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Resumo:
岷江上游地区高山/亚高山植被分布的坡向性分异显著,阴阳坡高山林线不仅物种组成差异明显,并且分布海拔呈现出阴坡高阳坡低的格局.阳坡林线树种主要是圆柏属乔木,林线类型多为渐变型,海拔高度大约在3 400m~3 800m;阴坡林线树种主要是冷杉,林线类型多为骤变型,海拔高度约在3 800m~4 400m.本研究采用土壤种子库物理筛选、室内萌发实验及野外群落调查等方法,对岷江上游地区阴坡岷江冷杉和阳坡祁连圆柏两类林线树种不同海拔梯度上土壤种子库以及幼苗库特征进行了调查,从土壤种子库和幼苗更新特征的角度对林线乔木树种种群更新特征进行了分析,进而对该地区高山林线在阴阳坡分布差异的原因进行了探讨,结果显示: 1.土壤种子库 阴坡:阴坡高山林线附近岷江冷杉土壤种子的平均密度大约为50.96粒/m2,其中树线以上10m处土壤种子密度为1.00粒/m2,树线处大约19.33粒/m2,林线交错带内土壤种子密度最高为136.83粒/m2,郁闭林内种子密度小于林线交错带,只有30.50粒/m2,种子平均空壳率为52%,霉变率达34%,完好种子只有6%.土壤种子库垂直分布特征为地被物层含种子比重最大,大约在67.50%左右;其次为0~2cm层,约18.84%左右;2~5cm层所占种子比例最小,约13.66%左右.霉变种子数量与土壤深度呈负相关. 阳坡:阳坡祁连圆柏土壤种子的平均密度为60.16粒/m2.树线以上10m处密度为1.92粒/m2,树线位置大约108.16粒/m2,林线交错带内平均为75.80粒/m2,郁闭林内种子密度小于林线交错带,只有20.00粒/m2.种子平均空壳率为36%,完好种子占49%,霉变率较低,大约为10%.阴阳坡林线树种土壤种子库垂直分布特征为:地被物层含种子最多,其次为0~4cm层,4~10cm层所占种子比例最小,霉变种子数量与土壤深度也呈负相关. 2. 幼苗库调查 阳坡:在树线以上区域没有发现幼苗,林线交错带内幼苗密度平均达3 250株/hm2,郁闭林内仅2 750株/ hm2.整个样地内1~2a幼苗很少甚至没有出现,3~10a的幼苗相对较多.空间分布上,祁连圆柏幼苗在林线交错带内接近随机分布,郁闭林内则介于随机分布和均匀分布之间. 阴坡:在树线以上幼苗密度为1 250株/ hm2,全部为1~2a幼苗,林线交错带内幼苗密度平均达7 000株/ hm2,郁闭林内达6 250株/ hm2.林线附近岷江冷杉幼苗丰富度以及幼苗的出现频率明显高于祁连圆柏,年龄结构也较祁连圆柏完整.岷江冷杉幼苗空间分布除了树线处幼苗的分布为随机分布,其他海拔则为集群分布. 3.从不同土壤深度的种子总量和幼苗数量的相关性检验发现,当年生幼苗数量跟表层种子总量相关性极显著, 但是两年生幼苗的数量与底层种子数量相关性显著.土壤种子在土壤中的垂直分布格局从一定程度上可以反映种子库的年际特征.岷江冷杉土壤种子库较丰富,种子散布后的存活力随着时间的变化逐渐下降,属于季节性瞬时种子库;祁连圆柏土壤种子散布格局为集群型分布,成熟种子大部分散布在母株冠幅内,属于永久性土壤种子库. 4.在阴坡林线交错带及以上区域还存在较为丰富的乔木土壤种子,并且在树线以上区域还发现了少量的岷江冷杉幼苗.从样地乔木的年龄结构发现,在林线交错带内上部到树线位置主要以幼龄林为主,且年龄结构完整,基本符合入侵性林线特征;阳坡林线交错带内幼苗出现频率很低,树线以上区域虽然存在种子库,但是没有幼苗出现,在林线交错带内乔木径级差距很大,年龄结构异常不完整,这种特征的林线将会面临两个可能结果:一种是维持现有状态,保持平衡;另外一种就是退化,但阳坡林线的实际动态趋势还有待长期定点研究. Treelines on the upper region of Minjiang River differ between the north aspect and the south aspect in their appearances, altitudes and tree species. On the north aspect, trees of Abies form a sharp and abrupt treeline ranging from 3800m to 4400m, while on the south the treeline is generally lower(3 400~3 800m), more open and gradual and mostly composed of Sabina. In this study, we examined the altitudinal gradients of soil seed banks and seedling recruitments at the treeline ecotones of a N-aspect and a S-aspect by using soil sieving, germination experiment and field investigations, analyzed the characteristics of population regeneration of tree species at the transitional zone and presented a analysis of the causes to the aspect-related difference in treeline patterns in the study area. Major results of our study include: 1. Soil seed bank N-aspect: Of the 50 plots investigated, the average density of soil seeds is 50.96/m2, in which well-formed seeds account for 6%, empty seeds 52%, parasitized seeds34%, and seeds damaged by animals 8%. The size of soil seed bank varies along altitude, being 1.00 seeds /m2 at the 10m above the treeline and ca.19.33 seeds/m2 at the upper limit of treeline. The highest density (136.83 seeds/m2) occurs at the treeline ecotone. By contrast, the density of soil seed for the closed forest is only 30.50 seeds/m2. In terms of vertical strata, 67.50% of the total seeds are at the surface layer, 18.84% at the middle layer (0~2cm) and 13.66% at deeper layer (2~5cm). The number of parasitized seeds is negatively correlated to soil depth. S-aspect: Of the 50 plots investigated, the average density of soil seeds is 60.16 seeds/m2, and the well-formed seeds account for 49%, empty seeds 36%, parasitized seeds10%, and seeds damaged by animals 1%. The size of soil seed bank varies along altitude, with 1.92 seeds/m2 recorded at the10m above the treeline,108.16 seeds/m2 at the upper limit of treeline, and 75.80 seeds/m2 at the treeline ecotone, while that for the closed forest is 20.00 seeds/m2. The number of seeds decreases with the depth of soil. As is on the N-aspect, the size of soil bank, from large to small, follows the order of the surface layer, the middle layer (0~4cm) and the bottom layer (4~10cm). The number of parasitized seeds is also negatively correlated to the depth of the soil. 2. Seedling bank N-aspect: A mean maximum seedling abundance of 31 000 seedlings/hm2 was recorded near alpine treeline at growing season. The density of seedlings is 1 250 seedlings/ha (all being 1 or 2 years old) at the alpine meadow 10m away above treeline, 7 000 seedlings/ha at treeline ecotone and 6 250 seedlings/ha for closed forest.The spatial distribution of Abies faxoniana seedlings is random at the upper limit of the treeline but clumped at other altitudes. S-aspect: No seedlings were found at the alpine meadow 10m away from the treeline. The density of seedlings was 3 250 seedlings/ha at treeline ecotone and 2 750 seedlings/ha for the closed forest.Hardly any 1 year current and 2 year-old seedlings appeared at the plots. The spatial distribution of Sabina przewalskii seedlings is random at treeline ecotone and between “random” and “even” forest closed forest. 3.Correlation tests of seedling population and seed bank at different soil layers indicated that the emergents were strongly correlated to seed bank at surface layer while the number of two-year seedlings was significantly correlated to the seed bank at the bottom of soil layer, indicating that germination mainly occurs at the soil surface while the middle or bottom layer was the reserve for non-germination or dead seeds. It can thus be postulated that Abies faxoniana soil seed bank is of seasonal transient type. By contrast, the soil seed bank of Sabina przewalskii is of persistent type and the soil seeds and seedlings of this species occurred more frequently near the islands of adult trees. 4.A good many soil seeds of both tree species were found near the treeline ecotone and above at N- and S-aspects. A few young seedlings were found above the Abies treeline. Investigation of five altitudinal transects respectively on N- and S-aspects indicated that Abies faxoniana has a more complete age structure than the stands of Sabina przewalskii. The age of firs decreased from closed forest to the upper limit of treeline, which suggests that the Abies treeline is advancing to higher altitude. While on the south aspect, only few Sabina przewalskii soil seeds and nearly no seedlings were found above the treeline ecotone. The stands exhibit extremely great difference in diameter classes with significantly incomplete age structure. This would lead to two possible results for the treelines: maintaining an equilibrium state at the current position or degenerating. But more studies should be carried out at longer time scales or larger spatial scales to understand whether the Sabina treeline is degenerating.
Resumo:
青藏高原东部分布着世界最高的林线,该区域也是由欧亚北温带物种形成的林线的南界。在大面积野外踏勘的基础上,选择青藏高原东部具有典型高山林线分布的三个地点(滇西北白马雪山、川西北鹧鸪山及岷江源地区)作为研究区,从种群的结构、生存特征、分布格局及分形特征等方面对青藏高原东缘高山林线乔木种群生态学特征进行了研究,并在此基础上探讨了人类活动对林线种群生态特征及林线格局的影响。结果表明,林线区乔木树种多以单种群形式存在,林线区群落结构简单,乔木层多为单一树种组成,其生长型较之郁闭林发生了急剧的变化:树木高度急剧下降,而发展多茎多分枝的生长型。生长型的转变是高山林线乔木对恶劣自然条件的形态适应。 研究发现,在青藏高原东缘,阴坡林线乔木主要是冷杉(Abies spp.),阳坡主要由圆柏(Sabina spp.)组成,少数地方还有云杉(Picea spp.)。阴坡乔木种群结构多表现为增长型,幼苗和幼树在种群中占较大比重,种群潜在自然更新能力较强,但幼龄个体死亡率非常高,存活曲线多接近Deevey-Ⅲ型;阳坡乔木种群幼苗个体数极少,幼树相对增加。野外调查表明,人为活动较频繁的阳坡林线区幼苗数量极少甚至缺失,而受人为活动干扰较小的样地中幼苗和幼树数量明显增多,从一个侧面说明放牧等人类活动可能对林线种群的更新带来较大影响,而对卡卡沟围栏内外的样地分析也进一步证明了这一结果。 所研究林线乔木种群各龄级的空间格局在不同尺度上表现为聚集、随机和均匀分布,以聚集分布为主;各龄级在不同尺度上表现出显著的相关性,幼苗通常与另外两个龄级的关联性较密切。各龄级间显著的相关性表明不同龄级个体在空间交错分布,有利于对各种资源的充分利用,对种群的生存和发展非常有利,反映了高山生态系统恶劣生境中种群的一种适应对策。 林线乔木种群各龄级分布格局的计盒维数有差别,林线种群的计盒维数总是小于郁闭林种群的计盒维数。另外,郁闭林各龄级计盒维数通常也高于林线各龄级,表明不同海拔或者不同群落类型中的乔木树种具有不同的水平空间占据能力。林线区种群分布格局的计盒维数都很低,占据现实水平空间的程度较低,具有相对较高的生态间隙维,其潜在占据空间的能力较高,群落还可提供给种群的最大空间限度较大,但实际上由于受群落中种内、种间的竞争及林线区恶劣的生态环境条件的限制,其潜在空间占据能力可能难以表现出来。 青藏高原东缘高海拔地带以季节性游牧为主要的资源利用和生产方式,阳坡森林郁闭度低于阴坡,灌丛数量和种类较阴坡少,融雪早且积雪时间短,所以阳坡包括高山林线区成为当地牧民游牧路线的必经之地。牲畜的践踏、啃食使得幼龄乔木树种个体数量大大减少,严重阻碍了林线乔木种群的自然更新,同时种群占据空间的能力也明显降低。因此可以认为,在青藏高原东部地区,山地游牧等人为干扰叠加于恶劣的自然条件,阳坡林线的自然更新潜力受到抑制,其生存状态较之阴坡林线显著恶化,并可使阳坡林线高度逐渐降低。高山林线区森林一旦破坏在短时间内很难有效更新和恢复,因此,对于处于恶劣高山生境中的乔木种群应加强保护,同时适度控制人为干扰强度和幅度以减少其直接和间接破坏,防止阳坡林线退化并促进高山生态系统的自然恢复。 Eastern Qinghai-Tibetan Plateau has the highest timberline of the world. On the basis of field surveys and literature reviews, three typical alpine timberlines were chosen for in-depth studies, i.e., Baima Snow Mountain in northwest Yunnan, Zhegu Mountain and the waterhead area of Minjiang River in west Sichuan. Using the methodologis of population ecology, we analyzed the population structure, survival characteristics, spatial point patterns and fractal dimensions of the timberline tree populations and discussed the impacts of grazing on the structure and spatial pattern of alpine timberline. Compared with closed forests, the community structure of timberline is simpler, usually with one or two species constituting the tree layer. Differences also exist in the growth forms: the trees were significantly shorter with more stems and branches, reflecting morphological adaptation of trees to the severe conditions at timberline. In the eastern Qinghai-Tibetan Plateau, Abies spp. often formed alpine timberline in the north-facing slope while Sabina spp. and sometimes Picea spp. in the south- facing slope. The population structures of north-facing slope showed an increasing trend, with numerous seedlings and saplings. However, the survival curves tend to follow Deevy-III because of high dead ratio of young individuals. There are only few seedlings in the south-facing slope with heavy grazing, demonstrating that human disturbance may prevent regeneration at alpine timberline, which was confirmed by comparisons between fenced enclosures and control plots in the Kaka Valley. Depending on the spatial scales on consideration, the individuals of different age-classes showed clumping, random or even distribution, but mostly with clumping distribution. At all scales, individuals in different age-classes were all significantly correlated with each other while the seedlings were usually more correlated to two other age classes. This high degree of correlation among different age classes indicates that individuals of different age classes are spatially interlocked with each other, which helps sufficient utilization of various resources and is conducive to the survival and development of population. It is another adaptation strategy for trees at the severe environment. The spatial patterns of different age classes had different box dimension. In general, the box dimensions of total individuals and each age class at timberline are always smaller than that of closed forests, suggesting that space occupation capacity is not the same for populations at different altitude or in different communities. Populations on both the south- and the north-facing slopes had a very low box dimensions (far away from the max., 2), however, the lower the box dimension, the bigger the potential space provided by community. In fact, because of inner- and inter- competition as well as the severe conditions at timberline, this kind of potential ability can hardly be realized. Mountain pastoralism is the major type of as well as the only most effective way of resource uses in the high elevation regions of the eastern Qinghai-Tibetan Plateau. Due to lower canopy cover, less bushes and short snow-cover time, south-facing slopes became the favorite pastures. Damages from livestock through tramping, browsing and others have greatly reduced the number of young individuals. As a result, the potential of timberline trees to regenerate and their ability to occupy more space are greatly inhitibted. We conclude that human disturbances (mountain pastoralism) as well as harsh environmental conditions co-worked to inhibit the regeneration of tree populations in the south-facing slope and made south slopes more difficult than the north-facing slopes for trees to survive and develop, resulting a gradual retreat of timberline in the north-facing slopes. Forests at alpine timberline are susceptible to disturbance and difficult to regenerate and restore once damaged and controlling human disturbances is important for protecting the forest ecosystems at the timberline area.
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In this paper, the regularity and changes of the forest landscape along the major rivers, namely, Nuomin River,Bila River and Zhawen River in Daxing'an Mountains, Bilahe Forestry Bureau based on the interpretation of TM data were studied. The results showed that the regularity has changed a lot due to the gradually stronger human intervention on forest landscape. The most obvious change was the cultivated lands had been expanding alongside the major rivers. With the increasing of population, the only way to satisfy the increasing needs of the local people for subsistence is by expanding cultivated lands because of the backwardness of agriculture productivity. The regularity of conifer distribution along rivers of 1997 has changed in the diverse direction of that of 1988. The proportion of conifer gradually increases with 1 000 m further away from the major rivers. That is due to the favorable availability of conifer alongside river bank, the most populated area in the forest region.
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SR型人工降雨装置是一种多喷头、多单元组合式的间歇降雨装置。选用目前国内外较理想的喷头 ,在喷头处辅以可改变喷头降水方式的机械传动装置 ,以间歇方式降雨来满足其降雨强度 ,雨滴直径大小及其分布与自然降雨相似。每个单元的有效降雨面积为 2 m× 5 m;如果 4个单元组合成 ,其长度可增加 4倍 ,有效降雨面积即 2 m× 2 0 m。装置采用轻型铝合金材料制成 ,结构简单 ,易于安装拆卸 ,适用于野外工作。
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We developed a direct partitioning method to construct a seamless discrete global grid system (DGGS) with any resolution based on a two-dimensional projected plane and the earth ellipsoid. This DGGS is composed of congruent square grids over the projected plane and irregular ellipsoidal quadrilaterals on the ellipsoidal surface. A new equal area projection named the parallels plane (PP) projection derived from the expansion of the central meridian and parallels has been employed to perform the transformation between the planar squares and the corresponding ellipsoidal grids. The horizontal sides of the grids are parts of the parallel circles and the vertical sides are complex ellipsoidal curves, which can be obtained by the inverse expression of the PP projection. The partition strategies, transformation equations, geometric characteristics and distortions for this DGGS have been discussed. Our analysis proves that the DGGS is area-preserving while length distortions only occur on the vertical sides off the central meridian. Angular and length distortions positively correlate to the increase in latitudes and the spanning of longitudes away from a chosen central meridian. This direct partition only generates a small number of broken grids that can be treated individually.
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CE/tris(2,2-bipyridyl) ruthenium(ll) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL), CEECL, with an ionic liquid (IL) detection system was established for the determination of bioactive constituents in Chinese traditional medicine opium poppy which contain large amounts of coexistent substances. A minimal sample pretreatment which involves a one-step extraction approach avoids both sample loss and environmental pollution. As the nearby hydroxyl groups in some alkaloid such as morphine may react with borate to form complexes and IL, as a high-conductivity additive in running buffer, could cause an enhanced field-amplified effect of electrokinetic injection. Running buffer containing 25 mM borax-8 mM 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF(4)) IL (pH 9.18) was used which resulted in significant changes in separation selectivity and obvious enhancement in ECL intensities for those alkaloids with similar structures. Sensitive detection could be achieved when the distance between the Pt working electrode and the outlet of separation capillary was set at 150 mu m and the stainless steel cannula was fixed approximately 1 cm away from the outlet of the capillary. Quantitative analysis of four alkaloids was achieved at a detection voltage of 1.2 V and a separation voltage of 15 kV in less than 7 min.
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HigWy efficient DCJTB-doped device was realized by enhanced electron injection and exciton confinement. A fluorine end-capped linear phenylene/oxadiazole oligomer 2,5-bis(4-fluorobiphenyl-4'-yl)-1,3,4-oxadiazole (1) and a trifluoromethyl end-capped oligomer 2,5-bis(4-trifluoromethylbiphenyl-4'-yl)-1,3,4-oxadiazole (2) were designed and incorporated as an electron transporting/hole blocking material in the device structure ITO/NPB (60 mn)/DCJTB:Alq(3) (0.5%, 10 nm)/1 or 2 (20 nm)/Alq(3) (30 mn)/LiF (1 nm)/Al (100 nm). The devices showed highly efficient red luminescence. In particular, the device based on 1 achieved pure red luminescence at 620 run originating from DCJTB, with a narrow FWHI of 65 nm, maximal brightness of 13,300 cd/m(2) at voltage of 20.8 V and current density of ca. 355 mA/cm(2). High current and power efficiencies (> 3.6 cd/A. 1.01m/W) were retained within a wide range of current densities. Our results show efficient and stable DCJTB-doped red electroluminescence could be anticipated for practical applications by taking advantage of the present approaches. The control experiments using BCP were also studied.
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capillary electrophoresis (CE) is characterized. A 300 mum diameter Pt working electrode was used to directly couple with a 75 mum inner diameter separation capillary without an electric field decoupler. The hydrodynamic cyclic voltammogram (CV) of Ru(bpy)(3)(2+) showed that electrophoretic current did not affect the ECL reaction. The presence of high-voltage (HV) field only resulted in the shift of the ECL detection potential. The distance of capillary to electrode was an important parameter for optimizing detection performance as it determined the characteristics of mass transport toward the electrode and the actual concentration of Ru(bpy)(3)(2+) in the detection region. The optimum distance of capillary to electrode was decided by the inner diameter of the capillary, too. For a 75 mum capillary, the working electrode should be placed away from the capillary outlet at a distance within the range of 20-260 mum. The effects of pH value of ECL solution and molecular structure of analytes on peak height and theoretical plate numbers were discussed. Using the 75 mum capillary, under the optimum conditions, the method provided a linear range for tripropylamine (TPA) between 1 x 10(-10) and 1 X 10(-5) mol/L with correlation coefficient of 0.998. The detection limit (signal-to-noise ratio S/N = 3) was 5.0 x 10(-11) mol/L. The relative standard deviation in peak height for eight consecutive injections was 5.6%. By this new technique lidocaine spiked in a urine sample was determined. The method exhibited the linear range for lidocaine from 5.0 x 10(-8) to 1.0 X 10(-5) mol/L with correlation efficient of 0.998. The limit of detection (S/N = 3) was 2.0 x 10(-1) mol/L.
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The oxidation and adsorption of the temperature-denatured DNA at GC electrode are studied by differential pulse voltammetry and in situ FTIR spectroelectrochemistry. The temperature-denatured DNA is adsorbed and formed a DNA multilayer at electrode surface. The temperature-denatured DNA showing partly reversible process was first observed based on the reduction peaks appearing at negative scans and the reversible spectral change. The oxidation product of the temperature-denatured DNA can not diffuse away from the electrode surface easily due to the impediment of the DNA multilayer, so it can be partly reduced.
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The hexafluorophosphate salts [Fe((C5H4Bu)-Bu-t)(2)]PF6 (1) and [Co((C5H4Bu)-Bu-t)(2)]PF6 (2) crystallize in isotypic structures with centrosymmetric cations which have a staggered (transoid) conformation of the exactly parallel ring Ligands (conformational angle tau = 180 degrees). The tetrachlorocobaltate salt, [CO((C5H4Bu)-Bu-t)(2)](2)CoCl4 (3), contains one almost eclipsed (tau = 140.4 degrees) and one almost staggered (tau = 101.4 degrees) cobaltocenium cation; in both cases, the cyclopentadienyl ring planes are slightly inclined (by alpha = 5.4 degrees and 4.1 degrees, respectively) to give more room to the tert-butyl substituents which are bent away from the metal in all three complexes 1 - 3.
Resumo:
The microregion approximation explicit finite difference method is used to simulate cyclic voltammetry of an electrochemical reversible system in a three-dimensional thin layer cell with minigrid platinum electrode. The simulated CV curve and potential scan-absorbance curve were in very good accordance with the experimental results, which differed from those at a plate electrode. The influences of sweep rate, thickness of the thin layer, and mesh size on the peak current and peak separation were also studied by numerical analysis, which give some instruction for choosing experimental conditions or designing a thin layer cell. The critical ratio (1.33) of the diffusion path inside the mesh hole and across the thin layer was also obtained. If the ratio is greater than 1.33 by means of reducing the thickness of a thin layer, the electrochemical property will be far away from the thin layer property.
Resumo:
Epitaxial crystallization of syndiotactic polypropylene (sPP) on 2-quinoxalinol (2-Quin) yields, in the lower part of the crystallization range, the less common and metastable form II based on the packing of isochiral helices, rather than the stable antichiral form I. The contact plane is (110)(II). Form II exits only as a thin layer (< 50 nm) near the substrate surface. During further growth away from the surface, a transition takes place to the disordered form I, observed in "conventional" thin film growth. The epitaxial relationship rests only partly on dimensional matching with the chain axis repeat distance (which would be valid for both forms I and II) and on interchain distances. Whereas a better dimensional match would be achieved with form I, selection of the isochiral form II results from better correspondence of the surface topographies of the deposit (110)(II) sPP and substrate 2-Quin (001) contact faces.
Resumo:
A liquid crystalline (LC) copolyether has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane with 1,7-dibromoheptane and 1,11-dibromoundecane with a 50/50 (both in %) equal composition of the 7- and 11-methylene monomers [coTPP-7/11(5/5)]. A mono-domain with a homeotropic alignment can be induced by a thin film surface in the LC phase. When an electrostatic field is applied to the surface-induced mono-domains parallel to the thin film surface normal, the molecular alignment undergoes a change from the homeotropic to uniaxial homogeneous arrangement. However, when the field is applied to a direction perpendicular to the thin film surface normal. the molecular alignment is about 10 degrees -tilt with respect to the homeotropic alignment toward the a*-axis. This is because the permanent dipole moment of the copolyether is not right vertical to the molecular direction. The calculation of molecular dipoles indicates that the permanent dipole moment of this copolyether is about 70 degrees away from the molecular axis, which leads to a negative dielectric anisotropy. It is speculated that the 10 degrees- rather than 20 degrees -tilt is due to a balance between the alignment induced by the electrostatic field and the surface. In the electrostatic field, molecules are subjected to a torque tau, which is determined by the permanent dipole moment P and the electrostatic field E: tau = P x E. The molecular realignment in both parallel and perpendicular directions to the thin film surface normal is determined by satisfying the condition of tau = P x E = 0. (C) 2001 Elsevier Science Ltd. All rights reserved.
Resumo:
In-situ Fourier transform infra-red (FTIR) spectra of native and thermally denatured calf thymus DNA (CT DNA) adsorbed and/or oxidized at a glassy carbon (GC) electrode surface are reported. The adsorption of native DNA occurs throughout the potential range (-0.2 similar to 1.3 V) studied, and the adsorbing state of DNA at electrode surface is changed from through the C=O band of bases and pyrimidine rings to through the C=O of cytosine and imidazole rings while the potential shifts negatively from 1.3 V to -0.2 V. An in-situ FTIR spectrum of native CT DNA adsorbed at GC electrode surface is similar to that of the dissolved DNA, indicating that the structure of CT DNA is not distorted while it is adsorbed at the GC electrode surface. In the potential range of -0.2 similar to 1.30 V, the temperature-denatured CT DNA is adsorbed at the electrode surface first, then undergoes electrochemical oxidation reaction and following that, diffuses away from the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.
Resumo:
The interactions of lanthanide ions and the Ln-DTPA (DTPA = diethylenetriaminepentaacetate) complex with di palmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylethanolamine (DPPE) bilayers are studied by 2D NOESY and FT-Raman spectroscopy. Proton NMR spectroscopic results show that lanthanide ions combine with phosphate groups in the polar region of the outer layer of DPPC liposomes, leading to the separation in chemical shift of the proton signal of N(CH3)(3) The conformational change of the O-C-C-N+ backbone from the gauche conformer to the trans one is not found; i.e., the orientation of the polar headgroup is still parallel to the surface of the bilayers. The Ln-DTPA complex at low concentration in a pH 7.4 solution localizes far away from bilayers and thereby has little effect on the structure of bilayers. The FT-Raman spectroscopic results indicate that lanthanide ions affect strongly the fluidity of acyl chains of DPPE bilayers while the Ln-DTPA complex affects it slightly.