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The experimental and theoretical basis of a recently proposed reassignment of the bands in the PE. spectra of pyridine, pyridazine, pyrimidine and pyrazine is discussed in detail. A characteristic feature of the derived orbital sequence is that it takes the ‘through-space’ and ‘through-bond’ interaction between the ‘lone pair’ basis orbitals explicitly into account. A simple parametrization of the orbital energies, based on HMO-type models for the π-orbitals and for the ‘lone pair’ linear combinations, yields excellent agreement with the observed band positions in the PE. spectra of s-triazine and s-tetrazine. Our new assignment is compared to those proposed previously. 相似文献
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The IR- and RAMAN -spectra are reported from OP(OCH3)2Cl, OP(OCH3)Cl2, SP(OCH3)Cl, SP(OCH3)Cl2. The assignement to the fundamental vibration is given and all Valence-force-constants are calculated. With increasing number of chlorine atoms decrease f P? OCH3 and f P? Cl. In the contrary, f O? P and f S? P increase. Here the influence of decreasing electro negativity is compensated by the change from an element of the first period of eight elements to an element of the second period. 相似文献
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The low-temperature conductivity of uncompensated insulating Si:P with P concentration just below the metal-insulator (MI) transition shows with decreasingN a crossover from Mott variable range hopping (VRH) to Efros-Shklovskii VRH. From the concentration dependence of the Mott temperatureT M a correlation-length exponent ν=1.1 is obtained which is compatible with the conductivity exponent μ=1.3 for metallic samples. 相似文献
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Hornung R Fehr MK Walt H Wyss P Berns MW Tadir Y 《Photochemistry and photobiology》2000,72(5):696-700
Photodynamic therapy (PDT) of malignancies uses light to activate a photosensitizer preferentially accumulated in cancer cells. The first pegylated photosensitizer, tetrakis-(m-methoxypolyethylene glycol) derivative of 7,8-dihydro-5,10,15,20-tetrakis(3-hydroxyphenyl)-21-23-[H]-porphyrin (PEG-m-THPC), was evaluated in non-tumor-bearing rats. The aim of this study was to assess the photodynamic threshold for damage and its sequelae in normal rat tissue. Thirty-five Fischer rats were sensitized with 3, 9 or 30 mg/kg body weight PEG-m-THPC. Colon, vagina and perineum were irradiated with laser light of 652 nm wavelength and an optical dose of 50, 150 or 450 J/cm fiber length. Temperature in the pelvis was measured during PDT. Three days following PDT the effect on skin, vagina, colon, striated muscle, connective tissue, nerves and blood vessels was assessed by histology. The healing of the above-mentioned tissues was assessed on two rats 3 and 8 weeks after PDT using 9 mg/kg PEG-m-THPC activated with 450 J/cm laser light. No dark toxicity was observed. PDT using 30 mg/kg PEG-m-THPC induced severe necrosis irrespective of the optical dose. Body weight of 9 or 3 mg/kg activated with less than 450 J/cm induced moderate or no damage. No substantial increase in body temperature was seen during PDT. Tissues with severe PDT-induced damage seem to have a good tendency to regenerate. We conclude that within the dose required for tumor treatment PEG-m-THPC is a safe photosensitizer with promising properties. PDT of the colon mucosa below 9 mg/kg PEG-m-THPC and 150 J/cm seems to be safe. All other tissues can be exposed to 9 mg/kg PEG-m-THPC activated with less than 450 J/cm laser light with little side effects. 相似文献
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F. Preuss M. Steidel M. Vogel G. Overhoff G. Hornung W. Towae W. Frank G. Reiß S. Müller-Becker 《无机化学与普通化学杂志》1997,623(8):1220-1228
Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds tC4H9N?VCp(NHtC4H9)[P(SiMe3)2] and tC4H9N?VCp(NiProp2)(PR2) (R?SiMe3, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF2)2V2Cl2)(NtC4H9)2]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [tC4H9N?VCl2 · PPh3]+PF6? has been isolated. 1 reacts with an excess of diisopropylamine forming tC4H9N?V(NiProp2)Cl2 ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds tC4H9N?VCp(NiProp2)Cl ( 3 ) and tC4H9N?V(NiProp2)X2 (X?CH2CMe3, OtC4H9, CH3COO) has been prepared. All compounds obtained are characterized by 1H, 51V, 31P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom. 相似文献
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Mark Brouar Helen Chadwick Sean D. S. Gordon Cornelia G. Hei Balazs Hornung Bethan Nichols Jacek K?os Pablo G. Jambrin F. Javier Aoiz 《化学物理学报》2020,33(2):217-233
本文对NO(X)-Xe碰撞系统在碰撞能量为519 cm-1,测量了完全?-双峰分解的微分截面和碰撞引起的旋转准直力矩. 同时结合初始量子态选择,使用六极杆的非均质电场,借助量子态分辨的测量,利用(1+1'')共振增强的多光子电离和速度离子成像. 结果显示,微分截面以及偏振相关的微分截面均显示与从头算势能面上进行的量子力学散射计算[J. K?os etal. J. Chem. Phys. 137, 014312 (2012)]一致. 通过与准经典轨迹、硬壳势能的量子力学散射以及运动近端模型的比较,评估了势能对所测微分截面和碰撞引起的旋转准直力矩的影响. 相似文献
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