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1.
Triphilic Ionic‐Liquid Mixtures: Fluorinated and Non‐fluorinated Aprotic Ionic‐Liquid Mixtures 下载免费PDF全文
Dr. Oldamur Hollóczki Dr. Marina Macchiagodena Henry Weber Martin Thomas Dr. Martin Brehm Prof. Dr. Annegret Stark Dr. Olga Russina Dr. Alessandro Triolo Prof. Dr. Barbara Kirchner 《Chemphyschem》2015,16(15):3325-3333
We present here the possibility of forming triphilic mixtures from alkyl‐ and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains—polar and nonpolar—three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self‐associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long‐range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment. 相似文献
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Dr. Natalie Spomer Dr. Sven Holl Dr. Larissa Zherlitsyna Dr. Fariba Maysamy Andreas Frost Prof. Dr. Norbert Auner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5600-5616
Amorphous silicon is synthesized by treating the tetrahalosilanes SiX4 (X=Cl, F) with molten sodium in high boiling polar and non‐polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine‐containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO?H versus the Me?OH bond either yields H‐ and/or methyl‐substituted methoxy functional silanes. Moreover, compounds, such as MenSi(OMe)4?n (n=0–3) are simply accessible in more than 75 % yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes MenSi(OMe)4?n in excellent (n=0:100 %) to acceptable yields (n=1:51 %; n=2:27 %); the yield of HSi(OMe)3 is about 85 %. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon‐based products. 相似文献
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Serum proteins represent an important class of drug and imaging agent delivery vectors. In this minireview, key advantages of using serum proteins are discussed, followed by the particular advantages and challenges associated with employing soluble folate binding protein. In particular, approaches employing drugs that target folate metabolism are reviewed. Additionally, the slow-onset, tightbinding interaction of folate with folate binding protein and the relationship to a natural oligomerization mechanism is discussed. These unique aspects of folate binding protein suggest interesting applications for the protein as a vector for further drug and imaging agent development. 相似文献
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Casey A. Dougherty Joseph C. Furgal Dr. Mallory A. van Dongen Prof. Theodore Goodson III Prof. Mark M. Banaszak Holl Dr. Janet Manono Prof. Stassi DiMaggio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4638-4645
Fluorescent dyes are commonly conjugated to nanomaterials for imaging applications using stochastic synthesis conditions that result in a Poisson distribution of dye/particle ratios and therefore a broad range of photophysical and biodistribution properties. We report the isolation and characterization of generation 5 poly(amidoamine) (G5 PAMAM) dendrimer samples containing 1, 2, 3, and 4 fluorescein (FC) or 6‐carboxytetramethylrhodamine succinimidyl ester (TAMRA) dyes per polymer particle. For the fluorescein case, this was achieved by stochastically functionalizing dendrimer with a cyclooctyne “click” ligand, separation into sample containing precisely defined “click” ligand/particle ratios using reverse‐phase high performance liquid chromatography (RP‐HPLC), followed by reaction with excess azide‐functionalized fluorescein dye. For the TAMRA samples, stochastically functionalized dendrimer was directly separated into precise dye/particle ratios using RP‐HPLC. These materials were characterized using 1H and 19F NMR spectroscopy, RP‐HPLC, UV/Vis and fluorescence spectroscopy, lifetime measurements, and MALDI. 相似文献
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An Abnormal N‐Heterocyclic Carbene–Carbon Dioxide Adduct from Imidazolium Acetate Ionic Liquids: The Importance of Basicity 下载免费PDF全文
Zsolt Kelemen Barbara Péter‐Szabó Dr. Edit Székely Dr. Oldamur Hollóczki Dzmitry S. Firaha Prof. Dr. Barbara Kirchner Dr. József Nagy Prof. Dr. László Nyulászi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(40):13002-13008
In the reaction of 1‐ethyl‐3‐methylimidazolium acetate [C2C1Im][OAc] ionic liquid with carbon dioxide at 125 °C and 10 MPa, not only the known N‐heterocyclic carbene (NHC)–CO2 adduct I , but also isomeric aNHC‐CO2 adducts II and III were obtained. The abnormal NHC‐CO2 adducts are stabilized by the presence of the polarizing basic acetate anion, according to static DFT calculations and ab initio molecular dynamics studies. A further possible reaction pathway is facilitated by the high basicity of the system, deprotonating the initially formed NHC‐CO2 adduct I , which can then be converted in the presence of the excess of CO2 to the more stable 2‐deprotonated anionic abnormal NHC–CO2 adduct via the anionic imidazolium‐2,4‐dicarboxylate according to DFT calculations on model compounds. This suggests a generalizable pathway to abnormal NHC complex formation. 相似文献
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