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Mechanism of Thermal Dehydration of Sodium Dihydrogenphosphate The thermal dehydration of sodium dihydrogenphosphate (P1) to sodium cyclotriphosphate (CP3) and sodium polyphosphate, the so-called Maddrell's salt (MS), is controlled by nucleation and crystallization of CP3 and MS, respectively. The wellknown influence of various formation conditions on the CP3:MS product ratio is caused by amorphous and crystalline intermediate phases and their ability to form CP3 or MS nuclei. On seeding P1 with CP3 or MS the dehydration proceeds structure-controlled via dihydrogendiphosphate to pure CP3 or pure MS. The particularities of thermal dehydration of crystalline sodium dihydrogendiphosphate, and also the dehydration and reorganization of sodium phosphate glasses (Na:P = 1:1) with different mean chain lengths, under formation of CP3 or MS are described. 相似文献
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Based on the phenomenon of freezing point depression of a solvent byT, experimental evidence is presented to show that the distance between the junction points can be calculated fromT. Direct measurements of the temperature-time-curve of the cooling network and the Differential Scanning Calorimetry offer the determination ofT. Except the mean distances ¯d
c
in dependence on cross-linking density, swelling degree, and other network parameters, the distribution of the distance between the junction pointsH(dc) can be determined, which allows conclusions on the course of cross-linking reaction. This paper attempts to give experimental evidence of influences of the breadth ofH(dc) on application-relevant properties. 相似文献
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Meinhard Wlaschek Gudrun Heinen Arndt Poswig Agatha Schwarz Thomas Krieg Karin Scharffetter-Kochanek 《Photochemistry and photobiology》1994,59(5):550-556
Abstract— Previous work has shown that fibroblast-derived collagenase/matrix-metalloproteinase-1(MMP–1), responsible for the breakdown of dermal interstitial collagen, was dose-dependently induced in vitro and in vivo by UVA irradiation and this induction was at least partly mediated byinterleukin–6(IL–6). We here provide evidence that UVA-inducedIL–1α andIL–1β play a central role in the induction of the synthesis both ofIL–6 and collagenase/MMP–1. In contrast to the late increase ofIL–1α andIL–1β mRNA levels at 6 h postirradiation, bioactivity ofIL–1 is already detectable at 1 h postirradiation. This early peak ofIL–1 bioactivity appears to be responsible for the induction ofIL–6 synthesis and together withIL–6 lead to an increase of the steady-state mRNA level of collagenase/MMP–1 as deduced from studies usingIL–1α andIL–1β antisense oligonucleotides or neutralizing antibodies againstIL–1α andIL–1β Besides the early posttranslationally controlled release of intracellularIL–1, a latter pretranslationally controlled synthesis and release ofIL–1 perpetuates the UV response. From these data we suggest a UV-induced cytokine network consisting ofIL–1α,IL–1β andIL–6, which via interrelated autocrine loops induce collagenase/MMP–1 and thus may contribute to the loss of interstitial collagen in cutaneous photoaging. 相似文献
16.
V. V. Burlakov A. V. Letov P. Arndt W. Baumann A. Spannenberg Ch. Fischer L. I. Strunkina M. Kh. Minacheva Ya. S. Vygodskii U. Rosenthal V. B. Shur 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):63-67
Zwitterionic titanoxanes {Cp[η5-C5H4B(C6F5)3]Ti}2O (I) and {(η5-iPrC5H4)[η5-1,3-iPrC5H3B(C6F5)3]Ti}2O (II), which contain two positively charged Ti(IV) centres in the molecule, are able to catalyse the ring-opening polymerization of -caprolactone (-CL) in toluene solution and in bulk. The process proceeds with a noticeable rate even at room temperature and accelerates strongly on raising the temperature to 60 °C. The best results have been obtained on carrying out the reaction in bulk. Under these conditions, the use of I as a catalyst (-CL:I = 1000:1) gives at 60 °C close to quantitative yield of poly--CL with the molecular mass of 197 000. An increase in the -CL:I ratio to 6000:1 increases the molecular mass of poly--CL to 530 000. Tetrahydrofuran (THF) is also polymerized under the action of I albeit with a lesser rate. However, the molecular mass of the resulting poly-THF can reach rather big values under optimal conditions (up to 217 000 at 20 °C and the THF:I ratio of 770:1). A rise in the reaction temperature from 20 to 60 °C results here to a decrease in the efficiency of the process. Titanoxane II is close to I in its catalytic activity in the -CL polymerization but it is much less active in the polymerization of THF. Propylene oxide (PO), in contrast to -CL and THF, gives with I only liquid oligomers in wide temperature and PO:I molar ratio ranges (−30 to +20 °C, PO:I = 500–2000:1). γ-Butyrolactone and 1-methyl-2-pyrrolidone are not polymerized under the action of I at room temperature. The reactions found are the first examples of catalysis of the cationic ring-opening polymerization by zwitterionic metallocenes of the group IVB metals. 相似文献
17.
Jürgen Khler Gunnar Svensson Arndt Simon 《Angewandte Chemie (International ed. in English)》1992,31(11):1437-1456
Metal clusters, discrete or condensed, are characteristic of the structures of many compounds which contain transition metals in low oxidation states. The highly reduced oxoniobates support the concept of condensed clusters. They contain Nb6O12 clusters which are either isolated or linked at the apices of the Nb6 octahedra to form oligomeric chains or networks. The analysis of the bonding relationships allows the identification of different types of Nb atoms and thus the quantitative prediction of valence electron concentrations for finite or infinite structures composed of these condensed M6X12 clusters. 相似文献
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Eu5Ge3 and EuIrGe2 were prepared from the elements in tantalum tubes, and their crystal structures were determined from single crystal X-ray data. Eu5Ge3 adopts the structure of Cr5B3: I4/mcm, a = 799.0(1)pm, c = 1 536.7(1)pm, Z = 4, wR2 = 0.0421 for 669 F2 values and 16 variables. The structure of Eu5Ge3 contains isolated germanium atoms and germanium atom pairs with a Ge? Ge distance of 256.0 pm. Eu5Ge3 may be described as a Zintl phase with the formulation [5 Eu2+]10+[Ge]4?[Ge2]6?. Magnetic investigations of Eu5Ge3 show Curie-Weiss behaviour above 50 K with a magnetic moment of μexp = 7.6(1) μB which is close to the free ion value of μeff = 7.94 μB for Eu2+. EuIrGe2 is isotypic with CeNiSi2: Cmcm, a = 445.5(2) pm, b = 1 737.4(4) pm, c = 426.6(1) pm, Z = 4, wR2 = 0.0507 for 295 F2 values and 18 variables. The structure of EuIrGe2 is an intergrowth of ThCr2Si2-like slabs with composition EuIr2Ge2 and AlB2-like slabs with composition EuGe2 in an AB stacking sequence. Both slabs are distorted when compared to the symmetry of the prototypes. The Ge? Ge distance of 256.6 pm in the AlB2-like fragment is comparable to that in Eu5Ge3. 相似文献