A STUDY ON THE LUMINESCENCE PROPERTIES OF EU3+ AND DY3+ IN M(2)RE(8)(SIO4)(6)O-2 (M=MG, CA RE=Y, GD, LA)

In this paper, the luminescence properties of Eu3+ and Dy3+ in the oxyapatites M(2)RE(8)(SiO4)(6)O-2 (M=Mg, Ca; RE=Y, Gd, La) were studied. The spectral characters of Eu3+ were discussed in relation to the crystal structure. The dependence of the red-to-orange intensity ratio and the position of the charge transfer band of Eu3+ and the yellow-to-blue intensity ratio of Dy3+ together with their fluorescence intensities (I-R for Eu3+ and I-Y for Dy3+) On the M(2+) and the substitution of BO45- and PO43- for SiO44- was discussed. Finally, the concentration quenching of Dy3+ luminescence was reported.

THE RELATIONSHIP AMONG OXYGEN-CONTENT, DEFECT DISTRIBUTION AND SUPERCONDUCTIVITY IN BISRCACUO SYSTEMS

The effect of oxygen content on superconductivity of the 2212 and 2223 phase has been studied. By comparing the excess oxygen, the modulation vector, the XRD patterns, and the electric resistivity of 2212 and 2223 phase samples obtained with different post-annealing conditions, i.e., annealing at 600-degrees-C or quenching from 860-degrees-C, it was found that the superconductivity is markedly influenced by both the defect distribution in non-Bi layers and the interstitial oxygens incorporated in the Bi-O layers. A tentative explanation for this is given.

THERMAL-OXIDATION OF POLYPROPYLENE CONTAINING HINDERED PIPERIDINE COMPOUNDS

The thermal oxidation behaviour of polypropylene containing tetramethylpiperidine compounds and corresponding pentamethylpiperidine compounds are compared using air oven aging, oxygen uptake and thermogravimetry. Carbonyl formation, the induction period of oxygen absorption and weight loss have been selected to characterize the degree of oxidation. The results show that the stabilizing effectiveness of pentamethylpiperidines is always higher than that of tetramethyl types. Radical-trapping mechanisms cannot explain this, because large amounts of nitroxyl radicals are formed by the tetramethylpiperidine compounds. The quenching of singlet oxygen appears to be involved in thermal oxidation of polypropylene containing pentamethylpiperidine compounds. Specific hydrogen bonding between pentamethylpiperidines and hydroperoxide may account for their better thermal stabilizing action than tetramethylpiperidines.

INVESTIGATION ON THE LUMINESCENCE PROPERTIES OF DY3+ AND EU3+ IN M3LN2(BO3)4 (M=CA, SR, BA, LN= LA, GD, Y)

In this paper, the luminescence properties of Dy3+ and Eu3+ in M3Ln2 (BO3)4 (M = Ca,Sr,Ba; Ln = La, Gd, Y) were systematically studied. The hypersensitive transitions of Dy3+ and Eu3+ were investigated in relation to the host compositions; the relationship between the energy of Eu3+ charge-transfer band and M2+ ion was discussed, and the concentration quenching of Dy3+ luminescence was reported.

Three-stage transformation of chlorophyll transient fluorescence pattern under sustained dehydration and the discovery of critical water content in seaweeds

The chlorophyll fluorescence kinetics of marine red alga Grateloupia turutunt Yamada, green alga Ulva pertusa Kjellm and brown alga Laminaria japonica Aresch during natural sustained dehydration were monitored and investigated. The pulse amplified modulation (PAM) system was used to analyze the distinct fluorescence parameters during thallus dehydration. Results proved that the fluorescence kinetics of different seaweed all showed three patterns of transformation with sustained water loss. These were: 1) peak kinetic pattern (at the early stage of dehydration fluorescence enhanced and quenched subsequently, representing a normal physiological state). 2) plateau kinetic pattern (with sustained water loss fluorescence enhanced continuously but quenching became slower, finally reaching its maximum). 3) Platform kinetic pattern (fluorescence fell and the shape of kinetic curve was similar to plateau kinetic pattern). A critical water content (CWC) could be found and defined as the percentage of water content just prior to the fluorescence drop and to be a significant physiological index for evaluation of plant drought tolerance. Once thallus water content became lower than this value the normal peak pattern can not be recovered even through rehydration, indicating an irreversible damage to the thylakoid membrane. The CWC value corresponding to different marine species were varied and negatively correlated with their desiccation tolerance, for example. Laminaria japonica had the highest CWC value (around 90%) and the lowest dehydration tolerance of the three. In addition, a fluorescence "burst" was found only in red algae during rehydration. The different fluorescence parameters F-o, F-v and F-v, F-m were measured and compared during water loss. Both F-o and F-v increased in the first stage of dehydration but F-v/F-m. kept almost constant. So the immediate response of in vivo chlorophyll fluorescence to dehydration was an enhancement. Later with sustained dehydration F-o increased continuously while F-v decreased and tended to become smaller and smaller. The major changes in fluorescence (including fluorescence drop during dehydration and the burst during rehydration) were all attributed to the change in F-o instead of F-v This significance of F-o indicates that it is necessary to do more research on F-o as well as on its relationship with the state of thylakoid membrane.

Temperature tolerance of young sporophytes from two populations of Laminaria japonica revealed by chlorophyll fluorescence measurements and short-term growth and survival performances in tank culture

The cold-water subtidal brown alga Laminaria japonica has been commercially fanned in the Far East and has been on top of all marine-fanned species in terms of farming area and annual output worldwide. The successful trials of transplantation of young sporophytes from the north to the south in winter along the Chinese coast in the 1950s led to the spreading of cultivation activities down to a latitude of 25-26 degrees N. Up to today, nearly 50% of the annual output of this farmed alga, as a cold-water species, comes from the sub-tropical south in China. The demand to have high-temperature-tolerant strains/ecotypes in farming area calls for a practical method to judge and select the desired parental plants for breeding programs and for seedling production. In this paper, we report our results on using chlorophyll fluorescence measurement and short-term growth performance in tank culture to estimate the temperature tolerance of offspring from two populations, Fujian Farmed Population (FFP) sampled from Fujian province (latitude: 25-26 degrees N) in subtropical area and Qingdao Wild Population (QWP) sampled from Qingdao (latitude: 36 degrees N). Contrary to what has been usually thought, the results revealed that offspring from Qingdao wild population in the north showed better performance both in short-term growth and survival rates and in optimal quantum efficiency (F-v/F-m) when exposed to higher temperature (20-25 degrees C). This result was further confirmed by fluorescence quenching analysis. QWP distributed along the southern distribution limit at a latitude of 36 degrees N in the Pacific west coast is thus taken as a more ideal one than the fanned population in subtropical region as a source of parental plants for breeding high-temperature-tolerant varieties. (c) 2006 Elsevier B.V. All rights reserved.

雨生红球藻Rubisco在虾青素积累过程中的表达分析

虾青素因其具有极强的抗氧化性及优越的着色作用，被广泛应用于营养保健和水产养殖中，备受国内外研究者的关注。红球藻是目前虾青素的生物来源中较有优势的一条途径。 我们选取雨生红球藻作为研究材料，收集其生长过程中四个不同的阶段，分别为绿色游动细胞阶段，绿色不动细胞阶段，绿褐色不动细胞阶段（开始积累虾青素），以及红色不动孢子阶段。本研究中提取了核酮糖-1,5-二磷酸羧化/加氧酶（Rubisco）的粗提液，并测定了酶活。其编码基因rbcL的mRNA表达量也被测定。另外，光合速率与呼吸速率的比值（P/R）通过测定与计算得出，各个阶段藻细胞中虾青素的含量由分析得出。本研究还应用了叶绿素荧光测定方法，确定了光系统II潜在最大活性（Fv / Fm），光系统II实际活性（ΦPSII），电子传递速率（ETR）和非光化学淬灭参数（NPQ）。 结果表明，绿色游动细胞的生长状态最佳，其P/R、Fv / Fm、ΦPSII均为最大，NPQ为最小。这说明在此状态的细胞中，光系统II的活性最强；但是其Rubisco活性与rbcL表达量均为最小。相比之下，在绿褐色不动细胞中，P/R和NPQ的值较低，Fv / Fm、ΦPSII和ETR值都最小，但Rubisco活性与rbcL表达量均为最高。 结合工业生产虾青素的方法，我们认为，Rubisco或许参与了虾青素的合成，而非Calvin循环为色素合成提供前体和能量。因此，在生产过程中适当加入碳源，比如CO2，可以有效增大虾青素的产量。

Response of chlorophyll fluorescence to dynamic light in three alpine species differing in plant architecture

A study was carried out to examine the effect of dynamic photosynthetically active photon flux density (PPFD) on photoinhibition and energy use in three herbaceous species, prostrate Saussurea superba, erect-leaved S. katochaete, and half-erect-leaved Gentiana straminea, from the Qinghai-Tibet Plateau. Chlorophyll fluorescence response was measured under each of three sets of high-low PPFD combinations: 1700-0, 1400-300, and 1200-500 mu mol m(-2) s(-1), illuminating in four dynamic frequencies: 1, 5, 15, and 60 cycles per 2 h. The total light exposure time was 2h and the integrated PPFD was the same in all treatments. The highest frequency of PPFD fluctuation resulted in the lowest photochemical activity, the highest level of non-photochemical quenching, and the greatest decrease of F-v/F-m (maximal photochemical efficiency of PSII). The 5 and 15 cycles per 2h treatments resulted in higher photochemical activity than the 1 cycle per 2h treatment. The 1700-0 PPFD combination led to the lowest photochemical activity and more serious photoinhibition in all species. S. superba usually exhibited the highest photochemical activity and CO2 uptake rate, the lowest reduction of F-v/F-m,F- and the smallest fraction of energy in thermal dissipation. With similar fractions of thermal dissipation, S. katochaete had relatively less photoinhibition than G. straminea owing to effective F-o quenching. The results suggest that high frequency of fluctuating PPFD generally results in photoinhibition, which is more serious under periods of irradiation with high light intensity. (c) 2005 Elsevier B.V. All rights reserved.

基于人工神经网络的PC钢棒力学性能预报模型

提出一种PC钢棒抗拉强度的人工神经网络模型方法,采用4×9×1的三层前向BP网络结构,模型主要因素为淬火温度、回火温度、含碳量和单位长度质量。经1500余次训练后,误差平方和

高温高压下水热体系中黄铁矿-金原电池的腐蚀电化学原位测量研究

水流体-导电性矿物相互作用是自然界中水流体-固体相互作用的重要组成部分，是许多矿床形成和演化的核心过程。迄今为止，绝大多数地质和地球化学家们对导电性矿物在水流体中的溶解机制普遍存在模糊的认识，认为水流体中导电性矿物的溶解和定位是一种简单的化学溶解和沉淀或简单的氧化溶解和还原定位过程，而实质上导电性矿物（组合）在水流体中的溶解是一种由电极电位差驱使下的类似于金属腐蚀的复杂电化学过程。当具有不同电极电位的矿物在溶液中相互接触，就会形成短路原电池发生电化学腐蚀。其中，电极电位低的矿物作为原电池的阳极，其溶解会加剧，而电极电位高的矿物作为原电池的阴极，其溶解会受到抑制。鉴于前人对水流体-导电性矿物相互作用的腐蚀原电池反应机理的模糊认识，本论文工作基于腐蚀原电池观点对高温高压条件下NaCl水流体体系中黄铁矿与金之间的原电池反应进行了研究。 在本工作中，作者与所在的研究小组一道，首先自行研制了一套可用于高温高压水热体系中导电性矿物腐蚀电化学原位测量的高压釜反应装置。该装置主体部件选用在高温高压下具有高强度、抗腐蚀等优良性能的工业纯钛制成。在该装置中，通过将热电偶直接插入高压釜釜腔内，成功地实现了釜内流体温度的准确测量和精确控制。对高压釜不同部位的测温结果表明，沿高压釜的径向与轴向均存在显著的温度梯度，其中釜塞保护锥体处的温度比釜内流体的温度低约8℃，釜外壁中心处与釜内的温度差约10℃；对400℃保温条件下釜内流体温度的直接测量表明，釜内温度波动小于0.5℃。在该装置中，通过将脆性导电性矿物制作成锥形电极，采用耐高温无机绝缘材料制作密封部件，利用锥体自紧式密封技术，成功地解决了脆性电极和电极引线的高压密封与高温绝缘问题；通过引入另一根辅助性的矿物电极引线，成功地解决了原位监测实验过程中矿物电极与引线接触处是否进水的难题，确保了实验的可信度。可行性试验结果表明，该方法不仅可用于高温高压下水流体-导电性矿物，而且可广泛用于水流体-金属间相互作用的腐蚀电化学原位测量研究。 利用上述自行研制的腐蚀电化学实验装置，本工作对高温高压（250-400℃；10-35 MPa）NaCl水流体体系中黄铁矿-自然金原电池的热力学和动力学进行了实验研究。原位测量结果表明： （1）黄铁矿-金原电池的腐蚀电流变化与其开路电压的变化一致； （2）汽-液平衡条件下，黄铁矿-金原电池的开路电压和腐蚀电流在液相中比在汽相中要大； （3）在温度为400 C、压力远离临界点的过热蒸气和超临界区域，压力在实验研究的范围内（10-35 MPa）对黄铁矿-金原电池的开路电压和腐蚀电流均无显著的影响，随压力的增加两者仅略有增大，但当温度压力跨越临界点时，包括温压从汽-液平衡曲线同时进入超临界区以及温度恒定在400 C、压力跨越临界点时，黄铁矿-金原电池的开路电压和腐蚀电流在临界点附近均发生突变。 （4）在本工作中实验的温度、压力和水流体体系条件下，由黄铁矿与金构成的原电池在大多数情况下黄铁矿为阳极，因此在原电池短路时黄铁矿在水流体中发生氧化溶解，而金则为阴极，在原电池短路时金的溶解受到保护，仅在个别狭窄的温度压力范围内情况才相反。 上述原位测量结果与电极表面水流体的性质以及黄铁矿和金的能带结构密切相关，运用混合电位理论、Butler-Volmer方程以及半导体电化学的波动能级模型对实验结果能进行很好的解释。

硫化物矿物原电池腐蚀实验研究与应用启示

作为自然界最常见、可开发的矿物之一，硫化物矿物通常具有半导体性质，在溶液的作用下，必然发生原电池腐蚀。硫化物矿物原电池效应广泛存在并影响湿法冶金(如磨矿、浮选和浸出)、次生硫化物矿物过程、地电化学勘探、重金属离子污染和酸性矿山排水污染和治理等方面。 以前对硫化物矿物腐蚀研究多见于静止的溶液体系，少见于流动溶液体系，而实际情况是硫化物矿物经常处于流动溶液体系中。以矿山环境为例，硫化物矿物经常处于流动的地表水，地下水和雨水淋漓的环境体系中。因此，在流动体系中进行硫化物矿物原电池腐蚀实验研究，无疑对矿山环境治理有着直接的指导作用。另一方面，以前对于硫化物矿物原电池腐蚀的研究多是在无应力作用的条件下进行的，而事实上，无论是人类在开采利用硫化物矿物资源上，还是硫化物矿物本身在自然界的演化进程中，应力作用无时不在，无处不有。硫化物矿物应力原电池也无时不在，无处不有。应力作用下，应变能转化为电化学能，从而改变硫化物矿物的电极电位，必将进一步对硫化物矿物的原电池腐蚀产生重要影响。考察应力作用下的硫化物矿物原电池腐蚀，一方面可以为硫化物矿物的湿法冶金提供实验依据；另一方面，它将为硫化物矿物的元素活化、迁移、浓集和定位等各种地球化学作用解释提供理论指导。 鉴于硫化物矿物原电池腐蚀实验研究的重要意义以及前人对硫化物矿物原电池腐蚀研究在流动体系和应力作用等领域的研究空白，本论文展开了对上述领域的原电池腐蚀实验研究。 在本工作中，我们设计了一套用于溶液静止和溶液流动条件下的硫化物矿物原电池腐蚀实验装置。在流动条件下，对处在不同溶液组分(Na+、Cu2+、Fe3+)、浓度和流速的黄铁矿-黄铜矿、黄铁矿-方铅矿及应力残余黄铁矿-方铅矿原电池腐蚀进行了实验研究；设计了一套用于溶液静止条件下的硫化物矿物应力原电池腐蚀实验装置。展开了在不同溶液组分(Na+、Fe3+)及弹性轴压应力条件黄铁矿和黄铜矿腐蚀电位下的Tafel曲线及交流阻抗谱实验；在不同溶液组分(Na+、Fe3+)及差应力条件下黄铁矿-黄铜矿原电池混合电位下的Tafel曲线及交流阻抗谱实验。 实验结果表明： (1) 溶液中惰性离子(Na+)浓度的改变对原电池腐蚀电流密度和混合电位无明显影响；溶液中氧化性离子(Cu2+、Fe3+)浓度增大，原电池的腐蚀电流密度和混合电位增大。但是，当黄铁矿-黄铜矿原电池中氧化性离子为Cu2+时，增大Cu2+浓度，腐蚀电流密度先增大后减小，最后增大。 (2) 本实验条件下，溶液流速越大，腐蚀电流密度越大，混合电位增大。 (3) 应力残余黄铁矿由于残余应变能的缘故，其电极电位比处在相同条件的溶液下的方铅矿电极电位更低，应力残余黄铁矿-方铅矿原电池腐蚀情况与无应力的黄铁矿-方铅矿原电池腐蚀情况不同。 (4) 弹性轴压应力下，黄铁矿、黄铜矿电极电位和弹性轴压应力呈较好的负线性关系；黄铁矿、黄铜矿弹性轴压应力越大，腐蚀电位越小，腐蚀电流密度越大；电化学阻抗谱测试等效电路拟合的电极电荷传递电阻越小，极化电阻越小，双电层的离子迁移电阻越小，弥散效应越严重。 (5) 差应力作用下的黄铁矿-黄铜矿原电池腐蚀： 黄铜矿阳极弹性轴压应力越大，腐蚀电位越小，腐蚀电流密度越大；电化学阻抗谱测试等效电路拟合的电极电荷传递电阻越小，极化电阻越小，双电层的离子迁移电阻越小，弥散效应越严重。 黄铁矿阴极弹性轴压应力越大，腐蚀电位越大，腐蚀电流密度越小；电化学阻抗谱测试等效电路拟合的反应电阻越大，极化电阻越大，双电层的离子迁移电阻越大，弥散效应越轻微。 上述流动体系下的硫化物矿物原电池腐蚀结果可用Butler-Volmer方程结合原电池模型和双电层结构很好地解释；应力原电池腐蚀结果可用硫化物矿物半导体的热力学势、电化学势、力学应变能、结合原电池模型和双电层结构很好地解释。

Comparative X-ray photoelectron spectroscopic study on the desulfurization of thiophene by Raney Nickel and rapidly quenched skeletal nickel

The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C Is peak has disappeared, leaving nickel sulfide on the surface.