Additions- und SubstitutionsReaktionen an Tetrafluor- und Tetrachlordiboran(4)

Addition and Substitution Reactions at Tetrafluoro- and Tetrachlorodiborane(4) From equimolar mixtures of B₂F₄ and Me_nN(SiMe₃)_3-n (n = 0–3) the mono-addition products 1–4 are formed at low temperatures. By elimination of Me₃SiF the adduct 2 gives the dimeric monosubstituted diborane 8 , which slowly decomposes at room temperature to the aminoborane 6 and (BF)_n. The course of the reactions was studied by means of ¹¹B and ¹⁹F NMR spectroscopy and by measuring the vapor pressures. According to the ¹¹B and ³¹P NMR spectra the reaction of B₂Cl₄ with PCl₅ or [Me₄N]Cl in liquid hydrogen chloride at 0°C does not yield [PCl₄]₂⁺[B₂Cl₆]^2? or [Me₄N]₂⁺[B₂Cl₆]^2? but gives [PCl₄]⁺[BCl₄]^?, PCl₃ and BCl₃ or [Me₄N]⁺[BCl₄]^? and BCl₃ besides (BCl)_n.     

Chiroptical detection during liquid chromatography,part 5: On-line measurement of circular dichroism spectra Δε(λ) during stops of chromatographic flow

Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke.     

Fluordiazadiphosphetidine, 11. Mitt.: Eine neue Methode zur Herstellung der doppelt zwitterionischen Verbindung (CH3N)6P4F8

A new synthetic route for the preparation of the betain-like compound (CH₃N)₆P₄F₈ from (CH₃NPF₃)₂,N-methyl-hexamethyldisilazane andN,N-dimethyl-urea has been found. The steps of this multi-stage reaction could be rationalized to a far extent.

10. Mitteilung:Kubjacek M., Utvary K., Mh. Chem.112, 305 (1981).     

Application of a micro carbon rod atomizer as Br-spezific gas-chromatographic detector

Summary A micro carbon rod atomizer has been employed for specific and quantitative bromine determinations. This Br-specific gas-chromatographic detector works by help of InBr-bands and measurement at 372.7 nm. The performance of this flame band emission detector (FBD) is demonstrated by calibration curves and the detection limits of 2 examples (ethyl bromide, ethylene dibromide), the latter being 5 and 36 ng of bromine, respectively. The reproducibility has been found to be 4.3%. An example of this detector in comparison with a thermoconductivity detector (TCD) is presented.

---

Verwendung einer Mikro-Graphitküvette als Br-spezifischer Detektor für die Gas-Chromatographie

Zusammenfassung Eine Mikro-Graphit-Küvette wird für spezifische quantitative Brombestimmungen nach der Indium-Methode bei 372,7 nm benützt und in Verbindung mit einem Gas-Chromatographen als Br-spezifischer Detektor eingesetzt. Die Leistungsfähigkeit dieses Detektors wird an 2 Beispielen (Äthylbromid, Dibromäthan) mit Hilfe von Eichkurven, Bestimmung von Nachweisgrenzen u. ä. demonstriert. Die Nachweisgrenzen liegen bei 5 bzw. 36 ng Brom für die 2 genannten Substanzen. Die Reproduzierbarkeit der Messungen liegt bei 4,3%. Ein Beispiel für die Registrierung eines Gemisches verschiedener Substanzen, gemessen mit dem GC + Flammen-Banden-emissions-Detektor (FBD) und zum Vergleich mit einem Wärmeleitfähigkeitsdetektor (TCD), wird dargestellt.

This research work was supported by financial help of the Bundesminister für Forschung und Technologie in Bonn (GFR).     

Vibrational spectra,normal coordinate analyses,and molecular configurations of crystalline propionic acid

Temperature dependence of the IR spectra of crystalline propionic acid were examined in the temperature range 242–50 K. The intensities of most absorption bands increased on lowering the temperature, but some bands diminished until they disappeared at temperatures lower than about 120 K. Normal coordinate analyses indicate that the former bands are due to the stable cis dimer and the latter due to the less stable trans dimer which would be produced from the cis dimer by simultaneous proton transfer along two hydrogen bonds.     

Insights on the origin of the structural phase transition in BaV10O15 from electronic structure calculations and the effect of Ti-doping on its structure and electrical transport properties

Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV₁₀O₁₅ and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV_10−xTi_xO₁₅, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi₁₀O₁₅”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti²⁺ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10⁻³ emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T^1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T^1/2 law, was seen, in sharp contrast to BaV₁₀O₁₅ where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role.     

磁性纳米标记检测技术在生物医学即时检测领域的研究进展

基于磁性纳米材料的磁标记检测技术具有灵敏度高、线性范围广、信号检测便捷等优点。由于生物样品自身磁背景信号极低,相比于光学标记检测技术,磁标记检测技术在蛋白质、核酸、细胞、病原体及生物组织检测中均表现出更高的灵敏度,在生物医学即时检测领域展现了良好的应用前景。该文围绕磁性纳米粒在即时检测领域的最新研究进展,重点介绍了其在蛋白质、核酸以及几类病原体检测方面的应用,并对基于磁性纳米粒的即时检测技术发展方向及应用前景进行了展望。     

一种低磁矩、大功率复合稀土石榴石铁氧体的工艺和性能研究

为满足低场区几百兆赫的超大功率器件的性能要求,以钇铁石榴石铁氧体为基础,制备了一种低磁矩复合稀土石榴石铁氧体YGd CaVInIG,研究了少量Mn3+替代Fe3+和预烧温度、烧结温度对铁氧体性能和结构的影响。实验表明,以少量Mn3+替代Fe3+可以提高铁氧体电阻率,降低磁损耗和介电损耗。Mn3+掺入量以x为0.04～0.06比较合适,铁氧体最佳予烧温度为1050℃,最佳烧结温度1350～1380℃,保温5h,氧气中烧结,其性能为:4πMs=500±10%kA·m-1,ΔH=5.25～5.55kA·m-1,TC>180℃,tgδe≤0.5×10-5,这种材料适合微波低频段器件性能要求。X射线衍射分析指出,掺Mn3+的YGdCaVInIG铁氧体相变完全,呈单相复合石榴石铁氧体,空间群为I230,点阵常数1.25057～1.25101nm,单胞分子数n为7.75～7.80。     

Diffusion Mechanisms of Zeolite Catalysts

The diffusion mechanisms within zeolite catalysts, such as resistance to diffusion at pore mouths, configurational diffusion, adsorption-controlled diffusion, influence of co-existing molecules and pore blocking, were overviewed. Two kinds of diffusivities, the intracrystalline diffusivity and the effective diffusivity, were discussed separately to clarify the diffusion mechanism.     

Gradient of the ZAPT2 energy

 An explicit expression for the analytical first derivative of the Z-averaged perturbation theory taken to second order energy, due to Lee and Jayatilaka, is presented for application to high-spin systems described by a restricted open-shell Hartree–Fock wavefunction. The use of frozen core orbitals is incorporated into the derivation. Received: 23 April 2001 / Accepted: 31 August 2001 / Published online: 9 January 2002