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1.
Angew Chem Int Ed Engl ; : e202408271, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38837513

RESUMO

To explore the chirality induction and switching of topological chirality, poly[2]catenanes composed of helical poly(phenylacetylenes) (PPAs) main chain and topologically chiral [2]catenane pendants are described for the first time. These poly[2]catenanes with optically active [2]catenanes on side chains were synthesized by polymerization of enantiomerically pure topologically chiral [2]catenanes with ethynyl polymerization site and/or point chiral moiety. The chirality information of [2]catenane pendants was successfully transferred to the main chain of polyene backbones, leading to preferred-handed helical conformations, while the introduction of point chiral units has negligible effect on the overall helices. More interestingly, attributed to unique dynamic feature of the [2]catenane pendants, these polymers revealed dynamic response behaviors to solvents, temperature, and sodium ions, resulting in the fully reversible switching on/off of the chirality induction. This work provides not only new design strategy for novel chiroptical switches with topologically chiral molecules but also novel platforms for the development of smart chiral materials.

2.
Chem Sci ; 15(19): 7178-7186, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38756822

RESUMO

In order to investigate the effect of macrocyclization and catenation on the regulation of vibration-induced emission (VIE), the typical VIE luminogen 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) was introduced into the skeleton of a macrocycle and corresponding [2]catenane to evaluate their dynamic relaxation processes. As investigated in detail by femtosecond transient absorption (TA) spectra, the resultant VIE systems revealed precisely tunable emissions upon changing the solvent viscosity, highlighting the key effect of the formation of [2]catenane. Notably, the introduction of an additional pillar[5]arene macrocycle featuring unique planar chirality endows the resultant chiral VIE-active [2]catenane with attractive circularly polarized luminescence in different states. This work not only develops a new strategy for the design of new luminescent systems with tunable vibration induced emission, but also provides a promising platform for the construction of smart chiral luminescent materials for practical applications.

3.
Huan Jing Ke Xue ; 45(2): 952-960, 2024 Feb 08.
Artigo em Chinês | MEDLINE | ID: mdl-38471933

RESUMO

In order to clarify the impact of no-tillage on the quality of farmland soil aggregates in China and promote the adaptive application of no-tillage practices, a Meta-analysis was conducted by collecting data from 116 published studies. The effects of no-tillage on aggregate size distribution, mean weight diameter (MWD), and aggregate-associated C were studied. The results showed that compared with that under tillage, no-tillage significantly increased the proportion of macroaggregates (10.9%) and MWD (12.8%) and decreased the proportion of clay and silt (-15.5%) but had no significant effect on soil microaggregate and aggregate-associated C. The subgroup and Meta regression analysis showed that no-tillage significantly increased the proportion of macroaggregates in Northwest China (17.6%) and MWD in North China (15.4%). In upland and clay loam, no-tillage increased MWD by 12.6% and 18.4%, respectively. The effect of no-tillage on increasing the proportion of macroaggregates increased with the soil pH. When straw returned, no-tillage significantly increased the proportion of macroaggregates (9.6%) and MWD (11.6%), but no significant effect of no-tillage on aggregates was found after straw removal. Regarding test duration, short-term ( < 5 a) no-tillage could significantly increase the proportion of macroaggregates, whereas long-term ( > 10 a) no-tillage could improve the MWD. In different soil layers, no-tillage could only significantly improve the aggregate size distribution and MWD in topsoil (0-20 cm) but had no effect in subsoil ( > 20 cm). In summary, no-tillage could improve aggregate size distribution and stability but had no effect on aggregate-associated C. Production region, soil properties, field management methods, and other factors should be fully considered in production practice to effectively improve the quality of soil aggregates.

4.
Angew Chem Int Ed Engl ; 63(12): e202319502, 2024 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-38279667

RESUMO

Aiming at the construction of novel stimuli-responsive fluorescent system with precisely tunable emissions, the typical 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration-induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli-responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC-functionalized [2]rotaxanes display interesting VIE behaviors including white-light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra. In addition, ascribed to the regulation of chirality information transmission through anion-induced motions of chiral wheel, the resolved chiral [2]rotaxanes reveal unique switchable CPL upon the addition of anion, leading to significant increase in the dissymmetry factors (glum ) values with excellent reversibility. Interestingly, upon doping the chiral [2]rotaxanes in stretchable polymer, the blend films reveal remarkable emission change from white light to light blue with significant 6.5-fold increase in glum values up to -0.035 under external tensile stresses. This work provides not only a new design strategy for developing molecular systems with fluorescent tunability but also a novel platform for the construction of smart chiral luminescent materials for practical use.

5.
Huan Jing Ke Xue ; 44(12): 6847-6856, 2023 Dec 08.
Artigo em Chinês | MEDLINE | ID: mdl-38098409

RESUMO

As a soil amendment, biochar has been widely used to ameliorate agricultural soil. To ensure the effect of biochar on the carbon sequestration of farmlands in China, a Meta-analysis was carried out via collecting published literatures. We quantitatively analyzed the response of biochar application to soil aggregates, aggregate carbon, and soil organic carbon to different experimental conditions. The results showed that the application of biochar significantly increased the proportion of soil macroaggregates(10.8%) and MWD(13.3%) but had no significant effect on soil microaggregates and silty-clay compared with those in the non-biochar-added treatment. Moreover, biochar addition significantly increased soil organic carbon content(56.9%), with the largest increased area in North China(39.4%), and enhanced intra-aggregate carbon contents of each particle size. Biochar could significantly increase soil organic carbon content under different experimental designs. Compared with that under non-fertilization, biochar combined with fertilization could also significantly improve soil structure and soil fertility. We also found that more than two years of biochar application significantly increased the proportion of macroaggregates(15.7%), MWD(21.2%), macroaggregate carbon(31.7%), and soil organic carbon(40.0%). Meanwhile, biochar produced from crop straw had better soil improvement effects than that of wood and sawdust. Biochar applied in high-nitrogen soil was more beneficial to improve soil stability. Thus, we concluded that biochar could meliorate soil structure and promote the accumulation of soil organic carbon, which was of importance for the fertility maintenance and improvement of the farmland.


Assuntos
Carbono , Solo , Carbono/análise , Solo/química , Carvão Vegetal/química , Agricultura , China
6.
Behav Res Methods ; 2023 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-37697207

RESUMO

Nonverbal numerical ability supports individuals' numerical information processing in everyday life and is also correlated with their learning of mathematics. This ability is typically measured with an approximate number comparison paradigm, in which participants are presented with two sets of objects and instructed to choose the numerically larger set. This paradigm has multiple task variants, where the two sets are presented in different ways (e.g., two sets are presented either simultaneously or sequentially, or two sets are presented either intermixed or separately). Despite the fact that different task variants have often been used interchangeably, it remains unclear whether these variants measure the same aspects of nonverbal numerical ability. Using a latent variable modeling approach with 270 participants (Mage = 20.75 years, SDage = 2.03, 94 males), this study examined the degree to which three commonly used task variants tapped into the same construct. The results showed that a bi-factor model corresponding to the hypothesis that task variants had both commonalities and uniqueness was a better fit for the data than a single-factor model, corresponding to the hypothesis that task variants were construct equivalent. These findings suggested that task variants of approximate number comparison did not measure the same construct and cannot be used interchangeably. This study also quantified the extent to which general cognitive abilities were involved in both common and unique parts of these task variants.

7.
Research (Wash D C) ; 6: 0226, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37746659

RESUMO

Asia stands out as a priority for urgent biodiversity conservation due to its large protected areas (PAs) and threatened species. Since the 21st century, both the highlands and lowlands of Asia have been experiencing the dramatic human expansion. However, the threat degree of human expansion to biodiversity is poorly understood. Here, the threat degree of human expansion to biodiversity over 2000 to 2020 in Asia at the continental (Asia), national (48 Asian countries), and hotspot (6,502 Asian terrestrial PAs established before 2000) scales is investigated by integrating multiple large-scale data. The results show that human expansion poses widespread threat to biodiversity in Asia, especially in Southeast Asia, with Malaysia, Cambodia, and Vietnam having the largest threat degrees (∼1.5 to 1.7 times of the Asian average level). Human expansion in highlands induces higher threats to biodiversity than that in lowlands in one-third Asian countries (most Southeast Asian countries). The regions with threats to biodiversity are present in ∼75% terrestrial PAs (including 4,866 PAs in 26 countries), and human expansion in PAs triggers higher threat degrees to biodiversity than that in non-PAs. Our findings provide novel insight for the Sustainable Development Goal 15 (SDG-15 Life on Land) and suggest that human expansion in Southeast Asian countries and PAs might hinder the realization of SDG-15. To reduce the threat degree, Asian developing countries should accelerate economic transformation, and the developed countries in the world should reduce the demands for commodity trade in Southeast Asian countries (i.e., trade leading to the loss of wildlife habitats) to alleviate human expansion, especially in PAs and highlands.

8.
Nat Commun ; 14(1): 5307, 2023 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-37652914

RESUMO

Aiming at the creation of polymers with attractive dynamic properties, herein, rotaxane-branched dendronized polymers (DPs) with rotaxane-branched dendrons attached onto the polymer chains are proposed. Starting from macromonomers with both rotaxane-branched dendrons and polymerization site, targeted rotaxane-branched DPs are successfully synthesized through ring-opening metathesis polymerization (ROMP). Interestingly, due to the existence of multiple switchable [2]rotaxane branches within the attached dendrons, anion-induced reversible thickness modulation of the resultant rotaxane-branched DPs is achieved, which further lead to tunable thermal and rheological properties, making them attractive platform for the construction of smart polymeric materials.

9.
J Am Chem Soc ; 145(26): 14498-14509, 2023 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-37328923

RESUMO

Aiming at the construction of novel soft actuators through the amplified motions of molecular machines at the nanoscale, the design and synthesis of a new family of photoresponsive rotaxane-branched dendrimers through an efficient controllable divergent approach was successfully realized for the first time. In the third-generation rotaxane-branched dendrimers, up to 21 azobenzene-based rotaxane units located at each branch, thus making them the first successful synthesis of light-control integrated artificial molecular machines. Notably, upon alternative irradiation with UV and visible light, photoisomerization of the azobenzene stoppers leads to the collective and amplified motions of the precisely arranged rotaxane units, resulting in controllable and reversible dimension modulation of the integrating photoresponsive rotaxane-branched dendrimers in solution. Moreover, novel macroscopic soft actuators were further constructed based on these photoresponsive rotaxane-branched dendrimers, which revealed fast shape transformation behaviors with an actuating speed up to 21.2 ± 0.2° s-1 upon ultraviolet irradiation. More importantly, the resultant soft actuators could produce mechanical work upon light control that has been further successfully employed for weight-lifting and cargo transporting, thus laying the foundation toward the construction of novel smart materials that can perform programmed events.

10.
J Exp Child Psychol ; 232: 105666, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37043876

RESUMO

A fundamental research question in quantitative cognition concerns the developmental relationship between nonsymbolic and symbolic quantitative abilities. This study examined this developmental relationship in abilities to process nonsymbolic and symbolic fractions. There were 99 6th graders (Mage = 11.86 years), 101 10th graders (Mage = 15.71 years), and 102 undergraduate and graduate students (Mage = 21.97 years) participating in this study, and their nonsymbolic and symbolic fraction abilities were measured with nonsymbolic and symbolic fraction comparison tasks, respectively. Nonsymbolic and symbolic fraction abilities were significantly correlated in all age groups even after controlling for the ability to process nonsymbolic absolute quantity and general cognitive abilities, including working memory and inhibitory control. Moreover, the strength of nonsymbolic-symbolic correlations was higher in 6th graders than in 10th graders and adults. These findings suggest a weakened association between nonsymbolic and symbolic fraction abilities during development, and this developmental pattern may be related with participants' increasing proficiency in symbolic fractions.


Assuntos
Cognição , Memória de Curto Prazo , Adulto , Humanos , Criança , Adolescente , Adulto Jovem , Matemática
11.
Huan Jing Ke Xue ; 44(1): 482-493, 2023 Jan 08.
Artigo em Chinês | MEDLINE | ID: mdl-36635836

RESUMO

This study was conducted to clarify the structure and function of the fungal community and the microecology change characteristics of farmland soil fertility response to different fallow rotation patterns. It aimed to provide a reference for promoting farmland ecological restoration and farmland quality improvement in the alluvial plain of the lower Yellow River. Farmland soil subject to a long-term rotation fallow experiment since 2018 was studied using Illumina MiSeq high-throughput sequencing technology, and the 'FUNGuild' fungal function prediction tool was used to analyze differences in soil fungal community structure and function under the following four rotation fallow regimes: long fallow (LF), winter wheat and summer fallow (WF), winter fallow and summer maize (FM), and annual rotation of winter wheat and summer maize (WM). The results showed that LF (fallow lasting two years) increased the richness and diversity of fungal communities in the topsoil (0-20 cm layer), whereas WF increased the richness and diversity of fungi in the deep soil (20-40 cm layer) after winter wheat harvest. A total of 2262 OTU were obtained from all soil samples, which were divided into 14 phyla, 34 classes, 75 orders, 169 families, 309 genera, and 523 species. OTU shared by the two soil layers included 420 types (0-20 cm layer) and 253 types (20-40 cm layer), respectively. The fungal community structure of the four rotation fallow soils was similar at the phylum level, mainly including Ascomycota, Basidiomycota, and Mortierellomycota. The total abundances of the three dominant bacteria were 91.69%-96.91% (0-20 cm layer) and 91.67%-94.86% (20-40 cm layer), respectively. Principal component analysis showed that the first principal component (PC1) and the second principal component (PC2) could explain the difference in community structure by 45.56% (0-20 cm layer) and 46.20% (20-40 cm layer). Additionally, the LDA results of LEfSe (threshold was 4.0) showed that there were 64 fungal evolutionary branches in LF, FM, WF, and WM with statistically significant differences (P<0.05). According to RDA analysis, total organic carbon (TOC), total phosphorus (TP), available nitrogen (AN), and soil water content (SWC) were the main environmental factors that significantly affected fungal community in the 0-40 cm soil layer (P<0.05). The functional prediction with FUNGuild showed that the main nutrient types among different treatments in different soil layers were saprotrophic, saprotrophic-symbiotrophic, pathotrophic-saprotrophic-symbiotrophic, and pathotrophic. In LF, the nutrient type of topsoil was mainly pathotrophic-saprotrophic-symbiotrophic, whereas in deep soil, the relative abundance of pathotrophic fungi was the highest. Additionally, in the treatments with planted wheat or corn (FM, WF, and WM), saprotrophic was the main type in both soil layers. Therefore, different fallow patterns were linked to variation in the structure, diversity, and nutrient types of soil fungal communities. Based on these results, seasonal fallow practices could regulate the farmland soil micro-ecological environment of intensive planting and promote the health and harmony of farmland soil ecosystems.


Assuntos
Micobioma , Solo , Humanos , Solo/química , Ecossistema , Fazendas , Rios , Rotação , Triticum , Microbiologia do Solo
12.
Appl Biochem Biotechnol ; 195(7): 4196-4214, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-36662424

RESUMO

Adipose-derived stem cells (ADSCs) are a type of adult mesenchymal stem cell that show a repair effect on ischemic tissues owing to their capacity for endothelial differentiation. MicroRNA-221/222 (miR-221/222) has been extensively studied in endothelial cells (ECs). However, the mechanism that regulates ADSCs differentiation into ECs remains unknown. In this study, we investigated the effects of miR-221/222-overexpression/silence in ADSCs on endothelial differentiation by constructing lentiviral vectors. Differentiation capacity was assessed by measuring the expression of endothelial markers (CD31, CD34, and CD144). In addition, low-density lipoprotein (LDL) uptake and tube-like formation were performed for evaluation of functional characterization. The PTEN/PI3K/AKT/mTOR signaling pathway was investigated using western blotting to clarify the action mechanism of this gene. The revascularization of miR-221/222-transfeted ADSCs was further verified in a rat hind limb ischemia model. The results confirmed that transfection with miR-221/222 promoted the expression of endothelial markers, LDL uptake, and tube-like formation. As expected, the PI3K/AKT signaling pathway was effectively activated when ADSCs showed high expression of miR-221/222 during endothelial differentiation. Furthermore, injection of miR-221/222 transfected ADSCs significantly improved rat hindlimb ischemia, as evidenced by increased blood flow and structural integrity and reduce inflammatory infiltration. The results of this study suggest that miR-221/222 is essential for endothelial differentiation of ADSCs and provides a novel strategy for modulating vascular formation and ischemic tissue regeneration.


Assuntos
Células-Tronco Mesenquimais , MicroRNAs , Ratos , Animais , Proteínas Proto-Oncogênicas c-akt/genética , Proteínas Proto-Oncogênicas c-akt/metabolismo , Fosfatidilinositol 3-Quinases/genética , Fosfatidilinositol 3-Quinases/metabolismo , Células Endoteliais , Diferenciação Celular/genética , Serina-Treonina Quinases TOR/genética , MicroRNAs/genética , MicroRNAs/metabolismo , Tecido Adiposo
13.
Shock ; 59(2): 256-266, 2023 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-36427100

RESUMO

ABSTRACT: Dendritic cell (DC)-mediated immune dysfunction is involved in the process of severe hemorrhagic shock that leads to sepsis. Although post-hemorrhagic shock mesenteric lymph (PHSML) induces immune organs injuries and apoptosis, whether PHSML exerts adverse effects on splenic DCs remains unknown. In this study, we established a hemorrhagic shock model (40 ± 2 mm Hg for 60 min) followed by fluid resuscitation with the shed blood and equal Ringer's solution and drained the PHSML after resuscitation. At 3 h after resuscitation, we harvested the splenic tissue to isolate DCs using anti-CD11c immunomagnetic beads and then detected the necrotic and apoptotic rates in splenocytes and splenic DCs. We also detected the levels of TNF-α, IL-10, and IL-12 in the culture supernatants and surface marker expressions of MHC-II, CD80, and CD86 of splenic DCs following LPS stimulation for 24 h. Second, we purified the DCs from splenocytes of normal mice to investigate the effects of PHSML treatment on cytokine production and surface marker expression following LPS stimulation. The results showed that PHSML drainage attenuated LPS-induced cell death of splenocytes and DCs. Meanwhile, PHSML drainage enhanced the DC percentage in splenocytes and increased the TNF-α and IL-12 production by DCs and the expressions of CD80, CD86, and MHCII of DCs treated by LPS. Furthermore, PHSML treatment reduced the productions of TNF-α, IL-10, and IL-12 and the expressions of CD80 and CD86 in normal DCs after treatment with LPS. In summary, the current investigation demonstrated that PHSML inhibited the cytokine production and surface marker expressions of DCs stimulated by LPS, suggesting that PHSML plays an important role in hemorrhagic shock-induced immunosuppression through the impairment of DC function and maturation.


Assuntos
Choque Hemorrágico , Humanos , Choque Hemorrágico/terapia , Interleucina-10/metabolismo , Fator de Necrose Tumoral alfa/metabolismo , Lipopolissacarídeos/farmacologia , Interleucina-12/metabolismo , Células Dendríticas/metabolismo
14.
Plants (Basel) ; 11(24)2022 Dec 14.
Artigo em Inglês | MEDLINE | ID: mdl-36559627

RESUMO

Heat stress around flowering is harmful to maize growth and yield. Ear traits are closely related to yield; however, the effects of heat stress before and after flowering on ear development and yield traits remain unclear for different heat-tolerant cultivars. In this study, field experiments were conducted in 2020 and 2021, including (i) three sowing dates, (ii) three temperature regimes: control (CK), heated before silking (V9-R1, TBS) and heated after silking (R1-R1 + 15 d, TAS), and (iii) two hybrids (ZD958: heat-tolerant; DH605: heat-sensitive). The results showed that heating had negative effects on all surveyed ear and yield traits except for increased ear length under TBS. The negative effects were larger (i) for TAS than for TBS, (ii) for DH605 than for ZD958, and (iii) for kernel number per plant (KNP) than for kernel weight (KW). The decreased ear traits were a result of a decreased growth rate during rapid ear growth periods. Floret pollination failure and kernel abortion were the main reasons for the decrease in KNP, mainly depending on the daily maximum temperature during V15-R1 + 7 d. The strong linear relationships between ear and yield traits suggested that ear traits could be used as important indicators for breeding heat-resistant varieties in the future.

15.
PLoS One ; 17(11): e0276373, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36331931

RESUMO

The algorithm unfolding networks with explainability of algorithms and higher efficiency of Deep Neural Networks (DNN) have received considerable attention in solving ill-posed inverse problems. Under the algorithm unfolding network framework, we propose a novel end-to-end iterative deep neural network and its fast network for image restoration. The first one is designed making use of proximal gradient descent algorithm of variational models, which consists of denoiser and reconstruction sub-networks. The second one is its accelerated version with momentum factors. For sub-network of denoiser, we embed the Convolutional Block Attention Module (CBAM) in previous U-Net for adaptive feature refinement. Experiments on image denoising and deblurring demonstrate that competitive performances in quality and efficiency are gained by compared with several state-of-the-art networks for image restoration. Proposed unfolding DNN can be easily extended to solve other similar image restoration tasks, such as image super-resolution, image demosaicking, etc.


Assuntos
Processamento de Imagem Assistida por Computador , Redes Neurais de Computação , Processamento de Imagem Assistida por Computador/métodos , Algoritmos
16.
Angew Chem Int Ed Engl ; 61(44): e202210542, 2022 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-36000407

RESUMO

Aiming at the construction of novel circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (glum ), topologically chiral [2]catenanes were employed as the key platform to construct a novel multistate CPL switching system. Taking advantage of the precise co-conformation regulations of the resultant pyrene-functionalized [2]catenanes under different external stimuli, reversible transformations between three emission states with different CPL performances, i.e. the initial "closed" form with a |glum | value of 0.012, the "open" form with an almost complete turn-off of CPL emission, and the "protonated" form with a boosted |glum | value of 0.022, were successfully realized. This study demonstrates the successful construction of not only the first topological chirality-based CPL switch, but also a novel bidirectional CPL switch, thus providing a promising platform for the construction of novel chiral materials.

17.
Nat Commun ; 13(1): 4955, 2022 08 24.
Artigo em Inglês | MEDLINE | ID: mdl-36002452

RESUMO

Most intensive human activities occur in lowlands. However, sporadic reports indicate that human activities are expanding in some Asian highlands. Here we investigate the expansions of human activities in highlands and their effects over Asia from 2000 to 2020 by combining earth observation data and socioeconomic data. We find that ∼23% of human activity expansions occur in Asian highlands and ∼76% of these expansions in highlands comes from ecological lands, reaching 95% in Southeast Asia. The expansions of human activities in highlands intensify habitat fragmentation and result in large ecological costs in low and lower-middle income countries, and they also support Asian developments. We estimate that cultivated land net growth in the Asian highlands contributed approximately 54% in preventing the net loss of the total cultivated land. Moreover, the growth of highland artificial surfaces may provide living and working spaces for ∼40 million people. Our findings suggest that highland developments hold dual effects and provide new insight for regional sustainable developments.


Assuntos
Povo Asiático , Ecossistema , Ásia , Sudeste Asiático , Humanos
18.
Chem Commun (Camb) ; 58(12): 2006-2009, 2022 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-35050273

RESUMO

The precise synthesis of novel rotaxane-branched radical dendrimers Gn-TEMPO (n = 1-3) with up to 24 TEMPO radicals as termini was successfully achieved, from which nanoparticles with a good longitudinal relaxivity were further prepared, thus making them potential candidates as promising contrast agents for magnetic resonance imaging.

19.
Acc Chem Res ; 54(21): 4091-4106, 2021 11 02.
Artigo em Inglês | MEDLINE | ID: mdl-34676764

RESUMO

During recent decades, the blossoming of the field of mechanically interlocked molecules (MIMs), i.e., molecules containing mechanical or topological bonds such as rotaxanes, catenanes, and knots, has been reported in the literature. Taking advantage of the rapid development of diverse synthetic strategies, the precise control of both the architectures and topologies of MIMs has become realizable, which thus enables the construction of MIMs with specially desired functions. By mimicking biomolecular machines, a variety of MIM-based artificial molecular machines such as molecular shuttles, molecular muscles, molecular motors, and molecular assemblers have been constructed and operated by relying on the unique interlocked structures and controllable intramolecular movements. Two pioneers in this field, J. Fraser Stoddart and Jean-Pierre Sauvage, were awarded the 2016 Nobel Prize in Chemistry, thereby marking a golden age of MIMs. Along with the burgeoning of MIMs, the engineering of mechanical bonds into macromolecular scaffolds such as polymers or dendrimers has become an attractive topic since the targeted novel mechanically bonded macromolecules would feature interesting processable and mechanical properties, making them excellent candidates for practical applications such as device fabrication or smart materials. In particular, rotaxane dendrimers, attributed to the combination of the advantageous features of both rotaxanes (controllable dynamic motions) and dendrimers (nanoscale highly branched architectures), have evolved as versatile platforms for extensive applications such as gene delivery, light harvesting, and molecular nanoreactors. However, compared with the widely investigated polyrotaxanes and polycatenanes, in-depth investigations on rotaxane dendrimers have rarely been explored mainly because of the synthetic challenge that makes the preparation of diverse rotaxane dendrimers, especially high-generation ones, extremely difficult. During recent years, through the rational design and synthesis of organometallic rotaxane units as key building blocks, the employment of a controllable divergent approach led to the successful synthesis of a variety of rotaxane dendrimers with precise arrangements of rotaxane units as well as stimuli-responsive sites and functional groups. More importantly, on the basis of the synthetic accessibility to diverse rotaxane dendrimers, rotaxane dendrimers have been proven to hold great promise for extensive applications in diverse fields such as light harvesting, photocatalysis, and soft actuators. In this Account, we summarize our expedition in rotaxane dendrimers, including addressing the synthetic challenges, investigating their stimuli-responsive properties, expanding their potential applications, and inventing higher-order daisy chain dendrimers. We believe that this Account will inspire scientists from various disciplines to explore these appealing and versatile higher-order mechanically bonded macromolecules.

20.
ACS Omega ; 6(38): 24683-24692, 2021 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-34604650

RESUMO

In recent years, the explosion accidents of liquefied petroleum gas (LPG) have induced tremendous losses. To analyze the deflagration danger of LPG, the explosion pressure and flame propagation features of the premixed LPG-air mixture in a closed pipeline at increased initial pressures and temperatures were examined by the numerical method. It has been shown that with an increase in the initial temperature, the highest explosion pressure and explosion induction period decrease, while the maximum flame temperature increases. As the initial temperature rises, the formation of the tulip flame accelerates, and the depression of the flame front increases at the same time. The elevated initial pressure raises the highest explosion pressure and the maximum flame temperature. Nevertheless, when the initial pressure exceeds 0.5 MPa, its impact on the flame temperature slowly diminishes. In addition, the gray relational analysis approach was utilized to evaluate the correlation between the initial condition and the derived parameters. The findings indicate that the initial pressure exerts the largest influence on the four explosion parameters. The research finding is important for exposing the deflagration risk features of LPG under complicated working situations, evaluating the explosion risk of correlated procedures and devices, and formulating scientific and effective explosion-proof measures.

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