Dielectric relaxation of ball-like labels in polyisoprene

Ball-like molecules with strong dipoles (labels) were mixed with synthetic polyisoprene (IR305) in low concentrations (<1%) and measured dielectrically in the frequency range 10^–2–10⁷ Hz and the temperature range –70–0°C (glass relaxation region). Calorimetric measurements showed that this type of label has a plasticizing effect on the polymeric matrix. The dielectric measurements showed that these ball-like molecules relax through cooperative rotations with the polymeric segments and at the same relaxation frequency. In addition, the label molecules showed a high-frequency local relaxation process. The relaxation strength ratio of the local process (X _local) to the total relaxation strength of the label was found to be dependent on the volume as well as on the shape of the label. A comparison between the relaxation behaviors of the ball-and rod-like molecules, having the same volume, showed that the length of the label is also an important parameter for the determination of the local contribution as well as of the cooperative relaxation mechanism of the label. The label relaxation process is discussed in relation to the molecular packing of the host polymer.     

用ICP研究鹿科动物骨质疏松症的微量元素特征

鹿科动物的骨质疏松症是近几年出现的一种疾病，它影响鹿的生长发育和繁殖，病重者死亡。我们采集梅花鹿和白唇鹿的毛，血样，用低温灰化方法和温法消解处理样品，用ＩＣＰ分析了毛，血清中微量元素的含量。病梅花鹿毛样中Ｍｇ，Ａｌ，Ｃａ，Ｔｉ，Ｆｅ，Ｃｕ，Ｚｎ的含量比正常组高，Ｔｉ，Ｃｕ，Ｚｎ的偏差率大于１５％，而Ｓｉ，Ｍｎ，Ｐ，Ｐ，Ａｇ，Ｂａ，Ｌａ，Ｃｅ，Ｐｂ比正常组低，Ｖ，Ａｇ，Ｂａ，Ｌａ，Ｃｅ，Ｐｂ存在...     

Changes in the Solubility of β-Cyclodextrin on Complex Formation: Guest Enforced Solubility of β-Cyclodextrin Inclusion Complexes

The most common native host molecule, -cyclodextrin (cycloheptaamylose) is able toform inclusion complexes with a large variety of guestmolecules (or ions) of different size and shape. Theproperties of the included guest molecule are highlyinfluenced by the host-guest interaction, and thepractical usefulness of -cyclodextrin isdependent on these effects. These changes are mainlyinvestigated from the point of view of the guest andto a lesser extent from that of the host. In spite ofthis, the kind of guests and that of the host-guestinteractions during the formation of the inclusioncomplex seem to influence the properties of thehydrophilic domain of -cyclodextrin (i.e. thatof the supramolecule itself), too, and this effect canbe well demonstrated by the change of solubility ofdifferent -cyclodextrin inclusion complexes.This change can be best correlated with the solubilityof the guest as if the guest enforced its solubilityon the supramolecule.     

Formation of color centers and paramagnetic species by alkaline hydrolysis of polydiphenylenesulfophthalide

Blue color centers (CC) (an intense absorption band (AB) at 566 nm and a weaker AB at 350 nm) and paramagnetic species (PMS) that give an ESR singlet withg=2.0028 and δH=10 Oe are formed by the treatment of a DMSO solution of polydiphenylenesulfophthalide with an excess of LiOH. The formation of blue CC is accompanied by a decrease in the intensity of the absorption band of the phenyl groups of the polymer at 270 nm. The blue CC were attributed to quinoid structures like the Chichibabin hydrocarbon. The long-wave absorption at 650–800 nm was assigned to the regions of quinoid-benzoid conjugation. The color centers and PMS were also observed when the polymer was hydrolyzed in cyclohexanone; however, in this case, the reaction was accompanied by polymer aggregation. The electronic spectrum of the Chichibabin hydrocarbon was calculated by the PM3 method. The identity of CC formed by alkaline hydrolysis and appearing in the polymer—aniline—cyclohexanone system was shown. The absence of “quinoid” CC for polyterphenyl sulfophthalide was explained by the energetically unfavorable singlet state for structures similar to the Müller hydrocarbon. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 2, pp. 295–300, February, 2000.     

Phonon spectroscopy of photochemical reactions in organic solids: Photodimerization of 2,6-dimethyl-p-benzoquinone

The Raman phonon spectroscopic study shows that the photodimerization of 2,6-dimethyl-p-benzoquinone. In the solid state is initially a homogeneous reaction but later becomes heterogeneous as the product accumulates. The Ion-temperature electronic absorption spectrum reveals that the reaction is phonon assisted by a polaron formed due to a strong electron- phonon coupling in the cxcited ¹nπ^* state.     

Structural chemistry of bimetallic hydride complexes of titanium and aluminium: I. Crystal and molecular structure of [(η5-C5H5)2,Ti(μ-H)2AlH2]2(CH3)2NCH2CH2N(CH3)2C6H6

The structure of a titanium aluminium hydride complex of composition [(C₅H₅)₂TiAlH₄]₂(CH₃)₂NC₂H₄N(CH₃)₂C₆H₆ has been determined by X-ray diffraction. The complex forms triclinic crystals with unit cell dimensions a = 8.406(2), b = 10.117(2), c = 11.269(3) Å; α = 112.01(2)°, β = 109.25(2)°, γ = 87.04(2)°, space group P$\text{1}$, Z = 2 and density d = 1.21 g/cm³. The structure was refined to give a discrepancy index R = 0.056. The crystals are composed of centrosymmetric molecules of (Cp₂TiAlH₄)₂TMEDA (Cp = η⁵-cyclopentadienyl) and molecules of crystal benzene. Two moieties of Cp₂TiH₂AlH₂ are linked by a tetramethylethylenediamine molecule (r_AlN 2.11 Å). The aluminium atom is bonded to a titanium atom by a double hydride bridge (r_AlH b = 1.8, 1.6 Å, r_TiH b = 1.6 Å), and has trigonal bipyramidal stereochemistry, [H₄N] (r_AlH t = 1.6 Å).     

Adsorption properties and porous structure of new carbon materials

The adsorption properties of the new carbon materials, sibunites, which are mesoporous samples with a developed surface of pores, were studied. The isotherms of the adsorption of benzene vapor were determined to estimate the porous structure of these materials. The principal methods for calculating the parameters of the porous structure of sibunites were analyzed. The application of the BET equation even in the presence of a small number of micropores can distort the results, therefore the most suitable method for estimating the surface of mesopores is one that is based on the Dubinin—Zaverina equation. The estimation of the surface of sibunites using water vapor adsorption is demonstrated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1377–1380, August, 1993.     

Ba2Cu3O5+δ as an intermediate phase during the synthesis of YBa2Cu4O8

We propose a reaction model for the synthesis of YBa₂Cu₄O₈ under normal pressure conditions, which contains 4 partial reaction steps. In a first step bariumnitrate and copperoxide react to Ba₂Cu₃O_5+δ. This substance will be formed for each mixtures Ba:Cu=2∶3...3∶2. The following two partial reaction steps are connected to Ba₂Cu₃O_5+δ, which reacts with Y₂O₃ and CuO to YBa₂Cu₄O₈ or decomposes to BaCuO₂ and CuO. In a last step parts of BaCuO₂ reacts with Y₂O₃ and CuO to YBa₂Cu₄O₈.     

化学计量一级站量值传递工作及经验

介绍了国防科工委化学计量一级站为保证化学量值的准确与统一,在计量标准建立、标准物质研制、测量方法研究等方面所做的工作和经验。