长白山地区近50年气候变化及其预估

收集长白山地区15个气象站1953-2007年气温、降水、蒸发、日照时数和水汽压观测数据和国家气候中心整理的2001-2099年的 气温、降水预估资料，利用数理统计方法，系统分析长白山地区气候现状、变化及其预估，为气候变化对人类生存环境影响研究并制定适应对策提供依据。主要结论如下： 1.长白山地区气温、降水日数、日照时数和不同界限温度（≥0℃、≥5℃、≥10℃和<0℃）积温均有显著趋势。年极端最低、年平均、平均最高/最低气温和气温日/年较差在1984、1992、1995、1985、1972和1979年发生突变。所有最高/最低气温与日照百分率有显著负相关关系，一定程度是温室效应结果；最高、最低气温变化不同步造成气温日较差和年较差的非对称性。 2.长白山地区生长季节合计降水量和降水强度日际变化较大。降水以7月30日为界，呈现前升后降极显著的线性趋势，且发生均值突变。降水强度以6月27日和9月3日为分界点，分为三个阶段。降水集中度、集中期和集中时段时空非均一性分布明显。 3.在SRES A1B、SRES A2和SRES B1三种情景下年平均气温均为上升趋势，年内变化一致为冬季升温最迅速，夏季则相对缓慢；而年降水强度总体增加，年内变化比较一致：冬季增加最为明显，而夏季变化不大。 4.未来长白山地区各站≥0℃、≥5℃和≥10℃的积温均有不同程度增加，持续时间延长。负积温增加，持续时间缩短，开始日期推迟，而结束时间提前。

Effects of molecular weight, solvent and substrate on the dewetting morphology of polystyrene films

Surface morphology of polystyrene (PS) films on different substrates by spin-coating before and after annealing was observed using atomic force microscopy (AFM). The effects of polymer molecular weight, substrates, solvents, and annealing conditions on the morphology of the films were investigated. Before annealing, the grain height decreases, and simultaneously the grain diameter increases with molecular weight (M-w) within the measured molecular weight. After annealing. the situation is opposite, i.e., the grain height increases while the grain diameter decreases with M-w. Furthermore, after annealing the smaller surface roughness (Ra) was obtained. It was also found that film surface roughness (Ra) depends on the vapor pressure and dipole moment of different used solvents as well as the substrates. The experimental results show that when the used solvents have similar dipole moment but different vapor pressure, the Ra of PS film decreased with the decreasing vapor pressure of solvents whether on silicon or on mica. And when the used solvents have close vapor pressure but different dipole moment, the Ra decreased with the increasing of solvent dipole moments on both substrates.

Application of ionic liquids in organic reactions

Room-temperature ionic liquids are good solvents for a wide of organic, inorganic and organometallic compounds. Typically consisting of nitrogen-containing organic cations and inorganic anions, they are easy to recycle, nonflammable, and have no detectable vapor pressure. More recently, ionic liquids have been found to be excellent solvents for a number of chemical reactions, e. g. hydrogenation, alkylation, epoxidation, Heck-vinylation, Suzuki cross-coupling reactions and enzyme catalyzed organic reactions. This paper focuses on the recent development of using ionic liquids as solvents for transition metal and enzyme catalyzed reactions.

Carbon Dioxide Exchange Between the Atmosphere and an Alpine Shrubland Meadow During the Growing Season on the Qinghai-Tibetan Plateau

In the present study, we used the eddy covariance method to measure CO2 exchange between the atmosphere and an alpine shrubland meadow ecosystem (37°36'N, 101°18'E; 3 250 m a.s.l.) on the Qinghai-Tibetan Plateau, China, during the growing season in 2003, from 20 April to 30 September. This meadow is dominated by formations of Potentilla fruticosa L. The soil is Mol-Cryic Cambisols. During the study period, the meadow was not grazed. The maximum rates of CO2 uptake and release derived from the diurnal course of CO2 flux were -9.38 and 5.02 μmol•m-2•s-1, respectively. The largest daily CO2 uptake was 1.7 g C•m-2•d-1 on 14 July, which is less than half that of an alpine Kobresia meadow ecosystem at similar latitudes. Daily CO2 uptake during the measurement period indicated that the alpine shrubland meadow ecosystem may behave as a sink of atmospheric CO2 during the growing season. The daytime CO2 uptake was correlated exponentially or linearly with the daily photo synthetic photon flux density each month. The daytime average water use efficiency of the ecosystem was 6.47 mg CO2/g H2O. The efficiency of the ecosystem increased with a decrease in vapor pressure deficit.

CO2H2O and energy exchange of an Inner Mongolia steppe ecosystem during a dry and wet year

We used an eddy covariance technique to measure evapotranspiration and carbon flux over two very different growing seasons for a typical steppe on the Inner Mongolia Plateau, China. The rainfall during the 2004 growing season (344.7 mm) was close to the annual average (350.43 mm). In contrast, precipitation during the 2005 growing season was significantly lower than average (only 126 mm). The wet 2004 growing season had a higher peak evapotranspiration (4 mm day(-1)) than did the dry 2005 growing season (3.3 mm day(-1)). In 2004, latent heat flux was mainly a consumption resource for net radiation, accounting for similar to 46% of net radiation. However, sensible heat flux dominated the energy budget over the whole growing season in 2005, accounting for 60% of net radiation. The evaporative rate (LE/R-n) dropped by a factor of four from the non-soil stress to soil water limiting conditions. Maximum half-hourly CO2 uptake was -0.68 mg m(-2) s(-1) and maximum ecosystem exchange was 4.3 g CO2 m(-2) day(-1) in 2004. The 2005 drought growing stage had a maximum CO2 exchange value of only -0.22 mg m(-2) s(-1) and a continuous positive integrated-daily CO2 flux over the entire growing season, i.e. the ecosystem became a net carbon source. Soil respiration was temperature dependent when the soil was under non-limiting soil moisture conditions, but this response declined with soil water stress. Water availability and a high vapor pressure deficit severely limited carbon fixing of this ecosystem; thus, during the growing season, the capacity to fix CO2 was closely related to both timing and frequency of rainfall events. (c) 2007 Published by Elsevier Masson SAS.

Short-term variation of CO2 flux in relation to environmental controls in an alpine meadow on the Qinghai-Tibetan Plateau

[1] The alpine meadow ecosystem on the Qinghai-Tibetan Plateau may play a significant role in the regional carbon cycle. To assess the CO2 flux and its relationship to environmental controls in the ecosystem, eddy covariance of CO2, H2O, and energy fluxes was measured with an open-path system in an alpine meadow on the plateau at an elevation of 3,250 m. Net ecosystem CO2 influx (Fc) averaged 8.8 g m(-2) day(-1) during the period from August 9 to 31, 2001, with a maximum of 15.9 g m(-2) day(-1) and a minimum of 2.3 g m(-2) day(-1). Daytime Fc averaged 16.7 g m(-2) day(-1) and ranged from 10.4 g m(-2) day(-1) to 21.7 g m(-2) day(-1) during the study period. For the same photosynthetic photon flux density (PPFD), gross CO2 uptake (Gc) was significantly higher on cloudy days than on clear days. However, mean daily Gc was higher on clear days than on cloudy days. With high PPFD, Fc decreased as air temperature increased from 10degreesC to 23degreesC. The greater the difference between daytime and nighttime air temperatures, the more the sink was strengthened. Daytime average water use efficiency of the ecosystem (WUEe) was 8.7 mg (CO2)(g H2O)(-1); WUEe values ranged from 5.8 to 15.3 mg (CO2)(g H2O)(-1). WUEe increased with the decrease in vapor pressure deficit. Daily albedo averaged 0.20, ranging from 0.19 to 0.22 during the study period, and was negatively correlated with daily Fc. Our measurements provided some of the first evidence on CO2 exchange for a temperate alpine meadow ecosystem on the Qinghai-Tibetan Plateau, which is necessary for assessing the carbon budget and carbon cycle processes for temperate grassland ecosystems.

IDENTIFYING AND MONITORING THE ROLES OF CAVITATION IN HEATING FROM HIGH-INTENSITY FOCUSED ULTRASOUND

For high-intensity focused ultrasound (HIFU) to continue to gain acceptance for cancer treatment it is necessary to understand how the applied ultrasound interacts with gas trapped in the tissue. The presence of bubbles in the target location have been thought to be responsible for shielding the incoming pressure and increasing local heat deposition due to the bubble dynamics. We lack adequate tools for monitoring the cavitation process, due to both limited visualization methods and understanding of the underlying physics. The goal of this project was to elucidate the role of inertial cavitation in HIFU exposures in the hope of applying noise diagnostics to monitor cavitation activity and control HIFU-induced cavitation in a beneficial manner. A number of approaches were taken to understand the relationship between inertial cavitation signals, bubble heating, and bubble shielding in agar-graphite tissue phantoms. Passive cavitation detection (PCD) techniques were employed to detect inertial bubble collapses while the temperature was monitored with an embedded thermocouple. Results indicate that the broadband noise amplitude is correlated to bubble-enhanced heating. Monitoring inertial cavitation at multiple positions throughout the focal region demonstrated that bubble activity increased prefocally as it diminished near the focus. Lowering the HIFU duty cycle had the effect of maintaining a more or less constant cavitation signal, suggesting the shielding effect diminished when the bubbles had a chance to dissolve during the HIFU off-time. Modeling the effect of increasing the ambient temperature showed that bubbles do not collapse as violently at higher temperatures due to increased vapor pressure inside the bubble. Our conclusion is that inertial cavitation heating is less effective at higher temperatures and bubble shielding is involved in shifting energy deposition at the focus. The use of a diagnostic ultrasound imaging system as a PCD array was explored. Filtering out the scattered harmonics from the received RF signals resulted in a spatially- resolved inertial cavitation signal, while the amplitude of the harmonics showed a correlation with temperatures approaching the onset of boiling. The result is a new tool for detecting a broader spectrum of bubble activity and thus enhancing HIFU treatment visualization and feedback.

Conversion of natural forests to managed forest plantations decreases tree resistance to prolonged droughts

© 2015 Published by Elsevier B.V.Throughout the southern US, past forest management practices have replaced large areas of native forests with loblolly pine plantations and have resulted in changes in forest response to extreme weather conditions. However, uncertainty remains about the response of planted versus natural species to drought across the geographical range of these forests. Taking advantage of a cluster of unmanaged stands (85-130year-old hardwoods) and managed plantations (17-20year-old loblolly pine) in coastal and Piedmont areas of North Carolina, tree water use, cavitation resistance, whole-tree hydraulic (Ktree) and stomatal (Gs) conductances were measured in four sites covering representative forests growing in the region. We also used a hydraulic model to predict the resilience of those sites to extreme soil drying. Our objectives were to determine: (1) if Ktree and stomatal regulation in response to atmospheric and soil droughts differ between species and sites; (2) how ecosystem type, through tree water use, resistance to cavitation and rooting profiles, affects the water uptake limit that can be reached under drought; and (3) the influence of stand species composition on critical transpiration that sets a functional water uptake limit under drought conditions. The results show that across sites, water stress affected the coordination between Ktree and Gs. As soil water content dropped below 20% relative extractable water, Ktree declined faster and thus explained the decrease in Gs and in its sensitivity to vapor pressure deficit. Compared to branches, the capability of roots to resist high xylem tension has a great impact on tree-level water use and ultimately had important implications for pine plantations resistance to future summer droughts. Model simulations revealed that the decline in Ktree due to xylem cavitation aggravated the effects of soil drying on tree transpiration. The critical transpiration rate (Ecrit), which corresponds to the maximum rate at which transpiration begins to level off to prevent irreversible hydraulic failure, was higher in managed forest plantations than in their unmanaged counterparts. However, even with this higher Ecrit, the pine plantations operated very close to their critical leaf water potentials (i.e. to their permissible water potentials without total hydraulic failure), suggesting that intensively managed plantations are more drought-sensitive and can withstand less severe drought than natural forests.

Phase transition and decomposition temperatures, heat capacities and viscosities of pyridinium ionic liquids

Ionic liquids are organic salts with low melting points. Many of these compounds are liquid at room temperature in their pure state. Since they have negligible vapor pressure and would not contribute to air pollution, they are being intensively investigated for a variety of applications, including as solvents for reactions and separations, as non-volatile electrolytes, and as heat transfer fluids. We present melting temperatures, glass transition temperatures, decomposition temperatures, heat capacities, and viscosities for a large series of pyridinium-based ionic liquids. For comparison, we include data for several imidazolium and quaternary ammonium salts. Many of the compounds do not crystallize, but form glasses at temperatures between 188 K and 223 K. The thermal stability is largely determined by the coordinating ability of the anion, with ionic liquids made with the least coordinating anions, like bis(trifluoromethylsulfonyl)imide, having the best thermal stability. In particular, dimethylaminopyridinium bis(trifluoromethylsulfonyl)imide salts have some of the best thermal stabilities of any ionic liquid compounds investigated to date. Heat capacities increase approximately linearly with increasing molar mass, which corresponds with increasing numbers of translational, vibrational, and rotational modes. Viscosities generally increase with increasing number and length of alkyl substituents on the cation, with the pyridinium salts typically being slightly more viscous than the equivalent imidazolium compounds. (c) 2005 Elsevier Ltd. All rights reserved.

Superoleophobicity under vacuum

By using superoleophobic alumina and low vapor pressure oils we have been able to study wetting behavior at high vacuum. Here, we show that a superoleophobic state can exist for some probe liquids, even under high vacuum. However, with other liquids the surfaces are only superoloephobic because air is trapped beneath the droplet and the contact angle decreases dramatically (150 degrees-120 degrees) if this air is removed. These observations open up the possibility of designing materials which fully exploit the potential of physically trapped air to achieve extreme oleophobicity and/or hydrophobicity. (C) 2011 American Institute of Physics. [doi:10.1063/1.3589352]

Physical properties of a new Deep Eutectic Solvent based on lithium bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as superionic suitable electrolyte for lithium ion batteries and electric double layer capacitors

Herein we present a study on the physical/chemical properties of a new Deep Eutectic Solvent (DES) based on N-methylacetamide (MAc) and lithium bis[(trifluoromethyl)sulfonyl]imide (LiTFSI). Due to its interesting properties, such as wide liquid-phase range from -60°C to 280°C, low vapor pressure, and high ionic conductivity up to 28.4mScm at 150°C and at x=1/4, this solution can be practically used as electrolyte for electrochemical storage systems such as electric double-layer capacitors (EDLCs) and/or lithium ion batteries (LiBs). Firstly, relationships between its transport properties (conductivity and viscosity) as a function of composition and temperature were discussed through Arrhenius' Law and Vogel-Tamman-Fulcher (VTF) equations, as well as by using the Walden classification. From this investigation, it appears that this complex electrolyte possesses a number of excellent transport properties, like a superionic character for example. Based on which, we then evaluated its electrochemical performances as electrolyte for EDLCs and LiBs applications by using activated carbon (AC) and lithium iron phosphate (LiFePO) electrodes, respectively. These results demonstrate that this electrolyte has a good compatibility with both electrodes (AC and LiFePO) in each testing cell driven also by excellent electrochemical properties in specific capacitance, rate and cycling performances, indicating that the LiTFSI/MAc DES can be a promising electrolyte for EDLCs and LiBs applications especially for those requiring high safety and stability. © 2013 Elsevier Ltd.

Physicochemical Investigation of Adiponitrile-Based Electrolytes for Electrical Double Layer Capacitor

Gas Hydrate Inhibition: A Review of the Role of Ionic Liquids

Ionic liquids (ILs) are popular designer green chemicals with great potential for use in diverse energy-related applications. Apart from the well-known low vapor pressure, the physical properties of ILs, such as hydrogen-bond-forming capacity, physical state, shape, and size, can be fine-tuned for specific applications. Natural gas hydrates are easily formed in gas pipelines and pose potential problems to the oil and natural gas industry, particularly during deep-sea exploration and production. This review summarizes the recent advances in IL research as dual-function gas hydrate inhibitors. Almost all of the available thermodynamic and kinetic inhibition data in the presence of ILs have been systematically reviewed to evaluate the efficiency of ILs in gas hydrate inhibition, compared to other conventional thermodynamic and kinetic gas hydrate inhibitors. The principles of natural gas hydrate formation, types of gas hydrates and their inhibitors, apparatuses and methods used, reported experimental data, and theoretical methods are thoroughly and critically discussed. The studies in this field will facilitate the design of advanced ILs for energy savings through the development of efficient low-dosage gas hydrate inhibitors.

Développement de nouveaux sels Binol-imidazoliums : de la catalyse asymétrique aux applications biologiques

Le 1,1'-bi-2-naphtol ou Binol, présentant une chiralité axiale, est un ligand très utilisé en catalyse asymétrique. Au cours des vingt dernières années, le Binol a servi de synthon à l’élaboration de très nombreux ligands permettant la catalyse asymétrique de tous types de réactions, allant de l’hydrogénation, à l’alkylation, en passant par diverses réactions péricycliques. Le grand intérêt pour ce ligand vient de sa versatilité et des nombreuses possibilités de fonctionnalisation qu’il offre, permettant d’altérer ses propriétés catalytiques à volonté, aussi bien en modifiant son caractère électronique, qu’en introduisant des facteurs stériques autour du site catalytique. Parallèlement aux développements de la catalyse par des dérivés de Binol, le domaine des liquides ioniques a connu un intérêt croissant ces dernières années. Les liquides ioniques, sels dont le point de fusion est inférieur à 100°C, cumulent de nombreuses qualités convoitées : faible pression de vapeur, stabilité thermique et chimique et fort pouvoir de solvatation. Dû à ces propriétés, les liquides ioniques ont principalement été étudiés dans l’optique de développer une gamme de solvants recyclables. Alors que les propriétés des liquides ioniques sont facilement modulables en fonction de l’anion et du cation choisi, le concept de liquide ionique à tâche spécifique va plus loin et propose d’introduire directement, sur le cation ou l’anion, un groupement conférant une propriété particulière. En suivant cette approche, plusieurs ligands ioniques ont été rapportés, par simple couplage d’un cation organique à un ligand déjà connu. Étonnamment, le Binol a fait l’objet de très peu de travaux pour l’élaboration de ligands ioniques. Dans cette thèse, nous proposons l’étude d’une famille de composés de type Binol-imidazolium dont les unités Binol et imidazolium sont séparées par un espaceur méthylène. Différents homologues ont été synthétisés en variant le nombre d’unités imidazolium et leur position sur le noyau Binol, la longueur de la chaîne alkyle portée par les unités imidazolium et la nature du contre-anion. Après une étude des propriétés thermiques de ces composés, l’utilisation des Binol-imidazoliums en tant que ligands dans une réaction asymétrique d’éthylation d’aldéhydes aromatique a été étudiée en milieu liquide ionique. La réaction a été conduite en solvant liquide ionique dans le but de recycler aussi bien le ligand Binol-imidazolium que le solvant, en fin de réaction. Cette étude nous a permis de démontrer que la sélectivité de ces ligands ioniques dépend grandement de leur structure. En effet, seuls les Binols fonctionnalisés en positions 6 et 6’ permettent une sélectivité de la réaction d’éthylation. Alors que les dérivés de Binol fonctionnalisés en positions 3 et 3’ ne permettent pas une catalyse énantiosélective, il a déjà été rapporté que ces composés avaient la capacité de complexer des anions. D’autre part, il a déjà été rapporté par notre groupe, que les composés comportant des unités imidazolium pouvaient permettre le transport d’anions à travers des bicouches lipidiques en fonction de leur amphiphilie. Ceci nous a amenés à la deuxième partie de cette thèse qui porte sur les propriétés ionophores des Binols fonctionnalisés en positions 3 et 3’ par des unités imidazoliums. Dans un premier temps, nous nous sommes intéressés à l’étude de la relation structure-activité et au mécanisme de transport de ces composés. Le transport d’anions étant un processus clé dans la biologie cellulaire, l’activité biologique des composés présentant une activité ionophore dans des systèmes modèles (liposomes) a été étudiée par la suite. L’activité antibactérienne des nos composés a été testée sur quatre souches de bactéries. Il s’est avéré que les composés Binol-imidazolium sont actifs uniquement sur les bactéries Gram positives. Finalement, la cytotoxicité des composés présentant une activité antibactérienne a été étudiée sur des cellules humaines.

Sels d’imidazolium avec des anions catalytiques : vers le développement de nouveaux catalyseurs bio-hybrides actifs en milieu liquide ionique

Les liquides ioniques connaissent depuis quelques décennies un essor particulier en raison de leurs nombreuses propriétés physico-chimiques intéressantes, telles qu’une faible pression de vapeur saturante, une viscosité limitée, une faible miscibilité avec la plupart des solvants communs, ou encore des propriétés d’agencement supramoléculaire, qui en font des outils puissants dans de nombreux domaines de la chimie. Les sels d’imidazolium représentent la plus grande famille de liquides ioniques à ce jour. Leur modulabilité leur permet d’être dérivés pour de nombreuses applications spécifiques, notamment en synthèse organique, où ils sont utilisés majoritairement comme solvants, et plus récemment comme catalyseurs. Les travaux présentés dans cette thèse se concentrent sur leur utilisation en synthèse organique, à la fois comme solvants et principalement comme catalyseurs chiraux, catalyseurs pour lesquels l’anion du sel est l’espèce catalytique, permettant d’ajouter de la flexibilité et de la mobilité au système. En tirant parti de la tolérance des liquides ioniques envers la majorité des macromolécules naturelles, l’objectif principal des travaux présentés dans cette thèse est le développement d’un nouveau type de catalyseur bio-hybride reposant sur l’encapsulation d’un sel d’imidazolium dans une protéine. Par le biais de la technologie biotine-avidine, l’inclusion supramoléculaire de sels d’imidazolium biotinylés portant des contre-anions catalytiques dans l’avidine a été réalisée et exploitée en catalyse. Dans un premier temps, le développement et l’étude de deux sels de 1-butyl-3-méthylimidazolium possédant des anions chiraux dérivés de la trans-4-hydroxy-L-proline sont rapportés, ainsi que leur comportement dans des réactions énantiosélectives d’aldol et d’addition de Michael. Ces types de composés se sont révélés actifs et performants en milieu liquide ionique. Dans un second temps, la préparation de sels d’imidazolium dont le cation est biotinylé et portant un contre-anion achiral, a été réalisée. Le comportement de l’avidine en milieu liquide ionique et son apport en termes de chiralité sur le système bio-hybride ont été étudiés. Les résultats montrent le rôle crucial des liquides ioniques sur la conformation de la protéine et l’efficacité du catalyseur pour des réactions d’aldol. Dans un dernier temps, l’influence de la structure du cation et de l’anion sur le système a été étudiée. Différents espaceurs ont été introduits successivement dans les squelettes cationiques et anioniques des sels d’imidazolium biotinylés. Dans le cas du cation, les résultats ne révèlent aucune influence majeure sur l’efficacité du catalyseur. La structure de l’anion se montre cependant beaucoup plus importante : la préparation de différents catalyseurs bio-hybrides possédant des anions aux propriétés physico-chimiques différentes a permis d’obtenir de plus amples informations sur le mode de fonctionnement du système bio-hybride et de la coopérativité entre l’avidine et l’anion du sel d’imidazolium.La nature ionique de la liaison cation-anion offrant une liberté de mouvement accrue à l’anion dans la protéine, la tolérance à différents substrats a également été abordée après optimisation du système.