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31.
32.
Zdzisław Wawrzak Paweł Grochulski Zdzisław Gałdecki William L. Duax Phyllis D. Strong D. N. Kirk 《Journal of chemical crystallography》1991,21(5):649-652
The title compound crystallizes in space groupP212121 with lattice constantsa=16.253(3),b=17.107(3), andc=8.486(2) Å. The A ring has 1,2-half-chair conformation. The calculated steric energy of a 6-methyl-17-ester progesterone molecule is lower by about 4 kJ/mol for the normal A-ring conformation. The progesterone side chain has typical conformation for 17-ester steroids; the C(16)-C(17)-C(20)-O(20) torsion angle is –24.9(4)°. 相似文献
33.
Zdzisław Gałdecki Paweł Grochulski Zdzisław Wawrzak William L. Duax Phyllis D. Strong 《Journal of chemical crystallography》1989,19(3):561-568
The crystal and molecular structure of 3,12-dihydroxy-2-morpholino-5-pregnan-20-one, C25H41O4N, has been determined:M
r
=419.6,P21,a=13.5778(8),b=14.4340(8),c=5.8943(5) Å,=94.32(1)°,V
c
=1151.9(3) Å3,Z=2,D
x
=1.21 g cm–3,
(CuK) = 1.5418 Å, =5.6 cm–1,F(000)=460,R=0.039,R
w
=0.040 for 2421 unique observed reflections. All six-membered rings have chair conformations, and theD ring has a 13-envelope conformation. The progesterone side chain has an unusual conformation, and the C16-C17-C20-O20 torsion angle, which defines the conformation, is –152.6(3)°. The unusual conformation seems to be forced by the intramolecular hydrogen bond between the hydroxyl group at C12 and the O20 atom from the side-chain. 相似文献
34.
Eliezer Ortiz Madeline M. Evarts Zachary H. Strong Jonathan Z. Shezaf Prof. Michael J. Krische 《Angewandte Chemie (International ed. in English)》2023,62(23):e202303345
The first metal-catalyzed oxidative alkynylations of primary alcohols or aldehydes to form α,β-acetylenic ketones (ynones) are described. Deuterium labelling studies corroborate a novel reaction mechanism in which alkyne hydroruthenation forms a transient vinylruthenium complex that deprotonates the terminal alkyne to form the active alkynylruthenium nucleophile. 相似文献
35.
MJ Briones R Bol D Sleep L Sampedro D Allen 《Rapid communications in mass spectrometry : RCM》1999,13(13):1300-1304
Changes in the specific diet of earthworms with time in relation to landuse changes and two different climates were studied by analysing (13)C and (15)N natural abundance in soils and animals. Soil samples from three depths (0-10, 10-20 and 20-30 cm) and earthworms were collected from two sites: Santiago (Northwest Spain) and North Wyke (Southwest England) both consisting of replicated long-term grasslands and recently converted to maize plots. Earthworms were hand-sorted in the field at the peak of the maize growth and after harvesting at both sites. In the Spanish plots, nine and eight earthworm species, all belonging to the three ecological categories (epigeic, anecic and endogeic), were found under maize and permanent pasture, whereas at the English site five and seven different species were, respectively, identified. At both sites (13)C isotopic values of the earthworm tissues reflected changes in diet from C(3) to C(4) with epigeic and epi/anecic worms in the maize plots showing one delta unit difference in relation to the ones found in the grassland plots. Anecic worms seemed to be less responsive to landuse changes. The higher (13)C values of the Spanish soils were also reflected in the earthworm tissues when compared with the English samples. (15)N values showed no clear relationship with the cropping treatments but were clearly related to the ecological grouping, with endogeic worms reaching the highest values whereas for the epigeic and epi/anecic species the lowest values were obtained. This finding was also previously recorded by other authors1 and suggests that, in the future, stable isotope techniques could also be a useful tool in taxonomic studies. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
36.
RD Harris WS Baker Van Stipdonk MJ RM Crooks EA Schweikert 《Rapid communications in mass spectrometry : RCM》1999,13(14):1374-1380
A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd. 相似文献
37.
38.
MJ Singh DO Kataria N Madhavan P Sugathan JJ Das DK Awasthi AK Sinha R Shanker 《Pramana》1999,53(4):743-764
A projectile ion-recoil ion coincidence technique has been employed to study the multiple ionization and the charge transfer
processes in collisions of 60–120 MeV Si
q+ (q = 4−14) ions with neutral argon atoms. The relative contribution of different ionization channels, namely; direct ionization,
electron capture and electron loss leading to the production of slow moving multiply charged argon recoil ions have been investigated.
The data reported on the present collision system result from a direct measurement in the considered impact energy for the
first time. The total ionization cross-sections for the recoil ions are shown to scale as q
1.7/E
p
0.5
, where E
p is the energy in MeV of the projectile and q its charge state. The recoil fractions for the cases of total- and direct ionizations are found to decrease with increasing
recoil charge state j. The total ionization fractions of the recoils are seen to depend on q and to show the presence of a ‘shell-effect’ of the target. Further, the fractions are found to vary as 1/j
2 upto j = 8+. The average recoil charge state 〈j〉 increases slowly with q and with the number of lost or captured electrons from or into the projectile respectively. The projectile charge changing
cross-sections σ
qq′ are found to decrease with increasing q for loss ionization and to increase with q for direct-and capture ionization processes respectively. The physics behind various scaling rules that are found to follow
our data for different ionization processes is reviewed and discussed. 相似文献
39.
Abergel RJ Moore EG Strong RK Raymond KN 《Journal of the American Chemical Society》2006,128(34):10998-10999
The mammalian protein siderocalin binds and inactivates the ferric complex of the bacterial siderophore enterobactin with a Kd value similar to that of the bacterial receptor FepA. However, microorganisms can evade this immune response by structural modifications of the siderophore. The binding of siderophores by siderocalin relies in part on electrostatic interactions and does not depend greatly on what metal is in the complex. It is also sterically limited by the rigid conformation of the protein calyx; methylation of the three catecholate rings of enterobactin hinders siderocalin recognition. The siderocalin binding has been probed for a series of enterobactin analogues in order to investigate in detail the specificity of siderocalin recognition. 相似文献
40.