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11.
Pu Duan Bo Zhi Luke Coburn Christy L. Haynes Klaus Schmidt-Rohr 《Magnetic resonance in chemistry : MRC》2020,58(11):1130-1138
The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by 13C, 13C{1H}, 1H─13C, 13C{14N}, and 15N solid-state nuclear magnetic resonance (NMR) experiments. 13C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. 15N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved 13C NMR peaks, including an unusual ═CH signal at 84 ppm (1H chemical shift of 5.8 ppm) and ═CN2 at 155 ppm, and two distinctive 15N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a 1H─13C HETCOR spectrum with brief 1H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative 13C and 15N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in 13C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation. 相似文献
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DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex
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Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
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Nonclassical light states are important for both conceptual and practical reasons: they are basic ingredients in testing and exploring quantum foundations, and are crucial resources in quantum technologies. Various useful criteria have been developed to detect nonclassicality in the literature, and several meaningful measures of nonclassicality have been introduced and measured experimentally. In this work, by use of a non-Hermitian generalization of the Wigner-Yanase-Dyson skew information and playing with operator ordering in evaluating average photon number, we develop a novel family of criteria for detecting nonclassicality of light based on Lieb's concavity, which is a deep and powerful result concerning interaction between quantum states and observables. We elucidate the information-theoretic as well as the physical meaning of the criteria, and illustrate their effectiveness in capturing and quantifying nonclassicality of various important light states. 相似文献
15.
Lan-Lan Zhang Dr. Wen-Ke Miao Dr. Li-Jun Ren Yu-Kun Yan Dr. Yue Lin Prof. Wei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(58):13396-13401
Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non-solvent to its dilute solution is reported. A three-dimensional network of tangled and snake-like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non-solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application. 相似文献
16.
双掺(Tm3+,Tb3+)LiYF4激光器1.5 μm波长激光阈值分析 总被引:1,自引:0,他引:1
由速率方程推出了双掺(Tm^3 ,Tb^3 )离子准四能级系统的激光阈值解析式,讨论了Tm^3 和Tb^3 离子之间的相互作用。分析了1.5μm波长附近的激光阈值和Tm^3 、Tb^3 离子的掺杂原子数分数及晶体长度的关系。结果表明,对于对应Tm^3 离子^3H4→^3F4跃迁的约1.5μm波长的激光,激活离子Tm^3 的掺杂原子数分数过大时,交叉弛豫作用将使系统阈值迅速增加。Tb^3 离子的加入,一方面能抽空激光下能级,起到降低阈值的作用;另一方面亦减少了激光上能级的寿命,使阈值升高。故Tb^3 离子有最佳掺杂原子数分数。对于Tm原子数分数为y=0.01的Tm:LiYF4晶体,Tb^3 离子的最佳掺杂原子数分数为0.002左右,同时表明,激光阈值与晶体长度有关。最佳晶体长度与Tm^3 、Tb^3 离子的掺杂原子数分数以及晶体的衍射损耗和吸收损耗有关。 相似文献
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19.
Wen Zhang Hui Huang Yu Ding Margherita Gavagnin Ernesto Mollo Guido Cimino Yue‐Wei Guo 《Helvetica chimica acta》2006,89(4):813-820
Three new polyoxygenated steroids, muricesteroid ( 1 ), and menellsteroids A ( 2 ) and B ( 3 ), were isolated from two species of the South China Sea gorgonian Muricella flexuosa and Menella verrucosa Brundin , respectively. The structures of these new compounds were elucidated on the basis of extensive spectroscopic analysis, chemical methods and comparison with known related compounds. 相似文献
20.
Newton-Leibniz integration rule only applies to commuting functions of continuum variables, while operators made of Dirac’s symbols (ket versus bra, e.g., |q〉〈q| of continuous parameter q) in quantum mechanics are usually not commutative. Therefore, integrations over the operators of type |〉〈| cannot be directly performed by Newton-Leibniz rule. We invented an innovative technique of integration within an ordered product (IWOP) of operators that made the integration of non-commutative operators possible. The IWOP technique thus bridges this mathematical gap between classical mechanics and quantum mechanics, and further reveals the beauty and elegance of Dirac’s symbolic method and transformation theory. Various applications of the IWOP technique, including constructing the entangled state representations and their applications, are presented. 相似文献