Ions in the soil solution traverse many layers (epidermis, exodermis, central cortex, and endodermis) within the root to reach the stele. The endodermis is present in almost all vascular plants while the exodermis is found only in majority of angiosperm roots tested. The maturation of the exodermis and the death of epidermis alter the plasma membrane surface areas (PMSA) potentially available for ion uptake. Do these changes reduce the ion uptake in proportion to the loss of absorptive surface areas? To answer this question onion (Allium cepa L cv. Wolf) adventitious root segments representing above features: Immature Exodermis Live Epidermis (IEXLEP), Mature Exodermis Live Epidermis (MEXLEP), Mature Exodermis Dead Epidermis (MEXDEP) were excised. Using a compartmental elution technique, radioactive sulphate and phosphate present in various internal compartments were quantified. Quantities of ions moved across the plasma membrane, a summation of quantities in the cytoplasm, ‘vacuole’, and ‘bound’ compartments, indicated that the maturation of the exodermis reduces the uptake of sulphate but not phosphate. In contrast, epidermal death reduced the movement of both ions across the plasma membranes. Although there is a reduction in the available PMSA with the maturation of the exodermis and death of the epidermis, these events do not necessarily reduce the ion movement into the plasma symplast. The endodermal cells of onion roots deposit suberin lamellae as secondary walls. As seen in cross-sections some cells remain without these lamellae and are known as ‘passage cells’. What is the pattern of suberin lamella deposition along the root? Is the suberin lamella a continuous layer? To answer these questions, endodermal layers isolated from onion adventitious roots were used in the present study. These layers were observed using four stains (Sudan Red 7B, Fluorol yellow 088 [Fy], berberine, and Nile red) and three microscopes (compound-white light, compound-epifluorescence and confocal scanning). In differentiating cells with and without suberin lamellae in endodermal layers Sudan Red 7B served the best results for compound-white light microscope, Fy for compound-epifluorescence microscope and Nile for confocal laser scanning microscope (CLSM). Suberin lamellae deposition initiated almost in a random manner; they continued to be deposited resulting in the production of longitudinal files alternating with files with passage cells, and were ultimately deposited in almost all cells at a distance of 255 mm from the tip. The suberin lamellae are perforated with pores, a consistent feature even as far as 285 mm from the tip. These pores may serve as portals for water, ions, and pathogen movement.

Ions in the soil solution traverse many layers (epidermis, exodermis, central cortex, and endodermis) within the root to reach the stele. The endodermis is present in almost all vascular plants while the exodermis is found only in majority of angiosperm roots tested. The maturation of the exodermis and the death of epidermis alter the plasma membrane surface areas (PMSA) potentially available for ion uptake. Do these changes reduce the ion uptake in proportion to the loss of absorptive surface areas? To answer this question onion (Allium cepa L cv. Wolf) adventitious root segments representing above features: Immature Exodermis Live Epidermis (IEXLEP), Mature Exodermis Live Epidermis (MEXLEP), Mature Exodermis Dead Epidermis (MEXDEP) were excised. Using a compartmental elution technique, radioactive sulphate and phosphate present in various internal compartments were quantified. Quantities of ions moved across the plasma membrane, a summation of quantities in the cytoplasm, ‘vacuole’, and ‘bound’ compartments, indicated that the maturation of the exodermis reduces the uptake of sulphate but not phosphate. In contrast, epidermal death reduced the movement of both ions across the plasma membranes. Although there is a reduction in the available PMSA with the maturation of the exodermis and death of the epidermis, these events do not necessarily reduce the ion movement into the plasma symplast. The endodermal cells of onion roots deposit suberin lamellae as secondary walls. As seen in cross-sections some cells remain without these lamellae and are known as ‘passage cells’. What is the pattern of suberin lamella deposition along the root? Is the suberin lamella a continuous layer? To answer these questions, endodermal layers isolated from onion adventitious roots were used in the present study. These layers were observed using four stains (Sudan Red 7B, Fluorol yellow 088 [Fy], berberine, and Nile red) and three microscopes (compound-white light, compound-epifluorescence and confocal scanning). In differentiating cells with and without suberin lamellae in endodermal layers Sudan Red 7B served the best results for compound-white light microscope, Fy for compound-epifluorescence microscope and Nile for confocal laser scanning microscope (CLSM). Suberin lamellae deposition initiated almost in a random manner; they continued to be deposited resulting in the production of longitudinal files alternating with files with passage cells, and were ultimately deposited in almost all cells at a distance of 255 mm from the tip. The suberin lamellae are perforated with pores, a consistent feature even as far as 285 mm from the tip. These pores may serve as portals for water, ions, and pathogen movement.

Made available in DSpace on 2014-10-09T12:41:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:03Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:41:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:03Z (GMT). No. of bitstreams: 0 / O titânio e suas ligas são biomateriais metálicos extensamente utilizados em aplicações médicas e odontológicas, apesar de não formarem ligação química com o osso circundante. Por isto é desejável técnicas que proporcionem a bioatividade na superfície desses metais. A proposta deste estudo foi avaliar e comparar, por testes in vitro e in vivo o comportamento de Ticp e da liga Ti-13Nb-13Zr utilizando diferentes tratamentos de superfície frente à formação do recobrimento biomimético e ao processo de osteointegração. Foram utilizadas placas comerciais de Ti e amostras da liga e de Ticp, obtidas por M/P. As amostras foram submetidas a quatro diferentes tratamentos de superfície (padrão - tratamento alcalino; 1°- tratamento alcalino e térmico; 2°- tratamento ácido e alcalino; 3º- tratamento alcalino, CaCl2, térmico e água quente), analisadas quanto à formação de apatita em SBF em períodos de 1 a 21 dias. Os recobrimentos obtidos foram caracterizado por MEV e DRIFT. Para a avaliação in vivo dos implantes, obtidos por M/P, de Ticp e da liga, com e sem tratamentos superficiais, foram utilizados coelhos adultos machos. A avaliação teve duração de 7 semanas em que foram aplicados marcadores celulares ósseos em tempos e sequência específicos do pós-operatório. Na avaliação in vitro, os recobrimentos de maior espessura foram nas amostras obtidas por M/P, comparativamente à amostra laminada. Todos os tratamentos foram efetivos na promoção da bioatividade. O 2º tratamento obteve recobrimento com maior espessura nos períodos avaliados para todas as superfícies. Na avaliação in vivo, ocorreu crescimento ósseo com osteointegração em todos os implantes com e sem tratamentos superficiais. O crescimento ósseo na interface osso/implante ocorreu de forma contínua em todo o período de reparação para o Ticp, o Ticp com tratamento padrão, o Ticp com o 2º tratamento e a liga com o 1° tratamento; e ocorreu de forma mais intensa no primeiro e terceiro período de reparação para os demais implantes. Os resultados dos testes in vitro e in vivo não são passíveis de analogia direta neste estudo, pois forneceram informações importantes sobre a formação, morfologia e taxa de aposição do recobrimento aos diferentes tratamentos de superfície e a efetividade da osteointegração destes tratamentos de superfície em modelo animal. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Zr and Hf based MOFs with enhanced pore accessibility for large molecules and good hydrothermal stability were obtained using a bent dithienothiophene dicarboxylate and Zr4+ or Hf4+ source. A modulator (benzoic acid) facilitates formation of an eight-connecting cluster leading to a new framework which adopts reo topology. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

A series of boron-containing conjugated microporous polymers with hierarchical porous structures have been readily prepared via typical transition metal-catalyzed coupling reactions. The distribution of micro- and mesopores in the networks as well as the specific surface areas are tunable via tailoring the structures of the building blocks. The distinct capability of the resulting Lewis acid-based neutral porous polymers to selectively capture fluoride ions provides a high-efficiency conversion into stable anionic porous polymers. For the first time, fluoride anion binding to boron atoms in a solid sample was essentially characterized by solid-state 11B MAS NMR spectroscopy, clearly revealing such an efficient conversion from a neutral network to a negatively charged one only through Lewis acid–base adduct formation. Upon a simple ion-exchange process, various heavy metal cations were facile to be loaded into the networks of the anionic porous polymers. Furthermore, the cobalt(II)-loaded porous polymers were shown to promote the stoichiometric homocoupling reactions of the different aryl Grignard regents, and exert distinct size selectivities for the homocoupling products, highly dependent on their porous structures. Such a successful loading strategy might be used for design and synthesis of new types of zeolite-like porous polymers with desirable catalytic properties for a certain organic transformation, as well as other functional materials.

Zr and Hf based MOFs with enhanced pore accessibility for large molecules and good hydrothermal stability were obtained using a bent dithienothiophene dicarboxylate and Zr4+ or Hf4+ source. A modulator (benzoic acid) facilitates formation of an eight-connecting cluster leading to a new framework which adopts reo topology. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

This article combines a systematic literature review on the fabrication of macroporous α-Al2O3 with increased specific surface area with recent results from our group. Publications claiming the fabrication of α-Al2O3 with high specific surface areas (HSSA) are comprehensively assessed and critically reviewed. An account of all major routes towards HSSA α-Al2O3 is given, including hydrothermal methods, pore protection approaches, dopants, anodically oxidized alumina membranes, and sol-gel syntheses. Furthermore, limitations of these routes are disclosed, as thermodynamic calculations suggest that γ-Al2O3 may be the more stable alumina modification for ABET > 175 m2/g. In fact, the highest specific surface area unobjectionably reported to date for α-Al2O3 amounts to 16–24 m2/g and was attained via a sol-gel process. In a second part, we report on some of our own results, including a novel sol-gel synthesis, designated as mutual cross-hydrolysis. Besides, the Mn-assisted α-transition appears to be a promising approach for some alumina materials, whereas pore protection by carbon filling kinetically inhibits the formation of α-Al2O3 seeds. These experimental results are substantiated by attempts to theoretically calculate and predict the specific surface areas of both porous materials and nanopowders.

A series of boron-containing conjugated microporous polymers with hierarchical porous structures have been readily prepared via typical transition metal-catalyzed coupling reactions. The distribution of micro- and mesopores in the networks as well as the specific surface areas are tunable via tailoring the structures of the building blocks. The distinct capability of the resulting Lewis acid-based neutral porous polymers to selectively capture fluoride ions provides a high-efficiency conversion into stable anionic porous polymers. For the first time, fluoride anion binding to boron atoms in a solid sample was essentially characterized by solid-state 11B MAS NMR spectroscopy, clearly revealing such an efficient conversion from a neutral network to a negatively charged one only through Lewis acid–base adduct formation. Upon a simple ion-exchange process, various heavy metal cations were facile to be loaded into the networks of the anionic porous polymers. Furthermore, the cobalt(II)-loaded porous polymers were shown to promote the stoichiometric homocoupling reactions of the different aryl Grignard regents, and exert distinct size selectivities for the homocoupling products, highly dependent on their porous structures. Such a successful loading strategy might be used for design and synthesis of new types of zeolite-like porous polymers with desirable catalytic properties for a certain organic transformation, as well as other functional materials.

Background: Addressing oil spills is crucial to protect the marine environment (Etkin, 2021). While physical and mechanical recovery methods have proven effective in controlling surface oil slicks (Doshi, 2018), subsurface challenges remain unaddressed. There is a need for low-cost, effective, and environmentally friendly solutions for subsurface oil removal. Bioinspired designs, based on nature’s evolutionary optimization, could offer promising solutions to oil spills. Objectives: The primary objective was to explore innovative and bioinspired approaches for effectively capturing and eliminating oil droplets from subsurface environments. The study aims to pioneer breakthroughs in biomimetic technologies for subsurface oil recovery. The objectives include developing a system inspired by humpback whales using bubbles, creating a fiber-based system inspired by copepods, and exploring sound as a separation technique for emulsions. Additionally, to decode the fluid mechanics within each capture system, unraveling the optimal processes responsible for successful oil droplet capture and separation in the emulsion simulation. And finally to assess system performance and potential for real-world scaling beyond the lab setting. Methods: A controlled environment simulating post-spill scenarios was established using different types of oil (crude oil, canola oil, fish oil). The emulsions were then exposed to three technology systems: micro-bubble redirection system, brush capture system, and sound wave modulations. The efficiency of oil removal and capture from the subsurface was measured using absorbent weight for the micro-bubble systems and lipid extraction for capture brush efficiency. High-speed camera images were taken to track oil droplet redirection in a flow tank, and ImageJ software to analyze droplet characteristics for effective control. Results: The analysis demonstrated that the Micro-Bubble air flotation method emerges as a highly efficient solution for post-spill oil recovery, consistently demonstrating exceptional performance. Cylinder-Ring Bubble Air Flotation method achieves a remarkable 72.4% recovery rate for canola oil, while fish oil exhibits a 14.0% recovery rate after 3 hours, highlighting the influence of oil viscosity. Be- 4 yond mere buoyancy, air bubbles showcase versatility, redirecting and containing oil droplets. The Micro-Bubble Redirection System, quantitatively assessed in a controlled environment, proves to be a significant breakthrough in controlling oil dispersion in aquatic settings. The biomimetic brush exhibited substantial oil capture capability. The fiber capture system at 360 RPM for 1-minute cycles, repeated 50 times, achieved over 46% oil removal. The modified brush at the same speed and duration captured over 19% of total oil. Post-treatment, the average size of oil droplets increased from 4.5 m to 5.5 m, showcasing changes in droplet size distribution with the fiber capture system. The sonic treatment effectively separated the majority of oil from water, revealing small oil droplets (x = 0.026 mm) in the central emulsion. This phenomenon warrants further investigation as a potential alternative to chemical surfactants. Conclusion: The development of biomimetic tools for oil spill clean-up represents a significant advancement in environmental protection. By addressing subsurface oil droplets, these methods contribute to safeguarding marine food webs from oil contamination. This study underscores the importance of innovative, natureinspired solutions in tackling complex environmental challenges. / Contexte : La lutte contre les déversements de pétrole est cruciale pour atténuer leur impact sur l’environnement marin (Etkin, 2021). Alors que les méthodes de récupération physique et m´ecanique se sont révélées efficaces pour contrôler les nappes de pétrole en surface (Doshi, 2018), les d´efis liés aux couches sous-marines restent non résolus. Il existe un besoin de solutions économiques, efficaces et respectueuses de l’environnement pour l’élimination du pétrole en sous-surface. Les conceptions bioinspirées, basées sur l’optimisation évolutive de la nature, pourraient offrir des solutions prometteuses aux déversements de pétrole. Objectifs : L’objectif principal était d’explorer des approches innovantes et bioinspirées pour capturer et éliminer efficacement les gouttelettes de pétrole des environnements sousmarins. L’étude vise à initier des percées dans les technologies biomimétiques pour la récupération du pétrole en sous-surface. Les objectifs incluent le développement d’un système inspiré des baleines à bosse utilisant des bulles, la création d’un système basé sur les fibres inspiré des copépodes, et l’exploration du son comme technique de séparation des émulsions. De plus, décoder la mécanique des fluides dans chaque système de capture, en démêlant les processus optimaux responsables de la capture et de la séparation réussies des gouttelettes de pétrole dans la simulation d’émulsion. Enfin, évaluer les performances du système et son potentiel de mise à l’échelle dans le monde réel au-delà du cadre du laboratoire. Méthodes : Un environnement contrôlé simulant des scénarios post-déversement a été établi en utilisant différents types de pétrole (pétrole brut, huile de colza, huile de poisson). Les émulsions ont ensuite été exposées à trois systèmes technologiques : système de redirection à micro-bulles, système de capture par brosse, et modulations des ondes sonores. L’efficacité de l’élimination et de la capture du pétrole en sous-surface a été mesurée en utilisant le poids absorbant pour les systèmes à micro-bulles et l’extraction des lipides pour l’efficacité de la brosse de capture. Des images de caméra haute vitesse ont été prises pour suivre la redirection des gouttelettes de pétrole dans 1 un réservoir à écoulement, et le logiciel ImageJ pour analyser les caractéristiques des gouttelettes pour un contrôle efficace. Résultats : L’analyse a démontré que la méthode de flottation d’air à microbulles émerge comme une solution très efficace pour la récupération d’huile après une fuite, montrant de manière cohérente des performances exceptionnelles. La méthode de flottation d’air à cylindre-anneau atteint un remarquable taux de récupération de 72,4% pour l’huile de canola, tandis que l’huile de poisson présente un taux de récupération de 14,0 % après 3 heures, mettant en évidence l’influence de la viscosité de l’huile. Au-delà de la simple flottabilité, les bulles d’air montrent leur polyvalence en redirigeant et en contenant les gouttelettes d’huile. Le système de redirection à microbulles, évalué de manière quantitative dans un environnement contôlé, s’avère être une avancée significative dans le contrôle de la dispersion de l’huile dans les milieux aquatiques. La brosse biomimétique a montré une capacité de capture substantielle de l’huile. Le système de capture de fibres à 360 tours par minute pendant des cycles d’1 minute, répété 50 fois, a atteint plus de 46% d’élimination de l’huile. La brosse modifiée à la même vitesse et durée a capturé plus de 19 % de l’huile totale. Après traitement, la taille moyenne des gouttelettes d’huile est passée de 4,5 m à 5,5 m, mettant en évidence des changements dans la distribution de la taille des gouttelettes avec le système de capture de fibres. Le traitement sonique a séparé efficacement la majorité de l’huile de l’eau, révélant de petites gouttelettes d’huile (x = 0,026 mm) dans l’émulsion centrale. Ce phénomène mérite une investigation plus approfondie en tant qu’alternative potentielle aux agents tensioactifs chimiques. Conclusion : Le développement d’outils biomimétiques pour le nettoyage des déversements de pétrole représente une avancée significative dans la protection de l’environnement. En s’attaquant aux gouttelettes de pétrole en sous-surface, ces méthodes contribuent à protéger les réseaux alimentaires marins de la contamination par le pétrole. Cette étude souligne l’importance de solutions innovantes et inspirées par la nature pour relever les défis environnementaux complexes.