Investigating the spectrum of biological activity of substituted quinoline-2-carboxamides and their isosteres

In this study, a series of thirty-five substituted quinoline-2-carboxamides and thirty-three substituted naphthalene-2-carboxamides were prepared and characterized. They were tested for their activity related to the inhibition of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. Primary in vitro screening of the synthesized compounds was also performed against four mycobacterial species. N-Cycloheptylquinoline-2-carboxamide, N-cyclohexylquinoline-2-carboxamide and N-(2-phenylethyl)quinoline-2-carboxamide showed higher activity against M. tuberculosis than the standards isoniazid or pyrazinamide and 2-(pyrrolidin-1-ylcarbonyl)quinoline and 1-(2-naphthoyl)pyrrolidine expressed higher activity against M. kansasii and M. avium paratuberculosis than the standards isoniazid or pyrazinamide. The most effective antimycobacterial compounds demonstrated insignificant toxicity against the human monocytic leukemia THP-1 cell line. The PET-inhibiting activity expressed by IC(50) value of the most active compound N-benzyl-2-naphthamide was 7.5 μmol/L. For all compounds, the structure-activity relationships are discussed.     

Opportunities for wavelength conversion with on‐chip diamond ring resonators

Recent progress in the fabrication of high‐quality synthetic diamond and of diamond waveguide structures has enabled photonics researchers to start exploiting the unique optical properties of diamond for various applications. In this article the promise of on‐chip diamond ring resonators for wavelength conversion based on Kerr and Raman‐resonant four‐wave mixing is numerically demonstrated. After examining to what extent both dispersion‐engineered phase‐matching and “automatic” quasi‐phase‐matching can be established in diamond ring converters, it is shown that such a “double‐matching” approach can yield high conversion efficiencies for a wide range of wavelengths in the near‐infrared/mid‐infrared domain, as well as in the ultraviolet/visible domain.     

A moment method for splashing and evaporation processes of polydisperse sprays

A new moment method for the modelling of polydisperse sprays is proposed that simultaneously takes into account the dispersion in droplet size and droplet velocity. For the derivation of this Eulerian method the kinetic spray equation is used which constitutes a partial differential equation for the probability density function of droplets. To reduce the complex kinetic spray equation to a form that can be managed with the available numerical procedures, moment transforms with respect to the droplet velocity and the droplet size are conducted. The resulting moment equations are closed by choosing an approximate probability density function which applies to polydisperse sprays. The method is successfully tested for configurations in which a polydisperse spray is either splashed, evaporated or effected by a Stokes drag force. The tests are organised in such a way that crossing of two spray distributions is always included. The new method is able to capture the polydisperse nature of sprays as well as the bi-(or multi-) modal character of the droplet velocity distribution function, for example, when droplets cross each other.     

Alkene insertion reactivity of a o-carboranyl-substituted 9-borafluorene

The synthesis of 9-borafluorene with an electron-withdrawing o-carboranyl substituent and its reactions with a series of alkenes are described. The o-carboranyl substituent is bonded via one of the cluster carbon atoms to the boron atom of the 9-borafluorene moiety. In all cases, the reactions afford partly saturated analogs of borepins (i.e. 6,7-dihydroborepins) by unprecedented alkene insertion into the endocyclic B–C bond of the borole ring. Comparative studies with 9-bromo-9-borafluorene illustrate the superior insertion reactivity of the carboranyl-substituted derivative. A suite of experimental and computational techniques disclose the unique properties of the 9-borafluorene and provide insight into how the 9-carboranyl substituent affects its chemical reactivity.

A 9-carboranyl-substituted 9-borafluorene is reported, which is capable of undergoing efficient ring expansion to 6,7-dihydroborepins by a previously unknown alkene insertion.     

Excited-State Kinetics of an Air-Stable Cyclometalated Iron(II) Complex

The complex class [Fe(N^N^C)(N^N^N)]⁺ with an Earth-abundant metal ion has been repeatedly suggested as a chromophore and potential photosensitizer on the basis of quantum chemical calculations. Synthesis and photophysical properties of the parent complex [Fe(pbpy)(tpy)]⁺ (Hpbpy=6-phenyl-2,2′-bipyridine and tpy=2,2′:6′,2′′-terpyridine) of this new chromophore class are now reported. Ground-state characterization by X-ray diffraction, electrochemistry, spectroelectrochemistry, UV/Vis, and X-ray spectroscopy in combination with DFT calculations proves the high impact of the cyclometalating ligand on the electronic structure. The photophysical properties are significantly improved compared to the prototypical [Fe(tpy)₂]²⁺ complex. In particular, the metal-to-ligand absorption extends into the near-IR and the ³MLCT lifetime increases by 5.5, whereas the metal-centered excited triplet state is very short-lived.     

THF-solvated Heavy Alkali Metal Benzyl Compounds (Na,Rb, Cs): Defined Deprotonation Reagents for Alkali Metal Mediation Chemistry

The incorporation of heavy alkali metals into substrates is both challenging and essential for many reactions. Here, we report the formation of THF-solvated alkali metal benzyl compounds [PhCH₂M ⋅ (thf)_n] (M=Na, Rb, Cs). The synthesis was carried out by deprotonation of toluene with the bimetallic mixture n-butyllithium/alkali metal tert-butoxide and selective crystallization from THF of the defined benzyl compounds. Insights into the molecular structure in the solid as well as in solution state are gained by single crystal X-ray experiments and NMR spectroscopic studies. The compounds could be successfully used as alkali metal mediating reagents. The example of caesium showed the convenient use by deprotonating acidic C−H as well as N−H compounds to gain insight into the aminometalation using these reagents.     

Cycloaddition of Alkenes and Alkynes to the P-centered Singlet Biradical [P(μ-NTer)]2

The reaction of biradical [P(μ-NTer)]₂ ( 1 , Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl) towards different alkenes (R = 2,3-dimethyl–butadiene, 2,5-dimethyl-2,4-hexadiene, 1,7-octadiene, 1,4-cyclohexadiene) and alkynes (R = 1,4-diphenyl-1,3-butadiyne) was studied experimentally. Although these olefins can react in different ways, only [2+2] cycloaddition products ( 1R ) were observed. The reaction with 2,3-dimethylbutadiene also led to the [2+2] product ( 1dmb ). Thermal treatment of 1dmb above 140 °C resulted in the recovery of biradical 1 upon homolytic bond cleavage of the two P–C bonds and the release of 2,3-dimethylbutadiene. In contrast to this reaction, all other [2+2] additions products ( 1R , R = 1,7-octadiene, 1,4-cyclohexadiene, 1,4-diphenyl-1,3-butadiyne) began to decompose at temperatures between 200 °C and 300 °C. Only unidentified products were obtained but no temperature-controlled equilibrium reactions were observed. Computations were carried out to shed light into the formal [2+2] as well as the possible [4+2] addition reaction.