Tb(111) and Ca(11) ion equilibria in the presence of glutamic acid and glutamine

Tb(111) and Ca(11) ion equilibria in the Presence of glutamic acid and glutamine were studied by potentiometric titration at 37 degrees C and an ionic strength of 0.15mol/L(NaCl). The stability constants for Tb(111) and Ca(11) complexes in the systems were obtained. The species and their distribution in the systems were discussed.

Yeast CA-11 fermentation in musts treated with brown and green propolis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Late Oligocene to Middle Miocene rifting and synextensional magmatism in the southwestern Sierra Madre Occidental, Mexico : the beginning of the Gulf of California rift

Although Basin and Range–style extension affected large areas of western Mexico after the Late Eocene, most consider that extension in the Gulf of California region began as subduction waned and ended ca. 14–12.5 Ma. A general consensus also exists in considering Early and Middle Miocene volcanism of the Sierra Madre Occidental and Comondú Group as subduction related, whereas volcanism after ca. 12.5 Ma is extension related. Here we present a new regional geologic study of the eastern Gulf of California margin in the states of Nayarit and Sinaloa, Mexico, backed by 43 new Ar-Ar and U-Pb mineral ages, and geochemical data that document an earlier widespread phase of extension. This extension across the southern and central Gulf Extensional Province began between Late Oligocene and Early Miocene time, but was focused in the region of the future Gulf of California in the Middle Miocene. Late Oligocene to Early Miocene rocks across northern Nayarit and southern Sinaloa were affected by major approximately north-south– to north-northwest– striking normal faults prior to ca. 21 Ma. Between ca. 21 and 11 Ma, a system of north-northwest–south-southeast high angle extensional faults continued extending the southwestern side of the Sierra Madre Occidental. Rhyolitic domes, shallow intrusive bodies, and lesser basalts were emplaced along this extensional belt at 20–17 Ma. Rhyolitic rocks, in particular the domes and lavas, often show strong antecrystic inheritance but only a few Mesozoic or older xenocrysts, suggesting silicic magma generation in the mid-upper crust triggered by an extension induced basaltic infl ux. In northern Sinaloa, large grabens were occupied by huge volcanic dome complexes ca. 21–17 Ma and filled by continental sediments with interlayered basalts dated as 15–14 Ma, a stratigraphy and timing very similar to those found in central Sonora (northeastern Gulf of California margin). Early to Middle Miocene volcanism occurred thus in rift basins, and was likely associated with decompression melting of upper mantle (inducing crustal partial melting) rather than with fluxing by fluids from the young and slow subducting microplates. Along the eastern side of the Gulf of California coast, from Farallón de San Ignacio island offshore Los Mochis, Sinaloa, to San Blas, Nayarit, a strike distance of >700 km, flat lying basaltic lavas dated as ca. 11.5–10 Ma are exposed just above the present sea level. Here crustal thickness is almost half that in the unextended core of the adjacent Sierra Madre Occidental, implying signifi cant lithosphere stretching before ca. 11 Ma. This mafic pulse, with subdued Nb-Ta negative spikes, may be related to the detachment of the lower part of the subducted slab, allowing an upward asthenospheric flow into an upper mantle previously modified by fluid fluxes related to past subduction. Widespread eruption of very uniform oceanic island basalt–like lavas occurred by the late Pliocene and Pleistocene, only 20 m.y. after the onset of rifting and ~9 m.y. after the end of subduction, implying that preexisting subduction-modified mantle had now become isolated from melt source regions. Our study shows that rifting across the southern-central Gulf Extensional Province began much earlier than the Late Miocene and provided a fundamental control on the style and composition of volcanism from at least 30 Ma. We envision a sustained period of lithospheric stretching and magmatism during which the pace and breadth of extension changed ca. 20–18 Ma to be narrower, and again after ca. 12.5 Ma, when the kinematics of rifting became more oblique.

The effect of blood glucose on the vasculature in young patients with type 1 diabetes

Background. Patients with type 1 diabetes are at markedly increased risk of vascular complications. In this respect it is noteworthy that hyperglycaemia that is shown to cause endothelial dysfunction, has clearly been shown to be a risk factor for diabetic microvascular disease. However, the role of hyperglycaemia as a predictor of macrovascular disease is not as clear as for microvascular disease, although type 1 diabetes itself increases the risk of cardiovascular disease substantially. Furthermore, it is not known whether it is the short-term or the long-term hyperglycaemia that confers possible risk. In addition, the role of glucose variability as a predictor of complications is to a large extent unexplored. Interestingly, although hyperglycaemia increases the risk of pre-eclampsia in women with type 1 diabetes, it is unclear whether pre-eclampsia, a condition characterized by endothelial dysfunction, is also a risk factor for microvascular complication, diabetic nephropathy. Aims. This doctoral thesis investigated the role of acute hyperglycaemia and glucose variability on arterial stiffness and cardiac ventricular repolarisation in male patients with type 1 diabetes as well as in healthy male volunteers. The thesis also explored whether acute hyperglycaemia leads to an inflammatory response, endothelial dysfunction and oxidative stress. Finally, the role of pre-eclampsia, as a predictor of diabetic nephropathy in type 1 diabetes was examined. Subjects and methods. In order to study glucose variability and the daily glycaemic control, 22 male patients with type 1 diabetes, without any diabetic complications, were monitored for 72-h with a continuous glucose monitoring system. At the end of the 72-h glucose monitoring period a 2-h hyperglycaemic clamp was performed both in the patients with type 1 diabetes and in the 13 healthy age-matched male volunteers. Blood pressure, arterial stiffness and QT time were measured to detect vascular changes during acute hyperglycaemia. Blood samples were drawn at baseline (normoglycaemia) and during acute hyperglycaemia. In another patient sample, women with type 1 diabetes were followed during their pregnancy and restudied eleven years later to elucidate the role of pre-eclampsia and pregnancy-induced hypertension as potential risk factors for diabetic nephropathy. Results and conclusions. Acute hyperglycaemia increased arterial stiffness as well as caused a disturbance in the myocardial ventricular repolarisation, emphasizing the importance of a strict daily glycaemic control in male patients with type 1 diabetes. An inflammatory response was also observed during acute hyperglycaemia. Furthermore, a high mean daily blood glucose but not glucose variability per se is associated with arterial stiffness. While glucose variability in turn correlated with central blood pressure, the results suggest that the glucose metabolism is closely linked to the haemodynamic changes in male patients with uncomplicated type 1 diabetes. Notably, the results are not directly applicable to females. Finally, a history of a pre-eclamptic pregnancy, but not pregnancy-induced hypertension was associated with increased risk of diabetic nephropathy.

生物小分子体系稀土和钙化学形态研究

随着稀土的广泛开发和利用，稀土日益进入环境，并且相继发现稀土具有多种生物效应。稀土与生物小分子配体多元体系中稀土化学形态的研究正是考察稀土在人体内的分布、代谢和生物效应的关键，对阐明稀土对环境和人体健康的影响及作用机理具有十分重要的意义。本论文进行了如下几方面的研究，并取得了创新性结果。1 稀土与生物小分子三元体系研究 在模拟生理条件下研究了Pr~(3+)、Gd~(3+)、Tb~(3+)、Yb~(3+)四种稀土离子和Ca~(2+)、Zn~(2+)两种生物金属离子分别与以天冬氨酸或柠檬酸为第一配体、分别以水扬酸、精氨酸、丝氨酸、异亮氨酸和苏氨酸为第二配体的三元溶液体系。经计算机程度优化得到体系中所生成的物种类型并计算得到各物种的稳定常数。在所研究的十个体系中，只是在金属离子-天冬氨酸-精氨酸、金属离子—柠檬酸-水杨酸和金属离子-柠檬酸-精氨酸三个体系中生成了两种三元配合物(1111型和1112型或1113型)，其它体系只生成了一种1112型三元配合物。重稀土配合物的稳定常数比轻稀土配合物的大。稀土配合物的稳定性明显强于钙配合物，接近或大于锌配合物的稳定常数，这表明稀土对钙有强竞争配位作用，对锌也有强竞争取代作用。以上稀土与生物小分子三元体系的研究取得了重要新结果。这些结果为考察稀土在体内的代谢、生物效应以及研究稀土对生物金属离子的拮抗、协同效应提供了重要科学依据。同时该研究也是多元体系数学模型法研究的基础。2. 金属离子生物小分子多元体系的数学模型法研究（1）对稀土与钙共存于两种生物配体（柠檬酸和精氨酸、天冬氨酸和精氨酸、柠檬酸和丝氨酸、柠檬酸和异亮氨酸、天冬氨酸和苏氨酸）的五个四元体系，经COMICS程序，利用已有二、三元配合物的稳定常数进行了计算。得到了稀土和钙的各物种随pH值变化的分布图。与三元体系相比，自由金属离子和二元配合物的含量显著增加。这表明稀土和钙之间存在着明显的竞争作用。（2）用数学模型法模拟研究了金属离子与血液中羧肽酶A的活性中心的作用。确定了Zn(II)和Tb(111)与该酶活性中心各残基的结合随pH的变化情况。当血液中稀Tb(III)的浓度较小时（与Zn(II)的浓度相近），Tb(III)对该酶活性中心的Zn(II)几乎没有影响；当Tb(III)达到较高浓度时，则能够与Zn(II)竞争活性中心各残基，从而可能影响该酶的结构和活性。（3）用数学模型法研究了人体血浆中生物小分子体系（二十种配体共存）Tb(III)和Ca(11)的分布情况及Tb(III)的存在对Ca(11)化学形态的影响。结果表明大部分铽与生物小分子配体形成多种形式的配合物，三元配合物占绝对优势。钙与铽明显不同，相当一部分的钙以自由离子形式存在，同时三元配合物也是钙的主要物种形式。模拟研究还表明当铽离子的浓度达到1E-4mol/L时，铽的存在会明显影响钙离子的物种形式及分布。以上多元体系的数学模型法研究所得创新性结果对考察稀土的分布、代谢及其生物效应和阐明稀土对钙的竞争取代作用都具有十分的重要意义。并且也进一步丰富和发展了稀土的生物无机化学。

岱海岩芯沉积的粒度组成与湖区全新世降水变化历史

Sediment cores DH99a and DH99b recovered in the central part of Daihai Lake in north-central China were analysed at 2- to 4-crn intervals for grain-size distribution. Grain-size distributions of the lake sediments are inferred to be a proxy for past changes in East Asian monsoon precipitation, such that greater silt-size percentage and higher median grain size reflect increased monsoonal precipitation rates. The grain-size record of Daihai Lake sediments spanning the last ca 11,000 yr indicates that the monsoonal precipitation in the lake region can be divided into three stages: the Early, Middle and Late Holocene. During the Early Holocene before ca 7900 cal yr BP, the median grain size (Md) and the silt-fraction content were relatively low and constant, suggesting relatively low precipitation over the lake region. The Middle Holocene between ca 7900 and 3100 cal yr BP was marked by intensified and highly variable monsoonal precipitation, as indicated by high and variable Md values and silt contents of the lake sediments. During this period, average precipitation rate gradually increased from ca 7900 to 6900 cal yr BP, displayed intense oscillations between ca 6900 and 4400 cal yr BP, and exhibited a decreasing trend while fluctuating from ca 4400 to 3100 cal yr BP Although generally high during the Middle Holocene, both the Md and the silt content assumed distinctly low values at the short intervals of ca 6500-6400, 6000-5900, 5700-5600, 4400-4200 cal yr BP, implying that monsoonal precipitation might have been significantly reduced during these intervals. During the Late Holocene since ca 3100 cal yr BP, grain-size values suggest that precipitation decreased. However, during the Late Holocene, relatively higher Md values and silt contents occurring between ca 1700 to 1000 cal yr BP may denote an intensification of hydrological cycles in the lake area. Changes in the East Asian monsoonal precipitation were not only directly linked with the changing seasonality of solar insolation resulting from progressive changes in the Earth's orbital parameters, but also may have been closely related to variations in the temperature and size of the Western Pacific Warm Pool, in the intensity of the El Nino-Southern Oscillation, and in the path and strength of the North Equatorial Current in the western Pacific.

贵州喀斯特山区植物营养元素含量特征

贵州喀斯特山区是我国乃至世界喀斯特分布面积最大的片区之一，由于其生态系统的脆弱性，加之人类活动的干扰，使得该区的植被退化较为严重。文章选择该区的12 种主要植物作为研究对象，对其营养元素进行了研究。结果表明：>1 000μg·g-1 的元素有N、P、K、Ca、Mg、S，100~1 000 μg·g-1 的元素有Fe、Mn、Al，10~100 μg·g-1 的元素有Zn、Sr，<10 μg·g-1的元素为Cu、Mo，其中Mo 含量最低，仅为0.17 μg·g-1。这些元素中，Ca、P、K 元素高于所报道的陆生植物的含量范围。元素含量特点是Ca>K>Mg 型。N、P、K、Mg 元素的频数分布为正态分布，Ca、Al、Fe、Mn、Cu、Zn、Sr、S 元素为对数正态分布。变异系数大于100%的元素有Al、Fe、Mn、Sr，变异系数小于60%的元素有N、P、K、Ca、Mg、S、Cu，其中Ca 的变异系数最小，仅为11.8%。不同生境下相同植物的营养元素含量有较大的差异，石灰土上植物的N、P、K、Ca、Mg、Al、Cu、Mo 元素含量要高于黄壤上植物的。元素间的相关分析表明：P 和K、P 和Cu、Al 和Fe、Al 和Zn、Fe 和Zn 元素具有显著相关关系；N 和P、P 和Mg、K 和Al、K 和Cu、Ca 和Sr、S 和Mo 元素具有一般相关关系。

贵州喀斯特山区植物营养元素和碳、氮、硫同位素组成研究--以贵阳花溪杨中流域为例

喀斯特的面积分布很广，占全球总面积的10%。我国喀斯特面积占国土面积的13%，主要集中在我国的南方。而贵州喀斯特山区位于西南喀斯特地貌最集中成片分布的中心区，是我国乃至世界热带、亚热带喀斯特地貌连续分布面积最大、发育最强烈的高原山区。和非喀斯特地区相比，贵州喀斯特山区由于碳酸盐岩的特殊理化特性，造成土层浅薄、土被不连续、岩石裸露率高、持水量低，适生树种少、群落结构单一、植被生长极其缓慢，生态环境十分的脆弱。加之人类不合理的活动，使得喀斯特山区植被退化非常严重。因此，开展贵州喀斯特山区植物的营养元素和碳、氮、硫同位素的研究是为了更好的了解该区植被的营养元素状况、生理生态特性以及营养元素的生物地球化学循环，更好地为该区森林、植被的治理、恢复以及生态系统的保护等提供决策依据。本研究选择典型喀斯特山区作为研究点，并以非喀斯特山区为对照。研究喀斯特山区植物的营养元素含量水平、分布状态、变异特征以及营养元素之间的相互关系和碳、氮、硫的同位素组成的种间差异、生境差异特征以及时空变化特征进行了研究。主要得到以下几点认识： 1、植物的N、P、K、Ca、Mg、S的平均含量大于1000 μg∙g-1； Fe、Mn、Al的平均含量在100 μg∙g¬-1～1000 μg∙g¬-1之间；Zn、Sr的平均含量为10 μg∙g¬-1～100 μg∙g¬-1之间；Cu和Mo的含量小于10 μg∙g¬-1，Mo最低(仅为0.17 μg∙g¬-1)。Ca、P、K、 Fe、Mn、S、Sr高于所报道的陆生植物元素的含量；Mg低于陆生植物的元素含量；其它元素在元素含量范围内。植物营养元素的特点为Ca>K>Mg型，和我国其它地区相比，喀斯特山区植被具有高钙的特征。 2、N、P、K、Mg为正态分布；Ca、Al、Fe、Mn、Cu、Zn、Sr、Mo、S为对数正态分布。Al、Fe、Mn、Sr的变异系数大于100%；N、P、K、Ca、Mg、S、Cu的变异系数小于60%。其中，Ca的变异系数最小(为11.8%)。P和K、P和Cu、Al和Fe、Al和Zn、Fe和Zn之间具有极显著的相关关系；N和P、P和Mg、K和Al、K和Cu、Ca和Sr、S和Mo之间具有显著的相关关系。 3、不同的生境下植物营养元素存在差异，差异在2倍范围内。其中，Mn、Al、Sr元素差异较大，分别达到2.1、1.5、1.4倍。 4、植物δ13C、δ15N、δ34S值的分布范围分别为-26.98‰～-29.15‰、-4.08‰～-0.79‰、-8.69‰～-6.04‰；平均值分别为-28.14‰、-2.41‰、-7.53‰。δ13C除了高于我国热带雨林区植物外，均低于其它地区，且变化范围较窄；不同地区之间植物的δ15N、δ34S值存在较大差异。 5、不同植物种之间的δ13C、δ15N、δ34S值存在较大的差异，不同生境条件下植物的δ13C、δ15N、δ34S值也存在差异。植物的δ13C值从生长初期到末期有降低的趋势；δ15N、δ34S则无一定的变化规律，不同的植物种的季节变化不同。植物的δ13C、δ34S随海拔的升高而增大，但δ15N随海拔的升高而降低。

Catalytic reduction of NO over in situ synthesized Ir/ZSM-5 monoliths

The catalytic performance of Ir-based catalysts was investigated for the reduction of NO under lean-burn conditions over binderless Ir/ZSM-5 monoliths, which were prepared by a vapor phase transport (VPT) technique. The catalytic activity was found to be dependent not only on the Ir content, but also on the ZSM-5 loading of the monolith. With the decreasing of the Ir content or the increasing of the ZSM-5 loading of the monolith, NO conversion increased. When the ZSM-5 loading on the cordierite monolith was raised up to ca. 11% and the metal Ir content was about 5 g/l, the NO conversion reached its maximum value of 73% at 533 K and SV of 20 000 h(-1). Furthermore, both the presence of 10% water vapor in the feed gas and the variation of space velocity of the reaction gases have little effect on the NO conversion. A comparative test between Ir/ZSM-5 and Cu/ZSM-5, as well as the variation of the feed gas compositions, revealed that Ir/ZSM-5 is very active for the reduction of NO by CO under lean conditions, although it is a poor catalyst for the C3H8-SCR process. This unique property of Ir/ZSM-5 makes it superior to the traditional three-way catalyst (TWC) for NO reduction under lean conditions. (C) 2001 Elsevier Science B.V. All rights reserved.

Projecting marine fish production and catch potential in Bangladesh in the 21st century under long-term environmental change and management scenarios

The fisheries sector is crucial to the Bangladeshi economy and wellbeing, accounting for 4.4% of national Gross Domestic Product (GDP) and 22.8% of agriculture sector production, and supplying ca.60% of the national animal protein intake. Fish is vital to the 16 million Bangladeshis living near the coast, a number that has doubled since the 1980s. Here we develop and apply tools to project the long term productive capacity of Bangladesh marine fisheries under climate and fisheries management scenarios, based on downscaling a global climate model, using associated river flow and nutrient loading estimates, projecting high resolution changes in physical and biochemical ocean properties, and eventually projecting fish production and catch potential under different fishing mortality targets. We place particular interest on Hilsa shad (Tenualosa ilisha), which accounts for ca.11% of total catches, and Bombay duck (Harpadon nehereus), a low price fish that is the second highest catch in Bangladesh and is highly consumed by low income communities. It is concluded that the impacts of climate change, under greenhouse emissions scenario A1B, are likely to reduce the potential fish production in the Bangladesh Exclusive Economic Zone (EEZ) by less than 10%. However, these impacts are larger for the two target species. Under sustainable management practices we expect Hilsa shad catches to show a minor decline in potential catch by 2030 but a significant (25%) decline by 2060. However, if overexploitation is allowed catches are projected to fall much further, by almost 95% by 2060, compared to the Business as Usual scenario for the start of the 21st century. For Bombay duck, potential catches by 2060 under sustainable scenarios will produce a decline of less than 20% compared to current catches. The results demonstrate that management can mitigate or exacerbate the effects of climate change on ecosystem productivity.

Photocatalytic activity indicator inks for the probing a wide range of surfaces

Three photocatalyst inks based on the redox dyes, Resazurin (Rz), Basic Blue 66 (BB66) and Acid Violet 7 (AV7), are used to assess the photocatalytic activities of a variety of different materials, such as commercial paint, tiles and glass and laboratory made samples of sol–gel coated glass and paint, which collectively exhibit a wide range of activities that cannot currently be probed by any one of the existing ISO tests. Unlike the ISO tests, the ink tests are fast (typically <10 min), simple to employ and inexpensive. Previous work indicates that the Rz ink test at least correlates linearly with other photocatalytic tests such as the photomineralisation of stearic acid. The average time to bleach 90% of the key RGB colour component of the ink, red for Rz and BB66 inks and green for AV7 ink, is determined, ttb(90), for eight samples of each of the different materials tested. Five laboratories conducted the tests and the results revealed an average repeatability and reproducibility of: ca. 11% and ca 21%, respectively, which compare well with those reported for the current ISO tests. Additional work on commercial self-cleaning glass using an Rz ink showed that the change in the red component of the RGB image of the ink correlated linearly with that of the change of absorbance at 608 nm, as measured using UV/vis spectroscopy, and the change in the a* component of the Lab colour analysis of the ink, as measured using diffuse reflectance spectroscopy. As a consequence, all three methods generate the same ttb(90). The advantages of the RGB digital image analysis method are discussed briefly.

In situ modification of a Pt catalyst supported on a mixed ionic-electronic conducting membrane

The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La_0.6Sr_0.4Co_0.2Fe_0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).

Dye-sensitized solar cells based on perylene derivatives

The oil price rises more and more, and the world energy consumption is projected to expand by 50 percent from 2005 to 2030. Nowadays intensive research is focused on the development of alternative energies. Among them, there are dye-sensitized nanocrystalline solar cells (DSSCs) “the third generation solar cells”. The latter have gained attention during the last decade and are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic. At present DSSCs with ruthenium based dyes exhibit highest efficiencies (ca 11%). The objective of the present work is to fabricate, characterize and improve the performance of DSSCs based on metal free dyes as sensitizers, especially on perylene derivatives. The work begins by a general introduction to the photovoltaics and dye-sensitized solar cells, such as the operating principles and the characteristics of the DSSCs. Chapter 2 and 3 discuss the state of the art of sensitizers used in DSSCs, present the compounds used as sensitizer in the present work and illustrate practical issues of experimental techniques and device preparation. A comparative study of electrolyte-DSSCs based on P1, P4, P7, P8, P9, and P10 are presented in chapter 4. Experimental results show that the dye structure plays a crucial role in the performance of the devices. The dye based on the spiro-concept (bipolar spiro compound) exhibited a higher efficiency than the non-spiro compounds. The presence of tert-butylpyridine as additive in the electrolyte was found to increase the open circuit voltage and simultaneously decrease the efficiency. The presence of lithium ions in the electrolyte increases both output current and the efficiency. The sensitivity of the dye to cations contained in the electrolyte was investigated in the chapter 5. FT-IR and UV-Vis were used to investigate the in-situ coordination of the cation to the adsorbed dye in the working devices. The open-circuit voltage was found to depend on the number of coordination sites in the dye. P1 with most coordination sites has shown the lowest potential drop, opposite to P7, which is less sensitive to cations in the working cells. A strategy to improve the dye adsorption onto the TiO2 surface, and thus the light harvesting efficiency of the photoanode by UV treatment, is presented in chapter 6. The treatment of the TiO2 film with UV light generates hydroxyl groups and renders the TiO2 surface more and more hydrophilic. The treated TiO2 surface reacts readily with the acid anhydride group of the dye that acts as an anchoring group and improves the dye adsorption. The short-circuit current density and the efficiency of the electrolyte-based dye cells was considerably improved by the UV treatment of the TiO2 film. Solid-state dye-sensitized solar cells (SSDs) based on spiro-MeOTAD (used as hole transport material) are studied in chapter 7. The efficiency of SSDs was globally found to be lower than that of electrolyte-based solar cells. That was due to poor pore filling of the dye-loaded TiO2 film by the spin-coated spiro-MeOTAD and to the significantly slower charge transport in the spiro-MeOTAD compared to the electrolyte redox mediator. However, the presence of the donor moieties in P1 that are structurally similar to spiro-MeOTAD was found to improve the wettability of the P1-loaded TiO2 film. As a consequence the performance of the P1-based solid-state cells is better compared to the cells based on non-spiro compounds.

Hydrogen bonded supramolecular elastomers : correlating hydrogen bonding strength with morphology and rheology

A series of six low molecular weight elastomers with hydrogen bonding end-groups have been designed, synthesised and studied. The poly(urethane) based elastomers all contained essentially the same hard block content (ca. 11%) and differ only in the nature of their end-groups. Solution state 1H NMR spectroscopic analysis of model compounds featuring the end-groups demonstrate that they all exhibit very low binding constants, in the range 1.4 to 45.0 M-1 in CDCl3, yet the corresponding elastomers each possess a markedly different nanoscale morphology and rheology in the bulk. We are able to correlate small variations of the binding constant of the end-groups with dramatic changes in the bulk properties of the elastomers. These results provide an important insight into the way in which weak non-covalent interactions can be utilized to afford a range of self-assembled polyurethane based materials that feature different morphologies.

Hydrology and climatology at Laguna La Gaiba, lowland Bolivia: complex responses to climatic forcings over the last 25,000 years

Diatom, geochemical and isotopic data provide a record of environmental change in Laguna La Gaiba, lowland Bolivia (17°450S, 57°350W), over the last ca. 25 000 years. High-resolution diatom analysis around the Last Glacial–Interglacial Transition provides new insights into this period of change. The full and late glacial lake was generally quite shallow, but with evidence of periodic flooding. At about 13 100 cal a BP, just before the start of the Younger Dryas chronozone, the diatoms indicate shallower water conditions, but there is a marked change at about 12 200 cal a BP indicating the onset of a period of high variability, with rising water levels punctuated by periodic drying. From ca. 11 800 to 10 000 cal a BP, stable, deeper water conditions persisted. There is evidence for drying in the early to middle Holocene, but not as pronounced as that reported from elsewhere in the southern hemisphere tropics of South America. This was followed by the onset of wetter conditions in the late Holocene consistent with insolation forcing. Conditions very similar to present were established about 2100 cal a BP. A complex response to both insolation forcing and millennial-scale events originating in the North Atlantic is noted.