Academic literature on the topic 'Lower critical solution temperature'

Poly(N-vinylcaprolactam), PNVCL, is a nonionic, nontoxic, water soluble, thermally sensitive and biocompatible polymer. It contains hydrophilic carboxylic and amide groups with hydrophobic carbon-carbon backbone chain so its hydrolysis does not produce small amide compounds which are often not desired for biomedical applications. Moreover PNVCL possesses lower critical solution temperature, (LCST) in the range of physiological temperature (32-34 oC). These properties make the polymer suitable for use in some biotechnology applications such as implantation of artificial organs and tissues, purification of enzymes, proteins and living cells, and in drug release systems. In this study PNVCL was synthesized by free radical polymerization with solution technique. Polymerization was done at different temperatures for different time periods in an oil bath. The activation energy for polymerization was found from Arrhenius plot as 108.4 kJ/mol. Polymer was characterized by FT-IR, 1H-NMR and 13C-NMR, DSC, TGA and XRD techniques. FT-IR and NMR measurements confirmed that the polymerization proceeded through the vinyl group.

The overall aim of my PhD research was to develop biocompatible materials, namely poly(2-oxazoline)s, in terms of chemical structures and chemical and physical properties for drug delivery systems. This thesis demonstrated novel strategies and unique approaches towards sophisticated drug delivery formulations. A combination of crosslinking chemistry, thermoresponsive properties, and drug conjugation was introduced to overcome common issues in typical drug delivery devices such as burst drug release and low drug efficiency. Ultimately, this thesis aimed to promote poly(2-oxazoline)s as the most promising emerging polymers in the future.

R??sum?? : Les copolym??res ?? blocs sensibles aux stimuli (SR-BCPs) et leurs assemblages, tels que les micelles, les v??sicules et les hydrogels, peuvent subir des changements physiques ou chimiques en r??ponse ?? l'??volution des conditions environnementales. Pour un excellent SR-BCP, habituellement, de l??g??res modifications de l'environnement sont suffisantes pour induire des modifications relativement drastiques dans la conformation, la structure ou les propri??t??s du polym??re. Ces polym??res sont aussi appel??s polym??res stimuli-r??actifs ou polym??res intelligents et ils ont un grand potentiel d'application dans de nombreux domaines. Au cours des deux derni??res d??cennies, un int??r??t de recherche et d??veloppement particulier a ??t?? port?? sur l'exploitation des SR-BCPs pour utilisation comme syst??mes de relargage de m??dicaments. Dans de nombreux cas, les changements induits par des stimuli dans la structure ou la morphologie des assemblages de BCPs peuvent entra??ner la lib??ration de l'esp??ce encapsul??e, parfois d'une mani??re contr??lable spatialement et temporellement par le choix d'un stimulus appropri?? et en ajustant les param??tres de la m??thode de stimulation utilis??e. De fa??on g??n??rale, le fait d???avoir un certain type de groupements r??actifs ?? un stimulus donn?? dans la structure permet aux SR-BCPs de reconna??tre et r??agir ?? ce stimulus. Malgr?? les ??normes progr??s r??alis??s sur les SR-BCPs, un certain nombre de questions fondamentales restent ?? r??soudre afin de leur permettre de se trouver dans des applications pratiques. Pour y arriver, la cl?? ou le d??fi r??side dans l???am??lioration du niveau et de la complexit?? de contr??le sur les SR-BCPs ainsi que la sensibilit?? avec laquelle ces polym??res r??agissent ?? des stimuli. G??n??ralement, il est souhaitable d'obtenir une r??action rapide sous l'action d'une stimulation mod??r??e. A cette fin, il est n??cessaire d???effectuer des recherches fondamentales sur la conception rationnelle de nouveaux SR-BCPs ainsi que sur le d??veloppement de m??thodes de stimulation qui peuvent amplifier l'effet d'un stimulus. Les travaux de recherche pr??sent??s dans cette th??se s'inscrivent dans ce domaine de recherche. Plus sp??cifiquement, nous avons ??tudi?? des micelles de BCPs qui r??pondent ?? deux types de stimuli. D'une part, nous avons ??tudi?? un m??canisme d'amplification bas?? sur l???effet des ultrasons combin?? ?? la thermosensibilit?? de BCPs. D'autre part, nous avons d??velopp?? une nouvelle conception de BCPs qui permet aux micelles d?????tre d??truites soit de mani??re photochimique, soit par des r??actions d'oxydo-r??duction, tout en ayant le nombre minimum des groupes stimuli-r??actifs dans la structure du polym??re. Notre recherche a g??n??r?? de nouvelles connaissances dans ce domaine et sugg??re de nouveaux moyens sur la fa??on dont les questions de sensibilit?? et de contr??le complexe des micelles SR-BCPs peuvent ??tre abord??es, contribuant ainsi ?? l'avancement des connaissances fondamentales. Le c??ur de cette th??se est compos?? de trois publications r??sultant des projets r??alis??s. Dans le premier projet, afin de coupler la sensibilit?? aux ultrasons et la thermosensibilit??, nous avons men?? une ??tude ayant pour but de trouver des structures possibles de polym??res qui sont susceptibles d'??tre affect??es par les ultrasons. Nous avons effectu?? une ??tude comparative sur la destruction des micelles form??es par divers BCPs et la lib??ration concomitante d'un colorant hydrophobe encapsul?? (rouge du Nil) par les ultrasons focalis??s de haute intensit?? (HIFU). Nous avons constat?? que toutes les micelles form??es par les quatre copolym??res diblocs synth??tis??s, ??tant constitu??s d'un m??me bloc du polyoxyde d'??thyl??ne (PEO) hydrophile et d???un bloc de polym??thacrylate hydrophobe diff??rent, peuvent ??tre perturb??es par les ultrasons. Toutefois, l'ampleur de la perturbation et la lib??ration du colorant encapsul?? dans la micelle est influenc??e par la structure chimique du block hydrophobe. En particulier, les micelles du PEO-b-PIBMA (poly(1-isobutoxym??thacrylate d'??thyle)) et du PEO-b-PTHPMA (poly(m??thacrylate de 2-t??trahydropyrannyle)), qui poss??dent une unit?? ac??tal labile dans le groupe lat??ral, subissent des perturbations plus importantes en raison, probablement, d???une r??action d???hydrolyse de l???ester induite par les ultrasons, donnant lieu ?? une lib??ration plus rapide du colorant. En revanche, les micelles du PEO-b-PMMA (poly(m??thacrylate de m??thyle)), dont le bloc polym??thacrylate est plus stable, sont plus r??sistantes aux ultrasons et pr??sentent une cin??tique de lib??ration du colorant plus lente que les autres micelles. De plus, l???analyse des spectres infrarouges des solutions micellaires, enregistr??s avant et apr??s l???exposition aux ultrasons, sugg??re une r??action d???hydrolyses pour le PEO-b-PIBMA et le PEO-b-PTHPMA, mais montre l'absence d???une quelconque r??action chimique pour le PEO-b-PMMA. L'effet de la structure de copolym??re ?? blocs sur la r??activit?? des micelles ?? l'irradiation HIFU ?? hautes fr??quences permet de mieux comprendre comment des micelles de BCPs sensibles aux ultrasons peuvent ??tre con??ues. Sur la base du premier projet, dans le deuxi??me projet, nous avons d??montr?? une nouvelle approche pouvant amplifier l'effet de HIFU sur la destruction des micelles de BCPs en solution aqueuse. L???id??e est d???introduire une petite quantit?? des unit??s comonom??res sensibles aux ultrasons dans le bloc thermosensible et initialement hydrophobe. On peut alors former une micelle dont le noyau est compos?? du polym??re sensible aux ultrasons. Si la r??action induite par les ultrasons sur le noyau permet d???augmenter la temp??rature de solution critique inf??rieure (LCST) du polym??re thermosensible au-dessus de la temp??rature de la solution micellaire, la micelle doit ??tre dissolue car tout le BCP est devenu soluble dans l???eau. Pour tester la validit?? de ce nouveau m??canisme, nous avons synth??tis?? et ??tudi?? un copolym??re dibloc de PEO-b-P(MEO[indice inf??rieur 2]MA-co-THPMA) (MEO[indice inf??rieur 2]MA repr??sente 2-(2-m??thoxy??thoxy) m??thacrylate d'??thyle), dans lequel le bloc thermosensible P(MEO[indice inf??rieur 2]MA-co-THPMA) est hydrophobe ?? T>LCST. Le THPMA a ??t?? choisi en raison de sa plus grande r??activit?? vis-??-vis des faisceaux HIFU que les autres monom??res ??tudi??s dans le premier projet. Les r??sultats montrent que les HIFU peuvent effectivement augmenter la LCST du bloc P(MEO[indice inf??rieur 2]MA-co-THPMA) et, par cons??quent, induire la dissociation des micelles ?? une temp??rature constante de la solution. Une analyse spectrale en RMN [indice sup??rieur 13]C a fourni des preuves montrant que l'hydrolyse des groupes THPMA se produit sous l???irradiation HIFU et que la destruction des micelles provient d'une augmentation de la LCST en raison de la conversion des motifs hydrophobes THPMA en motifs acides m??thacryliques (MAA) hydrophiles. Cette m??thode de modifier la LCST par une irradiation des ultrasons est g??n??rale et peut ??tre appliqu??e aux autres groupements sensibles aux ultrasons dans la conception de ce type de SR-BCPs. Cette ??tude a ainsi d??montr?? un nouveau m??canisme d'amplification et de contr??le des micelles de BCPs via la modification induite par les ultrasons de la temp??rature de transition de phase (LCST) du bloc constituant le noyau micellaire. Le troisi??me projet pr??sent?? dans cette th??se portait sur une conception rationnelle de BCPs ayant un but pr??cis: permettre aux micelles d?????tre perturb??es par deux types de stimuli en utilisant le nombre minimal des unit??s sensibles ?? des stimuli dans la structure de BCPs. Pour ce faire, nous avons con??u et synth??tis?? un nouveau copolym??re tribloc amphiphile de type ABC, soit le poly(oxyde d'??thyl??ne) - disulfure ??? polystyrene - o-nitrobenzyle - poly(2-(dim??thylamino) ??thylm??thacrylate) (PEO-S-S-PS-ONB-PDMAEMA). Il dispose d'une liaison disulfure redox-clivable entre les blocs PEO et PS ainsi que d'un groupe o-nitrobenzyle (ONB) photoclivable ?? la jonction des blocs PS et PDMAEMA. Nous avons montr?? que ce mod??le est une strat??gie utile pour permettre aux micelles de BCPs de r??pondre soit ?? un agent r??ducteur comme le dithiothr??itol (DTT) dans une solution, soit ?? l'exposition ?? la lumi??re UV, tout en ayant le nombre minimum des groups stimuli-r??actifs dans la structure du copolym??re (deux unit??s par cha??ne). Nos investigations ont r??v??l?? que les micelles de ce copolym??re tribloc peuvent ??tre perturb??es de diff??rentes fa??ons. Lorsqu'un seul stimulus est appliqu??, l'enl??vement d'un type des cha??nes de polym??re hydrophile ?? partir de la couronne de micelles, soit le PEO par clivage par oxydo-r??duction ou le PDMAEMA par photoclivage, entra??ne un effet limit?? de d??stabilisation sur la dispersion des micelles. L'agglom??ration de quelques micelles appara??t mais la dispersion reste essentiellement stable. En revanche, en cas d'utilisation combin??e des deux stimuli qui clivent ?? la fois le PEO et le PDMAEMA, une agr??gation importante du polym??re se produit ?? la suite de l'??limination de l'amphiphilicit?? du polym??re. // Abstract : Stimuli-responsive block copolymers (SR-BCPs) and their assemblies, such as micelles, vesicles and hydrogels, can undergo physical or chemical changes in response to changing environmental conditions. For an excellent SR-BCP, usually, slight changes in the environment are sufficient to induce relatively drastic changes in either the conformation or structure or properties of the polymer. Stimuli-reactive polymers are often referred to as smart polymers and they have great application potential in many fields. Over the past two decades, particular research and development interest has been focused on exploiting SR-BCP assemblies as drug delivery systems (DDSs). In many cases, stimuli-induced changes in the structure or morphology of BCP assemblies (drug carriers) can result in the release of loaded species, sometimes in a spatially and temporally controllable manner by choosing an appropriate stimulus and adjusting the parameters of the used stimulating method. Generally speaking, by having a certain type of stimuli-reactive moieties in the structure, SR-BCP assemblies have an ability to recognize a specific stimulus and react to its presence accordingly. Despite the tremendous progress achieved on SR-BCPs, a number of fundamental issues remain to be addressed in order to enable real-life applications of these smart polymers. Of them, an increasing level and complexity of control on SR-BCPs as well as the sensitivity with which these polymers react to stimuli are key and challenging. It is highly desirable to obtain a fast reaction under the action of a modest stimulation. To this end, fundamental research is necessary on rational and creative BCP structural design as well as on development of stimulation methods that can amplify the effect of a stimulus. The research work presented in this thesis falls into this important topic. More specifically, we studied BCP micelles that are responsive to two types of stimuli. On the one hand, we investigated an amplification mechanism based on coupling the ultrasound reactivity with the thermosensitivity of BCPs. On the other hand, we developed a BCP structural design that allows micelles to be disrupted by either light or redox agents while having the minimum number of stimuli-reactive moieties in the polymer structure. Our research provided new insights into and suggested new means on how the issues of sensitivity and complex control of SR-BCP micelles can be tackled, thus contributing to the advancement of fundamental knowledge. The core of this thesis is comprised of three publications resulting from the projects realized in our research work. In order to couple the ultrasound sensitivity and thermosensitivity, in the first project, we carried out studies to find possible polymer structures that are susceptible to be affected by ultrasound. We conducted a comparative study on the disruption of the micelles formed by various BCPs and the concomitant release of an encapsulated hydrophobic dye (Nile Red) by high-intensity focused ultrasound (HIFU). It was found that all micelles formed by the four synthesized diblock copolymers, being composed of a hydrophilic poly(ethylene oxide) (PEO) block and a different polymethacrylate hydrophobic block, could be disrupted by ultrasound. However, the extent of the micellar disruption and dye release was found to be influenced by the chemical structure of the micelle-core-forming hydrophobic polymethacrylate. In particular, micelles of PEO-b-PIBMA (poly(1-(isobutoxy)ethyl methacrylate)) and PEO-b-PTHPMA (poly(2-tetrahydropyranyl methacrylate)), whose hydrophobic blocks have a labile acetal unit in the side group and are more likely to undergo ester hydrolysis, could be disrupted more severely by ultrasound, giving rise to a faster release of Nile Red. By contrast, micelles of PEO-b-PMMA (poly(methyl methacrylate)), whose polymethacrylate block is more stable, appear to be more resistant to ultrasound irradiation and exhibit a slower rate of dye release than other BCPs. Moreover, infrared spectra recorded with micelles before and after ultrasound irradiation of the aqueous solution of the micelles give evidence for the occurrence of chemical reactions, most likely hydrolysis, for PEO-b-PIBMA and PEO-b-PTHPMA, but absence of chemical reactions for PEO-b-PMMA. The effect of BCP chemical structure on the reaction of micelles to high-frequency HIFU irradiation shows the perspective of designing and developing ultrasound-sensitive BCP micelles for ultrasound-based delivery applications. On the basis of the first project, in the second project, we demonstrated a new approach that could amplify the effect of HIFU on the disassembly of BCP micelles in aqueous solution. By introducing a small amount of ultrasound-labile comonomer units into the micelle core-forming thermosensitive polymer, the ultrasound-induced reaction of the comonomer could increase the lower critical solution temperature (LCST) of the thermosensitive polymer due to a polarity change, which renders the BCP soluble in water without changing the solution temperature and, consequently, results in disassembly of BCP micelles. To prove the validity of this new mechanism, we synthesized and investigated a diblock copolymer of PEO-b-P(MEO[subscript 2]MA-co-THPMA) (MEO[subscript 2]MA stands for 2-(2-methoxyethoxy)ethyl methacrylate). In the thermosensitive random copolymer block P(MEO[subscript 2]MA-co-THPMA), which is hydrophobic at T>LCST, THPMA was chosen due to its greater reactivity under HIFU than other monomer structures investigated in the first project. We found that HIFU could indeed increase the LCST of the P(MEO[subscript 2]MA-co-THPMA) block and, as a result, dissociate the BCP micelles at a constant temperature. A [superscript 13]C NMR spectral analysis provided critical evidence that hydrolysis of the THPMA groups occurs under HIFU irradiation and the micellar disassembly originates from an increase in the LCST due to the ultrasound-induced conversion of hydrophobic comonomer units of THPMA onto hydrophilic methacrylic acid (MAA). This ultrasound-changeable-LCST approach is general and can be applied by exploring other ultrasound-labile moieties in the BCP design. By transducing an ultrasound-induced effect into a changing thermosensitivity of the micelle core-forming block, this study demonstrated a new amplification and control mechanism for SR-BCP micelles. The third project presented in this thesis dealt with a rational BCP design that had a specific purpose: allowing BCP micelles to be disrupted by two types of stimuli while using the minimum number of stimuli-reactive moieties in the BCP structure. The unveiling of such BCP structures provides insight into how to make BCP micelles sensitive to stimuli. To do this, we designed and synthesized a new amphiphilic ABC-type triblock copolymer, namely, poly(ethylene oxide)-disulfide-polystyrene- o-nitrobenzyl-poly(2-(dimethylamino)ethylmethacrylate) (PEO-S-S-PS-ONB-PDMAEMA), which features a redox-cleavable disulfide linkage between the PEO and PS blocks as well as a photocleavable ONB group as the junction of the PS and PDMAEMA blocks. We demonstrated that this design is a useful strategy to allow BCP micelles to respond to both a reducing agent like dithiothreitol (DTT) in solution and exposure to UV light while having the minimum number of stimuli-reactive moieties in the block copolymer structure (two units per chain). Our investigations found that the micelles of this triblock copolymer could be disrupted in different ways. When only one stimulus is applied, the removal of one type of hydrophilic polymer chains from the micelle corona, either PEO by redox-cleavage or PDMAEMA by photocleavage, results in a limited destabilization effect on the dispersion of the micelles. The agglomeration between a few micelles appears but the dispersion remains essentially stable. By contrast, under combined use of the two stimuli that cleaves both PEO and PDMAEMA, severe polymer aggregation occurs as a result of elimination of the polymer amphiphilicity. Moreover, by loading the hydrophobic Nile Red in the micelles, the fluorescence quenching of the dye by aqueous medium under the different uses of the two stimuli appears to correlate with the different extents of the micellar disruption. // ?????? : ??????????????????????????????SR-BCPs???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????SR-BCP???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????-??????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????SR-BCP?????????????????????????????????DDSs???????????????????????????????????????BCP?????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????-????????????????????????SR-BCP??????????????????????????????????????????????????????????????????????????? ??????SR-BCPs?????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????SR-BCPs?????????????????????????????????????????????????????????????????????SR-BCPs???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????BCP???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????BCP???????????????????????????BCPs???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????-???????????????BCP???????????????????????????????????????????????????????????????????????????????????????SR-BCP???????????????????????????????????????????????????????????????????????????????????????????????????????????? ??????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????BCPs????????????????????????????????????????????????HIFU?????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????PEO-b-PIBMA????????? 1-????????????????????????????????????????????? ??????PEO-b-PTHPMA?????????2-???????????????????????????????????? ??????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? ??????????????????????????????????????????????????????????????????PEO-b-PMMA?????????????????????????????????????????????????????????????????????????????????????????????????????????PEO-b-PMMA????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????PEO-b-PIBMA???PEO-b-PTHPMA????????????????????????????????????????????????PEO-b-PMMA???????????????????????????????????????HIFU????????????BCP???????????????????????????????????????????????????????????????????????????-??????BCP????????????????????? ??????????????????????????????????????????????????????????????????????????????????????????????????????HIFU??????????????????BCP???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????LCST?????????????????????????????????????????????????????????BCP??????????????????????????????BCP??????????????????????????????????????????????????????????????????????????????????????????????????????PEO-b-P(MEO2MA-co-THPMA) ???MEO2MA ??????2-???2-??????????????????????????????????????????????????????T > LCST????????????????????????????????????P(MEO2MA-co-THPMA)?????????????????????THPMA?????????????????????????????????????????????????????????????????????????????????HIFU?????????????????????????????????????????????????????????????????? ??????HIFU???????????????????????????P(MEO2MA-co-THPMA)?????????LCST?????????BCP??????????????????????????????????????????13C NMR ???????????????????????????THPMA?????????????????????????????????????????????THPMA??????????????????????????????MAA?????????LCST?????????????????????????????????????????????????????????????????????LCST??????????????????????????????????????????????????????BCP???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????SR-BCP????????????????????????????????? ????????????????????????????????????????????????????????????????????????????????????????????????BCP????????????????????????????????????????????????????????????????????????BCP?????????????????????????????????????????????BCP?????????????????????????????????????????????????????????BCP????????????????????????????????????????????????????????????????????????ABC???????????????????????????????????????????????? - ???????????? - ???????????? - ??? - ???????????? - ?????? 2 - ???????????????????????????????????????????????? (PEO-S-S-PS-ONB-PDMAEMA)?????????PEO???PS???????????????????????????????????????????????????PS???PDMAEMA?????????????????????????????????ONB????????????????????????????????????????????????????????????-??????????????????????????????????????????????????????BCP????????????????????????????????????????????? ???DDT????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????PEO????????????????????????PDMAEMA?????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????PEO???PDMAEMA?????????????????????????????????????????????????????????????????????????????????????????????????????? ????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????

Les solvants eutectiques profonds (DES) forment une nouvelle famille de solvants qui a émergé ces dernières années. Les DES sont de plus en plus étudiés de par leur faible coût, leur faible toxicité et leurs propriétés qui devraient leur permettre de remplacer des solvants toxiques utilisés dans de nombreux domaines de la chimie. Lors de ma thèse, un premier travail a permis d’établir les diagrammes de phases solide-liquide de trois DES partiellement biosourcés. Par la suite, une comparaison entre ces DES et des mélanges idéaux a permis d’établir que ces systèmes peuvent être considérés comme solvants eutectiques « profonds ». Au cours de mes travaux, un premier solvant aqueux possédant une température de solution critique inférieure a été mis en évidence et l’origine de cette propriété remarquable a été élucidée. Au-delà des travaux sur la compréhension des DES, ces solvants ont été testés pour deux applications : le captage du dioxyde de carbone et l’extraction liquide-liquide de colorants
Deep Eutectics Solvents (DES) is a new class of solvent which has emerged during the last decades. DES have been increasingly studied because of their low cost and low toxicity. Because of these properties, DES could potentially replace toxic solvents used in large area of chemistry. To reach this goal, a broader knowledge of these new systems has to be acquired. Therefore, in the first work of this thesis, solid-liquid phase diagrams of three partially renewable DES have been established. The comparison of these diagrams to an ideal mixing model is showing a negative deviation that allows to considered them as “deep” eutectics solvents. Following this work on the binary mixture, water was added to these DES. A first aqueous - DES mixture with a lower critical solution temperature (LSCT) has been highlighted and the origin of this remarkable property has been elucidated. To complete the initial work aiming to get a deeper understanding of these new DES, these solvents have also been tested for two applications: carbon dioxide capture and liquid-liquid extractions of dyes

The world is at a pivotal crossroad in energy choices. There is a strong sense that our use of energy must be more sustainable. Moreover, many also broadly agree that a way must be found to rely increasingly on lower carbon energy sources. However, no single or clear solution exists on the means to carry out such a shift at either a national or international level. Traditional energy planning (when done) has revolved around limited cost projections that often fail to take longer term evidence and interactions of a wider set of factors into account. The good news is that evidence does exist on such change in case studies of different nations shifting toward low-carbon energy approaches. In fact, such shifts can occur quite quickly at times, alongside industrial and societal advance, innovation, and policy learning. These types of insights will be important for informing energy debates and decision-making going forward. Low Carbon Energy Transitions: Turning Points in National Policy and Innovation takes an in-depth look at four energy transitions that have occurred since the global oil crisis of 1973: Brazilian biofuels, Danish wind power, French nuclear power, and Icelandic geothermal energy. With these cases, Dr. Araújo argues that significant nationwide shifts to low-carbon energy can occur in under fifteen years, and that technological complexity is not necessarily a major impediment to such shifts. Dr. Araújo draws on more than five years of research, and interviews with over 120 different scientists, government workers, academics, and members of civil society in completing this study. Low Carbon Energy Transitions is written for for professionals in energy, the environment and policy as well as for students and citizens who are interested in critical decisions about energy sustainability. Technology briefings are provided for each of the major technologies in this book, so that scientific and non-scientific readers can engage in more even discussions about the choices that are involved.

AbstractHybrid rice technology is a viable strategy to increase rice production and productivity, especially in countries with limited cultivable land for agriculture and irrigation water, along with costlier chemical inputs. The three-line hybrid rice technology adoption rate is slowing down because of restricted heterosis per se, the availability of better combining ability in cytoplasmic male sterile lines, lower hybrid seed reproducibility, and limited market acceptability of hybrids. Two-line heterosis breeding could overcome these shortcomings. However, the wide-scale adoption and use of two-line hybrid rice technology are possible through systematic research and breeding efforts to develop temperature-sensitive genetic male sterile (TGMS) lines with low (<24 °C) critical sterility temperature point, which is discussed in this chapter. Research on the genetics, breeding, grain quality, and resistance to insect pests and diseases for TGMS line development and physiological characterization is also discussed. In addition, the identification and validation of natural sites for TGMS self-seed multiplication and hybrid rice seed production through GIS mapping and climatic data analytical tools are also tackled. The development of high-yielding two-line rice hybrids and improvement in hybrid rice seed reproducibility could help in their wide-scale adoption.

AbstractField-based screening and evaluation of banana plant tolerance or resistance to Fusarium oxysporum f. sp. cubense (Foc) Tropical Race 4 (TR4) or also known as Fusarium wilt TR4 is ideal though not always feasible. Alternatively, screening of banana plantlets at lab-stage seems to be an effective method for early detection of Foc TR4 tolerance. We present a simple hydroponic system, that allows plant to grow in a water-based condition. The system has two layers, the upper layer is a tray that has holes for plantlets to be placed where the root system is supported using an inert medium such as rock-wool. The lower layer is a perforated container filled with a water-based nutrient solution. For this lab-based screening, ex vitro gamma irradiated banana cv. Berangan (AAA) rooted plantlets with a pseudostem height of 10–15 cm were inoculated by soaking in a Foc TR4 conidial suspension (106 spores/ml) for 2 h under room temperature. The Foc TR4 inoculated rooted plantlets were screened using the hydroponic system and disease symptoms were scored. In this chapter, protocols on acclimatization of ex vitro irradiated rooted plantlets, inoculation with a Foc TR4 conidial suspension, lab- screening using hydroponic system, observation for early detection of disease symptoms and scoring of disease severity are presented.

Thermo-responsive hydrogel can change their swelling behavior and drug release characteristics in response to environmental temperature [1–5]. Poly(N-isopropylacrylamide) (PNIPA) hydrogel undergoes a phase transition when the temperatue is lower than a lower critical solution temperature (LCST) of ∼32°C in aqueous solution [8], and drug release profiles in PNIPA hydrogel can be controlled by the alternation of their solution temperatures.

The critical thickness of high temperature barrier coating is derived to avoid cycling of temperature from the finite speed heat conduction equations. When a cylinder is subject to a step change in temperature at the surface of the cylinder the transient temperature profile is obtained by the method of separation of variables. The finite speed of heat propagation is accounted for by using the modified Fourier’s law of conduction with a heat velocity of √α/τr. In order to avoid pulsations of temperature with respect to time the cylinder has to be maintained at a radius no less than 4.8096√ατr. In the asymptotic limit of infinite heat velocity the governing equation becomes parabolic diffusion equation. In the limit of zero velocity of heat and infinite relaxation time the wave equation result and solution can be obtained by a relativistic coordinate transformation. In the asymptote of zero velocity of heat and zero thermal diffusivity the solution for the dimensionless temperature is a decaying exponential in time. The average temperature of the naval warhead as indicated by UL 1709 test was estimated by using a idealized finite slab, and Leibnitz rule and an analytical expression for the average temperature was obtained using convective boundary condition. The solution is: For1/2&gt;=Bi,&lt;u&gt;=exp(−τ(1/2+sqrt(1/4−Bi*)))ForBi&gt;1/2,&lt;u&gt;=exp(−τ/2)Cos(τsqrt(−1/4+Bi*))) The average temperature is damped oscillatory in time domain. Further the transient temperature profile is represented by an infinite series of decaying exponential in time and Bessel function of the first kind and 0th order. The constant can be obtained from the principle of orthogonality. The bifurcated nature of the exact solution gives rise to the lower limit on the radius to avoid cycling of temperature with respect to time. The exact solution is thus, u=Σ0∝cnJ0(λnX)exp(−τ(1/2−sqrt(1/4−λn2))) and when λn &gt; 1/2 u=Σ0∝cnJ0(λnX)exp(−τ/2Cos(τsqrt(−1/4+λn2)) where, λn=(2.4048+(n−1)π)(√α/τr/R) cn is given by equation (53). The term in the infinite series onward where the contribution is oscillatory is identified.

The goal of the work is to investigate the abilities of the realizable k-ε and the k-ω turbulence models to predict phenomena expected in the lower plenum of the prismatic gas cooled reactor by benchmarking them against one another as well as verifying them against available experimental data [6]. Simulations were performed with CD-Adapco’s Star-CCM+ computational fluid dynamics (CFD) code utilizing the steady state approximation of the realizable k-ε turbulence model and the unsteady RANS approximations of the shear stress transport (SST) k-ω turbulence model. The unsteady results were averaged over a period of time corresponding to one full fluctuation cycle of the phenomena present with the lowest frequency. A case with a single jet of Reynolds number 12,700 was simulated as well as a case with dual jets of Reynolds numbers 6,300 and 12,700. Impingement of the jets occurred on the lower plane of the setup as occurs in the lower plenum. A two-layer shear driven [8] y+ wall treatment was used to satisfy the boundary layer profile. A mesh of 8.6 million polyhedral cells was generated to capture critical flow characteristics within the domain. Polyhedral cells were chosen for this application because they provided a better quality mesh and reduced the total number of cells necessary to achieve accurate results [4]. The simulations carried out were defined as having reached a converged solution when all residuals reduced to less than 10−5. The simulations of the flow in the rod bundle were successful in providing insight into locations of some key recirculation zones and the dependence they have on inlet conditions. The comparison between numerical and experimental results showed similar key flow patterns as well as aided in possible points of focus for future investigation. The information obtained and conclusions drawn will be critical in future numerical benchmarks in this area of research.

The nature and patterns of solution flow in hydrothermal autoclaves are critical to the quality, growth uniformity, and growth rates of synthetic single crystals. Small horizontal temperature deviations, which exist in industrial practice, were found to be critical in establishing flow patterns. However, the mechanism that determines how temperature deviations affect flow pattern is not well understood. In this study, an experimental system is set-up to study the flow in a model reactor (an enclosure). Temperature in the enclosure is visualized using liquid crystals. With the experimental results, a numerical model is validated and then used to simulate flows in enclosures that are subjected to similar thermal condition as industrial autoclaves. Flow patterns are obtained with various temperature deviations, for various aspect ratios and various Rayleigh (Ra) number between 4.05E8 to 3.24E9. Flows studied are unsteady in nature. Without temperature deviations, the overall flow pattern is anti-symmetric. With a temperature deviation, the wall layers are un-balanced. The impingement of streams on the wall layers does not affect the wall layer flow at low Ra numbers. At high Ra number, wall layers are broken by the impinging streams. The dominant heat transfer mechanism in the enclosure changes significantly as the aspect ratio of the enclosure changes. In enclosures of high aspect ratios that heat transfer resistance is mainly at the fluid exchange between the two halves, temperature deviations significantly affect heat transfer by stabilizing the direction of the streams.

Abstract Non-equilibrium heating between electrons and the crystalline lattice has been observed in numerous ultrashort pulsed laser applications yielding unexpected temperature profiles. Typically, laser induced damage threshold (LIDT) values for thin metal films are predicted using the melting temperature and the standard heat diffusion equation. A method is presented which accounts for non-equilibrium heating by solving the Parabolic Two Step (PTS) heat conduction model and deriving an analytical expression for the laser power that causes the film temperature to exceed a critical value. This critical temperature is a design parameter dependent on the material properties of the film and often the repetition rate of the source. In non-equilibrium heating, the predicted peak lattice temperature is significantly lower and occurs at some time after the deposition of energy, which can be orders of magnitude greater than the pulse duration. This minimizes the effect of the temporal shape of the pulse and allows for an analytical solution. This solution and an equation which can be used to calculate the thermal damage threshold value for non-equilibrium laser heating are presented.

Thermo-responsive wettability is studied for adaptive surface, which can potentially help to enhance the performance of thermal devices under various operation conditions. Poly(N-isopropylacrylamide) or PNIPAAm polymer brush can be grafted onto solid surfaces so that at temperatures below the lower critical solution temperature (LCST), the surface is hydrophilic, while at temperatures above LCST, it automatically becomes more hydrophobic. In this study, PNIPAAm is grafted on to aluminum alloy 6061, which is a multipurpose alloy commonly used in thermal mechanical systems. It is demonstrated by water static contact angle experiment at varies temperature that, the surface is hydrophobic at temperatures above LCST, and hydrophilic below LCST. The results are compared with bare aluminum surface at similar temperatures. Grafting PNIPAAm polymer brush on roughened aluminum surface would result in the ability to automatically switch between superhydrophobic state and superhydrophilic state in response to temperature change.

The dynamic buckling of a functionally graded material (FGM) circular plate subjected to thermal shock is studied in the Hamilton system. It is assumed that the lower surface of the circular plate is subjected to uniform thermal shock. Considering the one-dimensional heat conduction problem and basing on theory of Fourier heat conduction, the dynamic temperature fields of the FGM circular plate under thermal shock are obtained. The dynamic buckling problem of the FGM circular plate is finally reduced to zero-eigenvalue problem in the symplectic space. The critical loads and buckling modes of the functionally graded circular plate correspond to generalized eigenvalue and eigen solution, and can be obtained through bifurcation condition. In this study, the buckling characteristics of the FGM plate subjected to thermal shock are solved by symplectic method, and the solution process is given. The effects of the material constitution, structural geometric parameters and thermal shock load on the critical temperature are discussed.

The influence of bicarbonate ion (HCO3−) concentration and related environmental parameters such as pH and temperature on the passivation of API-X100 pipeline steel is the focus of this investigation. NS4 solution simulating groundwater trapped under disbonded coatings at regions where near-neutral stress corrosion cracking (SCC) occurs was used as a reference. Bicarbonate content in the solutions was increased steadily and the critical HCO3− concentration at which passivation becomes evident is found using potentiodynamic polarization sweeps. Multi-step dissolution is observed especially in higher pH solutions, owing to the involvement of hydroxide ions (OH−) in the adsorption of hydrous Fe(OH)2. Dynamic electrochemical impedance spectroscopy (DEIS) is used to study and compare interfacial processes in active, pre-passive, passive, and trans-passive regions. The results of the potentiodynamic and DEIS tests achieve good agreement. The protective properties of the passive film formed at three different HCO3− concentrations (critical passivation and two higher concentrations) and temperatures (25, 50, and 75 °C) are studied. The combined effect of HCO3− and temperature resulted in a pH range from ∼6.7 to 9.3 for the nine conditions in the corresponding test matrix. Passive films were formed at a suitable anodic potential and then studied with electrochemical impedance spectroscopy (EIS), Mott-Schottky, and cyclic voltammetry (CV) tests. Evidence of adsorption and diffusion, in addition to significant resistance from the passive film, is observed and accounted for in the equivalent circuit, which achieved good correspondence when fitted with the experimental data. The protective properties of the overall passive film are enhanced with increased bicarbonate and decreased temperature. Positive slopes in the Mott-Schottky plots reveal the n-type semi-conductive behavior of the passive films in all conditions and the CV results highlight the proposed reaction sequences occurring in different potential scan regions. CV measurements also confirm the enhanced protective properties of passive films with increased bicarbonate and lower temperatures observed in the EIS analysis.

The objective of this project is to develop a procedure for obtaining an accurate Master Curve from pipeline girth welds. This procedure will draw upon unique features of pipeline girth welds to develop an accurate Master Curve procedure for these welds. The Master Curve is a method of providing expected values of toughness versus temperature when a limited amount of information about the material is available. The Master Curve method also contains estimates of the variability of toughness at a given temperature, so that lower bound estimates of toughness are possible, even with limited data not obtained at that particular temperature. Corrections are also available for differences in material thickness.

The primary objective of this study was to determine the cathodic disbonding behavior of several pipeline coating materials under realistic conditions and to compare the results with laboratory tests that are commonly used to evaluate CD performance of coatings. Laboratory tests were run under more realistic conditions to simulate field conditions for three types of coatings. The move toward more realistic conditions was accomplished by:-substitution of soil extract solutions for the 3% NaCl solution,-application of a lower level of polarization during the test, either -1.0 or -1.1 VΠCCS instead of Π1.4 V-CCS for the standard test condition,-addition of sand to simulate a moist soil rather than a fully immersed condition,-elevated temperature to examine the effect of temperature.A standard cathodic disbondment test was run for direct comparison.

Reports, publications, papers, and databases were reviewed to better define risks and threats to plastic gas distribution piping. Failure modes were described for plastic PE piping with the most significant being slow crack growth (SCG). Short-term mechanical tests such as tensile, quick burst, melt index, and density tests did not show a correlation with a material's susceptibility to SCG failure. The bend-back test was able to visually identify 1971 low-ductile inner wall materials. PENT test failure times were reported for materials manufactured during the period1972-1985. The PENT test did not show correlations with the material's susceptibility to SCG failure for these materials. Life expectancy was determined to be a key measure of the susceptibility of PE gas pipe materials to SCG field failures. Long-term hydrostatic stress-rupture data combined with the Rate Process Method or with the Bi-Directional Shift Functions predicted the remaining life expectancy of several PE materials at 60�F average field temperature under varying loading conditions. Data showed rock impingement loads and pipe squeeze-offs can result in the greatest reduction in remaining life expectancy. Lower operating field temperatures and pressures significantly increased the predicted remaining life expectancy of PE materials. Fifty-five PE pipe samples that failed in field service were examined in the laboratory to identify the root cause of the failures. Eight of the samples underwent in-depth analysis, which included density and melts index tests and differential scanning calorimetry, infrared spectroscopy, and microscopic examination of the fracture surfaces. The samples were combined with another set of additional data resulting in 45 material, 36 procedural, 12 quality control, and 7 miscellaneous failures. A separate categorization method attributed a total of 321 failures to their respective pipe/component, with most occurring at joints. RCP in large diameter PE materials was investigated through laboratory testing. Critical pressure was determined for 6 pipe materials. The critical temperature was determined for 3 materials.

Multiple oil discoveries reveal the global scale and economic importance of a distinctive reservoir type composed of possible microbial lacustrine carbonates like the Lower Cretaceous pre-salt reservoirs in deepwater offshore Brazil and Angola. Marine microbialite reservoirs are also important in the Neoproterozoic to lowest Cambrian starta of the South Oman Salt Basin as well as large Paleozoic deposits including those in the Caspian Basin of Kazakhstan (e.g., Tengiz field), and the Cedar Creek Anticline fields and Ordovician Red River “B” horizontal play of the Williston Basin in Montana and North Dakota, respectively. Evaluation of the various microbial fabrics and facies, associated petrophysical properties, diagenesis, and bounding surfaces are critical to understanding these reservoirs. Utah contains unique analogs of microbial hydrocarbon reservoirs in the modern Great Salt Lake and the lacustrine Tertiary (Eocene) Green River Formation (cores and outcrop) within the Uinta Basin of northeastern Utah. Comparable characteristics of both lake environments include shallowwater ramp margins that are susceptible to rapid widespread shoreline changes, as well as compatible water chemistry and temperature ranges that were ideal for microbial growth and formation/deposition of associated carbonate grains. Thus, microbialites in Great Salt Lake and from the Green River Formation exhibit similarities in terms of the variety of microbial textures and fabrics. In addition, Utah has numerous examples of marine microbial carbonates and associated facies that are present in subsurface analog oil field cores.

Cracks and their formations in concrete structures have been a common and long-lived problem, mainly due to the intrinsic brittleness of the concrete. Concrete structures, such as rigid pavement and bridge decks, are prone to deformations and deteriorations caused by shrinkage, temperature fluctuation, and traffic load, which can affect their service life. Rehabilitation of concrete structures is expensive and challenging—not only from maintenance viewpoints but also because they cannot be used for services during maintenance. It is critical to significantly improve the ductility of concrete to overcome such issues and to enable better infrastructure quality. To this end, the self-healing cementitious composites (SHCC) investigated in this work could be a promising solution to the aforementioned problems. In this project, the team has designed a series of cementitious composites to investigate their mechanical performances and self-healing abilities. Firstly, various types of fibers were investigated for improving ductility of the designed SHCC. To enhance the self-healing of SHCC, we proposed and examined that the combination of the internal curing method with SHCC mixture design can further improve self-healing performance. Three types of internal curing agents were used on the SHCC mixture design, and their self-healing efficiency was evaluated by multiple destructive and non-destructive tests. Results indicated a significant improvement in the self-healing capacity with the incorporation of internal curing agents such as zeolite and lightweight aggregate. To control the fiber distribution and workability of the SHCC, the mix design was further adjusted by controlling rheology using different types of viscosity modifiers. The team also explored the feasibility of the incorporation of colloidal nano-silica into the mix design of SHCC. Results suggest that optimum amounts of nano-silica have positive influence on self-healing efficiency and mechanical properties of the SHCC. Better hydration was also achieved by adding the nano-silica. The bonding strength of the SHCC with conventional concrete was also improved. At last, a standardized mixing procedure for the large scale SHCC was drafted and proposed.

The objectives of the project were to develop a successful protocol for cryopreservation of penaeid germ plasm in order to preserve a pathogen-free broodstock nucleus for commercial exploitation of marine shrimp in aquaculture. The critical parameters to be characterized in the project were: 1. Determination of chill sensitivity and chill tolerant embryonic stages, including a full description and time course study of embryonic developmental stages. 2. Development of protocols for loading and removal of cryoprotectant agents (CPAs) from embryos; determination of optimal concentrations and duration of loading. 3. Characterization of the toxicity of the selected CP As and 4. Establishing optimal cooling and thawing procedures. Studies were performed on two penaeid species: Litopenaeus vannamei (in the USA) and P. semisulcatus (in Israel). The effect of incubation temperature on embryonic development rate and hatching success was studied in L. vannamei, showing that spawns maybe maintained at temperatures ranging from 24°C to 30°C, without compromising hatchability. Embryonic development extends from 12 hr to 19 hr at 30°C and 24°C, respectively. Studies showed that advanced embryonic developmental stages were chill tolerant in the two studied species, but P. semisulcatus could better endure lower temperatures than L. vannamei. A large number of experiments were performed to determine the optimal CP As, their concentration and duration of loading. Permeating (e.g. glycerol, methanol, DMSO, 1,2- propanediol, ethylene glycol, glucose) and non-permeating CPAs (sucrose, PVP, polyethylene glycol) were tested and several combinations of permeating and non-permeating CP As, on fertilized eggs (embryos), nauplii and protozoeae. In general, nauplii tolerated higher CPA concentrations than eggs and nauplii were also more permeable to radiolabeled methanol. Chlorine treatment intended to remove the chitinous envelop from eggs, did not increase dramatically the permeation of radiolabled methanol into eggs. Cooling eggs, nauplii or protozoeae to cryogenic temperatures, by either vitrification or slow cooling protocols, did not result in full survival of thawed samples, despite exhaustive attempts testing various protocols and CP As. Results seemed more encouraging in freezing of nauplii in comparison to eggs or protozoeae. Successful preliminary results in cryopreservation of spermatozoa of P. vannamei, will facilitate preservation of genetic specific to some extent.

Re-examination of the rare earth elements (REE) deposits in the Cornudas Mountains is warranted in light of today's economic importance of critical minerals, including REE that are essential in most of our electronic devices. New mapping, petrography, 40Ar/39Ar geochronology, and geochemical analyses have provided a better understanding of the emplacement of these intrusions and associated mineral deposits. The Cornudas Mountains form the northern Trans-Pecos alkaline magmatic province in the southern part of the North American Cordilleran alkaline-igneous belt. The igneous rocks in the Cornudas Mountains were emplaced in two pulses at 37.14-34.5 and 32.48-26.95 Ma, just prior to or during the early phases of Rio Grande rift extension, and consist of 1) larger nepheline syenite-syenite laccoliths and plugs, 2) phonolite plugs, sills, and dikes, 3) smaller syenite plugs and dikes that intrude Permian and Cretaceous sedimentary rocks, and 4) volcanic breccia dikes. New USGS geophysical data indicate that some of these intrusions extend deep into the subsurface, with additional buried intrusions potentially at depth. The focus of REE exploration is along the lower unit (PEnsp2) of the Wind Mountain nepheline syenite laccolith, as well as within syenite-phonolite and volcanic breccia dikes, plugs and skarns and carbonate-replacement deposits in Chess Draw. Some samples contain as much as 3110 ppm total REE. REE could be leached from a mineral concentrate of the REE-bearing minerals (eudialyte, zircon, monazite, bastnasite, calcio-catapleiite, vitusite, roumaite, xenotime). We incorporate whole rock and clinopyroxene chemistry of each intrusion into the clinopyroxene-liquid geothermobarometer (Masotta, 2013) to determine the temperatures and pressures of emplacement. This thermometer provides higher crystallization temperature estimates for the syenite intrusions (857-1027 deg. C) than the phonolite sills (760-869 deg. C). We then use the barometric estimates (0.3-3.3 kbar) to calculate emplacement depths (1.2-12.3 km). Pairing these depths with the new geochronology, minimum exhumation rates for intrusions in the Cornudas Mountains are estimated that range from 0.04-0.34 mm/yr crystallization temperatures and exhumation rates provide additional information to aid in developing a model for the formation of REE deposits.

The Heartland Inventory and Monitoring Network monitors plant communities at Tallgrass Prairie National Preserve and evaluates a variety of environmental variables that affect vegetation patterns, including climate and ecological disturbances such as fire and grazing. Here we report on 2002–2018 trends in management actions (fire and grazing) and key plant community indicators. Temperature has increased over the past 50 years in the region. Precipitation and a standardized precipitation-evapotranspiration index included a high degree of interannual variability and did not demonstrate directional change. We documented a decline in disturbance intensity (i.e., less frequent prescribed fire and lower stocking rates) since 2006. A preserve goal is to maintain 30 to 60% of the area as bare ground (soil and rock) for ideal greater prairie-chicken habitat. Bare areas have been in decline and minimally meet the goal preserve wide. Bare areas vary by pasture and year, with bare areas exceeding the threshold in earlier years and Big Pasture and Red House Pasture falling short in some recent years. Although the preserve-scale mean minimally met the objective, there was a great deal of heterogeneity across monitoring sites. Litter cover and depth were greater than ecological recommendations for the greater prairie-chicken, especially in 2018. Litter depth demonstrated a great deal of variability and included deep litter. Woody plants were targeted to remain below 5% cover. Preserve- and pasture-scale cover means were well below this threshold but are increasing. Species richness on a per site basis (alpha diversity) and preserve-wide richness (gamma diversity) showed no apparent directional change when corrected for differences in sample size. Comparison of native species composition between 2002 and 2018 revealed a 36.9% difference in the Sørensen Index, although observer error accounted for almost 2/3 of this apparent change. The preserve continues to have characteristic tallgrass prairie species, and nonnative species continue to be low. Similar to targeted invasive plant monitoring, we found the target species Kentucky bluegrass to be below park thresholds. Continued evaluation of fire frequency and grazing intensity will be critical to achieving ecological goals including conserving the greater prairie-chicken. Development of a grazing plan may assist with prescribing stocking rates that are consistent with the preserve’s ecological and cultural objectives and could include alternative herbivores, such as goats or expansion of bison.

Polymer flooding is one of the most promising EOR methods (Smalley et al. 2018). It is well known and has been used successfully (Pye 1964; Standnes & Skjevrak 2014; Sheng et al. 2015). From a technical perspective we recommend that polymer flooding should be considered as a viable EOR method on the Norwegian Continental Shelf for the following reasons: 1. More oil can be produced with less water injected; this is particularly important for the NCS which are currently producing more water than oil 2. Polymers will increase the aerial sweep and improve the ultimate recovery, provided a proper injection strategy 3. Many polymer systems are available, and it should be possible to tailor their chemical composition to a wide range of reservoir conditions (temperature and salinity) 4. Polymer systems can be used to block water from short circuiting injection production wells 5. Polymer combined with low salinity injection water has many benefits: a lower polymer concentration can be used to reach target viscosity, less mechanical degradation, less adsorption, and a potential reduction in Sor due to a low salinity wettability effect. There are some hurdles when considering polymer flooding that needs to be considered: 1. Many polymer systems are not at the present considered as green chemicals; thus, reinjection of produced water is needed. However, results from polymer degradation studies in the IORCentre indicates that a. High molecular weight polymers are quickly degraded to low molecular weight. In case of accidental release to the ocean low molecular weight polymers are diluted and the lifetime of the spill might be quite short. According to Caulfield et al. (2002) HPAM is not toxic, and will not degrade to the more environmentally problematic acrylamide. b. In the DF report for environmental impact there are case studies using the DREAM model to predict the transport of chemical spills. This model is coupled with polymer (sun exposure) degradation data from the IORCentre to quantify the lifetime of polymer spills. This approach should be used for specific field cases to quantify the environmental risk factor. 2. Care must be taken to prepare the polymer solution offshore. Chokes and vales might be a challenge but can be mitigating according to the results from the large-scale testing done in the IORCentre (Stavland et al. 2021). None of the above-mentioned challenges are server enough to not consider polymer flooding. HPAM is neither toxic, nor bio-accumulable, or bio-persistent and the CO2 footprint from a polymer flood may be significantly less than a water flood (Dupuis et al. 2021). There are at least two contributing factors to this statement, which we will return in detail to in the next section i) during linear displacement polymer injection will produce more oil for the same amount of water injected, hence the lifetime of the field can be shortened ii) polymers increase the arial sweep reducing the need for wells.

With the proliferation of Free Trade Agreements (FTAs) over the past decade, demand for quantitative analysis of their likely impacts has surged. The main quantitative tool for performing such analysis is Computable General Equilibrium (CGE) modeling. Yet these models have been widely criticized for performing poorly (Kehoe, 2002) and having weak econometric foundations (McKitrick, 1998; Jorgenson, 1984). FTA results have been shown to be particularly sensitive to the trade elasticities, with small trade elasticities generating large terms of trade effects and relatively modest efficiency gains, whereas large trade elasticities lead to the opposite result. Critics are understandably wary of results being determined largely by the authors’ choice of trade elasticities. Where do these trade elasticities come from? CGE modelers typically draw these elasticities from econometric work that uses time series price variation to identify an elasticity of substitution between domestic goods and composite imports (Alaouze, 1977; Alaouze, et al., 1977; Stern et al., 1976; Gallaway, McDaniel and Rivera, 2003). This approach has three problems: the use of point estimates as “truth”, the magnitude of the point estimates, and estimating the relevant elasticity. First, modelers take point estimates drawn from the econometric literature, while ignoring the precision of these estimates. As we will make clear below, the confidence one has in various CGE conclusions depends critically on the size of the confidence interval around parameter estimates. Standard “robustness checks” such as systematically raising or lowering the substitution parameters does not properly address this problem because it ignores information about which parameters we know with some precision and which we do not. A second problem with most existing studies derives from the use of import price series to identify home vs. foreign substitution, for example, tends to systematically understate the true elasticity. This is because these estimates take price variation as exogenous when estimating the import demand functions, and ignore quality variation. When quality is high, import demand and prices will be jointly high. This biases estimated elasticities toward zero. A related point is that the fixed-weight import price series used by most authors are theoretically inappropriate for estimating the elasticities of interest. CGE modelers generally examine a nested utility structure, with domestic production substitution for a CES composite import bundle. The appropriate price series is then the corresponding CES price index among foreign varieties. Constructing such an index requires knowledge of the elasticity of substitution among foreign varieties (see below). By using a fixed-weight import price series, previous estimates place too much weight on high foreign prices, and too small a weight on low foreign prices. In other words, they overstate the degree of price variation that exists, relative to a CES price index. Reconciling small trade volume movements with large import price series movements requires a small elasticity of substitution. This problem, and that of unmeasured quality variation, helps explain why typical estimated elasticities are very small. The third problem with the existing literature is that estimates taken from other researchers’ studies typically employ different levels of aggregation, and exploit different sources of price variation, from what policy modelers have in mind. Employment of elasticities in experiments ill-matched to their original estimation can be problematic. For example, estimates may be calculated at a higher or lower level of aggregation than the level of analysis than the modeler wants to examine. Estimating substitutability across sources for paddy rice gives one a quite different answer than estimates that look at agriculture as a whole. When analyzing Free Trade Agreements, the principle policy experiment is a change in relative prices among foreign suppliers caused by lowering tariffs within the FTA. Understanding the substitution this will induce across those suppliers is critical to gauging the FTA’s real effects. Using home v. foreign elasticities rather than elasticities of substitution among imports supplied from different countries may be quite misleading. Moreover, these “sourcing” elasticities are critical for constructing composite import price series to appropriate estimate home v. foreign substitutability. In summary, the history of estimating the substitution elasticities governing trade flows in CGE models has been checkered at best. Clearly there is a need for improved econometric estimation of these trade elasticities that is well-integrated into the CGE modeling framework. This paper provides such estimation and integration, and has several significant merits. First, we choose our experiment carefully. Our CGE analysis focuses on the prospective Free Trade Agreement of the Americas (FTAA) currently under negotiation. This is one of the most important FTAs currently “in play” in international negotiations. It also fits nicely with the source data used to estimate the trade elasticities, which is largely based on imports into North and South America. Our assessment is done in a perfectly competitive, comparative static setting in order to emphasize the role of the trade elasticities in determining the conventional gains/losses from such an FTA. This type of model is still widely used by government agencies for the evaluation of such agreements. Extensions to incorporate imperfect competition are straightforward, but involve the introduction of additional parameters (markups, extent of unexploited scale economies) as well as structural assumptions (entry/no-entry, nature of inter-firm rivalry) that introduce further uncertainty. Since our focus is on the effects of a PTA we estimate elasticities of substitution across multiple foreign supply sources. We do not use cross-exporter variation in prices or tariffs alone. Exporter price series exhibit a high degree of multicolinearity, and in any case, would be subject to unmeasured quality variation as described previously. Similarly, tariff variation by itself is typically unhelpful because by their very nature, Most Favored Nation (MFN) tariffs are non-discriminatory in nature, affecting all suppliers in the same way. Tariff preferences, where they exist, are often difficult to measure – sometimes being confounded by quantitative barriers, restrictive rules of origin, and other restrictions. Instead we employ a unique methodology and data set drawing on not only tariffs, but also bilateral transportation costs for goods traded internationally (Hummels, 1999). Transportation costs vary much more widely than do tariffs, allowing much more precise estimation of the trade elasticities that are central to CGE analysis of FTAs. We have highly disaggregated commodity trade flow data, and are therefore able to provide estimates that precisely match the commodity aggregation scheme employed in the subsequent CGE model. We follow the GTAP Version 5.0 aggregation scheme which includes 42 merchandise trade commodities covering food products, natural resources and manufactured goods. With the exception of two primary commodities that are not traded, we are able to estimate trade elasticities for all merchandise commodities that are significantly different form zero at the 95% confidence level. Rather than producing point estimates of the resulting welfare, export and employment effects, we report confidence intervals instead. These are based on repeated solution of the model, drawing from a distribution of trade elasticity estimates constructed based on the econometrically estimated standard errors. There is now a long history of CGE studies based on SSA: Systematic Sensitivity Analysis (Harrison and Vinod, 1992; Wigle, 1991; Pagon and Shannon, 1987) Ho