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141.
The incorporation of fluorescent organic dyes in an encapsulating matrix represents a route to generate stable and processable materials for optoelectronic devices. Here, we present a method to embed perylene dyes into a high refractive index (HRI) polysiloxane matrix applying an allyl functionalized perylene dye and hydrosilylation chemistry. In a first approach, the dye molecules were covalently integrated into the backbone of linear polyphenylmethylsiloxane chains. The fluorescent and liquid polymers were synthesized with molecular weights from 5660 up to 8400 g mol?1. In a second approach, the dye itself was used as a cross‐linking agent between linear polyphenylmethylsiloxane chains. These preformed fluorescent batch polymers are liquids with dye concentrations between 0.025 and 8 wt %. The applied synthetic methods incorporated the dye covalently into the polymer structure and avoided the crystallization of the dye molecules and thus the formation of excimers, which would reduce the optical emission. The resulting products can be easily incorporated into curable commercially available HRI polyphenylmethylsiloxane resins. The formed materials are ideal LED encapsulants with a solid and flexible consistency, a uniform dispersion of the dyes, and adjustable mechanical properties, realized by changing the amount of perylene polymers. Further properties of the obtained materials are thermal stabilities up to 478 °C, quantum yields larger than 0.97, and high photostabilities. Thus, the covalent integration of dyes into polyphenylsiloxane structures represents a possible route for the stabilization of the organic dyes against the extreme irradiance and thermal conditions in LED applications. © 2019 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1062–1073 相似文献
142.
Nils Bartels Bastian C. Krüger Daniel J. Auerbach Alec M. Wodtke Tim Schfer 《Angewandte Chemie (International ed. in English)》2014,53(50):13690-13694
The loss or gain of vibrational energy in collisions of an NO molecule with the surface of a gold single crystal proceeds by electron transfer. With the advent of new optical pumping and orientation methods, we can now control all molecular degrees of freedom important to this electron‐transfer‐mediated process, providing the most detailed look yet into the inner workings of an electron‐transfer reaction and showing how to control its outcome. We find the probability of electron transfer increases with increasing translational and vibrational energy as well as with proper orientation of the reactant. However, as the vibrational energy increases, translational excitation becomes unimportant and proper orientation becomes less critical. One can understand the interplay of all three control parameters from simple model potentials. 相似文献
143.
Denis Höfler Dr. Richard Goddard Julia B. Lingnau Nils Nöthling Prof. Dr. Benjamin List 《Angewandte Chemie (International ed. in English)》2018,57(27):8326-8329
How many carbanions can an organic molecule accommodate? The formation of purely organic carbanions with multiple charges is challenging as charge stabilization cannot be achieved through metal coordination. Previously, only quaternary ammonium dicarbanion salts had been reported. By using highly electron‐deficient trifluoromethanesulfonyl (triflyl or Tf) groups, the formation of a purely organic tricarbanion has been realized for the first time. 相似文献
144.
Back Cover: Breslow Intermediates from Aromatic N‐Heterocyclic Carbenes (Benzimidazolin‐2‐ylidenes,Thiazolin‐2‐ylidenes) (Angew. Chem. Int. Ed. 27/2018) 下载免费PDF全文
145.
Breslow Intermediates from Aromatic N‐Heterocyclic Carbenes (Benzimidazolin‐2‐ylidenes,Thiazolin‐2‐ylidenes) 下载免费PDF全文
Dr. Mathias Paul Dr. Nils E. Schlörer Dr. Jörg‐M. Neudörfl Prof. Dr. Albrecht Berkessel 《Angewandte Chemie (International ed. in English)》2018,57(27):8310-8315
We report the first generation and characterization of elusive Breslow intermediates derived from aromatic N‐heterocyclic carbenes (NHCs), namely benzimidazolin‐2‐ylidenes (NMR, X‐ray analysis) and thiazolin‐2‐ylidenes (NMR). In the former case, the diamino enols were generated by reaction of the free N,N‐bis(2,6‐diisopropylphenyl)‐ and N,N‐bis(mesityl)‐substituted benzimidazolin‐2‐ylidenes with aldehydes while the dimer of 3,4,5‐trimethylthiazolin‐2‐ylidene served as the starting material in the latter case. The unambiguous NMR identification of the first thiazolin‐2‐ylidene‐based Breslow intermediate rests on double 13C labeling of both the NHC and the aldehyde component. The acyl anion reactivity was confirmed by benzoin formation with excess aldehyde. 相似文献
146.
Polyphenols belonging to the class of secondary metabolites of plants and microorganisms play an important role as bioactive
food constituents as well as contaminants. Structure elucidation of polyphenols in plant extracts or polyphenol metabolites,
especially those arising during biotransformation, still represents a challenge for analytical chemistry. Various approaches
have been proposed to utilize fragmentation reactions in connection with mass spectrometry (MS) for structural considerations
on polyphenolic targets. We compiled and applied specific liquid chromatography (LC)–electrospray ionization in positive mode
[ESI(+)]–tandem MS (MS/MS) and gas chromatography (GC)–(electron impact, EI)–MS/MS fragmentation reactions with a special
focus on the analysis of isoflavones, whereby this technique was also found to be extendable to determine further polyphenols.
For ESI(+)-MS the basic retro-Diels–Alder (rDA) fragmentation offers information about the substitution pattern in the A-
and B-rings of flavonoids and the elimination of a protonated 4-methylenecyclohexa-2,5-dienone (m/z = 107) fragment can be used as a diagnostic tool for many isoflavanones. For GC-(EI)-MS/MS analysis after derivatization
of the analytes to their trimethylsilyl ethers, the elimination of methyl radicals, tetramethylsilane groups or the combined
loss of two methyl groups can be shown to be specific for certain substitution patterns in polyphenols. The applicability
of the fragmentation reactions presented is demonstrated exemplarily for three derivatives of the isoflavone irilone. With
the help of these fragmentation reactions of the two MS techniques combined, a reliable identification of polyphenols is possible.
Especially in such cases where NMR cannot be utilized owing to low analyte amounts being available or prior to purification,
valuable information can be obtained.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.
Ronald Maul and Nils Helge Schebb contributed equally to this work. 相似文献
147.
148.
Dihydrothiazolo ring-fused 2-pyridones have previously been shown to inhibit pilus assembly in uropathogenic Escherichia coli. Methods have now been developed to synthesize both dihydroimidazolo and dihydrooxazolo ring-fused 2-pyridones. To obtain the nitrogen analogs, Cbz-protected imidazolines were reacted with an acyl-Meldrum's acid derivative under acidic conditions. To prepare the oxygen analogs, a one-pot procedure was developed that allowed synthesis of dihydrooxazolo ring-fused 2-pyridones starting from acylated serine derivatives. After hydrolysis to their corresponding carboxylic acids and lithium carboxylates, biological evaluation revealed that the sulfur could be replaced by an oxygen atom and still maintains the ability to inhibit pilus assembly in uropathogenic E. coli. However, introducing a secondary amine instead of oxygen resulted in a substantial decrease in biological activity. 相似文献
149.
150.
Akbari A Marthinsen G Lifjeld JT Albregtsen F Wennerberg L Stenseth NC Jakobsen KS 《Electrophoresis》2008,29(6):1273-1285
In CE the charged DNA strands are fractionated according to fragment lengths as they migrate through the capillary, since shorter DNA fragments pass through the sieving matrix faster. Multiplexed internal size standards are used to estimate the size of unknown DNA fragments. In the literature there are statements about migration abnormalities for the 250 and 340 bp fragments in the GeneScan-500 (GS500) internal size standards. Such anomalous migration of size standards could obviously introduce errors in the estimation of unknown fragments. Therefore, a number of analysis programs simply exclude some of these fragments. In the present work we first evaluate the effect of excluding each of the fragments in the internal size standards used in CE. Next, a method which is based on estimating the true values of the anomalous fragments is presented. The results obtained by the new method indicate a significant improvement compared to results obtained when one (or both) of the anomalous fragments in GS500 is (are) excluded or included when estimating the size of unknown DNA fragments. In the higher-molecular-weight region, the average error is reduced from 1.91 bp in ABI GeneMapper (excluding 250 bp) to 0.15 bp in the new method (using the estimated values for 250 and 340 bp). In the lower-molecular-weight region, excluding both fragments will improve the results by an average of 0.74 bp compared to ABI GeneMapper. 相似文献