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41.
The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl3/(D6)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation. 相似文献
42.
V. Nastro D. Vuono M. Guzzo G. Niceforo I. Bruno P. De
Luca 《Journal of Thermal Analysis and Calorimetry》2006,84(1):181-184
The aim of this paper is to characterize some raw
materials used for ceramics material production. Five samples of clay have
been analyzed. It has been carried out a patterned sampling in a quarry in
Rosarno (South Italy).
Chemical-physical
properties on clay samples are determined. Test pieces have been prepared
and physical properties after firing are determined by DSC thermal analysis,
XRD analysis and X-ray fluorescence. It is important to note the high amount
of Fe2O3. The mixture principally
contains quartz, illite and oligoclase. It has been observed the colour and
the shape after firing: predominant colour is red. In this case the clay has
been used in mixtures covered with glazes. The colour of internal clay is
hidden by opaque of glazes. The analysed raw materials can be used in a slip
for single fired red tiles. The A2sp clay produces best ceramics at 1000°C. 相似文献
43.
44.
The gas-phase rearrangement of (1Z, 2′E)-, (1Z, 2′Z)-, (1E, 2′E)-, and (1E, 2′Z)- propenyl but-2′-enyl ether (Z, E)-, (Z, Z)-, (E, E)-, and (E, Z)-1) into erythro- and threo-2, 3-dimethyl-pent-4-en-al (erythro- and threo-2) was investigated over a temperature range from 142,5° to 190,0° at 20–35 Torr (for kinetic data and activation parameters see table 2). All four stereoisomeric ethers 1 rearrange preferentially via a chair-like transition state C into the aldehydes 2 (ΔΔG≠ (160°) = 2,5–2,7 kcal/mol for B – C (B = boat-like transition state). The relative rates (krel) for (Z, Z)-1, (Z, E)-1, (E,Z)-1, and (E,E)-1 at 160° are 1,0, 2,9, 4,3 and 9,0 respectively (see table 5). Taking into account the relative enthalpies of the ethers 1 and the steric interaction in the C transition state of the ethers 1 (see table 6), krel values can be estimated. They are in good agreement with those observed (see table 5). 相似文献
45.
46.
Zusammenfassung Die Herstellung von festen Komplexen des Uran(IV) mit Di-n-butylphosphorsäure in Kontakt mit Perchlor-, Schwefel-und Salpetersäure wird beschrieben. Es ergab sich für die beiden ersten Fälle eine Zusammensetzung U(DBP)4 und für den letzten U(NO3)(DBP)3, wobeiDBP für das Anion der Di-n-butylphosphorsäure steht. Auf Grund der Infrarotspektren im Bereich von 4000 bis 700 cm–1 wurde versucht, Anhaltspunkte über die Bindungsverhältnisse in den Komplexen zu erhalten. Die Absorptionsbanden des U(NO3)(DBP)3-Komplexes bei 1520 und 1275 cm–1 weisen darauf hin, daß das Nitrat im wesentlichen kovalent an das Uran(IV) gebunden ist.
Mit 1 Abbildung
Herrn Prof. Dr.O. Kratky zum 70. Geburtstag gewidmet. 相似文献
The preparation and characterization of solid complexes of uranium(IV) with di-n-butyl phosphoric acid in contact with perchloric, sulfuric and nitric acid solutions
The preparation of solid complexes of uranium(IV) with di-n-butyl phosphoric acid in contact with aqueous perchloric, sulfuric and nitric acid solutions is described. The formula was found to be U(DBP)4 for the complexes prepared in contact with the two first mentioned acids, and U(NO3)(DBP)3 for the complex prepared in contact with HNO3 (DBP stands for the anion of the di-n-butyl phosphoric acid). Absorption spectra were registered in the infrared region from 4000–700 cm–1. Due to the absorption bands at 1520 and 1275 cm–1 it seems, that the nitrato group is bound mainly covalent in the U(NO3)(DBP) complex.
Mit 1 Abbildung
Herrn Prof. Dr.O. Kratky zum 70. Geburtstag gewidmet. 相似文献
47.
48.
49.
50.
Bruno Cordani 《Communications in Mathematical Physics》1986,103(3):403-413
The manifoldM of null rays through the origin of 2,n+1 is diffeomorphic toS
1×S
n
, and it is a homogeneous space of SO(2,n+1). This group therefore acts onT*M, which we show to be the generating manifold of the extended phase space of the regularized Kepler Problem. A local canonical chart inT*M is found such that the restriction to the subbundle of the null nonvanishing covectors is given byp
0+H(q,p)=0, whereH(q,p) is the Hamiltonian of the Kepler Problem. By means of this construction, we get some results that clarify and complete the previous approaches to the problem. 相似文献