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1.
Nat Commun ; 13(1): 1393, 2022 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-35296669

RESUMO

Molecular necklaces have attracted much research attention due to their unique topological structures. Although numerous molecular necklaces with exquisite structures have been constructed, it remains a major challenge to exploit the functions and applications associated with their fascinating architectural and dynamic characteristics. Herein, we report a class of mechanically interlocked networks (MINs) cross-linked by a molecular necklace, in which multiple crown ethers are threaded on a hexagonal metallacyclic framework to furnish a cross-linker with delicate interlocked structures. The molecular necklace cross-linker possesses multiple peculiar advantages: multivalent interactions and rigid metallacycle framework guarantee robust features of MINs while the motion and dissociation of the interlocked structures bring in notable mechanical adaptivity. Moreover, the MINs could respond to the stimuli of K+ and Br-, which lead to the dethreading of crown ether and even the complete decomposition of molecular necklace, respectively, showing abundant active properties. These findings demonstrate the untapped potential of molecular necklaces as cross-linkers and open the door to extend their advanced applications in intelligent supramolecular materials.

2.
Int J Endocrinol ; 2022: 4412725, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35178086

RESUMO

BACKGROUND: The aim of this retrospective study was to evaluate the risk factors for central lymph node metastasis (CLNM) in papillary thyroid carcinoma (PTC), according to the guidelines of the 2017 Thyroid Imaging Report and Data System (TI-RADS) published by the American College of Radiology (ACR). METHODS: This study included a retrospective analysis of 844 patients with PTC who were pathologically diagnosed, treated with central lymph node dissection, and divided into CLNM and nonmetastatic groups. Univariate and multivariate analyses were performed to determine the relationship between the TI-RADS score and CLNM. RESULTS: Among 844 patients, 439 developed CLNM, with a metastasis rate of 52% and a TI-RADS score of 9.42 ± 2.262, which were higher than those of the non-CLNM group (P < 0.05). Univariate analysis demonstrated that the sex, location, maximum diameter of the nodule, multifocality, margin, shape, calcification, and TI-RADS score were related to CLNM (P < 0.05 for all). However, multivariate logistic regression analysis demonstrated that female, maximum diameter of the nodule, multifocality, a taller-than-wide shape, and high TI-RADS score were the independent risk factors for CLNM (P < 0.05 for all). CONCLUSION: The TI-RADS score combined with sex, nodule size, shape, and multifocality has a certain predictive effect on CLNM, which can provide a reference to the clinicians for further treatment strategies.

3.
J Am Chem Soc ; 144(2): 872-882, 2022 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-34932330

RESUMO

Mechanically interlocked networks (MINs) have emerged as an encouraging platform for the development of mechanically robust yet adaptive materials. However, the difficulty in reversibly breaking the mechanical bonds poses a real challenge to MINs as customizable and sustainable materials. Herein, we couple the vitrimer chemistry with mechanically interlocked structures to generate a new class of MINs─referred to as mechanically interlocked vitrimers (MIVs)─to address the challenge. Specifically, we have prepared the acetoacetate-decorated [2]rotaxane that undergoes catalyst-free condensation reaction with two commercially available multiamine monomers to furnish MIVs. Compared with the control whose wheels are nonslidable under applied force, our MIVs with slidable mechanically interlocked motifs showcase enhanced mechanical performance including Young's modulus (18.5 ± 0.9 vs 1.0 ± 0.1 MPa), toughness (3.7 ± 0.1 vs 0.9 ± 0.1 MJ/m3), and damping capacity (98% vs 72%). The structural basis behind unique property profiles is demonstrated to be the force-induced host-guest dissociation and consequential intramolecular sliding of the wheels along the axles. The peculiar behaviors represent a consecutive energy dissipation mechanism, which provides a complement to other pathways that mainly depend on the breaking of sacrificial bonds. Moreover, by virtue of the vitrimer chemistry of vinylogous urethanes, we impart reprocessability and chemical recyclability to the MINs, thereby empowering the reconfiguration of the networks without breaking of the mechanical bonds. Finally, it is disclosed that the intramolecular motions of [2]rotaxanes could accelerate the dynamic exchange of the vinylogous urethane bonds via loosening the network, suggestive of a synergistic effect between the dual dynamic entities.

4.
Environ Pollut ; 290: 118004, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34454196

RESUMO

It is widely recognized that green infrastructures in urban ecosystems provides important ecosystem services, including air purification. The potential absorption of nitrogen oxides (NOx) by urban trees has not been fully quantified, although it is important for air pollution mitigation and the well-being of urban residents. In this study, four common tree species (Sophora japonica L., Fraxinus chinensis Roxb., Populus tomentosa Carrière, Sabina chinensis (L.)) in Beijing, China, were studied. The dual stable isotopes (15N and 18O) and a Bayesian isotope mixing model were applied to estimate the sources contributions of potential nitrogen sources to the roadside trees based on leaf and soil sampling in urban regions. The following order of sources contributions was determined: soil > dry deposition > traffic-related NOx. The capacity of urban trees for NOx removal in the city was estimated using a remote sensing and GIS approach, and the removal capacity was found to range from 0.79 to 1.11 g m-2 a-1 across administrative regions, indicating that 1304 tons of NOx could be potentially removed by urban trees in 2019. Our finding qualified the potential NOx removal by urban trees in terms of atmospheric pollution mitigation, highlighting the role of green infrastructure in air purification, which should be taken into account by stakeholders to manage green infrastructure as the basis of a nature-based approach.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Poluentes Atmosféricos/análise , Poluição do Ar/análise , Teorema de Bayes , Pequim , China , Ecossistema , Monitoramento Ambiental , Isótopos
5.
Front Chem ; 9: 706269, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34277573

RESUMO

The structure of lead-technetium pyrochlore has been refined in space group F d 3 ¯ m with a = 10.36584(2) Å using a combination of synchrotron X-ray and neutron powder diffraction data and confirmed via Electron Diffraction. The oxide is found to be oxygen deficient with a stoichiometry of Pb2Tc2O7-d. Displacive disorder of the Pb cations is evident from the refinements, as has been observed in Bi2Tc2O7-d. X-ray absorption spectroscopic measurements at the Tc K-edge demonstrate the valence of the Tc is greater than 4.0 as anticipated from the refined oxygen stoichiometry. Raman spectroscopy confirms the presence of disorder leading us to conclude that this pyrochlore is the first example of a valence V technetium oxide.

6.
Chem Commun (Camb) ; 57(60): 7374-7377, 2021 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-34231574

RESUMO

Synergistic covalent-and-supramolecular polymers, in which covalent polymers and supramolecular polymers connect with each other through [2]pseudorotaxane moieties, are designed and synthesized. The unique topological structure effectively enhances the synergistic effect between these two polymers, thereby generating a novel class of mechanically adaptive materials.

7.
Angew Chem Int Ed Engl ; 60(29): 16224-16229, 2021 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-33979478

RESUMO

Mortise-and-tenon joints have been widely used for thousands of years in wooden architectures in virtue of their artistic and functional performance. However, imitation of similar structural and mechanical design philosophy to construct mechanically adaptive materials at the molecular level is a challenge. Herein, we report a mortise-and-tenon joint inspired mechanically interlocked network (MIN), in which the [2]rotaxane crosslink not only mimics the joint in structure, but also reproduces its function in modifying mechanical properties of the MIN. Benefiting from the hierarchical energy dissipative ability along with the controllable intramolecular movement of the mechanically interlocked crosslink, the resultant MIN simultaneously exhibits notable mechanical adaptivity and structural stability in a single system, as manifested by decent stiffness, strength, toughness, and deformation recovery capacity.

8.
Inorg Chem ; 60(7): 4517-4530, 2021 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-33688721

RESUMO

The long-range average and short-range local structures in the Tm2(Ti2-xTmx)O7-x/2 (x = 0.00-0.67) series were studied using a combination of diffraction and spectroscopic techniques. The long-range average structure, established from synchrotron X-ray and neutron powder diffraction data, shows the development of multiphase regions from x = 0.134 and the formation of antisite cation disorder from x = 0.402. The crystal field splitting of the Ti4+ ions, as derived from the Ti L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, decreases gradually from 2.17 to 1.92 eV with increasing Tm3+ content (x), reflecting the increase in coordination number from 6 to predominantly 7. This is consistent with a gradual evolution of the short-range local disorder from x = 0.00 to 0.67. These results suggest that local disorder develops gradually throughout the entire composition range, whereas changes in the long-range disorder occur more suddenly. Electrochemical impedance spectroscopic results show an increase in oxygen ionic conductivity at 1000 °C, by a factor of 4 upon doping at x = 0.268. This suggests that inducing small amounts of disorder into the pyrochlore structure, by stuffing, may lead to applications of this material as a solid electrolyte in solid-oxide fuel cells.

9.
Chem Commun (Camb) ; 57(14): 1794-1797, 2021 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-33475634

RESUMO

Preferred-handed propeller conformation was induced by circularly polarized light irradiation to three amorphous molecules with trigonal symmetry, and the molecules with induced chirality efficiently exhibited blue circularly polarized luminescence. In both chirality induction and luminescence, chirality appeared to be amplified due to intermolecular interactions through π-stacking.

10.
Inorg Chem ; 60(4): 2246-2260, 2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33512140

RESUMO

A systematic investigation examining the origins of structural distortions in rutile-related ternary uranium AUO4 oxides using a combination of high-resolution structural and spectroscopic measurements supported by ab initio calculations is presented. The structures of ß-CdUO4, MnUO4, CoUO4, and MgUO4 are determined at high precision by using a combination of neutron powder diffraction (NPD) and synchrotron X-ray powder diffraction (S-XRD) or single crystal X-ray diffraction. The structure of ß-CdUO4 is best described by space group Cmmm whereas MnUO4, CoUO4, and MgUO4 are described by the lower symmetry Ibmm space group and are isostructural with the previously reported ß-NiUO4 [Murphy et al. Inorg. Chem. 2018, 57, 13847]. X-ray absorption spectroscopy (XAS) analysis shows all five oxides contain hexavalent uranium. The difference in space group can be understood on the basis of size mismatch between the A2+ and U6+ cations whereby unsatisfactory matching results in structural distortions manifested through tilting of the AO6 polyhedra, leading to a change in symmetry from Cmmm to Ibmm. Such tilts are absent in the Cmmm structure. Heating the Ibmm AUO4 oxides results in reduction of the tilt angle. This is demonstrated for MnUO4 where in situ S-XRD measurements reveal a second-order phase transition to Cmmm near T = 200 °C. Based on the extrapolation of variable temperature in situ S-XRD data, CoUO4 is predicted to undergo a continuous phase transition to Cmmm at ∼1475 °C. Comparison of the measured and computed data highlights inadequacies in the DFT+U approach, and the conducted analysis should guide future improvements in computational methods. The results of this investigation are discussed in the context of the wider AUO4 family of oxides.

11.
J Am Chem Soc ; 143(2): 1162-1170, 2021 01 20.
Artigo em Inglês | MEDLINE | ID: mdl-33382241

RESUMO

Nature has been inspiring scientists to fabricate impact protective materials for applications in various aspects. However, it is still challenging to integrate flexible, stiffness-changeable, and protective properties into a single polymer, although these merits are of great interest in many burgeoning areas. Herein, we report an impact-protective supramolecular polymeric material (SPM) with unique impact-hardening and reversible stiffness-switching characteristics by mimicking sea cucumber dermis. The emergence of softness-stiffness switchability and subsequent protective properties relies on the dynamic aggregation of the nanoscale hard segments in soft transient polymeric networks modulated by quadruple H-bonding. As such, we demonstrate that our SPM could efficiently reduce the impact force and increase the buffer time of the impact. Importantly, we elucidate the underlying mechanism behind the impact hardening and energy dissipation in our SPM. Based on these findings, we fabricate impact- and puncture-resistant demos to show the potential of our SPM for protective applications.

12.
J Am Chem Soc ; 143(2): 902-911, 2021 01 20.
Artigo em Inglês | MEDLINE | ID: mdl-33251790

RESUMO

A thin filament stimulated by Ca2+ to combine with myosin is the structural basis to achieve filament sliding and muscle contraction. Though a large variety of artificial materials has been developed by mimicking muscle, the on-demand combination of the actin filament and myosin has never been precisely reproduced in polymeric systems. Herein, we show that both the combination process and the combined structure of actin filament and myosin have been mimicked to construct synergistic covalent and supramolecular polymers (CSPs). Specifically, photoirradiation as a stimulus induces the independently formed covalent polymers (CPs) and supramolecular polymers (SPs) to interact with each other through activated quadruple H-bonding. The resultant CSPs possess a unique network structure which not only facilitates the synergistic effect of CPs and SPs to afford stiff, strong, yet tough materials but also provides efficient pathways to dissipate energy with the damping capacity of the representative material being higher than 95%. Furthermore, muscle functions, for example, by becoming stiff during contraction and self-growth by training, are imitated well in our system via in situ phototriggered formation of CSP in the solid state. We hope that the fundamental understanding gained from this work will promote the development of synergistic CSP systems with emergent functions and applications by mimicking the principle of muscle movements.


Assuntos
Substâncias Macromoleculares/metabolismo , Miofibrilas/metabolismo , Polímeros/metabolismo , Actinas/química , Actinas/metabolismo , Humanos , Substâncias Macromoleculares/síntese química , Substâncias Macromoleculares/química , Estrutura Molecular , Contração Muscular , Miofibrilas/química , Miosinas/química , Miosinas/metabolismo , Processos Fotoquímicos , Polímeros/síntese química , Polímeros/química , Estresse Mecânico
13.
Sensors (Basel) ; 20(24)2020 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-33348752

RESUMO

Building extraction from high spatial resolution remote sensing images is a hot spot in the field of remote sensing applications and computer vision. This paper presents a semantic segmentation model, which is a supervised method, named Pyramid Self-Attention Network (PISANet). Its structure is simple, because it contains only two parts: one is the backbone of the network, which is used to learn the local features (short distance context information around the pixel) of buildings from the image; the other part is the pyramid self-attention module, which is used to obtain the global features (long distance context information with other pixels in the image) and the comprehensive features (includes color, texture, geometric and high-level semantic feature) of the building. The network is an end-to-end approach. In the training stage, the input is the remote sensing image and corresponding label, and the output is probability map (the probability that each pixel is or is not building). In the prediction stage, the input is the remote sensing image, and the output is the extraction result of the building. The complexity of the network structure was reduced so that it is easy to implement. The proposed PISANet was tested on two datasets. The result shows that the overall accuracy reached 94.50 and 96.15%, the intersection-over-union reached 77.45 and 87.97%, and F1 index reached 87.27 and 93.55%, respectively. In experiments on different datasets, PISANet obtained high overall accuracy, low error rate and improved integrity of individual buildings.

14.
Inorg Chem ; 59(17): 12166-12175, 2020 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-32822161

RESUMO

A uranium oxide hydrate framework, [U(H2O)2]{[(UO2)10O10(OH)2][(UO4)(H2O)2]} (UOF1), was synthesized hydrothermally using schoepite as a uranium precursor. The crystal strucutre of UOF1 was revealed with synchrotron single-crystal X-ray diffraction and confirmed with transmission electron miscroscopy. The typical uranyl oxide hydroxide layers similar to those in ß-U3O8 are further connected via double-pentagonal-bipyramidal uranium polyhedra to form a three-dimensional (3D) framework structure with tetravalent uranium species inside the channels. The presence of mixed-valence uranium was investigated with a combination of X-ray absorption near-edge structure and diffuse reflectance spectroscopy. Apart from the major hexavalent uranium, evidence for tetravalent uranium was also found, consistent with the bond valence sum calculations. The successful preparation of UOF1 as the first pure uranium oxide hydrate framework sheds light on the structural understanding of the alteration of UO2+x as either a mineral or spent nuclear fuel.

15.
Angew Chem Int Ed Engl ; 59(29): 12139-12146, 2020 07 13.
Artigo em Inglês | MEDLINE | ID: mdl-32293777

RESUMO

Nature has engineered delicate synergistic covalent and supramolecular polymers (CSPs) to achieve advanced life functions, such as the thin filaments that assist in muscle contraction. Constructing artificial synergistic CSP materials with bioinspired mechanically adaptive features, however, represents a challenging goal. Here, we report an artificial CSP system to illustrate the integration of a covalent polymer (CP) and a supramolecular polymer (SP) in a synergistic fashion, along with the emergence of notable mechanical and dynamic properties which are unattainable when the two polymers are formed individually. The synergistic effect relies on the peculiar network structures of the SP and CPs, which endow the resultant CSPs with overall improved mechanical performance in terms of the stiffness, strength, stretchability, toughness, and elastic recovery. Moreover, the dynamic properties of the SP, including self-healing, stimuli-responsiveness, and reprocessing, are also retained in the CSPs, thus leading to their application as programmable and tunable materials.

16.
Inorg Chem ; 59(9): 6613-6622, 2020 May 04.
Artigo em Inglês | MEDLINE | ID: mdl-32286805

RESUMO

The double perovskite Ba2CoOsO6, synthesized using solid-state methods at ambient pressure, is shown as a rare example of an oxide adopting the 6L-trigonal (S.G.: P3̅m1) perovskite structure. The structure, refined using a combination of X-ray and neutron diffraction data, showed the Co and Os were ordered over the two dimer sites with additional ordering over the corner-sharing sites. Bond valence calculations show the presence of the Co(II) and Os(VI) valence states, and the latter was confirmed using X-ray absorption spectroscopy. Bulk magnetic susceptibility measurements show Ba2CoOsO6 to undergo antiferromagnetic ordering near 100 K, and neutron diffraction showed an ordered moment on the Co3, Co4, and Os2 sites; whereas the Os1/Co1 remained disordered.

17.
Chem Commun (Camb) ; 56(58): 8031-8034, 2020 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-32167120

RESUMO

Herein, supramolecular polymeric elastomers crosslinked by metal-organic polyhedra (ElastoMOPs) were designed and developed as a novel hybrid system featuring not only tunable mechanical properties but also dynamic actuation behaviors in response to dichloromethane vapor.

18.
J Am Chem Soc ; 142(4): 2051-2058, 2020 01 29.
Artigo em Inglês | MEDLINE | ID: mdl-31905287

RESUMO

Supramolecular polymers based on host-guest molecular recognition have emerged as promising platforms for the development of smart materials. However, the studies on them are primarily conducted in solution and/or in the gel state. In contrast, little is known about dynamic properties and applications of supramolecular polymers in bulk. Herein, we present a self-cross-linking supramolecular polymer network (SPN) as a model system to understand the bulk properties controlled by noncovalent interactions. Specifically, the SPN monomer is composed of two benzo-21-crown-7 (B21C7) host units and two dialkylammonium salt guest moieties on a four-arm core, wherein complementary host-guest complexation drives the formation of the SPN with [2]pseudorotaxane linkages between B21C7 and ammonium motifs. The dynamic and reversible behaviors of the linkages are evaluated by measurement of viscoelasticity. The results indicate that the host-guest molecular recognition becomes highly dynamic at elevated temperature. Moreover, the relatively high activation energy of the SPN manifests itself as a new type of thermoplastic material with network topology freezing glass transition. Finally, we demonstrate how these findings provide insights into the malleability and processability of the SPN by simple demos. The fundamental understanding gained from the research on this SPN in bulk will facilitate the advancement and application of supramolecular materials.

19.
Environ Sci Pollut Res Int ; 27(4): 3849, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31883079

RESUMO

We found an error in the materials and methods section. Since our team used two methodsfor anesthesia in rats and the anesthesia method used in this paper was 3.5% chloralhydrate anesthesia, we mistakenly wrote the anesthetic as 3% sodium pentobarbital.

20.
Environ Sci Pollut Res Int ; 27(4): 3837-3848, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31732953

RESUMO

Exposure to di (2-ethylhexyl) phthalate (DEHP) induces lipid metabolism disorder and high-fat diet (HD) may have joint effects with DEHP. We aim to clarify the role of JAK2/STAT5 pathway in the process and reveal the effects of HD on the toxicity of DEHP. Wistar rats (160 animals) were fed with HD or normal diet (ND) respectively and exposed to DEHP 0, 5, 50, and 500 mg/kg/day for 8 weeks. Lipid levels, as well as the morphology of liver and adipose, mRNA levels, and protein levels of JAK2, STAT5A, STAT5B, FAS, ap2, and PDK4 were detected. The results showed that DEHP exposure leads to increased weight gain. The JAK2/STAT5 pathway was activated in adipose after DEHP exposure and promoted the expression of FAS, ap2, and PDK4 in ND rats. While in the liver, JAK2 was inhibited, and lipid synthesis and accumulation were increased. However, rats exposed to DEHP in combination with HD showed a complete disorder of lipid metabolism. Therefore, we conclude that DEHP affects lipid metabolism through regulating the JAK2/STAT5 pathway and promotes adipogenesis and lipid accumulation. High-fat diet may have a joint effect with DEHP on lipid metabolism disorder.


Assuntos
Dietilexilftalato , Janus Quinase 2/metabolismo , Metabolismo dos Lipídeos , Ácidos Ftálicos/química , Fator de Transcrição STAT5/química , Fator de Transcrição STAT5/metabolismo , Animais , Dieta Hiperlipídica , Janus Quinase 2/química , Ratos , Ratos Wistar
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