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1.
《Annales de Paléontologie》2017,103(4):271-281
Additional Cambrian Series 3, Stage 5, trilobite fauna comprising Peronopsis sp., Eosoptychoparia cf. Spinosa Gaotanaspis cf. pingzhaiensis and Gaotanaspis cf. transversa have been recorded just immediately above the known Oryctocephalus indicus biozone (Cambrian Series 3, Stage 5) in the Parahio valley section (Spiti region). The FAD of Peronopsis and LAD of Gaotanaspis are used to establish a PeronopsisGaotanaspis concurrent biozone immediately above the Oryctocephalus indicus biozone. The first records of Gaotanaspis cf. pingzhaiensis and G. transversa from the Cambrian of Spiti region and the other faunal elements are correlated with the Peronopsis taijiangensis biozone of the Kaili Formation (South China). The stratigraphic thickness from the base of the O. indicus biozone to the top of the PeronopsisGaotanaspis concurrent biozone in the Kunzam La (=Parahio) Formation and its comparison to the Kaili Formation (South China) indicate a possible stratigraphic condensation in the basal part of the Cambrian Series 3, Stage 5 of the Parahio valley (Spiti). Sedimentological and sequence stratigraphic analysis supports this contention.  相似文献   

2.
We present low-diversity acritarch assemblages, including Alliumella baltica, Bavlinella faveolata, Brocholaminaria nigrita, Brocholaminaria sp., Eliasum sp., Leiosphaeridia minutissima, Leiosphaeridia spp., Lophosphaeridium sp., Pterospermella solida, Satka colonialica, Siphonophycus sp., and Synsphaeridium sp., as well as filamentous algae and cryptospore-like microfossils recorded from 45 rock samples around the Oryctocephalus indicus Zone (Cambrian Series 3) in the Cambrian Kunzam La (Parahio) Formation at the Kaltarbo locality in the Parahio valley, Northwest Himalaya. One new species Synsphaeridium parahioense was established. The acritarch assemblages at the basal part of the Cambrian Series 3 in the Kunzam La (Parahio) Formation were dependent on the local marine environment. The new discovery of cryptospore-like microfossils from the Cambrian Kunzam La (Parahio) Formation supports the extensive distribution of possible cryptospores in the Cambrian stratigraphic sequences.  相似文献   

3.
《Palaeoworld》2015,24(4):430-437
A new eocrinoid locality of the Balang Formation (Cambrian Series 2) near Kaili City is reported. The fauna is associated with index trilobites, such as Redlichia (Pteroredlichia) murakamii Resser and Endo in Kobayashi, 1935 and Arthricocephalus chauveaui Bergeron, 1899, that are common in the Balang Biota (Cambrian Series 2) but absent in the younger Kaili Biota (Cambrian Series 3). This new locality contains a new eocrinoid fauna (n = 22) that is different from Guizhoueocrinus yui Zhao, Parsley and Peng, 2007a in bearing a smaller theca, a shorter stalk, and a robust attachment disk; thus, a taxon Globoeocrinus zhaoyuanlongensis n. sp. is proposed.  相似文献   

4.
A globally recorded negative carbon isotope excursion characterizes the transition from Cambrian Series 2 to Cambrian Series 3. This transition is also well exposed in sedimentary successions on the Yangtze Platform, and the Wuliu–Zengjiayan section, Guizhou Province, South China has been proposed as a potential Global Stratotype Section and Point (GSSP) for this boundary. Here, we report δ13Ccarb values for the Jianshan and the Wuliu–Zengjiayan sections. Both sections display a progressive decrease in δ13C from values around + 3‰ upwards in stratigraphy to a pronounced δ13C minimum with values as low as ? 6.9‰ at the proposed boundary level, and a return to δ13C values between 0 and + 1‰ in the upper part of the sections. The δ13C minimum is thought to be caused by a transgressive event, flooding the shelf area with 13C depleted basinal anoxic bottom water. Our δ13C data are in good agreement with carbon isotope profiles recorded elsewhere. These define the so called ROECE event (Redlichiid–Oleneliid Extinction Carbon Isotope Excursion, cf. Zhu et al., 2006, 2007) and may reflect the perturbation of the global carbon cycle during the Cambrian Series 2 to Cambrian Series 3 transition.  相似文献   

5.
《Palaeoworld》2008,17(2):108-114
The base of the Guzhangian Stage (Cambrian) has been ratified recently at the lowest occurrence of the cosmopolitan agnostoid trilobite Lejopyge laevigata (base of the Lejopyge laevigata Zone) in the Huaqiao Formation in the Luoyixi section, Guzhang County, Hunan Province, China.Sampling of the Luoyixi section in the boundary interval reveals 16 protoconodont and paraconodont taxa. The conodont succession can be correlated with the Gapparodus bisulcatus-Westergaardodina brevidens and the Shandongodus priscus-Hunanognathus tricuspidatus zones of South China and with the Laiwugnathus laiwuensis and the Shandongodus priscus zones of North China. Laiwugnathus laiwuensis occurs immediately below the lowest occurrence of Lejopyge laevigata. The first occurrence of Shandongodus priscus is 14.95 m above the base of the Lejopyge laevigata Zone. A significant change in the conodont associations occurs in the interval corresponding to the uppermost Lejopyge armata trilobite Zone. This interval is characterized by an increase in diversity with the appearance of the paracondont genera Furnishina and Laiwugnathus. Laiwugnathus laiwuensis, which occurs immediately below the lowest occurrence of Lejopyge laevigata, has a short stratigraphic record and allows confident correlation with North China.  相似文献   

6.
The first evidence for Cambrian glaciation is provided by two successions on the Avalon microcontinent. The middle lowest Cambrian (middle Terreneuvian Series and Fortunian Stage–Stage 2 boundary interval) has an incised sequence boundary overlain by a fluvial lowstand facies and higher, olive green, marine mudstone on Hanford Brook, southern New Brunswick. This succession in the lower Mystery Lake Member of the Chapel Island Formation may be related to melting of an ice sheet in Avalon. The evidence for this interpretation is a muddy diamictite with outsized (up to 10 cm in diameter), Proterozoic marble and basalt clasts that penetrated overlying laminae in the marine mudstone. That eustatic rise was associated with the mudstone deposition is suggested by an approximately coeval rise that deposited sediments with Watsonella crosbyi Zone fossils 650 km away in Avalonian eastern Newfoundland. A sea-level rise within the Watsonella crosbyi Chron, at ca. 535 Ma, may correspond to a unnamed negative 13C excursion younger than the basal Cambrian excursion (BACE) and the ZHUCE excursion in Stage 2 of the upper Terreneuvian Series. Cambrian dropstones are now also recognized on the northern (Gander) margin of Avalon in continental slope–rise sedimentary rocks in southeast Ireland. Although their age (Early–Middle Cambrian) is poorly constrained, dropstones in the Booley Bay Formation provide additional evidence for Cambrian glaciation on the Avalon microcontinent. Besides providing the first evidence of Cambrian glaciation, these dropstone deposits emphasize that Avalon was not part of or even latitudinally close to the terminal Ediacaran–Cambrian, tropical carbonate platform successions of West Gondwana.  相似文献   

7.
The Devonian–Carboniferous (D/C) boundary marks a major extinction event and an important evolutionary turnover in Paleozoic biotas, but understanding D/C boundary events is hampered by a lack of accurate and consistent ages. As a result, although a global stratotype section and point (GSSP) for the D/C boundary was defined in the section La Serre trench E’ (Montagne Noire, France) and accepted and ratified by the IUGS, problems arose concerning both the lithology of the La Serre section and the identification of S. sulcata. Due to these problems, in the very recent years, the ICS decided to reconsider the GSSP. The Daposhang section in Muhua, Guizhou, China, is one of the most important reference sections for the D/C boundary: it is a conformable succession across the D/C boundary that contains conodont faunas characteristic of restricted subtidal facies. A biostratigraphically well constrained tuff near the D/C boundary in the Daposhang section provides an excellent opportunity to date this important event in Paleozoic history. Sensitive high-mass resolution ion microprobe (SHRIMP) U–Pb analyses were conducted on single zircons extracted from the tuff (between beds 0 and 1, which may be temporally equivalent to the Hangenberg black shale) as well as an analysis of sedimentary facies and sequence stratigraphy across the D/C boundary in the Daposhang section. Bed 0 is below the D/C boundary, in the Upper praesulcata conodont zone, and bed 1 is directly above the D/C boundary, in the sulcata conodont zone. Zircon analyses yielded 20 concordant dates that form a cluster with a 206Pb/238U concordia age of 359.6 ± 1.9 Ma. An abundance of bioclastic packstone and wackestone and a lack of obvious high-energy sedimentary structures or evidence of reworking in layers spanning the D/C boundary suggest conformable deposition in a quiet, restricted subtidal paleoenvironment. Fifty-nine fifth-order cycles combine to depict a shallowing-upward succession (beds 029-01; highstand systems tract of a third-order sequence representing the terminal Devonian). The highstand systems tract is overlain by a deepening-upward succession (beds 0-29; maximum flooding surface and transgressive systems tract of a third-order sequence representing predominantly the basal Carboniferous) that begins at the D/C boundary. Fischer plot analysis of high-frequency cycles at the D/C boundary confirms this well developed sea-level pattern, which, together with the tuff and black shale depositional events, has potential for global correlation. On the basis of this new single-zircon SHRIMP age and previously published work on the biostratigraphy and sequence stratigraphy of the D/C transition interval, the deposition of tuff took place at approximately 359.6 Ma, and the age of the D/C boundary at Daposhang, Guizhou, China, is estimated at 359.58 Ma.  相似文献   

8.
Secoisolariciresinol diglucosides (SDGs) (S,S)-SDG-1 (major isomer in flaxseed) and (R,R)-SDG-2 (minor isomer in flaxseed) were synthesized from vanillin via secoisolariciresinol (6) and glucosyl donor 7 through a concise route that involved chromatographic separation of diastereomeric diglucoside derivatives (S,S)-8 and (R,R)-9. Synthetic (S,S)-SDG-1 and (R,R)-SDG-2 exhibited potent antioxidant properties (EC50 = 292.17 ± 27.71 μM and 331.94 ± 21.21 μM, respectively), which compared well with that of natural (S,S)-SDG-1 (EC50 = 275.24 ± 13.15 μM). These values are significantly lower than those of ascorbic acid (EC50 = 1129.32 ± 88.79 μM) and α-tocopherol (EC50 = 944.62 ± 148.00 μM). Compounds (S,S)-SDG-1 and (R,R)-SDG-2 also demonstrated powerful scavenging activities against hydroxyl [natural (S,S)-SDG-1: 3.68 ± 0.27; synthetic (S,S)-SDG-1: 2.09 ± 0.16; synthetic (R,R)-SDG-2: 1.96 ± 0.27], peroxyl [natural (S,S)-SDG-1: 2.55 ± 0.11; synthetic (S,S)-SDG-1: 2.20 ± 0.10; synthetic (R,R)-SDG-2: 3.03 ± 0.04] and DPPH [natural (S,S)-SDG-1: EC50 = 83.94 ± 2.80 μM; synthetic (S,S)-SDG-1: EC50 = 157.54 ± 21.30 μM; synthetic (R,R)-SDG-2: EC50 = 123.63 ± 8.67 μM] radicals. These results confirm previous studies with naturally occurring (S,S)-SDG-1 and establish both (S,S)-SDG-1 and (R,R)-SDG-2 as potent antioxidants and free radical scavengers for potential in vivo use.  相似文献   

9.
To improve our understanding of the ecological functioning of constructed wetlands, the macrofauna structure in the sediments of a constructed wetland planted with Panicum maximum treating domestic wastewater was studied. Two beds were planted with young P. maximum and two unplanted beds were used as controls. After 150 days of wastewater treatment on the beds, macrofauna was collected by taking five cores of sediment samples at the corners and the centre of each bed following three layers in the vertical profile. Globally, the planted beds removed COD, NH4+, and PO43? more (p < 0.05) than the control. Eleven taxa belonging to 6 classes and 11 orders were recorded. Macrofauna was significantly more diversified (Mann–Whitney test: p < 0.05) in terms of Shannon index of diversity in the planted beds (0.25–0.44 bits/ind.) than in the control (0.08–0.23 bits/ind.). But macrofauna settlement presents a relative homogeneity between the beds (index Jaccard = 0.63). Its abundance was three times higher in the planted bed than in the control. From the surface to the bottom of the beds, macrofauna diversity and abundance decreased and were heavily dominated by Annelida. The significant relationships were only observed between Insecta and Myriapoda in the control.  相似文献   

10.
《Comptes Rendus Palevol》2007,6(5):311-319
One new foraminiferal genus, Rectoformata gen. nov., with two new species, has been described from a Permian limestone block in the Karakaya Complex in the South of the Balya district (Balikesir, northwestern Turkey). The type species of Rectoformata, Rectoformata tekini sp. nov., is characterized by a quadrangular transverse section having a calcareous microgranular wall with fine alveolar structures, whereas Rectoformata acari sp. nov. is recognized by a pentagonal transverse section having a calcareous microgranular wall with fine alveolar structures. The age of the described taxa is assigned as Midian ( = Capitanian) based on the association with small foraminifers and fusulinids. These new taxa are included in the family Chitralinidae, which is emended herein.  相似文献   

11.
《Palaeoworld》2021,30(3):422-429
Schizopholis Waagen, 1885 is a genus of linguliform brachiopod, which is known from Cambrian Stage 4 to the Wuliuan Stage of Australia, Antarctica, Pakistan and China. Recently, new material of Schizopholis was discovered from the upper part of the Tsinghsutung Formation (Cambrian Series 2, Stage 4) near Balang village, Jianhe County, Guizhou Province, China. These specimens display the oval pedicle opening in the ventral valve, a median tongue and a pair of tubercles in the dorsal valve that are characteristic features of Schizopholis napuru (Kruse, 1990). This is the first time that this species has been described from Guizhou Province, China. Previously, fossils of this species are usually preserved in carbonate deposits, but the new material documented herein preserved in mudstone of the Tsinghsutung Formation, providing new information regarding both the paleogeographic distribution and paleoecology of this species.  相似文献   

12.
Clitostethus arcuatus is a major, cosmopolitan predator of some Aleyrodidae. Field collected adult beetles were reared in the laboratory on different diets: Siphoninus phillyreae eggs, Trialeurodes vaporariorum eggs, Sitotroga cerealella eggs, or an artificial diet consisting of honey, yeast, and pollen. All experiments were conducted at 25 ± 2 °C, 65 ± 5% RH and a photoperiod of 16:8 (L:D) h. Female and male C. arcuatus consumed a mean (± SE) of 61 ± 0.6 and 27 ± 0.9 T. vaporariorum eggs d? 1, respectively, and a mean of 56 ± 2.2 and 29 ± 1.1 S. phillyreae eggs d? 1, respectively. Significant differences were noted between sexes and between hosts consumed by female C. arcuatus. No feeding occurred on S. cerealella eggs. Although there was a significant difference between rates of oviposition due to diet, fertility rates on different diets did not show significant differences. The sex ratio of C. arcuatus (female:male) was 51.4:48.6, 55.2:44.8, and 54.6:45:4 when adults fed on T. vaporariorum, S. phillyreae, and artificial diet, respectively. These differences were not significantly different. Average longevity (± SE) was 66.4 ± 2.6, 54.9 ± 2.5; 77.3 ± 6.9, 67.5 ± 7.2; and 86.4 ± 4.5 70.3 ± 3.6 days for female and male C. arctuatus, respectively, on T. vaporariorum, S. phillyreae and artificial diet, respectively, with significant differences between sexes and diets. Although developmental duration on T. vaporariorum was longer than ash whitefly, this difference was not significant (mean 27.68 ± 0.31 and 25.09 ± 0.21 days for predators reared on T. vaporariorum and S. phillyreae, respectively). Given its longevity and fecundity on T. vaporariorum, C. arcuatus may be a good choice for mass release on glasshouse crops infected by greenhouse whitefly.  相似文献   

13.
The Valdavara-1 cave, located in the westernmost part of the Iberian Peninsula, is an archaeological site that has been excavated since 2007. At least two main sedimentary units have been identified: an upper one, 30 cm-thick, that has yielded many fragments of ceramic characteristic of the Recent Prehistory (with a radiocarbon age of 4.490 ± 40 years BP), and a lower one, 90 cm-thick, separated from the upper one by an erosive discontinuity and late Pleistocene in age (radiocarbon ages between 13.770 ± 70 and 15.120 ± 70 years BP). The small-vertebrate assemblages recovered from the sieving-washing of all the sediment from the excavation campaigns include a total of at least 34 taxa (six amphibians, nine squamate reptiles, five insectivores, two chiropterans and 12 rodents). The materials from this locality constitutes the first mention in northwestern Spain for Microtus (Iberomys) cabrerae and Micromys minutus, currently absent from this area, as well as the first mention in the fossil record for Chioglossa lusitanica, Discoglossus galganoi and Chalcides striatus. In both layers, such small-vertebrate associations suggest a patchy landscape dominated by humid meadows and woodland areas, with the existence of water areas in the vicinity of the cave. The climate shows a more continental pattern during the late Pleistocene, as evidenced by the presence of Microtus arvalis, Sorex minutus and Rana temporaria, and was milder during the Recent Prehistory, with the occurrence of typically Mediterranean taxa such as Crocidura russula, Chioglossa lusitanica, Discoglossus galganoi, Rana iberica, Chalcides striatus and Timon lepidus. The amphibian and squamate associations suggest that the climate change recorded at the Valdavara-1 cave between the latest Pleistocene and Holocene levels may correspond to a difference of 0.8 °C in terms of mean annual temperature, although the difference is 2.8 °C for the mean temperature of the coldest month.  相似文献   

14.
New Pliocene macrofloras and microfloras perfectly preserved from the Mont-Dore (Puy-de-Dôme, Massif central, France) have been reinvestigated. Samples come from different stratigraphical levels collected from three localities, Lac Chambon, La Gratade and Pont de Chocol. The 40Ar/39Ar radiometric datings bracketing the Chambon Lake and La Gratade fossil-bearing horizons give 4.46 ± 0.05 Ma and 3.94 ± 0.04 Ma, respectively, representative of the Zanclean Stage (= Brunssumian B and C), a period of the early Pliocene (5.32 to 3.6 Ma), much older than previously thought (i.e., Piacenzian). Pont de Chocol is considered to be close biostratigraphically, or even identical in age to La Gratade. Detailed morphological evaluation of leaf morphotypes completed with pollen analysis contributed to the better taxonomic knowledge of these palaeofloras. The overview focuses on floristic and phytostratigraphical characteristics of the defined stratigraphical units and their dating and correlation with previously defined palaeofloristic units of the Massif central. The study provides detailed identifications of plants representing 11 gymnosperms among which Pinaceae (pollen and winged seeds), Cupressaceae including “Taxodioid” pollen grains and Sciadopitaceae families (only pollen). Besides, different angiosperm trees and shrubs have been determined from both micro- and macro-remains. Fagaceae is the most diversified with several foliage of beech and deciduous oaks, while diversified Juglandaceae contribute mainly as abundant leaf remains of Carya, Pterocarya and Juglans; Ulmaceae with numerous leave of two Zelkova species, and also Ulmus. Various other deciduous dicotyledonous such as Alnus, Betula, Carpinus, Populus, Acer laetum and A. interrigenum are well documented. Leguminosae are recorded by a small number of leaflet imprints. Evergreen shrubs of Buxaceae (Buxus pliocenica) are scarce. All these taxa contribute to a rich biodiversity of these Pliocene assemblages. All three sites point towards riverine forest habitats dominated by hygrophilic diversified woody plants while in the surrounding plains and slopes the thermophilic elements were scarce and mesophilic taxa abundant as temperate elements. This vegetation can be compared with mixed mesophytic forests depicting a climate cooling during the two considered periods (ca. 4.46 and 3.95 Ma).  相似文献   

15.
Campuloclinium macrocephalum (Less.) DC. is a perennial herb widely distributed in the New World, but introduced to South Africa, where it is commonly called “pompom weed”. This species is considered one of the most important weeds from Brazil and it has been included among the plant invaders of South Africa. Results of the meiotic and embryological analyses of six populations of C. macrocephalum are reported in this paper. The microsporogenesis analysis revealed five triploid (2n = 3x = 30) and one diploid (2n = 2x = 20) populations with a basic chromosome number x = 10. The diploid specimens showed regular meiotic behavior, but the triploid plants presented irregular chromosome pairing which result in the formation of univalents, bivalents and trivalents at diakinesis. In consequence, laggard chromosomes, unbalanced nuclei and micronuclei were observed in subsequent phases of meiosis. The embryological analysis showed that the triploid specimens of C. macrocephalum have embryo sac development from a nucellar cell (apospory), which indicates that these specimens are apomictic. Almost all cases of apomixis found in tribe Eupatorieae are diplosporous apomixis. Campuloclinium macrocephalum constitutes the second species of the tribe and the first of the genus with apospory as reproductive system. The aposporous apomixis combined with the presence of xylopodium would be two important factors responsible for the invasiveness of C. macrocephalum.  相似文献   

16.
17.
Three new oleanane-type saponins, leptocarposide B-D (13), were isolated from the whole plant of Ludwigia leptocarpa (Nutt.) Hara, together with ten known compounds 4–13.The structures of these compounds were determined by interpretation of their spectral data, mainly HR-TOFESIMS, 1D-NMR (1H, 13C) and 2D-NMR (1H–1H COSY, HSQC, HMBC, and NOESY), and by comparison with the literature data. The structures of the new compounds were established as 28-O-β-d-xylopyranosyl-(1  4)-α-l-rhamnopyranosyl-(1  2)-[α-l-arabinopyranosyl-(1  3)]-4-O-(3′-hydroxybutanoyloxy-3-hydroxybutanoyloxy)-β-d-fucopyranosyl zanhic acid (1); 3-O-β-d-glucopyranosyl-28-O-β-d-xylopyranosyl-(1  4)-α-l-rhamnopyranosyl-(1  2)-4-O-(3′-hydroxybutanoyloxy-3-hydroxybutanoyloxy)-β-d-fucopyranosyl medicagenic acid (2); 3-O-β-d-glucopyranosyl-(1  4)-β-d-glucopyranosyl-28-O-β-d-xylopyranosyl-(1  4)-α-l-rhamnopyranosyl-(1  2)-[α-l- arabinopyranosyl-(1  3)]-4-O-(3′-hydroxybutanoyloxy-3-hydroxybutanoyloxy)-β-d-fucopyranosyl zanhic acid (3).  相似文献   

18.
Constructed wetlands have a good potential for wastewater treatment in developing countries due to the simple operation and low implementation costs. Ornamental plants like Canna and Heliconia are used in the wetlands to increase their aesthetic value and these two species were compared in this study. Six pilot scale horizontal subsurface flow constructed wetland units were constructed at the Asian Institute of Technology (AIT) campus in Bangkok, Thailand, of which three were planted with Heliconia psittacorum L.f. × H. Spathocircinata (Aristeguieta) and three with Canna × generalis L. Bailey. The beds were loaded with domestic wastewater in four trials with hydraulic loading rates ranging from 55 to 440 mm d?1 corresponding to nominal detention times between 12 h and 4 days. Both plant species grew well in the systems and especially Canna had high growth rates (3100 ± 470 g DW m?2 yr?1) compared to Heliconia (550 ± 90 g DW m?2 yr?1). TSS mass removal rates were very high with efficiencies >88% even at hydraulic loading rates of 440 mm d?1. COD mass removal rates varied between 42 and 83% depending on the loading rates. The removal rate constants for COD as fitted by the first-order kC* model were estimated to be 0.283 and 0.271 m d?1 for Canna and Heliconia beds, respectively (C* = 28.1 and 26.7 mg l?1). Removals of nitrogen (N) and phosphorus (P) were low compared to the loading rates, but removal of total-N was higher in the beds planted with Canna than in beds with Heliconia because of the higher growth rate of Canna. It is concluded that ornamental species like Canna and Heliconia can be used to enhance the aesthetic appearance and hence the public acceptance of wastewater treatment systems in tropical climates. Canna is the preferred species from a treatment perspective because of its more vigorous growth, but since Heliconia has an economic potential as cut flowers may be preferred in many cases.  相似文献   

19.
The bimetallic [M1M2(tren)2(CAn?)]m+ series, where M = GaIII or CrIII and CA is the chloranilate ligand which can take on diamagnetic (CAcat,cat)4? or paramagnetic (CAsq,cat)3? forms, comprises an electronically diverse series of compounds ranging from the closed-shell [Ga2(tren)2(CAcat,cat)]2+ to the S = 5/2 ground state of [Cr2(tren)2(CAsq,cat)]3+. This report deals with the interpretation of the EPR and ENDOR spectra of [Ga2(tren)2(CAsq,cat)](BPh4)2(BF4) (2) and the related derivative [Ga2(tren)2(DHBQ)](BPh4)2(BF4) (2a) (where DHBQ is the fully deprotonated trianionic form of 2,5-dihydroxy-1,4-benzoquinone) in an effort to further characterize the electronic structure of this radical species. The X-band (~9.5 GHz) EPR spectrum of complex 2 acquired in a butyronitrile/propionitrile glass at 4 K reveals a rhombic g-tensor with gxx = 2.0100, gyy = 2.0097, and gzz = 2.0060 with hyperfine interactions due to spin delocalization onto the two Ga nuclei (axx = 4.902 G, ayy = 4.124 G, azz = 3.167 G); the origin of the hyperfine coupling was confirmed by analysis of the room temperature spectra of complexes 2 and 2a. The low-temperature spectrum of complex 2 also indicates the presence of a triplet electronic state characterized by a g-value of 2.009 and axial zero-field splitting of D = 150 G (0.012 cm?1) as determined from measurements carried out at both X- and W-band (~95 GHz) frequencies. This triplet state is believed to arise due to a weak intermolecular Heisenberg exchange interaction between two aggregating complexes. ENDOR measurements on complex 2a at 20 K allowed for a determination of the magnitude of hyperfine coupling to the protons associated with the radical bridge as well as providing a rare example of an ENDOR signal arising from coupling to a gallium nucleus. Finally, these results were combined with literature data on the free semiquinone form of the bridging ligand in order to assess the extent to which density functional theory can predict unpaired spin density distribution in a complex molecule of this type. Although differences between theory and experiment were noted, DFT was able to provide a reasonably accurate picture of the electronic structure of this system as well as provide insight into the spin polarization mechanism(s) responsible for the observed hyperfine interactions.  相似文献   

20.
Two new protostemonine-type alkaloids, javastemonine A and B (3 and 4) have been isolated from the root extracts of Stemona javanica together with four known Stemona alkaloids, 13-demethoxy-11(S*),12(R*)-dihydroprotostemonine (1), isoprotostemonine (2), protostemonine and isomaistemonine. The structures and relative configurations of the new alkaloids were determined by spectroscopic analysis. The alkaloids 1 and 2 and protostemonine showed moderated antiplasmodial activities against the Plasmodium falciparum strains, TM4 (IC50 values of 17.7 ± 3.7, 16.8 ± 5.4, 16.0 ± 4.2 μg/mL, respectively) and K1 (IC50 values of 16.8 ± 3.1, 14.1 ± 3.7, 11.9 ± 3.3 μg/mL, respectively). These compounds showed no significant cytotoxicities against KB or Vero cells or acetylcholinesterase inhibitory activities.  相似文献   

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