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The increased use of wireless technology causes a significant exposure increase for all living organisms to radio frequency electromagnetic fields (RF-EMF). This comprises bacteria, animals, and also plants. Unfortunately, our understanding of how RF-EMF influences plants and plant physiology remains inadequate. In this study, we examined the effects of RF-EMF radiation on lettuce plants (Lactuca sativa) in both indoor and outdoor environments using the frequency ranges of 1890-1900 MHz (DECT) at 2.4 GHz and 5 GHz (Wi-Fi). Under greenhouse conditions, RF-EMF exposure had only a minor impact on fast chlorophyll fluorescence kinetics and no effect on plant flowering time. In contrast, lettuce plants exposed to RF-EMF in the field showed a significant and systemic decrease in photosynthetic efficiency and accelerated flowering time compared to the control groups. Gene expression analysis revealed significant down-regulation of two stress-related genes in RF-EMF-exposed plants: violaxanthin de-epoxidase (VDE) and zeaxanthin epoxidase (ZEP). RF-EMF-exposed plants had lower Photosystem II's maximal photochemical quantum yield (FV/FM) and non-photochemical quenching (NPQ) than control plants under light stress conditions. In summary, our results imply that RF-EMF might interfere with plant stress responses and reduced plant stress tolerance.

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A general, easy-to-implement strategy for mapping the structure of organic phases integrated in mesoporous silica drug delivery devices is presented. The approach based on a few straightforward solid-state NMR techniques has no limitations regarding concentrations of the active compounds and enables straightforward discrimination of various organic phases. This way, among a range of typical arrangements of the active compounds and solvent molecules, a unique, previously unknown organogel phase of the self-assembled tapentadol in glucofurol as a solvent was unveiled and clearly identified. Subsequently, with an aid of 2D 1H-1H MAS NMR and high-level quantum-chemical calculations this uncommon low-molecular-weight organogel phase, existing exclusively in the porous system of the silica carrier, was described in detail. The optimized model revealed the tendency of tapentadol molecules to form hydrophobic arrangements through -OH···π interactions combined with π-π stacking occurring in the core of API aggregates, thus precluding the formation of hydrogen bonds with the solvent. Overall, the proposed experimental approach allows for clear discrimination of a variety of local structures of active compounds loaded in mesoporous silica drug delivery devices in reasonably short time being applicable for advancement of novel drug delivery systems in pharmaceutical industry.

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A diolefin ether, trop2O (2), and a diolefin thioether, trop2S (3), have been investigated as ligand analogues of the well-established diolefin amine, trop2NH (1). Compounds 2 and 3 form different conformers in solution and in the solid state. Whereas 2 could be coordinated to Ni(0), 3 was found to be more suited for coordination to Rh(I). The coordination chemistry, electrochemical properties, and ligand exchange phenomena of the resulting complexes, [Ni(trop2O)(PPh3)] (5) and [Rh(trop2S)(L)n][OTf] (6: L = NCMe, n = 2; 7: L = 2,2'-bipy, n = 1) were investigated by analytical techniques including NMR spectroscopy, single crystal X-ray analysis, and cyclic voltammetry. The results were compared with those obtained for the amine analogues of 5, 6, and 7.

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A library of monodentate phosphane ligands, each bearing a guanidine receptor unit for carboxylates, was designed. Screening of the library gave some excellent catalysts for regioselective hydroformylation of beta,gamma-unsaturated carboxylic acids. A terminal alkene, but-3-enoic acid, was hydroformylated with a linear/branched (l/b) regioselectivity up to 41. An internal alkene, pent-3-enoic acid was hydroformylated with regioselectivity up to 18:1. Further substrate selectivity (e.g., acid vs. methyl ester) and reaction site selectivity (monofunctionalization of 2-vinylhept-2-enoic acid) were also achieved. Exploration of the structure-activity relationship and a practical and theoretical mechanistic study gave us an insight into the nature of the supramolecular guanidinium-carboxylate interaction within the catalytic system. This allowed us to identify a selective transition-state stabilization by a secondary substrate-ligand interaction as the basis for catalyst activity and selectivity.

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21 subjects (mean age 28,4 +/- 10,9, M +/- SD) without any damage of the visual system were examined with computer-based campimetric tests of near threshold stimulus detection whereby an artificial tunnel vision was induced. Campimetry was performed in four trials in randomized order using a within-subjects-design: 1. classical music, 2. Techno music, 3. music for relaxation and 4. no music. Results were slightly better in all music conditions. Performance was best when subjects were listening to Techno music. The average increase of correctly recognized stimuli and fixation controls amounted to 3 %. To check the stability of the effects 9 subjects were tested three times. A moderating influence of personality traits and habits of listening to music was tested but could not be found. We conclude that music has at least no negative influence on performance in the campimetric measurement. Reasons for the positive effects of music can be seen in a general increase of vigilance and a modulation of perceptual thresholds.

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The six-dimensional exchange density Gamma(X)(r1,r2) is a measure of electron delocalization at the Hartree-Fock level. Fixation of r1 to a constant point results in a three-dimensional function, which displays electron delocalization that originates from r1 in position space. In this work, the dimensionality of Gamma(X)(r1,r2) is lowered from six to four by integration with regard to r2 over sphere surfaces of radius d, centered at r1 = r. The resulting radial exchange density Gamma(X)(d,r) is visualized for constant d values as a function of r. This approach indicates regions of position space which are origins of delocalization over a certain distance d. The shape of these regions very strongly depends on d. Structures similar to pi orbital densities are observed at large d values (4.5 au) in unsaturated carbon compounds, while smaller values (1.5 au) can result in structures, which resemble the Laplacian of the electron density. The abundance of different spatial structures inherent in the radial exchange density implies interesting capabilities for the orbital-independent interpretation of electronic structures in position space.

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A convenient one-step synthesis for [Mn(CO)6]+ salts has been developed. The method involves the one-electron oxidation of Mn2(CO)10 by protons in solutions of Lewis acids (BF3, (CF3)3BCO) and anhydrous HF. The molecular structure of [Mn(CO)6][BF4].SO2 was determined by single-crystal X-ray diffraction. Crystal data: orthorhombic, space group Cmc2(1); a = 8.7001(2) A, b = 11.8497(3) A, and c = 11.7437(3) A; Z = 4; R1 = 0.0320 and wR2 = 0.1106. The structural, NMR, and vibrational spectroscopic properties of [Mn(CO)6]+ fit perfectly with those of the isoelectronic species [V(CO)6]-, Cr(CO)6, and [Fe(CO)6]2+.

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Treatment of Cs[(CF3)3BNH2] with the aminating agent H2NOSO3H in aqueous solution allowed the isolation of pure Cs[(CF3)3BH], which is stable up to 300 degrees C. Due to the strong electron-withdrawing effect of the CF3 substituents, the [(CF3)3BH]- anion behaves as a very unreactive hydride. It is stable in concentrated hydrochloric acid for many days but reacts cleanly with F2, Cl2, and Br2 to the corresponding haloborates. The molecular structure was determined by single-crystal X-ray diffraction. Crystal data: orthorhombic, space group Pnma; a = 11.4296(5) A, b = 7.9510(4) A, c = 9.7268(5) A; V = 883.94(7) A(3), Z = 4; R1 = 0.0294, wR2 = 0.0818. The anions exhibit only Cs symmetry in the lattice. The natural and deuterated anions were characterized by IR, Raman, and multinuclear NMR spectroscopy; vibrational assignments were supported by DFT calculations. QTAIM charges derived from the B3LYP electron density are given for [(CF3)3BH]- and several related anions.

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The Laplacian of the negative exchange-correlation density (with respect to coordinate r(2)), nabla<(r)2>(2)[-Gamma(sigma1)(sigma2)(XC) (r(1),r(2))] = nabla(r)2(2)X(sigma1)(sigma2)(r(1),r(2)), is proposed as an instrument for the analysis of electron delocalization in real space. It determines local concentrations in the amount of electrons that are delocalized from a reference point r(1) over space. Integration of the reference coordinate r(1) over an atomic basin Omega(n) gives the function nabla(2)X(sigma1)(sigma2)(Omega(n);r), which contains detailed information about the spatial shape of the delocalization that originates from an atom in a molecule. Its isosurface representations are richly structured and resemble molecular orbitals in their complexity and partly also in their shape. The sum over all nabla(2)X(sigma1)(sigma2)(Omega(n);r) functions of a molecule equals the Laplacian of the electron density nabla(2)rho(r), for which it provides a meaningful partitioning into atomic contributions.

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The benzophenone dianion [diphenyloxidomethanide, (Ph(2)CO)(2-)], which occurs in the well known deeply violet sodium/benzophenone tetrahydrofuran solutions, was crystallised with sodium cations in form of the two polymeric chain compounds [Na(2)(Ph(2)CO)(tetraglyme)](infinity) and [Na(2)(Ph(2)CO)(thf)(2)](infinity). It was found to aggregate with its conjugated acid, the alcoholate (Ph(2)CHO)(-), around a central unit of sodium hydroxide, resulting in the mixed cage compound [Na(13)(Ph(2)CO)(4)(Ph(2)CHO)(4)(OH)(mtbe)(4)].mtbe. The structural parameters of the benzophenone dianion indicate that a considerable amount of its negative charge is located within the phenyl rings, rather than on the formally anionic benzylic carbon atom. The topological analysis of the electron density of the monomeric model structure [Na(2)(Ph(2)CO)] reveals an even positive charge for this particular atom, hence (Ph(2)CO)(2-) is, despite its usual representation, not a vicinal dianion.

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Metal-stabilized phenoxyl radicals appear to be important intermediates in a variety of enzymatic oxidations. We report that transition metal coordination also supports an aminyl radical, resulting in a stable crystalline complex: [Rh(I)(trop2N.)(bipy)]+OTf- (where trop is 5-H-dibenzo[a,d]cycloheptene-5-yl, bipy is 2,2'-bipyridyl, OTf- is trifluorosulfonate). It is accessible under mild conditions by one-electron oxidation of the amide complex [Rh(I)(trop2N)(bipy)], at a potential of -0.55 volt versus ferrocene/ferrocenium. Both electron paramagnetic resonance spectroscopy and density functional theory support 57% localization of the unpaired spin at N. In reactions with H-atom donors, the Rh-coordinated aminyl behaves as a nucleophilic radical.

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Iridium(I) complexes containing a (5H-dibenzo[a,d]cyclohepten-5-yl)-phosphane (tropp(R); R = phosphorus-bound substituent = Ph, Cyc) as a rigid, concave-shaped, mixed phosphane olefin ligand were prepared and tested as catalyst precursors in the hydrogenation of imines. With the complex [Ir(tropp(Cyc))(cod)]OTf, turnover frequencies (TOFs) of >6000 h(-1) were reached in the hydrogenation of N-phenyl-benzylidenamine, PhN==CHPh. Lower activities (TOF>80 h(-1)) are observed with N-phenyl-(1-phenylethylidene)amine, PhN==CMePh. Chiral tropp-type ligands were prepared in few simple steps. Monosubstitution of the olefinic unit in the dibenzo[a,d]cycloheptenyl moiety with (R)- or (S)-mentholate gave mixtures of diastereomers that could be separated and isolated in enantiomerically pure form. Iridium(I) complexes with these ligands are rare examples of side-on bonded enolether complexes. In catalytic imine hydrogenations, complete conversion (>98 %) was reached in all cases (conditions: p[H(2)] = 50 bar, T = 50 degrees C, t = 2 h, substrate/catalyst 100:1). The best enantiomeric excess (ee = 86 % S isomer) was reached with PhN==CMePh as substrate and the R,R form of the (10-menthyloxy-5H-dibenzo[a,d]cyclohepten-5-yl)diphenylphosphane ligand. The iridium(I) complex containing the same phosphane gave a 60 % ee (S isomer) with the enamide N-(1-phenylvinyl)acetamide as substrate (conditions: p[H(2)] = 4 bar, T = 50 degrees C, t = 18 h, substrate/catalyst = 50:1). These reactions constitute the first examples in which chiral olefins have been used as steering ligands in catalytic enantioselective hydrogenations.

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A new class of potent electrophilic "R(+)" alkylating agents has been developed using weakly nucleophilic carborane anions as leaving groups. These reagents, R(CHB(11)Me(5)X(6)) (R = Me, Et, and i-Pr; X = Cl, Br), are prepared via metathesis reactions with conventional alkylating agents such as alkyl triflates, using the high oxophilicity of silylium ion-like species, Et(3)Si(carborane), as the driving force to obtain increased alkyl electrophilicity. The crystal structure of the isopropyl reagent, i-Pr(CHB(11)Me(5)Br(6)), has been determined, revealing covalence in the alkyl-carborane bonding. This contrasts with the free i-Pr(+) carbocation observed when the anion is less coordinating (e.g. Sb(2)F(11)(-)) or with tertiary alkyl centers, as in [tert-butyl][carborane] salts. In solution, the reagents exist as equilibrating isomers with the alkyl group at the 7-11 or 12 halide positions of the CB(11) icosahedral carborane anion. These alkylating agents are so electrophilic that they (a) react with alkanes at or below room temperature via hydride extraction to produce carbenium ions, (b) alkylate benzene without a Friedel-Crafts catalyst to give arenium ions, and (c) alkylate electron-deficient phosphorus compounds that are otherwise inert to conventional alkylating agents such as methyl triflate.

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[Na11(OtBu)10(OH)], a hydroxide enclosing 21-vertex cage compound, was found to crystallize from mixtures of sodium tert.butanolate with sodium hydroxide. Its structure can be derived from the known (NaOtBu)6-hexaprismane by replacing one butanolate unit with OH- and capping the latter with five additional units of NaOtBu. The hydroxide shows a signal at -3.21 ppm in the 1H NMR spectrum.