Quantification and Isolation of Plumbagin (Plumbago zeylanica Linn.) by High-Performance Thin-Layer Chromatography

JPC – Journal of Planar Chromatography – Modern TLC - A simple, rapid, selective, and quantitative high-performance thinlayer chromatographic (HPTLC) method has been developed for the...     

Zur plasmachemischen Umsetzung von CO/H2-Gemischen zu leichten Kohlenwasserstoffen in einer Glimmentladung

Mixtures of CO und H₂ can be partially converted into hydrocarbons (Hc), especially methane, by nonthermal activation in a glow discharge. The degree of conversion α CO → Hc and the partial pressure of methane reached values of 12% and 3% resp. The CO-conversion depends on the discharge parameters, the discharge time the energy input resp., and the rate of CO/H₂-mixture. The Hc formed are intermediate products which react further to higher Hc including solid Hc. According to mass spectrometrical analysis of plasma ions a reaction scheme was developed which is considered to be valid for the Hc formation based on an ion as well on neutral particle reactions.     

Synthesis of functionalized nitroarylmagnesium halides via an iodine-magnesium exchange

[reaction: see text] Various nitro-substituted aryl and heteroaryl iodides undergo an iodine-magnesium exchange reaction when treated with PhMgCl leading to nitro-containing magnesium organometallics. These Grignard reagents display an excellent stability at temperatures below -40 degrees C and do not undergo electron-transfer reactions. They react as expected with various electrophiles.     

Covalent attachment of a transition metal coordination complex to functionalized oligo(phenylene-ethynylene) self-assembled monolayers

We have investigated the reaction of tetrakis(dimethylamido)titanium, Ti[N(CH(3))(2)](4), with N-isopropyl-N-[4-(thien-3-ylethynyl) phenyl] amine and N-isopropyl-N-(4-{[4-(thien-3-ylethynyl) phenyl]ethynyl}phenyl) amine self-assembled monolayers (SAMs), on polycrystalline Au substrates. The structure of the SAMs themselves has also been investigated. Both molecules form SAMs on polycrystalline Au bound by the thiophene group. The longer-molecular-backbone molecule forms a denser SAM, with molecules characterized by a smaller tilt angle. X-ray photoelectron spectroscopy (XPS) and angle-resolved XPS have been employed to examine the kinetics of adsorption, the spatial extent of reaction, and the stoichiometry of reaction. For both the SAMs, adsorption is described well by first-order Langmuirian kinetics, and adsorption is self-limiting from T(s) = -50 to 30 degrees C. The use of angle-resolved XPS clearly demonstrates that the Ti[N(CH(3))(2)](4) reacts exclusively with the isopropylamine end group via ligand exchange, and there is no penetration of the SAM, followed by reaction at the SAM-Au interface. Moreover, the SAM molecules remain bound to the Au surface via their thiopene functionalites. From XPS, we have found that, in both cases, approximately one Ti[N(CH(3))(2)](4) is adsorbed per two SAM molecules.     

Electrical Properties of Sol-Gel Processed Amorphous BaTiO3 Thin Films

BaTiO₃ thin films were prepared on single crystal silicon (1 0 0) and platinum substrates by sol-gel technique. Amorphous films with thickness uniformity were obtained by spinning the solution at 3000 rpm for 30 s and by post-deposition annealing at 400°C. The films exhibited good dielectric and insulating properties. The dielectric constant and dissipation factor at a frequency of 100 kHz were 17 and 0.20, respectively, for 1400 Å thick film on platinum substrate (MIM). The corresponding values were 16 and 0.015 for films on Si (MIS). Dielectric properties were also studied as functions of frequency and voltage. The C-V curve for MIS structure exhibited a hysteresis. The density of interface states recharged during the bias cycle in hysteresis measurement was estimated to be of the order of 2.10 × 10¹¹ cm^–2 and total oxide charge density was about 4.28 × 10¹¹ cm^–2. I-V measurements were performed on films of different thicknesses. The leakage current densities at 5 V for the films having thicknesses 1400 and 2800 Å were 0.86 and 0.11 A/cm² respectively. The conduction mechanism is found to be Poole-Frenkel and Schottky mechanisms at low and high fields, respectively.     

Peri-Anthracenethioindigo: A Scaffold for Efficient All-Red-Light and Near-Infrared Molecular Photoswitching**

Molecular photoswitching with red light is greatly desired to evade photodamage and achieve specific photoresponses. In virtually all reported cases however, only one switching direction uses red light while for the reverse switching, UV or visible light is needed. All-red-light photoswitching brings with it the clear advantage of pushing photoswitching to the limit of the low-energy spectrum, but no viable system is available currently. Here we report on peri-anthracenethioindigo (PAT) as molecular scaffold for highly efficient all-red-light photoswitching with an outstanding performance and property profile. The PAT photoswitch provides near-infrared (NIR) absorption up to 850 nm, large negative photochromism with more than 140 nm maxima shifts and changes color from green to blue upon irradiation with two shades of red light. Thermal stability of the metastable Z isomer is high with a corresponding half-life of days at 20 °C. Application in red-light responsive polymers undergoing pronounced and reversible green to blue color changes demonstrate spatially resolved photoswitching. The PAT photoswitch thus offers unique responsiveness to very low energy light together with predictable and large geometrical changes within a rigid molecular scaffold. We expect a plethora of applications for PAT in the near future, e.g. in materials, molecular machines or biological context.     

Ionic liquid-promoted one-pot oxidative Michael addition of TMSCN to Baylis-Hillman adducts

The first example of ionic liquid-promoted one-pot oxidative conjugate hydrocyanation of Baylis-Hillman adducts with trimethylsilyl cyanide (TMSCN) is reported. The oxidation of Baylis-Hillman adducts with IBX/[bmim]Br or isomerization-oxidation with NaNO₃/[Hmim]HSO₄ systems affords β-ketomethylene compounds or [E]-cinnamaldehydes, respectively. These α,β-unsaturated carbonyl compounds undergo Michael addition with TMSCN in the same vessel to afford the corresponding thermodynamically more stable β-cyanated products. Thermodynamically less stable 1,2-addition products were not formed. The present regioselective reactions are promoted by ionic liquids, which can be recycled easily for further use without any loss of efficiency.     

Transmission of Unidirectional Molecular Motor Rotation to a Remote Biaryl Axis

Molecular motors undergo repetitive directional motions upon external energy input. A profound challenge is the defined transfer of directional motor motions to remote entities at the molecular scale. Herein, we present a molecular setup that allows for the transfer of the directional rotation of a light‐powered motor unit onto a remote biaryl axis via an ethylene glycol chain link. Based on a combination of X‐ray crystallographic analysis, ECD, and NMR experiments as well as a comprehensive theoretical assessment, we provide evidence for the coupled stepwise directional motions of both molecular units. With the presented setup, facile integration of molecular motor units into larger functional frameworks and complex molecular machines can be explored consciously in the future.     

Synthetic routes for phenazines: an overview

Phenazines are known to exhibit a diverse range of biological properties, such as antimicrobial, antitumor, antioxidant, antimalarial, neuroprotectant, etc. Owing to their significant applications in both medicinal and industrial fields, the phenazine framework has emerged as a remarkable synthetic target. The most general approaches for synthesis of phenazines include the Wohl–Aue method, Beirut method, condensation of 1,2-diaminobenzenes with 2C-units, reductive cyclization of diphenylamines, oxidative cyclization of 1,2-diaminobenzene/diphenylamines, Pd-catalyzed N-arylation, multicomponent approaches, etc. Advances in the exploitation of synthetic routes for assembly of this scaffold are reported in this review.     

Intra-Specific Chemotypic Variability of Forskolin Content in Coleus forskohlii (Wild.) Briq. Growing in Nilgiri Hills of India

JPC – Journal of Planar Chromatography – Modern TLC - Plant metabolite varies with season and geographic conditions. The present study is aimed at the identification of the potential...