76 resultados para HETEROGENEOUS ENVIRONMENTS


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The catastrophic failure of heterogeneous brittle materials under impact loading is not fully understood. To describe the catastrophic failure behavior of heterogeneous brittle materials under impact loading, an elasto-statistical-brittle (ESB) model is proposed in this paper. The ESB model characterizes the disordered inhomogeneity of material at mesoscopic scale with the statistical description of the shear strength of mesoscopic units. If the applied shear stress reaches the strength, the mesoscopic unit fails, which causes degradation in the shear modulus of the material. With a simplified ESB model, the failure wave in brittle material under uni-axial compression is analyzed. It is shown that the failure wave is a wave of strain or particle velocity resulted from the catastrophic fracture in an elastically stressed brittle media when the impact velocity reaches a critical value. In addition, the failure wave causes an increase in the rear surface velocity, which agrees well with experimental observations. The critical condition to generate failure wave and the speed of failure wave are also obtained.

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海拔梯度造成的环境异质性,如崎岖的地形、复杂的植被结构以及花期延迟等可能会极大地影响到物种的形态和遗传变异格局。理解物种形态和遗传变异的海拔格局对于物种多样性的管理和保护是非常重要的。尽管植物群体遗传学是一个飞速发展的研究领域,然而与海拔相关的形态变异、遗传变异及群体间遗传差异的研究却很少。到目前为止,还不清楚遗传变异与海拔之间是否必然的相关性。 川滇高山栎是一种重要的生态和经济型树种,广泛分布于中国西南的四川、西藏、贵州和云南省的高海拔地区,在保持水土、调节气候方面起着十分重要的作用。尽管主要受阳光限制而仅分布于阳坡,但其海拔梯度范围较大,表明川滇高山栎对不同的环境具有很强的适应性。本文通过叶型及生理响应、微卫星分子标记和扩增性片段长度多态性方法,试图探索川滇高山栎叶沿海拔梯度的形态和生理响应及其沿海拔梯度的遗传变异格局,为川滇高山栎的保护和利用提供进一步的遗传学理论依据和技术指导。 对叶形、含氮量及碳同位素的试验结果表明,平均比叶面积、气孔密度、气孔长度和气孔指数等气孔参数随海拔的升高呈非线性变化。在海拔大于2800 m时,川滇高山栎的比叶面积、气孔长度和气孔指数都随海拔升高而降低,但是在海拔小于2800 m时,这些指标都随海拔的升高而增大。相对而言,单位叶面积的含氮量和碳同位素则表现出相反的变化模式。另外,比叶面积是决定碳同位素沿海拔梯度变化的最重要参数。本研究结果表明,海拔2800 m附近是川滇高山栎生长和发育的最适地带,在这里生长的植物叶片厚度更薄、气孔更大、叶碳同位素值更小。 利用六对微卫星引物对五个不同海拔川滇高山栎群体遗传多样性进行研究,结果表明,群体内表现出较高的遗传多样性,平均每位点等位基因数11.33个,平均期望杂合度达0.820。群体间差异较小,分化仅为6.6%。聚类分析也并没有显示出明显的海拔格局。然而低频率等位基因却与海拔呈显著性正相关(R2=0.97, P < 0.01),表明在高海拔处,川滇高山栎以更多的稀有基因来适应恶劣的环境条件。本试验结果表明由海拔梯度形成的选择性压力对川滇高山栎群体的遗传变异影响并不明显。 为了进一步探讨川滇高山栎群体遗传变异与海拔之间的相互关系,我们还对其进行了扩增性片段长度多态性分析。结果表明:(1)随海拔的升高(从群体WL2到群体WL5),群体内遗传变异降低,而群体间遗传差异增加;(2)低海拔群体WL1表现出最低的遗传变异性(HE = 0.181),同时与其余四个群体间呈现出最大的遗传差异性(平均FST = 0.0596);(3)在除去低海拔群体WL1后,Mantel检测表明群体间遗传距离与海拔距离之间表现出正相关性。另外,研究结果还表明,遗传变异受生境条件(过度的湿热环境)及人为干扰(火烧、砍伐和放牧)的影响,这一点至少在低海拔群体WL1上发生了作用。 通过叶形态、生理及DNA分子水平的研究,结果表明叶形态特征和碳同位素与海拔紧密相关,与海拔之间呈非线性变化,海拔2,800 m附近是川滇高山栎生长和发育的最适地带。海拔梯度在一定程度上会影响到川滇高山栎群体的遗传变异结构,但在这样一个狭窄的地理分布区域里,这种影响并不足以导致群体间较大的遗传分化。同时生境条件及人为干扰也是影响遗传变异的限制性因子,不容忽视。 Altitudinal gradients impose heterogeneous environmental conditions, such as rugged topography, a complex pattern of vegetation and flowering delay, and they likely furthermore markedly affect the morphological and genetic variation pattern of a species. Understanding altitudinal pattern of morphological and genetic variation at a species is important for the management and conservation of species diversity. Although plant population genetics is a fast growing field of research, there are only few recent investigations, which analyzed the genetic differentiation and changes of intra-population variation along altitudinal gradients. At present, it is still unclear whether there are some common patterns of morphological and genetic variation with altitude. Quercus aquifolioides Rehder & E.H. Wilson, which is an important ecological and economical endemic woody plant species, is widely distributed in the Yunnan and Sichuan provinces, Southwest China. Its large range of habitat across different altitudes implies strong adaptation to different environments, although it is mainly restricted to sunny, south facing slopes. It plays a very important role in preventing soil erosion, soil water loss and regulating climate, as well as in retaining ecological stability. In this paper, we tried to understand the altitudinal pattern of morphological and genetic variation along altitudinal gradients through the experiments of leaf morphological and physiological responses, microsatellite analysis and AFLP markers. In leaf morphological and physiological responses experiment, we measured leaf morphology, nitrogen content and carbon isotope composition (as an indicator of water use efficiency) of Q. aquifolioides along an altitudinal gradient. We found that these leaf morphological and physiological responses to altitudinal gradients were non-linear with increasing altitude. Specific leaf area, stomatal length and index increased with increasing altitude below 2,800 m, but decreased with increasing altitude above 2,800 m. In contrast, leaf nitrogen content per unit area and carbon isotope composition showed opposite change patterns. Specific leaf area seemed to be the most important parameter that determined the carbon isotope composition along the altitudinal gradient. Our results suggest that near 2,800 m in altitude could be the optimum zone for growth and development of Q. aquifolioides, and highlight the importance of the influence of altitude in research on plant physiological ecology. Genetic variation and differentiation were investigated among five natural populations of Q. aquifolioides occurring along an altitudinal gradient that varied from 2,000 to 3,600 m above sea level in the Wolong Natural Reserve of China, by analyzing variation at six microsatellite loci. The results showed that the populations were characterized by relatively high intra-population variation with the average number of alleles equaling 11.33 per locus and the average expected heterozygosity (HE) being 0.779. The amount of genetic variation varied only little among populations, which suggests that the influence of altitude factors on microsatellite variation is limited. However, there is a significantly positive correlation between altitude and the number of low-frequency alleles (R2=0.97, P < 0.01), which indicates that Q. aquifolioides from high altitudes has more unique variation, possibly enabling adaptation to severe conditions. F statistics showed the presence of a slight deficiency of heterozygosity (FIS=0.136) and a low level of differentiation among populations (FST=0.066). The result of the cluster analysis demonstrates that the grouping of populations does not correspond to the altitude of the populations. Based on the available data, it is likely that the selective forces related to altitude are not strong enough to significantly differentiate the populations of Q. aquifolioides in terms of microsatellite variation. To further elucidate genetic variation pattern of Q. aquifolioides populations under sub-alpine environments, genetic variation and differentiation were investigated along altitudinal gradients using AFLP markers. The altitudinal populations with an average altitude interval of 400 m, i.e. WL1, WL2, WL3, WL4 and WL5, correspond to the altitudes 2,000, 2,400, 2,800, 3,200 and 3,600 m, respectively. Our results were as follows: (i) decreasing genetic variation (ranging from 0.253 to 0.210) and increasing genetic differentiation with altitude were obtained from the WL2 to the WL5 population; (ii) the WL1 population showed the lowest genetic variation (HE = 0.181) and the highest genetic differentiation (average FST = 0.0596) with the other four populations; (iii) the positive correlation was obtained using Mantel tests between genetic and altitude distances except for the WL1 population. Our results suggest that altitudinal gradients may have influenced the genetic variation pattern of Q. aquifolioides populations to some extent. In addition, habitat environments (unfavorable wet and hot conditions) and human disturbances (burning, grazing and felling) were possible influencing factors, especially to the low-altitude WL1 population. The present study shows that there were close correlations between morphological features and carbon isotope composition in our data. This indicates that a coordinated plant response modified these parameters simultaneously across different altitudes. Around 2,800 m altitude there seems to be an optimum zone for growth and development of Q. aquifolioides, as indicated by thinner leaves, larger stomata and more negative d13C values. All available evidence indicates altitudinal gradients may have influenced the genetic variation pattern of Q. aquifolioides to some extent. Decreasing genetic variation and increasing genetic differentiation with altitude was obtained except for the WL1 population. And the environment of habitats and human disturbances were also contributing factors, which impact genetic variation pattern, especially to the low-altitude WL1 population.

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近十年,植物群体遗传学的研究飞速发展,然而与海拔相关的植物群体遗传结构和遗传变异研究却相对较少。到目前为止,还不清楚遗传变异与海拔之间是否有一个通用的格局。在山区,各种生态因子,如温度、降水、降雪、紫外线辐射强度以及土壤成分都随海拔梯度急剧变化,造成了即使在一个小的空间区域,植被类型变化显著,这种高山环境的异质性和复杂性为我们研究植物群体遗传结构和分化提供了方便。沙棘(Hippophea)属于胡颓子科(Elaeagnaceae)为多年生落叶灌木或乔木,雌雄异株,天然种群分布极为广泛。中国沙棘(H. rhamnoides subsp. sinensis)是沙棘属植物中分布较广的一个亚种,种内形态变异非常丰富,加之其具有独特的繁育系统和广泛的生态地理分布,是研究沙棘属植物遗传变异和系统分化的理想材料。本文从1,800 m 到3,400 m 分5 个海拔梯度进行取样,用RAPD 和cpSSR 分子标记研究了卧龙自然保护区中国沙棘天然群体的遗传结构和遗传变异。5 个取样群体依次标记为A、B、C、D 和E,它们分别代表分布在海拔1,800,2,200,2,600,3,000 和3,400 m 的5 个天然群体。RAPD实验用11 条寡核苷酸引物,扩增得到151 个重复性好的位点,其中143 个多态位点,多态率达94.7%。在5 个沙棘群体中,总遗传多样性值(HT)为0.289,B群体内的遗传多样性值为0.315,这完全符合沙棘这种多年生、远交的木本植物具有高遗传变异的特性。5 个群体内遗传多样性随海拔升高呈低-高-低变异趋势,在2,200 m海拔处的B群体遗传多样性达最大值0.315,3,400 m海拔处的E群体则表现最小仅0.098。5 个群体间的遗传分化值GST=0.406,也即是说有40.6%的遗传变异存在于群体间,1,800 m海拔处的A群体与其它群体的明显分离是造成群体间遗传分化大的原因。UPGMA聚类图和PCoA散点图进一步确证了5 个群体间的关系和所有个体间的关系。最后,经过Mantel检测,遗传距离与海拔表现了明显的相关性(r = 0.646, P = 0.011)。cpSSR 实验中,经过对24 对cpSSR 通用引物筛选,11 对引物能扩增出特异性条带,只有2 对引物(ccmp2 和ARCP4)呈现多态性。4 个等位基因共组合出4 种单倍型,单倍型Ⅰ出现在A 群体的所有个体和B 群体的8 个个体中,C、D、E 三个群体均不含有,而单倍型Ⅱ出现在C、D、E 三个群体的所有个体及B 群体的18 个个体中,A 群体不含有。另外两种单倍型Ⅲ和Ⅳ为稀有类型,仅B 群体中的4 个个体拥有。这种单倍型分布模式和TFPGA 群体聚类图揭示了,C、D、E 群体可能来源于同一祖先种,而A 群体却是由另一祖先种发展起来的,B 群体则兼具了这两种起源种的信息,这可能是因为在历史上的某一时期,在中国沙棘群体高山分化的过程中,B 群体处某个或者某些个体发生了基因突变,具备了适应高海拔环境的能力,产生了高海拔沙棘群体的祖先种。 In recent ten years, studies about population genetics of plants developed rapidly,whereas their genetic structure and genetic variation along altitudinal gradients have beenstudied relatively little. So far, it is uncleared whether there is a common pattern betweengenetic variation and altitudinal gradients. In the mountain environments, importantecological factors, e.g., temperature, rainfall, snowfall, ultraviolet radiation and soil substratesetc., change rapidly with altitudes, which cause the vegetation distribution varying typically,even on a small spatial scale. The mountain environments, which are heterogeneous andcomplex, facilitate and offer a good opportunity to characterize population genetic structureand population differentiation.The species of the genus Hippophae L. (Elaeagnaceae) are perennial deciduous shrubs ortrees, which are dioecious, wind-pollinated pioneer plants. The natural genus has a widedistribution extending from Northern Europe through Central Europe and Central Asia toChina. According to the latest taxonomy, the genus Hippophae is divided into six species and12 subspecies. The subspecies H. rhamnoides ssp. sinensis shows significant morphologicalvariations, large geographic range and dominantly outcrossing mating system. Thesecharacteristics of the subspecies are favourable to elucidate genetic variation and systemevolution. To estimate genetic variation and genetic structure of H. rhamnoides ssp. sinensisat different altitudes, we surveyed five natural populations in the Wolong Natural Reserve at altitudes ranging from 1,800 to 3,400 m above sea level (a.s.l.) using random amplifiedpolymorphic DNA markers (RAPDs) and cpSSR molecular methods. The five populations A,B, C, D, and E correspond to the altitudes 1,800, 2,200, 2,600, 3,000 and 3,400 m,respectively.Based on 11 decamer primers, a total of 151 reproducible DNA loci were yielded, ofwhich 143 were polymorphic and the percentage of polymorphic loci equaled 94.7%. Amongthe five populations investigated, the total gene diversity (HT) and gene diversity within population B equaled 0.289 and 0.315, respectively, which are modest for a subspecies of H.rhamnoides, which is an outcrossing, long-lived, woody plant. The amount of geneticvariation within populations varied from 0.098 within population E (3,400 m a.s.l.) to 0.315within population B (2,200 m a.s.l.). The coefficient of gene differentiation (GST) amongpopulations equaled 0.406 and revealed that 40.6% of the genetic variance existed amongpopulations and 59.4% within populations. The population A (1,800 m a.s.l.) differed greatlyfrom the other four populations, which contributes to high genetic differentiation. A UPGMAcluster analysis and principal coordinate analyses based on Nei's genetic distances furthercorroborated the relationships among the five populations and all the sampling individuals,respectively. Mantel tests detected a significant correlation between genetic distances andaltitudinal gradients (r = 0.646, P = 0.011).Eleven of the original 24 cpSSR primer pairs tested produced good PCR products, onlytwo (ccmp2 and ARCP4) of which were polymorphic. Four total length variants (alleles) werecombined resulting in 4 haplotypes. The haplotype was present in all individuals of Ⅰpopulation A and 8 individuals of populations B, the other three populations (C, D and Epopulations) did not share. The haplotype was present in all individuals of populations C, D Ⅱand E and 18 individuals of populations B, population A did not share. The other twohaplotypes and were rare haplotypes, which were only shared in 4 individuals of Ⅲ Ⅳpopulation B. The distribution of haplotypes and TFPGA population clustering map showedthat the populations C, D and E might be origined from one ancestor seed and population Amight be from another, whereas population B owned information of the two ancestor seeds. Itwas because that gene mutation within some individual or seed in the location of population Bwas likely to happen in the history of H. rhamnoides, which was the original ancestor of thehigh-altitude populations.

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常绿阔叶林以其富饶的生物资源、丰富的生物多样性和巨大的生态与环境效益引起了人们越来越大的重视,它的研究已成为国际植被科学界关注的主题之一。我国分布着世界上面积最大的亚热带常绿阔叶林,在世界植被中具有重要地位,它的分布表现出明显的地带性差异,存在着多样的植物群系及其对应的气候特征。但是在植物功能性状领域,与全球范围其它生物群系相比,常绿阔叶林物种的研究较少,其功能性状间、功能性状与环境间的关系尚不清晰。 本研究以常绿阔叶林木本植物的当年生小枝为对象,试图从小枝水平上的生物量分配格局、叶片大小与数量的权衡关系、小枝茎的构型效应、叶片元素化学计量学,以及小枝大小的成本与效益分析等方面,较为系统地揭示小枝水平上的植物功能性状间及其与气候间的关系。因此,在华西雨屏带内部的不同纬度设置峨眉-青城-雷波-平武的温度梯度进行比较,并对有降水差异的川西南偏湿性(雷波)与偏干性常绿阔叶林(西昌)进行对比研究,同时在不同山体进行不同海拔梯度的比较研究。 本文主要研究结果如下: (1)小枝生物量分配格局叶水平上,叶片重-叶柄重(Y轴vs.X轴,下同)呈斜率小于1的异速生长关系,表明叶柄对叶内部的生物量分配影响显著。小枝水平上,叶和茎的生物量以及它们与小枝总生物量间基本呈等速生长关系,表明大的小枝或大叶物种不一定在叶生物量的分配上占优势。不同生活型间,在小枝或者茎的生物量一定时,常绿物种叶片的生物量比例较落叶物种稍高。与温度和水分较优越(峨眉及其低海拔)的生境相比,在相对低湿(螺髻)与低温(平武)的生境中的植物会减少对叶的投入而增加对支撑部分的投资比例。 (2)小枝叶片大小与数量的权衡无论是不同气候带还是不同生活型以及不同海拔梯度,叶片大小与出叶强度基本都是呈负的等速生长关系,表明了叶片大小-数量在小枝水平上的权衡。在不同气候梯度的对比中,叶片数量(出叶强度)一定时,高温和高水分生境(峨眉)比低温(平武)和低湿(螺髻山)生境中的物种的叶片大小(质量和面积)更大,表明不同生境的比较中,小的叶片可能具有较高的出叶强度和更高的适合度收益。“出叶强度优势”(Leafingintensitypremium)假说可能不适宜解释不同生境物种叶片大小差异。 (3)小枝茎的构型效应虽然茎长和茎径与叶片大小都呈正相关关系,与出叶强度都呈负相关关系,但茎长/茎径比与叶/茎生物量之比呈负相关关系;与叶片的大小呈负相关关系,与出叶强度呈正相关关系。这说明小枝构型能影响小枝叶/茎生物量分配和叶大小-数量的权衡关系。其影响机制可能是小枝内部的顶端优势。另外,茎长/茎径比在低湿和低温等不利生境中的植物中较高,而在降水和温度较适宜环境中较低。 (4)叶片C、N、P化学计量学N含量和P含量,C/N比和比叶重(LMA,leafmassperarea)呈正的等速生长关系,而N和LMA,P和LMA呈负的等速生长关系。在LMA一定时,C/N比随着生境胁迫压力的增加而降低,N、P含量随着生境压力的增加而增加。在P含量一定时,N含量随着生境压力的增加而降低,即N/P比在生境条件较优(峨眉及其低海拔)时较高。常绿和落叶植物叶片的N/P比没有差异,在LMA一定时,常绿植物的N、P含量较高、C/N比较低。总之,植物的C、N、P化学计量学特征受叶片属性如LMA与气候,及其相互作用的影响。 (5)小枝大小的代价与效益分析、TLA与小枝总重总叶面积(TLA,totalleafarea,Y轴,下同)与总叶重(X轴)均呈斜率小于1的异速生长关系,TLA与小枝横切面积呈斜率为1的等速生长关系。表明叶片面积的增加总是小于叶重和小枝总重的增加,随着小枝的增大,它的叶面积支撑效率下降。在热量和降水优越的生境(峨眉及其低海拔)中,相同小枝重或者相同茎横切面积的小枝,其叶面积支撑效率较低湿与低温环境下(螺髻山、平武及高海拔)的高。 总体上,本文初步研究了小枝水平上可能存在的以下三种权衡关系:叶-茎生物量分配权衡;叶片大小-数量的权衡;小枝茎长-茎径的权衡关系,以及气候要素等对这三种权衡关系的影响。在此基础上,我们还讨论了这些权衡关系的可能形成机制,及其与物种生态适应的联系。本研究丰富了生活史对策中关于权衡关系的研究内容,为我国常绿阔叶林功能生态学研究积累了材料。 Evergreen broad-leaved forests are attracting much more attention from vegetation ecologists than ever before because of their abundant nature resource and biological diversity, and also great ecological benefits. China has the largest distribution of subtropical evergreen broad-leaved forests (temperate rainforests) that are typical and representative in the world. The forests span over more than ten degrees in latitude and more than 30 degrees in longitude, providing an ideal place to study plant functional ecology, i.e., the climatic effect on plant functional traits and the relationship between the traits. However, relative to the other biomes, there are few studies addressing functional ecology of the plant species from subtropical evergreen broad-leaved forests. In this study, I focused on the leaf size-twig size spectrum of the woody species of subtropical evergreen broad-leaved forests in southwestern china. I collected data on leaf size and number, twig size in terms of both mass and volume, and stem architecture from five temperate mountains, and then I analyzed the relationships between leaf and stem biomass and between leaf size and number, the effect of stem length/diameter ratio on biomass allocation and on the relationship between leaf size and number, leaf C:N:P stoichiometry, and the twig efficiency of supporting leaf area in relation to twig size. I also addressed the climate effect on the spectrum. The temperature gradient from warm to cool sites was represented by Emei Mountain, Qingchengshan, Leibo, and Pingwu, and the rainfall gradient was assumed to emerge from the comparison between Leibo (High) and Luojishan (Low). In addition, altitudinal effects were analyzed with comparisons between low and high altitudes for each mountains. My main results are as follows. Isometric relationships were found between leaf mass and twig mass and between lamina mass and twig mass, suggesting that the biomass allocation to leaves or laminas was independent of twig mass. Petiole mass disproportionably increase with respect to lamina mass and twig mass, indicating the importance of leaf petioles to the within-twig biomass allocation. In addition, the investigated species tended to have a larger leaf and lamina mass, but a smaller stem mass at a given twig mass at favorable environments including warm and humid sites or at low altitude than unfavorable habitats, which might be due to the large requirements in physical support and transporting safety for the species living at unfavorable conditions. Moreover, the evergreen species invested more in leaves and laminas than the deciduous at given stem or twig biomass within any specified habitats. Negative, isometric scaling relationships between leaf number and size broadly existed in the species regardless of climate, altitude, and life forms, suggesting a leaf size/number trade-off within twigs. Along the climatic gradients, at given leaf number or leafing intensity, the leaves were larger in the favorable environments than the poor habitats. This suggested that the fitness benefit gained by small leaves could be larger than that with high leafing intensity in the stressful sites. I concluded that the “leafing intensity premium” hypothesis was not appropriate to interpreting between-habitat variation in leaf size. Both stem length and diameter were positively correlated to leaf size but negatively correlated to leafing intensity. The ratio of stem length to diameter was negatively correlated to leaf mass fraction, and it was negatively correlated to leaf size but positively correlated to leafing intensity. This suggested that the stem architecture influenced twig biomass allocation and the relationship between leaf size and number. The mechanism underlying the architectural effect might lie in the apical dominance within twig. Moreover, the ratio was greater in unfavorable habitats but smaller in favorable environments. Positive, isometric relationships were found between N and P contents per leaf mass, and between C/N ratio and leaf mass per area (LMA), but N and P contents scaled negatively to LMA. C/N ratio decreased but N and P increased with increasing habitat stress at a given LMA. N content declined with increasing habitat stress at given P content. These indicated that N/P and C/N were higher but LMA was lower in favorable habitats than in the other circumstances. The evergreen and deciduous species were non-heterogeneous in N/P, but the evergreen species have higher N and P contents and lower C/N than the deciduous ones. In general, C:N:P stoichiometry were related to both climatic conditions and other important functional traits like LMA. Total leaf area (TLA) allometricly scaled to leaf mass with a slope shallower than 1, similar to the relationship between TLA and total twig mass (leaf mass plus stem mass), suggesting that TLA failed to keep pace with the increase of leaf mass and twig size. However, TLA scaled isometricly to twig cross-sectional area. Thus, it could be inferred that the twig efficiency of displaying leaf area decreased with increasing twig size. In addition, the efficiency at a given twig size was large in favorable than unfavorable habitats. In general, in this preliminary study, I studied three tradeoff relationships within twigs, i.e., between leaf and stem biomass, between leaf number and size, and between stem length and diameter, as well as the climatic effect on the relationships. I discussed the mechanisms underlying the tradeoff relationships in view of biophysics and eco-physiology of plants. I believe that this study can serve as important materials advancing plant functional ecology of subtropical forest and that it will improve the understanding of life history strategies of plants from this particular biome.

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Heterogeneous PPh3-Rh/SiO2 catalysts for hydroformylation of olefins, prepared by direct doping of phosphine onto the heterogeneous Rh/SiO2 precursor, exhibited high activity and selectivity towards aldehydes, which originated from chemical coordination bond between the phosphine and Rh metal nantoparticles on the SiO2 support.

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A multistream reactor for high-throughput examining the surface acidity by NH3-TPD method by application of multistream mass spectrometer screening (MSMSS) technique has been developed. This method allows for examining the surface acidity of 10 catalyst samples in about 6 h, which is an improvement over the traditional process. The demonstration of the feasibility of high-throughput TPD can be significant in convincing the hardened traditionalists in the heterogeneous catalysis community that, combinatorial methods indeed should have an important place in scientific catalyst research and development. The developed method could also be used for almost all the temperature-programmed analysis theoretically with careful designed multistream reactors. (C) 2003 Elsevier B.V. All rights reserved.

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Some heterogeneous catalysts, cupric oxide supported on different supports, were prepared and employed to catalyze the cyclopropanation of styrene and 2,5-dimethyl-2,4-hexadiene with ethyl diazoacetate (EDA). The catalytic performance for cyclopropanation strongly depends on the nature of the support. A novel catalyst, CUO/TiO2-Al2O3, in which Al2O3 is modified with a monolayer TiO2, is found to be most active and selective for the cyclopropanation reaction. The yields of 93 and 94% cyclopropanes are obtained for styrene and 2,5-dimethyl-2,4-hexadiene at 40 degreesC as the substrates, respectively. The activity and selectivity in cyclopropanes are optimized with a monolayer dispersion of cupric oxide on the corresponding supports. (C) 2002 Elsevier Science B.V. All rights reserved.

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A high-throughput screening system for secondary catalyst libraries has been developed by incorporation of an 80-pass reactor and a quantified multistream mass spectrometer screening (MSMSS) technique. With a low-melting alloy as the heating medium, a uniform reaction temperature could be obtained in the multistream reactor (maximum temperature differences are less than 1 K at 673 K). Quantification of the results was realized by combination of a gas chromatogram with the MSMSS, which could provide the product selectivities of each catalyst in a heterogeneous catalyst library. Because the catalyst loading of each reaction tube is comparable to that of the conventional microreaction system and because the parallel reactions could be operated under identical conditions (homogeneous temperature, same pressure and WHSV), the reaction results of a promising catalyst selected from the library could be reasonably applied to the further scale-up of the system. The aldol condensation of acetone, with obvious differences in the product distribution over different kind of catalysts, was selected as a model reaction to validate the screening system.

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The Heck reaction of iodobenzene and methyl acrylate was investigated with CO2-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et3N) in the presence of CO2 under solventless conditions at 80 degrees C. The catalysts are not soluble in the organic phase in the absence Of CO2 and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO2, CO2 is dissolved into the organic phase and this promotes the dissolution of the I'd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect Of CO2 pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO2 molecules dissolved. Thus, the maximum conversion appears at a CO2 pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water.

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An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

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The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homoueneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width.

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In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.