Orientation and electrocatalysis of riboflavin adsorbed on carbon substrate surfaces

Based on scanning tunnelling microscopy and electrochemical measurements, orientation and electrocatalytic function of riboflavin adsorbed on carbon substrates have been described for the first time. Scanning tunnelling micrographs show clearly that tip induction may result in an orientation change of the adsorbed riboflavin molecule on highly oriented pyrolytic graphite from the initially vertical orientation to the stable flat form. The adsorbed riboflavin as an effective mediator can accelerate the reduction of dioxygen which accepts two electrons from the reduced riboflavin to generate hydrogen peroxide. The rate constants of the electrocatalytic reaction in various pH solutions were determined using a rotating disc electrode modified with riboflavin. The pH effect and possible catalytic mechanism are discussed in detail.

Plastic zone in front of mode I crack in phenolphthalein polyether ketone

The plastic zone size and crack opening displacement of phenolphthalein polyether ketone (PEK-C) at various conditions were investigated. Both of them increase with increasing temperature (decreasing strain rate), i.e. yield stress steadily falls. Thus, the mechanism increasing the yield stress leads to increased constraint in the crack tip and a corresponding reduction in the crack opening displacement and the plastic deformation zone. The effect of the plastic deformation on the fracture toughness is also discussed.

Growth rates of different polymorphs from interspherulitic boundary profiles

Quantitative data on the crystallization kinetics of polymorphic polymers can be derived from the investigation of gross spherulitic morphology formed in isothermal conditions. Depending on distance between centers, and the time lag between their formation and relative growth rates, various types of boundary lines can be generated by the impinging of two spherical bodies whose radii increase linearly with time, In polymorphic polymers, different types of spherulites often develop simultaneously at different rates from sporadic or predetermined nuclei. In same cases, the so-called growth transformation, in which a nucleus of the fast growing specie is formed at the tip of an advancing lamella of the slower crystal form, provides an alternative mode of nucleation, It is shown that if only one event of growth transformation takes place at the front of a slow growing body, the fast growing spherulite swallows the parent one and the resultant shape of interspherulitic boundary is described by two symmetrical logarithmic spirals whose parameters can be extracted from micrographs taken at the end of crystallization. These concepts are applied to determine the radial growth rate of gamma form spherulites of polypivalolactone in a wide range of temperatures through analysis of the alpha/gamma interspherulitic profiles formed in isothermal conditions and direct measurement of the growth rate of the alpha counterparts at the same temperature.

TEMPERATURE AND STRAIN-RATE DEPENDENCE OF FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

A strong strain-rate and temperature dependence was observed for the fracture toughness of phenolphthalein polyether ketone (PEK-C). Two separate crack-blunting mechanisms have been proposed to account for the fracture-toughness data. The first mechanism involves thermal blunting due to adiabatic heating at the crack tip for the high temperatures studied. In the high-temperature range, thermal blunting increases the fracture toughness corresponding to an effectively higher test temperature. However, in the low-temperature range, the adiabatic temperature rise is insufficient to cause softening and Jic increases with increasing temperature owing to viscoelastic losses associated with the p-relaxation there. The second mechanism involves plastic blunting due to shear yield/flow processes at the crack tip and this takes place at slow strain testing of the single-edge notched bending (SENB) samples. The temperature and strain-rate dependence of the plastic zone size may also be responsible for the temperature and strain-rate dependence of fracture toughness.

FRACTURE-TOUGHNESS OF PHENOLPHTHALEIN POLYETHER KETONE

The static and impact fracture toughness of phenolphthalein polyether ketone (PEK-C) were studied at different temperatures. The static fracture toughness of PEK-C was evaluated via the linear elastic fracture mechanics (LEFM) and the J-integral analysis. Impact fracture toughness was also analyzed using the LEFM approach. Temperature and strain rate effects on the fracture toughness were also studied. The enhancement in static fracture toughness at 70 degrees C was thought to be caused by plastic crack tip blunting. The increase in impact fracture toughness with temperature was attributed two different mechanisms, namely, the relaxation process in a relatively low temperature and thermal blunting of the crack tip at higher temperature. The temperature-dependent fracture toughness data obtained in static tests could be horizontally shifted to match roughly the data for impact tests, indicating the existence of a time-temperature equivalence relationship. (C) 1995 John Wiley & Sons, Inc.

TEMPERATURE EFFECT ON IMPACT FRACTURE-TOUGHNESS AND FRACTURE MECHANISM OF PHENOLPHTHALEIN POLY(ETHER KETONE)

Phenolphthalein poly(ether ketone) (PEK-C) was tested using an instrumented impact tester to determine the temperature effect on the fracture toughness K-c and critical strain energy release rate G(c). Two different mechanisms, namely the relaxation processes and thermal blunting of the crack tip were used to explain the temperature effect on the fracture toughness. Examination of the fracture surfaces revealed the presence of crack growth bands. It is suggested that these bands are the consequence of variations in crack growth along crazes that are formed in the crack tip stress field. As the crack propagates, the stress is relaxed locally, decreasing the growth rate allowing a new bundle of crazes to nucleate along which the crack advances.

ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY

An ECSTM apparatus with an ideal tip using a homemade SSX-1A STM instrument has been constructed. STM and ECSTM tips were made by electrochemical etching and insulating with paraffin, silicon rubber or epoxy resin under an optical microscope. In situ imag

Effect of heavy metals (Cd, Cu) on the gametophytes of Laminaria japonica Aresch

Effects of various concentrations of two heavy metals, namely Cd and Cu, on gametophytes of Laminaria japonica Aresch were determined by recording morphological changes of gametophytes, determining pH values and the heavy metal content of the culture solution, calculating the germination rate of sporophytes, and observing heavy metal (Cd) distribution using a fluorescence microscope. The results showed that heavy metals damaged the gametophytes, and were even lethal, and that the higher the concentration of heavy metal ions, the greater the injury to gametophytes. Gametophytes could not survive in culture solutions containing more than 100 mg/L Cd and 50 mg/L Cu and were only able to survive in culture solution containing a mixture of Cd and Cu tip to a concentration of 10 mg/L, which indicates that gametophytes have a higher tolerance to Cd than Cu and that multiple heavy metal ions in solution markedly aggravate the damage to gametophytes compared with individual heavy metal ions. With increases in the concentration of the heavy metal, the burgeoning rate of sporophytes decreased acutely, and solutions containing multiple heavy metal ions caused even more marked harm to sporophytes than solutions containing a single heavy metal ion, because most sporophytes died in mixed solutions. The pH value of the culture medium dropped immediately at the beginning (the first day) of treatment, increased over the following days, and then decreased again. The pH of culture media containing multiple heavy metal ions showed greater variation than media containing a single heavy metal ion, with the extent of the decrease in pH of culture media containing multiple ions being greatest during the last period of the experiment. With increases in the concentration of heavy metals, the capacity of gametophytes to accumulate these ions increased. The blue fluorescent light emitted by the Cd- and Cd-binding protein complex existing in gametophytes in media containing different concentrations of Cd showed clearly the distribution of the ion in gametophytes and the results obtained were consistent with distribution determined using other methods. All results of the present study showed that gametophytes of L. japonica play a remarkable role as heavy metal decontaminators, especially with regard to Cd.

Expression of a twist-related gene, Bbtwist, during the development of a lancelet species and its relation to cephalochordate anterior structures

Mesoderm formation plays a crucial role in the establishment of the chordate body plan. In this regard, lancelet embryos develop structures such as the anteriorly extended notochord and the lateral divertecula in their anterior body. To elucidate the developmental basis of these structures, we examined the expression pattern of a lancelet twist-related gene, Bbtwist, from the late gastrula to larval stages. In late-gastrula embryos, the transcripts of Bbtwist were detected in the presumptive first pair of somites and the middorsal wall of the primitive gut. The expression of Bbtwist was then upregulated in the lateral wall of somites and the notochord. At the late-neurula stage, it was also expressed in the anterior wall of the primitive gut, as well as in the evaginating lateral diverticula. No signal was detected in the left lateral diverticulum when it was separated from the gut, while in the right one, the gene was expressed later during the formation of the head coelom in knife-shaped larvae, and in the anterior part of the notochord in the same larvae. In 36-h larvae, only faint expression was detected in the differentiating notochordal and paraxial mesoderm in the caudal region. These expression patterns suggest that Bbtwist is involved in early differentiation of mesodermal subsets as seen in Drosophila and vertebrates. The expression in the anterior notochord may be related to its anterior expansion. The expression in the anterior wall of the primitive gut and its derivative, the lateral diverticula, suggests that lancelets share the capability to produce a mesodermal population from the tip of the primitive gut with nonchordate deuterostome embryos. (C) 1998 Academic Press.

Translocation of assimilates in Undaria and its cultivation in China

Undaria cultivation on a commercial scale began in China only in the last decade. Today, Undaria pinnatifida is the main species under cultivation concentrated in two provinces, Liaoning and Shandong. The annual production in the early nineties was 8000-13 000 tons dry weight, which is two or three times the pre-1980 figures. The raft cultivation method maintaining the alga at the desired depths generally ensures the light saturated rate of photosynthesis on clear days, and enhances production. Under the cultivated condition, the calculated annual primary productivity of this alga is 160 g C m(-2) y(-1). Translocation of C-14-labelled photoassimilates in rapidly growing sporophyte of Undaria pinnatifida was studied in the open sea. Samples from different parts of the blade with counterparts exposed to tracer ((NaHCO3)-C-14) showed that the translocation that occurred mainly from the tip of the blade to the growing region had obvious source-sink relationship. It took 20 minutes to translocate the labelled photoassimilates from the epidermis, via cortex, to the medulla of the midrib, where rates of translocation averaging 42-48 cm h(-1) were observed in the open sea. Production experiments of tip-cutting of the blades showed an increased production of 9%.

Axial growth of hexactinellid spicules: Formation of cone-like structural units in the giant basal spicules of the hexactinellid Monorhaphis

The glass sponge Monorhaphis chuni (Porifera: Hexactinellida) forms the largest bio-silica structures on Earth; their giant basal spicules reach sizes of up to 3 m and diameters of 8.5 mm. Previously, it had been shown that the thickness growth proceeds by appositional layering of individual lamellae; however, the mechanism for the longitudinal growth remained unstudied. Now we show, that the surface of the spicules have towards the tip serrated relief structures that are consistent in size and form with the protrusions on the surface of the spicules. These protrusions fit into the collagen net that surrounds the spicules. The widths of the individual lamellae do not show a pronounced size tendency. The apical elongation of the spicule proceeds by piling up cone-like structural units formed from silica. As a support of the assumption that in the extracellular space silicatein(-like) molecules exist that associate with the external surface of the respective spicule immunogold electron microscopic analyses were performed. With the primmorph system from Suberites domuncula we show that silicatein(-like) molecules assemble as string- and net-like arrangements around the spicules. At their tips the silicatein(-like) molecules are initially stacked and at a later stay also organized into net-like structures. Silicatein(-like) molecules have been extracted from the giant basal spicule of Monorhaphis. Applying the SDS-PAGE technique it could be shown that silicatein molecules associate to dimers and trimers. Higher complexes (filaments) are formed from silicatein(-like) molecules, as can be visualized by electron microscopy (SEM). In the presence of ortho-silicate these filaments become covered with 30-60 nm long small rod-like/cuboid particles of silica. From these data we conclude that the apical elongation of the spicules of Monorhaphis proceeds by piling up cone-like silica structural units, whose synthesis is mediated by silicatein(-like) molecules. (C) 2008 Elsevier Inc. All rights reserved.

An N-shape thermal front in the western South Yellow Sea in winter

An N-shape thermal front in the western South Yellow Sea (YS) in winter was detected using Advanced Very High Resolution Radiation (AVHRR) Sea Surface Temperature data and in-situ observations with a merged front-detecting method. The front, which exists from late October through early March, consists of western and eastern wings extending roughly along the northeast-southwest isobaths with a southeastward middle segment across the 20-50 m isobaths. There are north and south inflexions connecting the middle segment with the western and eastern wings, respectively. The middle segment gradually moves southwestward from November through February with its length increasing from 62 km to 107 km and the southern inflexion moving from 36.2A degrees N to 35.3A degrees N. A cold tongue is found to coexist with the N-shape front, and is carried by the coastal jet penetrating southward from the tip of the Shandong Peninsula into the western South YS as revealed by a numerical simulation. After departing from the coast, the jet flows as an anti-cyclonic recirculation below 10 m depth, trapping warmer water originally carried by the compensating Yellow Sea Warm Current (YSWC). A northwestward flowing branch of the YSWC is also found on the lowest level south of the front. The N-shape front initially forms between the cold tongue and warm water involved in the subsurface anti-cyclonical recirculation and extends upwards to the surface through vertical advection and mixing. Correlation analyses reveal that northerly and easterly winds tend to be favorable to the formation and extension of the N-shape front probably through strengthening of the coastal jet and shifting the YSWC pathway eastward, respectively.

古龙咀周围海区沉积物粒度特征及海底地形变化

对古龙咀周围浅海区沉积物的粒度进行了测试与分析，结合相关的地质水文资料，探讨了海岸形态对沉积物粒度的影响。研究区表层沉积物平均粒径在海湾浅海区呈带状由岸向海变细，中等水深和岬角处分布着细粒区，向外海粒径相对变粗；除险岛湾砂质区外，分选差；偏态多数为正偏或近正态；整体峰形极窄，峰型多样。底质类型以粘土质粉砂和砂质粉砂为主，由东北经古龙咀岬角向西南形成S形粘土质粉砂分布带，险岛湾地区沉积物呈带状由砂逐渐过渡到粉砂。潮汐和波浪是本区沉积物输运的主要水动力，岬角的存在影响了沉积物粒度的分布。粒度趋势分析表明沉积物整体有向岬角汇聚的输运趋势。 对收集到基于1954年、1969年、1982年测量绘成的地形图水深数据进行数字化，结合2005年测量的水深数据，分别建立各时期DEM图，在此基础上分析研究区的地形特征。四个时期海底DEM呈现出大体一致的趋势，在险岛湾及白沙口海湾内为浅水区，水深值在-1～-4 m之间，深水区主要分布在南黄岛南端至古龙咀连线以南区域，呈扇形展布，水深由南黄岛两侧向中间逐渐加深，水深值在-10～ -17 m之间。从整体上看，研究区海底地形呈NW-SE方向逐渐加深。 将数字化后的水深数据统一校正到1956黄海高程系，分别建立DEM，运用GIS的栅格计算分析得出冲淤变化图。相关结果表明：1954～1969年研究区整体近岸为冲（险岛湾除外），离岸海域为淤；1969～1982年研究区总体处于弱淤积状态；1982-2005研究区海域近岸为淤，外海以弱冲刷状态为主。

渤海南部海域沉积物-海水界面附近磷、硅赋存形态及其生物地球化学过程研究

本文系统研究了渤海南部海域沉积物-海水界面附近（包括上覆水、悬浮颗粒物和沉积物）P、Si的赋存形态及其生物地球化学过程。其特色在于提出了“自然粒度下形态研究”的概念，探讨了能真正参与循环的P、Si及其控制关键环节，为渤海资源特别是生物资源的可持续利用战略的制定提供理论基础。得到的主要结论包括：研究了渤海南部海域覆水、悬浮颗粒物中P、Si的变异特征。上覆水体PO_4-P、SiO_3-Si的平均含量均低于大洋底层水PO_4-P、SiO_3-Si的平均含量。悬浮颗粒物中TIP、BP的来源和循环控制机制不同，TISi、BSi有一定的相似性。稀释作用和表层沉积物中可交换态P、Si的循环控制上覆水体中P、Si的地球化学行为。颗粒物中TIP、TISi的行为受离子交换和化学吸附过程影响，其中化学吸附可能与Fe（III）的氧化物有关；生物过程对颗粒物中生源P、Si的地球化学行为有重要影响。渤海南部海域沉积物P、Si的分布特征及其成岩过程研究表明。表层沉积物可交换态磷中，OSF-P是磷的优势赋存形态，占总磷的10.7%；CF-Si是硅的优势赋存形态，占总硅的0.05%。 不同形态P的成岩过程有一定的相似性。TSi与其它相中的Si呈负相关或不呈显著相关，且可交换态Si的量仅占总Si的0.12%以下，说明以往采用测定总Si含量来研究Si的生物地球化学过程不可能得出有价值的信息。IMOF-P、OSF-P、IMOF-Si、CF-Si在P、Si的生物地球化学循环中有重要作用。CaCO_3、Fe（III）和Corg等对P、Si界面循环有重要影响，有机质的钙化导OSF-P的矿化作用而释放P；Fe（III）的还原引起IMOF-P， CF-P和CF-Si对P、Si的释放。Corg的成岩过程对CF-Si有影响。约79%的BP和75%的BSi沉积后转化为相对稳定状态，在较短时间内不再参与循环。柱状沉积物中，OSF-P和CF-P之间存在沉积转化。CF-Si呈双指数分布。P、Si在表层沉积物中垂向分布的差异，表明底栖生物扰动对加强界面P、Si交换的作用。室内模拟沉积物-海水界面附近P、Si交换过程表明，P、Si在沉积物、上覆海水间的交换通量分别为0.8μ mol/ (m~2 · h)。P、Si的埋藏与释放主要受OSF-P、IMOF-Si 和平共处BSi的影响。对渤海P、Si年循环的估算显示，P在渤海湾、莱州湾的年循环量达30.9 * 10~5kg 和13.8 * 10~5kg， Si则分别为22.8 * 10~7 kg和15.5 * 10~7 kg，这其中沉积物向上覆海水扩散的P占87.7%和87.0%， Si占22.4%和14.2%。就整个渤海而言，沉积物向海水释放的磷、硅在其总循环中分别占88.7%和34.0%，所以沉积物-海水界面过程对磷、硅在渤海的生物地球化学循环有重要影响，是渤海P、Si循环的关键控制过程之一。

Stress corrosion cracking of AISI 321 stainless steel in acidic chloride solution

The stress corrosion cracking (SCC) of LambdaISI 321 stainless steel in acidic chloride solution was studied by slow strain rate (SSR) technique and fracture mechanics method. The fractured surface was characterized by cleavage fracture. In order to clarify the SCC mechanism, the effects of inhibitor KI on SCC behaviour were also included in this paper. A study showed that the inhibition effects of KI on SCC were mainly attributed to the anodic reaction of the corrosion process. The results of strain distribution in front of the crack tip of the fatigue pre-cracked plate specimens in air, in the blank solution (acidic chloride solution without inhibitor KI) and in the solution added with KI measured by speckle interferometry (SPI) support the unified mechanism of SCC and corrosion fatigue cracking (CFC).