oligomers

低聚物
  • 文章类型: Journal Article
    对由小分子前体制备的碳点(CD)低聚物的深入了解对于研究CD的碳化机理以及我们对其复杂结构的了解非常重要。在这里,使用柠檬酸(CA)和乙二胺(EDA)作为小分子前体在水溶液中制备CD。首先使用密度泛函理论研究了从不同摩尔比的CA和EDA获得的低聚物的结构及其形成过程,包括色散校正(DFT-D3)方法。结果表明,二聚体环化的能障高于其线性聚合的能障,但是环化产物的自由能远低于其反应物的自由能,因此,在某些条件下可以获得IPCA(5-氧代-1,-2,3,5-四氢咪唑并[1,2-a]吡啶-7-羧酸)。从不同摩尔比的EDA和CA获得的低聚物是由短聚酰胺链通过分子间力形成的分子簇;除了当EDA与CA的摩尔比为0.5时,过量的CA不经历酰胺化反应,而是直接通过分子间力获得分子簇。这些低聚物在其表面官能团方面表现出显著差异,这将影响CD的碳化过程和表面结构。
    In-depth insights into the oligomers of carbon dots (CDs) prepared from small-molecule precursors are important in the study of the carbonization mechanism of CDs and for our knowledge of their complex structure. Herein, citric acid (CA) and ethylenediamine (EDA) were used as small-molecule precursors to prepare CDs in an aqueous solution. The structure of oligomers acquired from CA and EDA in different molar ratios and their formation process were first studied using density functional theory, including the dispersion correction (DFT-D3) method. The results showed that the energy barrier of dimer cyclization was higher than that of its linear polymerization, but the free energy of the cyclized product was much lower than that of its reactant, and IPCA (5-oxo-1,-2,3,5-tetrahydroimidazo [1,2-a]pyridine-7-carboxylic acid) could therefore be obtained under certain conditions. The oligomers obtained from different molar ratios of EDA and CA were molecular clusters formed by short polyamide chains through intermolecular forces; with the exception of when the molar ratio of EDA to CA was 0.5, excessive CA did not undergo an amidation reaction but rather attained molecular clusters directly through intermolecular forces. These oligomers exhibited significant differences in their surface functional groups, which would affect the carbonization process and the surface structure of CDs.
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  • 文章类型: Journal Article
    Tau蛋白错误折叠和聚集是阿尔茨海默病和20多种神经退行性疾病的病理标志。然而,体内tau聚集的分子机制仍未完全了解。脑中存在两种类型的tau聚集体:可溶性聚集体(寡聚物和原纤维)和不溶性细丝(原纤维)。与丝状聚集体相比,可溶性聚集体毒性更大,表现出朊病毒样传播,为模板化的错误折叠提供种子。奇怪的是,在它的原生状态,tau是一种高度可溶的,本身不形成原纤维的热稳定蛋白质,甚至在过度磷酸化时也没有。体外研究发现,带负电荷的分子如肝素,RNA,或花生四烯酸通常需要诱导tau聚集。最近的两个突破为tau聚合机制提供了新的见解。首先,作为一种内在无序的蛋白质,发现tau在体外和细胞内都经历液-液相分离(LLPS)。第二,低温电子显微镜显示了与不同神经退行性疾病相关的不同纤维状tau构象。尽管如此,只有纤芯在结构上得到解决,其余的蛋白质显示为“模糊的外套”。从这篇评论来看,似乎需要进一步的研究(1)阐明LLPS在tau聚集中的作用;(2)揭示可溶性tau聚集体的结构特征;(3)了解模糊涂层区域在低聚物和原纤维形成中的参与。
    Tau protein misfolding and aggregation are pathological hallmarks of Alzheimer\'s disease and over twenty neurodegenerative disorders. However, the molecular mechanisms of tau aggregation in vivo remain incompletely understood. There are two types of tau aggregates in the brain: soluble aggregates (oligomers and protofibrils) and insoluble filaments (fibrils). Compared to filamentous aggregates, soluble aggregates are more toxic and exhibit prion-like transmission, providing seeds for templated misfolding. Curiously, in its native state, tau is a highly soluble, heat-stable protein that does not form fibrils by itself, not even when hyperphosphorylated. In vitro studies have found that negatively charged molecules such as heparin, RNA, or arachidonic acid are generally required to induce tau aggregation. Two recent breakthroughs have provided new insights into tau aggregation mechanisms. First, as an intrinsically disordered protein, tau is found to undergo liquid-liquid phase separation (LLPS) both in vitro and inside cells. Second, cryo-electron microscopy has revealed diverse fibrillar tau conformations associated with different neurodegenerative disorders. Nonetheless, only the fibrillar core is structurally resolved, and the remainder of the protein appears as a \"fuzzy coat\". From this review, it appears that further studies are required (1) to clarify the role of LLPS in tau aggregation; (2) to unveil the structural features of soluble tau aggregates; (3) to understand the involvement of fuzzy coat regions in oligomer and fibril formation.
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  • 文章类型: Journal Article
    空穴传输材料(HTMs)的π-共轭体系和空间构型会极大地影响其各种性质和相应的钙钛矿太阳能电池效率。这里,提出了一种将不同量的对甲氧基苯胺取代的二苯并呋喃作为π桥引入HTM的分子工程策略,以开发低聚物HTM,名为mDBF,bDBF,和tDBF。在扩展HTM的π共轭时,他们的HOMO能级略有加深,显著提高了热稳定性和空穴迁移率。对甲氧基苯胺桥的结合建立了一个或两个额外的三苯胺螺旋桨结构,导致更致密的薄膜。这里,基于tDBF的n-i-p柔性钙钛矿太阳能电池创造了冠军效率,给出了19.46%的功率转换效率。tDBF的简单合成和纯化工艺使其在实验室生产成本低。该工作为开发低成本、高效的HTM提供了参考。
    The π-conjugated system and the steric configuration of hole transport materials (HTMs) could greatly affect their various properties and the corresponding perovskite solar cells\' efficiencies. Here, a molecular engineering strategy of incorporating different amounts of p-methoxyaniline-substituted dibenzofurans as π bridge into HTMs was proposed to develop oligomer HTMs, named mDBF, bDBF, and tDBF. Upon extending the π-conjugation of HTMs, their HOMO energy levels were slightly deepened, significantly increasing the thermal stability and hole mobility. The incorporation of p-methoxyaniline bridges built one or two additional triphenylamine propeller structures, resulting in a denser film. Here, the tDBF-based n-i-p flexible perovskite solar cells createdchampion efficiency, giving a power conversion efficiency of 19.46%. And the simple synthesis and purification process of tDBF contributed to its low manufacturing cost in the laboratory. This work provided a reference for the development of low-cost and efficient HTMs.
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  • 文章类型: Journal Article
    三硅氧烷乙氧基化物(TSEOn)由于其与农药活性成分的显着协同作用而被广泛用作农业表面活性剂,一般来说,包括三个典型的端基为羟基(TSEOn-H),甲氧基(TSEOn-CH3),和乙酰氧基(TSEOn-COCH3),分别。然而,TSEOn同类物的潜在生态毒理学和内分泌干扰风险最近引起了越来越多的关注。最重要的是,关于农业生态系统中TSEOn浓度水平的研究有限。这项研究,通过改良的QuEChERS(快速,easy,便宜,有效,崎岖,并且安全)提取与超高效液相色谱-串联质谱(UPLC-MS/MS)耦合。TSEOn的方法检出限(MDL)和方法定量限(MQL)为0.003-0.07μg/kg和0.01-0.20μg/kg,分别。土壤中TSEOn低聚物的回收率为81%〜106%,相关标准偏差(RSD)<7%。这种新开发的UPLC-MS/MS方法具有高灵敏度和稳定性,使我们能够成功地追踪中国3个省和1市柑橘园土壤中TSEOn同源物的发生。在采样土壤中检测到的TSEOn-H低聚物的浓度范围为0.02至0.288μg/kg(干重)。TSEOn-H的同类物剖面在土壤中由TSEOn-H(n=6-8)主导。此外,土壤中TSEOn-H同源物(ΣTSEOn-H)的总浓度在0.03至1.49μg/kg的范围内。对不同柑橘园土壤中ΣTSEOn-H分布的比较表明,从浙江省收集的土壤样品中ΣTSEOn-H的含量较高。值得注意的是,在测试的土壤中未检测到TSEOn-CH3或TSEOn-COCH3低聚物。据我们所知,这是有关TSEOn同源物在农业土壤中的发生和分布的第一份报告。
    Trisiloxane ethoxylates (TSEOn) are widely used as agricultural surfactants due to their significant synergism with the active ingredients of pesticides, generally, including three typical end groups which are hydroxyl (TSEOn-H), methoxy (TSEOn-CH3), and acetoxy (TSEOn-COCH3), respectively. However, the potential ecotoxicological and endocrine-disrupting risks of TSEOn congeners have recently attracted ever-growing concern. Above all, there is limited research on the concentration levels of TSEOn in agroecosystems. This study, simultaneous analysis of 39 TSEOn oligomers in citrus orchard soils in China was implemented by the modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The method detection limits (MDLs) and the method quantification limits (MQLs) for TSEOn were 0.003-0.07 μg/kg and 0.01-0.20 μg/kg, respectively. The recoveries for TSEOn oligomers in soils ranged from 81 % ∼ 106 % with related standard deviations (RSDs) < 7 %. This newly developed UPLC-MS/MS method with high sensitivity and stability allows us to successfully trace the occurrence of TSEOn congeners in the citrus orchard soils from 3 provinces and 1 municipality in China. The detected concentrations of TSEOn-H oligomers in the sampled soils ranged from 0.02 to 0.288 μg/kg (dry weight). The congener profiles of TSEOn-H were dominated by TSEOn-H (n = 6- 8) in the soils. Additionally, the total concentrations of TSEOn-H congeners (ΣTSEOn-H) in the soils were in the range of 0.03 to 1.49 μg/kg. A comparison of ΣTSEOn-H distribution among the different citrus orchard soils indicated a higher level of ΣTSEOn-H in the soil samples collected from Zhejiang Province. Notably, TSEOn-CH3 or TSEOn-COCH3 oligomers were not detected in the tested soils. To the best of our knowledge, this is the first report on the occurrence and distribution of TSEOn congeners in agricultural soils.
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  • 文章类型: Journal Article
    烯烃臭氧分解可以产生稳定的Criegee中间体(SCI),在低聚物的形成中起关键作用。尽管苯乙烯和异戊二烯作为重要的人为和生物次级有机气溶胶(SOA)前体在环境大气中共存,分别,他们的交叉反应没有引起注意。这项研究首次研究了苯乙烯和异戊二烯臭氧分解的SCIs的相互作用。高分辨率Orbitrap质谱仪用于确定异戊二烯-苯乙烯-O3混合物的独特离子质谱。结果表明,在苯乙烯-异戊二烯-O3混合体系的质谱中,新离子的信号强度占总离子的8.4%以上。苯乙烯和异戊二烯臭氧分解可以分别产生特征性的C7-SCI和C4-SCI。C7-SCI和C4-SCI可以参与交叉反应,串联质谱的结果直接证实了C7-SCI和C4-SCI均为链单元。交叉产品的O/C和H/C比分别在0.38-1.07和1.00-1.50范围内,与交叉反应产物一致。添加C7-SCI单位比添加C4-SCI单位降低了1.3-1.4个数量级。因此,C4-SCI可以与C7-SCI竞争,与苯乙烯衍生的RO2/RC(O)OH反应,产生更多的挥发性交叉产物,而当异戊二烯衍生的RO2/RC(O)OH与C7-SCI代替C4-SCI反应时,可以形成挥发性较低的交叉产物。混合体系的SOA产率低于单一苯乙烯-O3体系,但高于单一异戊二烯-O3体系。还收集了环境颗粒,并确定了5种可能的SCI相关交叉产品。这项研究说明了SCI相关的交叉反应对SOA成分和理化性质的影响,为未来研究环境大气中频繁发生的SCI相关交叉反应提供基础。
    Alkene ozonolysis can produce stabilized Criegee intermediates (SCIs), which play a key role in oligomers\' formation. Though styrene and isoprene coexist in the ambient atmosphere as important anthropogenic and biogenic secondary organic aerosol (SOA) precursors, respectively, their cross-reactions have not received attention. This study investigated the interactions of SCIs from styrene and isoprene ozonolysis for the first time. The high-resolution Orbitrap mass spectrometer was used to determine the unique ion mass spectra of the isoprene-styrene-O3 mixture. The results show that the signal intensities of new ions account for >8.4% of total ions in the mass spectra of the styrene-isoprene-O3 mixed system. Styrene and isoprene ozonolysis can produce characteristic C7-SCI and C4-SCI, respectively. C7-SCI and C4-SCI can be involved in the cross-reactions, and the results of tandem mass spectra directly confirmed both C7-SCI and C4-SCI as chain units. The O/C and H/C ratios of cross-products are in the range of 0.38-1.07 and 1.00-1.50, respectively, which are consistent with cross-reaction products. Adding a C7-SCI unit reduces the oligomer\'s volatility by 1.3-1.4 orders of magnitude lower than adding a C4-SCI unit. Thus, C4-SCI can compete with C7-SCI to react with styrene-derived RO2/RC(O)OH to produce more volatile cross-products, while the less volatile cross-products can be formed when isoprene-derived RO2/RC(O)OH reacted with C7-SCI instead of C4-SCI. The SOA yield of the mixed system is lower than that of the single styrene-O3 system but higher than that of the single isoprene-O3 system. Ambient particles were also collected, and 5 possible SCI-related cross-products were identified. This study illustrates the effects of SCI-related cross-reactions on SOA components and physicochemical properties, providing a basis for future research on SCI-related cross-reactions that frequently occur in the ambient atmosphere.
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  • 文章类型: Journal Article
    环境塑料废物是潜在的健康危害,因为它们的普遍性以及它们在物理引发方面的多功能性,化学,以及生物相互作用和转化。的确,最近的研究暗示了微米和纳米塑料的不利影响,包括它们的神经毒性,然而,塑料颗粒如何影响与神经系统疾病病理相关的淀粉样蛋白的聚集途径和毒性仍然未知。这里,电喷雾电离飞行时间质谱(ESI-TOF-MS)用于揭示NACore的多晶型寡聚化,与帕金森病发病机制相关的α-突触核蛋白的替代物。这些数据表明,NACore低聚物的生产率和种群是通过暴露于聚苯乙烯纳米塑料来调节的。这些细胞分析进一步揭示了纳米塑料引起的小胶质细胞中NACore毒性的升高。这些模拟证实了纳米塑料-NACore缔合是通过它们的疏水相互作用促进的。斑马鱼孵化的损伤证实了这些发现,生存,并在胚胎暴露于纳米塑料后在体内发育。一起,这项研究揭示了纳米塑料引发剂引起的淀粉样蛋白生成的动力学和机制,揭示了塑料污染的神经负担。
    Environmental plastic wastes are potential health hazards due to their prevalence as well as their versatility in initiating physical, chemical, and biological interactions and transformations. Indeed, recent research has implicated the adverse effects of micro- and nano-plastics, including their neurotoxicity, yet how plastic particulates may impact the aggregation pathway and toxicity of amyloid proteins pertinent to the pathologies of neurological diseases remains unknown. Here, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) is employed to reveal the polymorphic oligomerization of NACore, a surrogate of alpha-synuclein that is associated with the pathogenesis of Parkinson\'s disease. These data indicate that the production rate and population of the NACore oligomers are modulated by their exposure to a polystyrene nanoplastic, and these cellular assays further reveal an elevated NACore toxicity in microglial cells elicited by the nanoplastic. These simulations confirm that the nanoplastic-NACore association is promoted by their hydrophobic interactions. These findings are corroborated by an impairment in zebrafish hatching, survival, and development in vivo upon their embryonic exposure to the nanoplastic. Together, this study has uncovered the dynamics and mechanism of amyloidogenesis elevated by a nanoplastic trigger, shedding a new light on the neurological burden of plastic pollution.
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  • 文章类型: Journal Article
    Lindenane倍半萜单体和低聚物,其特征是空间阻塞的环戊烷和不寻常的反式5/6环连接,主要存在于Chlothanthaceae物种和LinderaThunb属(Lauraceae)中。大量研究表明,林均烷倍半萜单体和低聚物表现出广泛的生物活性,如细胞毒性,抗炎,神经保护,抗真菌药,和抗疟疾活动。这篇综述涵盖了1925年至2023年首次鉴定的亚麻黄醇的出版物,并将亚麻黄烷倍半萜衍生物分类为倍半萜单体,倍半萜-单萜共轭物,倍半萜同源二聚体,倍半萜异二聚体,和三聚体倍半萜。此外,对其生物活性进行了总结。这篇综述将为利用这类独特的天然产物作为潜在的先导化合物开发其在治疗与炎症相关的疾病中的应用奠定科学依据并提供指导。癌症,还有疟原虫.
    Lindenane sesquiterpenoid monomers and oligomers, characterized by a sterically congested cyclopentane and an unusual trans-5/6 ring junction, are mainly found in Chloranthaceae species and the genus Lindera Thunb (Lauraceae). Numerous studies have shown that lindenane sesquiterpenoid monomers and oligomers exhibit a broad range of biological activities, such as cytotoxicity, anti-inflammation, neuroprotection, antifungal, and anti-malarial activities. This review covers publications from the first identification of lindeneol in 1925-2023 and classifies the lindenane sesquiterpenoid derivatives into sesquiterpenoid monomers, sesquiterpenoid-monoterpene conjugates, sesquiterpenoid homodimers, sesquiterpenoid heterodimers, and trimeric sesquiterpenoids. In addition, their biological activities are summarized. This review will establish a scientific basis and provide guidance for utilizing this unique class of natural products as potential lead compounds to develop their application in treating diseases corresponding to inflammation, cancer, and plasmodium.
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  • 文章类型: Journal Article
    (具有独特的手性光-物质相互作用的超紧密手性等离子体纳米结构对于未来的光子技术至关重要。然而,以前的研究仅限于报告其稳态性能,对具有偏振灵敏度的高速光学器件的发展构成了根本障碍。这里,我们使用时间分辨偏振测量对手性金纳米低聚物的超快手性响应进行了全面分析。我们观察到吸收强度方面的显着差异,因此产生热电子,和偏振光泵浦时的热载流子衰减时间,这是由螺旋度分辨光学跃迁的现象学模型解释的。此外,通过反转泵浦脉冲的方向可以切换基频信号,演示了在单个设备中偏振选择的通用调制。我们的结果为光激发手性等离子体中的螺旋度分辨光学跃迁提供了基本见解,并且可以促进高速偏振敏感平面光学器件的开发,并在纳米光子学和量子光学中具有潜在应用。)本文受版权保护。保留所有权利。
    Ultracompact chiral plasmonic nanostructures with unique chiral light-matter interactions are vital for future photonic technologies. However, previous studies are limited to reporting their steady-state performance, presenting a fundamental obstacle to the development of high-speed optical devices with polarization sensitivity. Here, a comprehensive analysis of ultrafast chiroptical response of chiral gold nano-oligomers using time-resolved polarimetric measurements is provided. Significant differences are observed in terms of the absorption intensity, thus hot electron generation, and hot carrier decay time upon polarized photopumping, which are explained by a phenomenological model of the helicity-resolved optical transitions. Moreover, the chiroptical signal is switchable by reversing the direction of the pump pulse, demonstrating the versatile modulation of polarization selection in a single device. The results offer fundamental insights into the helicity-resolved optical transitions in photoexcited chiral plasmonics and can facilitate the development of high-speed polarization-sensitive flat optics with potential applications in nanophotonics and quantum optics.
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  • 文章类型: Journal Article
    具有近红外II(NIRII)光吸收的有机分子对于许多生物和光电应用至关重要。在这里,我们报告了单分散低聚物作为NIRII光吸收剂,使用共振N-B-N单元的新分子设计策略,即平衡共振硼-氮共价键(B-N)和硼-氮配位键(B-N)。我们合成了一系列具有噻吩稠合的4,4-二氟-4-硼-3a的单分散低聚物,4a-二氮杂-s-茚并苯(TB),其中包含共振N-B-N单位,作为重复单元。TB五聚体的最大吸收波长为1169nm,这是迄今为止报道的低聚物最长的。以TB四聚体为电子受体的有机光电探测器(OPD)在零偏压下在1180nm处显示出2.98×1011Jones的比探测率。此性能是NIRIIOPD的最佳性能之一。这些结果表明一种新型的NIRII吸收分子是优异的光电材料。
    Organic molecules with near-infrared II (NIR II) light absorption are essential for many biological and opto-electronic applications. Herein, we report monodispersed oligomers as NIR II light absorber using a new molecular design strategy of resonant N-B←N unit, i.e. balanced resonant boron-nitrogen covalent bond (B-N) and boron-nitrogen coordination bond (B←N). We synthesize a series of monodispersed oligomers with thiophene-fused 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (TB), which contains resonant N-B←N unit, as the repeating unit. The TB pentamer exhibits the maximum absorption wavelength of 1169 nm, which is the longest for oligomers reported so far. Organic photodetectors (OPDs) with the TB tetramer as the electron acceptor shows the specific detectivity of 2.98×1011 Jones at 1180 nm under zero bias. This performance is among the best for NIR II OPDs. These results indicate a new kind of NIR II absorbing molecules as excellent opto-electronic materials.
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  • 背景:从番荔枝科植物中分离出一系列具有各种类型和复杂骨架的新型寡聚体,表现出抗炎作用,抗疟药,抗菌和其他生物活性。因此,它们的结构和功能受到越来越多的关注。
    目的:这篇综述的目的是为寡聚体的化学结构和生物活性提供系统的参考,并为从番荔枝科寻找更多的类似物提供一些线索。
    方法:从WebofScience和SciFinder检索了与番荔枝科相关的出版物,并进行了文献综述。
    结果:本文总结了化学结构,基础来源植物和番荔枝科低聚物的生物功能。
    结论:番荔枝科的寡聚体具有多种连接方式和丰富的官能团的特征,这为发现具有新的或更高的生物活性的先导化合物提供了更多的可能性。
    A series of novel oligomers with various types and complex skeletons are isolated from Annonaceae plants, which displayed anti-inflammatory, antimalarial, antibacterial and other biological activities. Thus, their structures and functions have received more and more attention.
    The purpose of this review is to provide a systematic reference for chemical structures and biological activities of oligomers and some clues for finding more analogues from Annonaceae.
    Publications relevant to Annonaceae were retrieved from the Web of Science and SciFinder and surveyed for a literature review.
    This article summarized the chemical structures, the base source plants and the biofunctions of oligomers from Annonaceae.
    The oligomers from Annonaceae have the characteristics of various connection modes and rich functional groups, which provides more possibilities for the discovery of lead compounds with new or higher biological activities.
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