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1.
Wacker oxidation is an industry-adopted process to transform olefins into value-added epoxides and carbonyls. However, traditional Wacker oxidation involves the use of homogeneous palladium and copper catalysts for the olefin addition and reductive elimination. Here, we demonstrated an ultrahigh loading Cu single atom catalyst(14% Cu, mass fraction) for the palladium-free Wacker oxidation of 4-vinylanisole into the corresponding ketone with N-methylhydroxylamine hydrochloride as an additive under mild conditions. Mechanistic studies by 18O and deuterium isotope labelling revealed a hydrogen shift mechanism in this palladium-free process using N-methylhydroxylamine hydrochloride as the oxygen source. The reaction scope can be further extended to Kucherov oxidation. Our study paves the way to replace noble metal catalysts in the traditional homogeneous processes with single atom catalysts. 相似文献
2.
A Savitzky–Golay filtering for smoothing and peak search written in Python is presented in this paper alongside its applications in the list-mode digital data acquisition dual gamma–gamma coincidence bismuth germanate (BGO) detector. The study has demonstrated that the software provides a reliable and effective way to quantify trace amounts of 22Na and 7Be in aerosol samples collected at Resolute Bay, Canada with a critical limit of 3 mBq and 5 Bq respectively for a 20 h counting interval, which are believed to be the inherent limitations of the dual-BGO system.
相似文献3.
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5.
Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling
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Sukang Yun Soonchang Hong Jesus A. I. Acapulco Jr. Ho Young Jang Songyi Ham Kyungeun Lee Prof. Seong Kyu Kim Prof. Sungho Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6165-6172
Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements. 相似文献
6.
Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts
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Debapriya Banerjee Kenneth S. Schweizer 《Journal of Polymer Science.Polymer Physics》2015,53(16):1098-1111
The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non‐microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials‐of‐mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption‐strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degree of dispersion also depends strongly on nanoparticle diameter relative to the block contour length. Small particles in copolymers with longer block lengths experience a more homopolymer‐like environment which renders them relatively insensitive to copolymer chemical heterogeneity and hinders dispersion. Larger particles (sufficiently larger than the monomer diameter) in copolymers of relatively short block lengths provide better dispersion than either a homopolymer or random copolymer. The theory also predicts a novel widening of the miscibility window for large particles upon increasing the overall molecular weight of copolymers composed of relatively long blocks. The influence of a positive chi‐parameter in the pure copolymer melt is briefly studied. Quantitative application to fullerenes in specific copolymers of experimental interest is performed, and miscibility predictions are made. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1098–1111 相似文献
7.
Sze-Jack Tan Chee-Keong Lee Chee-Yuen Gan Olusegun Abayomi Olalere 《Molecules (Basel, Switzerland)》2021,26(7)
In this study, the combination of parameters required for optimal extraction of anti-oxidative components from the Chinese lotus (CLR) and Malaysian lotus (MLR) roots were carefully investigated. Box–Behnken design was employed to optimize the pH (X1: 2–3), extraction time (X2: 0.5–1.5 h) and solvent-to-sample ratio (X3: 20–40 mL/g) to obtain a high flavonoid yield with high % DPPHsc free radical scavenging and Ferric-reducing power assay (FRAP). The analysis of variance clearly showed the significant contribution of quadratic model for all responses. The optimal conditions for both Chinese lotus (CLR) and Malaysian lotus (MLR) roots were obtained as: CLR: X1 = 2.5; X2 = 0.5 h; X3 = 40 mL/g; MLR: X1 = 2.4; X2 = 0.5 h; X3 = 40 mL/g. These optimum conditions gave (a) Total flavonoid content (TFC) of 0.599 mg PCE/g sample and 0.549 mg PCE/g sample, respectively; (b) % DPPHsc of 48.36% and 29.11%, respectively; (c) FRAP value of 2.07 mM FeSO4 and 1.89 mM FeSO4, respectively. A close agreement between predicted and experimental values was found. The result obtained succinctly revealed that the Chinese lotus exhibited higher antioxidant and total flavonoid content when compared with the Malaysia lotus root at optimum extraction condition. 相似文献
8.
Da Hyeon Choi Jiwon Park Ju Kwang Choi Kyeong Eun Lee Won Hee Lee Jinho Yang Ju Yeon Lee Yoon Jeong Park Chan Oh Ho-Ryun Won Bon Seok Koo Jae Won Chang Yoon Shin Park 《Experimental & molecular medicine》2020,52(9):1564
Oral microbes have the capacity to spread throughout the gastrointestinal system and are strongly associated with multiple diseases. Given that tonsils are located between the oral cavity and the laryngopharynx at the gateway of the alimentary and respiratory tracts, tonsillar tissue may also be affected by microbiota from both the oral cavity (saliva) and the alimentary tract. Here, we analyzed the distribution and association of the microbial communities in the saliva and tonsils of Korean children subjected to tonsillectomy because of tonsil hyperplasia (n = 29). The microbiome profiles of saliva and tonsils were established via 16S rRNA gene sequencing. Based on the alpha diversity indices, the microbial communities of the two groups showed high similarities. According to Spearman’s ranking correlation analysis, the distribution of Treponema, the causative bacterium of periodontitis, in saliva and tonsils was found to have a significant positive correlation. Two representative microbes, Prevotella in saliva and Alloprevotella in tonsils, were negatively correlated, while Treponema 2 showed a strong positive correlation between saliva and tonsils. Taken together, strong similarities in the microbial communities of the tonsils and saliva are evident in terms of diversity and composition. The saliva microbiome is expected to significantly affect the tonsil microbiome. Furthermore, we suggest that our study creates an opportunity for tonsillar microbiome research to facilitate the development of novel microbiome-based therapeutic strategies.Subject terms: Comparative genomics, Metagenomics 相似文献
9.
Gary W. Breton Lauren A. Hahn Kenneth L. Martin 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(9):1208-1212
Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C25H30N4O4, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl3). A tentative reaction pathway for its dissociation based on 1H NMR spectral evidence is provided. 相似文献
10.
Solid‐state 31P NMR investigation on the status of guanine nucleotides in paclitaxel‐stabilized microtubules
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Ga Hyang Lee Su Young Oh Kwon Joo Yeo Taslima Ferdous Meeyeon Cho Younkee Paik 《Magnetic resonance in chemistry : MRC》2015,53(5):330-336
Microtubule dynamics is a target for many chemotherapeutic drugs. In order to understand the biochemical effects of paclitaxel on the GTPase activity of tubulin, the status of guanine nucleotides in microtubules was investigated by 31P cross‐polarization magic angle spinning (CPMAS) NMR. Microtubules were freshly prepared in vitro in the presence of paclitaxel and then lyophilized in sucrose buffer for solid‐state NMR experiments. A 31P CPMAS NMR spectrum with the SNR of 25 was successfully acquired from the lyophilized microtubule sample. The broadness of the 31P spectral lines in the spectrum indicates that the molecular environments around the guanine nucleotides inside tubulin may not be as crystalline as reported by many diffraction studies. Deconvolution of the spectrum into four spectral components was carried out in comparison with the 31P NMR spectra obtained from five control samples. The spectral analysis suggested that about 13% of the nucleotides were present as GTP and 37% as GDP in the β‐tubulin (E‐site) of the microtubules. It was found that most of the GDPs were present as GDP‐Pi complex in the microtubules, which seems to be one of the effects of paclitaxel binding. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献