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Lucile Andna, Laurence Miesch
Enamides equipped with N-acyliminium ion precursors were obtained through reduction of ynamides tethered to N-imides. Intramolecular TMSOTf-mediated trapping of N-acyliminium ions provided a variety of polyfunctionalized medium-sized diaza-heterocycles of putative pharmacological interest.
May 23, 2018: Organic Letters
Renjie Chen, Linwei Zeng, Bo Huang, Yangyong Shen, Sunliang Cui
A novel decarbonylative coupling of α-keto acids and ynamides with extrusion of CO for synthesis of β-keto imides is reported. This process features mild reaction conditions, a broad substrate scope, and high efficiency. An isotope-labeling reaction and GC analysis were conducted to elucidate a plausible reaction mechanism.
May 23, 2018: Organic Letters
Neng Xiao, Gerald Gourdin, Yiying Wu
In the superoxide batteries based on O2/O2- redox chemistry, identifying an electrolyte to stabilize both alkali metal and superoxide remains challenging due to their reactivity towards electrolyte components. Bis(fluorosulfonyl)imide (FSI-) has been recognized as a "magical anion" for passivating alkali metals. Herein, we illustrate the chemical reactions between FSI- and superoxide, and the resultant dilemma when considering an anode-compatible electrolyte vs. a cathode-compatible one in K-O2 batteries...
May 22, 2018: Angewandte Chemie
Abdullah M Khan, Jameel Muzaffar, Hermant Murthy, John R Wingard, Jan S Moreb
Lenalidomide maintenance following autologous stem cell transplant (ASCT) is considered the standard of care for eligible patients with multiple myeloma (MM). A recent meta-analysis has provided additional evidence that lenalidomide maintenance is associated with a higher incidence of second primary malignancies, including both hematologic and solid malignancies. Acute lymphoblastic leukemia (ALL) as a second primary malignancy is rarely described in the literature. Herein, we describe two patients with MM treated with induction therapy, ASCT, and lenalidomide maintenance that experienced cytopenias while on maintenance...
2018: Case Reports in Hematology
Mounesha N Garaga, Vassilios Dracopoulos, Ulrike Werner-Zwanziger, Josef W Zwanziger, Manuel Maréchal, Michael Persson, Lars Nordstierna, Anna Martinelli
We report enhanced protonic and ionic dynamics in an imidazole/protic ionic liquid mixture confined within the nanopores of silica particles. The ionic liquid is 1-octylimidazolium bis(trifluoromethanesulfonyl)imide ([HC8Im][TFSI]), while the silica particles are microsized and characterized by internal well connected nanopores. We demonstrate that the addition of imidazole is crucial to promote a proton motion decoupled from molecular diffusion, which occurs due to the establishment of new N-HN hydrogen bonds and fast proton exchange events in the ionic domains, as evidenced by both infrared and 1H NMR spectroscopy...
May 21, 2018: Nanoscale
Markus Kinauer, Martin Diefenbach, Heiko Bamberger, Serhiy Demeshko, Edward J Reijerse, Christian Volkmann, Christian Würtele, Joris van Slageren, Bas de Bruin, Max C Holthausen, Sven Schneider
The iridium(iii/iv/v) imido redox series [Ir(N t Bu){N(CHCHP t Bu2 )2 }]0/+/2+ was synthesized and examined spectroscopically, magnetically, crystallographically and computationally. The monocationic iridium(iv) imide exhibits an electronic doublet ground state with considerable 'imidyl' character as a result of covalent Ir-N t Bu bonding. Reduction gives the neutral imide [Ir(N t Bu){N(CHCHP t Bu2 )2 }] as the first example of an iridium complex with a triplet ground state. Its reactivity with respect to nitrene transfer to selected electrophiles (CO2 ) and nucleophiles (PMe3 ), respectively, is reported...
May 14, 2018: Chemical Science
Aleksandr Savateev, Bogdan Kurpil, Artem Mishchenko, Guigang Zhang, Markus Antonietti
Potassium poly(heptazine imide), a carbon nitride based semiconductor with high structural order and a valence band potential of +2.2 V vs. NHE, in the presence of hole scavengers and under visible light irradiation gives the corresponding polymeric radical anion, in which the specific density of unpaired electrons reaches 112 μmol g-1 . The obtained polymeric radical anion is stable under anaerobic conditions for several hours. It was characterized using UV-vis absorption, time resolved and steady state photoluminescence spectra...
April 14, 2018: Chemical Science
Aude Le Roy, Thomas Prébet, Rémy Castellano, Armelle Goubard, Florence Riccardi, Cyril Fauriat, Samuel Granjeaud, Audrey Benyamine, Céline Castanier, Florence Orlanducci, Amira Ben Amara, Frédéric Pont, Jean-Jacques Fournié, Yves Collette, Jean-Louis Mege, Norbert Vey, Daniel Olive
Immunomodulatory drugs (IMiDs) are anticancer drugs with immunomodulatory, anti-angiogenesis, anti-proliferative, and pro-apoptotic properties. IMiDs are currently used for the treatment of multiple myeloma, myelodysplastic syndrome, and B-cell lymphoma; however, little is known about efficacy in acute myeloid leukemia (AML). We proposed in this study to investigate the relevance of IMiDs therapy for AML treatment. We evaluated the effect of IMiDs on primary AML blasts ( n  = 24), and the impact in natural killer (NK) cell-mediated immunosurveillance of AML...
2018: Frontiers in Immunology
Ilaria Sauzullo, Rossana Scrivo, Paola Sessa, Fabio Mengoni, Vincenzo Vullo, Guido Valesini, Claudio Maria Mastroianni
The aim of the study was to clarify the effect of long-term anti-TNF therapy on T cell function in patients with rheumatologic immune-mediated inflammatory diseases (IMID). The production of IFNγ by T cells was evaluated at baseline and after 1, 2, 4, and 8 years of anti-TNF agents by means of a QuantiFERON-TB Gold In-Tube assay. The T cell proliferation and surface co-expression of CD25/CD134 in response to phytohaemagglutinin together with the in vitro impact of anti-TNF therapy on the functional capacity of T cells were evaluated after 8 years from the onset of the biological treatment...
May 18, 2018: Scientific Reports
Manthena Chaitanya, Pazhamalai Anbarasan
An efficient and chemodivergent palladium-catalyzed thiolation (C-S) and imidation (C-N) of directing group-assisted C-H bonds have been accomplished employing N-(arylthio)imides in combination with either Brønsted acid or Lewis acid, respectively. Notable features of the developed methodologies include excellent diversity, high functional group tolerance, wide substrate scope, and use of a single N-S reagent. Importantly, the developed hypothesis was also successfully extended to the amidation of C-H bonds...
May 18, 2018: Organic Letters
Ravindra Kumar Gupta, Ammathnadu Sudhakar Achalkumar
A high yielding microwave-assisted synthetic method to obtain unsymmetrical perylene diester monoimide (PEI), by treating the perylene tetrester (PTE) with requisite amine is reported. Perylene-based molecules are widely used in the construction of self-assembled supramolecular structures because of their propensity to aggregate under various conditions. In comparison to perylene bisimides (PBIs), PEIs are less studied in organic electronics/self-assembly due to the synthetic difficulty and low yields in their preparation...
May 18, 2018: Journal of Organic Chemistry
R Muthupradeepa, M Sivakumar, R Subadevi, V Suryanarayanan, Wei-Ren Liu
The present study emphases on the effect of toting of TiO2 filler on the electrochemical enactment of polymer electrolyte containing PVdF-co-HFP(30) + SEt3TFSI(10) + EC/PC(60) + TiO2(x) wt% (Poly (vinylidene fluoride-co-hexafluoropropylene + Triethylsulfoniumbis(trifluoromethylsulfonyl)imide + Ethylene carbonate/Propylene carbonate (1:1 ratio) + Titanium dioxide) for lithium battery applications. Composite electrolytes with different weight percentages of TiO2 were prepared and characterized by different surface analytical, thermal and electrochemical techniques...
January 1, 2018: Journal of Nanoscience and Nanotechnology
Tomoya Sato, Matt W England, Liming Wang, Chihiro Urata, Hiroshi Kakiuchida, Atsushi Hozumi
Polyurethane (PU)-based transparent and flexible ionogels, showing unusual thermo-responsive optical properties, were successfully prepared by mixing PU-precursor and a hydrophobic ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIM-TFSI). Although the initial ionogels were transparent at room temperature, significant increases in opacity were observed with increasing temperature up to 120°C, because of macroscopic phase separation of the PU-matrix and hydrophobic EMIM-TFSI. In addition, the optical transition temperature could be arbitrarily controlled simply by varying the mixing ratio of EMIM-TFSI within the PU-matrix...
January 1, 2018: Journal of Nanoscience and Nanotechnology
Nivedita S Mahajani, John D Chisholm
1,1'-Diarylbutyl groups are a common pharmacophore found in many biologically active small molecules. To access these systems under mild conditions, the reaction of diarylmethyl trichloroacetimidates with allyltributylstannanes was explored. Simply heating allyltributylstannane with the trichloroacetimidate resulted in substitution of the imidate with an allyl group. Unlike other methods used to access these systems, no strong base, transition metal catalyst, Brønsted acid or Lewis acid promoter was required to affect the transformation...
May 16, 2018: Organic & Biomolecular Chemistry
Jennifer Chapman Varela, Karthika Sankar, Alexander Hino, Xinrong Lin, Won-Seok Chang, David Coker, Mark Grinstaff
The synthesis and physicochemical properties of a series of non-flammable, thermally stable alkyl ether containing piperidinium ionic liquid electrolytes, containing lithium bis(trifluoromethanesulfonyl)imide, are described along with the superior performance of a lithium-ion supercapacitor containing a piperidinium electrolyte compared to a standard carbonate-based electrolyte at 100 °C.
May 16, 2018: Chemical Communications: Chem Comm
Jared T Stritzinger, Janelle E Droessler, Brian L Scott, George S Goff
The structural determination of the ionic liquid, caesium bis-[(tri-fluoro-meth-yl)sulfon-yl]imide or poly[[μ4 -bis-[(tri-fluoro-meth-yl)sulfon-yl]imido]caesium(I)], Cs[N(SO2 CF3 )2 ] or Cs[Tf2 N], reveals a second polymorph that also crystallizes in a layer structure possessing monoclinic P 21 / c symmetry at 120 K instead of C 2/ c for the known polymorph [Xue et al. (2002 ▸). Solid State Sci. 4 , 1535-1545]. The caesium ions in the cationic layers are coordinated by the sulfonyl groups of the bis-triflimide mol-ecules from anion layers while the tri-fluoro-methyl groups are oriented in the opposite direction, forming a non-polar surface separating the layers...
April 1, 2018: Acta Crystallographica. Section E, Crystallographic Communications
Urszula Maria Domanska, Marek Królikowski, Michal Wlazlo, Mikolaj Wieckowski
Ionic liquids (ILs) are important new solvents proposed for applications in different separation processes. Herein, an idea of the possible use of high pressure in general strategy of production of 2-phenylethanol (PEA) is discussed. In this work we presentthe influence of pressure on the density in binary systems of {1-hexyl-1-methylpyrrolidyne bis{(trifluoromethyl)sulfonyl}imide, [HMPYR][NTf2], or 1-dodecyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [DoMIM][NTf2] + 2-phenylethanol (PEA)} in a wide range of temperature (298...
May 15, 2018: Journal of Physical Chemistry. B
Elaheh Sedghamiz, Majid Moosavi
The surface properties of three symmetric linear tricationic ionic liquids (LTILs) with the common anion, bis(trifluoromethylsulfonyl)imide ([NTf2]-), were studied using atomistic molecular dynamics simulation and identification of the truly interfacial molecules (ITIM) analysis. A refined version of the CL&P force field with the partial charges based on quantum calculations for isolated ion quartets was used to calculate the number densities, orientation of the cations, charge densities and surface tensions...
May 15, 2018: Physical Chemistry Chemical Physics: PCCP
Tian Lan, Francesca Soavi, Massimo Marcaccio, Pierre-Louis Brunner, Jonathan Sayago, Clara Santato
The n-type organic semiconductor phenyl-C61-butyric acid methyl ester (PCBM), a soluble fullerene derivative well investigated for organic solar cells and transistors, can undergo several successive reversible, diffusion-controlled, one-electron reduction processes. We exploited such processes to shed light on the correlation between electron transfer properties, ionic and electronic transport as well as device performance in ionic liquid (IL)-gated transistors. Two ILs were considered, based on bis(trifluoromethylsulfonyl)imide [TFSI] as the anion and 1-ethyl-3-methylimidazolium [EMIM] or 1-butyl-1-methylpyrrolidinium [PYR14] as the cation...
May 14, 2018: Chemical Communications: Chem Comm
Yathish Kurapati, Sumit Sharma
We report adsorption behavior of imidazolinium-type surfactant molecules in different aggregation states on metal-water interfaces studied using all-atom molecular dynamics simulations. Surfactant molecules with two different alkyl tail lengths, a 10-carbon and a 17-carbon tail (henceforth referred to as imid-10 and imid-17 respectively) have been considered. Six layers of face-centered cubic lattice of gold atoms submerged in water represent the metal-water interface. Our simulations reveal that in infinite dilution, both types of surfactant molecules strongly adsorb onto the metal-water interface in a configuration with their alkyl tail lying parallel to the surface...
May 11, 2018: Journal of Physical Chemistry. B
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