876 resultados para Roma - Politica e governo - 30 A.C.-476


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Morphological and culture studies of tetraspores of Gracilaria lemaneiformis were carried out under laboratory conditions. Relationships of germination rate, diameter and survival rate of tetraspores from 1st generation branches with grads of temperature and irradiance were determined, respectively. The result showed that 1st generation branches is in the majority of the tetraspores shedding and tetraspores from which had highest survival rates than other parts of the sporophytic plant. The time tetraspores used developing from giant unicells to diads, which both existed on the epidermis, then to tetraspores off the matrix, was only approximately 3 weeks all through. However, tetraspores spent more than two months developing into germlings of gametophytes. It was shown that temperature variation (10, 15, 25, 30 degrees C) with the light of 30 mu mol m(-2) s(-1) had significant effects on the germination rate and diameter, but had no apparent effect on survival rate (ANOVA, P < 0.01). Germination rates of tetraspores reached the maximum at 20 degrees C, which was significantly higher than those at other temperature levels (P < 0.01), whereas 15 degrees C seemed to be optimal temperature for the diameter. All the three growth parameters (germination rate, diameter and survival rate) yield highly significant variations with irradiance treatments at room temperature (ANOVA, P < 0.01). The optimal germination rate was detected at the irradiance of 30 mu mol m(-2) s(-1) (P < 0.01). The photon flux density which exceeds 480 nnol m(-2) s(-1) have apparently negative effect on diameter and survival rate. (c) 2005 Elsevier B.V. All rights reserved.

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近年来,由于对海区不合理的开发,我国浅海贝类筏式养殖接连遭受重创,这亟需从理论上和实践中确定养殖容量和养殖模式。本文在我国北方典型养殖海湾四十里湾对筏式养殖的贝类开展了现场生理生态学研究,对贝类对浮游植物等悬浮颗粒物的处理过程即贝类对颗粒有机物及营养元素C、N、P的摄食、吸收、排泄、排粪和生长进行了剖析,分析了贝类在沿岸养殖生态系中的物质和营养循环中所扮演的角色,为海区贝类养殖容量和养殖模式的最终确定提供了基础数据。另外,本文还对海水、沉积物及生物体中磷的分析方法进行了大量的实验工作。主要结果如下:① 比较系统地评述了双壳贝类的生物沉积(biodeposition)的原理、测定方法及其生态效应。贝类通过生物沉积在沿岸生态系中的物质和营养循环中扮演着重要的角色。国际上已有不少研究专门报道了贝类在海区现场的生物沉积。而在我国,这方面的研究却罕见。② 综述了双壳贝类各种形态的 N 和 P 排泄及其生态效应。对于我国广泛养殖 的栉孔扇贝、海湾扇贝和牡蛎等双壳贝类的TDN、TP排泄尚未见报道。 ③ 在6~7月,在四十里湾的不同养殖海区(8个站位)对扇贝的生物沉积进行了现场测定。在整个四十里湾海区,一龄栉孔扇贝(壳高 41.1±4.1mm,软体干重 0.48±O.10 g/ind))每个每天所产生生物沉积物干重平均为59.9mg,对颗粒有机质(POM)、颗粒有机碳(POC)、颗粒有机氮(PON)和颗粒有机磷(POP)的生物沉积速率范围及平均值分别为: 6.88、3.09、0.392 和 0.022mg/ind·d。还在一个站位测定了海湾扇贝(壳高 24.6±2.3mm;软体干重 O.14g/ind)的生物沉积速率为 24.3mg/ind·d,或179.2mg/g·d。不同站位一龄栉孔扇贝的生物沉积速率有较大变化,这主要与饵料浓度不同有关。二龄栉孔扇贝(壳高60.9±8.2mm;软体干重1.91±0.32 g/ind)的生物沉积速率平均为 112.7mg/ind·d,对POM、POC、PON和POP的沉积速率分别是一龄扇贝的1.85倍、1.68倍、1.77倍和2.33倍。养殖海区与非养殖海区比较,前者近海底沉积速率是后者的 1.51~3.47 倍。根据以上数据,作者计算了中等规格栉孔扇贝(用壳高 41.1±4.8mm 扇贝估算)在四十里湾在夏季每天的生物沉积量达 162 吨(干重),或18.6tPOM、8.37tPOC、1.06tPON和60kgPP。在四十里湾的贝类筏式养殖海区,可以估计贝类每年因生物沉积的生产而循环427tN和98.OtP(包括20.0t OP的贡献),它们能分别满足浮游藻类生产所需求N和P的17.0%和28.3%(其中OP贡献 6.9%)。可见,贝类在养殖生态系的物质和营养盐循环中扮演着重要的角色。高密度、大面积的贝类养殖使大量的生物沉积物聚集于海底,可能对海区环境产生冲击。作者分析,98年8月份烟台养殖区赤潮的发生很可能与海底生物沉积物营养盐的快速释放以及栉孔扇贝大面积死亡而使浮游藻类失去了摄食控制有关,而风平浪静和养殖笼对水流的阻挡也为赤潮的发生提供了有利条件。④ 采用半现场流水系统法测定了栉孔扇贝在不同养殖密度、不同养殖模式(扇贝单养、贝藻混养、贝藻参混养)中的生物沉积。实验时间尺度大,前后计80天。结果说明扇贝的生物沉积速率与其养殖密度呈反比关系。养殖密度的高低影响饵料浓度的变化(两者呈负相关的对数函数关系),而饵料浓度的高低直接决定着扇贝的生物沉积速率的高低,两者呈正相关关系(生物沉积速率与POC和叶绿 a 分别呈对数和指数函数关系)。不仅生物沉积物的数量与养殖密度(或饵料浓度)有关,生物沉积物的质量同样与养殖密度(或饵料浓度)有关。栉孔扇贝的养殖使沉积物的有机质含量及C、N 和 P 含量降低,且密度越高,它们的含量越低。这反映了扇贝对环境的适应能力。在海带和扇贝的混养模式中,海带对扇贝生物沉积物的数量和质量不构成影响,当然这是在海带不影响浮游植物数量的前提下得出的结果。而实际上在自然海区两者可能是竞争关系。⑤ 对从海区取回到实验室的多种滤食性动物,包括经济双壳贝类(栉孔扇贝、海湾扇贝、长牡蛎、贻贝、菲律宾蛤仔等)和养殖中的污损动物(栖海鞘、玻璃海鞘、藤壶、玟斑稜蛤)的 N 和 P 排泄进行了测定,包括排泄成分和排泄速率。在N排泄中,NH_4-H 占主要部分,如笼式养殖的双壳贝类 NH_4-N 占总N排泄的70%以上,平均值范围为70.8~80.1%。氨基酸是第二大排泄成分,平均占总N排泄的10~25%。其它形态的N,如尿素、亚硝酸盐和硝酸盐也有检出,如双壳贝类尿素氮在总氮排泄中占 2~5%。但在双壳贝类中未检出尿酸氮。比较而言,海鞘、藤壶的尿素氮相对高一些。在P排泄中,OP约占TDP排泄的15~27%。栉孔扇贝TDP排泄速率为0.281μmol/h·ind。作者以实验室测定结果计算,在整个四十里湾的夏季,所养殖的双壳贝类每天将排泄4.54t总溶解氮,其中NH_4-N 3.36t、Amino-N 0.69t、Urea-N 0.2t。 同时每天磷的排泄为0.57t TDP,其中OP O.15t。对面积为1.3 * 10~4hm~2的海区而言,贝类的N、P排泄分别能满足浮游植物生产所需N、P的44%和40%。尽管Urea-N所占比例有限,但也能满足海区浮游植物所需 N 的 2%左右。以上说二月高密度的贝类养殖对海区生态系统营养盐循环的影响是很显著的。附着动物(柄海鞘等)的N、P 排泄也不容忽视,它们分别能满足浮游藻类生产所需 N、P 的 ll%和 12%。它们一方面通过排泄和排粪加速营养盐和物质的循环对浮游植物的生长产生刺激作用;另一方面,对藻类产生摄食控制,如果海区中滤食性动物太多,即使营养盐再丰富也难以使浮游植物大量繁殖,这无疑将影响滤食性动物的生长速率。⑥ 运用近年来发展起来的生物沉积法对四十里湾半现场流水系统中贝类的滤水率、吸收率、生长率、生态效率等生理生态学参数进行了测定。栉孔扇贝(收获时规格0.194~0.412g软体干重/ind)滤水率平均为3.65 1/ind·h。扇贝放养密度和饵料浓度没有显著关系。扇贝的总摄食率平均为3.98mg/ind·h,对POM、POC、PON的 摄食率范围为0.84~1.87、0.335~0.748、0.0515~O.1293mg/ind·h。扇贝的摄食率随放养密度的升高而降低,与POM呈正相关关系。扇贝的吸收速率受密度和饵料浓度的影响不明显。扇贝对N的吸收效率较C、P稍高,对总有机质的吸收效率为75.9±4.1%,如此高的吸收效率与低饵料浓度有关。扇贝氨基酸泄漏所损失的能量高于排氨的能量损失。代谢能与吸收能呈明显的正相关关系。SFG与饵料浓度呈正相关关系。总生长效率K1(* 100)变化较大,范围为20~49;净生长效率K,K_2(* 100)随POM的升高而升高。扇贝对N的总生态效率范围为6.2~12.8%(平均9.9%),这高于对C(平均5.9%)和P(平均4.1%)的总生态效率。扇贝对POC、PON和PP的生长余力(SFG_C、SFG_N、SFG_P)平均分别为197、46.8和6.2μg/ind·h,它们分别与POC、PON和PP呈正比关系。扇贝对N的净生长率高于对C和P的净生长率。在N的预算中,如果仅考虑NH_4-N的排泄而忽视其它形态氮的排泄,将会产生很大偏差(平均约20%)。扇贝贝壳生长所需的能量在整个扇贝生长所需能量的9.0~15.1%(平均 11.2%);贝壳C、N和P在扇贝生长中所占的比例分别为10.5~17.8%、9.4~16.1%和8.7~15.O%。可见,贝壳不管在能量预算还是在元素预算中都不应该被忽视。理论计算而得到的SFG和SFG_C、SFG_N、SFG_P与扇贝的实际生长和扇贝C、N、P的实际增长量之间呈正相关关系,但前者明显过高地估计了扇贝的生长。⑦ 运用生物沉积法在四十里湾养殖海区现场对栉孔扇贝的生理生态学特征进行了研究。不同海区扇贝的滤水率有变化,一龄扇贝(41.1±4.1mm,软体干重 0.48±O.10g/ind)滤水率变化范围为 0.72~2.54(平均 1.27)1/ind·h 或 1.65~5.97(平均 2.61)1/g·h。与半现场研究结果一致,滤水率与TPM没有明显关系,而摄食率却与TPM呈正相关关系。二龄扇贝(软体干重 1.91±0.32g/ind)滤水率为 2.09~3.99(平均 3.10)1/ind·h。吸收速率与POM(或TDM)呈正相关关系,与饵料质量(POM/TPM)无明显的相关关系。吸收效率AE_(POM)与TPM(或POM)没有相关关系,却与饵料质量呈明显 的正相关关系。扇贝对POC、PON和PP的吸收效率平均分别为68.9%、64.0%和63.6%。不同海区SFG差别很大。一龄扇贝SFG范围为-O.174~24.08 J/ind·h,SFG与饵料浓度POM呈正相关关系。SFG负值的出现主要与低饵料浓度有关。SFG_C、SFG_N、SFG_P分别与POC、PON和PP呈正相关关系。在N的生长余力计算中,如果仅考虑NH_4-N排泄,而不考虑其它形态N的排泄,就可能产生相当大的偏差,偏差范围为11~360%,这高于半现场的偏差值,显然SFG_N越低,产生的偏差就越大。这说明在饵料不足、扇贝生长受到限制的环境下进行N生长余力的计算时必须考虑其它形态N的排泄。⑧ 对四十里湾养殖海区一些双壳贝类和藻类的化学组成和有机净生产量进行了讨论。不同双壳贝类的软体有机碳含量差别不大,而N含量差异较大。栉孔扇贝N含量最高(占软体干重的12.36%),而牡蛎、毛蚶软体N含量相对较低,为 8~9%。从双壳贝类贝壳的组成来看,贻贝和菲律宾蛤仔贝壳中N含量最高,分别为 0.55% 和 0.56%;而栉孔扇贝贝壳N含量相对较低,在 O.1%左右。贻贝贝壳有机磷含量 (308ppm) 也明显高于栉孔扇贝贝壳(62.1 ppm)。不同海区海带的 C/N 比值较高,变化明显,范围为17.36~30.23。石莼与此相似。大型藻类高 C/N 比值说明海区营养元素N的不足。海带的不同部位N含量差别很大,中带部和边叶在不同海区有较大变化,即对环境的营养状况比较敏感。紫贻贝贝壳中C、H、N 和 P 的含量在整个贻贝中占有相对大的比例,分别为 30.4%、30.2%、31.8%和 29.6%。

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To investigate the effects of body size and water temperature on feeding and growth in the sea cucumber Apostichopus japonicus (Selenka), the maximum rate of food consumption in terms of energy (C-maxe; J day(-1)) and the specific growth rate in terms of energy (SGRe; % day(-1)) in animals of three body sizes (mean +/- SE) - large (134.0 +/- 3.5 g), medium (73.6 +/- 2.2 g) and small (36.5 +/- 1.2 g) - were determined at water temperatures of 10, 15, 20, 25 and 30 degrees C. Maximum rate of food consumption in terms of energy increased and SGRe decreased with increasing body weight at 10, 15 and 20 degrees C. This trend, however, was not apparent at 25 and 30 degrees C, which could be influenced by aestivation. High water temperatures (above 20 degrees C) were disadvantageous to feeding and growth of this animal; SGRe of A. japonicus during aestivation was negative. The optimum temperatures for food consumption and for growth were similar and were between 14 and 15 degrees C, and body size seemed to have a slight effect on the optimal temperature for food consumption or growth. Because aestivation of A. japonicus was temperature dependent, the present paper also documented the threshold temperatures to aestivation as indicated by feeding cessation. Deduced from daily food consumption of individuals, the threshold temperature to aestivation for large and medium animals (73.3-139.3 g) was 24.5-25.5 degrees C, while that for small animals (28.9-40.7 g) was between 25.5 and 30.5 degrees C. These values are higher than previous reports; differences in sign of aestivation, experimental condition and dwelling district of test animals could be the reasons.

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1. This paper investigated the bioenergetic responses of the sea cucumber Apostichopus japonicus (wet weights of 36.5 +/- 1.2 g) to different water temperatures (5, 10, 15, 20, 25 and 30 degrees C) in the laboratory. 2. Results showed that theoretically the optimal temperatures for energy intake and scope for growth (SFG) of sub-adult A. japonicus was at 15.6 and 16.0 degrees C, respectively. The aestivation threshold temperature for this life-stage sea cucumber could be 29.0 degrees C by taking feeding cessation as the indication of aestivation. 3. Our data suggests that A. japonicus is thermo-sensitive to higher temperature, which prevents it from colonising sub-tropical coastal zones. Therefore, water temperature plays an important role in its southernmost distribution limit in China. 4. The potential impact of global ocean warming on A. japonicus might be a northward shift in the geographical distribution. Crown Copyright (C) 2009 Published by Elsevier Ltd, All rights reserved.

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A two-stage process with temperature-shift has been developed to enhance the anthocyanin yield in suspension cultures of strawberry cells. The effect of the temperature-shift interval and the shift-time point was investigated for the optimization of this strategy. In this process, strawberry cells were grown at 30 degrees C (the optimum temperature for cell growth) for a certain period as the first stage, with the temperature shifted to a lower temperature for the second stage. In response to the temperature shift-down, anthocyanin synthesis was stimulated and a higher content could be achieved than that at both boundary temperatures but cell growth was suppressed. When the lower boundary temperature was decreased, cell growth was lowered and a delayed, sustained maximum anthocyanin content was achieved. Anthocyanin synthesis was strongly influenced by the shift-time point but cell growth was not. Consequently, the maximum anthocyanin content of 2.7 mg.g-fresh cell(-1) was obtained on day 9 by a temperature-shift from 30 degrees C, after 3-d culture, to 15 degrees C. The highest anthocyanin yield of 318 mg.L-1 on day 12 was achieved when the temperature was shifted from 30 degrees C, after 5-d culture, to 20 degrees C. For a global optimization of both the yield and productivity, the optimum anthocyanin yield and productivity of 272 mg.L-1 and 30.2 mg.L-1.d(-1) on day 9 were achieved by a two-stage culture with a temperature-shift from 30 degrees C after 3 d to 20 degrees C.

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The major components of the plant curcuma longa are the curcuminoids that include curcumin, demethoxycurcumin and bisdemethoxycurcumin. It has been reported the curcuminoids have some important activities. A new CZE method with diode array detection has been developed for the separation and determination of the curcumin, demethoxycurcumin and bisdemethoxycurcumin. Three curcuminoids could be readily separated within 7 min with a 15 mM sodium tetraborate buffer containing 10% methanol (v/v) at pH 10.8, 25 kV and 30 degrees C. The method has been validated and shows good performance with respect to selectivity, reproducibility, linearity, limits of detection and recovery. The proposed method was successfully applied to determine the curcuminoids in urine. (c) 2004 Elsevier B.V. All rights reserved.

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A novel poly sulfone/polyethylene oxide/silicone rubber (PSOPEO/SR) multilayer composite membrane was fabricated by double coating polysulfone substrate membrane with polyethylene oxide and silicone rubber. Gas permeation experiments were performed at 30 degrees C for hydrogen and nitrogen. PSf(PEO/SR membrane displayed high and steady performance for H-2/N-2: permeances of H-2 and N-2 of 49.51 and 0.601 GPU, respectively, and H-2/N-2 ideal separation factor of 82.3. It was explained that layer interfaces due to the introduction of PEO layer act as the permselective media and are responsible for the higher H-2/N-2 ideal separation factor which has exceeded the intrinsic permselectivities of the three polymers used in this study. (c) 2005 Elsevier B.V. All rights reserved.

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Small rodents with a large surf ace-area-to-volume ratio and a high thermal conductance are likely to experience conditions where they have to expend large: amounts of energy in order to maintain a constant body temperature at low ambient temperatures. The survival of small rodents is thus dependent on their ability to reduce heat loss and increase heat production at low ambient temperatures. Two such animals are the social subterranean rodents Cryptomys damarensis (the Damaraland mole-rat) and Cryptomys hottentotus natalensis (the Natal mole-rat). This study examined the energy savings associated with huddling as a behavioural thermoregulatory mechanism to conserve energy in both these species. Individual oxygen consumption (VO2) was measured in groups ranging in size from one to 15 huddling animals for both species at ambient temperatures of 14, 18, 22, 26 and 30 degrees C. Savings in energy (VO2) were then compared between the two species. Significant differences in VO2 (p

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The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point = 30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility proper-ties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). H-1 NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G(+)/G(-). These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

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The effect of Al incorporation and pH adjustment during hydrolysis of the silica precursor on the thermal and structural stability of ordered microporous silica films with a 2D structure is presented. The structural stability of the films was determined from a combination of LA XRD/TEM data with porosity data obtained from ethanol adsorption isotherms. Thermogravimetric analysis and MR data were used to determine the template removal and the thermal stability. Stability of aluminium incorporated silica films has further been examined in several organic solvents with different polarity. A solvent with a higher polarity interacts more strongly with the films; the long-order structure disappeared after exposure to polar solvents. After exposure to non-polar solvents, the pore size uniformity was retained after 48 h. The samples with an Al/Si ratio of 0.007 showed the smallest d-spacing shift after exposure to hexane. The stability was further tested in the hydrogenation of phenylacetylene performed in a batch reactor over 1 wt.% Pd/Si(Al)O-2/Si (Al/Si = 0.007) films at 30 degrees C and 10 bar H-2 with hexane as solvent. No deactivation was observed in two subsequent hydrogenation runs. (C) 2009 Elsevier Inc. All rights reserved.

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The kinetics of photomineralization of 4-chlorophenol (4-CP) sensitized by Degussa P25 TiO2 in O2-saturated solution is studied as a function of the following different experimental parameters: pH, [TiO2], percentage O2 [O2], [4-CP], T, I, lambda and [KNO3]. At pH 2 and T=30-degrees-C the initial relative rate of CO2 photogeneration R(CO2) conforms to a Langmuir-Hinshelwood-type kinetic scheme and the relationship between R(CO2) and the various experimental parameters may be summarized as follows: R(CO2) = gammaK(O2)[O2](I(a))(theta)K(4-CP]0/(1 + K(O2])(1 + K(4-CP)[4-CP]0) where gamma is a proportionality constant, K(O2) = 0.044 +/- 0.005[O2]-1, theta = 0.74 +/- 0.05 and K(4-CP) = (29 +/- 3) x 10(3) dm3 mol-1. The overall activation energy for this photosystem was determined as 16 +/- 2 kJ mol-1. This work forms part of an overall characterization study in which it is proposed that the 4-CP-TiO2-O2 photosystem is adopted as a standard test system for incorporation into all future semiconductor-sensitized photomineralization studies in order to facilitate comparisons between the results of the different studies.

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The chromium bearing wastewater in this study was used to simulate the low concentration discharge from a major aerospace manufacturing facility in the UK. Removal of chromium ions from aqueous solutions using raw dolomite was achieved using batch adsorption experiments. The effect of; initial Cr(VI) concentration, amount of adsorbent, solution temperature, dolomite particle size and shaking speed was studied. Maximum chromium removal was found at pH 2.0. A kinetic study yielded an optimum equilibrium time of 96 h with an adsorbent dose of 1 g/L Sorption studies were conducted over a concentration range of 5-50 mg/L Cr(VI) removal decreased with an increase in temperature (q(max): 20 degrees C = 10.01 mg/g; 30 degrees C = 8.385 mg/g; 40 degrees C = 6.654 mg/g; and 60 degrees C = 5.669 mg/g). Results suggest that the equilibrium adsorption was described by the Freundlich model. The kinetic processes of Cr(VI) adsorption onto dolomite were described in order to provide a more clear interpretation of the adsorption rate and uptake mechanism. The overall kinetic data was acceptably explained by a pseudo first-order rate model. Evaluated Delta G degrees and Delta H degrees specify the spontaneous and exothermic nature of the reaction. The adsorption takes place with a decrease in entropy (Delta S degrees is negative). (C) 2011 Elsevier B.V. All rights reserved.

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The electrical conductivity of a range of concrete mixes, with and without supplementary cementitious materials (SCM), is studied through multiple cycles of heating and cooling over the extended temperature range −30/+70 °C. When presented in an Arrhenius format, the experimental results display hysteresis effects at the low-temperature end of the thermal cycle and, in those concretes containing supplementary cementitious materials at higher water/binder ratios, hysteresis effects were evident over the entire temperature range becoming more discernible with increasing number of thermal cycles. The depression in both the freezing and thawing point could be clearly identified and was used to estimate pore-neck and pore-cavity radii. A simplified approach is presented to evaluate the volumetric ratio of frozen pore water in terms of conductivity measurements. The results also show that the conductivity and activation energy of the concrete specimens were related to the water/binder ratio, type of SCM, physical state of the pore water and the thermal cycling regime.

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A new homologous series of side-chain liquid crystal polymers, the poly[omega-(4-cyanoazobenzene-4'-oxy)alkyl methacrylate]s, have been prepared in which the length of the flexible alkyl spacer is varied from 3 to 12 methylene units. All the polymers exhibit liquid crystalline behaviour; specifically, crystal E, smectic A and nematic phases are observed. The glass transition temperatures decrease on increasing spacer length before reaching a limiting value at ca. 30 degrees C. The clearing temperatures exhibit an odd-even effect on varying the length and parity of the spacer. This is attributed to the change in the average shape of the side chain as the parity of the spacer is varied. This rationalization also accounts for the observed alternation in the entropy change associated with the clearing transition. A weak relaxation is observed theologically for several members of this polymer series at temperatures above their respective glass transition temperatures. This is attributed either to specific motions of the smectic layers or to 180 degrees reorientational jumps of the long axis of the mesogenic unit about the polymer backbone. (C) 1997 Elsevier Science Ltd. All rights reserved.

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A relatively simple, selective, precise and accurate high performance liquid chromatography (HPLC) method based on a reaction of phenylisothiocyanate (PITC) with glucosamine (GL) in alkaline media was developed and validated to determine glucosamine hydrochloride permeating through human skin in vitro. It is usually problematic to develop an accurate assay for chemicals traversing skin because the excellent barrier properties of the tissue ensure that only low amounts of the material pass through the membrane and skin components may leach out of the tissue to interfere with the analysis. In addition, in the case of glucosamine hydrochloride, chemical instability adds further complexity to assay development. The assay, utilising the PITC-GL reaction was refined by optimizing the reaction temperature, reaction time and PITC concentration. The reaction produces a phenylthiocarbamyl-glucosamine (PTC-GL) adduct which was separated on a reverse-phase (RP) column packed with 5 microm ODS (C18) Hypersil particles using a diode array detector (DAD) at 245 nm. The mobile phase was methanol-water-glacial acetic acid (10:89.96:0.04 v/v/v, pH 3.5) delivered to the column at 1 ml min-1 and the column temperature was maintained at 30 degrees C. Galactosamine hydrochloride (Gal-HCl) was used as an internal standard. Using a saturated aqueous solution of glucosamine hydrochloride, in vitro permeation studies were performed at 32+/-1 degrees C over 48 h using human epidermal membranes prepared by a heat separation method and mounted in Franz-type diffusion cells with a diffusional area 2.15+/-0.1 cm2. The optimum derivatisation reaction conditions for reaction temperature, reaction time and PITC concentration were found to be 80 degrees C, 30 min and 1% v/v, respectively. PTC-Gal and GL adducts eluted at 8.9 and 9.7 min, respectively. The detector response was found to be linear in the concentration range 0-1000 microg ml-1. The assay was robust with intra- and inter-day precisions (described as a percentage of relative standard deviation, %R.S.D.) <12. Intra- and inter-day accuracy (as a percentage of the relative error, %RE) was <or=-5.60 and <or=-8.00, respectively. Using this assay, it was found that GL-HCl permeates through human skin with a flux 1.497+/-0.42 microg cm-2 h-1, a permeability coefficient of 5.66+/-1.6x10(-6) cm h-1 and with a lag time of 10.9+/-4.6 h.