880 resultados para Two-body correlation
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When an intersubband relaxation is involved in vertical transport in a tunneling heterostructure, the magnetic suppression of the intersubband LO or LA phonon scattering may also give rise to a noticeable depression of the resonant tunneling current, unrelated to the Coulomb correlation effect. The slowdown of the intersubband scattering rate makes fewer electrons able to tunnel resonantly between two adjacent quantum wells (QWs) in a three-barrier, two-well heterostructure. The influence of the magnetic field on the intersubband relaxation can be studied in an explicit way by a physical model based on the dynamics of carrier populations in the ground and excited subbands of the incident QW. (C) 1998 American Institute of Physics. [S0003-6951(98)00925-5].
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Based on the phase-conjugate polarization interference between two two-photon processes, we obtained an analytic closed form for the second-order or fourth-order Markovian stochastic correlation of the four-level attosecond sum-frequency polarization beat (FASPB) in the extremely Doppler-broadened limit. The homodyne-detected FASPB signal is shown to be particularly sensitive to the statistical properties of the Markovian stochastic light fields with arbitrary bandwidth. The different roles of the amplitude fluctuations and the phase fluctuations can be understood physically in the time-domain picture. The field correlation has a weak influence on the FASPB signal when the laser has narrow bandwidth. In contrast, when the laser has broadband linewidth, the FASPB signal shows resonant-nonresonant cross-correlation, and drastic difference for three Markovian stochastic fields. The maxima of the two two-photon signals are shifted from zero time delay to the opposite direction, and the signal exhibits damping oscillation when the laser frequency is off-resonant from the two-photon transition. A Doppler-free precision in the measurement of the energy-level sum can be achieved with an arbitrary bandwidth. As an attosecond ultrafast modulation process, it can be extended intrinsically to any sum frequency of energy levels.
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Cd in GaAs is an acceptor atom and has the largest atomic diameter among the four commonly-used group-II shallow acceptor impurities (Be, Mg, Zn and Cd). The activation energy of Cd (34.7 meV) is also the largest one in the above four impurities, When Cd is doped by ion implantation, the effects of lattice distortion are expected to be apparently different from those samples ion-implanted by acceptor impurities with smaller atomic diameter. In order to compensate the lattice expansion and simultaneously to adjust the crystal stoichiometry, dual incorporation of Cd and nitrogen (N) was carried out into GaAs, Ion implantation of Cd was made at room temperature, using three energies (400 keV, 210 keV, 110 keV) to establish a flat distribution, The spatial profile of N atoms was adjusted so as to match that of Cd ones, The concentration of Cd and N atoms, [Cd] and [N] varied between 1 x 10(16) cm(-3) and 1 x 10(20) cm(-3). Two type of samples, i.e., solely Cd+ ion-implanted and dually (Cd+ + N+) ion-implanted with [Cd] = [N] were prepared, For characterization, Hall effects and photoluminescence (PL) measurements were performed at room temperature and 2 K, respectively. Hall effects measurements revealed that for dually ion-implanted samples, the highest activation efficiency was similar to 40% for [Cd] (= [N])= 1 x 10(18) cm(-3). PL measurements indicated that [g-g] and [g-g](i) (i = 2, 3, alpha, beta,...), the emissions due to the multiple energy levels of acceptor-acceptor pairs are significantly suppressed by the incorporation of N atoms, For [Cd] = [N] greater than or equal to 1 x 10(19) cm(-3), a moderately deep emission denoted by (Cd, N) is formed at around 1.45-1.41 eV. PL measurements using a Ge detector indicated that (Cd, N) is increasingly red-shifted in energy and its intensity is enhanced with increasing [Cd] = [N], (Cd, N) becomes a dominant emission for [Cd] = [N] = 1 x 10(20) cm(-3). The steep reduction of net hole carrier concentration observed for [Cd]/[N] less than or equal to 1 was ascribed to the formation of (Cd, N) which is presumed to be a novel radiative complex center between acceptor and isoelectronic atoms in GaAs.
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Photoluminescence (PL) from Er-implanted hydrogenated amorphous silicon suboxide (a-SiOX:H
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通过趾骨切片可以准确鉴定年龄,了解一个物种的最长寿命,也为我们研究确定一个物种的生长特点、性成熟期,以及一个地区一个物种的年龄结构、种群生态(Marnell,1998)和群落生态提供重要信息(Morrison,et a1.,2004)。 本论文使用骨骼鉴龄法对中国浙江省宁波市北仑瑞岩寺林场的镇海棘螈(Echinotriton chinhaiensis)雌性繁群进行了年龄结构研究。结果显示:第一次参加繁殖的年龄为3龄;繁群中数量占优势的是5龄、6龄。而在6龄以后参加繁殖的雌性个体数便开始随着年龄的增大而逐渐减少。参加繁殖的雌性年龄最大个体为8龄。平均年龄为5.13龄。同时对其年龄和头体长、体全长的相关性检验,发现其年龄与头体长和体全长不相关,镇海棘螈雌性的生长方式表现为性成熟后能量主要用于繁殖。 另外,对李子坪大凉疣螈(Tylototriton taliangensis) 雄性繁群进行了年龄结构研究。结果显示:大凉疣螈雄性第一次参加繁殖的年龄为4龄;繁群中数量占优势的是5龄、6龄、7龄。而在7龄以后参加繁殖的雄性个体数便开始随着年龄的增大而逐渐减少。参加繁殖的雄性中年龄最大的个体为10龄。平均年龄为6.7龄。对其年龄和头体长、体全长的相关性检验,发现其年龄与头体长和体全长不相关,大凉疣螈雄性生长特点也表现为性成熟后生长缓慢的特点。 研究材料方面,本文采用野外采样与标本馆标本相结合的方式获得了中国蝾螈科2个重要保护物种繁殖群体的剪(指)趾材料,使得建立于其上的年龄结构工作更加可靠、更加具有代表性。 此外,本论文讨论了镇海棘螈瑞岩寺种群繁殖总量年度间的差异及其产生原因。将1998、1999、2000、2008、2009年镇海棘螈(Echinotriton chinhaiensis) 瑞岩寺种群的繁殖量进行比较,发现虽然雌性平均窝卵数比较稳定,但繁殖总量小于1998、1999、2000年任何一年总产卵量的50%。对2008年镇海棘螈繁殖量大幅下降的原因分析发现, 2007年9、10月影响严重台风的两次强台风、瑞岩寺景区开发等因素可能是造成近年该种群繁殖量大幅下降的原因。而2008年初50年不遇的低温是否影响镇海棘螈的繁殖值得进一步追踪研究。2009年繁殖量较2008年没有明显的增长,可能是由于2007年的台风影响了其繁殖营养的积累。台风的影响可能存在滞后现象,对此有待进一步监测证明。 本研究首次对中国蝾螈科物种进行的年龄结构鉴定,为进一步了解中国蝾螈科动物的种群生态打下了坚实的基础。 Using skeletochronology, we can know the life span of a species, age of reaching sexual mature, and of course age structure, which are vital(Morrison,et a1.,2004). Skeletochronology was performed on Echinotriton chinhaiensis Ruiyansi female population. The result shows that: The oldest individuals were 8 years old and the youngest ones were 3 years old. Individuals of age class 5(39.13%) and 6(21.74%) were most numerous. The number of individuals participated in reproduction decreased with the increase of age after the sixth year. Average age is 5.13 years. There is no correlation between age and body size (SVL and TL). For female chinhai salamander, energy is devoted to reproduction after reaching sexual maturation. While using skeletochronology to study Tylototriton taliangensis Liziping male population, the oldest individuals is 10 years old, and the youngest ones is 4 years old. Individuals of the age class 5, 6, and 7 dominat this population. The number of individuals decrease with the increase of age also after the seventh year. Average age is 6.7 years old in this population. there is also no correlation between age and body size (SVL and TL).It turned out that T. taliangensis tend to grow slowly after reaching sexual maturation. In this thesis, specimens from both wild and museum were used to gain enough toe clipping samples. A big sample size guarantees the reliability of this study. In the meantime, E. chinhaiensis’s annual reproduction of the year 1998, 1999, 2000 ,2008,and 2009 was compared. The result shows there is a huge decline in E. chinhaiensis’s annual reproduction in 2008,even the egg clutch is very stable. After analyzing, it turned out the huge decline in 2008 was probably caused by typhoon in 2007, besides the effect of tourism development and cash crop planting. While the impact of extreme weather of 2008 on reproduction needs further investigation. In the year 2009, there is no obvious increase in annual reproduction. It maybe due to lasting impact of typhoon in 2007. It is the first age-structure study on these two Chinese salamanders. A solid foundation was laid for further population ecology study of these two species.
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角蟾科(Megophryidae)是以角蟾属(Megophrys Kuhl and Van Hasselt, 1822)为模式属而建立的,隶于无尾目(Anura),变凹型亚目(Anomocoela)。角蟾科包括2 亚科11 属142 种,分布于东洋界,从巴基斯坦、中国西部向东直到菲律宾和苏达群岛;中国有9 属75 种分布于华中和华南地区。角蟾科被认为是原始的两栖动物之一,其分类学、系统学、生态学、动物地理学的研究均深受中外科学家的瞩目。近年来,通过形态学、古生物学、细胞学、生态学、支序系统学的研究,角蟾科的分类与系统学研究取得了较大进展。与成体形态和分子系统学研究结果相比较,蝌蚪的研究存在更多的问题和挑战,尚需深入研究:(1)角蟾科蝌蚪的形态多样性分析;(2)角蟾科的系统发育关系与蝌蚪的演化,以及口漏斗的起源;(3)角蟾科蝌蚪表型分化与栖息环境和觅食行为的适应演化。针对上述问题,本文对角蟾科9 属30 种蝌蚪的形态特征,包括外部宏观形态和口器外部结构特征、口器内部显微结构、唇齿和角质颌的亚显微结构作了深入细致、多层次的比较研究;通过12s rRNA 和cytochrome b 基因构建最大简约树,采用贝叶斯系统发育进行分析,蝌蚪型的演化采用祖先性状的重建方法分析;得到如下结论:1)初步将角蟾科蝌蚪分为4 种类型;并且建立了2 种新的角蟾科蝌蚪类型。A 型:拟髭蟾型蝌蚪,该型蝌蚪包括拟髭蟾属、髭蟾属、齿蟾属和齿突蟾属的物种;B 型:新类型,掌突蟾型蝌蚪,该型蝌蚪在本文中包括掌突蟾属、小臂蟾属的物种;C 型:新类型,短腿蟾型蝌蚪,一种特化类型,该型蝌蚪在本文中仅包括短腿蟾属的物种;D 型:角蟾型蝌蚪,该型蝌蚪在本文中包括无耳蟾属、小口拟角蟾属和异角蟾属的物种。2)对角蟾科的分类进行了修订:(1)支持角蟾科两个亚科的分类系统;(2)角蟾亚科包括拟角蟾属、异角蟾属、无耳蟾属和短腿蟾属;该亚科形态差异小,系统学关系比较复杂,暂不作族级分类的再划分;(3)拟髭蟾亚科分为2 个族:拟髭蟾族,该族物种具有类型A 的蝌蚪,包括4 个属:拟髭蟾属、髭蟾属、齿蟾属、齿突蟾属;掌突蟾族,该族物种具有类型B 的蝌蚪,包括2 个属:掌突蟾属和小臂蟾属。3)结合分子系统进化关系探讨了4 种蝌蚪类型的演化。(1)角蟾科蝌蚪的最近共同祖先来自于一类具有拟髭蟾型蝌蚪性状的蝌蚪;(2)掌突蟾型蝌蚪和角蟾亚科的蝌蚪是由具有拟髭蟾型蝌蚪性状的祖先蝌蚪分别演化而来;(3)短腿蟾型蝌蚪是角蟾型蝌蚪的一种特化类型;(4)外群蝌蚪具有与拟髭蟾型蝌蚪相似的性状,进一步印证了类拟髭蟾型蝌蚪是角蟾科蝌蚪的最近共同祖先的假说;(5)具有口漏斗的蝌蚪类型是由不具口漏斗的蝌蚪类型演化而来,在角蟾科中口漏斗是一种衍生性状。4)分析了角蟾科四种蝌蚪类型与栖息环境的适应演化。(1)角蟾科蝌蚪的口部和体形的变化反映了该科蝌蚪由缓流向类似静水生境的回水凼的渐变式适应,角蟾科蝌蚪的形态显示了多方面的适应变化;(2)随着蝌蚪类型由A 向D的演化,当水速较大时,拟髭蟾型的蝌蚪营流水攀吸型生活方式;当水速递减时,掌突蟾型蝌蚪营流水附着型生活方式;当水速进一步递减时,具有较小口漏斗的短腿蟾型蝌蚪和具有大漏斗的角蟾型蝌蚪营流水浮泳型生活。角蟾科蝌蚪对于水流递减的适应演化说明蝌蚪的生态学适应是具有进化意义的;(3)蝌蚪口器内部结构的分化揭示了蝌蚪和食性的适应关系,蝌蚪以口部的唇齿与角质颌刮取或吞吸水中的物质,然后,通过口乳突有选择地过滤进入口腔中食物。拟髭蟾亚科蝌蚪的唇齿多而窄,唇齿间距宽,颌鞘粗而稀,反映了其植食性为主的特点;它们的舌前乳突一般为指状,在口腔入口处所占面积小,其机械过滤的作用很多被唇齿和角质颌分担了;而角蟾亚科的蝌蚪,其角质颌弱,其舌前乳突一般为匙状,几乎填满了口腔入口处,因此舌前乳突起了主要的机械过滤作用。The family Megophryidae is the largest and most diverse families inArchaeobatrachia, and most of its species occur in India, Pakistan, and eastward intoChina, Southeast Asia, Borneo and the Philippines to the Sunda Islands. Currently thefamily includes 142 species have been grouped into two subfamilies, Megophryinaeand Leptobrachiinae. The mountains of central and southern China are rich in speciesof Megophryidae, 75 species belong to 9 genera and two subfamilies.The family was supposed to be ideal materials of studies in many fields of biology,such as taxonomy, evolution, systematics, ecology, and biogeography. Recently, therehave a great development in taxonomy and systematics of megophryids throughstudied by morphology, paleontology, cytology, ecology, and cladistics. However,larvae of megophryids were generally unknown, although the tadpoles might be veryimportant for above studies.In this paper, we examined the evolutionary scenario of the tadpoles’ morphologyin the context of a phylogenetic framework. Our objectives are (1) to evaluate thedivergence of larval body shape and oral discs in the family Megophryidae, (2) toexplore the evolutionary trends of the larvae in megophryidae, and test if thefunnel-shaped oral disc is apomorphic, and (3) to explore the relationship of the larvalstructure, diet and microhabitat.We examined larval morphology of 30 megophryid species, the larval body shape,oral discs, the buccopharyngeal cavity, and jaw sheaths and denticles of the Chinesemegophryid frogs were re-examined. We constructed a phylogeny of the species on thebasis of published mitochondrial cytochrome b and 16S rRNA gene segments usingpartitioned Bayesian analyses. Furthermore, hypothetical changes of larval morphologywere inferred using parsimony principle on the phylogeny. The results showed that:1) Four tadpole types in Megophryidae. The larval morphological charactersseries in Chinese megophryids fall into four general categories according to the bodyshape and oral discs: (A) Leptobrachiini type, species from genera Leptobrachium,Oreolalax, Scutiger and, Vibrissaphora share this type of tadpoles. (B) Leptolalax type,species of genus Leptolalax have this type of tadpoles. (C) Brachytarsophrys type,species of the genus Brachytarsophrys have this type of tadpoles. (D) Megophryinitype, species of the genera Atympanophrys, Ophryophryne, and Xenophrys share this type of tadpoles. Of which B and C are two novel types.2)Taxonomic implications. The present study leads us to reconsider the generalclassification of tribes attributed to members of Megophryidae. More specifically,concerning the phylogenetic relationships and the two novel tadpole types describedherein, we propose a provisional taxonomy for the family but suggest that further taxasampling of other megophryids be performed to confirm this taxonomic change. TheMegophryidae is composed of two subfamilies (Leptobrachiinae and Megophryinae).The Leptobrachiinae was recogonized the two tribes: (1) tribe Leptobrachiini sensuDubois, corresponding to the tadpole of type A, including four genera, i.e.,Leptobrachium, Oreolalax, Scutiger and, Vibrissaphora; (2) tribe Leptolalaxini,corresponding to the tadpole of novel type B, including two genera, i.e., Leptolalaxand Leptobrachella. However, the relationships among the genera of Megophryinaewere largely unresolved, they recognized no monophyletic groups above the generalevel. A more thorough sampling will likely foster a better taxonomic solution.3) The larval evolutionary scenario in Megophryidae.Type A is characteristicof normal-mouthed with multiple tooth rows, representing the tadpole type of theMRCA of Chinese megophryids. Type B is characteristic of normal-mouthed withreduced tooth rows, prolonging labium, and integumetary glands. Type C ischaracteristic of no labial teeth and smaller umbeliform oral disc. Type D ischaracteristic of no labial teeth, enlarged umbeliform oral disc, representing the tadpoleof the MRCA of subfamily Megophryinae. A previous hypothesis, referring tofunnel-shaped oral discs as an apomorphy, is supported.4) The larval adaptation to habitats in Megophryidae. Tadpoles generallyadhere to substrates using their mouths, and the microhabitat that the tadpoles occupyreflects the degree of adhesion and oral complexity. The morphological changes inmegophryid tadpoles virtually allow a progressive adaptation to a changing habitatfrom faster water to slower water. Within the tadpoles of Type A to type D, the TOTbecomes smaller and smaller, and the oral disc orientates from anteroventral toumbelliform upturned, and eye position orientates from dorsal to lateral, and the trunkis more and more depressed and tail becomes relatively longer and slender. Within therunning water, the normal-mouthed with multiple tooth rows of Leptobrachiini tadpoles are correlated with lotic-suctorial, benthic feeders with anteroventral oraldisc and the largest body. With the water’s velocity decreasing, the lotic-adherentfeeders of Leptolalax tadpoles have tube-shaped labium with reduced tooth rows andintegumetary glands. And then, the smaller umbeliform in Brachytarsophrys tadpolesand the enlarged umbeliform oral disc in the Megophryini tadpoles are inhabitmicrohabitats of non-flowing backwaters of rivers, indicative of adaptive traits oflotic-neustonic surface feeders. The scheme of megophryid tadpoles andmicrohabitats provided the first clear evidence which congruent with the hypothesis ofAltig and Johnston (1989). The ecological divergence plays a general role in thedivergence and evolution of megophrid larvae. There is a definite correlation amongthe buccopharyngeal cavity, diet and feeding mechanisms, the tadpole graze orswallow the food particles, then through papillae which like a sieve and sort out foodparticles to the oesophagus. The tadpole of Leptobrachiinae possess multiple toothrows, wide intertooth distance as well as thick and sparse jaw sheath, these tadpolesinhabit bottom of the streams and graze on epiphyton or major detritus of organicmatter on the substrates, their prelingual papillae like single finger, the mechanicalpurpose of papillae served share in by tooth and jaw. The tadpoles of Megophryinaeoccur near the water surface of small streams and are the filter feeder, their dietincludes plankton and organic debris floating on the water surface, those tadpolepossess weak jaw, their prelingual papillae like spoon, the mechanical purpose ofpapillae served mostly for sieve.
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Over the past two decades, magnetoclimatological studies of loess-paleosol sequences in the Chinese Loess Plateau (CLP) have made outstanding achievements, which greatly promote the understanding of East Asian paleomonsoon evolution, inland aridification of Asia, and past global climate changes. Loess magnetic properties of the CLP have been well studied. In contrast, loess magnetic properties from outside the CLP in China have not been fully understood. We have little knowledge about the magnetic properties of loess in the Ili Basin, an intermontane depression of the Tianshan (or Tien Shan) Mountains. Here, we present the results of rock magnetic measurements of the Ili loess including mass magnetic susceptibility (χ) and anhysteretic remanent magnetization (ARM), high/low temperature dependence of susceptibility (TDS) and hysteresis, as well as X-ray diffraction (XRD) for mineral analysis. Based on the comparison with loess-paleosol sequences in the CLP (hereafter referred to as the Chinese loess), we discuss the possible magnetic susceptibility enhancement mechanism of the Ili loess. The results show that 1) the total magnetic mineral concentration of the Ili loess is far lower than that of the Chinese loess, though they have similar magnetic mineral compositions. The ferrimagnetic minerals in the Ili loess are magnetite and maghemite, and the antiferromagnetic mineral is hematite; XRD analysis also identifies the presence of ilmenite. The ratio of maghemite is lower in the Ili loess than in the Chinese loess, but the ratios of magnetite and hematite are higher in the Ili loess than in the Chinese loess. 2) The granularity of magnetic minerals in the Ili loess, dominated by pseudo-single domain (PSD) and multi-domain (MD) grains, is generally much coarser than that of the Chinese loess. Ultrafine pedogenically-produced magnetic grains have a very limited contribution to the susceptibility enhancement. Rather, PSD and MD particles of magnetite and maghemite are the main contributors to the enhancement of susceptibility in the Ili loess. 3) The susceptibility enhancement mechanism for the Ili loess is complicated and superimposes both a wind velocity/vigor model (Alaskan or Siberian model) and the in situ ultrafine grain pedogenic model; the former might play an important role in the Ili loess. 4) Magnetic susceptibility enhancements of the Ili loess are related not only to the eolian input of the source area, but also to the local climate, landform, and geological background. Therefore, great care should be taken when reconstructing paleoclimate using magnetic susceptibility data from the Ili loess.
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We construct microscopic three-nucleon forces consistent with the Bonn and Nijmegen two-nucleon potentials, and including , Roper, and nucleon-antinucleon excitations. Recent results for the choice of the meson parameters are discussed. The forces are used in Brueckner calculations and the saturation properties of nuclear matter are determined.
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We report the first three-particle coincidence measurement in pseudorapidity (Delta eta) between a high transverse momentum (p(perpendicular to)) trigger particle and two lower p(perpendicular to) associated particles within azimuth |Delta phi| < 0.7 in root s(NN) = 200 GeV d + Au and Au + Au collisions. Charge ordering properties are exploited to separate the jetlike component and the ridge (long range Delta eta correlation). The results indicate that the correlation of ridge particles are uniform not only with respect to the trigger particle but also between themselves event by event in our measured Delta eta. In addition, the production of the ridge appears to be uncorrelated to the presence of the narrow jetlike component.
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An experiment of Mg-22 and Ne-20 beams bombarding on a C-12 target at an energy of 60 similar to 70 A MeV has been performed at the RIKEN projectile fragment separator (RIPS)in the RIKEN Ring Cyclotron Facility to study the two-proton correlated emission from Mg-22 and Ne-20 excited states. The two-protons momentum correlation functions have been obtained for Mg-22 and Ne-20, respectively. The trajectories of the Mg-22 decayed products (Ne-20 + p + p) were also measured to get the angular correlations between the two protons in Center of Mass of decaying system by relativistic-kinematics reconstruction. The results exhibit that Mg-22 has the features of He-2 cluster decay mechanism.
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Microscopic three-nucleon force consistent with the Bonn B two-nucleon potential is constructed, which includes Delta(1232), Roper, and nucleon-antinucleon excitation contributions. Recent results for the choice of the meson parameters are discussed. The forces are used in Brueckner calculations and the saturation properties of nuclear matter are determined. At the high densities,the nuclear equation of state and the symmetry energy are calculated. The corresponding neutron star mass-radius relations are presented.
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In this paper, preliminary experimental results are presented on pressure drop characteristics of single and two-phase flows through two T-type rectangular microchannel mixers with hydraulic diameters of 528 and 333 mum, respectively. It is shown that both N-2 and water single-phase laminar flows in microchannels, with consideration of experimental uncertainties, are consistent with classic theory, if additional effects, such as entrance effects that will interfere with the interpretation of experimental results, are eliminated by carefully designing the experiments. The obtained pressure drop data of N-2-water two-phase flow in micromixers are analyzed and compared with existing flow pattern-independent models. It is found that the Lockhart-Martinelli method generally underpredicts the frictional pressure drop. Thereafter, a modified correlation of C value in the Chisholm's equation based on linear regression of experimental data is proposed to provide a better prediction of the two-phase frictional pressure drop. Also among the homogeneous flow models investigated, the viscosity correlation of McAdams indicates the best performance in correlating the frictional pressure drop data (mean deviations within +/-20% for two micromixers both). Finally it is suggested that systematic studies are still required to accurately predict two-phase frictional performance in microchannels. (C) 2004 Elsevier B.V. All rights reserved.
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Ni - V - O series catalysts for the oxidative dehydrogenation (ODH) of propane were prepared and characterized by BET, XRD, H-2- TPR, O-2-TPD-MS and electrical conductivity. At 425 degreesC a C3H6 selectivity of 49.9% was observed on Ni0.9V0.1OY at a C3H8 conversion of 19.4%, and the obtained selectivity is almost two times higher than that over NiO at the roughly same conversion of C3H8. The mobile oxygen species created by the interaction of NiO and V2O5 has been found in the composite catalysts by O-2-TPD-MS and electrical conductivity studies, which seems to be responsible for the enhanced selectivity of the propane oxidative dehydrogenation.
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The structural properties for various SiCO isomers in the singlet and triplet states have been investigated using CASSCF methods with a 6-311 +G* basis set and also using three DFT and MP2 with same basis set for those systems except for the linear singlet state. The detailed bonding character is discussed, and the state-state correlations and the isomerization mechanism are also determined. Results indicate that there are four different isomers for each spin state, and for all isomers, the triplet state is more stable than the corresponding singlet state. The most stable is the linear SiCO ((3)Sigma(-)) species and may be refer-red to the ground state. At the CASSCF-MP2(full)/6-311+G* level, the state-state energy separations of the other triplet states relative to the ground state are 43.2 (cyclic), 45.2 (linear SiOC), and 75.6 kcal/mol (linear CSiO), respectively, whereas the triplet-singlet state excitation energies for each configuration are 17.3 (linear SiCO), 2.2 (cyclic SiCO), 10.2 (linear SiOC), and 18.5 kcal/mol (linear CSiO), respectively. SiCo ((3)Sigma(-)) may be classified as silene (carbonylsilene), and its COdelta- moiety possesses CO- property. The dissociation energy of the ground state is 42.5 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and falls within a range of 36.5-41.5 kcal/mol at DFT level, and of 23.7-28.9 kcal/mol at the wave function-correlated level, whereas the vertical IP is 188.8 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and is very close to the first IP of Si atom. Three linear isomers (SiCO, SiOC, and CSiO) have similar structural bonding character. SiOC may be referred to the iso-carbonyl Si instead of the aether compound, whereas the CSiO isomer may be considered as the combination of C (the analogue of Si) with SiO (the analogue of CO). The bonding is weak for all linear species, and the corresponding potential energy surfaces are flat, and thus these linear molecules are facile. Another important isomer is of cyclic structure, it may be considered as the combination of CO with Si by the side pi bond. This structure has the smallest triplet state-singlet state excitation energy (similar to2.2 kcal/mol); the C-O bonds are longer, and the corresponding vibrational frequencies are significantly smaller than those of the other linear species. This cyclic species is not classified as an epoxy compound. State-state correlation analysis and the isomerization pathway searches have indicated that there are no direct correlations among three linear structures for each spin state, but they may interchange by experiencing two transition states and one cyclic intermediate. The easiest pathway is to break the Si-O bond to go to the linear SiCO, but its inverse process is very difficult. The most difficult process is to break the C-O bond and to go to the linear CSiO.
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The effect of rare-earth ion Eu3+ on hemoglobin (Hb) was studied by using two-dimensional Raman correlation spectroscopy. The results show that with the variation of Eu3+ concentrations as perturbation, the oxidation state of Hb and its spin state are both sensitive to the perturbation. Eu3+ added to Hb affects the oxidation and spin state synchronously. The four structure-sensitive bands of Hb are more accessible to the Eu3+ than other bands.