whole brain. However, examining regional graph-theory features may provide unique insights into the development of cognitive abilities. Utilizing a large and longitudinal rsfMRI dataset from the UNC/UMN Baby Connectome Project, we investigated the developmental trajectories of regional efficiency and evaluated the relationships between these changes and cognitive abilities using Mullen Scales of Early Learning during the first twenty-eight months of life. Our results revealed a complex and spatiotemporally heterogeneous development pattern of regional global and local efficiency during this age period. Furthermore, we found that the trajectories of the regional global efficiency at the left temporal occipital fusiform and bilateral occipital fusiform gyri were positively associated with cognitive abilities, including visual reception, expressive language, receptive language, and early learning composite scores (P < 0.05, FDR corrected). However, these associations were weakened with age. These findings offered new insights into the regional developmental features of brain topologies and their associations with cognition and provided evidence of ongoing optimization of brain networks at both whole-brain and regional levels.

Versatile crosslinking synthesis of an EDTA-modified UiO-66-NH2/cotton fabric composite for simultaneous capture of heavy metals and dyes and efficient degradation of organophosphate.

The metal-organic frameworks/cotton fabric composites (MOFs/CFCs) have emerged as a new type of prospective materials for environmental cleanup, due to their convenient recyclability and high removal efficiency towards hazardous pollutants. However, their practical applications are limited by complicated synthetic conditions, insufficient interface bonding and poor adsorption capacity. Herein, for the first time, a robust ethylenediaminetetraacetic acid (EDTA)-functionalized MOFs/CFC is prepared based on UiO-66-NH2 crystals by using EDTA dianhydride as the cross-linking agent, and applied for simultaneous removal of heavy metals and dyes, as well as degradation of chemical warfare agents. The as-prepared EDTA-UiO-66-NH2/CFC shows extraordinary monocomponent adsorption performance with maximum adsorption capacity of 158.7, 126.2, 131.5, 117.4 and 104.5 mg/g for Cd(II), Cu(II), methylene blue, crystal violet and safranin O, respectively. Interestingly, in metal-dyes binary system, the uptake of Cu(II) by EDTA-UiO-66-NH2/CFC increases significantly when co-existing high concentration of dyes. The results indicate that the synergistic and simultaneous removal of both dyes and metal from complex systems can be realized by EDTA-UiO-66-NH2/CFC via multiple mechanisms. The EDTA-UiO-66-NH2/CFC also exhibits an outstanding catalytic performance for degrading dimethyl 4-nitrophenylphosphate. Besides, it can be reused for several times without obvious decrease of its adsorption and catalysis efficiencies. More impressively, the cross-linking reaction approach can not only anchor UiO-66-NH2 crystals firmly onto cotton fabric, but also facilitate in-situ formation of abundant adsorption sties on the adsorbent surface. Therefore, this work offers a simple and versatile synthetic strategy to develop high-performance environmental material for multiple pollutants remediation.

Super-amphiphilic graphene promotes peroxymonosulfate-based emulsion catalysis for efficient oil purification.

Oil fractions containing highly toxic and hazardous organic contaminants can not only cause severe environmental disasters, but also an undesired waste of resources. Given the exceptional performance of persulfates in the removal of persistent and refractory organic pollutants from aqueous media, herein, a peroxymonosulfate-based Pickering emulsion catalytic (PPEC) system was constructed for the hazardous oil purification, using super-amphiphilic graphene as a solid emulsifier and a heterogeneous catalyst simultaneously. Combined detailed instrumental analysis with theoretical calculations, we find that the incorporation of pyridinic N and its oxide significantly facilitated the formation of super-amphiphilic graphene and successfully induced the formation of Pickering emulsion. In addition to stabilizing the PPEC system, super-amphiphilic graphene can also achieve efficient removal of Sudan III (simulated lipophilic organic pollutant) by activating peroxymonosulfate (PMS) to generate •O2- and 1O2. Results showed that 80 mg/L Sudan III (20 mL) could be fully degraded within 30 min using 10 mL 5 mmol PMS. More significantly, our proposed PPEC system also exhibited excellent property in the purification of practical waste engine oil. This study provides new insights into the purification and recovery of waste oil.

Polyaminophosphoric Acid-Modified Ion-Imprinted Chitosan Aerogel with Enhanced Antimicrobial Activity for Selective La(III) Recovery and Oil/Water Separation.

In this study, polyaminophosphoric acid (PA)-functionalized ion-imprinted chitosan (CS) aerogel was fabricated for the first time, exhibiting good antibacterial property for selective La(III) recovery and oil/water separation. The as-prepared PA-CS-IIA-2 shows a remarkable adsorption capacity of 114.6 mg/g toward La(III) and high selectivity in the competitive adsorption systems, which is attributed to its abundant imprinting sites and surface functional groups. Benefiting from the amphiphilic property, the PA-CS-IIA-2 also exhibits an excellent adsorption performance for the extractant, oils, and organic solvents. Besides, the PA-CS-IIA-2 presents excellent regeneration and reusability characteristics. Moreover, compared with CS, the PA-CS-IIA-2 exhibits a significantly improved antibacterial activity originating from the PA component. Most importantly, the PA-CS-IIA-2 aerogel is capable of removing multiple pollutants all together and effectively inhibiting bacteria in the complex wastewater environments. Therefore, this study paves the way for developing high-performance rare-earth capture materials with multiple functions to meet diverse applications.

Associations of lifetime concussion history and repetitive head impact exposure with resting-state functional connectivity in former collegiate American football players: An NCAA 15-year follow-up study.

The objective of this study was to examine associations of lifetime concussion history (CHx) and an advanced metric of lifetime repetitive head impact exposure with resting-state functional connectivity (rsFC) across the whole-brain and among large-scale functional networks (Default Mode; Dorsal Attention; and Frontoparietal Control) in former collegiate football players. Individuals who completed at least one year of varsity collegiate football were eligible to participate in this observational cohort study (n = 48; aged 36-41 years; 79.2% white/Caucasian; 12.5±4.4 years of football played; all men). Individuals were excluded if they reported history/suspicion of psychotic disorder with active symptoms, contraindications to participation in study procedures (e.g., MRI safety concern), or inability to travel. Each participant provided concussion and football playing histories. Self-reported concussion history was analyzed in two different ways based on prior research: dichotomous "High" (≥3 concussions; n = 28) versus "Low" (<3 concussions; n = 20); and four ordinal categories (0-1 concussion [n = 19]; 2-4 concussions [n = 8]; 5-7 concussions [n = 9]; and ≥8 concussions [n = 12]). The Head Impact Exposure Estimate (HIEE) was calculated from football playing history captured via structured interview. Resting-state fMRI and T1-weighted MRI were acquired and preprocessed using established pipelines. Next, rsFC was calculated using the Seitzman et al., (2020) 300-ROI functional atlas. Whole-brain, within-network, and between-network rsFC were calculated using all ROIs and network-specific ROIs, respectively. Effects of CHx and HIEE on rsFC values were examined using separate multivariable linear regression models, with a-priori α set to 0.05. We observed no statistically significant associations between rsFC outcomes and either CHx or HIEE (ps ≥ .12). Neither CHx nor HIEE were associated with neural signatures that have been observed in studies of typical and pathological aging. While CHx and repetitive head impacts have been associated with changes in brain health in older former athletes, our preliminary results suggest that associations with rsFC may not be present in early midlife former football players.

Altered neural flexibility in children with attention-deficit/hyperactivity disorder.

Attention-deficit/hyperactivity disorder (ADHD) is one of the most common neurodevelopmental disorders of childhood, and is often characterized by altered executive functioning. Executive function has been found to be supported by flexibility in dynamic brain reconfiguration. Thus, we applied multilayer community detection to resting-state fMRI data in 180 children with ADHD and 180 typically developing children (TDC) to identify alterations in dynamic brain reconfiguration in children with ADHD. We specifically evaluated MR derived neural flexibility, which is thought to underlie cognitive flexibility, or the ability to selectively switch between mental processes. Significantly decreased neural flexibility was observed in the ADHD group at both the whole brain (raw p = 0.0005) and sub-network levels (p < 0.05, FDR corrected), particularly for the default mode network, attention-related networks, executive function-related networks, and primary networks. Furthermore, the subjects with ADHD who received medication exhibited significantly increased neural flexibility (p = 0.025, FDR corrected) when compared to subjects with ADHD who were medication naïve, and their neural flexibility was not statistically different from the TDC group (p = 0.74, FDR corrected). Finally, regional neural flexibility was capable of differentiating ADHD from TDC (Accuracy: 77% for tenfold cross-validation, 74.46% for independent test) and of predicting ADHD severity using clinical measures of symptom severity (R2: 0.2794 for tenfold cross-validation, 0.156 for independent test). In conclusion, the present study found that neural flexibility is altered in children with ADHD and demonstrated the potential clinical utility of neural flexibility to identify children with ADHD, as well as to monitor treatment responses and disease severity.

Selective capture of Pd(II) from aqueous media by ion-imprinted dendritic mesoporous silica nanoparticles and re-utilization of the spent adsorbent for Suzuki reaction in water.

The development of highly efficient adsorptive material for the selective capture of Pd(II), and re-utilization of spent Pd(II)-loaded adsorbent as an efficient catalyst for organic synthesis are of great significance, but challenging. Particularly, the heterogeneous palladium-catalyzed Suzuki reaction in aqueous media is much more challenging than that of homogeneous. Herein, several novel Pd(II) ion-imprinted polymers (PIIPs) based on dendritic fibrous silica particles are constructed by surface ion imprinting technology (SIIT), using Schiff base and pyridine groups functionalized organosilicon as functional monomer. The PIIP-3 prepared by 3 g of functional monomer exhibits the best adsorption performance, and shows ultrafast (10 min) and selective capture of Pd(II) with high uptake capacity (382.5 mg/g). Moreover, the waste Pd(II) loaded PIIP-3 (PIIP-3-Pd) can serve as a catalyst towards the Suzuki reaction in water, affording 94.2 % yield of the desired product. Interestingly, the PIIP-3-Pd can be reused 12 times without an appreciable decrease in catalytic activity, which is probably due to the imprinted cavity and specific recognition site of PIIP-3 can match and recapture Pd active species in a complex catalytic environment. Thus, this work demonstrates huge potentials of SIIT to enhance the selectivity of adsorption process and increase the lifetime of catalysts.

Neural alterations in opioid-exposed infants revealed by edge-centric brain functional networks.

Prenatal opioid exposure has been linked to adverse effects spanning multiple neurodevelopmental domains, including cognition, motor development, attention, and vision. However, the neural basis of these abnormalities is largely unknown. A total of 49 infants, including 21 opioid-exposed and 28 controls, were enrolled and underwent MRI (43 ± 6 days old) after birth, including resting state functional MRI. Edge-centric functional networks based on dynamic functional connections were constructed, and machine-learning methods were employed to identify neural features distinguishing opioid-exposed infants from unexposed controls. An accuracy of 73.6% (sensitivity 76.25% and specificity 69.33%) was achieved using 10 times 10-fold cross-validation, which substantially outperformed those obtained using conventional static functional connections (accuracy 56.9%). More importantly, we identified that prenatal opioid exposure preferentially affects inter- rather than intra-network dynamic functional connections, particularly with the visual, subcortical, and default mode networks. Consistent results at the brain regional and connection levels were also observed, where the brain regions and connections associated with visual and higher order cognitive functions played pivotal roles in distinguishing opioid-exposed infants from controls. Our findings support the clinical phenotype of infants exposed to opioids in utero and may potentially explain the higher rates of visual and emotional problems observed in this population. Finally, our findings suggested that edge-centric networks could better capture the neural differences between opioid-exposed infants and controls by abstracting the intrinsic co-fluctuation along edges, which may provide a promising tool for future studies focusing on investigating the effects of prenatal opioid exposure on neurodevelopment.

Fabrication of superhydrophobic Enteromorpha-derived carbon aerogels via NH4H2PO4 modification for multi-behavioral oil/water separation.

Hydrophobic and oleophilic biomass-based block materials are considered to be highly promising candidates used for oil/water separation. However, the crucial hydrophobic modification process often involves various toxic and hazardous organic substances or requires high energy inputs. Inspired by the flame retardant principle of phosphorus-containing flame retardants, herein, an Enteromorpha-derived carbon (ADP-EP) aerogel with a water contact angle of 144.2° was prepared by successive freeze-shaping, freeze-drying and low-temperature carbonization treatment (300 °C), using NH4H2PO4 (ADP) as a modifier. The results demonstrated that the introduction of NH4H2PO4 could largely facilitate the removal of oxygenated groups from the pristine EP aerogels and enhance their surface roughness, thereby achieving surface hydrophobic modification. Featuring intrinsic low density, rich porosity and strong lipophilicity, the as-fabricated ADP-EP aerogels exhibited exceptional performance in both oil spill adsorption (~140 g/g) and water-in-oil emulsion separation. Moreover, the good reusability for oil uptake was also realized thanks to its robust mechanical compressibility and thermal stability. This work provides a facile, economical and eco-friendly route to obtain a desirable hydrophobic/oleophilic surface.

Phytic acid and graphene oxide functionalized sponge with special-wettability and electronegativity for oil-in-water emulsion separation in single-step.

Developing an emulsion separation material with one-step in-situ purifying capability and improved security in applications, especially for subsequent scale-up, is valuable but remains a challenge. Herein, the amphiphilic sponge (PA@RGO@MS) was prepared via impregnation and in-situ growth of the negatively charged hydrophilic phytic acid (PA) and the hydrophobic reduced graphene oxide (RGO) on the surface of the melamine sponge (MS) and applied in emulsion purification. The mechanics, wettability, absorption performance of the PA@RGO@MS were analyzed to identify its potential for stable demulsification. Results show that the PA@RGO@MS could purify emulsions (turbidity removal rate = 99.7%; TOC removal rate = 94.14%) in-situ in one step by simple shock absorption, profited from the hydrophilic and demulsification capability of PA, oil absorption of RGO, and wide reaction and storage space of MS. Targeting the emulsion with distinct properties (density, viscosity, and concentration) of the oil phase, the PA@RGO@MS could efficiently enable the purification. Meanwhile, the powerful flame-retardant granted from PA ensures the safe shipment and storage of sponges. The favorable cyclability (turbidity removal rate > 98.5% and TOC removal rate > 89.5% after 10 cycles) and diversified operating modes enhance the practical value of the PA@RGO@MS.

Decorating UiO-66-NH2 crystals on recyclable fiber bearing polyamine and amidoxime bifunctional groups via cross-linking method with good stability for highly efficient capture of U(VI) from aqueous solution.

Although polyacrylonitrile fiber (PANF) and metal-organic frameworks (MOFs) have been extensively investigated to remove U(VI) from water, their practical applications are seriously hindered by the relatively low stability of PANF in acidic solution and great difficulty of separating MOFs nanoparticles from solution, beside that, little attention is paid to the fabrication of MOFs and PANF composite materials (MPCMs) with excellent adsorption capacity for U(VI). Herein, we report the synthesis of novel MPCMs by decorating different concentrations of UiO-66-NH2 crystals onto polyamine and amidoxime groups functionalized PANF (PA-AO-PANF) through cross-linking method for U(VI) extraction. The characterization results reveal that the combination of PA-AO-PANF and UiO-66-NH2 crystals endows MPCMs with excellent separation ability, large surface area, good stability and plentiful surface functional groups, which contributes to good selectivity and enhanced adsorption performance. Consequently, the obtained UN-PA-AO-PANF-2 shows the maximum uptake capacity of 441.8 mg/g and equilibrium uptake time of 30 min towards U(VI). Besides, the U(VI) uptake ability and structure of UN-PA-AO-PANF-2 are well preserved after ten adsorption-desorption cycles. With these outstanding properties, the adsorbent has great potential for the capture of U(VI) from aqueous solutions. Importantly, this work provides a cost-effective and efficient way to construct extremely stable MPCMs hybrid fibers.

Synthesis of rice husk-based ion-imprinted polymer for selective capturing Cu(II) from aqueous solution and re-use of its waste material in Glaser coupling reaction.

With the deepening of the concept of recycling economy and green chemistry, selective capture of Cu(II) from wastewater by biosorbent and reuse of the spent Cu(II)-loaded adsorbent are of great significance. Herein, we synthesized composite of rice husk (RH) with mesoporous silica MCM-41 (RH@MCM-41) modified by organosilane containing amino and schiff groups as functional monomer and cross-linking agent. The silica modified RH@MCM-41 was employed as supporter to fabricate copper ion-imprinted polymers as absorbents (named as RM-CIIPs) via surface ion imprinting technique. Adsorption isotherms, kinetics, selectivity and mechanism of RM-CIIPs to remove Cu(II) were investigated with respect to different adsorption condition. Furthermore, we explored the catalytic activity of spent Cu(II)-loaded adsorbent in Glaser coupling reaction. Batch adsorption studies revealed that RM-CIIP-3 prepared with functional monomer shows the best adsorption capacity (91.4 mg/g) for Cu(II), and adsorption equilibrium could be reached within 30 min. RM-CIIP-3 exhibited an excellent selectivity for capturing Cu(II) and reusability in six adsorption/desorption cycles. More importantly, the spent Cu(II)-loaded adsorbent could be used as bio-heterogeneous catalyst and afford the desired product (1,4-diphenylbutadiyne) in 99.1% yield. Our research indicates an eco-friendly systematic strategy to utilize the waste material as an adsorbent for removing heavy metals and catalyst for industry.

Effects of prenatal opioid exposure on functional networks in infancy.

Prenatal opioid exposure has been linked to altered neurodevelopment and visual problems such as strabismus and nystagmus. The neural substrate underlying these alterations is unclear. Resting-state functional connectivity MRI (rsfMRI) is an advanced and well-established technique to evaluate brain networks. Few studies have examined the effects of prenatal opioid exposure on resting-state network connectivity in infancy. In this pilot study, we characterized network connectivity in opioid-exposed infants (n = 19) and controls (n = 20) between 4-8 weeks of age using both a whole-brain connectomic approach and a seed-based approach. Prenatal opioid exposure was associated with differences in distribution of betweenness centrality and connection length, with positive connections unique to each group significantly longer than common connections. The unique connections in the opioid-exposed group were more often inter-network connections while unique connections in controls and connections common to both groups were more often intra-network. The opioid-exposed group had smaller network volumes particularly in the primary visual network, but similar network strength as controls. Network topologies as determined by dice similarity index were different between groups, particularly in visual and executive control networks. These results may provide insight into the neural basis for the developmental and visual problems associated with prenatal opioid exposure.

Versatile 3D reduced graphene oxide/poly(amino-phosphonic acid) aerogel derived from waste acrylic fibers as an efficient adsorbent for water purification.

The fabrication of multifunctional materials to remove soluble heavy metal ions and dyes, as well as insoluble oils from waste water is urgently required, yet remains a daunting challenge because of difficulty in controlling their structure and property to satisfy various demands. Herein, for the first time, novel 3D reduced graphene oxide/poly(amino-phosphonic acid) (PAPA) aerogels (rGO/PAPAs) with different PAPA content were developed by solvothermal reduction of the graphene oxide and cross-linking with PAPA chain, and subsequently employed as versatile adsorbent for the removal of complex pollutants such as Cr(III) ion, methylene blue (MB) dye and various kinds of organic solvents from water. Benefiting from the synergistic effect of the reduced graphene oxide (rGO) sheet and PAPA component, as well as its unique 3D structure, the resultant aerogel (rGO/PAPA-2) gained amphiphilic, ultralight, and multifunctional properties. Thus, it showed a fast adsorption rate (within 15 min) and high adsorption capacity (up to 327.1 mg/g) for Cr(III) ion at an optimal pH of 5.5 due to its unique 3D network structure with abundant amino-phosphonic acid functional groups. The uptake of Cr(III) by rGO/PAPA-2 was fitted well with the Langmuir isotherm and pseudo-second-order kinetic model. The adsorption mechanism of Cr(III) onto rGO/PAPA-2 can be attributed to electrostatic attraction and surface complexation with APA groups. In addition, the rGO/PAPA-2 displayed an excellent adsorption performance for MB (694.5 mg/g) and several organic solvents (83.2 to 254.3 g/g). Moreover, the rGO/PAPA-2 exhibited a good regeneration (around 99%) and satisfactory recovery abilities for the tested adsorbates. Notably, PAPA chains can be easily prepared from waste acrylic fibers, making it become a cost effective but versatile candidate to prepare new material. Therefore, this work provides a new design strategy to fabricate the rGO/PAPA-2 aerogel with great prospect for sophisticated industrial wastewater cleanup.

Reference-Relation Guided Autoencoder with Deep CCA Restriction for Awake-to-Sleep Brain Functional Connectome Prediction.

The difficulty of acquiring resting-state fMRI of early developing children under the same condition leads to a dedicated protocol, i.e., scanning younger infants during sleep and older children during being awake, respectively. However, the obviously different brain activities of sleep and awake states arouse a new challenge of awake-to-sleep connectome prediction/translation, which remains unexplored despite its importance in the longitudinally-consistent delineation of brain functional development. Due to the data scarcity and huge differences between natural images and geometric data (e.g., brain connectome), existing methods tailored for image translation generally fail in predicting functional connectome from awake to sleep. To fill this critical gap, we unprecedentedly propose a novel reference-relation guided autoencoder with deep CCA restriction (R2AE-dCCA) for awake-to-sleep connectome prediction. Specifically, 1) A reference-autoencoder (RAE) is proposed to realize a guided generation from the source domain to the target domain. The limited paired data are thus greatly augmented by including the combinations of all the age-restricted neighboring subjects as the references, while the target-specific pattern is fully learned; 2) A relation network is then designed and embedded into RAE, which utilizes the similarity in the source domain to determine the belief-strength of the reference during prediction; 3) To ensure that the learned relation in the source domain can effectively guide the generation in the target domain, a deep CCA restriction is further employed to maintain the neighboring relation during translation; 4) New validation metrics dedicated for connectome prediction are also proposed. Experimental results showed that our proposed R2AE-dCCA produces better prediction accuracy and well maintains the modular structure of brain functional connectome in comparison with state-of-the-art methods.

The emergence of a functionally flexible brain during early infancy.

Adult brains are functionally flexible, a unique characteristic that is thought to contribute to cognitive flexibility. While tools to assess cognitive flexibility during early infancy are lacking, we aimed to assess the spatiotemporal developmental features of "neural flexibility" during the first 2 y of life. Fifty-two typically developing children 0 to 2 y old were longitudinally imaged up to seven times during natural sleep using resting-state functional MRI. Using a sliding window approach, MR-derived neural flexibility, a quantitative measure of the frequency at which brain regions change their allegiance from one functional module to another during a given time period, was used to evaluate the temporal emergence of neural flexibility during early infancy. Results showed that neural flexibility of whole brain, motor, and high-order brain functional networks/regions increased significantly with age, while visual regions exhibited a temporally stable pattern, suggesting spatially and temporally nonuniform developmental features of neural flexibility. Additionally, the neural flexibility of the primary visual network at 3 mo of age was significantly and negatively associated with cognitive ability evaluated at 5/6 y of age. The "flexible club," comprising brain regions with neural flexibility significantly higher than whole-brain neural flexibility, were consistent with brain regions known to govern cognitive flexibility in adults and exhibited unique characteristics when compared to the functional hub and diverse club regions. Thus, MR-derived neural flexibility has the potential to reveal the underlying neural substrates for developing a cognitively flexible brain during early infancy.

Development of Dynamic Functional Architecture during Early Infancy.

Uncovering the moment-to-moment dynamics of functional connectivity (FC) in the human brain during early development is crucial for understanding emerging complex cognitive functions and behaviors. To this end, this paper leveraged a longitudinal resting-state functional magnetic resonance imaging dataset from 51 typically developing infants and, for the first time, thoroughly investigated how the temporal variability of the FC architecture develops at the "global" (entire brain), "mesoscale" (functional system), and "local" (brain region) levels in the first 2 years of age. Our results revealed that, in such a pivotal stage, 1) the whole-brain FC dynamic is linearly increased; 2) the high-order functional systems tend to display increased FC dynamics for both within- and between-network connections, while the primary systems show the opposite trajectories; and 3) many frontal regions have increasing FC dynamics despite large heterogeneity in developmental trajectories and velocities. All these findings indicate that the brain is gradually reconfigured toward a more flexible, dynamic, and adaptive system with globally increasing but locally heterogeneous trajectories in the first 2 postnatal years, explaining why infants have rapidly developing high-order cognitive functions and complex behaviors.

Mechanism of sonication time on structure and adsorption properties of 3D peanut shell/graphene oxide aerogel.

A 3D pretreated peanut shell-supported graphene oxide (PPS/GO) aerogel has been facilely prepared through a brief sonication + freeze-shaping technique, avoiding the traditional application of hydrothermal method which suffered from high temperature and long reaction time as well as significant loss of oxygen-containing functional groups. It was then employed to efficient norfloxacin (NOR) removal from aqueous medium. The mechanism of sonication time on the structure and adsorption properties of as-obtained PPS/GO aerogels was emphatically discussed via combining instrumental analyses, batch adsorption experiments and density functional theory (DFT) calculations. Results showed that the 3D PPS/GO aerogel with a decrease in oxygen functional groups and an increase in sp2-derived sp3 hybridization regions was observed as sonication time provided in excess, causing the worse removal efficiency towards NOR. The resulting PPS/GO(5:1) aerogel obtained at sonication of 2 min and GO loading content of 200 mg/(PPS)g exhibited the optimal NOR adsorption capacity (pH 6.2, 228.83 mg g-1). DFT calculations further identified that the sp3-hybridized areas in PPS/GO aerogel had much lower adsorption energy (ΔE, -6.69 kcal/mol) towards NOR as compared with that of sp2-hybridized zones (-12.45 kcal/mol). In addition, multiple interactions were involved in the adsorption of NOR by 3D PPS/GO aerogel, including electrostatic attraction, H-bonding, π-π conjugation and hydrophobic effect.

Brain functional development separates into three distinct time periods in the first two years of life.

Recently, resting functional MRI has provided invaluable insight into the brain developmental processes of early infancy and childhood. A common feature of previous functional development studies is the use of age to separate subjects into different cohorts for group comparisons. However, functional maturation paces vary tremendously from subject to subject. Since this is particularly true for the first years of life, an alternative to physical age alone is needed for cluster analysis. Here, a data-driven approach based on individual brain functional connectivity was employed to cluster typically developing children who were longitudinally imaged using MRI without sedation for the first two years of life. Specifically, three time periods were determined based on the distinction of brain functional connectivity patterns, including 0-1 month (group 1), 2-7 months (group 2), and 8-24 (group 3) of age, respectively. From groups 1 to 2, connection density increased by almost two-fold, local efficacy (LE) is significantly improved, and there was no change in global efficiency (GE). From groups 2 to 3, connection density increased slightly, LE showed no change, and a significant increase in GE were observed. Furthermore, 27 core brain regions were identified which yielded clustering results that resemble those obtained using all brain regions. These core regions were largely associated with the motor, visual and language functional domains as well as regions associated with higher order cognitive functional domains. Both visual and language functional domains exhibited a persistent and significant increase within domain connection from groups 1 to 3, while no changes were observed for the motor domain. In contrast, while a reduction of inter-domain connection was the general developmental pattern, the motor domain exhibited an interesting "V" shape pattern in its relationship to visual and language associated areas, showing a decrease from groups 1 to 2, followed by an increase from groups 2 to 3. In summary, our results offer new insights into functional brain development and identify 27 core brain regions critically important for early brain development.