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1.
ACS Nano ; 18(20): 12808-12819, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38717026

RESUMO

Considerable progress has already been made in sweat sensors based on electrochemical methods to realize real-time monitoring of biomarkers. However, realizing long-term monitoring of multiple targets at the atomic level remains extremely challenging, in terms of designing stable solid contact (SC) interfaces and fully integrating multiple modules for large-scale applications of sweat sensors. Herein, a fully integrated wristwatch was designed using mass-manufactured sensor arrays based on hierarchical multilayer-pore cross-linked N-doped porous carbon coated by reduced graphene oxide (NPCs@rGO-950) microspheres with high hydrophobicity as core SC, and highly selective monitoring simultaneously for K+, Na+, and Ca2+ ions in human sweat was achieved, exhibiting near-Nernst responses almost without forming an interfacial water layer. Combined with computed tomography, solid-solid interface potential diffusion simulation results reveal extremely low interface diffusion potential and high interface capacitance (598 µF), ensuring the excellent potential stability, reversibility, repeatability, and selectivity of sensor arrays. The developed highly integrated-multiplexed wristwatch with multiple modules, including SC, sensor array, microfluidic chip, signal transduction, signal processing, and data visualization, achieved reliable real-time monitoring for K+, Na+, and Ca2+ ion concentrations in sweat. Ingenious material design, scalable sensor fabrication, and electrical integration of multimodule wearables lay the foundation for developing reliable sweat-sensing systems for health monitoring.


Assuntos
Eletrólitos , Grafite , Suor , Dispositivos Eletrônicos Vestíveis , Suor/química , Humanos , Grafite/química , Eletrólitos/química , Íons/análise , Cálcio/análise , Sódio/análise , Sódio/química , Técnicas Biossensoriais/instrumentação , Técnicas Eletroquímicas/instrumentação , Técnicas Eletroquímicas/métodos , Potássio/análise
2.
Anal Chem ; 96(22): 9069-9077, 2024 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-38749062

RESUMO

Solid contact (SC) calcium ion-selective electrodes (Ca2+-ISEs) have been widely applied in the analysis of water quality and body fluids by virtue of the unique advantages of easy operation and rapid response. However, the potential drift during the long-term stability test hinders their further practical applications. Designing novel redox SC layers with large capacitance and high hydrophobicity is a promising approach to stabilize the potential stability, meanwhile, exploring the transduction mechanism is also of great guiding significance for the precise design of SC layer materials. Herein, flower-like copper sulfide (CunS-50) composed of nanosheets is meticulously designed as the redox SC layer by modification with the surfactant (CTAB). The CunS-50-based Ca2+-ISE (CunS-50/Ca2+-ISE) demonstrates a near-Nernstian slope of 28.23 mV/dec for Ca2+ in a wide activity linear range of 10-7 to 10-1 M, with a low detection limit of 3.16 × 10-8 M. CunS-50/Ca2+-ISE possesses an extremely low potential drift of only 1.23 ± 0.13 µV/h in the long-term potential stability test. Notably, X-ray absorption fine-structure (XAFS) spectra and electrochemical experiments are adopted to elucidate the transduction mechanism that the lipophilic anion (TFPB-) participates in the redox reaction of CunS-50 at the solid-solid interface of ion-selective membrane (ISM) and redox inorganic SC layer (CunS-50), thereby promoting the generation of free electrons to accelerate ion-electron transduction. This work provides an in-depth comprehension of the transduction mechanism of the potentiometric response and an effective strategy for designing redox materials of ion-electron transduction triggered by lipophilic anions.

3.
Anal Chim Acta ; 1306: 342612, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38692793

RESUMO

Despite the widespread utilization of variable valence metals in electrochemistry, it is still a formidable challenge to enhance the valence conversion efficiency to achieve excellent catalytic activity without introducing heterophase elements. Herein, the in-situ precipitation of Co particles on Co2VO4 not only enhanced the concentration of oxygen vacancies (Ov) but also generated a greater number of low-valence metals, thereby enabling efficient reduction towards Hg(II). The electroanalysis results demonstrate that the sensitivity of Co/Co2VO4 towards Hg(II) was measured at an impressive value of 1987.74 µA µM-1 cm-2, significantly surpassing previously reported results. Further research reveals that Ov acted as the main adsorption site to capture Hg(II). The redox reactions of Co2+/Co3+ and V3+/V4+ played a synergistic role in the reduction of Hg(II), accompanied by the continuous supply of electrons from zero-valent Co to expedite the valence cycle. The Co/Co2VO4/GCE presented remarkable selectivity towards Hg(II), with excellent stability, reproducibility, and anti-interference capability. The electrode also exhibited minimal sensitivity fluctuations towards Hg(II) in real water samples, underscoring its practicality for environmental applications. This study elucidates the mechanism underlying the surface redox reaction of metal oxides facilitated by zero-valent metals, providing us with new strategies for further design of efficient and practical sensors.

4.
Anal Chem ; 96(13): 5232-5241, 2024 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-38447030

RESUMO

Although utilizing nanomaterial-modified electrodes for lead ion detection has achieved great success, most of them are carried out under acidic conditions and ignore the variation of Pb(II) speciation at different pH conditions, leading to the potential inaccuracy of Pb(II) detection in a neutral natural water environment. Thus, designing a novel catalyst with high accuracy for the detection of various forms of the total amount of Pb(II) (Pb2+ and Pb(OH)+) in neutral waters is significant. Herein, Pt nanoclusters (Pt NCs) were elaborately constructed and stabilized on the Co single-atom-doped g-C3N4 with abundant N vacancies (Pt NCs/VN-C3N4), which achieved the ultrasensitive detection (102.16 µM µA-1) of Pb(II) in neutral conditions. The dynamic simulation and theoretical calculations reveal that the parallel deposition of Pb2+ and Pb(OH)+ occurs on the electrode surface modified by Pt NCs/VN-C3N4, and the current peaks of Pb(II) are cocontributed by Pb2+ and Pb(OH)+ species. An "electron inverse" phenomenon in Pt NCs/VN-C3N4 from the VN-C3N4 substrate to Pt NCs endows Pt NCs in an electron-rich state, serving as active centers to promote rapid and efficient reduction for both Pb2+ and Pb(OH)+, facilitating the accurate detection of the total amount of Pb(II) in all forms in the actual water environment.

5.
Bioresour Technol ; 399: 130561, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38460558

RESUMO

During the wastewater treatment and resource recovery process by attached microalgae, the chemical oxygen demand (COD) can cause biotic contamination in algal culture systems, which can be mitigated by adding an appropriate dosage of antibiotics. The transport of COD and additive antibiotic (chloramphenicol, CAP) in algal biofilms and their influence on algal physiology were studied. The results showed that COD (60 mg/L) affected key metabolic pathways, such as photosystem II and oxidative phosphorylation, improved biofilm autotrophic and heterotrophic metabolic intensities, increased nutrient demand, and promoted biomass accumulation by 55.9 %, which was the most suitable COD concentration for attached microalgae. CAP (5-10 mg/L) effectively stimulated photosynthetic pigment accumulation and nutrient utilization in pelagic microalgal cells. In conclusion, controlling the COD concentration (approximately 60 mg/L) in the medium and adding the appropriate CAP concentration (5-10 mg/L) are conducive to improving attached microalgal biomass production and resource recovery potential from wastewater.


Assuntos
Microalgas , Microalgas/metabolismo , Cloranfenicol/metabolismo , Análise da Demanda Biológica de Oxigênio , Águas Residuárias , Biofilmes , Biomassa , Nitrogênio/metabolismo
6.
Analyst ; 149(7): 2097-2102, 2024 Mar 25.
Artigo em Inglês | MEDLINE | ID: mdl-38421038

RESUMO

In this work, we developed a rapid and sensitive label-free ratiometric fluorescent (FL) probe for the detection of bleomycin (BLM). The probe consists of a DNA sequence (D6) and two fluorophore groups, 2-amino-5,6,7-trimethyl-1,8-naphthalene (ATMND) and SYBR Green I (SGI). The D6 sequence could be folded into a three-way junction structure containing a C-C mismatch position in the junction pocket. The unique "Y" structure not only could entrap ATMND in the mismatch pocket with high affinity, leading to FL quenching at 408 nm, but also embed SGI in the grooves of the double-stranded portion, resulting in FL enhancement at 530 nm. In the presence of BLM-Fe(II), the "Y" structure of D6 was destroyed due to the specific cleavage of the BLM recognition site, the 5'-GT-3' site in D6. This caused the release of ATMND and SGI and thus the ratiometric signal change of FL enhancement by ATMND and FL quenching by SGI. Under optimal conditions, the ratiometric probe exhibited a linear correlation between the intensity ratio of F408/F530 and the concentration of BLM in the range of 0.5-1000 nM, with a detection limit of 0.2 nM. In addition, the probe was applied to detect BLM in human serum samples with satisfactory results, indicating its good clinical application potential.


Assuntos
Benzotiazóis , Bleomicina , Diaminas , Corantes Fluorescentes , Quinolinas , Humanos , Corantes Fluorescentes/química , Limite de Detecção , Espectrometria de Fluorescência/métodos
7.
Ann Plast Surg ; 92(1S Suppl 1): S27-S32, 2024 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-38285992

RESUMO

BACKGROUND: Patients with traumatic brain injuries (TBIs) often experience concurrent facial bone fractures. In 2021, a prediction model with 10 variables was published and precisely predicted concomitant facial fractures in TBI patients. Herein, external validation and simplification of this model was performed. METHODS: Traumatic brain injury patients treated at a major referral trauma center were retrospectively reviewed for 1 year. The original prediction model (published in 2021), which was developed from a rural level II trauma center, was applied for external validation. A new and simplified model from our level I trauma center was developed and backwardly validated by rural level II trauma center data. RESULTS: In total, 313 TBI patients were enrolled; 101 (32.3%) had concomitant facial fractures. When the previous prediction model was applied to the validation cohort, it achieved acceptable discrimination, with an area under the receiver operating characteristic curve (AUC) of 0.713 and good precision, with a Brier score of 0.083. A new and simplified model with 6 variables (age, tooth rupture, epistaxis, facial lesion, eye injury, and intracranial hemorrhage) was created with excellent discrimination (AUC = 0.836) and good precision (Brier score of 0.055). The backward validation of this new model also showed excellent discrimination in the cohort used to develop the original model (AUC = 0.875). CONCLUSION: The original model provides an acceptable and reproducible prediction of concomitant facial fractures among TBI patients. A simplified model with fewer variables and the same accuracy could be applied in the emergency department and at higher- and lower-level trauma centers.


Assuntos
Lesões Encefálicas Traumáticas , Fraturas Cranianas , Humanos , Estudos Retrospectivos , Fraturas Cranianas/complicações , Fraturas Cranianas/diagnóstico , Lesões Encefálicas Traumáticas/complicações , Lesões Encefálicas Traumáticas/diagnóstico , Curva ROC , Centros de Traumatologia
8.
Int Immunopharmacol ; 128: 111464, 2024 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-38224627

RESUMO

Colorectal cancer (CRC) is a leading cause of cancer-related deaths worldwide, characterized by molecular and clinical heterogeneity. Interleukin (IL)-27, a heterodimeric cytokine composed of p28 and EBI3 subunits, has been reported to exert potent antitumor activity in several cancer models. However, the precise role of IL-27 in the pathogenesis of CRC remains unclear. Here, we show that during the azoxymethane (AOM)/dextran sodium sulfate (DSS)-induced CRC development, IL-27p28 levels are dramatically increased in peripheral blood and tumor tissues, and the cytokine is mainly produced by tumor-infiltrating myeloid cells. IL-27p28 deficient mice display tumor resistances in both inflammation-associated CRC model and syngeneic MC38 colon cancer model. Administration with IL-27p28 neutralizing antibody also reduces the tumor formation in AOM/DSS-treated mice. Mechanically, CD8+ T cells in IL-27p28-/- mice exhibit enhanced tumor infiltration and cytotoxicity, which can be largely attributed to activation of the Akt/mTOR signaling pathway. Furthermore, selective depletion of CD8+ T cells in IL-27p28-/- mice markedly accelerate tumor growth and almost abrogate the protective effects of IL-27p28 deficiency. Most interestingly, the expression of IL-27p28 is also upregulated in tumor tissues of CRC patients and those with high expression of IL-27p28 tend to have a poorer overall survival. Our results suggest that loss of IL-27p28 suppresses colorectal tumorigenesis by augmenting CD8+ T cell-mediated anti-tumor immunity. Targeting IL-27p28 could be developed as a novel strategy for the treatment of colorectal cancers.


Assuntos
Colite , Neoplasias do Colo , Neoplasias Colorretais , Animais , Humanos , Camundongos , Azoximetano , Carcinogênese , Linfócitos T CD8-Positivos/metabolismo , Colite/induzido quimicamente , Neoplasias Colorretais/patologia , Citocinas/metabolismo , Sulfato de Dextrana/farmacologia , Camundongos Endogâmicos C57BL , Transdução de Sinais
9.
ACS Sens ; 9(1): 415-423, 2024 01 26.
Artigo em Inglês | MEDLINE | ID: mdl-38154098

RESUMO

The high selectivity and fast ion response of all-solid sodium ion selective electrodes were widely applied in human sweat analysis. However, the potential drift due to insufficient interfacial capacitance leads to the deterioration of its stability and ultimately affects the potential accuracy of ion analysis. Designing a novel ion-electron transduction layer between the electrode and the ion selective membrane is an effective method to stabilize the interfacial potential. Herein, the SnS2-MoS2 heterojunction material was constructed by doping Sn in MoS2 nanosheets and used as the ion electron transduction layers of an all-solid sodium ion selective electrode for the first time, achieving the stable and efficient detection of Na+ ions. The proposed electrode exhibited a Nernst slope of 57.86 mV/dec for the detection of Na+ ions with a detection limit of 10-5.7 M in the activity range of 10-6-10-1 M. Via the electronic interaction at the heterojunction interfaces between SnS2 and MoS2 materials, the micro-nanostructure of the SnS2-MoS2 heterojunction was changed and SnS2-MoS2 as the ion-electron transduction layer acquired excellent capacitance (699 µF) and hydrophobicity (132°), resulting in a long-term potential stability of 1.37 µV/h. It was further proved that the large capacitance and high hydrophobicity of the ion-electron transduction layer are primary reasons for the excellent stability of the all-solid sodium ion selective electrode toward Na+ ions.


Assuntos
Eletrodos Seletivos de Íons , Molibdênio , Humanos , Elétrons , Capacitância Elétrica , Íons
10.
Zool Res ; 45(1): 39-54, 2024 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-38114432

RESUMO

The dynamics of animal social structures are heavily influenced by environmental patterns of competition and cooperation. In folivorous colobine primates, prevailing theories suggest that larger group sizes should be favored in rainforests with a year-round abundance of food, thereby reducing feeding competition. Yet, paradoxically, larger groups are frequently found in high-altitude or high-latitude montane ecosystems characterized by a seasonal scarcity of leaves. This contradiction is posited to arise from cooperative benefits in heterogeneous environments. To investigate this hypothesis, we carried out a six-year field study on two neighboring groups of golden snub-nosed monkey ( Rhinopithecus roxellana), a species representing the northernmost distribution of colobine primates. Results showed that the groups adjusted their movement and habitat selection in response to fluctuating climates and spatiotemporal variability of resources, indicative of a dynamic foraging strategy. Notably, during the cold, resource-scarce conditions in winter, the large group occupied food-rich habitats but did not exhibit significantly longer daily travel distances than the smaller neighboring group. Subsequently, we compiled an eco-behavioral dataset of 52 colobine species to explore their evolutionary trajectories. Analysis of this dataset suggested that the increase in group size may have evolved via home range expansion in response to the cold and heterogeneous climates found at higher altitudes or latitudes. Hence, we developed a multi-benefits framework to interpret the formation of larger groups by integrating environmental heterogeneity. In cold and diverse environments, even smaller groups require larger home ranges to meet their dynamic survival needs. The spatiotemporal distribution of high-quality resources within these expanded home ranges facilitates more frequent interactions between groups, thereby encouraging social aggregation into larger groups. This process enhances the benefits of collaborative actions and reproductive opportunities, while simultaneously optimizing travel costs through a dynamic foraging strategy.


Assuntos
Colobinae , Presbytini , Animais , Ecossistema , Colobinae/fisiologia , Clima , China
11.
Int J Biol Macromol ; 258(Pt 1): 128880, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38141713

RESUMO

TGA transcription factors (TFs), belonging to the D clade of the basic region leucine zipper (bZIP) family, exhibit a specific ability to recognize and bind to regulatory elements with TGACG as the core recognition sequence, enabling the regulation of target gene expression and participation in various biological regulatory processes. In plant growth and development, TGA TFs influence organ traits and phenotypes, including initial root length and flowering time. They also play a vital role in responding to abiotic stresses like salt, drought, and cadmium exposure. Additionally, TGA TFs are involved in defending against potential biological stresses, such as fungal bacterial diseases and nematodes. Notably, TGA TFs are sensitive to the oxidative-reductive state within plants and participate in pathways that aid in the elimination of reactive oxygen species (ROS) generated during stressful conditions. TGA TFs also participate in multiple phytohormonal signaling pathways (ABA, SA, etc.). This review thoroughly examines the roles of TGA TFs in plant growth, development, and stress response. It also provides detailed insights into the mechanisms underlying their involvement in physiological and pathological processes, and their participation in plant hormone signaling. This multifaceted exploration distinguishes this review from others, offering a comprehensive understanding of TGA TFs.


Assuntos
Fatores de Transcrição de Zíper de Leucina Básica , Fatores de Transcrição , Fatores de Transcrição/genética , Fatores de Transcrição de Zíper de Leucina Básica/genética , Proteínas de Plantas/genética , Reguladores de Crescimento de Plantas , Plantas/metabolismo , Estresse Fisiológico/genética , Regulação da Expressão Gênica de Plantas
12.
Anal Chem ; 96(1): 179-187, 2024 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-38100653

RESUMO

Achieving accurate detection of different speciations of heavy metal ions (HMIs) in an aqueous solution is an urgent problem due to the different bioavailabilities and physiological toxicity. Herein, we nominated a novel strategy to detect HCrO4- and Cr(OH)2+ at a trace level via the electrochemical sensitive surface constructed by Co3O4-rGO modified with amino and carboxyl groups, which revealed that the interactions between distinct functional groups and different oxygen-containing groups of target ions are conducive to the susceptible and anti-interference detection. The detection sensitivities of 19.46 counts µg-1 L for HCrO4- and 13.44 counts µg-1 L for Cr(OH)2+ were obtained under optimal conditions, while the limits of detection were 0.10 and 0.12 µg L-1, respectively. Satisfactory anti-interference and actual water sample analysis results were obtained. A series of advanced optical techniques like X-ray photoelectron spectroscopy, X-ray absorption near-edge structure technology, and density functional theory calculations under an electric field demonstrated that chemical interactions between groups contribute more to the fixation of target ions than electrical attraction alone. The presence of oxygen-containing groups distinct from simple ionic forms was a critical factor in the selectivity and anti-interference detection. Furthermore, the valence cycle of Co(II)/(III) synergistically boosted the detection performance. This research provides a promising tactic from the microscopic perspective of groups' interactions to accomplish the precise speciation analysis of HMIs in the water environment.

13.
Mikrochim Acta ; 190(12): 487, 2023 11 27.
Artigo em Inglês | MEDLINE | ID: mdl-38010451

RESUMO

A new ratiometric fluorescent probe for efficient determination of ALP was developed. The probe was constructed by combining Ce3+-crosslinked copper nanoclusters (Ce3+-CuNCs) which exhibit the aggregation-induced emission (AIE) feature with carbon dots (CDs). The introduction of phosphate (Pi) induced the generation of CePO4 precipitation, resulting in significant decrease of fluorescence emission of CuNCs at 634 nm. At the same time, the fluorescence of CDs at 455 nm was obviously enhanced, thus generating ratiometric fluorescence response. Based on the fact that the hydrolysis of pyrophosphate (PPi) by ALP can produce Pi, the CD/Ce3+-CuNCs ratiometric probe was successfully used to determine ALP. A good linear relationship between the ratiometric value of F455/F634 and ALP concentrations ranging from 0.2 to 80 U·L- 1 was obtained, with a low detection limit of 0.1 U·L- 1. The ratiometric responses of the probe resulted in the visible fluorescence color change from orange red to blue with the increase of ALP concentration. The smartphone-based RGB recognition of the fluorescent sample images was used for ALP quantitative determination. A novel ratiometric fluorescent system based on Ce3+-CuNCs with AIE feature and CDs were constructed for efficient detection of ALP.


Assuntos
Pontos Quânticos , Cobre , Fosfatase Alcalina , Carbono , Fluorescência
14.
Artigo em Inglês | MEDLINE | ID: mdl-37824318

RESUMO

Effective spatio-temporal modeling as a core of video representation learning is challenged by complex scale variations in spatio-temporal cues in videos, especially different visual tempos of actions and varying spatial sizes of moving objects. Most of the existing works handle complex spatio-temporal scale variations based on input-level or feature-level pyramid mechanisms, which, however, rely on expensive multistream architectures or explore multiscale spatio-temporal features in a fixed manner. To effectively capture complex scale dynamics of spatio-temporal cues in an efficient way, this article proposes a single-stream architecture (SS-Arch.) with single-input namely, adaptive multi-granularity spatio-temporal network (AMS-Net) to model adaptive multi-granularity (Multi-Gran.) Spatio-temporal cues for video action recognition. To this end, our AMS-Net proposes two core components, namely, competitive progressive temporal modeling (CPTM) block and collaborative spatio-temporal pyramid (CSTP) module. They, respectively, capture fine-grained temporal cues and fuse coarse-level spatio-temporal features in an adaptive manner. It admits that AMS-Net can handle subtle variations in visual tempos and fair-sized spatio-temporal dynamics in a unified architecture. Note that our AMS-Net can be flexibly instantiated based on existing deep convolutional neural networks (CNNs) with the proposed CPTM block and CSTP module. The experiments are conducted on eight video benchmarks, and the results show our AMS-Net establishes state-of-the-art (SOTA) performance on fine-grained action recognition (i.e., Diving48 and FineGym), while performing very competitively on widely used Something-Something and Kinetics.

15.
World J Surg ; 47(12): 3116-3123, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37851065

RESUMO

PURPOSE: This study aimed to validate the previously reported association between delayed bladder repair and increased infection rates using the National Trauma Data Bank (NTDB). METHODS: Bladder injury patients with bladder repair in the NTDB from 2013 to 2015 were included. Propensity score matching (PSM) was used to compare mortality, infection rates, and hospital length of stay (LOS) between patients who underwent bladder repair within 24 h and those who underwent repair after 24 h. Linear regression and multivariate logistic regression analyses were also performed. RESULTS: A total of 1658 patients were included in the study. Patients who underwent bladder repair after 24 h had significantly higher infection rates (5.4% vs. 1.2%, p = 0.032) and longer hospital LOS (17.1 vs. 14.0 days, p = 0.032) compared to those who underwent repair within 24 h after a well-balanced 1:1 PSM (N = 166). Linear regression analysis showed a positive correlation between time to bladder repair and hospital LOS for patients who underwent repair after 24 h (B-value = 0.093, p = 0.034). Multivariate logistic regression analysis indicated that bladder repair after 24 h increased the risk of infection (odds = 3.162, p = 0.018). Subset analyses were performed on patients who underwent bladder repairs within 24 h and were used as a control group. These analyses showed that the time to bladder repair did not significantly worsen outcomes. CONCLUSIONS: Delayed bladder repair beyond 24 h increases the risk of infection and prolongs hospital stays. Timely diagnosis and surgical intervention remain crucial for minimizing complications in bladder injury patients.


Assuntos
Traumatismos Abdominais , Traumatismos Torácicos , Humanos , Bexiga Urinária/cirurgia , Tempo de Internação , Procedimentos Cirúrgicos Urológicos , Resultado do Tratamento , Estudos Retrospectivos
16.
IEEE Trans Pattern Anal Mach Intell ; 45(12): 15802-15819, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37782579

RESUMO

Global covariance pooling (GCP) as an effective alternative to global average pooling has shown good capacity to improve deep convolutional neural networks (CNNs) in a variety of vision tasks. Although promising performance, it is still an open problem on how GCP (especially its post-normalization) works in deep learning. In this paper, we make the effort towards understanding the effect of GCP on deep learning from an optimization perspective. Specifically, we first analyze behavior of GCP with matrix power normalization on optimization loss and gradient computation of deep architectures. Our findings show that GCP can improve Lipschitzness of optimization loss and achieve flatter local minima, while improving gradient predictiveness and functioning as a special pre-conditioner on gradients. Then, we explore the effect of post-normalization on GCP from the model optimization perspective, which encourages us to propose a simple yet effective normalization, namely DropCov. Based on above findings, we point out several merits of deep GCP that have not been recognized previously or fully explored, including faster convergence, stronger model robustness and better generalization across tasks. Extensive experimental results using both CNNs and vision transformers on diversified vision tasks provide strong support to our findings while verifying the effectiveness of our method.

17.
Chem Sci ; 14(36): 9678-9688, 2023 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-37736653

RESUMO

Single-atom catalysts have been extensively utilized for electrocatalysis, in which electronic metal-support interactions are typically employed to stabilize single atoms. However, this neglects the metal-metal interactions of adjacent atoms, which are essential for the fine-tuning of selective sites. Herein, the high-loading of Ir single atoms (Ir SAs) (8.9 wt%) were adjacently accommodated into oxygen vacancy-rich Co3O4 nanosheets (Ir SAs/Co3O4). Electronic perturbations for both Ir single atoms and Co3O4 supports were observed under electronic metal-support and metal-metal interactions, thus generating Ir-O-Co/Ir units. Electrons were transferred from Co and Ir to O atoms, inducing the depletion of 3d/5d states in Co/Ir and the occupation of 2p states in O atoms to stabilize the Ir SAs. Moreover, the O atoms of Ir-O-Ir functioned as the main active sites for the electrocatalysis of As(iii), which reduced the energy barrier for the rate-determining step. This was due to the stronger electronic affinities for intermediates from reduction of As(iii), which were completely distinct from other coordinated O atoms of Co3O4 or IrO2. Consequently, the resultant Ir SAs/Co3O4 exhibited far more robust electrocatalytic activities than IrO2/Co3O4 and Co3O4 in the electrocatalysis of As(iii). Moreover, there was a strong orbital coupling effect between the coordinated O atoms of Ir SAs and the -OH of H3AsO3, thus exhibiting superior selectivity for As(iii) in contrast to other common heavy metal cations. This work offers useful insights into the rational design of intriguing SACs with high selectivity and stability for the electrocatalysis and electrochemical analysis of pollutants on an electronic level.

18.
Anal Chim Acta ; 1277: 341676, 2023 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-37604614

RESUMO

The mutual interference in the sensing detection of heavy metal ions (HMIs) is considerably serious and complex. Besides, the co-existed ions may change the stripping peak intensity, shape and position of the target ion, which partly makes peak current analysis inaccurate. Herein, a promising approach of partial peak area analysis was proposed firstly to research the mutual interference. The interference between two species on their electrodeposition processes was investigated by simulating different kinetics parameters, including surface coverage, electro-adsorption, -desorption rate constant, etc. It was proved that the partial peak area is sensitive and regular to these interference kinetics parameters, which is favorable for distinctly identifying different interferences. Moreover, the applicability of the partial peak area analysis was verified on the experiments of Cu2+, As(III) interference at four sensing interfaces: glassy carbon electrode, gold electrode, Co3O4, and Fe2O3 nanoparticles modified electrodes. The interference behaviors between Cu2+ and As(III) relying on solid-solution interfaces were revealed and confirmed by physicochemical characterizations and kinetics simulations. This work proposes a new descriptor (partial peak area) to recognize the interference mechanism and provides a meaningful guidance for accurate detection of HMIs in actual water environment.

19.
Pest Manag Sci ; 79(12): 5073-5086, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37572366

RESUMO

BACKGROUND: As a highly prevalent epidemic disease of potato, late blight caused by Phytophthora infestans poses a serious threat to potato yield and quality. At present, chemical fungicides are mainly used to control potato late blight, but long-term overuse of chemical fungicides may lead to environmental pollution and human health threats. Endophytes, natural resources for plant diseases control, can promote plant growth, enhance plant resistance, and secrete antifungal substances. Therefore, there is an urgent need to find some beneficial endophytes to control potato late blight. RESULTS: We isolated a strain of Bacillus subtilis H17-16 from potato healthy roots. It can significantly inhibit mycelial growth, sporangia germination and the pathogenicity of Phytophthora infestans, induce the resistance of potato to late blight, and promote potato growth. In addition, H17-16 has the ability to produce protease, volatile compounds (VOCs) and form biofilms. After H17-16 treatment, most of the genes involved in metabolism, virulence and drug resistance of Phytophthora infestans were down-regulated significantly, and the genes related to ribosome biogenesis were mainly up-regulated. Moreover, field and postharvest application of H17-16 can effectively reduce the occurrence of potato late blight, and the combination of H17-16 with chitosan or chemical fungicides had a better effect than single H17-16. CONCLUSION: Our results reveal that Bacillus subtilis H17-16 has great potential as a natural fungicide for controlling potato late blight, laying a theoretical basis for its development as a biological control agent. © 2023 Society of Chemical Industry.


Assuntos
Fungicidas Industriais , Phytophthora infestans , Solanum tuberosum , Humanos , Phytophthora infestans/genética , Solanum tuberosum/genética , Bacillus subtilis , Fungicidas Industriais/farmacologia , Raízes de Plantas , Doenças das Plantas/prevenção & controle , Doenças das Plantas/microbiologia
20.
J Hazard Mater ; 459: 132104, 2023 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-37490798

RESUMO

The perplexity of double peaks in Pb(II) detections has been a threat to the reliability of Pb(II) electroanalysis results for a long term. For the complexity of electrode interfaces, rare studies were taken on mechanisms of Pb(II) double peaks through interfacial kinetics. In this work, analyses on experimental signals and interfacial simulations were working together to reveal that the generation of Pb(II) double peaks in Pb(II)-Cu(II) systems is the deposition of Pb(II) on Cu deposits occurring in parallel. By applying anode stripping voltammetry and cyclic voltammetry, a parallel deposition reaction was found to influence the shape of Pb(II) peaks, and the existence of the second peak was controlled through the adjustment of experimental conditions. A kinetic model was built to reveal the interference of electroanalysis signals caused by a parallel deposition reaction and simulations based on the model were combined with experiments to illustrate that double peaks of Pb(II) were caused by the parallel deposition on Cu(II) deposits. This work proposes another insight of Pb(II) double peaks from macroscale kinetics and pays more attention on the dynamic procedure of electroanalysis interfaces, which makes the study on environmental electroanalysis interface phenomena more clear and is enlightening to develop efficient electrical methods for pollutant monitoring.

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