140 resultados para maximum electron transport rate (ETRmax)


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We study the spin-dependent electron transport in a special magnetic-electric superlattice periodically modulated by parallel ferromagnetic metal stripes and Schottky normal-metal stripes. The results show that, the spin-polarized current can be well controllable by modulating the magnetic strength of the ferromagnetic stripes or the voltage applied to the Schottky normal-metal stripes. It is obvious that, to the system of the magnetic superlattice, the polarized current can be enhanced by the magnetic strength of ferromagnetic stripes. Nevertheless, it is found that, for the magnetic-electric superlattice, the polarized current can also be remarkably advanced by the voltage applied to the Schottky normal-metal stripes. These results may indicate a useable approach for tunable spintronic devices. (c) 2006 Elsevier B.V. All rights reserved.

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Molecular beam epitaxy is employed to manufacture self-assembled InAs/AlAs quantum-dot resonant tunneling diodes. The resonant tunneling current is superimposed on the thermal current, and together they make up the total electron transport in devices. Steps in current-voltage characteristics and peaks in capacitance-voltage characteristics are explained as electron resonant tunneling via quantum dots at 77 or 300 K, and thus resonant tunneling is observed at room temperature in III-V quantum-dot materials. Hysteresis loops in the curves are attributed to hot electron injection/emission process of quantum dots, which indicates the concomitant charging/discharging effect. (c) 2006 The Electrochemical Society.

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Real-time detection of single electron tunneling through a T-shaped double quantum dot is simulated, based on a Monte Carlo scheme. The double dot is embedded in a dissipative environment and the presence of electrons on the double dot is detected with a nearby quantum point contact. We demonstrate directly the bunching behavior in electron transport, which leads eventually to a super-Poissonian noise. Particularly, in the context of full counting statistics, we investigate the essential difference between the dephasing mechanisms induced by the quantum point contact detection and the coupling to the external phonon bath. A number of intriguing noise features associated with various transport mechanisms are revealed.

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We have conducted numerical studies of ballistic electron transport in a semiconductor II-structure when an external transverse electric field is applied. The device conductance as a function of electron energy and the strength of the transverse electric field is calculated on the basis of tight-binding Green's function formalism. The calculations show that a relatively weak electric field can induce very large decrease in the electron transmission across the structure. When the transverse electric field is sufficiently strong, electrons can hardly be transported through the device. Thus the performance of the device can be greatly improved for it is much easier to control electron transport through the device with an external transverse electric field.

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本研究通过粗枝云杉不同种群进行的温室半控制试验,采用植物生态学、生理学和生物化学的研究方法,系统地研究了粗枝云杉不同种群抗旱性的生长、形态、生理和生化机理,并结合有关研究进行综合分析,得出主要研究结论如下: 1.粗枝云杉对干旱胁迫的综合反应 粗枝云杉在干旱胁迫下的适应机制为:(1)相对生长速率及植株结构的调整:干旱胁迫下虽然植株相对生长速率显著降低,且有相对较多的生物量向根部分配,但并未发现细根/总根比增加。(2)粗枝云杉对干旱胁迫的光合作用表现为:干旱胁迫显著地降低了控制的理想条件下的气体交换,但干旱胁迫对PSII最大光化学效率(Fv/Fm)没有影响,表明干旱并未影响到光合机构。(3)干旱还影响了很多生理生化过程,包括渗透调解物质(游离脯氨酸)、膜脂过氧化产物、脱落酸(ABA)含量的增加,以及保护酶活性的升高。这些结果证明植物遭受干旱胁迫后发生了一系列的形态、生理和生化响应,这些变化能提高干旱时期植物的存活和生长能力。 2.粗枝云杉不同种群对干旱胁迫反应的种群差异 粗枝云杉三个种群-干旱种群(四川丹巴和甘肃迭部)和湿润种群(四川黑水)对干旱适应不同,这种不同应归因于它们采用的用水策略不同:在水分良好和干旱胁迫条件下,受试种群在相对生长速率和水分利用效率(WUE)方面都表现出显著的种群间差异。与湿润种群相比,干旱种群在两种水分条件下有更高的WUE。粗枝云杉不同种群的碳同位素组分(δ13C)只在干旱胁迫下有显著差异,并且这种差异在水分良好时比干旱胁迫条件下小,说明生理响应和干旱适应性之间的关系受植物内部抗旱机制和外部环境条件(如水分可利用性)或两者互作效应的影响。这些结果说明干旱种群和湿润种群所采用的用水策略不同。干旱种群有更强的抗旱能力,采用的是节水型的用水策略,而湿润种群抗旱能力较弱,采用的是耗水型的用水策略。 3. 遮荫对粗枝云杉不同种群抗旱性影响 干旱胁迫显著降低了全光条件下叶相对含水量(RWC)、相对生长速率、气体交换参数、PSII的有效量子产量(Y),提高了非光化学猝灭效率(qN)、水分利用效率、脯氨酸(PRO)积累、脱落酸(ABA)含量及保护酶活性。然而这种变化在遮荫条件下不明显。我们得出结论适度遮荫降低了干旱对植物的胁迫作用。另一方面,在干旱条件下,与湿润种群相比,干旱种群抗旱性更强,表现在干旱种群净光合速率与单位重量上叶氮含量(Nmass)降低较少。另外,干旱种群表现出更为敏感的气孔导度,更高的热耗散能力(qN)能力、用水效率、ABA积累、保护酶活性,以及更低的总用水量、相对生长速率。这一结果表明这两种群采用不同的生理策略对干旱和遮荫做出反应。许多生长和生理反应差异与这两个种群原产地气候条件相适应。 4. 外源脱落酸(ABA)喷施对粗枝云杉不同种群抗旱性影响 外源ABA喷施在干旱和水分良好条件下均不同程度地提高了根/茎比,表明根和茎对ABA敏感程度不同。实验结果还表明,外源ABA喷施对这两个种群在干旱胁迫期间影响不同。干旱胁迫期间,伴随着ABA喷施,湿润种群净光合速率(A)显著降低,而干旱种群净光合速率变化不明显。另一方面,外源ABA喷施显著提高了干旱条件下干旱种群的单位叶面积重(LMA)、根/茎比、细根/总根(Ft)比、水分利用效率(WUE)、ABA含量, 以及保护酶活性。然而,外源ABA喷施对湿润种群的上述测定指标没有显著影响。这一结果表明干旱种群对外源ABA喷施更为敏感, 反应在更大的气孔导度降低,更高的生物量可塑性,及更高的水分利用效率、ABA含量和保护酶活性。综上所述,我们得出结论,粗枝云杉对外源ABA敏感性因种群的不同而不同。该研究结果可为两个明显不同种群在适应分化方面提供强有力的证据。 Arid or semi-arid land covers more than half of China's land territory. In arid systems, severe shortages of soil water often coincide with periods of high temperatures and high solar radiation, producing multiple stresses on plant performance. Protection from high radiation loads in shaded microenvironments during drought may compensate for a loss of productivity due to reduced irradiance when water is available. Additionally, ABA, a well-known stress-inducible plant hormone, has long been studied as a potential mediator for induction of drought tolerance in plants. Picea asperata Mast., which is one of the most important tree species used for the production of pulp wood and timber, is a prime reforestation species in western China. In this experiment, different population of P. asperata were used as experiment material to study the adaptability to drought stress and population differences in adaptabiliy, and the effects of shade and exogenous abscisic acid (ABA) application on the drought tolerance. Our results cold provide a strong theoretical evidence and scientific direction for the afforestation, and rehabilitation of ecosystem in the arid and semi-arid area, and provide a strong evidence for adaptive differentiation of different populations, and so may be used as criteria for species selection and tree improvement. The results are as follows: 1. A large set of parallel response to drought stress Drought stress caused pronounced inhibition of the growth and increased relatively dry matter allocation into the root; drought stress also caused pronounced inhibition of photosynthesis, while drought showed no effects on the maximal quantum yield of PSII photochemistry (Fv/Fm) in dark-adapted leaves, indicating that drought had no effects on the primary photochemistry of PSII. However, in light-adapted leaves, drought reduced the quantum yield of PSII electron transport (Y) and increased the non-photochemical quenching (qN). Drought also affected many physiological and biochemical processes, including increases in superoxide dismutase (SOD), ascorbate peroxidase (APX) activities, malondialdehyde and ABA content. These results demonstrate that there are a large set of parallel changes in the morphological, physiological and biochemical responses when plants are exposed to drought stress; these changes may enhance the capability of plants to survive and grow during drought periods. 2. Difference in adaptation to drought stress between contrasting populations of Picea asperata There were significant population differences in growth, dry matter allocation and water use efficiency. Compared with the wet climate population (Heishui), the dry climate population (Dan ba and Jiebu) showed higher LMA, fine root/total root ratio and water use efficiency under drought-stressed treatments. The results suggested that there were different water-use strategies between the dry population and the wet population. The dry climate population with higher drought tolerance may employ a conservative water-use strategy, whereas the wet climate population with lower drought tolerance may employ a prodigal water-use strategy. These variations in drought responses may be used as criteria for species selection and tree improvement. 3. The effects of shade on the drought tolerance For both populations tested, drought resulted in lower needle relative water content (RWC), relative growth rate (RGR), gas exchange parameters and effective PSII quantum yield (Y), and higher non-photochemical quenching (qN), water use efficiency (WUE), proline (PRO) and abscisic acid (ABA) accumulation, superoxide dismutase (SOD), ascorbate peroxidase (APX) activities as well as malondialdehyde (MDA) levels and electrolyte leakage in sun plants, whereas these changes were not significant in shade plants. Our study results implied that shade, applied together with drought, ameliorated the detrimental effects of drought. On the other hand, compared with the wet climate population, the dry climate population was more tolerant to drought in the sun treatment, as indicated by less decreases in A and mass-based leaf nitrogen content (Nmass), more responsive stomata, greater capacity for non-radiative dissipation of excitation energy as heat (analysed by qN), and higher WUE,higher level of antioxidant enzyme activities,higher ABA accumulation as well as lower MDA content and electrolyte leakage. Many of the differences in growth and physiological responses reported here are consistent with the climatic differences between the locations of the populations of P. asperata. 4. The effects of exogenous abscisic acid (ABA) application on the drought tolerance For both populations tested, exogenous ABA application increased root/shoot ratio (Rs) under well-watered and drought-stressed conditions, indicating that there was differential sensitivity to ABA in the roots and shoots. However, it appeared that ABA application affected the two P. asperata populations very differently during drought. CO2 assimilation rate (A) was significantly decreased in the wet climate population, but only to a minor extent in the dry climate population following ABA application during soil drying. On the other hand, ABA application significantly decreased stomatal conductance (gs), transpiration rate (E) and malondialdehyde (MDA) content, and significantly increased leaf mass per area (LMA), Rs, fine root/total root ratio (Ft), water use efficiency (WUE), ABA contents, superoxide dismutase (SOD), ascorbate peroxidase (APX) and catalase (CAT) activities under drought condition in the dry climate population, whereas ABA application did not significantly affect these parameters in the wet population plants. The results clearly demonstrated that the dry climate population was more responsive to ABA application than the wet climate population, as indicated by the strong stomata closure and by greater plasticity of LMA and biomass allocation, as well as by higher WUE, ABA content and anti-oxidative capacity to defense against oxidative stress, possibly predominantly by APX. We concluded that sensitivity to exogenous ABA application is population dependent in P. asperata. Our results provide strong evidence for adaptive differentiation between populations of P. asperata.

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由于人类活动所引起的地球大气层中温室气体的富集已导致全球地表平均温度在20 世纪升高了0.6 ¡æ,并预测在本世纪将上升1.4-5.8 ¡æ。气候变暖对陆地植物和生态系统产生深远影响,并已成为全球变化研究的重要议题。位于青藏高原东部的川西亚高山针叶林是研究气候变暖对陆地生态系统影响的重要森林类型。森林采伐迹地和人工云杉林下作为目前该区人工造林和森林更新的两种重要生境,二者截然不同的光环境对亚高山针叶林不同物种更新及森林动态有非常重要的影响。 本文以青藏高原东部亚高山针叶林几种主要森林树种为研究对象,采用开顶式增温法(OTCs)模拟气候变暖来研究增温对生长在两种不同光环境下(全光条件和林下低光环境)的几种幼苗早期生长和生理的影响,旨在从更新角度探讨亚高山针叶林生态系统不同树种对气候变暖在形态或生理上的响应差异,其研究结果可在一定程度上为预测气候变暖对亚高山针叶林物种组成和演替动态提供科学依据,同时也可为未来林业生产管理者提供科学指导。 1、与框外对照相比,OTCs 框内微环境发生了一些变化。OTCs 框内与框外对照气温年平均值分别为5.72 ¡æ和5.21 ¡æ,而地表温度年平均值分别为5.34 ¡æ和5.04 ¡æ,OTCs 使气温和地表年平均温度分别提高了0.51 ¡æ和0.34 ¡æ;OTCs框内空气湿度年平均值约高于框外对照,二者分别为90.4 %和85.3 %。 2、增温促进了三种幼苗生长和生物量的积累,但增温效果与幼苗种类及所处的光环境有关。无论在全光或林下低光条件下,增温条件下云杉幼苗株高、地径、分支数、总生物量及组分生物量(根、茎、叶重)都显著地增加;增温仅在全光条件下使红桦幼苗株高、地径、总生物量及组分生物量(根、茎、叶重)等参数显著地增加,而在林下低光条件下增温对幼苗生长和生物量积累的影响效果不明显;冷杉幼苗生长对增温的响应则与红桦幼苗相反,增温仅在林下低光条件下对冷杉幼苗生长和形态的影响才有明显的促进作用。 增温对三种幼苗的生物量分配模式产生了不同的影响,并且这种影响也与幼苗所处的光环境有关。无论在全光或林下低光环境下,增温都促使云杉幼苗将更多的生物量分配到植物地下部分,从而导致幼苗在增温条件下有更高的R/S 比;增温仅在林下低光条件下促使冷杉幼苗将更多的生物量投入到植物叶部,从而使幼苗R/S 比显著地降低;增温在全光条件下对红桦幼苗生物量分配的影响趋势与冷杉幼苗在低光条件下相似,即增温在全光条件下促使红桦幼苗分配更多的生物量到植物同化部分—叶部。 3、增温对亚高山针叶林生态系统中三种幼苗气体交换和生理表现的影响总体表现为正效应(Positive),即增温促进了几种幼苗的生理活动及其表现:(i)无论在全光或林下低光环境下,增温使三种幼苗的光合色素含量都有所增加;(ii)增温在一定程度上提高了三种使幼苗的PSII 光系统效率(Fv/Fm),从而使幼苗具有更强的光合电子传递活性;增温在一定程度使三种幼苗潜在的热耗散能力(NPQ)都有所增强,从而提高幼苗防御光氧化的能力;(iii)从研究结果来看,增温通过增加光合色素含量和表观量子效率等参数而促进幼苗的光合作用过程。总体来说增温对幼苗生理过程的影响效果与幼苗种类及所处的光环境有关,增温仅在全光条件下对红桦幼苗光合过程的影响才有明显的效果,而冷杉幼苗则相反,增温仅在低光条件下才对幼苗的生理过程有显著的影响。 4、增温对三种幼苗的抗氧化酶系统产生了一定的影响。从总体来说,增温使几种幼苗活性氧含量及膜脂过氧化作用降低,从而在一定程度上减轻了该区低温对植物生长的消极影响;增温倾向表明使三种幼苗体内抗氧化酶活性和非酶促作用有所提高,从而有利于维持活性氧代谢平衡。但增温影响效果与幼苗种类所处的光环境及抗氧化酶种类有关,增温对冷杉幼苗抗氧化酶活性的影响仅在林下低光环境下效果明显,而对红桦幼苗抗氧化酶活性的影响仅在全光条件下才有明显的效果。 总之,增温促进了亚高山针叶林生态系统中三种幼苗的生长和生理表现,但幼苗生长和生理对增温的响应随植物种类及所处的光环境不同而变化,这种响应差可能异赋予了不同植物种类在未来气候变暖背景下面对不同环境条件时具有不同的适应力和竞争优势,从而对亚高山针叶林生态系统物种组成和森林动态产生潜在的影响。 Enrichment of atmospheric greenhouse gases resulted from human activities suchas fossil fuel burning and deforestation has increased global mean temperature by 0.6¡æ in the 20th century and is predicted to increase it by 1.4-5.8 ¡æ. The globalwarming will have profound, long-term impacts on terrestrial plants and ecosystems.The ecoologcial consequences arising from global warming have also become thevery important issuses of global change research. The subalpine coniferous forests inthe eastern Qinghai-Tibet Plateau provide a natural laboratory for the studying theeffects of climate warming on terrestrial ecosystems. The light environment differssignificantly between clear-outs and spruce plantations, which is particularlyimportant for plant regeneration and forest dynamics in the subalpine coniferous forests. In this paper, the short-term effects of two levels of air temperature (ambient andwarmed) and light (full light and ca. 10% of full light regimes) on the early growthand physiology of Picea asperata, Abies faxoniana and Betula albo-sinensis seedlingswas determined using open-top chambers (OTCs). The aim of the present study wasto understand the differences between tree species in their responses to experimentalwarming from the perspective of regeneration. Our results could provide insights intothe effects of climate warming on community composition and regeneration behavior for the subalpine coniferous forest ecosystem processes, and provide scientificdirection for the production and management under future climate change. 1. The OTCs manipulation slightly altered thermal conditions during the growingseason compared with the outside chambers. The annual mean air temperature andsoil surface temperature was 5.72 and 5.34 ¡æ (within the chambers), and 5.21 and5.04 ¡æ (outside the chambers), respectively. The OTCs manipulation increased airtemperature and soil surface temperature by 0.51 and 0.34 ¡æ on average, respectively.Air relative humidity was slightly higher inside the OTCs compared with the controlplots, with 90.4 and 85.3 %, respectively. 2. Warming generally stimulated the growth and biomass accumulation of thethree tree species, but the effects of warming on growth and development variedbetween light conditions and species. Irrespective of light regimes, warmingsignificantly increased plant height, root collar diameter, total biomass, componentbiomass (stem, foliar and root biomass) and the number of branches in P. asperataseedlings; For A. faxoniana seedlings, significant effects of warming on all the tested parameters (plant height, root collar diameter, total biomass, and component biomass) were found only under low light conditions; In contrast, the growth responses of B.albo-sinensis seedlings to warming were found only under full light conditions. Warming had pronounced effects on the pattern of carbon allocation. Irrespectiveof light regimes, the P. asperata seedlings allocated relatively more biomass to rootsin responses to warming, which led to a higher R/S. Significant effects of warming onbiomass allocation were only found for the A. faxoniana seedlings grown under lowlight conditions, with significantly increased in leaf mass ratio (LMR) and decreasedin R/S in responses to warming manipulation. The carbon allocation responses of B.albo-sinensis seedling to warming under full light conditions were similar with theresponse of A. faxoniana seedlings grown under low light conditions. Warmingsignificantly decreased root mass ratio (RMR), and increased leaf mass ratio (LMR)and shoot/root biomass ratio (S/R) for the B. albo-sinensis seedlings grown under full light conditions. 3. Warming generally had a beneficial effect on physiological processes of dominant tree species in subalpine coniferous forest ecosystems: (i) Warming markedincreased the concentrations of photosynthetic pigments in both tree species, but theeffects of warming on photosynthetic pigments were greater under low lightconditions than under full light conditions for the two conifers; (ii) Warming tended toenhance the efficiency of PSII in terms of increase in Fv/Fm, which was related tohigher chloroplast electron transport activity; and enhance non-radiative energydissipation in terms of in increase in NPQ, which may reflect an increased capacity inpreventing photooxidation; (iii) Warming may enhance photosynthesis and advancephysiological activity in plants by increasing photosynthetic pigment concentration,the efficiency of PSII and apparent quantum yield (Φ) etc. From the results, theeffects of warming on seedlings’ physiological performance varied between lightenvironment and species. The effects of warming on photosynthesis performance of B.albo-sinesis seedlings were pronounced only under full light conditions, while thephysiological responses of A. faxoniana seedlings to warming were found only underthe 60-year plantation. These results provided further support for the observationsabove on growth responses of seedlings to warming. 4. Warming had marked effects on antioxidative systems of the three seedlings.Warming generally decreased H2O2 accumulation and the rate of O2- production, andalleviated degree of lipid peroxidation in terms of decreased MDA content, whichalleviated to some extent the negative effects of low temperature on the plant growthand development in this region; Warming tended to increase the activities ofantioxidative enzymes and stimulate the role of non-enzymatic AOS scavenging,which helped to create an balance in maintaining AOS metabolites for the threeseedlings. Nevertheless, the effects of warming on antioxidative defense systems werepronounced only under the 60-year plantation for the A. faxoniana seedlings. Incontrast, the marked effects of warming on antioxidative defense systems for the B.albo-sinesis seedlings were found only under the full light conditions. In sum, warming is considered to be generally positive in terms of growth andphysiological process. However, the responses of growth and physiology performanceto warming manipulation varied between species and light regimes. Competitive and adaptive relationships between tree species may be altered as a result of responsedifferences to warming manipulation, which is one mechanism by which globalwarming will alter species composition and forest dynamics of subalpine coniferousforest ecosystems under future climate change.

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The structures, properties and electron transfer reactivity of the ClO/ClO+ coupling system are studied in this paper at ab initio (HF and MP2) levels and the density functional theory (DFT: B3LYP, B3P86, B3PW91) levels employing 6311 + G(3df) basis set and on the basis of the golden-rule of the time-dependent perturbation theory. Investigations indicate that the results got from the B3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated by using the B3LYP/6-311 + G(3df) method, and then the electron transfer rates are determined at this level. The electronic coupling matrix element of EC.6 is very small, only 0.03 kcal/mol, while that of EC.7 is the biggest, being 12.41 kcal/mol, the corresponding electron transfer rate is also the fastest among these seven encounter complexes. The averaged electron transfer rate is about 1.672 X 10(11) M-1 s(-1). It is indicated that the structures optimized by B3LYP method are more reliable than the results got from the other four methods. It also testified that the electronic coupling matrix element is the vital factor that significantly affects the electron transfer rate. (C) 2003 Elsevier B.V. All rights reserved.

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The structures, properties and electron transfer reactivity of the ClO/ClO- coupling system are studied in this paper at ab initio (UHF and UMP2) levels and the Density Functional Theory (DFT: UB3LYP, UB3P86, UB3PW91) levels employing 6311 + G(3df) basis set and on the basis of the Golden-rule of the time-dependent perturbation theory. Investigations indicate that the results obtained using the UB3LYP method employing 6-311 + G(3df) basis set is in excellent agreement with the experiment. For this coupling system, six stable coupling modes have been found which correspond to six different encounter complexes and denote six different electron transfer mechanism: four O-O directly linked structures (one collinear: D-h, one anti-parallel: C-s, two twist: C-2) and two Cl-O linked structures (cis- and anti- C-s structures). The activation energies, the stabilization energies and the electronic coupling matrix elements have also been calculated for the electron transfer reactions via these six different mechanism at the UB3LYP/6-311 + G(3df) level, and then the electron transfer rates are determined at the same level. The most favorable coupling mode to the electron transfer is the anti-parallel mechanism. The averaged electron transfer rate is about 5.58 X 10(11) M-1 s(-1). It is also implied that the B3LYP method can give more reasonable results for the electron transfer reactivity of this system. (C) 2003 Elsevier B.V. All rights reserved.

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The dependence of electron conduction of oligo(1,4-phenylene ethynylene)s (OPEs) on length, terminal group, and main chain structure was examined by conductive probe-atomic force microscopy (CP-AFM) via a metal substrate-molecular wire monolayer-conductive probe junction. The electron transport in the molecular junction was a highest occupied molecule orbital (HOMO)-mediated process following a coherent, non-resonant tunneling mechanism represented by the Simmons equation.

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In this paper, it was found that glucose oxidase (GOD) has been stably immobilized on glassy carbon electrode modified with mesoporous carbon FDU-15 (MC-FDU-15) and Nafion by simple technique. The sorption behavior of GOD immobilized on MC-FDU-15 matrix was characterized by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis), FTIR, respectively, which demonstrated that MC-FDU-15 could facilitate the electron exchange between the active center of GOD and electrode. The direct electrochemistry and electrocatalysis behavior of GOD on the modified electrode were characterized by cyclic voltammogram (CV) which indicated that GOD immobilized on Nafion and MC-FDU-15 matrices display direct, reversible and surface-controlled redox reaction with an enhanced electron transfer rate constant of 4.095 s(-1) in 0.1 M phosphate buffer solution (PBS) (pH 7.12).

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Supramolecular organized multilayers were constructed by multiwalled carbon nanotubes modified with ferrocene-derivatized poly(allylamine) redox polymer and glucose oxidase by electrostatic self-assembly. From the analysis of voltammetric signals and fluorescence results, a linear increment of the coverage of enzyme per bilayer was estimated, which demonstrated that the multilayer is constructed in a spatially ordered manner. The cyclic voltammograms obtained from the indium tin oxide (ITO) electrodes coated by the (Fc-PAH@CNT/GOx)(n) multilayers revealed that bioelectrocatalytic response is directly correlated to the number of deposited bilayers; that is, the sensitivity is tunable by controlling the number of bilayers associated with ITO electrodes. The incorporation of redox-polymer-functionalized carbon nanotubes (CNT) into enzyme films resulted in a 6-10-fold increase in the glucose electrocatalytic current; the bimolecular rate constant of FADH(2) oxidation (wiring efficiency) was increased up to 12-fold. Impedance spectroscopy data have yielded the electron diffusion coefficient (D-e) of this nanostructure to be over 10(-8) cm(2) s(-1), which is typically higher than those systems without CNT by at least a factor of 10, indicating that electron transport in the new supramolecular architecture was enhanced by communication of the redox active site of enzyme, redox polymer, and CNT.

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New carbazole-based copolymers, which contain various concentrations of 9-alkyl-3, 6-carbazole fragments in the main chain connected via alkylene spacers, have been synthesized by Ni(0)-catalyzed Yamamoto-type aryl-aryl coupling reactions. Full characterization of the copolymer structure by NMR spectroscopy and elemental analysis is presented. These compounds represent amorphous materials of high thermal stability with glass transition temperatures of 151-162 degrees C and thermal decomposition starting at temperatures > 390 degrees C. UV-Vis absorption and photoluminescence emission of the copolymers confirmed that the effectively conjugated segment in the 3,6-linked carbazole-type copolymers is limited to dyads (dimeric units). However, copolymers with varying concentrations of the oligocarbazole chromophores demonstrate different charge injection and transport properties in multilayer light-emitting diodes with the copolymers as the hole transport and Alq(3) as the electroluminescent/electron transport layer. The device based on a copolymer composed of oligocarbazole blocks with an average length of around four carbazoles exhibited the best overall performance with a turn-on voltage of 3.5 V, a maximal photometric efficiency of 4.1 cd center dot A(-1) and maximum brightness of about 4 200 cd center dot m(-2).

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Lithium acetylacetonate [Li(acac)] covered with aluminium was used as an efficient electron injection layer in organic light-emitting devices (OLEDs) consisting of NPB as the hole transport layer and Alq(3) as the electron transport and light emitting layer, resulting in lower turn- on voltage and increased current efficiency. The turn- on voltage (the voltage at a luminance of 1 cd m(-2)) was decreased from 5.5 V for the LiF/Al and 4.4 V for Ca/Al to 4.0 V for Li(acac)/Al, and the device current efficiency was enhanced from 4.71 and 5.2 to 7.0 cd A(-1). The performance tolerance to the layer thickness of Li(acac) is also better than that of the device with LiF. LiF can only be used when deposited as an ultra- thin layer because of its highly insulating nature, while the Li(acac) can be as thick as 5 nm without significantly affecting the EL performance. We suppose that the free lithium released from Li(acac) improves the electron injection when Li(acac) is covered with an Al cathode.

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We analyze current versus voltage data obtained using single carrier injection in several metal/polymer/metal sandwich structures. The polymer used in each case is a soluble blue-emitting alternating block copolymer. Our experimental results demonstrate that the electron transport is space-charge limited by the high density of traps having an exponential energy distribution (temperature dependent characteristic energy) in the copolymer. The electron mobility of 8x10(-10) cm(2)/V s is directly determined using space-charge-limited current analytical expressions. Hole transport is also space-charge limited, with a mobility of 2x10(-6) cm(2)/V s. A hole trap with energy 0.17 eV is observed. We compare these results with those obtained for related block copolymers with different spacer and conjugated segment lengths and discuss the influence of spacer length and conjugated segment length on the charge transport properties. (C) 2000 American Institute of Physics. [S0021-8979(00)04501-1].

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The heterogeneous electron transfer rate constants (k(s)) of seven ferrocene derivatives were estimated using cyclic voltammograms under mixed spherical/semi-infinite linear diffusion and steady-state voltammetry at a microdisk electrode in polymer electrolyte. The k(s) and diffusion coefficient (D) are both 100 to 1000-fold smaller in polymer solvent than in monomeric solvents, and the D and k(s) decrease with increasing polymer chain length. The results conform to the difference of viscosity (eta) or relaxation time (tau(L)) for these different solvents. The k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction are obtained. The influences of the substituting group in the ferrocene ring on k(s) and D are discussed. The k(s) are proportional to the D of the ferrocene derivatives, which indicates that solvent dynamics control the electrode reaction. (C) 1998 Elsevier Science S.A.