High-throughput proteomic analysis of extracellular vesicles from saliva by chemical probe-based array.

Extracellular vesicles (EVs) are cell-released, nucleus-free particles with a double-membrane structure that effectively prevents degradation of internal components by a variety of salivary enzymes. Saliva is an easily accessible biofluid that contains a wealth of valuable information for disease diagnosis and monitoring and especially reflect respiratory and digestive tract diseases. However, the lack of efficient and high-throughput methods for proteomic analysis of salivary biomarkers poses a significant challenge. Herein, we designed a salivary EV amphiphile-dendrimer supramolecular probe (SEASP) array which enables efficient enrichment and in situ detection of EVs protein biomarkers. Detergent Tween-20 washing of SEASP arrays removes high abundance of heteroproteins from saliva well. This array shows good analytical performance in the linear range of 10 µL-150 µL (LOD = 0.4 µg protein, or 10 µL saliva), exhibiting a good recovery (80.0 %). Compared to ultracentrifugation (UC), this procedure provides simple and convenient access to high-purity EVs (1.3 × 109 particles per mg protein) with good physiological status and structure. Coupling with mass spectrometry based proteomic analysis, differentially expressed proteins as selected asthma biomarkers have been screened. Then, we validated the proteomics primary screening results through clinical samples (100 µL each) using the SEASP array. Utilizing the dual antibody fluorescence technology, SEASP enables the simultaneous high-throughput detection of two proteins. Therefore, the EVs marker protein CD81 could be used as an internal standard to normalize the number of EVs, which was stably expressed in EVs. Proteomics and array results suggested that HNRNPU (P = 4.9 * 10-6) and MUC5B (P = 4.7 * 10-11) are promising protein biomarkers for infantile asthma. HNRNPU and MUC5B may be associated with disease onset and subtypes. The SEASP arrays provide a significant advancement in the field of salivary biomarker. The array enables high-throughput in situ protein detection for highly viscous and complex biological samples. It provides a rapid, low-cost, highly specific screening procedure and experimental basis for early disease screening and diagnosis in the field of liquid biopsy.

Mechanistic insights into CO2 conversion chemistry of copper bis-(terpyridine) molecular electrocatalyst using accessible operando spectrochemistry.

The implementation of low-cost transition-metal complexes in CO2 reduction reaction (CO2RR) is hampered by poor mechanistic understanding. Herein, a carbon-supported copper bis-(terpyridine) complex enabling facile kilogram-scale production of the catalyst is developed. We directly observe an intriguing baton-relay-like mechanism of active sites transfer by employing a widely accessible operando Raman/Fourier-transform infrared spectroscopy analysis coupled with density functional theory computations. Our analyses reveal that the first protonation step involves Cu-N bond breakage before the *COOH intermediate forms exclusively at the central N site, followed by an N-to-Cu active site transfer. This unique active site transfer features energetically favorable *CO formation on Cu sites, low-barrier CO desorption and reversible catalyst regeneration, endowing the catalyst with a CO selectively of 99.5 %, 80 h stability, and a turn-over efficiency of 9.4 s-1 at -0.6 V vs. the reversible hydrogen electrode in an H-type cell configuration. We expect that the approach and findings presented here may accelerate future mechanistic studies of next-generation CO2RR electrocatalysts.

Pd homojunctions enable remarkable CO2 electroreduction.

3D Pd aerogels with a controllable homojunction density are synthesized using an innovative melting-casting technology. The homojunction-rich Pd aerogels selectively reduce CO2 to CO with a 92.3% faradaic efficiency and durability over 10 h, benefiting from the strong coupling between the electrons and the adsorbed intermediates at the phase-mismatch interface.

Developing Atomically Thin Li1.81H0.19Ti2O5·2H2O Nanosheets for Selective Photocatalytic CO2 Reduction to CO.

Solar-driven CO2 conversion to carbon-based fuels is an attractive approach to alleviate the worsening global climate change and increasing energy issues. However, exploring and designing efficient photocatalysts with excellent activity and stability still remain challenging. Herein, layered Li1.81H0.19Ti2O5·2H2O (LHTO) nanosheets were explored as the photocatalyst for photocatalytic CO2 reduction, and atomically thin LHTO nanosheets with one-unit-cell thickness were successfully constructed for photocatalytic CO2 reduction. The atomically thin LHTO nanosheets exhibited excellent performance for CO2 photoreduction to CO, with a yield rate of 4.0 µmol g-1 h-1, a selectivity of 93%, and over 25 h photostability, dramatically outperforming the bulk LHTO. The better performance of the atomically thin LHTO nanosheets was experimentally verified to benefit from more sites for CO2 adsorption, faster electron transfer rate, and a more negative conduction band edge compared with bulk LHTO. This work provided a methodological basis for designing more efficient photocatalytic CO2 reduction catalysts.

A comprehensive annotation dataset of intact LTR retrotransposons of 300 plant genomes.

LTR retrotransposons (LTR-RTs) are ubiquitous and represent the dominant repeat element in plant genomes, playing important roles in functional variation, genome plasticity and evolution. With the advent of new sequencing technologies, a growing number of whole-genome sequences have been made publicly available, making it possible to carry out systematic analyses of LTR-RTs. However, a comprehensive and unified annotation of LTR-RTs in plant groups is still lacking. Here, we constructed a plant intact LTR-RTs dataset, which is designed to classify and annotate intact LTR-RTs with a standardized procedure. The dataset currently comprises a total of 2,593,685 intact LTR-RTs from genomes of 300 plant species representing 93 families of 46 orders. The dataset is accompanied by sequence, diverse structural and functional annotation, age determination and classification information associated with the LTR-RTs. This dataset will contribute valuable resources for investigating the evolutionary dynamics and functional implications of LTR-RTs in plant genomes.

Synthesis of a Gold-Metal Oxide Core-Satellite Nanostructure for In†Situ SERS Study of CuO-Catalyzed Photooxidation.

This work reports on an assembling-calcining method for preparing gold-metal oxide core-satellite nanostructures, which enable surface-enhanced Raman spectroscopic detection of chemical reactions on metal oxide nanoparticles. By using the nanostructure, we study the photooxidation of Si-H catalyzed by CuO nanoparticles. As evidenced by the in situ spectroscopic results, oxygen vacancies of CuO are found to be very active sites for oxygen activation, and hydroxide radicals (*OH) adsorbed at the catalytic sites are likely to be the reactive intermediates that trigger the conversion from silanes into the corresponding silanols. According to our finding, oxygen vacancy-rich CuO catalysts are confirmed to be of both high activity and selectivity in photooxidation of various silanes.

Etchable SERS nanosensor for accurate pH and hydrogen peroxide sensing in living cells.

No methodology has been built to distinguish intracellular SERS nanosensors from cell outer membrane bound-ones. Here we propose a "turning off" strategy by combining etchable SERS nanosensors with a non-permeable etchant. The SERS signals outside the living cells can be rapidly removed, leaving only the internalized nanosensors for imaging and thereby allowing accurate intracellular pH and H2O2 sensing.

Augmentation agents to serotonin reuptake inhibitors for treatment-resistant obsessive-compulsive disorder: A network meta-analysis.

BACKGROUND: Various agents for augmentation of serotonin reuptake inhibitors have been investigated for treatment-resistant obsessive-compulsive disorder (OCD). We aimed to comprehensively compare different augmentation agents for treatment-resistant OCD in adults. METHODS: PubMed, Embase, Web of Science, CENTRAL, the WHO's ICTRP, and ClinicalTrials.gov were searched on February 20, 2018. Pairwise meta-analysis and Bayesian network meta-analysis were performed. The primary outcome was efficacy measured by the Yale-Brown Obsessive Compulsive Scale. The secondary outcomes were tolerability (side-effect discontinuation) and acceptability (all cause discontinuation). Mean differences (MDs) and odds ratios (ORs) were reported with 95% confidence intervals (CIs). RESULTS: Thirty-three articles with 34 trials (1216 patients) were included. Memantine (MD, -8.94; 95% CI, -14.42 to -3.42), risperidone (-4.47, -8.75 to -0.17), topiramate (-6.05, -10.89 to -1.20), lamotrigine (-6.07, -11.61 to -0.50), and aripiprazole (-5.14, -9.95 to -0.28) were significantly superior to placebo. Antipsychotic (-4.09, -6.22 to -1.93) and glutamatergic (-5.22, -7.53 to -2.84) agents were significantly superior to placebo. Considerable heterogeneity was found across studies, and baseline symptom severity was identified as a significant moderator. After baseline severity adjustment, quetiapine (-5.00, -8.59 to -1.29) and olanzapine (-8.28, -15.34 to -1.13) became significantly superior to placebo. CONCLUSIONS: Our study supports the use of antipsychotic or glutamatergic agents as augmentation agents for treatment-resistant OCD. Topiramate, lamotrigine, aripiprazole, olanzapine, risperidone, memantine, and quetiapine are alternative augmentation drugs; however, a definitive conclusion of the best drug remains undetermined because of the considerable heterogeneity and limited numbers of studies and patients for each agent.

Black N/H-TiO2 Nanoplates with a Flower-Like Hierarchical Architecture for Photocatalytic Hydrogen Evolution.

A facile two-step strategy was used to prepare black of hydrogenated/nitrogen-doped TiO2 nanoplates (NHTA) with a flower-like hierarchical architecture. In situ nitriding and self-assembly was realized by hydrothermal synthesis using tripolycyanamide as a N source and as a structure-directing agent. After thorough characterization, it was found that the hydrogenation treatment did not damage the flower-like architecture but distorted the anatase crystal structure and significantly changed the band structure of NHTA owing to the increased concentration of oxygen vacancies, hydroxyl groups, and Ti3+ cations. Under AM 1.5 illumination, the photocatalytic H2 evolution rate on the black NHTA was approximately 1500 µmol g-1 h-1 , which was much better than the N-doped TiO2 nanoplates (≈690 µmol g-1 h-1 ). This improvement in the hydrogen evolution rate was attributed to a reduced bandgap, enhanced separation of the photogenerated charge carriers, and an increase in the surface-active sites.

Ordered mesoporous black TiO(2) as highly efficient hydrogen evolution photocatalyst.

Mesoporous TiO2 has gained increasing interest because of its outstanding properties and promising applications in a wide range of fields. Herein, we report the facile synthesis of ordered mesoporous black TiO2 (OMBT) materials, which exhibit excellent photocatalytic hydrogen evolution performances. In this case, the employment of a thermally stable and high-surface-area mesoporous TiO2 as the hydrogenation precursor is the key for fabricating the OMBT materials, which not only facilitate H2 gas diffusion into TiO2 and interaction with their structures but also maintain the ordered mesoporous structures as well as inhibit the phase transformation (from anatase to rutile) and crystal growth during hydrogenation at 500 °C. The resultant OMBT materials possess a relatively high surface area of ∼124 m(2) g(-1) and a large pore size and pore volume of ∼9.6 nm and 0.24 cm(3) g(-1), respectively. More importantly, the OMBT materials can extend the photoresponse from ultraviolet to visible and infrared light regions and exhibit a high solar-driven hydrogen production rate (136.2 µmol h(-1)), which is almost two times as high as that of pristine mesoporous TiO2 (76.6 µmol h(-1)).