91 resultados para Order-disorder effects
Resumo:
The compounds (het)(PtCl6)2H(2)O 1, (het)(HgI4).H2O 2 (het = 2-(alpha-hydroxyethyl)thiamine) and (hpt)(Hg2Br6) 3 (hpt = 2-(alpha-hydroxypropyl)thiamine) have been prepared and structurally characterized by X-ray crystallography in order to study the influence of the anion and molecular conformation on the formation of supramolecular architectures that adsorb anionic species. Both het and hpt molecules adopt the usual S conformation for C2-substituted thiamine but differ from the F conformation for C2-free thiamine derivatives. Two types of characteristic ligand-anion complexation are observed, being of the forms C(6')-H...anion...thiazolium-ring (in 1 and 2) and N(4'1)-H...anion...thiazolium-ring (in 3). The reaction of het with PtCl62- or HgI42- gives a 1-D double-chain in 1, consisting of two hydrogen-bonded het chains, which are cross-linked by anions through hydrogen bonding and anion...aromatic-ring interactions, or a cationic 3-D framework in 2 formed by the stacking of hydrogen-bonded sheets with anion-and-water-filled channels. In the case of 3, hydrogen-bonded hpt dimers and HgBr62- anions form alternate cation-anion columns. A comparison with the cases of C2-free thiamine-anion complexes indicates that the change in molecular conformation results in novel supramolecular assemblies in 1 and 2 and an analogous architecture in 3, which also depends on the nature of the anions.
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In order to investigate the influence of different alkyl side chain substitution on the structures and properties of P3ATs, X-ray diffraction, differential scanning calorimetry (DSC), thermal gravity analysis (TGA), Fourier transform infrared spectra (FTIR) and ultraviolet-visible spectra (W-VIS) were applied to characterizing the samples of ploy(3-octylthiophene) (P3OT), poly(3-dodecylthiophene) (P3DDT) and poly(3-octadecylthiophene) (P3ODT). It is found that the different length of alkyl group substitution leads to great difference in molecular chain packings, according to the room temperature X-ray diffraction results. The temperature dependence of X-ray diffraction experiments were also performed to study the melting processes of P3ATs. With the increase in the number of carbon atoms in alkyl side chains, the melting point decreases, and the thermal stability decreases too. The results of both FTIR and W-VIS spectra indicate that the conjugation length of P3DDT is the longest. among the three P3ATs. (C) 2001 Elsevier Science B.V. All rights reserved.
Resumo:
The effect of the elastomer stiffness on brittle-tough transition in elastomer toughening thermoplastics was quantitatively studied. A correlation between brittle-tough transition temperature and the elastomer stiffness was obtained. The calculation from this correlation showed that the brittle-tough transition temperature (T-bt) Of elastomer toughening thermoplastics slowly increased up to one tenth of the modulus of matrix, thereafter it increased rapidly with increasing the modulus of elastomer. The results indicated that the modulus of the elastomer must be one-tenth or less of that of the matrix in order to be effective at low temperature. (C) 2001 Elsevier Science Ltd. All rights reserved.
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Organic electroluminescent devices with a structure of ITO/ploy (9-vinylcarbazole)/tris (8-hydroxyquinoline) aluminum (Alq3)/Mg:Ag are fabricated at different substrate temperatures (77, 298, and 438 K) during Alq3 deposition. It is found that the surface morphologies of Alq3 thin films greatly affect the I-V characteristics of the devices by the contact area between metal cathode and light-emitting layer. There is an increase in the luminous efficiency of the devices in the order 77 K < 298 K < 438 K. We attribute this trend to different structures of Alq3 thin films. (C) 2001 American Institute of Physics.
Resumo:
The adsorption of an electroinactive product greatly influences an irreversible electrochemical reaction in three ways, including self-block, self-inhibition, and self-acceleration, and changes not only the heterogeneous electron-transfer rate constant but also the modified formal potential and electron-transfer coefficient of the electrochemical reaction. In order to study these adsorption effects, a double logarithmic method was suggested to be used in processing the potential-controlled thin layer spectroelectrochemical data. The result shows three types of double logarithmic plots for three kinds of adsorption effects. These double logarithmic plots can be a diagnostic criterion of the adsorption effects and enable us to determine some thermodynamic and kinetic parameters. The combination of nonlinear regression with double logarithmic method is a convenient way to examine the suggested mechanism and to extract more information from the limited experimental data. Some examples are given to test the theoretical results. (C) 1999 The Electrochemical Society. S0013-4651(98)05-012-5. All rights reserved.
Resumo:
Permeability coefficients of H-2, O-2, and N2 were measured under 10 atm at the temperature from ambient temperature up to 150 degrees C in a series of structurally different aromatic homo- and copolyimides, which were prepared from 4,4'-oxydianiline (ODA) or 4,4'-methylene dianiline (MDA) with various aromatic dianhydrides. The study shows that the molecular structure of the polyimides strongly influences gas permeability and permselectivity. As a result, the permeability coefficients of the polyimide membranes for each gas vary by over two orders of magnitude. In general, among the polyimide membranes studied, the increase in permeability of polymers is accompanied by the decrease in permselectivity, and the MDA-based polyimide membranes have higher permeability than ODA-based ones. Among the polyimides prepared from bridged dianhydrides, the permeability coefficients to H-2, O-2, and N-2 are progressively increased in the order BPDA < BTDA < ODPA similar to TDPA < DSDA ( SiDA < 6FDA, while H-2/N-2 and O-2/N-2 permselectivity coefficients are progressively decreased in the same order. The copolyimide membranes, which were prepared from 3,3',4,4' biphenyltetracarboxylic dianhydride (BPDA), bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride (SiDA), and ODA, have favorable gas separation properties and are useful for H-2/N-2 separation applications. (C) 1996 John Wiley & Sons, Inc.
Resumo:
The effects of metal ions and lanthanide complexes on the gel-to-liquid crystal phase transition temperature T-m of dipalmitoylphosphatidylethanolamine liposomes have been studied by differential scanning calorimetry (DSC) method. The results show that the addition of metal ions to the dipalmitoylphosphatidylethanolamine (DPPE) liposomes dispersions increases the main phase transition temperature T-m in the order of monovalent< divalent< trivalent cations. The enhancement of T-m is not large as increasing the lanthanide ions concentration. The enhancement of Pr3+ is larger than that of La3+. Remarkable differences were observed between La-citrate and La-lactate complexes at different pH solutions. At pH 7.0, La-citrate complex has no effect on the T-m, La-lactate complex, however, increases the T-m value, and the increase is larger than that of free lanthanide ions at the same concentration. The decrease of pH of complexes solutions lowers the phase transition temperature. We have preliminarily discussed the mechanism of the enhancements of lanthanide ions and the synergism of lanthanide ion and lactate ligand follow the ion induced dehydration of lipid and the potential effects of ion-lipid interaction.
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Effects of food availability on larval growth and survival of Meretrix meretrix were studied in two experiments by feeding the larvae with different algae diets and by starving the larvae for different periods of time. Newly hatched larvae of M meretrix were fed with five different marine microalgae species, singly and in various mixtures. Best growth was with Isochrysis galbana as a single species diet. Nutritional value of the other single species diets was in the order of Dunaliella sp.> Phaeodactylum tricornutum > Platymonas subcordiformis > Pavlova viridis. Of the mixtures tested, 50% I. galbana/50% Dunaliella sp., 50% I. galbana/50% P tricornutum, and 50% 1 galbana/50% P subcordiformis, supported growth and metamorphosis equivalent to those of the I. galbana control. At 25 degrees C, larvae of M meretrix were deprived of food for various days to study the growth compensation from the outset of development. The results showed that M meretrix larvae could survive long feeding delays, and even reach metamorphosis without food added, although starvation had significant effects on growth. These results suggested that M meretrix larvae had the capacity to survive 'starvation' using alternative sources of energy. It also showed that growth, survival and metamorphosis of M meretrix were affected by many factors besides food quality and quantity. (c) 2005 Elsevier B.V. All rights reserved.
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Fractional energy losses of waves due to wave breaking when passing over a submerged bar are studied systematically using a modified numerical code that is based on the high-order Boussinesq-type equations. The model is first tested by the additional experimental data, and the model's capability of simulating the wave transformation over both gentle slope and steep slope is demonstrated. Then, the model's breaking index is replaced and tested. The new breaking index, which is optimized from the several breaking indices, is not sensitive to the spatial grid length and includes the bottom slopes. Numerical tests show that the modified model with the new breaking index is more stable and efficient for the shallow-water wave breaking. Finally, the modified model is used to study the fractional energy losses for the regular waves propagating and breaking over a submerged bar. Our results have revealed that how the nonlinearity and the dispersion of the incident waves as well as the dimensionless bar height (normalized by water depth) dominate the fractional energy losses. It is also found that the bar slope (limited to gentle slopes that less than 1:10) and the dimensionless bar length (normalized by incident wave length) have negligible effects on the fractional energy losses.
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Based on the second-order random wave solutions of water wave equations in finite water depth, statistical distributions of the depth- integrated local horizontal momentum components are derived by use of the characteristic function expansion method. The parameters involved in the distributions can be all determined by the water depth and the wave-number spectrum of ocean waves. As an illustrative example, a fully developed wind-generated sea is considered and the parameters are calculated for typical wind speeds and water depths by means of the Donelan and Pierson spectrum. The effects of nonlinearity and water depth on the distributions are also investigated.
Resumo:
The effects of the timing of first feeding (0, 1 and 2 days after yolk exhaustion) and starvation on the point-of-no-return (PNR), survival and growth of laboratory-reared rock bream larvae were studied under controlled conditions. Larvae began to feed exogenously at 3 days after hatching (dah) and reached PNR on 54 h after yolk exhaustion at 22 +/- 1.5 degrees C. Larvae growth was significantly affected by the time of first exogenous feeding. The growth of 0 day delayed first feeding larvae was obviously faster than those of the other delayed first feeding larvae (P<0.05) whether at 7 dab (SL=3.40 mm, SGR=5.7, CV=4.0) or at 15 dah (SL=4.85 mm, SGR=6.1, CV=8.2) with a more uniform size distribution. Survival of 0 day delayed first feeding larvae and I day delayed first feeding larvae was 13% and 8% at the end of experiment, respectively, while no larvae survived up to 7 dah for 2 days delayed first feeding larvae and unfed larvae. Food resulted in a progressive deterioration of the larval digestive system and atrophy of skeletal muscle fibre. The ratios of head length to SL (standard length), body height to SL and eye diameter to SL were the most sensitive morphometric indices to detect the effects of fasting on larval condition. Present results showed that the combination of morphological and morphometric variables could be used to evaluate the nutritional condition of rock bream larvae. In order to avoid the potential mortality and gain better development, survival and growth in industrial production, the rock bream larvae must establish successful first feeding within 2 days after yolk exhaustion. (C) 2008 Elsevier B.V. All rights reserved.
Resumo:
In order to study the effects of different nitrogen source and concentration on the growth rate and fatty acid composition, a marine microalga Ellipsoidion sp. with a high content of eicosapentaenoic acid (EPA) was cultured in media with different nitrogen sources and concentrations. During the pre-logarithmic phase, the alga grew faster with ammonium as N source than with nitrate, but the reverse applied during the post-logarithmic phase. The alga grew poorly in N-free medium or medium with urea as the sole N source. In the same growth phase, ammonium medium resulted in higher yield of total lipid, but the EPA yield did not differ significantly different from that using nitrate medium. The maximum growth rate occurred in medium containing 1.28 mmol L-1 sodium nitrate, while maximum EPA and total lipid contents were reached at 1.92 mmol L-1, when EPA accounted for 27.9% total fatty acids. The growth rate kept stable when NH4Cl ranged from 0.64 to 2.56 mmol L-1, and the maximum content of total lipid and EPA occurred in the medium with 2.56 mmol L-1 NH4Cl. The EPA content was higher in the pre- than post-logarithmic phase, though the total lipid content was lower. The highest EPA content expressed as percent total fatty acid was 27.9% in nitrate medium and and 39.0% in ammonium medium.
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Biosorption of Cu2+ and Pb2+ by Cladophora fascicularis was investigated as a function of initial pH, initial heavy metal concentrations, temperature and other co-existing ions. Adsorption equilibriums were well described by Langmuir and Freundlich isotherm models. The maximum adsorption capacities were 1.61 mmol/ g for Cu2+ and 0.96 mmol/ g for Pb2+ at 298K and pH 5.0. The adsorption processes were endothermic and biosorption heats calculated by the Langmuir constant b were 39.0 and 29.6 kJ/ mol for Cu2+ and Pb2+, respectively. The biosorption kinetics followed the pseudo- second order model. No significant effect on the uptake of Cu2+ and Pb2+ by co-existing cations and anions was observed, except EDTA. Desorption experiments indicated that Na(2)EDTA was an efficient desorbent for the recovery of Cu2+ and Pb2+ from biomass. The results showed that Cladophora fascicularis was an effective and economical biosorbent material for the removal and recovery of heavy metal ions from wastewater.
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In order to determine the optimum seed pre??sowing treatments and patterns of germination,a greenhouse experiment was conducted to study the effects of abrasion,sulphuric acid,boiling water,cold stratification and seed exudate treatments on the germination of ten Calligonum species.The results showed that the response of seed germination to the different pretreatments was similar for all ten Calligonum species.The abrasion,sulphuric acid and cold stratification treatments significantly promoted overall germinability.Compared with the control,the exudate treatment significantly decreased the percent germination,hampered the rate of germination and bolstered dormancy for almost all species.The cold stratification treatment can break the dormancy of viable Calligonum seeds and increased the germination,but it has a little lethal effect on viable seeds probably as well as the boiling water treatments.The germinaton patterns performed significant difference between the pre-sowing treatments for all ten Calligonum species,and the speed and percent germination of the Calligonum species can be greatly increased by mechanical scarification or sulphuric acid treatments.The results showed that seeds of C.junceum have strong ability of germinating.
Resumo:
The increasing trend of air temperature along with the climate warming has been accepted gradual-ly by scientists and by the general public. Qinghai-Xizang Plateau, a unique geographic unit due to high-altitude climate, is one of the most susceptible regions to climate warming. Its ecosystem is very fragile and sensi-tive to climate change. In order to get a better understanding of the impacts of climate warming on the nutrient contents of herbage grown in Qinghai-Xizang Plateau, a simulative study was implemented at Daban Moutain by using temperature differences resulted from sites selected at different altitudes and nutrient contents and in vitro digestibility were determined for assessing the quality of the grown herbage. There were significant downtrends in crude protein (CP), ether extract (EE) and nitrogen free extract (NFE) contents of herbage along with the increase of temperature. It had a positive correlation between temperature and content of acid detergent fibre (ADF), acid detergent lignin (ADL) in herbage. In vitro digestibility of herbage decreased along with the in-crease of temperature. The results of this study indicated that climate warming significantly influence nutrient contents and in vitro digestibility of herbage grown in Qinghai-Xizang Plateau. It is suggested that the future climate warming especially the gradual rise of the night temperature could cause negative effect on herbage quality grown in Qinghai-Xizang Plateau by decreasing CP, EE, and NFE contents and increasing some indi-gestible ingredients such as crude fibre (CF), neutral detergent fibre (NDF), ADF, and ADL. This, conse-quently, decreases the ruminant assimilation ability.