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81.
Takeshi Ohkuma 《复旦学报(自然科学版)》2005,44(5)
1Introduction
Asymmetric hydrogenation of ketones is one of the most reliable methods for obtaining chiral secondary alcohols. This transformation is not only of academic interest, but also of industrial significance because of its simplicity, environmental friendliness, and economic viability. Chiral RuXY(binap)(1,2-diamine) complexes (BINAP = 2,2'-bis(diphenyl-phosphino)-1, 1'-binaphthyl,X = Y = C1 or X = H, Y = BH4) with[1] or without[2] a strong base catalyze rapid, highly productive asymmetric hydrogenation of various simple ketones in 2-propanol. This reaction, unlike conventional hydrogenation, proceeds selectively at a C = O bond leaving coexisting C = C linkages intact. A range of chiral alcohols are accessible in high enantiomeric purity from aromatic,heteroaromatic, olefinic, and amino ketones by this method[1,2]. However, no universal chiral catalysts exist due to the structural diversity of ketonic substrates. Thus, tert-alkyl ketones and 1-tetralones have remained difficult to be hydrogenated with high reactivity and enantioselectivity. We here report that this problem can be resolved by the use of BINAP/PICA-Ru (PICA = α-picolylamine)[3] or BINAP/1,4-diamine-Ru[4] complexes as catalysts. 相似文献
82.
Takeshi Ohkuma 《复旦学报(自然科学版)》2005,44(5):762-763
Asymmetric hydrogenation of ketones is one of the most reliable methods for obtaining chiral secondary alcohols. This transformation is not only of academic interest, but also of industrial significance because of its simplicity, environmental friendliness, and economic viability. Chiral RuXY(binap)(1,2-diamine) complexes (BINAP= 2,2'-bis(diphenyl-phosphino)-1, 1'-binaphthyl,X = Y = C1 or X = H, Y = BH4) with or without a strong base catalyze rapid, highly productive asymmetric hydrogenation of various simple ketones in 2-propanol. This reaction, unlike conventional hydrogenation, 相似文献
83.
Second messenger cascades involving G proteins and calcium are known to modulate neurotransmitter release. A prominent effect of such a cascade is the downmodulation of presynaptic calcium influx, which markedly reduces evoked neurotransmitter release. Here we show that G-protein-mediated signalling, such as through GABA (gamma-amino butyric acid) subtype B (GABA(B)) receptors, retards the recruitment of synaptic vesicles during sustained activity and after short-term depression. This retardation occurs through a lowering of cyclic AMP, which blocks the stimulatory effect of increased calcium concentration on vesicle recruitment. In this signalling pathway, cAMP (functioning through the cAMP-dependent guanine nucleotide exchange factor) and calcium/calmodulin cooperate to enhance vesicle priming. The differential modulation of the two forms of synaptic plasticity, presynaptic inhibition and calcium-dependent recovery from synaptic depression, is expected to have interesting consequences for the dynamic behaviour of neural networks. 相似文献
84.
Radixin deficiency causes conjugated hyperbilirubinemia with loss of Mrp2 from bile canalicular membranes 总被引:9,自引:0,他引:9
Kikuchi S Hata M Fukumoto K Yamane Y Matsui T Tamura A Yonemura S Yamagishi H Keppler D Tsukita S Tsukita S 《Nature genetics》2002,31(3):320-325
The ezrin-radixin-moesin (ERM) family of proteins crosslink actin filaments and integral membrane proteins. Radixin (encoded by Rdx) is the dominant ERM protein in the liver of wildtype mice and is concentrated at bile canalicular membranes (BCMs). Here we show that Rdx(-/-) mice are normal at birth, but their serum concentrations of conjugated bilirubin begin to increase gradually around 4 weeks, and they show mild liver injury after 8 weeks. This phenotype is similar to human conjugated hyperbilirubinemia in Dubin-Johnson syndrome, which is caused by mutations in the multidrug resistance protein 2 (MRP2, gene symbol ABCC2), although this syndrome is not associated with overt liver injury. In wildtype mice, Mrp2 concentrates at BCMs to secrete conjugated bilirubin into bile. In the BCMs of Rdx(-/-) mice, Mrp2 is decreased compared with other BCM proteins such as dipeptidyl peptidase IV (CD26) and P-glycoproteins. In vitro binding studies show that radixin associates directly with the carboxy-terminal cytoplasmic domain of human MRP2. These findings indicate that radixin is required for secretion of conjugated bilirubin through its support of Mrp2 localization at BCMs. 相似文献
85.
Evidence from the AD 2000 Izu islands earthquake swarm that stressing rate governs seismicity 总被引:1,自引:0,他引:1
Magma intrusions and eruptions commonly produce abrupt changes in seismicity far from magma conduits that cannot be associated with the diffusion of pore fluids or heat. Such 'swarm' seismicity also migrates with time, and often exhibits a 'dog-bone'-shaped distribution. The largest earthquakes in swarms produce aftershocks that obey an Omori-type (exponential) temporal decay, but the duration of the aftershock sequences is drastically reduced, relative to normal earthquake activity. Here we use one of the most energetic swarms ever recorded to study the dependence of these properties on the stress imparted by a magma intrusion. A 1,000-fold increase in seismicity rate and a 1,000-fold decrease in aftershock duration occurred during the two-month-long dyke intrusion. We find that the seismicity rate is proportional to the calculated stressing rate, and that the duration of aftershock sequences is inversely proportional to the stressing rate. This behaviour is in accord with a laboratory-based rate/state constitutive law, suggesting an explanation for the occurrence of earthquake swarms. Any sustained increase in stressing rate--whether due to an intrusion, extrusion or creep event--should produce such seismological behaviour. 相似文献
86.
M. Nakayama S. Nishimura T. Matsui S. Hayashi K. Fukui 《Cellular and molecular life sciences : CMLS》1971,27(8):875-876
Zusammenfassung Die Synthese von Toxicarol Isoflavon (2, 2-Dimethylpyrano(6, 5: 7,8)-5-hydroxy-2,4 5-trimethoxyisoflavon) aus 2,2-dimethyl-5-hydroxy-7-methoxychroman wird beschrieben. 相似文献
87.
Terasawa T Tanaka YT Takei Y Kawai N Yoshida A Nomoto K Yoshikawa I Saito Y Kasaba Y Takashima T Mukai T Noda H Murakami T Watanabe K Muraki Y Yokoyama T Hoshino M 《Nature》2005,434(7037):1110-1111
The massive flare of 27 December 2004 from the soft gamma-ray repeater SGR 1806-20, a possible magnetar, saturated almost all gamma-ray detectors, meaning that the profile of the pulse was poorly characterized. An accurate profile is essential to determine physically what was happening at the source. Here we report the unsaturated gamma-ray profile for the first 600 ms of the flare, with a time resolution of 5.48 ms. The peak of the profile (of the order of 10(7) photons cm(-2) s(-1)) was reached approximately 50 ms after the onset of the flare, and was then followed by a gradual decrease with superposed oscillatory modulations possibly representing repeated energy injections with approximately 60-ms intervals. The implied total energy is comparable to the stored magnetic energy in a magnetar (approximately 10(47) erg) based on the dipole magnetic field intensity (approximately 10(15) G), suggesting either that the energy release mechanism was extremely efficient or that the interior magnetic field is much stronger than the external dipole field. 相似文献
88.
Sako S Yamashita T Kataza H Miyata T Okamoto YK Honda M Fujiyoshi T Terada H Kamazaki T Jiang Z Hanawa T Onaka T 《Nature》2005,434(7036):995-998
The birth of very massive stars is not well understood, in contrast to the formation process of low-mass stars like our Sun. It is not even clear that massive stars can form as single entities; rather, they might form through the mergers of smaller ones born in tight groups. The recent claim of the discovery of a massive protostar in M17 (a nearby giant ionized region) forming through the same mechanism as low-mass stars has therefore generated considerable interest. Here we show that this protostar has an intermediate mass of only 2.5 to 8 solar masses (M(o), contrary to the earlier claim of 20M(o) (ref. 8). The surrounding circumstellar envelope contains only 0.09M(o) and a much more extended local molecular cloud has 4-9M(o). 相似文献
89.
In vertebrates, internal organs are positioned asymmetrically across the left-right (LR) axis, placing them in a defined area within the body. This LR asymmetric placement is a conserved feature of the vertebrate body plan. Events determining LR asymmetry occur during embryonic development, and are regulated by the coordinated action of genetic mechanisms that are evolutionarily conserved among vertebrates. Recent studies using zebrafish have provided new insights into how the Kupffer's vesicle organizer region is generated, and how it relays LR asymmetry information to the lateral plate mesoderm. In this review, we summarize recent advances in zebrafish and describe our current understanding of the mechanisms underlying these processes. 相似文献
90.
Kagami M Sekita Y Nishimura G Irie M Kato F Okada M Yamamori S Kishimoto H Nakayama M Tanaka Y Matsuoka K Takahashi T Noguchi M Tanaka Y Masumoto K Utsunomiya T Kouzan H Komatsu Y Ohashi H Kurosawa K Kosaki K Ferguson-Smith AC Ishino F Ogata T 《Nature genetics》2008,40(2):237-242
Human chromosome 14q32.2 carries a cluster of imprinted genes including paternally expressed genes (PEGs) such as DLK1 and RTL1 and maternally expressed genes (MEGs) such as MEG3 (also known as GTL2), RTL1as (RTL1 antisense) and MEG8 (refs. 1,2), together with the intergenic differentially methylated region (IG-DMR) and the MEG3-DMR. Consistent with this, paternal and maternal uniparental disomy for chromosome 14 (upd(14)pat and upd(14)mat) cause distinct phenotypes. We studied eight individuals (cases 1-8) with a upd(14)pat-like phenotype and three individuals (cases 9-11) with a upd(14)mat-like phenotype in the absence of upd(14) and identified various deletions and epimutations affecting the imprinted region. The results, together with recent mouse data, imply that the IG-DMR has an important cis-acting regulatory function on the maternally inherited chromosome and that excessive RTL1 expression and decreased DLK1 and RTL1 expression are relevant to upd(14)pat-like and upd(14)mat-like phenotypes, respectively. 相似文献