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41.
Gerhard Holxe Titus A. Jenny Petr Nesvadba Albert Gossauer Ludger Ernst Walter Keller Christoph Kratky 《Helvetica chimica acta》1991,74(6):1287-1295
On treatment with H2SO4/MeOH, epimerization of hexamethyl cis-5,6-dihydroxycobyrinate c,8-lactam ( 3 ) takes place quantitatively at C(6), yielding the corresponding trans-diol 4 . The corresponding lactone 7 , whose structure has been established by X-ray analysis, is obtained from xanthocorrinoids 5 and 6 under similar conditions. 相似文献
42.
M. J. Folkes A. Keller J. Stejny P. L. Goggin G. V. Fraser P. J. Hendra 《Colloid and polymer science》1975,253(5):354-361
The recently observed very low-frequencyRaman bands in polyethylene open up the possibility of determining the straight-chain stem lengths within the crystal as opposed to the full periodicity constituted by crystal core plus amorphous surface layer given by lowangle X-ray diffraction. Past works (6–10) have established the correlation with lamellar thickness but leave doubts about the possibility of making the distinction just indicated. The first objective of the present work was to examine this point on crystals where the chains are inclined to different extents with respect to the lamellar surface. The samples include single-crystals grown from solution at different temperatures and oriented bulk polyethylenes. It is concluded that the low-frequencyRaman peaks correspond to the inclined chain length as opposed to the layer thickness, hence providing a measure of a chain as opposed to a platelet property. TheRaman based length figures are only slightly below those of the appropriately inclined straight traverses across the full lamellae, hence on the basis of existing understanding non-trans chain sequences are confined to a surface region which must be much narrower than required by the usually envisaged amorphous crystalline two-phase structure. Similar studies were carried out also on single crystals of the linear polyester poly(decamethylene sebacate). These demonstrate in the first place that polymers other than polyethylene can also be amenable to suchRaman studies and secondly that in this particular instance, changes in the relative thicknesses of crystal core and surface layer could be registered. The two studies in conjunction affirm the potential of the low-frequencyRaman technique for the study of polymer crystal morphology. 相似文献
43.
G. Münzenberg S. Hofmann H. Folger F. P. Heßberger J. Keller K. Poppensieker B. Quint W. Reisdorf K. H. Schmidt H. J. Schött P. Armbruster M. E. Leino R. Hingmann 《Zeitschrift für Physik A Hadrons and Nuclei》1985,322(2):227-235
In irradiations of207Pb and208Pb, respectively, with54Cr theα-decay of the isotopes259106,260106, and261106 could be observed for the first time. For260106 a spontaneous fission branch of (50 ?20 +30 )% was observed. The isotopes were identified by genetic relationships of α-decay after separation in-flight with the velocity filter SHIP and implantation into a position-sensitive silicon surface-barrier detector. The measured partial fission halflife of the doubly even isotope260106 of (7.2 ?2.7 +4.8 )ms exceeds the predicted values by at least a factor of 40. This result could be explained by the high shell corrections of the ground state mass, derived from the measured α-decay energies. The experimental results show evidence for an island of purely shell stabilized nuclei in the region of deformed isotopes beyond the actinides. 相似文献
44.
The 12-vertex closo-phosphaborane 1,7-P2B10Cl10 (1) has been prepared in low yield from the pyrolysis reaction of B2Cl4 with PCl3 at temperatures above 400 degrees C. A single-crystal X-ray structure determination of 1 (monoclinic space group P2(1)/n with a = 9.239(2) A, b = 16.786(3) A, c = 15.739(3) a, beta = 93.25(3) degrees, and Z = 4) confirmed that, consistent with its 26 skeletal electron count, the phosphaborane adopts a distorted icosahedral structure with the phosphorus atoms in the 1,7-positions. Crystals of 1 contain toluene in a 1:1 molar ratio embedded between each P atom of neighboring cluster molecules. Alteration of the pyrolytic conditions resulted in the formation of the phosphaboranes P4B8Cl6 (2) and P2B8Cl8 (3), which were characterized spectroscopically. Copyrolysis of B2Cl4 with a mixture of PCl3 and AsCl3 at 450 degrees C generated the six-vertex arsaphosphaborane AsPB4Cl4 (4) and traces of the icosahedral arsaphosphaborane AsPB10Cl10. These compounds are examples of heteroboranes which contain two different group-15 atoms within a single molecule. 相似文献
45.
Whereas uranyl compounds at most show electron transfer satellites at 3 eV higher I in the U4f region, mixed oxides containing uranium(V) show a characteristic satellite at 7.9 eV higher I. Uranium-cerium blue and certain U(IV) compounds are also discussed. 相似文献
46.
While the basic fermented (sour) milk products, such as yogurt and kefir can be produced only in live flora version, the post
heat-treatment is preferred in their flavored variations to increase the storage time. Casein being in sour coagulum precipitates
during heat-treatment; therefore protective colloids surrounding the protein should be used to prevent it. Protective colloids
are plant extracts, the most known of them are pectin and amylopectin. Basic requirement of protective colloid effect is the
lower swelling temperature of hydrocolloid than the temperature of precipitation of sour coagulum. In this work we have examined
the precipitation of sour coagulum as a function of the type of lactic acid bacteria cultures applied during fermentation
as well as the swelling of heat protective plant hydrocolloids as a function of the composition (mainly of sugar content)
of medium. To investigate the precipitation of fermented coagulum skimmed milk was fermented with mesophilic butter culture,
thermophilic yogurt culture as well as with exopolysaccharide (EPS)-producing Prebiolact-2 culture. Precipitation was indicated
in the increase of great extent of viscosity. Amylopectin was dispersed into aqueous solution of pH 4.5, the saccharose concentration
of which was changed during the investigation of the swelling of heat protective hydrocolloids. A definite exothermic peak
was assigned to the swelling of hydrocolloids during the DSC experiments. We could conclude that the precipitation temperature
was increasing in the mesophilic-thermophilic-EPS producing microbes line, i.e. the heat stability and swelling temperature
of hydrocolloids depend on the saccharose content of aqueous medium and they increase with rising the concentration of saccharose. 相似文献
47.
The effects of storage of size-exclusion column packing materials in methanolic or azide-water solutions on subsequent separations were tested. Three commercially available columns were used in these studies; the Toyo-Soda Bio-Sil TSK 125, Bio-Sil TSK 250 and the DuPont Bio-Series GF-250. Upon initial chromatography, all three columns bound up to 760 micrograms of cytochrome c tryptic peptides. Sample binding to packing material is probably a function of the positively charged basic groups on peptides or proteins interacting with silanol groups. The larger the peptide, the less the opportunity for silanol-charged group interaction, hence, less binding. Initial samples introduced to a new column occupy the binding sites. Equilibration with neat methanol removes the bound protein revealing sites which bind sample. After absorption of peptides to binding sites on the packing material, storage in neat methanol regenerates the binding sites. Storage in 10% methanol diminished the binding phenomenon, but storage in azide-water reduced binding to a range below detection at the microgram level. Our recommendation to users of size-exclusion chromatographic columns is that one satisfy the absorption capacity of a new column by injecting a sufficient quantity of a basic peptide standard or other convenient sample to reduce available binding sites before using the column for important separations. Store columns in azide-water or 10% methanol to prevent the regeneration of exposed silanol groups. 相似文献
48.
The platelet component of shish-kebabs crystallizes after the core, during cooling or storage below the formation temperature of the core. Three basic platelet morphologies were previously identified which were mutually interconvertible, a process we have termed “hairdressing”. In this paper we show that these three categories are special cases of a continuous range of overgrowth spacings. Crystallization at high temperatures gives widely spaced overgrowths and, as the crystallization temperature is reduced, so the overgrowth spacing decreases gradually. In the extreme case (only obtainable by quenching) the overgrowths become so close as to overlap and appear continuous. We also report a variety of further effects which were caused by exposing the shish-kebabs, while in solvent, to temperatures above their initial formation temperature. A new theoretical approach is described which considers the depletion of material available to form new overgrowths during crystallization. Two versions of this theory are presented (one a computer simulation and one analytic); interpreting our results on the basis of this theory we show that shish-kebabs crystallize at high temperatures even when quenched (90°C and above except in a few exceptional circumstances) and we are able to explain all the features of shish-kebab crystallization that we have observed. 相似文献
49.
Lorraine P. McDonnell Bushnell Eric R. Evitt Robert G. Bergman 《Journal of organometallic chemistry》1978,157(4):445-456
Reactions of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)2-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes. 相似文献
50.
Pierre Thuéry Nelly Keller Monique Lance Julien-Daniel Vigner Martine Nierlich 《Journal of inclusion phenomena and macrocyclic chemistry》1994,20(1):89-96
The doubly deprotonated form of calix[6]arene, with two protonated triethylamines as counter-ions, crystallizes in the monoclinic system: space groupP21/n,a=8.465(4),b=17.822(8),c=15.182(6) Å,=90.18(4)°,V=2291(2) Å3,Z=2. Refinement led to a final conventionalR value of 0.063 for 1046 reflections. The macrocycle conformation is not apinched cone, usual for freeR-calix[6]arene, but a distorted 1,2,3-alternate cone, since the molecule lies on a symmetry center. Furthermore, one of the torsion angles defined by the methylene bridges is near to zero, which is unusual in calixarene structures.
Supplementary Data relating to this article (atomic coordinates for hydrogen atoms, anisotropic displacement parameters for oxygen and nitrogen atoms, and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82182 (7 pages). 相似文献