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1.
J Am Chem Soc ; 2024 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-38714344

RESUMO

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2═CHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2═CHO*, as well as accelerating hydrogenation of the C═C bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.

2.
Acta Biochim Biophys Sin (Shanghai) ; 56(2): 174-183, 2024 02 25.
Artigo em Inglês | MEDLINE | ID: mdl-38273784

RESUMO

The most frequent primary brain tumor in adults is glioma, yet no effective curative treatments are currently available. Our previous study demonstrated the enhancing effects of JARID2 on glioma sensitivity to TMZ treatment. In this study, miR-155 is predicted to target JARID2. miR-155 is overexpressed in clinical glioma specimens and cell lines. miR-155 overexpression in glioma cells enhances cell viability and represses cell apoptosis. Through targeting, miR-155 inhibits JARID2 expression. miR-155 inhibition inhibits glioma cell viability and enhances cell apoptosis, whereas JARID2 knockdown enhances cell viability and inhibits cell apoptosis; JARID2 knockdown partially reverses miR-155 inhibition effects on glioma phenotypes. miR-155 inhibition reduces but knockdown of JARID2 promotes the tumor formation ability of glioma cells in vivo. Valproic acid (VPA) upregulates JARID2 expression, inhibits glioma cell viability and enhances cell apoptosis. VPA downregulates the expression level of miR-155 by increasing the methylation level of the miR-155 promoter, suggesting that the miR-155/JARID2 axis is implicated in VPA inhibition of glioma cell viability and enhancement of glioma cell apoptosis. This study demonstrates a new mechanism of VPA treatment of gliomas by affecting the miR-155/JARID2 axis, which could be regarded as a new strategy for the prevention and treatment of glioma.


Assuntos
Neoplasias Encefálicas , Glioma , MicroRNAs , Humanos , Ácido Valproico/farmacologia , Linhagem Celular Tumoral , Glioma/tratamento farmacológico , Glioma/genética , Glioma/metabolismo , MicroRNAs/metabolismo , Metilação , Proliferação de Células/genética , Apoptose/genética , Neoplasias Encefálicas/tratamento farmacológico , Neoplasias Encefálicas/genética , Neoplasias Encefálicas/metabolismo , Regulação Neoplásica da Expressão Gênica
3.
Environ Sci Technol ; 57(51): 21855-21865, 2023 Dec 26.
Artigo em Inglês | MEDLINE | ID: mdl-38086098

RESUMO

Per- and polyfluoroalkyl substances (PFAS) represent significant stress to organisms and are known to disrupt microbial community structure and function. Nevertheless, a detailed knowledge of the soil microbial community responding to PFAS stress at the metabolism level is required. Here we integrated UPLC-HRMS-based metabolomics data with 16S rRNA and ITS amplicon data across soil samples collected adjacent to a fluoropolymer production facility to directly identify the biochemical intermediates in microbial metabolic pathways and the interactions with microbial community structure under PFAS stress. A strong correlation between metabolite and microbial diversity was observed, which demonstrated significant variations in soil metabolite profiles and microbial community structures along with the sampling locations relative to the facility. Certain key metabolites were identified in the metabolite-PFAS co-occurrence network, functioning on microbial metabolisms including lipid metabolism, amino acid metabolism, and secondary metabolite biosynthesis. These results provide novel insights into the impacts of PFAS contamination on soil metabolomes and microbiomes. We suggest that soil metabolomics is an informative and useful tool that could be applied to reinforce the chemical evidence on the disruption of microbial ecological traits.


Assuntos
Ácidos Alcanossulfônicos , Fluorocarbonos , Microbiota , Solo/química , RNA Ribossômico 16S/genética , Fluorocarbonos/análise , Polímeros de Fluorcarboneto
4.
Inorg Chem ; 62(46): 19006-19014, 2023 Nov 20.
Artigo em Inglês | MEDLINE | ID: mdl-37930938

RESUMO

The application of X-ray imaging in military, industrial flaw detection, and medical examination is inseparable from the wide application of scintillator materials. In order to substitute for lead, lower costs, and reduce self-absorption, organic-inorganic hybrid lead-free perovskite scintillators are emerging as a new option. In this work, novel (TEA)2Zr1-xTexCl6 perovskite microcrystals (MCs) were successfully synthesized by a hydrothermal method, with Te4+ doping, which leads to yellow triplet-state self-trapped excitons emission. The emission peak of (TEA)2Zr1-xTexCl6 located at 605 nm under X-ray excitation, which was applied to X-ray imaging, shows a clear wiring structure inside the USB connector. The detection limit (DL) of 820 nGyair/s for (TEA)2Zr0.9Te0.1Cl6 is well below the dose rate corresponding to a standard medical X-ray diagnosis is 5.5 µGyair/s. This work opens up a new path for organic-inorganic hybrid lead-free scintillators.

5.
Adv Sci (Weinh) ; 10(34): e2305069, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37870173

RESUMO

Wavelength conversion based on hybrid inorganic-organic sensitized triplet-triplet annihilation upconversion (TTA-UC) is promising for applications such as photovoltaics, light-emitting-diodes, photocatalysis, additive manufacturing, and bioimaging. The efficiency of TTA-UC depends on the population of triplet excitons involved in triplet energy transfer (TET), the driving force in TET, and the coupling strength between the donor and acceptor. Consequently, achieving highly efficient TTA-UC necessitates the precise control of the electronic states of inorganic donors. However, conventional covalently bonded nanocrystals (NCs) face significant challenges in this regard. Herein, a novel strategy to exert control over electronic states is proposed, thereby enhancing TET and TTA-UC by incorporating ionic-bonded CsPbBr3 and lanthanide Ce3+ ions into composite NCs. These composite-NCs exhibit high photoluminescence quantum yield, extended single-exciton lifetime, quantum confinement, and uplifted energy levels. This engineering strategy of electronic states engendered a comprehensive impact, augmenting the population of triplet excitons participating in the TET process, enhancing coupling strength and the driving force, ultimately leading to an unconventional, dopant concentration-dependent nonlinear enhancement of UC efficiency. This work not only advances fundamental understanding of hybrid TTA-UC but also opens a door for the creation of other ionic-bonded composite NCs with tunable functionalities, promising innovations for next-generation optoelectronic applications.

6.
Adv Mater ; 35(52): e2306102, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37669761

RESUMO

Great research efforts are devoted to exploring the miniaturization of chip-scale coherent light sources possessing excellent lasing performance. Despite the indispensable role in Si photonics, SiO2 is generally considered not contributing to the starting up and operation of integrated lasers. Here, this work demonstrates an extraordinary-performance subwavelength-scale perovskite vertical cavity laser with all-transparent SiO2 cavity, whose cavity is ultra-simple and composed of only two parallel SiO2 plates. By introducing a ligand-assisted thermally co-evaporation strategy, highly luminescent perovskite film with high reproducibility and excellent optical gain is grown directly on SiO2 . Benefitting from their high-refractive-index contrast, low-threshold, high-quality factor, and single-mode lasing is achieved in subwavelength range of ≈120 nm, and verified by long-range coherence distance (115.6 µm) and high linear polarization degree (82%). More importantly, the subwavelength perovskite laser device could operate in water for 20 days without any observable degradation, exhibiting ultra-stable water-resistant performance. These findings would provide a simple but robust and reliable strategy for the miniaturized on-chip lasers compatible with Si photonics.

7.
Angew Chem Int Ed Engl ; 62(43): e202309319, 2023 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-37673793

RESUMO

Electroreduction of CO2 to multi-carbon (C2+ ) products is a promising approach for utilization of renewable energy, in which the interfacial water quantity is critical for both the C2+ product selectivity and the stability of Cu-based electrocatalytic sites. Functionalization of long-chain alkyl molecules on a catalyst surface can help to increase its stability, while it also tends to block the transport of water, thus inhibiting the C2+ product formation. Herein, we demonstrate the fine tuning of interfacial water by surface assembly of toluene on Cu nanosheets, allowing for sustained and enriched CO2 supply but retarded water transfer to catalytic surface. Compared to bare Cu with fast cathodic corrosion and long-chain alkyl-modified Cu with main CO product, the toluene assembly on Cu nanosheet surface enabled a high Faradaic efficiency of 78 % for C2+ and a partial current density of 1.81 A cm-2 . The toluene-modified Cu catalyst further exhibited highly stable CO2 -to-C2 H4 conversion of 400 h in a membrane-electrode-assembly electrolyzer, suggesting the attractive feature for both efficient C2+ selectivity and excellent stability.

8.
Sci Total Environ ; 905: 167162, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-37730066

RESUMO

Antibiotic resistance gene (ARG) spread in anthropogenic polluted soils is believed to be accelerated by the incidental inputs of antibiotics via fertilizing and irrigation, and endangering food and human health. However, due to the complex nature of substrates and uncertain microbial responses, the primary drivers of ARG dissemination remain unclear. To address this concern, the effects of antibiotic inputs on soil microbes and antibiotic resistance under simulated natural conditions was investigated in this study. Specifically, four flow-through reactors with gravity flow were established, and the oxytetracycline (OTC) a typical antibiotic in agricultural soils was studied at environmental concentrations (i.e. 0.1, 1 and 10 mg/kg) for 31 days. The vertical distribution and dissipation of OTC were profiled by measuring the residuals in layers over time. Correspondingly, the effects of antibiotic exposure on microbial communities and ARG abundances were studied. The results showed that the average exposure intensity of OTC in different soil layers ranged in 0.03-6.45 mg/kg, and resulted in different dissipation kinetics. In addition, top layer was found to be the main site of OTC reduction, where OTC dissipated at magnitude of 74.0-96.6 %, depending on the initial OTC concentration. OTC migration and dissipation resulted in the shift of community composition to the extent of 0.25-0.33 in terms of Bray-Curtis distance, which partially recovered over time. And the achievement of alternative community compositions was supposed to be largely affected by the microbial interaction. Along with the community changes, a short-term accumulation of resistance genes was detected, while the relative abundance of indicator ARGs, i.e. tetG and mexB, rising up to 10-fold higher than the initial, although eventually decayed. Collective findings of this study indicated that antibiotics at environmental concentrations might trigger extra microbial interactions and thereby reducing the demand for ARGs accumulation. It provided valuable understandings in the risk of antibiotic spillage, especially for the incident exposure at the environmentally relevant concentrations.


Assuntos
Microbiota , Oxitetraciclina , Humanos , Genes Bacterianos , Microbiologia do Solo , Antibacterianos/farmacologia , Resistência Microbiana a Medicamentos/genética , Solo , Esterco
9.
J Phys Chem Lett ; 14(35): 7903-7909, 2023 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-37643347

RESUMO

Miniaturized coherent light sources on the nanoscale are highly desired for on-chip photonics integration. However, when approaching the diffraction limit, the sub-wavelength-scale all-dielectric lasers are difficult to realize due to the trade-off between lasing performance and physical size. Especially for a thin-film laser, usually an externally complex cavity is required to provide the necessary optical feedback. Herein, we successfully shrink the MAPbBr3 perovskite thin-film laser to sub-wavelength scale (300 nm) with simplified cavity design using only an ultraviolet glue layer and a quartz glass. The morphology quality and the gain properties of the film are enhanced by introducing ionic liquid. Consequently, the stable and low-threshold single-mode laser with a highly linear polarization degree of 78.6% and a narrow line width of 0.35 nm is achieved under two-photon excitation. The excellent single-mode laser with sub-wavelength scale and ultrasimplified structure could provide a facile and versatile platform for future integrated optoelectronic devices.

10.
Adv Healthc Mater ; 12(27): e2300516, 2023 10.
Artigo em Inglês | MEDLINE | ID: mdl-37285596

RESUMO

Reactive oxygen species (ROS)-involved tumor therapeutic strategy, chemodynamic therapy (CDT), has attracted extensive research interest in the scientific community. However, the therapeutic effect of CDT is insufficient and unsustainable owing to the limited endogenous H2 O2 level in the tumor microenvironment. Here, peroxidase (POD)-like RuTe2 nanozyme with the immobilization of glucose oxidase (GOx) and allochroic 3,3',5,5'-tetramethylbenzidine (TMB) molecule have been synthesized to construct RuTe2 -GOx-TMB nanoreactors (RGT NRs) as cascade reaction systems for tumor-specific and self-replenishing cancer therapy. GOx in sequential nanocatalysts can effectively deplete glucose in tumor cells. Meanwhile, a sustainable supply of H2 O2 for subsequent Fenton-like reactions catalyzed by RuTe2 nanozyme is achieved in response to the mild acidic tumor microenvironment. Through this cascade reaction, highly toxic hydroxyl radicals (·OH) are produced, which can further oxidize TMB to trigger tumor-specific "turn-on" photothermal therapy (PTT). In addition, PTT and massive ROS can stimulate the tumor immune microenvironment and activate the systematic anti-tumor immune responses, exerting a notable effect on hindering tumor recurrence and metastasis. This study paves a promising paradigm for synergistic starvation therapy, PTT, and CDT cancer therapy with high efficiency.


Assuntos
Neoplasias , Humanos , Espécies Reativas de Oxigênio , Neoplasias/tratamento farmacológico , Glucose , Glucose Oxidase/uso terapêutico , Peroxidase , Microambiente Tumoral , Peróxido de Hidrogênio , Linhagem Celular Tumoral
11.
Opt Express ; 31(13): 22040-22054, 2023 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-37381287

RESUMO

Fourier-transform spectral imaging captures frequency-resolved images with high spectral resolution, broad spectral range, high photon flux, and low stray light. In this technique, spectral information is resolved by taking Fourier transformation of the interference signals of two copies of the incident light at different time delays. The time delay should be scanned at a high sampling rate beyond the Nyquist limit to avoid aliasing, at the price of low measurement efficiency and stringent requirements on motion control for time delay scan. Here we propose, what we believe to be, a new perspective on Fourier-transform spectral imaging based on a generalized central slice theorem analogous to computerized tomography, using an angularly dispersive optics decouples measurements of the spectral envelope and the central frequency. Thus, as the central frequency is directly determined by the angular dispersion, the smooth spectral-spatial intensity envelope is reconstructed from interferograms measured at a sub-Nyquist time delay sampling rate. This perspective enables high-efficiency hyperspectral imaging and even spatiotemporal optical field characterization of femtosecond laser pulses without a loss of spectral and spatial resolutions.

12.
Opt Express ; 31(12): 19777-19793, 2023 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-37381386

RESUMO

Ultrafast electron microbunch trains have broad applications in which the individual bunch length and the bunch-to-bunch interval are critical parameters that need to be precisely diagnosed. However, directly measuring these parameters remains challenging. This paper presents an all-optical method that simultaneously measures the individual bunch length and the bunch-to-bunch spacing through an orthogonal THz-driven streak camera. For a 3 MeV electron bunch train, the simulation indicates that the temporal resolution of individual bunch length and the bunch-to-bunch spacing is 2.5 fs and 1 fs, respectively. Through this method, we expect to open a new chapter in the temporal diagnostic of electron bunch trains.

13.
Front Neurol ; 14: 1209701, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37234780

RESUMO

[This corrects the article DOI: 10.3389/fneur.2023.1100933.].

14.
Brain Pathol ; 33(4): e13160, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-37186490

RESUMO

The pathological diagnosis of intracranial germinoma (IG), oligodendroglioma, and low-grade astrocytoma on intraoperative frozen section (IFS) and hematoxylin-eosin (HE)-staining section directly determines patients' treatment options, but it is a difficult task for pathologists. We aimed to investigate whether whole-slide imaging (WSI)-based deep learning can contribute new precision to the diagnosis of IG, oligodendroglioma, and low-grade astrocytoma. Two types of WSIs (500 IFSs and 832 HE-staining sections) were collected from 379 patients at multiple medical centers. Patients at Center 1 were split into the training, testing, and internal validation sets (3:1:1), while the other centers were the external validation sets. First, we subdivided WSIs into small tiles and selected tissue tiles using a tissue tile selection model. Then a tile-level classification model was established, and the majority voting method was used to determine the final diagnoses. Color jitter was applied to the tiles so that the deep learning (DL) models could adapt to the variations in the staining. Last, we investigated the effectiveness of model assistance. The internal validation accuracies of the IFS and HE models were 93.9% and 95.3%, respectively. The external validation accuracies of the IFS and HE models were 82.0% and 76.9%, respectively. Furthermore, the IFS and HE models can predict Ki-67 positive cell areas with R2 of 0.81 and 0.86, respectively. With model assistance, the IFS and HE diagnosis accuracy of pathologists improved from 54.6%-69.7% and 53.5%-83.7% to 87.9%-93.9% and 86.0%-90.7%, respectively. Both the IFS model and the HE model can differentiate the three tumors, predict the expression of Ki-67, and improve the diagnostic accuracy of pathologists. The use of our model can assist clinicians in providing patients with optimal and timely treatment options.


Assuntos
Astrocitoma , Neoplasias Encefálicas , Aprendizado Profundo , Oligodendroglioma , Humanos , Oligodendroglioma/diagnóstico por imagem , Oligodendroglioma/cirurgia , Antígeno Ki-67 , Neuropatologia , Neoplasias Encefálicas/diagnóstico por imagem , Neoplasias Encefálicas/cirurgia
15.
Front Immunol ; 14: 1168244, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37122727

RESUMO

Objective: This meta-analysis aimed to evaluate the efficacy and safety of PD-1/PD-L1 inhibitors in patients with glioma. Methods: PubMed, EMBASE, Web of Science, and the Cochrane library were searched from inception to January 2023 without language restriction. Primary outcomes included overall survival (OS), progression-free survival (PFS), objective response rate (ORR), and adverse events (AEs). The risk of bias was assessed by subgroup analysis, sensitivity analysis, and publication bias, including funnel plot, Egger's test, and Begg's test. Results: A total of 20 studies involving 2,321 patients were included in this meta-analysis. In the analysis of the included phase III clinical trials, the forest plot showed that PD-1/PD-L1 inhibitors did not improve the OS (HR=1.15, 95% CI: 1.03-1.29, P=0.02, I2 = 14%) and PFS (HR=1.43, 95% CI: 1.03-1.99, P=0.03, I2 = 87%). In the single-arm analysis, the forest plot demonstrated that the 6-month OS was 71% (95% CI: 57%-83%, I2 = 92%), 1-year OS was 43% (95% CI: 33%-54%, I2 = 93%), and the 2-year OS was 27% (95% CI: 13%-44%, I2 = 97%). The pooled estimate of the median OS was 8.85 months (95% CI: 7.33-10.36, I2 = 91%). Furthermore, the result indicated that the 6-month PFS was 28% (95% CI: 18%-40%, I2 = 95%), 1-year PFS was 15% (95% CI: 8%-23%, I2 = 92%), and the 18-month PFS was 10% (95% CI: 3%-20%, I2 = 93%). The pooled estimate of the median PFS was 3.72 months (95% CI: 2.44-5.00, I2 = 99%). For ORR, the pooled estimate of ORR was 10% (95% CI: 2%-20%, I2 = 88%). We further analyzed the incidence of PD-1/PD-L1 inhibitor-related AEs, and the pooled incidence of AEs was 70% (95% CI: 58%-81%, I2 = 94%). The incidence of AEs ≥ grade 3 was 19% (95% CI: 11%-30%, I2 = 94%). The funnel plot for the median PFS and median OS was symmetric with no significant differences in Egger's test and Begg's test. The sensitivity analysis revealed that our results were stable and reliable. Conclusion: The results of this meta-analysis suggest that anti-PD-1/PD-L1 therapy is relatively safe but could not prolong survival in glioma. More randomized controlled trials are needed to confirm our results. Systematic review registration: https://www.crd.york.ac.uk/prospero/, identifier CRD42023396057.


Assuntos
Antígeno B7-H1 , Glioma , Inibidores de Checkpoint Imunológico , Humanos , Glioma/tratamento farmacológico , Inibidores de Checkpoint Imunológico/uso terapêutico
16.
Front Neurol ; 14: 1100933, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37064206

RESUMO

Background: A deep learning (DL) model based on representative biopsy tissues can predict the recurrence and overall survival of patients with glioma, leading to optimized personalized medicine. This research aimed to develop a DL model based on hematoxylin-eosin (HE) stained pathological images and verify its diagnostic accuracy. Methods: Our study retrospectively collected 162 patients with glioma and randomly divided them into a training set (n = 113) and a validation set (n = 49) to build a DL model. The HE-stained slide was segmented into a size of 180 × 180 pixels without overlapping. The patch-level features were extracted by the pre-trained ResNet50 to predict the recurrence and overall survival. Additionally, a light-strategy was introduced where low-size digital biopsy images with clinical information were inputted into the DL model to ensure minimum memory occupation. Results: Our study extracted 512 histopathological features from the HE-stained slides of each glioma patient. We identified 36 and 18 features as significantly related to disease-free survival (DFS) and overall survival (OS), respectively, (P < 0.05) using the univariate Cox proportional-hazards model. Pathomics signature showed a C-index of 0.630 and 0.652 for DFS and OS prediction, respectively. The time-dependent receiver operating characteristic (ROC) curves, along with nomograms, were used to assess the diagnostic accuracy at a fixed time point. In the validation set (n = 49), the area under the curve (AUC) in the 1- and 2-year DFS was 0.955 and 0.904, respectively, and the 2-, 3-, and 5-year OS were 0.969, 0.955, and 0.960, respectively. We stratified the patients into low- and high-risk groups using the median hazard score (0.083 for DFS and-0.177 for OS) and showed significant differences between these groups (P < 0.001). Conclusion: Our results demonstrated that the DL model based on the HE-stained slides showed the predictability of recurrence and survival in patients with glioma. The results can be used to assist oncologists in selecting the optimal treatment strategy in clinical practice.

17.
Nat Commun ; 14(1): 917, 2023 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-36801865

RESUMO

The formation of polaron, i.e., the strong coupling process between the carrier and lattice, is considered to play a crucial role in benefiting the photoelectric performance of hybrid organic-inorganic halide perovskites. However, direct observation of the dynamical formation of polarons occurring at time scales within hundreds of femtoseconds remains a technical challenge. Here, by terahertz emission spectroscopy, we demonstrate the real-time observation of polaron formation process in FAPbI3 films. Two different polaron resonances interpreted with the anharmonic coupling emission model have been studied: P1 at ~1 THz relates to the inorganic sublattice vibration mode and the P2 at ~0.4 THz peak relates to the FA+ cation rotation mode. Moreover, P2 could be further strengthened than P1 by pumping the hot carriers to the higher sub-conduction band. Our observations could open a door for THz emission spectroscopy to be a powerful tool in studying polaron formation dynamics in perovskites.

18.
Environ Sci Technol ; 57(7): 2981-2991, 2023 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-36749182

RESUMO

The interactions between dissolved organic matter (DOM) and iron (Fe) oxyhydroxide are crucial in regulating the biogeochemical cycling of nutrients and elements, including the preservation of carbon in soils. The mechanisms of DOM molecular assembly on mineral surfaces have been extensively studied at the mesoscale with equilibrium experiments, yet the molecular-level evolution of the DOM-mineral interface under dynamic interaction conditions is not fully understood. Here, we designed a microfluidic reactor coupled with an online solid phase extraction (SPE)-LC-QTOF MS system to continually monitor the changes in DOM composition during flowing contact with Fe oxyhydroxide at circumneutral pH, which simulates soil minerals interacting with constant DOM input. Time-series UV-visible absorption spectra and mass spectrometry data showed that after aromatic DOM moieties were first preferentially sequestered by the pristine Fe oxyhydroxide surface, the adsorption of nonaromatic DOM molecules with greater hydrophobicity, lower acidity, and lower molecular weights (<400) from new DOM solutions was favored. This is accompanied by a transition from mineral surface chemistry-dominated adsorption to organic-organic interaction-dominated adsorption. These findings provide direct molecular-level evidence to the zonal model of DOM assembly on mineral surfaces by taking the dynamics of interfacial interactions into consideration. This study also shows that coupled microfluidics and online high-resolution mass spectrometry (HRMS) system is a promising experimental platform for probing microscale environmental carbon dynamics by integrating in situ reactions, sample pretreatment, and automatic analysis.


Assuntos
Matéria Orgânica Dissolvida , Microfluídica , Espectrometria de Massas , Minerais/química , Solo/química , Carbono
19.
Sci Bull (Beijing) ; 67(10): 1042-1048, 2022 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-36546248

RESUMO

Although many catalysts have been reported for the CO2 electroreduction to C1 or C2 chemicals, the insufficient understanding of fundamental correlations among different products still hinders the development of universal catalyst design strategies. Herein, we first discover that the surface *CO coverage is stable over a wide potential range and reveal a linear correlation between the partial current densities of CH4 and C2 products in this potential range, also supported by the theoretical kinetic analysis. Based on the mechanism that *CHO is the common intermediate in the formation of both CH4 (*CHO â†’ CH4) and C2 (*CHO + *CO â†’ C2), we then unravel that this linear correlation is universal and the slope can be varied by tuning the surface *H or *CO coverage to promote the selectivity of CH4 or C2 products, respectively. As proofs-of-concept, using carbon-coated Cu particles, the surface *H coverage can be increased to enhance CH4 production, presenting a high CO2-to-CH4 Faradaic efficiency ( [Formula: see text] ∼52%) and an outstanding CH4 partial current density of -337 mA cm-2. On the other hand, using an Ag-doped Cu catalyst, the CO2RR selectivity is switched to the C2 pathway, with a substantially promoted [Formula: see text] of 79% and a high partial current density of -421 mA cm-2. Our discovery of tuning intermediate coverages suggests a powerful catalyst design strategy for different CO2 electroreduction pathways.

20.
J Phys Chem Lett ; 13(49): 11398-11404, 2022 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-36458835

RESUMO

Two-dimensional transition metal dichalcogenides (TMDs) have great potential application for seamless on-chip integration due to their strong photon-electron-spin-valley coupling. However, the contact-free measurements of the valley-coupled photocurrent in TMDs is still challenging. Here, ultrafast terahertz emission spectroscopy is employed to investigate the photocurrent dynamics in monolayer WSe2, and an interface-induced drift current amplification is found in the WSe2/Si heterostructure. The amplification of terahertz emission comes from the photocurrent enlarged by band bending in the WSe2 and Si junction, and the amplification ratio increase further near the valley resonant transition of WSe2. In addition, the valley-momentum locked photocurrent in the WSe2/Si heterostructure reserves the same chirality with monolayer WSe2 at room temperature. These findings could provide a new method for manipulating valley-momentum locked photocurrent by photon helicity and open new avenues for TMD-based valley-polarized terahertz emission devices.

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