Synthese von substituierten Calcium-bis(disilylamiden) mittels der Transmetallierung von Zinn(II)- und Zinn(IV)-amiden

Synthesis of Substituted Calcium-bis(disilylamides) by Transmetalation of Tin(II) and Tin(IV) Amides Stannylenes as well as stannanes with substituted disilylamino groups are valuable synthons for the synthesis of alkaline earth metal bis(disilylamides) via the transmetallation reaction. Whereas bis[2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentyl]stannylene 1 is a suitable reagent for this type of reaction, bis[trimethylsilyl-tris(trimethylsilyl)silylamino]stannylene 2 (monoclinic, P2₁/c, a = 1492.6(2), b = 1705.2(2), c = 1865.3(3) pm, β = 109.03(2)º, Z = 4) is not only attacked at the Sn? N-bond but also the N? Si-bond is cleaved by calcium metal. Similar light sensitivity as for 2 is observed for the mercury bis[trimethylsilyl-tris(trimethylsilyl)silylamide] 3 , the homolytic M? N-bond cleavage leads to the formation of the trimethylsilyl-tris(trimethylsilyl)silylamino radical (g = 2.00485; a(N) = 16.2 G). The calcium tin exchange reaction of 1 in THF yields tris(tetrahydrofuran-O)calcium-bis[2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentanide] 4 (monoclinic, P2₁/n, a = 1060.9(2), b = 1919.3(5), c = 1686.0(3) pm, β = 90.30(2)º, Z = 4). The stannanes Me_n-4Sn[N(SiMe₃)₂]_n with n = 1 or 2 are also valuable materials for the synthesis of bis(tetrahydrofuran-O)calcium-bis[bis(trimethylsilyl)amide].     

Oxidative and Photochemical Stability of Ionomers for Fuel‐Cell Membranes

To predict hydroxyl‐radical‐initiated degradation of new proton‐conducting polymer membranes based on sulfonated polyetherketones (PEK) and polysulfones (PSU), three nonfluorinated aromatics are chosen as model compounds for EPR experiments, aiming at the identification of products of HO^.‐radical reactions with these monomers. Photolysis of H₂O₂ was chosen as the source of HO^. radicals. To distinguish HO^.‐radical attack from direct photolysis of the monomers, experiments were carried out in the presence and absence of H₂O₂. A detailed investigation of the pH dependence was performed for 4,4′‐sulfonylbis[phenol] ( SBP ), bisphenol A (= 4,4′‐isopropylidenebis[phenol]; BPA ), and [1,1′‐biphenyl]‐4,4′‐diol ( BPD ). At pH ≥ pK_A of HO^. and H₂O₂, reactions between the model compounds and O₂^.? or ¹O₂ are the most probable ways to the phenoxy and ‘semiquinone’ radicals observed in this pH range in our EPR spectra. A large number of new radicals give evidence of multiple hydroxylation of the aromatic rings. Investigations at low pH are particularly relevant for understanding degradation in polymer‐electrolyte fuel cells (PEFCs). However, the chemistry depends strongly on pH, a fact that is highly significant in view of possible pH inhomogeneities in fuel cells at high currents. It is shown that also direct photolysis of the monomers leads to ‘semiquinone’‐type radicals. For SBP and BPA , this involves cleavage of a C? C bond.     

Application of stress induces ascorbate peroxidases of S. polyrhiza for green-synthesis Cu nanoparticles

The objective of this study was to assess the effects of stress on physiology/biochemical component of S. polyrhiza and its impact on CuNPs synthesis and bioethanol production. NaCl with RV5 provokes oxidative stress in S. polyrhiza and significantly increase MAD, Proline, H₂O₂, ROS, SOD and APX activity compare to control condition. Starch accumulation in S. polyrhiza was found 354% higher and correspond 4.4 times higher ethanol yield under stress condition compare to control. CuNPs were synthesized with an average size of 23–26 nm by purified fraction of APX having 37 KDa MW, 1.44 IU specific activity. Synthesized CuNPs were stable up to 15 consecutive cycles and potency against wide range of reactive dyes. The maximum remedial efficiency of synthesized CuNPs for COD and BOD was 55263.3 ± 3298.5 mg/m³min. and 30560.3 ± 1987.5 mg/m³min. respectively for RV5 wastewater. 0.072 mg/g of bioethanol was produced from the wet pulp remaining after nanoparticles synthesis. High efficiency of CuNPs and significant production of Ethanol, indicate that the feasibility for circular model for continuous industrial wastewater treatment.     

New Eremophilane Sesquiterpenes from a Rhizome Extract of Petasites hybridus

A total of 21 natural products, 1 – 21 , were isolated from a supercritical CO₂ extract of the rhizomes of Petasites hybridus. Thereby, seven new eremophilane (= (1S,4aR,7R,8aR)‐decahydro‐1,8a‐dimethyl‐7‐(1‐methylethyl)naphthalene) sesquiterpenes, compounds 4, 5, 9, 11, 12, 15 , and 17 , were identified. The new constituent 9‐hydroxyisobakkenolide ( 15 ) is the first representative of a group of compounds closely related to the well‐known, but rare, bakkenolides. Tsoongianolide B ( 18 ) and its degradation product ligularenolide ( 19 ) were found as new Petasites constituents as well. The known eremophilanolide 2 was isolated from a plant source for the first time and the oxofuranopetasin 16 was isolated for the first time from the rhizomes of P. hybridus, together with eight other known compounds. The C(8)‐epimeric 2‐[(tigloyl)oxy]eremophilanolides 3 and 8 could clearly be differentiated. All structures were established by extensive 1D‐ and 2D‐NMR experiments (Tables 1–3), and confirmed by in‐depth GC/MS and HPLC/MS experiments.     

Vibrational spectrum and structure of the second stable rotamer of butadiene-1,3

The dependence of the calculated vibrational frequencies of the second stable rotamer of butadiene- 1,3 on the torsional angle about the central single C---C bond has been studied in the interval from 0° (planar syn-form) to 50°. The force field was described by scaled force constants obtained from CNDO/2 calculations. The best agreement between the calculated and experimental vibrational frequencies was found at 25° from the planar syn-form. The results of the vibrational frequency calculations for this configurations of some isotopomers of butadiene- 1,3 are given. In addition, in the light of the theoretical results obtained and new experimental evidence, the assignment of certain out-of-plane normal modes of the anti-form of C₄D₆ is also discussed.     

Proton‐Coupled Electron Transfer of Unsaturated Fatty Acids and Mechanistic Insight into Lipoxygenase

A proton‐coupled electron transfer (PCET) process plays an important role in the initial step of lipoxygenases to produce lipid radicals which can be oxygenated by reaction with O₂ to yield the hydroperoxides stereoselectively. The EPR spectroscopic detection of free lipid radicals and the oxygenated radicals (peroxyl radicals) together with the analysis of the EPR spectra has revealed the origin of the stereo‐ and regiochemistry of the reaction between O₂ and linoleyl (= (2Z)‐10‐carboxy‐1‐[(1Z)‐hept‐1‐enyl]dec‐2‐enyl) radical in lipoxygenases. The direct determination of the absolute rates of H‐atom‐transfer reactions from a series of unsaturated fatty acids to the cumylperoxyl (= (1‐methyl‐1‐phenylethyl)dioxy) radical by use of time‐resolved EPR at low temperatures together with detailed kinetic investigations on both photoinduced and thermal electron‐transfer oxidation of unsaturated fatty acids provides the solid energetic basis for the postulated PCET process in lipoxygenases. A strong interaction between linoleic acid (= (9Z,12Z)‐octadeca‐9,12‐dienoic acid) and the reactive center of the lipoxygenases (Fe^III? OH) is suggested to be involved to make a PCET process to occur efficiently, when an inner‐sphere electron transfer from linoleic acid to the Fe^III state is strongly coupled with the proton transfer to the OH group.     

Ca3Al2Ge3O12:Cr3+的光谱性质及晶场参数计算

为了解Cr3+离子在钙铝锗酸盐Ca₃Al₂Ge₃O₁₂:石榴石中的光谱性质, 合成了Ca₃Al₂Ge₃O₁₂:Cr³⁺多晶材料；测量了其X射线衍射图, 漫反射光谱, 激发、发射光谱等；分析了Cr3+离子在钙铝锗酸盐中的发光特性；计算了其晶场强度(Dq/B), Stokes位移(ΔEs)及黄昆-里斯因子(S)等. 在450 nm激发下, Ca₃Al₂Ge₃O₁₂:Cr³⁺室温发射光谱主要由三个宽带及附加其上的弱R线构成, 分别对应于Cr3+离子的4T1、 4T2、2T2到 4A2 能级跃迁. 低温时R线变得强而锐. 通过计算, Dq/B=2.43, ΔEs=1884 cm-1, S=5.21. 表明在Ca₃Al₂Ge₃O₁₂中Cr³⁺离子处于较弱的晶场强度, 电子-声子耦合较强, 为发展可调谐激光材料提供重要线索.     

Combined laser induced ignition and plasma spectroscopy: Fundamentals and application to a hydrogen–air combustor

Combined Laser Induced Ignition and Plasma Spectroscopy (LI2PS) has the potential to give the exact local composition of a mixture at the ignition point and at the ignition time. However, as different laser energies are required to ignite a particular mixture as function of space, the typical approach using two power meters to calibrate the plasma spectroscopy measurement is not well suited. Furthermore, LI2PS requires single shot measurements and therefore high accuracy. In this paper, a novel calibration scheme is presented for application of Laser Induced Plasma Spectroscopy (LIPS) to gaseous analyses. Numerical simulations of air spectra are used to show that species emission can be used directly from the broadband spectra to determine the plasma conditions. The ratio of nitrogen emission around 744 nm and around 870 nm is found to be a sensitive indication of temperature in the emission ranging from 700 to 890 nm. Comparisons with experimental spectra show identical tendencies and validate the findings of the simulations. This approach is used in a partially-premixed hydrogen–air burner. First, helium is used instead of hydrogen. After an explanation of timing issue related to LIPS, it is shown that the calibration required depends only on nitrogen excitation and nitrogen–hydrogen ratio, without the need to know the deposited power. Measurements of the fuel distribution as function of injection momentum and spatial localization are reported. To illustrate the use of such a single shot approach, combined laser ignition and plasma spectroscopy is proposed. In this case, the calibration is based on hydrogen excitation and hydrogen–oxygen and hydrogen–nitrogen ratio. Results obtained with LI2PS show that ignition is successful only for high power and relatively high hydrogen concentration compared to the local mean. It is expected that LI2PS will become an important tool when dealing with partially-premixed or diffusion flame ignition.     

Synthesis of a Chiral 3,3′-Di-<Emphasis Type="Italic">tert</Emphasis>-butyl-2,2′-bipyrrole

Summary.  Diethyl 3,3′-di-tert-butyl-4,4′-dimethyl-2,2′-bipyrrole-5,5′-dicarboxylate was synthesized in four steps from ethyl 3,5-dimethyl-1H-pyrrole-2-carboxylate. The CH₂ hydrogens of the ethyl ester groups of the former are diastereotopic in the ¹H-NMR, consistent with axial chirality of the bipyrrole and restricted rotation about the 2,2′-bipyrrole bond, due to the tert-butyl groups. An X-ray structure of the crystalline target compound shows the pyrrole rings are twisted out of coplanarity by 84.5°. Corresponding author. E-mail: lightner@scs.unr.edu Received September 2, 2002; accepted September 13, 2002 Published online February 20, 2003     

Rotational analysis of the v7,v11 (a′,a″) pair of bands of the infrared spectrum of the deuterium substituted propynal molecule C2H-CDO

The mid-infrared spectrum of the v₇,v₁₁ (a′,a″) pair of bands of the deuterium substituted propynal molecule C₂H-CDO was recorded at a resolution of about 0.08 cm⁻¹. An analysis of the pair of bands was completed using the method of simulation of the observed bands with synthetic spectra taking into account the effects of second order Coriolis interactions between the energy levels of the two bands. Best fit values for the changes in the rotational constants (A″ − A′), (B″ − B′) and (C″ − C′), the second order Coriolis constant ζ_7,11 and the δ_7,11 = v₁₁ − v₇ constant have been derived.