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101.
The generation of white light requires the combination of two or more chromophores that emit simultaneously. The observed color of a mixture of light-emitting molecules, however, originates generally only from the lowest band-gap species because of efficient energy transfer between the chromophores which is difficult to avoid. Here we report on a nanocomposite material designed to yield pure and stable white photo- and electroluminescence. In this material, red, green, and blue emitting conjugated polymers are confined within the galleries of a layered semiconducting host matrix. The host hinders polymer pi-pi interactions which are responsible for the energy transfer between polymer chains, consequently, emission from the three chromophores is observed simultaneously resulting in white photoluminescence. The efficacy of the nanocomposites is demonstrated in simple single-layer white-emitting polymer diodes. The mechanism suggested here for white light generation, supported by extensive luminescence measurements, is in contrast to that previously reported in white-emitting polymer diodes where efficient energy transfer between polymer chains was essential for obtaining white light. 相似文献
102.
Pfaffen C Infanger D Ottiger P Frey HM Leutwyler S 《Physical chemistry chemical physics : PCCP》2011,13(31):14110-14118
The N-H···π hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr·Bz, Pyr·Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H···π hydrogen bond to the benzene ring. The pyrrole is tipped by ω(S(0)) = ±13° relative to the surface normal of Bz. The N···ring distance is 3.13 ?. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle ω(S(1)) = ±21°. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H···π interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1)←S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr·Bz in the same region exhibits a weak 0 band that is red-shifted by 58 cm(-1) relative to that of Bz (38?086 cm(-1)). The origin appears due to symmetry-breaking of the π-electron system of Bz by the asymmetric pyrrole NH···π hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0 band. The Bz moiety in Pyr·Bz exhibits a 6a band at 0 + 518 cm(-1) that is about 20× more intense than the origin band. The symmetry breaking by the NH···π hydrogen bond splits the degeneracy of the ν(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by ~6 cm(-1). Both the 0 and 6 bands of Pyr·Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration ω', in agreement with the change of the ω tipping angle predicted by SCS-MP2 and SCS-CC2 calculations. 相似文献
103.
Quantitative measurements are important for imaging fluid content in porous media. Conventional MRI methods suffer from contrast because of relaxation times in porous media, resulting in measurements of apparent fluid content, not the true fluid content. We compare four magnetic resonance imaging methods for fluid content imaging in several water‐saturated reservoir core plugs: frequency‐encoded spin echo, single point ramped imaging with T1 enhancement, hybrid spin echo single point imaging (SE‐SPI), and T2 mapping SE‐SPI. 1‐D profiles obtained with each method were compared in terms of image quality, image sensitivity, and quantification of water content. The image quality of short T2 lifetime samples suffered from blurring in hybrid SE‐SPI images. Image sensitivity was the highest in the profiles obtained with frequency‐encoded spin echo. The quantification of frequency‐encoded spin echo, T2 mapping SE‐SPI, and hybrid SE‐SPI suffered in core plugs with a significant population of short T2 components because of T2 attenuation. Overall, single point ramped imaging with T1 enhancement was found to be the most general method for fluid content imaging. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
104.
Dr. Johannes Moritz Bauer Dr. Wolfgang Frey Prof. Dr. René Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(16):5767-5777
The streamlined catalytic access to enantiopure allylic amines as valuable precursors towards chiral β‐ and γ‐aminoalcohols as well as α‐ and β‐aminoacids is desirable for industrial purposes. In this article an enantioselective method is described that transforms achiral allylic alcohols and N‐tosylisocyanate in a single step into highly enantioenriched N‐tosyl protected allylic amines via an allylic carbamate intermediate. The latter is likely to undergo a cyclisation‐induced [3,3]‐rearrangement catalysed by a planar chiral pentaphenylferrocene palladacycle in cooperation with a tertiary amine base. The otherwise often indispensable activation of palladacycle catalysts by a silver salt is not required in the present case and there is also no need for an inert gas atmosphere. To further improve the synthetic value, the rearrangement was used to form dimethylaminosulfonyl‐protected allylic amines, which can be deprotected under non‐reductive conditions. 相似文献
105.
Dipl.‐Chem. Alexander Schwenger Dr. Wolfgang Frey Prof. Clemens Richert 《Angewandte Chemie (International ed. in English)》2016,55(44):13706-13709
Tetrakis(dimethoxyphenyl)adamantane (TDA) readily forms crystalline inclusion complexes with reactive, toxic, or malodorous reagents, such as benzoyl chloride, acetyl chloride, cyclohexyl isocyanide, phosphorus trichloride, and trimethylsilyl chloride. The crystals are stable and largely free of the problematic properties of the free reagents. When exposed to solvents such as DMSO or MeOH, the reagents react, and a large portion of the TDA precipitates. The TDA‐coated reagents may lead to a safer way of storing, handling, and delivering reagents, and ultimately to synthetic protocols that do not require fume hoods. 相似文献
106.
Three silylated γ-alkynylfurans were prepared and subjected to both gold and platinum catalysts. The TMS- and the TBDMS-substituted furans reacted. With AuCl3 and the binuclear [(Ph3PAu)2Cl][BF4] catalyst a hydroarylation of the alkyne was observed. Na[AuCl4] gave phenols as the product, but these were formed only after in situ desilylation of the starting material by the gold catalyst and thus the wrong isomer dominated. Only with PtCl2(MeCN)2 phenols with a silyl group were formed. The TBDPS-substituted furan failed to react. Two alkynylsilanes were synthesized, but they also failed to react. 相似文献
107.
Fabienne Barroso-Bujans Ricardo Martínez Mehrdad Yazdani-Pedram Holger Frey 《European Polymer Journal》2007,43(4):1288-1301
Long chain aliphatic alcohols have been used as model compounds to develop a preparative method for a water-soluble material, which could be a carrier for triacontanol, a highly hydrophobic plant growth regulator. New polyesters from long chain aliphatic (C = 12, 18 and 22) mono-1-alkyl citrates and poly(ethylene glycol) were synthesized and characterized by NMR spectroscopy. The polyester containing the triacontyl moiety was obtained from mono-1-triacontyl citrate, which was synthesized from the corresponding alcohol extracted from the Agave fourcroydes. The molecular weight of the polyesters depends on experimental conditions during synthesis such as reaction time, atmosphere, catalyst concentration and temperature. The reaction is second order in the early stage of the polyester synthesis. The reaction rate constant is independent of the length of the aliphatic chain, but it decreases with increasing of the poly(ethylene glycol) employed. Turbidity measurements have been used to study the polyester solubility. Solubility characteristics were found to depend on the of poly(ethylene glycol), the aliphatic-chain length and the value of for the polyester. These preparations could potentially be used to release triacontanol. 相似文献
108.
Matthias Worm Biao Kang Carsten Dingels Frederik R. Wurm Holger Frey 《Macromolecular rapid communications》2016,37(9):775-780
Poly ((ethylene oxide)‐b‐(propylene oxide)‐b‐(ethylene oxide)) triblock copolymers commonly known as poloxamers or Pluronics constitute an important class of nonionic, biocompatible surfactants. Here, a method is reported to incorporate two acid‐labile acetal moieties in the backbone of poloxamers to generate acid‐cleavable nonionic surfactants. Poly(propylene oxide) is functionalized by means of an acetate‐protected vinyl ether to introduce acetal units. Three cleavable PEO‐PPO‐PEO triblock copolymers (Mn,total = 6600, 8000, 9150 g·mol−1; Mn,PEO = 2200, 3600, 4750 g·mol−1) have been synthesized using anionic ring‐opening polymerization. The amphiphilic copolymers exhibit narrow molecular weight distributions (Ð = 1.06–1.08). Surface tension measurements reveal surface‐active behavior in aqueous solution comparable to established noncleavable poloxamers. Complete hydrolysis of the labile junctions after acidic treatment is verified by size exclusion chromatography. The block copolymers have been employed as surfactants in a miniemulsion polymerization to generate polystyrene (PS) nanoparticles with mean diameters of ≈200 nm and narrow size distribution, as determined by dynamic light scattering and scanning electron microscopy. Acid‐triggered precipitation facilitates removal of surfactant fragments from the nanoparticles, which simplifies purification and enables nanoparticle precipitation “on demand.”
109.
Karl O. Gelotte David N. Mason Harold Meckler Wen-Chung Shieh Colleen M. Starkey 《Journal of heterocyclic chemistry》1990,27(6):1549-1552
An efficient synthesis of the novel triazoloquinazoline adenosine antagonist, CGS 15943, is reported in five steps in approximately 50% overall yield. A key reaction in the synthetic sequence is the double cyclization of an N-(substituted-2-cyanophenyl)carbamate with a carboxylic acid hydrazide to afford a [1,2,4]triazolo-[1,5-c]quinazolin-5(6H)-one in high yield without either a Dimroth or “translocative” rearrangement occurring. Another key reaction is the condensation of a 2-(1H-1,2,4-triazol-5-yl)benzenamine with cyanamide under acidic conditions to prepare a guanidine. 相似文献
110.
Ethylene diamine (EDA)/salt solvent systems can dissolve cellulose without any pretreatment. A comparison of the electrical
conductivity of different salts in EDA was made at 25 °C, and conductivity decreased in the order of KSCN>KI>NaSCN at the
same molar concentration. Among the salts tested, potassium thiocyanate (KSCN) was capable of dissolving both high molecular
weight (DP>1000) and low molecular weight (DP = 210) cellulose, and this was confirmed by polarized light microscopy. 39K and 14N NMR experiments were conducted at 70 °C as a function of cellobiose concentration with EDA/KSCN as the solvent. The results
showed that the K+ ion interacts with cellobiose more than the SCN− ion does. Recovered cellulose was studied by infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). Changes
in the FTIR absorption bands at 1,430 and 1,317 cm−1 were associated with a change in the conformation of the C-6CH2OH group. The changes in positions and/or intensities of absorption bands at 2,900, 1,163, and 8,97cm−1 were related to the breaking of hydrogen bonds in cellulose. X-ray diffraction studies revealed that cellulose, recovered
by precipitating cellulose solutions with water, underwent a polymorphic transformation from cellulose I to cellulose II. 相似文献