Optoelectronically navigated nano-kirigami microrotors.

With the rapid development of micro/nanofabrication technologies, the concept of transformable kirigami has been applied for device fabrication in the microscopic world. However, most nano-kirigami structures and devices were typically fabricated or transformed at fixed positions and restricted to limited mechanical motion along a single axis due to their small sizes, which significantly limits their functionalities and applications. Here, we demonstrate the precise shaping and position control of nano-kirigami microrotors. Metallic microrotors with size of ~10 micrometers were deliberately released from the substrates and readily manipulated through the multimode actuation with controllable speed and direction using an advanced optoelectronic tweezers technique. The underlying mechanisms of versatile interactions between the microrotors and electric field are uncovered by theoretical modeling and systematic analysis. This work reports a novel methodology to fabricate and manipulate micro/nanorotors with well-designed and sophisticated kirigami morphologies, providing new solutions for future advanced optoelectronic micro/nanomachinery.

Oligo(phenylenevinylene)-Based Covalent Organic Frameworks with Kagome Lattice for Boosting Photocatalytic Hydrogen Evolution.

Covalent organic frameworks (COFs) have shown great advantages as photocatalysts for hydrogen evolution. However, the effect of linkage geometry and type of linkage on the extent of π-electron conjugation in the plane of the framework and photocatalytic properties of COFs remains a significant challenge. Herein, two Kagome (kgm) topologic oligo(phenylenevinylene)-based COFs are designed and synthesized for boosting photocatalytic hydrogen evolution via a "two in one" strategy. Under visible light irradiation, COF-954 with 5 wt% Pt as cocatalyst exhibits high hydrogen evolution rate (HER) of 137.23 mmol g-1 h-1 , outperforming most reported COF-based photocatalysts. More importantly, even in natural seawater, COF-954 shows an average HER of 191.70 mmol g-1 h-1 under ultraviolet-visible (UV-vis) light irradiation. Additionally, the water-drainage experiments indoors and outdoors demonstrate that 25 and 8 mL hydrogen gas could be produced in 80 min under UV-vis light and natural sunlight, respectively, corresponding to a high HER of 167.41 and 53.57 mmol h-1 g-1 . This work not only demonstrates an effective design strategy toward highly efficient COF-based photocatalysts, but also shows the great potential of using the COF-based photocatalysts for photocatalytic hydrogen evolution.

Enhanced degradation of chloramphenicol via heterogeneous activation of peroxymonosulfate by Fe3O4 and gallic acid.

In this study, we demonstrated the effective degradation of wide-spectrum antibiotic chloramphenicol (CAP) by Fe3O4/peroxymonosulfate (PMS) system modified by gallic acid (GA). GA/Fe3O4/PMS showed a substantially higher degradation rate (77.6%) than Fe3O4/PMS (8.3%). The active components were detected by electron spin-resonance spectroscopy (ESR) and the quenching experiments. The results showed that the hydroxyl radical (HO•) was the main reason for the degradation of CAP. In the GA/Fe3O4/PMS system, the trace amount of dissolved iron ion were not the main species that activated PMS. Surface characterization and theoretical simulations showed that Fe atoms on Fe3O4 were responsible for PMS activation rather than a homogenous reaction. Five probable CAP degradation pathways were identified by density functional theory (DFT) calculations and liquid-phase mass spectrometry. Finally, the reusability of Fe3O4 was measured, and the GA/Fe3O4/PMS system maintained high efficiency after 5 times applications. The total organic carbon (TOC) removal rate reached 46.5% after reacting for 12 h. The gallic acid effectively promotes the circulation of Fe(II)/Fe(III) on solid surfaces and enhanced the degradation capacity of the original system. The research proposed a new way of directly employing plant polyphenols to boost the degradation ability of contaminants in heterogeneous systems.

Locality in amino-acid based imidazolium ionic liquids.

Several amino-acid based imidazolium ILs are investigated through the use of ab initio molecular dynamics (AIMD), which includes full polarization. The electric dipole moment distribution and polarization is used as a means of characterizing and understanding these complex systems. Various charge scheme methods were analyzed (Wannier function, Blöchl, Löwdin and Mulliken charge schemes and Voronoi tessellation) to determine their ability to predict dipole moments. These results and the following comparison of methods further deepen the knowledge of polarization by highlighting the importance of the anion and cation separately on polarizability contribution and the need to select a suitable method to predict these. The angular probability distribution is utilized to measure the degree of locality in monopole-dipole electrostatic interactions, which showed no preferential alignment over 700 pm. In addition, the IR and Raman spectra from Voronoi tessellation of [C2C1Im][ala] were analyzed. In these, the strongest signalling peaks showed consistency with experiment and the ability to differentiate between anion and cation components of the IL.

Site-specific N-glycan changes during semen liquefaction.

Normal liquefaction of semen is one of the key steps to ensure the smooth progress of fertilization, and glycosylation has been reported to be involved in the whole process of fertilization. Till now, it is still unclear whether and how glycosylation changes during the liquefaction process of semen. In this study, by performing a glycoproteomic analysis of human semen with the liquefaction process (liquefaction time of semen: 0 min vs 30 min) using our recently developed StrucGP software combined with the Tandem Mass Tags (TMT) based quantification, we identified 25 intact glycopeptides (IGPs) from 10 glycoproteins in semen that were significantly changed during liquefaction, including 23 up-regulated and two down-regulated. Among the 23 up-regulated glycopeptides, half were modified with sialylated glycans, suggesting that sialylated glycans may play a key role in the semen liquefaction process. The data provide an invaluable resource for further studies on the role of glycosylation during semen liquefaction.

Multi-View Deep Gaussian Processes for Supervised Learning.

Multi-view learning is a widely studied topic in machine learning, which considers learning with multiple views of samples to improve the prediction performance. Even though some approaches have sprung up recently, it is still challenging to jointly explore information contained in different views. Multi-view deep Gaussian processes have shown strong advantages in unsupervised representation learning. However, they are limited when dealing with labeled multi-view data for supervised learning, and ignore the application potential of uncertainty estimation. In this paper, we propose a supervised multi-view deep Gaussian process model (named SupMvDGP), which uses the label of the views to further improve the performance, and takes the quantitative uncertainty estimation as a supplement to assist humans to make better use of prediction. According to the diversity of views, the SupMvDGP can establish asymmetric depth structure to better model different views, so as to make full use of the property of each view. We provide a variational inference method to effectively solve the complex model. Finally, we conduct comprehensive comparative experiments on multiple real world datasets to evaluate the performance of SupMvDGP. The experimental results show that the SupMvDGP achieves the state-of-the-art results in multiple tasks, which verifies the effectiveness and superiority of the proposed approach. Meanwhile, we provide a case study to show that the SupMvDGP has the ability to provide uncertainty estimation than alternative deep models, which can alert people to better treat the prediction results in high-risk applications.

Improved photocatalytic activity of TiO2 with a regulated covalent organic framework thin film.

In this work, one-dimensional TiO2 nanotube arrays are coupled with a covalent organic framework (COF) thin film with a controlled thickness to form a three-dimensional heterojunction, which exhibits a 3.3-fold higher hydrogen evolution rate than that of TiO2, and becomes active for CO2 conversion, compared to the bare COF. Such high activity results from the large difference in Fermi levels forming an internal electric field at the interface.

Partial Multiview Representation Learning With Cross-View Generation.

Multiview learning has made significant progress in recent years. However, an implicit assumption is that multiview data are complete, which is often contrary to practical applications. Due to human or data acquisition equipment errors, what we actually get is partial multiview data, which existing multiview algorithms are limited to processing. Modeling complex dependencies between views in terms of consistency and complementarity remains challenging, especially in partial multiview data scenarios. To address the above issues, this article proposes a deep Gaussian cross-view generation model (named PMvCG), which aims to model views according to the principles of consistency and complementarity and eventually learn the comprehensive representation of partial multiview data. PMvCG can discover cross-view associations by learning view-sharing and view-specific features of different views in the representation space. The missing views can be reconstructed and are applied in turn to further optimize the model. The estimated uncertainty in the model is also considered and integrated into the representation to improve the performance. We design a variational inference and iterative optimization algorithm to solve PMvCG effectively. We conduct comprehensive experiments on multiple real-world datasets to validate the performance of PMvCG. We compare the PMvCG with various methods by applying the learned representation to clustering and classification. We also provide more insightful analysis to explore the PMvCG, such as convergence analysis, parameter sensitivity analysis, and the effect of uncertainty in the representation. The experimental results indicate that PMvCG obtains promising results and surpasses other comparative methods under different experimental settings.

A strain-reinforcing elastomer adhesive with superior adhesive strength and toughness.

Strong and ductile adhesives often undergo both interfacial and cohesive failure during the debonding process. Herein, we report a rare self-reinforcing polyurethane adhesive that shows the different phenomenon of only interfacial failure yet still exhibiting superior adhesive strength and toughness. It is synthesized by designing a hanging adhesive moiety, hierarchical H-bond moieties, and a crystallizable soft segment into one macromolecular polyurethane. The former hanging adhesive moiety allows the hot-melt adhesive to effectively associate with the target substrate, providing sufficient adhesion energy; the latter hierarchical H-bond moieties and a crystallizable soft segment cooperate to enable the adhesive to undergo large lap-shear deformations through sacrificing weak bonds and mechano-responsive strength through the fundamental mechanism of strain-induced crystallization. As a result, this polyurethane adhesive can keep itself intact during the debonding process while still withstanding a high lap-shear strength and dissipating tremendous stress energy. Its adhesive strength and work of debonding are as high as 11.37 MPa and 10.32 kN m-1, respectively, outperforming most reported tough adhesives. This self-reinforcing adhesive is regarded as a new member of the family of strong and ductile adhesives, which will provide innovative chemical and structural inspirations for future conveniently detachable yet high-performance adhesives.

Maximal performance of intact N-glycopeptide enrichment using sequential HILIC and MAX columns.

Low abundance and heterogeneity of N-glycosylation at the peptide level poses a great challenge to the structural and functional analysis of glycosylation in the field of glycobiology. Solving this conundrum requires a sufficient and specific method for intact N-glycopeptide enrichment. Using the C18 or HLB desalting column followed by the mixed-mode strong anion exchange (MAX) or hydrophilic interaction chromatography (HILIC) glycopeptide enrichment column are commonly applied approaches for sample preparation of intact N-glycopeptides from complex samples. Herein, we compared the effects of different combinations of two desalting columns and two enrichment columns using equal amounts of mouse brain tissues from the same source. The results revealed the C18 column was a bit superior to the HLB column, and the MAX and HILIC columns were complementary on intact N-glycopeptides enrichment. Additionally, the results also demonstrated that enriching glycopeptides using a HILIC column followed by a MAX column from the flow-through solution got a better enrichment performance than the reversed order. Based on these results, the sequential enrichment of glycopeptides using HILIC and then MAX columns could maximize the enrichment performance of intact N-glycopeptides, and therefore is an option for in-depth analysis of site-specific glycoproteome.

Quantitative probing of reactive oxygen species and their selective degradation on contaminants in peroxymonosulfate-based process enhanced by picolinic acid.

The processes of Fe(III) activated peroxymonosulfate (PMS) in degrading contaminants have been extensively studied. Herein, a biodegradable chelating agent, picolinic acid (PICA), was introduced to the PMS/Fe(III) process to improve the reaction efficiency. The emphases of this study were placed on the quantification of steady-state concentrations of reactive oxygen species (ROS). Experiments presented that five types of ROS, including Fe(IV), SO4•-, HO•, 1O2 and O2•- coexisted in this system. Four typical probe compounds were used to quantify the steady-state concentration of ROS under different variables. The steady-state concentration of Fe(IV) ([Fe(IV)]ss) was 3-5 orders of magnitude higher than that of other ROS, followed by 1O2 and SO4•-, whereas HO• had the lowest concentration. The reaction between PMS and PICA was first explored in our study and results showed that 1O2 and O2•- would form in this reaction. Owing to the hybrid oxidation by multiple ROS, this system showed high oxidation capacity, and could effectively degrade a variety of pollutants. The contributions of ROS to the alleviation of pollutants varied depending on their concentrations and specific reactivity of substrates. Generally, organic contaminants with phenol structures were prone to react with Fe(IV). Overall, this study compared the steady-state concentrations of different ROS and revealed the intrinsic ROS formation mechanisms.

Using bioinformatics and systems biology methods to identify the mechanism of interaction between COVID-19 and nonalcoholic fatty liver disease.

Nonalcoholic fatty liver disease (NAFLD) is considered a risk factor for severe COVID-19, but the mechanism remains unknown. This study used bioinformatics to help define the relationship between these diseases. The GSE147507 (COVID-19), GSE126848 (NAFLD), and GSE63067 (NAFLD-2) datasets were screened using the Gene Expression Omnibus. Common differentially expressed genes were then identified using a Venn diagram. Gene ontology analysis and KEGG pathway enrichment were performed on the differentially expressed genes. A protein-protein interaction network was also constructed using the STRING platform, and key genes were identified using the Cytoscape plugin. GES63067 was selected for validation of the results. Analysis of ferroptosis gene expression during the development of the 2 diseases and prediction of their upstream miRNAs and lncRNAs. In addition, transcription factors (TFs) and miRNAs related to key genes were identified. Effective drugs that act on target genes were found in the DSigDB. The GSE147507 and GSE126848 datasets were crossed to obtain 28 co-regulated genes, 22 gene ontology terms, 3 KEGG pathways, and 10 key genes. NAFLD may affect COVID-19 progression through immune function and inflammatory signaling pathways. CYBB was predicted to be a differential ferroptosis gene associated with 2 diseases, and the CYBB-hsa-miR-196a/b-5p-TUG1 regulatory axis was identified. TF-gene interactions and TF-miRNA coregulatory network were constructed successfully. A total of 10 drugs, (such as Eckol, sulfinpyrazone, and phenylbutazone) were considered as target drugs for Patients with COVID-19 and NAFLD. This study identified key gene and defined molecular mechanisms associated with the progression of COVID-19 and NAFLD. COVID-19 and NAFLD progression may regulate ferroptosis through the CYBB-hsa-miR-196a/b-5p-TUG1 axis. This study provides additional drug options for the treatment of COVID-19 combined with NAFLD disease.

Intermediate Formation of Macrocycles for Efficient Crystallization of 2D Covalent Organic Frameworks with Enhanced Photocatalytic Hydrogen Evolution.

Covalent organic frameworks (COFs) have gained significant attention as key photocatalysts for efficient solar light conversion into hydrogen production. Unfortunately, the harsh synthetic conditions and intricate growth process required to obtain highly crystalline COFs greatly hinder their practical application. Herein, we report a simple strategy for the efficient crystallization of 2D COFs based on the intermediate formation of hexagonal macrocycles. Mechanistic investigation suggests that the use of 2,4,6-triformyl resorcinol (TFR) as the asymmetrical aldehyde build block allows the equilibration between irreversible enol-to-keto tautomerization and dynamic imine bonds to produce the hexagonal ß-ketoenamine-linked macrocycles, the formation of which could provide COFs with high crystallinity in half hour. We show that COF-935 with 3 wt % Pt as cocatalyst exhibit a high hydrogen evolution rate of 67.55 mmol g-1 h-1 for water splitting when exposed to visible light. More importantly, COF-935 exhibits an average hydrogen evolution rate of 19.80 mmol g-1 h-1 even at a low loading of only 0.1 wt % Pt, which is a significant breakthrough in this field. This strategy would provide valuable insights into the design of highly crystalline COFs as efficient organic semiconductor photocatalysts.

A comparative study on Fe(III)/H2O2 and Fe(III)/S2O82- systems modified by catechin for the degradation of atenolol.

The processes of Fe(III) activated persulfate (PS) and H2O2 modified by catechin (CAT) had been shown to be effective in degrading contaminants. In this study, the performance, mechanism, degradation pathways and products toxicity of PS (Fe(III)/PS/CAT) and H2O2 (Fe(III)/H2O2/CAT) systems were compared using atenolol (ATL) as a model contaminant. 91.0% of ATL degradation was reached after 60 min in H2O2 system which was much higher than that in PS system (52.4%) under the same experimental condition. CAT could react directly with H2O2 to produce small amounts of HO• and the degradation efficiency of ATL was proportional to CAT concentration in H2O2 system. However, the optimal CAT concentration was 5 µM in PS system. The performance of H2O2 system was more susceptible to pH than that of PS system. Quenching experiments were conducted indicating that SO4•- and HO• were produced in PS system while HO• and O2•- accounted for ATL degradation in H2O2 system. Seven pathways with nine byproducts and eight pathways with twelve byproducts were put forward in PS and H2O2 systems respectively. Toxicity experiments showed that the inhibition rates of luminescent bacteria were both decreased about 25% after 60 min reaction in two systems. Although the software simulation result showed few intermediate products of both systems were More toxic than ATL, but the amounts of them were 1-2 orders of magnitude lower than ATL. Moreover, the mineralization rates were 16.4% and 19.0% in PS and H2O2 systems respectively.

Yarn-Level Simulation of Hygroscopicity of Woven Textiles.

Simulating liquid-textile interaction has received great attention in computer graphics recently. Most existing methods take textiles as particles or parameterized meshes. Although these methods can generate visually pleasing results, they cannot simulate water content at a microscopic level due to the lack of geometrically modeling of textile's anisotropic structure. In this paper, we develop a method for yarn-level simulation of hygroscopicity of textiles and evaluate it using various quantitative metrics. We model textiles in a fiber-yarn-fabric multi-scale manner and consider the dynamic coupled physical mechanisms of liquid spreading, including wetting, wicking, moisture sorption/desorption, and transient moisture-heat transfer in textiles. Our method can accurately simulate liquid spreading on textiles with different fiber materials and geometrical structures with consideration of air temperatures and humidity conditions. It visualizes the hygroscopicity of textiles to demonstrate their moisture management ability. We conduct qualitative and quantitative experiments to validate our method and explore various factors to analyze their influence on liquid spreading and hygroscopicity of textiles.

Isomeric Oligo(Phenylenevinylene)-Based Covalent Organic Frameworks with Different Orientation of Imine Bonds and Distinct Photocatalytic Activities.

Imine-linked covalent organic frameworks (COFs) have been extensively studied in photocatalysis because of their easy synthesis and excellent crystallinity. The effect of imine-bond orientation on the photocatalytic properties of COFs, however, is still rarely studied. Herein, we report two novel COFs with different orientations of imine bonds using oligo(phenylenevinylene) moieties. The COFs showed similar structures but great differences in their photoelectric properties. COF-932 demonstrated a superior hydrogen evolution performance compared to COF-923 when triethanolamine was used as the sacrificial agent. Interestingly, the use of ascorbic acid led to the protonation of the COFs, further altering the direction of electron transfer. The photocatalytic performances were increased to 23.4 and 0.73 mmol g-1 h-1 for protonated COF-923 and COF-932, respectively. This study provides a clear strategy for the design of imine-linked COF-based photocatalysts and advances the development of COFs.

Recognition of Core-Fucosylated Glycopeptides Based on the Y1+Fuc/Y1 Ratio in Low-Energy HCD Spectra.

Accurate identification of core fucosylation on N-glycopeptides remains challenging due to fucose migration during mass spectrometry analysis. Here, we introduce a simple and straightforward method for core-fucosylated glycopeptide recognition based on the relative intensities of Y1+Fuc ions compared with their corresponding Y1 ions (labeled as Y1+Fuc/Y1 or simply Y1F/Y1 ratio > 0.1) in low-energy HCD-based spectra. The method was first developed by systematically evaluating the influence of fucose migration on the Y1F ion from antenna fucoses based on the distribution of the Y1F/Y1 ratios in the MS/MS spectra of antenna-fucosylated glycopeptides from Fut8-/- mouse brain. The feasibility of the method was then confirmed by using two standard glycoproteins, comparison with glycopeptides in Fut8+/+ mouse brain with/without in silico core-fucosylation removal, and Y1F/Y1 ratio alterations under a lower HCD energy. This method will be applicable to the manual interpretation and software-based high-throughput analysis of core-fucosylated glycopeptides.

Solvent engineering to regulate the phase of copper zinc tin sulfide nanocrystals.

Copper zinc tin sulfide (Cu2ZnSnS4, CZTS) is attracting interest in photovoltaic applications due to its proper band gap, low cost and low toxicity. It has been found that two phases can be fabricated, i.e. kesterite and wurtzite CZTS structures. Though kesterite CZTS is proven to be thermodynamically stable, the free energy difference between kesterite and wurtzite CZTS is rather small. So, wurtzite CZTS can also stably exist under ambient conditions. Controlling the phase formation can expand the dimensions to optimize the performance of applications based on CZTS. In this study, we found that phase control can be achieved by simply using a mixed solvent of ethylene glycol and triethylenetetramine (TETA) in a two-stage heating process. It is found that the incorporation of the reductive solvent of TETA during the 1st heating process converts the phase of the precipitates from CuS (TETA poor) to Cu7S4 (TETA rich). In the subsequent 2nd heating stage, the phase of the final products is determined to be kesterite CZTS originating from CuS and wurtzite CZTS from Cu7S4, respectively. Thus, the key to control the phases of the final products is to control the chemical environment of Cu under Cu1+-rich or Cu2+-rich conditions in the fabrication process, which corresponds to the phase of the final products of wurtzite CZTS or kesterite CZTS, respectively. This summarized principle can not only be used to explain the previous versatile experimental results but also to guide the controlled synthesis of various phases of CZTS and CZTS-like materials in applications.

Mechanism of the improved Fe(III)/persulfate reaction by gallic acid for ibuprofen degradation.

Gallic acid (GA), a natural plant polyphenol, was applied as amendment of Fe(III)/persulfate (PS) system for ibuprofen (IBP) degradation in this study. The impacts of all agentia (GA, Fe(III), PS) concentration and initial pH values on IBP removal efficiency were investigated, and their corresponding observed pseudo-first-order rate constants (kobs) were calculated. The addition of GA has significantly improved elimination efficiency of IBP due to the enhanced Fe(III)/Fe(II) cycle. Electron paramagnetic resonance (EPR) results confirmed that SO4•-, HO• and O2•- were involved in GA/Fe(III)/PS system. However, quenching experiments further affirmed the impact of SO4•- and HO• towards IBP decomposition instead of O2•-, with contribution ratio to IBP removal was 69.12% and 30.88%, respectively. SO4•- was the main radicals formed by directly activation of PS with Fe(II), while HO• was the transformation product of SO4•-. Based on instrumental analysis (stopped-flow UV-vis spectrum and MS) and theoretical calculation, the potential reaction mechanism between GA and Fe(III) in the presence of PS was further proposed. GA complexed with Fe(III) firstly and the Fe(III)-GA complex was then converted into quinone substance, accompanied by the generation of Fe(II). Furthermore, the application of GA extended the optimal pH range to neutral as well, which made it a promising treatment in practical application.

De-sialylation of glycopeptides by acid treatment: enhancing sialic acid removal without reducing the identification.

Sialic acid, a common terminal monosaccharide on many glycoconjugates, plays essential roles in many biological processes such as immune responses, pathogen recognition, and cancer development. For various purposes, sialic acids may need to be removed from glycopeptides or glycans, mainly using enzymatical or chemical approaches. In this study, we found that most commonly used chemical methods couldn't completely remove sialic acids from glycopeptides. Although the de-sialylation efficiency could be further enhanced by increasing the treatment time or acid concentration, the undesirable side reactions on the peptide portion would decrease glycopeptide identification. By adding the deamidation on carbamidomethyl-cysteine (C), asparagine (N), and glutamine (Q) residues as a variable modification during database search, most of the unidentified spectra could be recovered. This optional acid-treatment and database search method for the complete removal of sialic acids without losing much spectral identification should be quite useful for many glycomic and glycoproteomic studies.