Metal-acetylide addition to tetracyanoethylene

Two push-pull chromophores that have shown utility in the field of molecular electronics and non-linear optics are DDMEBT (1, 2-(4-dimethylamino)phenyl)-3-((4-(dimethylamino)phenyl)ethynyl)buta-1,3-diene-1,1,4,4-tetracarbonitrile) and TDMEE (2, 4-(4-dimethylamino)phenyl)but-1-en-3-yne-1,1,2-tricarbonitrile). Unfortunately, the methods reported for their synthesis give variable yields, use toxic solvents, and only provide small amounts of material. We report improved synthetic protocols, providing access to larger quantities of material. By investigating multiple metal-acetylides of 4-ethynyl-N,N-dimethylaniline and their subsequent addition to TCNE, we obtained various products depending on the identity of the metal ion. This led to the simple synthesis of push-pull chromophoric compounds.     

Heat and brine transport in porous media: the Oberbeck-Boussinesq approximation revisited

This paper discusses the Oberbeck-Boussinesq approximation for heat and solute transport in porous media. In this commonly used approximation all density variations are neglected except for the gravity term in Darcy’s law. However, in the limit of vanishing density differences this gravity term disappears as well. The main purpose of this paper is to give the correct limits in which the gravity term is retained, while other density effects can be neglected. We show that for isothermal brine transport, fluid volume changes can be neglected when a condition is fulfilled for a dimensionless number, which is independent of the density difference and specific discharge. For heat transfer an additional condition is required. One-dimensional examples of simultaneous heat and brine transport are given for which similarity solutions are constructed. These examples are included to elucidate the volume effects and the corresponding induced specific discharge variations. Finally, a two-dimensional example illustrates the relative effects of volume changes and gravity.     

Potential of the dietary antioxidants resveratrol and curcumin in prevention and treatment of hematologic malignancies

Despite considerable improvements in the tolerance and efficacy of novel chemotherapeutic agents, the mortality of hematological malignancies is still high due to therapy relapse, which is associated with bad prognosis. Dietary polyphenolic compounds are of growing interest as an alternative approach, especially in cancer treatment, as they have been proven to be safe and display strong antioxidant properties. Here, we provide evidence that both resveratrol and curcumin possess huge potential for application as both chemopreventive agents and anticancer drugs and might represent promising candidates for future treatment of leukemia. Both polyphenols are currently being tested in clinical trials. We describe the underlying mechanisms, but also focus on possible limitations and how they might be overcome in future clinical use--either by chemically synthesized derivatives or special formulations that improve bioavailability and pharmacokinetics.     

Total Synthesis and Configurational Assignment of Chondramide A

The first total synthesis of the cyclodepsipeptide chondramide A ( 2 b ) is described. This depsipeptide is composed of four subunits, namely L ‐alanine, N‐Me‐D ‐tryptophan, 3‐amino‐2‐methoxy‐propionic acid (β‐tyrosine derivative), and a 7‐hydroxy‐alkenoic acid. While the configuration of the stereogenic centers in the 7‐hydroxy‐alkenoic acid were known, the configuration of the tyrosine derivative required clarification and turned out to be (2S,3R) or (2L ,3L ), respectively. The synthesis of the 3‐amino‐2‐methoxy‐3‐arylpropanoic ester 20 b relied on an asymmetric dihydroxylation yielding diol ent‐ 15 a followed by a regioselective Mitsunobu substitution leading to 3‐azido‐2‐hydroxypropanoate 18 b . We could also show that the ester bond in the seco compound 26 b can be fashioned by a Mitsunobu esterification by using hydroxy ester (7S)‐ 7 and the tripeptide acid 25 b . This synthesis should allow for the preparation of various analogues.     

Solvatochromism as an efficient tool to study N,N‐dimethylamino‐ and cyano‐substituted π‐conjugated molecules with an intramolecular charge‐transfer absorption

A representative data set has been gained by the measurement of the electronic absorption spectra of 12 systematically selected push–pull systems with an intramolecular charge‐transfer (CT) absorption and the general structure D–π–A (D = donor, A = acceptor) featuring electron‐withdrawing CN groups, electron‐donating N(CH₃)₂ groups, and various π‐conjugated backbones in 32 solvents with different polarities. The longest‐wavelength absorption maxima λ_max and the corresponding wavenumbers $\tilde {v}_{{\rm max}} $ were evaluated from the UV/Vis spectra measured in 32 well‐selected solvents. The D–π–A push–pull systems were further characterized by quantum‐chemical quantities and simple structural parameters. Structure–solvatochromism relationships were evaluated by multidimensional statistic methods. Whereas solvent polarizability and solvent cavity size proved to be the most important factors affecting the position of λ_max, the solvent polarity was less important. The most important characteristics of organic CT compounds are the energy of the LUMO, the permanent dipole moment, the COSMO (COnductor‐like Screening MOdel) area, the COSMO volume, the number, and ratio of N,N‐dimethylamino and cyano groups, and eventually the number of triple bonds (π‐linkers). A relation between the first‐order polarizability α, the longest‐wavelength absorption maxima λ_max, and the structural features has also been found. The higher‐order polarizabilities β and γ are not related to the observed solvatochromism. Copyright © 2010 John Wiley & Sons, Ltd.