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1.
Nat Commun ; 15(1): 8157, 2024 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-39289393

RESUMO

Intermetallic nanoparticles (NPs) possess significant potentials for catalytic applications, yet their production presents challenges as achieving the disorder-to-order transition during the atom ordering process involves overcoming a kinetic energy barrier. Here, we demonstrate a robust approach utilizing atomic gas-migration for the in-situ synthesis of stable and homogeneous intermetallic alloys for propane dehydrogenation (PDH). This approach relies on the physical mixture of two separately supported metal species in one reactor. The synthesized platinum-zinc intermetallic catalysts demonstrate exceptional stability for 1300 h in continuous propane dehydrogenation under industrially relevant industrial conditions, with extending 95% propylene selectivity and propane conversions approaching thermodynamic equilibrium values at 550-600 oC. In situ characterizations and density functional theory/molecular dynamics simulation reveal Zn atoms adsorb on the particle surface and then diffuse inward, aiding in the formation of ultrasmall and highly ordered intermetallic alloys. This in-situ gas-migration strategy is applicable to a wide range of intermetallic systems.

2.
Heliyon ; 10(17): e36931, 2024 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-39281588

RESUMO

Objective: This study aim to quantify the differences in knee biomechanics during gait between knee osteoarthritis (KOA) patients and healthy individuals. Methods: Twenty KOA patients (4 males and 16 females, 66.2 ± 7.7 years) and twenty controls (16 males and 4 females, 64.8 ± 5.4 years) were recruited for gait test using the motion capture system and force-platform system. The spatiotemporal parameters, knee kinematics and kinetics, and tibiofemoral contact force (TFCF) were calculated using an improved musculoskeletal model. Results: KOA patients walked with reduced speed (48.6 %), stride length (32.9 %), stride height (33.0 %), time proportions of single-support phases (19.2 %), increased gait cycle time (31.0 %), time proportions of stance (8.5 %) and double-support phases (57.7-75.9 %). KOA patients had significant smaller peak flexion angle (29.1 %), flexion ROM (50.6 %) and peak flexion moment (90.2 %), greater peak adduction moment (KAM) (40.7 %), peak rotation moments (KRM) (50.0 %), KAM impulse (106.2 %) and KRM impulse (126.0 %). In proximodistal direction, greater medial TFCF impulse (238 %), total and medial first-peak TFCF (9.6 % and 15.2 %), and smaller lateral peak TFCF (33.3 %) and TFCF impulse (38.4 %) were found in KOA patients. Besides, significant differences were found in the total, medial and lateral peak TFCFs and TFCF impulses in mediolateral direction, and the medial and lateral TFCFs and TFCF impulses in anteroposterior direction. Conclusions: Significant differences were found in the spatiotemporal parameters, knee kinematics and kinetics, and TFCF between the two groups. The results of this study have important implication for clinicians and rehabilitation physicians. These quantified biomechanical differences can provide data support for the personalized and quantified rehabilitation strategies, give suggestions for the exercises of KOA patients, help monitor disease, evaluate surgical treatment, and develop more effective preoperative planning and postoperative rehabilitation strategies.

3.
Micromachines (Basel) ; 14(10)2023 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-37893249

RESUMO

In order to reduce the energy consumption of human daily movement without providing additional power, we considered the biomechanical behavior of the knee during external impedance interactions. Based on the theory of human sports biomechanics, combined with the requirements of human-machine coupling motion consistency and coordination, an unpowered exoskeleton-assisted device for the knee joint is proposed in this paper. The effectiveness of this assisted device was verified using gait experiments and distributed plantar pressure tests with three modes: "not wearing exoskeleton" (No exo.), "wearing exoskeleton with assistance " (Exo. On), and "wearing exoskeleton without assistance" (Exo. Off). The experimental results indicate that (1) This device can effectively enhance the function of the knee, increasing the range of knee movement by 3.72% (p < 0.001). (2) In the early stages of the lower limb swing, this device reduces the activity of muscles in relation to the knee flexion, such as the rectus femoris, vastus lateralis, and soleus muscles. (3) For the first time, it was found that the movement length of the plantar pressure center was reduced by 6.57% (p = 0.027). This basic principle can be applied to assist the in-depth development of wearable devices.

4.
PeerJ Comput Sci ; 9: e1199, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37346598

RESUMO

Anomaly detection of high-dimensional data is a challenge because the sparsity of the data distribution caused by high dimensionality hardly provides rich information distinguishing anomalous instances from normal instances. To address this, this article proposes an anomaly detection method combining an autoencoder and a sparse weighted least squares-support vector machine. First, the autoencoder is used to extract those low-dimensional features of high-dimensional data, thus reducing the dimension and the complexity of the searching space. Then, in the low-dimensional feature space obtained by the autoencoder, the sparse weighted least squares-support vector machine separates anomalous and normal features. Finally, the learned class labels to be used to distinguish normal instances and abnormal instances are outputed, thus achieving anomaly detection of high-dimensional data. The experiment results on real high-dimensional datasets show that the proposed method wins over competing methods in terms of anomaly detection ability. For high-dimensional data, using deep methods can reconstruct the layered feature space, which is beneficial for gaining those advanced anomaly detection results.

5.
Adv Mater ; 34(33): e2204638, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35748197

RESUMO

Reducing particle size in supported metal catalysts to single-atom level isolates the active metal sites and maximizes the atomic utilization efficiency. However, the large inter-atom distance, particularly in low-loading single-atom catalyst (SAC), is not favorable for a complex reaction where two (or more) reactants have to be activated. A key question is how to control the inter-atom distances to promote dinuclear-type coactivation at the adjacent metal sites. Here, it is reported that reducing the average inter-atom distance of copper SACs supported on carbon nitride (C3 N4 ) to 0.74 ± 0.13 nm allows these catalysts to exhibit a dinuclear-type catalytic mechanism in the nitrile-azide cycloaddition. Operando X-ray absorption fine structure study reveals a dynamic ligand exchange process between nitrile and azide, followed by their coactivation on dinuclear Cu SAC sites to form the tetrazole product. This work highlights that reducing the nearest-neighbor distance of SAC allows the mechanistic pathway to diversify from single-site to multisite catalysis.

6.
Nat Commun ; 13(1): 2807, 2022 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-35589718

RESUMO

Single-atom catalysts (SACs) offer many advantages, such as atom economy and high chemoselectivity; however, their practical application in liquid-phase heterogeneous catalysis is hampered by the productivity bottleneck as well as catalyst leaching. Flow chemistry is a well-established method to increase the conversion rate of catalytic processes, however, SAC-catalysed flow chemistry in packed-bed type flow reactor is disadvantaged by low turnover number and poor stability. In this study, we demonstrate the use of fuel cell-type flow stacks enabled exceptionally high quantitative conversion in single atom-catalyzed reactions, as exemplified by the use of Pt SAC-on-MoS2/graphite felt catalysts incorporated in flow cell. A turnover frequency of approximately 8000 h-1 that corresponds to an aniline productivity of 5.8 g h-1 is achieved with a bench-top flow module (nominal reservoir volume of 1 cm3), with a Pt1-MoS2 catalyst loading of 1.5 g (3.2 mg of Pt). X-ray absorption fine structure spectroscopy combined with density functional theory calculations provide insights into stability and reactivity of single atom Pt supported in a pyramidal fashion on MoS2. Our study highlights the quantitative conversion bottleneck in SAC-mediated fine chemicals production can be overcome using flow chemistry.

7.
Inorg Chem ; 61(16): 6063-6072, 2022 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-35420792

RESUMO

Comparatively revealing the complexation behavior of trivalent actinides and lanthanides with functional ligands in aqueous solution is of great importance to enrich our knowledge on the fundamental coordination chemistry of trivalent f-block elements and to control the fate of minor actinides in nuclear fuel cycles. In this work, the complexation of Am(III) and Nd(III), representatives for trivalent actinides and lanthanides, respectively, with a N,O-hybrid ligand 6-(dimethylcarbamoyl)picolinic acid (DMAPA, denoted as HL) was investigated by absorption spectroscopy, calorimetry, X-ray crystallography, and density functional theory (DFT) calculations. Successive formation of 1:1, 1:2, and 1:3 (metal/ligand) complexes of Am(III) and Nd(III) with DMAPA was identified, and the corresponding thermodynamic parameters were determined. The binding strength of Am(III) with DMAPA is slightly stronger than that of Nd(III), and the complexation of Nd(III) with DMAPA is mainly entropy-driven. The crystal structure of the 1:2 Nd(III)/DMAPA complex and the DFT calculation shed additional light on the coordination and structural characteristics of the complexes. In contrast to the Nd-N bond in the Nd(III)/DMAPA complex, the Am-N bond in the Am(III)/DMAPA complex exhibits more covalency, which contributes to the slightly stronger complexation of Am(III) with DMAPA.

8.
Sci Rep ; 11(1): 3130, 2021 02 04.
Artigo em Inglês | MEDLINE | ID: mdl-33542300

RESUMO

For pre-operative osteoarthritis (OA) patients with varus knee, previous studies showed inconsistent results. Therefore, we conducted this study to better identify the association of Hospital for Special Surgery (HSS) score and mechanical alignment. 44 patients (51 knees) with constitutional varus knee caused by combined deformities (LDFA (lateral distal femoral angle) > 90°and MPTA (medial proximal tibial angle) < 85°)) were selected and analyzed with a mean follow-up period of 14 months after total knee arthroplasty (TKA). From January 2015 to December 2016, patients were collected consecutively after primary TKA. After filtering, fifty-one knees (44patients) were analyzed with a mean follow-up period of 14 months. All patients were divided into two groups based on post-operative hip-knee-ankle (HKA) acute angle: varus mechanical alignment (VMA) group (HKA < - 3°) and neutral mechanical axis (NMA) group (- 3° ≤ HKA ≤ 3°). 30 knees were included in the NMA group, and 21 knees in the VMA group. Comparisons of HSS between NMA group and VMA group were performed. After adjusting for age and Body Mass Index (BMI) confounders, Compared with NMA group, the HSS score in VMA group decreased by 0.81 units (95% CI, - 3.37 to 1.75) p = 0.5370). For pre-operative constitutional varus knee caused by combined deformities in chinese populations, no significant association between post-operative lower limb mechanical alignment and HSS score was found.


Assuntos
Fêmur/cirurgia , Articulação do Joelho/cirurgia , Osteoartrite do Joelho/cirurgia , Pé Cavo/cirurgia , Tíbia/cirurgia , Fatores Etários , Idoso , Articulação do Tornozelo/diagnóstico por imagem , Articulação do Tornozelo/patologia , Artroplastia do Joelho/métodos , Índice de Massa Corporal , Feminino , Fêmur/diagnóstico por imagem , Fêmur/patologia , Humanos , Articulação do Joelho/diagnóstico por imagem , Articulação do Joelho/patologia , Masculino , Pessoa de Meia-Idade , Osteoartrite do Joelho/diagnóstico por imagem , Osteoartrite do Joelho/patologia , Radiografia , Estudos Retrospectivos , Pé Cavo/diagnóstico por imagem , Pé Cavo/patologia , Tíbia/diagnóstico por imagem , Tíbia/patologia , Resultado do Tratamento
9.
Biomed Res Int ; 2021: 6644071, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33490274

RESUMO

Diabetic retinopathy is one of the main causes of blindness in human eyes, and lesion segmentation is an important basic work for the diagnosis of diabetic retinopathy. Due to the small lesion areas scattered in fundus images, it is laborious to segment the lesion of diabetic retinopathy effectively with the existing U-Net model. In this paper, we proposed a new lesion segmentation model named FFU-Net (Feature Fusion U-Net) that enhances U-Net from the following points. Firstly, the pooling layer in the network is replaced with a convolutional layer to reduce spatial loss of the fundus image. Then, we integrate multiscale feature fusion (MSFF) block into the encoders which helps the network to learn multiscale features efficiently and enrich the information carried with skip connection and lower-resolution decoder by fusing contextual channel attention (CCA) models. Finally, in order to solve the problems of data imbalance and misclassification, we present a Balanced Focal Loss function. In the experiments on benchmark dataset IDRID, we make an ablation study to verify the effectiveness of each component and compare FFU-Net against several state-of-the-art models. In comparison with baseline U-Net, FFU-Net improves the segmentation performance by 11.97%, 10.68%, and 5.79% on metrics SEN, IOU, and DICE, respectively. The quantitative and qualitative results demonstrate the superiority of our FFU-Net in the task of lesion segmentation of diabetic retinopathy.


Assuntos
Aprendizado Profundo , Retinopatia Diabética/diagnóstico por imagem , Interpretação de Imagem Assistida por Computador/métodos , Retinopatia Diabética/patologia , Técnicas de Diagnóstico Oftalmológico , Humanos , Retina/diagnóstico por imagem , Retina/patologia
10.
Mar Pollut Bull ; 163: 111955, 2021 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-33453511

RESUMO

Mangrove has been destroyed and reforestation is often undertaken, but whether a regenerated forest could restore its ecological function is not clear. This study compares microbial community structure and function in sediment of the 17-years old natural regenerated mangrove forest (Y17) with the original forest (Y74). No significant differences in phospholipid fatty acid (PLFA) profiles and microbial metabolism of most carbon substrates were found between these two forests. However, activities of dehydrogenase, protease, cellulase and phosphatase were lower in Y17 than Y74, and some specific microbial functions were also different. Both forests exhibited significant seasonal differences in enzyme activities and microbial characteristics, but such difference was larger in Y17 than Y74, indicating the regenerated forest was more sensitive to season. Correspondence analysis based on PLFA profiles and enzyme activities revealed the microbial community in Y17 was comparable to Y74, suggesting sediment microbial characteristics in natural regenerated mangroves could be restored.


Assuntos
Microbiota , Áreas Alagadas , Carbono/análise , China , Florestas , Solo , Microbiologia do Solo
11.
Life Sci ; 267: 118933, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33359744

RESUMO

AIMS: Non-small cell lung cancer (NSCLC) is considered a highly fatal tumor. Importantly, angiogenesis is critical for tumor progression. Long non-coding RNAs (lncRNAs), which are untranslatable, control cell functions through different pathways. lncRNA EPIC1 has been reported to promote cell viability, cell cycle progression, and invasion. However, the relationship between EPIC1 and tumor angiogenesis remains an enigma. We explored the role of EPIC1 in tumor angiogenesis in NSCLC. MATERIALS AND METHODS: First, EPIC1 expression was analyzed using the GEPIA database and was further verified using qPCR in tumor tissues from patients with NSCLC and NSCLC cell lines. Next, EPIC1 function was detected using loss-of-function and gain-of-function assays. Moreover, EdU staining, flow cytometry, and channel formation assays were performed to assess HUVEC proliferation and channel the formation in the NSCLC-HUVEC transwell co-culture system. KEY FINDINGS: EPIC1 expression was significantly upregulated in NSCLC tissues and cell lines. Furthermore, the overexpression of EPIC1 in NSCLC cells stimulated HUVEC channel formation and proliferation by activating Ang2/Tie2 signaling, and the opposite results were obtained when EPIC1 was silenced in NSCLC cells. The density of new blood vessels was simultaneously increased by EPIC1 overexpression in vivo, using CAM angiogenesis model and a nude mouse tumor model. Finally, all these experimental findings could be established in the samples from patients with NSCLC. We postulate that EPIC1 promotes tumor angiogenesis by activating the Ang2/Tie2 axis in NSCLC. SIGNIFICANCE: Elucidating the molecular and cellular mechanisms of EPIC1 in tumor angiogenesis provides a novel perspective on NSCLC clinical therapy.


Assuntos
Angiopoietina-2/metabolismo , Carcinoma Pulmonar de Células não Pequenas/genética , Neoplasias Pulmonares/genética , RNA Longo não Codificante/genética , Receptor TIE-2/metabolismo , Angiopoietina-2/genética , Animais , Carcinoma Pulmonar de Células não Pequenas/irrigação sanguínea , Carcinoma Pulmonar de Células não Pequenas/metabolismo , Carcinoma Pulmonar de Células não Pequenas/patologia , Linhagem Celular Tumoral , Proliferação de Células/fisiologia , Sobrevivência Celular/fisiologia , Embrião de Galinha , Bases de Dados Genéticas , Modelos Animais de Doenças , Xenoenxertos , Células Endoteliais da Veia Umbilical Humana , Humanos , Neoplasias Pulmonares/irrigação sanguínea , Neoplasias Pulmonares/metabolismo , Neoplasias Pulmonares/patologia , Masculino , Camundongos , Camundongos Endogâmicos BALB C , Camundongos Nus , Neovascularização Patológica/genética , Neovascularização Patológica/patologia , RNA Longo não Codificante/metabolismo , Receptor TIE-2/genética , Transdução de Sinais
12.
Sensors (Basel) ; 21(1)2020 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-33374842

RESUMO

As a detection tool to identify metal or alloy, metallographic quantitative analysis has received increasing attention for its ability to evaluate quality control and reveal mechanical properties. The detection procedure is mainly operated manually to locate and characterize the constitution in metallographic images. The automatic detection is still a challenge even with the emergence of several excellent models. Benefiting from the development of deep learning, with regard to two different metallurgical structural steel image datasets, we propose two attention-aware deep neural networks, Modified Attention U-Net (MAUNet) and Self-adaptive Attention-aware Soft Anchor-Point Detector (SASAPD), to identify structures and evaluate their performance. Specifically, in the case of analyzing single-phase metallographic image, MAUNet investigates the difference between low-frequency and high-frequency and prevents duplication of low-resolution information in skip connection used in an U-Net like structure, and incorporates spatial-channel attention module with the decoder to enhance interpretability of features. In the case of analyzing multi-phase metallographic image, SASAPD explores and ranks the importance of anchor points, forming soft-weighted samples in subsequent loss design, and self-adaptively evaluates the contributions of attention-aware pyramid features to assist in detecting elements in different sizes. Extensive experiments on the above two datasets demonstrate the superiority and effectiveness of our two deep neural networks compared to state-of-the-art models on different metrics.

13.
Annu Int Conf IEEE Eng Med Biol Soc ; 2020: 1002-1006, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-33018154

RESUMO

This research focuses on the gait phase recognition using different sEMG and EEG features. Seven healthy volunteers, 23-26 years old, were enrolled in this experiment. Seven phases of gait were divided by three-dimensional trajectory of lower limbs during treadmill walking and classified by Library for Support Vector Machines (LIBSVM). These gait phases include loading response, mid-stance, terminal Stance, pre-swing, initial swing, mid-swing, and terminal swing. Different sEMG and EEG features were assessed in this study. Gait phases of three kinds of walking speed were analyzed. Results showed that the slope sign change (SSC) and mean power frequency (MPF) of sEMG signals and SSC of EEG signals achieved higher accuracy of gait phase recognition than other features, and the accuracy are 95.58% (1.4 km/h), 97.63% (2.0 km/h) and 98.10% (2.6 km/h) respectively. Furthermore, the accuracy of gait phase recognition in the speed of 2.6 km/h is better than other walking speeds.


Assuntos
Marcha , Caminhada , Adulto , Eletroencefalografia , Voluntários Saudáveis , Humanos , Velocidade de Caminhada , Adulto Jovem
14.
Appl Bionics Biomech ; 2020: 7451683, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32322301

RESUMO

The knee joint, as the main lower limb motor joint, is the most vulnerable and susceptible joint. The knee injuries considerably impact the normal living ability and mental health of patients. Understanding the biomechanics of a normal and diseased knee joint is in urgent need for designing knee assistive devices and optimizing a rehabilitation exercise program. In this paper, we systematically searched electronic databases (from 2000 to November 2019) including ScienceDirect, Web of Science, PubMed, Google Scholar, and IEEE/IET Electronic Library for potentially relevant articles. After duplicates were removed and inclusion criteria applied to the titles, abstracts, and full text, 138 articles remained for review. The selected articles were divided into two groups to be analyzed. Firstly, the real movement of a normal knee joint and the normal knee biomechanics of four kinds of daily motions in the sagittal and coronal planes, which include normal walking, running, stair climbing, and sit-to-stand, were discussed and analyzed. Secondly, an overview of the current knowledge on the movement biomechanical effects of common knee musculoskeletal disorders and knee neurological disorders were provided. Finally, a discussion of the existing problems in the current studies and some recommendation for future research were presented. In general, this review reveals that there is no clear assessment about the biomechanics of normal and diseased knee joints at the current state of the art. The biomechanics properties could be significantly affected by knee musculoskeletal or neurological disorders. Deeper understanding of the biomechanics of the normal and diseased knee joint will still be an urgent need in the future.

15.
Inorg Chem ; 59(6): 3905-3911, 2020 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-32133859

RESUMO

The selective separation of trivalent americium from lanthanides in a nitric acid medium by a tetradentate ligand, N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (Et-Tol-DAPhen), in an ionic liquid (IL), C4mimNTf2, was studied by batch solvent extraction and spectroscopic approaches. The effect of various parameters such as the contact time, temperature, extractant concentration, and acidity on the extraction of Am3+ and Eu3+ have been evaluated. A significant enhancement in the extraction ability of Et-Tol-DAPhen dissolved in IL was observed as compared to that in molecular diluents under low-acid conditions. The chemical stoichiometry of Am3+ and Eu3+ complexes during extraction was determined to be 1:2 (metal/ligand) by slope analysis of the extraction data. The extraction mechanism of Am3+ and Eu3+ by Et-Tol-DAPhen in IL was determined to be cation exchange on the basis of the effect of nitrate, NTf2-, and C4mim+ ions on extraction. The coordination chemistry of Ln3+ with the ligand in C4mimNTf2 was studied by spectroscopic titrations, which helped to further identify and confirm the extracted species as well as the extraction mechanism. Results from the present study emphasize the unique role of IL in altering the extraction behavior and suggest that the Et-Tol-DAPhen/IL system has potential applications in trivalent actinide/lanthanide separation under low-acid conditions.

16.
Sci Total Environ ; 707: 136030, 2020 Mar 10.
Artigo em Inglês | MEDLINE | ID: mdl-31869617

RESUMO

Microplastics are ubiquitous pollutants found in environments. Mangrove sediments containing vegetal litter are different from other environmental matrices such as river and marine sediments. The presence of vegetal litter leads to an under-estimation of microplastic pollution, particularly classical digestion methods are not suitable for removing this type of organic matter. The present study aims to develop a digestion method to remove vegetal litter and improve the determination of microplastic pollution in mangrove sediments. Results showed that our three-stage method with repeatedly addition of hydrogen peroxide had the highest efficiency in removing mangrove vegetal litter when compared with the three classical digestion methods. The high match scores of Fourier Transform Infrared Spectroscopy proved that the developed method had little impacts on the integrity of five polymer types of microplastics. The developed method also achieved high efficiency in extracting microplastics from mangrove sediments containing different content of vegetal litter. CAPSULE: A digestion method was developed for extracting microplastics in clayey mangrove sediments rich in vegetal litter.

17.
Inorg Chem ; 58(17): 11664-11671, 2019 Sep 03.
Artigo em Inglês | MEDLINE | ID: mdl-31436978

RESUMO

Revealing the complexation behavior of high-valent actinides in solutions is of great importance to better understand the fundamental chemistry of actinides as well as to control the separation property of actinides in nuclear fuel cycles. In this work, the complexation of hexavalent actinide cations U(VI), Np(VI), and Pu(VI) with two dipicolinic acid derivatives, 6-(dimethylcarbamoyl)picolinic acid (DMAPA, denoted as HL) and N2,N2,N6,N6-tetramethylpyridine-2,6-dicarboxamide (TMPDA), in aqueous solutions were investigated by absorption spectrophotometry, X-ray crystallography, and DFT calculations. Formation of 1/1 and 1/2 (metal:ligand) complexes of U(VI), Np(VI), and Pu(VI) with DMAPA were identified and the corresponding stability constants were determined. The binding strengths of the three hexavalent actinide cations with DMAPA follow the order of U(VI) > Np(VI) > Pu(VI) in both 1/1 and 1/2 complexes, indicating that the driving force for the complexation is mainly electrostatic interactions. In addition, the relationships between the features of the absorption spectra and the symmetry of Pu(VI) and Np(VI) complexes with DMAPA have been established. The crystal structure of the 1/2 U(VI)/DMAPA complex as well as the DFT optimized structures of An(VI)/DMAPA complexes shed additional light on the structural characters of the hexavalent actinide cation complexes. In contrast to DMAPA, TMPDA exhibits no observable complexation with the three hexavalent actinide cations in aqueous solution, which could be attributed to low electron density on the donor atoms of TMPDA as well as steric hindrance effect by dimethyl carbamoyl groups as elucidated by DFT calculations. The results from this work provide new insights into the complexation trends of hexavalent actinide cations in aqueous solutions.

18.
J Hazard Mater ; 379: 120788, 2019 11 05.
Artigo em Inglês | MEDLINE | ID: mdl-31254788

RESUMO

Polybrominated diphenyl ethers (PBDEs) are one of the persistent toxic organic pollutants in watersheds near electrical and electronic waste (e-waste) sites (EWS). Spatial redistribution, translocation and bioaccumulation of PBDEs in natural sediment-plant ecosystems, however, are still unclear. The contamination and distribution of PBDEs in core sediments and wetland plants from two EWS and two mangrove forest sites (MFS) were investigated. The eight PBDE congeners were all detected in plant tissue and sediment samples, indicating PBDE contamination was common and severe, and their spatial variations were significant. Although sediments from EWS had higher PBDE concentrations than those in MFS, with an extremely high value of 36392 ±â€¯5992 ng g-1 dw, mangroves could be the sink of PBDEs, as high concentrations (327 ±â€¯48 ng g-1 dw) were also detected in mangrove sediments. The historical usage of PBDEs was reflected by their distribution in mangrove sediment core but not so in e-waste sediment core. PBDEs were taken up and accumulated in six wetland plants, with more accumulation in mangrove plants. These results demonstrated that PBDEs were not only contaminated in sediments adjacent to e-waste sites but also plant tissues. PBDEs could enter other environments via plant littering and/or herbivorous processes that must not be neglected.

19.
Inorg Chem ; 58(7): 4420-4430, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30869514

RESUMO

Recently, phenanthroline-based ligands have received increasing attention due to their excellent separation capabilities for trivalent actinides over lanthanide. In this work, we designed a soft-hard donor combined tetradentate phenanthroline-based extractant, tetraethyl (1,10-phenanthrolin-2,9-diyl)phosphonate (C2-POPhen), for the selective separation of trivalent Am(III) over Ln(III) from HNO3 media. The solvent extraction and complexation behaviors of Am(III) and Ln(III) by C2-POPhen were investigated both experimentally and theoretically. C2-POPhen could selectively extract Am(III) over Eu(III) with an extremely fast extraction kinetics. NMR titration studies suggest that only 1:1 complexes of Ln(III) with C2-POPhen formed in CH3OH in the presence of a significant amount of nitrate, while both 1:1 and 2:1 complexes species could form between C2-POPhen and Ln(III) perchlorate in CH3OH without nitrate ions. The stability constants for the complexation of Am(III) and Ln(III) with C2-POPhen in CH3OH were determined by spectrophotometric titrations and the Am(III) complexes are approximately 1 order of magnitude stronger than those of Ln(III), which is consistent with the extraction results. Theoretical calculations indicate that the Am-N bonds in Am/C2-POPhen complexes possess more covalent characters than the Eu-N bonds in Eu/C2-POPhen complexes, shedding light on the underlying chemical force responsible for the Am/Eu selectivity by C2-POPhen. This work represents the first report utilizing phenanthroline-based phosphonate ligands for selective separation of actinides from highly acidic solutions.

20.
Small ; 15(7): e1804974, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30667601

RESUMO

The dynamic optical switch of plasmonic nanostructures is highly desirable due to its promising applications in many smart optical devices. To address the challenges in the reversibility and transmittance contrast of the plasmonic electrochromic devices, here, a strategy is reported to fabricate color switchable electrochromic films through electro-responsive dissolution and deposition of Ag on predefined hollow shells of Au/Ag alloy. Using the hollow Au/Ag alloy nanostructures as stable seeds for site-specific deposition of Ag, elimination of the random self-nucleation events is enabled and optimal reversibility in color switching is allowed. The hollow structure further enables excellent transmittance contrast between the bleached and colored states. With its additional advantages such as the convenience for preparation, high sensitivity, and field-tunable optical property, it is believed that this new electrochromic film represents a unique platform for designing novel smart optical devices.

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