Chromatographic speciation of anionic and neutral selenium compounds in Se-accumulating Brassica juncea (Indian mustard) and in selenized yeast

Selenium-accumulating plants such as Brassica juncea (Indian mustard) concentrate the element in plant shoots and roots. Such behavior may provide a cost-effective technology to clean up contaminated soils and waters that pose major environmental and human health problems (phytoremediation). Such ability to transform selenium into bioactive compounds has important implications for human nutrition and health. Element selective characterization of B. juncea grown in the presence of inorganic selenium under hydroponic conditions provides valuable information to better understand selenium metabolism in plants. The present work determines both previously observed organoselenium species such as selenomethionine and Se-methylselenocysteine and for the first time detects the newly characterized S-(methylseleno)cysteine in plant shoots and roots when grown in the presence of selenate or selenite as the only selenium source. A key feature of this study is the complementary role of selenium and sulfur specific chromatographic detection by HPLC with interfaced inductively coupled plasma mass spectrometry (ICP-MS) detection and by derivatization GC with interfaced atomic spectral emission. HPLC-ICP-MS limits of detection for such species were in the range 5-50 ng Se mL(-1) in the injected extracts. Speciation profiles are compared with those of selenium-enriched yeast by both HPLC-ICP-MS and GC-AED.     

Synthesis of Tricyclic beta-Methylene Spiro Lactones Related to Bakkenolides by Successive Radical Cyclization-High Pressure Diels-Alder Reactions

The synthesis of some novel bakkenolides and their epi-spiro analogues was achieved by a new approach. Photolysis of allyl 1-(phenylseleno)-2-oxocyclopentanecarboxylates 7-9 afforded the corresponding spiro lactones 10-12 by radical cyclization via group transfer of the phenylseleno group. Selenoxide elimination of 11 and 12 produced the corresponding beta-methylene lactones 14 and 15. Diels-Alder cycloaddition of lactone11 with piperylene failed at ambient pressure, but proceeded in generally good yield in the presence of various Lewis acids at pressures of ca. 16 kbar, to give mixtures of beta-exo, alpha-endo, and beta-endo cycloadducts 19, 21, and 23, respectively. The preponderance of endo products 21 and 23, formed via highly hindered, but more compact, transition states was attributed to the high pressure and resulted in trans-dimethyl configurations of the products. The facial selectivity was dependent upon the Lewis acids, and the greatest alpha:beta ratio was observed with catalysts of the type TiCl(2)(OR)(2). Epimerization of the C-4 methyl group in 21 and 23 to furnish the corresponding cis-dimethyl analogues was achieved via exo-epoxidation, regioselective reduction, oxidation to the corresponding 3-keto derivatives, and base-catalyzed equilibration, thereby affording (+/-)-3,6-dioxobakkenolide-A (39) and its epi-spiro derivative 28, respectively. When the radical cyclization step was performed subsequent to the Diels-Alder cycloaddition by photolysis of perhydrindane 43, only the epi-spiro product 44 was obtained.     

Alkali Blues: Blue-Emissive Alkali Metal Pyrrolates

2-Iminopyrroles [H^tBuL, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(^tBuL), aggregate to dimers, [M(^tBuL)(NCR)]₂ (M=Li, R=CH₃, CH(CH₃)CNH₂), or polymers, [M(^tBuL)]_n (M=Na, K). In solution (solv=CH₃CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(^tBuL)(solv)_m with N,N′-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(^tBuL) chromophore possesses a low-energy intraligand charge-transfer (ILCT) excited state. The chelated alkali cations rigidify the chromophore, restricting intramolecular motions (RIM) by the chelation-enhanced fluorescence (CHEF) effect in solution and, consequently, switch-on a blue fluorescence emission.     

Hybrid polymer sol–gel material for UV-nanoimprint: microstructure and thermal densification

Hybrid polymer solutions suitable for UV-nanoimprint were synthesized by combination of an alkoxysilane binder mixture with silica nanoparticles. Hydrolysis and condensation reactions were monitored by NMR and viscosity measurements. Thereby long-term stable systems were produced as a prerequisite for industrial application. Dip-coating of glass substrates and subsequent UV-curing yielded thin films. Their thermal densification and microstructural evolution resulted in pure glassy porous coatings, which were in detail characterized by N₂-sorption measurements and ellipsometric porosimetry. Results emphasize the importance of the binder-particle interaction within these materials that are destined for the fabrication of microstructured surfaces by cost efficient and industrially feasible UV-based soft lithography. Structured glassy layers with high inorganic content show thermal stability up to >500 °C and have a high structure accuracy >85 %.     

Efficient Diketopyrrolopyrrole‐Based Small‐Molecule Bulk‐Heterojunction Solar Cells with Different Electron‐Donating End‐Groups

A series of small molecules that contained identical π‐spacers (ethyne), a central diketopyrrolopyrrole (DPP) unit, and different aromatic electron‐donating end‐groups were synthesized and used in organic solar cells (OSCs) to study the effect of electron‐donating groups on the device performance. The three compounds, DPP‐A‐Ph , DPP‐A‐Na , and DPP‐A‐An , possessed intense absorption bands that covered a wide range, from 350 to 750 nm, and relatively low HOMO energy levels, from ?5.50 to ?5.55 eV. DPP‐A‐An , which contained anthracene end‐groups, demonstrated a stronger absorbance and a higher hole mobility than DPP‐A‐Ph , which contained phenyl groups, and DPP‐A‐Na , which contained naphthalene units. The power‐conversion efficiencies (PCEs) of OSCs based on organic:PC₇₁BM blends (1:1, w/w) with a processed DIO additive were 3.93 % for DPP‐A‐An , 3.02 % for DPP‐Na , and 2.26 % for DPP‐A‐Ph . These findings suggest that a DPP core that is functionalized with electron‐donating capping groups constitutes a promising new class of solution‐processable small molecules for OSC applications.     

Hexameric MnII Dendrimer as MRI Contrast Agent

A Mn^II chelating dendrimer was prepared as a contrast agent for MRI applications. The dendrimer comprises six tyrosine‐derived [Mn(EDTA)(H₂O)]^2? moieties coupled to a cyclotriphosphazene core. Variable temperature ¹⁷O NMR spectroscopy revealed a single water co‐ligand per Mn^II that undergoes fast water exchange (k_ex=(3.0±0.1)×10⁸ s^?1 at 37 °C). The 37 °C per Mn^II relaxivity ranged from 8.2 to 3.8 mM ^?1 s^?1 from 0.47 to 11.7 T, and is sixfold higher on a per molecule basis. From this field dependence a rotational correlation time was estimated as 0.45(±0.02) ns. The imaging and pharmacokinetic properties of the dendrimer were compared to clinically used [Gd(DTPA)(H₂O)]^2? in mice at 4.7 T. On first pass, the higher per ion relaxivity of the dendrimer resulted in twofold greater blood signal than for [Gd(DTPA)(H₂O)]^2?. Blood clearance was fast and elimination occurred through both the renal and hepatobiliary routes. This Mn^II containing dendrimer represents a potential alternative to Gd‐based contrast agents, especially in patients with chronic kidney disease where the use of current Gd‐based agents may be contraindicated.     

A Pressure-Induced Inverse Order–Disorder Transition in Double Perovskites

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure-induced disordering could require recognition of an order–disorder transition in solid-state physics/chemistry and geophysics. Double perovskites Y₂CoIrO₆ and Y₂CoRuO₆ polymorphs synthesized at 0, 6, and 15 GPa show B-site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long-range ferrimagnetic ordering in the B-site ordered samples are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit-cell compressions under external pressures unexpectedly stabilize the disordered phases of Y₂CoIrO₆ and Y₂CoRuO₆.     

A Pressure‐Induced Inverse Order–Disorder Transition in Double Perovskites

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure‐induced disordering could require recognition of an order–disorder transition in solid‐state physics/chemistry and geophysics. Double perovskites Y₂CoIrO₆ and Y₂CoRuO₆ polymorphs synthesized at 0, 6, and 15 GPa show B‐site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long‐range ferrimagnetic ordering in the B‐site ordered samples are gradually overwhelmed by B‐site disorder. Theoretical calculations suggest that unusual unit‐cell compressions under external pressures unexpectedly stabilize the disordered phases of Y₂CoIrO₆ and Y₂CoRuO₆.