Synthesis, characterization, and DFT/TD-DFT calculations of highly phosphorescent blue light-emitting anionic iridium complexes

Highly phosphorescent blue-light-emitting anionic iridium complexes (C4H9)4N[Ir(2-phenylpyridine)2(CN)2] (1), (C4H9)4N[Ir(2-phenyl-4-dimethylaminopyridine)2(CN)2] (2), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-pyridine)2(CN)2] (3), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (4), and (C4H9)4N[Ir(2-(3,5-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (5) were synthesized and characterized using NMR, UV-vis absorption, and emission spectroscopy and electrochemical methods. In these complexes color and quantum yield tuning aspects are demonstrated by modulating the ligands with substituting donor and acceptor groups on both the pyridine and phenyl moieties of 2-phenylpyridine. Complexes 1-5 display intense photoluminescence maxima in the blue region of the visible spectrum and exhibit very high phosphorescence quantum yields, in the range of 50-80%, with excited-state lifetimes of 1-4 micros in acetonitrile solution at 298 K. DFT and time dependent-DFT calculations were performed on the ground and excited states of the investigated complexes to provide insight into the structural, electronic, and optical properties of these systems.     

Induced Production,Synthesis, and Immunomodulatory Action of Clostrisulfone,a Diarylsulfone from Clostridium acetobutylicum

The anaerobe Clostridium acetobutylicum belongs to the most important industrially used bacteria. Whereas genome mining points to a high potential for secondary metabolism in C. acetobutylicum, the functions of most biosynthetic gene clusters are cryptic. We report that the addition of supra-physiological concentrations of cysteine triggered the formation of a novel natural product, clostrisulfone ( 1 ). Its structure was fully elucidated by NMR, MS and the chemical synthesis of a reference compound. Clostrisulfone is the first reported natural product with a diphenylsulfone scaffold. A biomimetic synthesis suggests that pentamethylchromanol-derived radicals capture sulfur dioxide to form 1 . In a cell-based assay using murine macrophages a biphasic and dose-dependent regulation of the LPS-induced release of nitric oxide was observed in the presence of 1 .     

Liquid–liquid extraction of actinides,lanthanides, and fission products by use of ionic liquids: from discovery to understanding

Liquid–liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented.     

Forensic examination of ink by high-performance thin layer chromatography--the United States Secret Service Digital Ink Library

Forensic examinations of ink have been performed since the beginning of the 20th century. Since the 1960s, the International Ink Library, maintained by the United States Secret Service, has supported those analyses. Until 2009, the search and identification of inks were essentially performed manually. This paper describes the results of a project designed to improve ink samples' analytical and search processes. The project focused on the development of improved standardization procedures to ensure the best possible reproducibility between analyses run on different HPTLC plates. The successful implementation of this new calibration method enabled the development of mathematical algorithms and of a software package to complement the existing ink library.     

Fast screening for presence of muddy/earthy odorants in wine and in wine must using a hyphenated gas chromatography-differential ion mobility spectrometry (GC/DMS)

Rapid, hyphenated detection techniques involving a gas chromatograph (GC) coupled to a classical time-of-flight ion mobility (IMS) spectrometer, or more recently, to a micro-machined, miniature differential ion mobility spectrometer (DMS) are quite attractive for in-situ detection of many kinds of volatile organic compounds (VOCs) of concern and notably of natural contaminants appearing in the headspaces of selected foodstuff. This work aims at a rapid detection, identification and quantification of geosmin in the headspace of grape must and of wine. Samples of white and red wines have both been analyzed with a hyphenated GC/DMS and by Solid Phase Micro-Extraction (SPME) coupled to GC/MS taken as a reference. The detection of geosmin at concentrations below the human olfactory threshold of 50 ng/L has been demonstrated.     

Synthesis and characterization of 2,8-diazaperylene-1,3,7,9-tetraone, a new anthracene diimide containing six-membered imide rings

A successful synthesis of novel diimides, namely anthracene diimide containing six-membered imide rings, with potential application in organic electronics is reported. The single crystal of 5a exhibits a close interplanar spacing of 3.45 ? between molecules in a stack.     

A Divergent Approach to the Marine Diterpenoids (+)‐Dictyoxetane and (+)‐Dolabellane V

We present a full account of the development of a strategy that culminated in the first total syntheses of the unique oxetane‐containing natural product (+)‐dictyoxetane and the macrocyclic diterpene (+)‐dolabellane V. Our retrosynthetic planning was guided by both classical and nonconventional strategies to construct the oxetane, which is embedded in an unprecedented 2,7‐dioxatricyclo[4.2.1.0^3,8]nonane ring system. Highlights of the successful approach include highly diastereoselective carbonyl addition reactions to assemble the full carbon skeleton, a Grob fragmentation to construct the 11‐membered macrocycle of (+)‐dolabellane V, and a bioinspired 4‐exo‐tet, 5‐exo‐trig cyclization sequence to form the complex dioxatricyclic framework of (+)‐dictyoxetane. Furthermore, an unprecedented strain‐releasing type I dyotropic rearrangement of an epoxide‐oxetane substrate was developed.     

Synthesis and characterization of a new red-emitting Ca2+ indicator, calcium ruby

Calcium Ruby m-Cl (X = H, Y = Cl) is a visible-light excited red-emitting calcium concentration ([Ca2+]) indicator dye (579/598 nm peak excitation/emission) with a side arm for conjugation via EDC or click chemistry. Its large molar extinction and high quantum yield rank it among the brightest long-wavelength Ca2+ indicators. Calcium Ruby is a promising alternative to existing dyes for imaging [Ca2+] in multicolor fluorescence applications or in the presence of yellow-green cellular autofluorescence.     

Positive curvature effects and interparticle capillary condensation during nitrogen adsorption in particulate porous materials

The adsorption of nitrogen in a collection of spheres that touch or merge in a sintering-like manner is modeled using a Derjaguin-Broeckhof-de Boer approach. The proposed model accounts for both positive curvature effects and for capillary condensation at the contact between two spheres. A methodology is proposed to fit the P/P(0)>0.4 adsorption region with the coordination number of the spheres as the only adjustable parameter. The use of the model is illustrated on a series of silica aerogels. The suitability of various standard isotherms needed for the modeling is also discussed.     

Gold(I)‐Catalyzed N‐Desulfonylative Amination versus N‐to‐O 1,5‐Sulfonyl Migration: A Versatile Approach to 1‐Azabicycloalkanes

Valuable 1‐azabicycloalkane derivatives have been synthesized through a novel gold(I)‐catalyzed desulfonylative cyclization strategy. An ammoniumation reaction of ynones substituted at the 1‐position with an N‐sulfonyl azacycle took place in the presence of a gold cation by intramolecular cyclization of the disubstituted sulfonamide moiety onto the triple bond. Depending on the size of the heterocyclic ring and substitution of the substrates, two unprecedented forms of nucleophilic attack on the sulfonyl group were exploited, that is, a N‐desulfonylation in the presence of an external protic O nucleophile (37–87 %, 10 examples) and a unique N‐to‐O 1,5‐sulfonyl migration (60–98 %, 9 examples).