Positional Thiophene Isomerization: A Geometric Strategy for Precisely Regulating the Electronic State of Covalent Organic Frameworks to Boost Oxygen Reduction.

With the oxygen conversion efficiency of metal-free carbon-based fuel cells dramatically improved, the building blocks of covalent organic frameworks (COFs) raised principal concerns on the catalytic active sites with indistinct electronic states. Herein, to address this issue, we demonstrate COFs for oxygen reduction reaction (ORR) by regulating the edge-hanging thiophene units, and the molecular geometries are further modulated via positional thiophene isomerization strategy, affording isomeric COF-α with 2-substitution and COF-ß with 3-substitution on the frameworks. The electronic states and intermediate adsorption ability are well-regulated through geometric modification, resulting in controllable chemical activity and local density of π-electrons. Notably, the introduction of thiophene units with different substitution positions into a pristine pure carbon-based COF model COF-Ph achieves excellent activity with a half-wave potential of 0.76 V versus the reversible hydrogen electrode, which is higher than most of those metal-free or metal-based electrocatalysts. Utilizing the combination of theoretical prediction and in situ Raman spectra, we show that the isomeric thiophene skeleton (COF-α and COF-ß) can induce the dangling unit activation, accurately identifying the pentacyclic-carbon (thiophene α-position) adjacent to sulfur atom as active sites. The results suggest that the isomeric dangling groups in COFs are suitable for the ORR with promising geometry construction.

Topology Control of Covalent Organic Frameworks with Interlaced Unsaturated 2D and Saturated 3D Units for Boosting Electrocatalytic Hydrogen Peroxide Production.

Modulating the electronic state of multicomponent covalent organic framework (COF) electrocatalysts is crucial for enhancing catalytic activity. However, the effect of dimensionality on their physicochemical functionalities is still lacking. Herein, we report an interlaced unsaturated 2D and saturated 3D strategy to develop multicomponent-regulated COFs with tunable gradient dimensionality for high selectivity and activity electrocatalysis. Compared with the two-component 2D and 3D model COFs, the 2D/3D framework interlaced COFs with locally irregular dimensions and electronic structures are more practical in optimizing the intrinsic electrode surface reaction and mass transfer. Remarkably, the unsaturated 2D-inserted 3D TAE-COF regulates the adsorption mode of OOH* species to supply a favorable dynamic pathway for the H2O2 process, thereby achieving an excellent production rate of 8.50 mol gcat -1 h-1. Moreover, utilizing theoretical calculation and in situ ATR-FTIR experiment, we found that the central carbon atom of the tetraphenyl-based unit (site-1 and site-6) are potential active sites. This strategy of operating the adsorption ability of reactants with dimensionality-interconnected building blocks provides an idea for designing durable and efficient electrocatalysts.

Heterocyclic Modulated Electronic States of Alkynyl-Containing Conjugated Microporous Polymers for Efficient Oxygen Reduction.

The oxygen reduction reaction (ORR) is a key process in green energy conversion technology. Heteroatom doping has been proven to be a prospective strategy to prepare metal-free carbon-based electrocatalysts, but such methods often suffer from uncontrollable catalyst frameworks and imprecise active sites. Herein, an organic heterocyclic strategy is adopted to modulate the charge redistribution of alkynyl-containing conjugated microporous polymers (CMPs) by introducing varied five-membered heterocyclic structures. Among these CMPs, the S, 2N-containing thiadiazole heterocyclic molecule (CMP-Tdz) with carbonized alginate materials (CCA ) displays a remarkable quasi-four-electron-transfer ORR pathway, exhibiting an excellent half-wave potential (E1/2 ) of 0.77 V, coupled with superior methanol tolerance and electrochemical stability, which are among the highest performance in the metal-free organic catalytic material systems. Density functional theory calculations prove that the high catalytic performance of these catalysts originates from the sp-hybridized C atom (site-2) which is activated by their adjacent heterocyclic structures. Importantly, the five-membered heterocyclic structures can also modulate the local charge distribution, and increase dipole moment, with significantly improved catalytic kinetics. This incorporation of chemically designed heterocyclic-containing alkynyl-CMPs provides a new approach to developing efficient metal-free carbon-based electrocatalysts for fuel cells.

High-resolution on-chip spatial heterodyne Fourier transform spectrometer based on artificial neural network and PCSBL reconstruction algorithm.

A novel compact on-chip Fourier transform (FT) spectrometer has been proposed based on the silicon-on-insulator (SOI) platform with wide operating bandwidth and high resolution. The spectrometer consists of a 16-channel power splitter and a Mach-Zehnder interferometer (MZI) array of 16 MZIs with linearly increasing optical path length (OPL) difference. We have also developed a spectral retrieval algorithm based on the pattern-coupled sparse Bayesian learning (PCSBL) algorithm and artificial neural network (ANN). The experimental results show that the designed spectrometer has a flat transmission characteristic in the wavelength range between 1500 nm and 1600 nm, indicating that the device has a wide operating bandwidth of 100 nm. In addition, with the assistance of the spectral retrieval algorithm, our spectrometer has the ability to reconstruct narrowband signals with full width at half maximum (FWHM) of 0.5 nm and a triple-peaked signal separated by a 3-nm distance.

Deep Learning-Based Multiclass Brain Tissue Segmentation in Fetal MRIs.

Fetal brain tissue segmentation is essential for quantifying the presence of congenital disorders in the developing fetus. Manual segmentation of fetal brain tissue is cumbersome and time-consuming, so using an automatic segmentation method can greatly simplify the process. In addition, the fetal brain undergoes a variety of changes throughout pregnancy, such as increased brain volume, neuronal migration, and synaptogenesis. In this case, the contrast between tissues, especially between gray matter and white matter, constantly changes throughout pregnancy, increasing the complexity and difficulty of our segmentation. To reduce the burden of manual refinement of segmentation, we proposed a new deep learning-based segmentation method. Our approach utilized a novel attentional structural block, the contextual transformer block (CoT-Block), which was applied in the backbone network model of the encoder-decoder to guide the learning of dynamic attentional matrices and enhance image feature extraction. Additionally, in the last layer of the decoder, we introduced a hybrid dilated convolution module, which can expand the receptive field and retain detailed spatial information, effectively extracting the global contextual information in fetal brain MRI. We quantitatively evaluated our method according to several performance measures: dice, precision, sensitivity, and specificity. In 80 fetal brain MRI scans with gestational ages ranging from 20 to 35 weeks, we obtained an average Dice similarity coefficient (DSC) of 83.79%, an average Volume Similarity (VS) of 84.84%, and an average Hausdorff95 Distance (HD95) of 35.66 mm. We also used several advanced deep learning segmentation models for comparison under equivalent conditions, and the results showed that our method was superior to other methods and exhibited an excellent segmentation performance.

Oxygen Reduction Activity of B←N-Containing Organic Molecule Affected by Asymmetric Regulation.

Organic molecular catalysts have received great attention as they have the merits of well-controlled molecular structures for the development of catalytic chemistry. Herein, the electronic distribution of active sites is regulated by asymmetrically introducing S-heterocycle on one side of the molecular core. As a result, the asymmetric as-PYT and as-BNT show higher oxygen reduction performance than their symmetric counterparts without (s-PY, s-PY2T) or with two S-heterocycle units (s-BN, s-BN2T). Density functional theory calculations reveal that the carbon atoms (site-12) at symmetric s-BN and s-BN2T are the catalytic active sites, while for asymmetric as-BNT, it has changed to amino-N atom (site-14). Due to the non-uniform charge distribution and increased dipole moment of as-BNT caused by asymmetric molecular configuration, the kinetics of catalytic reaction has changed significantly. The catalytically active sites of specific N atoms are further verified experimentally and theoretically by using sterically hindered phenyl groups. This work provides a simple but efficient method to design metal-free oxygen reduction electrocatalysts.

Optical performance monitoring using SOI-based spectral analysis.

A novel optical performance monitoring (OPM) method based on Fourier transform spectrum analysis (FTSA) is designed for optical signal-to-noise ratio (OSNR) monitoring, modulation format and baud rate recognition in the presence of fiber nonlinearities. The interference intensities, which reflect spectral features of signals, are obtained by exploiting the FTSA consisting of two-stage Mach-Zehnder interferometer (MZI) arrays. Then, the mapping between the OPM parameters and modulated interference intensity (MII) is characterized using neural networks without prior knowledge of the configuration of the communication network. Results show that optical performance parameters are monitored simultaneously. Meanwhile, the accuracy of modulation format and baud rate recognition is 94.8% and most (over 86%) OSNR monitoring errors are less than ±1 dB under complex transmission conditions in presence of frequency offset and delay jitter. Besides, the FTSA can be fabricated on a silicon on insulator (SOI) platform with a large fabrication tolerance, and it has broad working bandwidth to support the full optical communication band. Therefore, the proposed OPM method is capable of integration and miniaturization, which can be ubiquitously applied in network intermediate nodes to support the construction of smart optical networks.

An Unsaturated Bond Strategy to Regulate Active Centers of Metal-Free Covalent Organic Frameworks for Efficient Oxygen Reduction.

Unsaturated environment is the key to affect catalytic activity of the oxygen reduction reaction (ORR). Unveiling the effect of unsaturated sites toward ORR activity is of importance due to the vague unsaturated states. Reported here is a proof-of-concept strategy on the evaluation of unsaturated bonds (UBs) on adjacent carbon environment by precisely developing two metal-free vinyl-/azo-decorated covalent organic frameworks (Vinyl-COF and Azo-COF) as catalysts. The as-prepared UB-COFs exhibit good performance than the control Py-COF and comparable to the most reported carbon catalysts. Supported by theory calculations and in situ Raman spectra-electrochemistry, it is revealed that the UBs in organic catalysts can produce para-activation, identifying the para C=N groups as active centers. Importantly, the intrinsic UBs can induce local charge redistribution, and make the molecular skeleton possess high isosurface map distribution, with an efficient affinity for oxygen intermediates.

Highly accelerated magnetic resonance acoustic radiation force imaging for in vivo transcranial ultrasound focus localization: A comparison of three reconstruction methods.

Magnetic resonance acoustic radiation force imaging (MR-ARFI) is a promising tool for transcranial neurosurgery planning and monitoring. However, the ultrasound dose during ARFI is quite high due to the high intensity required and the repetitive ultrasound sonication. To reduce the ultrasound deposition and prevent unwanted neurological effects, undersampling in k-space data acquisition is adopted in the current study. Three reconstruction methods, keyhole, k-space hybrid and temporal differences (TED) compressed sensing, the latter two of which were initially proposed for MR thermometry, were applied to the in vivo transcranial focus localization based on MR-ARFI data in a retrospective way. The accuracies of the three methods were compared with the results from the fully sampled data as reference. The results showed that the keyhole method tended to smooth the displacement map and underestimate the peak displacement. The K-space hybrid method was better at recovering the displacement map and was robust to the undersampling pattern, while the TED method was more time efficient under a higher image resolution. For an image of a lower resolution, the K-space hybrid and TED methods were comparable in terms of accuracy when a high undersampling rate was applied. The results reported here facilitate the choice of appropriate undersampled reconstruction methods in transcranial focal localization based on MR-ARFI.

Controlled Asymmetric Charge Distribution of Active Centers in Conjugated Polymers for Oxygen Reduction.

Active center reconstruction is essential for high performance oxygen reduction reaction (ORR) electrocatalysts. Usually, the ORR activity stems from the electronic environment of active sites by charge redistribution. We introduce an asymmetry strategy to adjust the charge distribution of active centers by designing conjugated polymer (CP) catalysts with different degrees of asymmetry. We synthesized asymmetric backbone CP (asy-PB) by modifying B←N coordination bonds and asymmetric sidechain CP (asy-PB-A) with different alkyl chain lengths. Both CPs with backbone and sidechain asymmetry exhibit superior ORR performance to their symmetric counterparts (sy-P and sy-PB). The asy-PB with greater asymmetry shows higher catalytic activity than asy-PB-A with relatively smaller asymmetry. DFT calculations reveal that the increased dipole moment and non-uniform charge distribution caused by asymmetric structure endows the center carbon atom of bipyridine with efficient catalytic activity.

A review of removal technology for antimony in aqueous solution.

Antimony (Sb) and its compounds, toxic metalloid, have been classified as high-priority pollutants. Increasing Sb released into the water environment by natural processes and anthropogenic activities, which exposure threatens to human health and ecosystems. Therefore, it is of unquestionable importance to remove Sb from polluted water. Keeping in view the extreme importance of this issue, we summarize the source, chemistry, speciation, distribution, toxicity, and polluted situation of Sb about aqueous solution. Then, we provide the recent and common technology to remove Sb, which are based on adsorption, coagulation/flocculation, electrochemical technology, membrane technology, ion exchange, etc. In this review, we focus in detail on the adsorption method, researchers at present have been investigating to discover more advanced, cost-effective, eco-friendly, reusable adsorbents. However, to date the Sb-containing wastewater treatment technologies are not sufficiently developed and most of research have been tested only in controlled lab conditions. Few reports are available that include field studies and applications. We critically analyzed the salient features and removal mechanisms, evaluating benefits and limitations of these technologies, hoping to provide more references for further research. Finally, we considered the Fe- or Mn-based technologies was the most promising technique to remove Sb for field application.

Antimony speciation in the environment: Recent advances in understanding the biogeochemical processes and ecological effects.

Antimony (Sb) is a toxic metalloid, and its pollution has become a global environmental problem as a result of its extensive use and corresponding Sb-mining activities. The toxicity and mobility of Sb strongly depend on its chemical speciation. In this review, we summarize the current knowledge on the biogeochemical processes (including emission, distribution, speciation, redox, metabolism and toxicity) that trigger the mobilization and transformation of Sb from pollution sources to the surrounding environment. Natural phenomena such as weathering, biological activity and volcanic activity, together with anthropogenic inputs, are responsible for the emission of Sb into the environment. Sb emitted in the environment can adsorb and undergo redox reactions on organic or inorganic environmental media, thus changing its existing form and exerting toxic effects on the ecosystem. This review is based on a careful and systematic collection of the latest papers during 2010-2017 and our research results, and it illustrates the fate and ecological effects of Sb in the environment.

Heterocyclization Strategy for Construction of Linear Conjugated Polymers: Efficient Metal-Free Electrocatalysts for Oxygen Reduction.

Exploring cost-effective and efficient metal-free electrocatalysts for the oxygen reduction reaction (ORR) is crucial for the development of energy conversion and storage technologies. Reported here is a novel heterocyclization strategy to construct efficient ORR catalysts based on linear conjugated polymers (LCPs), which are composed of N-, S-, or Se-heterocycles. Among these polymers, the covalently linked pyridine and thiophene molecule (P-T) with reduced graphene oxide (rGO) exhibits a remarkable half-wave potential of 0.79 V (vs. RHE) and excellent electrochemical stability, which are among the highest values for metal-free polymers as ORR catalysts. Density-functional theory (DFT) calculations reveal that the molecule with a phenyl unit (P-Ph) is catalytically inactive, and when a thiophene unit is introduced to replace the phenyl unit in the conjugated backbone it features highly efficient electrocatalytic active sites. More importantly, the well-defined molecular structures and controllable active sites in the pyrolysis and metal-free polymers highlight new opportunities for the catalytic metal-free ORR.

Activatable Small-Molecule Photoacoustic Probes that Cross the Blood-Brain Barrier for Visualization of Copper(II) in Mice with Alzheimer's Disease.

Copper enrichment in the brain is highly related to Alzheimer's disease (AD) pathogenesis, but in vivo tracing of Cu2+ in the brain by imaging techniques is still a great challenge. In this work, we developed a series of activatable photoacoustic (PA) probes with low molecular weights (less than 438 Da), RPS1-RPS4, which can specifically chelate with Cu2+ to form radicals with turn-on PA signals in the near-infrared (NIR) region. Introducing the electron-donating group N,N-dimethylaniline into the probe was found to significantly enhance the radical stability and PA intensity. The best probe in the series, RPS1, showed a fast response (within seconds) to Cu2+ with high selectivity and a low PA detection limit of 90.9 nm. Owing to the low molecular weight and amphiphilic structure, RPS1 could effectively cross the blood-brain barrier (BBB) and thus allowed us, for the first time, to visualize Cu2+ in vivo via PA imaging in the brains of AD mice.

Objective method for evaluating orthodontic treatment from the lay perspective: An eye-tracking study.

INTRODUCTION: Currently, few methods are available to measure orthodontic treatment need and treatment outcome from the lay perspective. The objective of this study was to explore the function of an eye-tracking method to evaluate orthodontic treatment need and treatment outcome from the lay perspective as a novel and objective way when compared with traditional assessments. METHODS: The scanpaths of 88 laypersons observing the repose and smiling photographs of normal subjects and pretreatment and posttreatment malocclusion patients were recorded by an eye-tracking device. The total fixation time and the first fixation time on the areas of interest (eyes, nose, and mouth) for each group of faces were compared and analyzed using mixed-effects linear regression and a support vector machine. The aesthetic component of the Index of Orthodontic Treatment Need was used to categorize treatment need and outcome levels to determine the accuracy of the support vector machine in identifying these variables. RESULTS: Significant deviations in the scanpaths of laypersons viewing pretreatment smiling faces were noted, with less fixation time (P <0.05) and later attention capture (P <0.05) on the eyes, and more fixation time (P <0.05) and earlier attention capture (P <0.05) on the mouth than for the scanpaths of laypersons viewing normal smiling subjects. The same results were obtained when comparing posttreatment smiling patients, with less fixation time (P <0.05) and later attention capture on the eyes (P <0.05), and more fixation time (P <0.05) and earlier attention capture on the mouth (P <0.05). The pretreatment repose faces exhibited an earlier attention capture on the mouth than did the normal subjects (P <0.05) and posttreatment patients (P <0.05). Linear support vector machine classification showed accuracies of 97.2% and 93.4% in distinguishing pretreatment patients from normal subjects (treatment need), and pretreatment patients from posttreatment patients (treatment outcome), respectively. CONCLUSIONS: The eye-tracking device was able to objectively quantify the effect of malocclusion on facial perception and the impact of orthodontic treatment on malocclusion from the lay perspective. The support vector machine for classification of selected features achieved high accuracy of judging treatment need and treatment outcome. This approach may represent a new method for objectively evaluating orthodontic treatment need and treatment outcome from the perspective of laypersons.

An Electron-Deficient Building Block Based on the B←N Unit: An Electron Acceptor for All-Polymer Solar Cells.

A double B←N bridged bipyridyl (BNBP) is a novel electron-deficient building block for polymer electron acceptors in all-polymer solar cells. The B←N bridging units endow BNBP with fixed planar configuration and low-lying LUMO/HOMO energy levels. As a result, the polymer based on BNBP units (P-BNBP-T) exhibits high electron mobility, low-lying LUMO/HOMO energy levels, and strong absorbance in the visible region, which is desirable for polymer electron acceptors. Preliminary all-polymer solar cell (all-PSC) devices with P-BNBP-T as the electron acceptor and PTB7 as the electron donor exhibit a power conversion efficiency (PCE) of 3.38%, which is among the highest values of all-PSCs with PTB7 as the electron donor.

n-Type boron ß-diketone-containing conjugated polymers for high-performance room temperature ammonia sensors.

Organic semiconductor (OSC) gas sensors with good mechanical flexibility have received considerable attention as commercial and wearable devices. However, due to poor resistance to moisture and low conductivity, the improvement in the sensing capability of individual OSCs is limited. Reported here is a promising pathway to construct a series of conjugated organic polymers (COPs) with well-defined pyrimidine (Py-COP) or boron ß-diketone (BF-COP) units. Unlike traditional metal- or carbon-based hybrid materials, the developed COPs can provide abundant absorption sites for gaseous analytes. As a result, the as-prepared BF-COP results in an excellent sensing response of over 1500 (Ra/Rg) toward 40 ppm of NH3 at room temperature, which is the highest value among those of pristine COPs as n-type sensing materials. Notably, they can maintain their initial sensing responses for two months and 90% relative humidity resistance. Combining the results of in situ Fourier transform infrared spectroscopy and theoretical calculations, the ß-diketone skeleton is found to activate the surface electronic environment, verifying that the electron-deficient B ← O groups are adsorption centers. The B/N-heterocyclic decoration effectively modulates the redox properties and electronic interactions, as well as perturbs charge transfer in typical π-conjugated COPs. These results offer insight into developing highly efficient OSC gas sensors, which potentially have broadened sensing applications in the areas of organoboron chemistry.

Preparation of high-strength photochromic alginate fibers based on the study of flame-retardant properties.

Color-changing fibers have attracted much attention for their wide applications in camouflage, security warnings, and anti-counterfeiting. The inorganic color-changing material tungsten trioxide (WO3) has been widely investigated for its good stability, controllability, and ease of synthesis. In this study, photochromic alginate fibers (WO3@Ca-Alg) were prepared by incorporating UV-responsive hybrid tungsten trioxide nanoparticles in the fiber production process. The prepared photochromic alginate fibers changed from white to dark blue after 30 min of UV irradiation and returned to their original color after 64 h. It can be seen that WO3@Ca-Alg has the advantage of long color duration. The strength of this fiber reached 2.61 cN/dtex and the limiting oxygen index (LOI) was 40.9 %, which indicates that the fiber exhibited mechanical resistance and flame-retardant properties. After the cross-linking of WO3@Ca-Alg by sodium tetraborate, a new core-shell structure was generated, which was able to encapsulate tungsten trioxide in it, thus reducing the amount of tungsten trioxide loss, and its salt and washing resistance was greatly improved. This photochromic alginate fiber can be mass produced and spun into yarn.

High-Performance Room Temperature Ammonia Sensors Based on Pure Organic Molecules Featuring B-N Covalent Bond.

Exploring organic semiconductor gas sensors with high sensitivity and selectivity is crucial for the development of sensor technology. Herein, for the first time, a promising chemiresistive organic polymer P-BNT based on a novel π-conjugated triarylboron building block is reported, showcasing an excellent responsivity over 30 000 (Ra/Rg) against 40 ppm of NH3, which is ≈3300 times higher than that of its B-N organic small molecule BN-H. More importantly, a molecular induction strategy to weaken the bond dissociation energy between polymer and NH3 caused by strong acid-base interaction is further executed to optimize the response and recovery time. As a result, the BN-H/P-BNT system with rapid response and recovery times can still exhibit a high responsivity of 718, which is among the highest reported NH3 chemiresistive sensors. Supported by in situ FTIR spectroscopy and theoretical calculations, it is revealed that the N-H fractions in BN-H small molecule promoted the charge distribution on phenyl groups, which increases charge delocalization and is more conducive to gas adsorption in such molecular systems. Notably, these distinctive small molecules also promoted charge transfer and enhanced electron concentration of the P-BNT sensing polymer, thus achieving superior B-N-containing organic molecules with excellent sensing performance.

Spatiotemporal Distributions of Acoustic Propagation in Skull During Ultrasound Neuromodulation.

There is widespread interest and concern about the evidence and hypothesis that the auditory system is involved in ultrasound neuromodulation. We have addressed this problem by performing acoustic shear wave simulations in mouse skull and behavioral experiments in deaf mice. The simulation results showed that shear waves propagating along the skull did not reach sufficient acoustic pressure in the auditory cortex to modulate neurons. Behavioral experiments were subsequently performed to awaken anesthetized mice with ultrasound targeting the motor cortex or ventral tegmental area (VTA). The experimental results showed that ultrasound stimulation (US) of the target areas significantly increased arousal scores even in deaf mice, whereas the loss of ultrasound gel abolished the effect. Immunofluorescence staining also showed that ultrasound can modulate neurons in the target area, whereas neurons in the auditory cortex required the involvement of the normal auditory system for activation. In summary, the shear waves propagating along the skull cannot reach the auditory cortex and induce neuronal activation. Ultrasound neuromodulation-induced arousal behavior needs direct action on functionally relevant stimulation targets in the absence of auditory system participation.