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The alluring order in which complex biological networks exist in nature stimulated the interest of chemists to replicate such systems synthetically. With such examples as the deoxyribonucleic acid (DNA) double helix and the phospholipid bilayers, the influence of forces within these networks are solely credited for their excellent stability. The synthetically ordered chemical networks are also held together by interactions within them with little or no external force as seen in the natural systems. This spontaneous and reversible association of molecules or ions to form larger, more complex entities according to the intrinsic information contained in the molecules themselves is known as self-assembly. The self-assembly process is pre-eminent to the formation of ordered structures emerging spontaneously from the precursors in which, the overall structure of the final assemblies is controlled by the symmetry of each of the building blocks. The highly ordered and thermodynamically stable scaffolds are formed via non-covalent interactions including hydrophobic interaction, π-stacking, dipole-dipole interaction, ion-dipole interaction, hydrogen bonding, Van der Waals forces, solvophobic interaction and reversible metal-ligand coordination. These non-covalent interactions are termed as supramolecular interactions. Among several of these self-assembly protocols, the directional metal-ligand coordination strategy has evolved to be a well-established process for the preparation of supramolecular ensembles with pre-defined shapes, cavities and functionalities in a “one-pot” synthesis. Coordination-driven self-assembly strategy is governed by the combination of electron-deficient metal centres and electron-rich organic ligands. The outcome of the final supramolecular architecture is determined by the choice of the pre-designed metal acceptor building blocks as well as the flexibility and steric demands of the ancillary organic ligands. Accurate stoichiometry of each of the building blocks is also a very important factor in coordination-driven self-assembly; although serendipity sometimes happen which is quite unexpected. A large number of these self-assembled supramolecular networks have found useful applications in optoelectronics, material chemistry, adsorption, drug delivery, catalysis, host-guest chemistry, photo- and electro-chemical sensing as well as prospective chemotherapeutics. Transition metals are widely desired as electron-deficient building blocks in supramolecular chemistry. They readily accept lone pair of electrons from electron-rich building blocks. The functional properties of these metals have also been considered during the pre-design of these electron acceptors such that the functional property of each metal can be induced in the final architecture. Pd(II) and Pt(II) metals are highly desirable electron acceptors in supramolecular self-assembly because of their rigid square-planar nature. Nonetheless, Ru(II) and Fe(II) have also been explored as electron acceptors based on their octahedral geometry. Electron-rich building blocks have lone pairs of electrons on their donor sites (nitrogen, oxygen or sulphur) which effortlessly donate electrons to electron-deficient building blocks. The pyridyl appended ligands have been mostly used as the electron-rich building blocks in the construction of supramolecular architectures because of their predictable coordination modes and the symmetrical nature. However, imidazole appended ligands holds a distinctive spot in supramolecular chemistry because of its rotational flexibility and unpredictable binding modes which may lead to uncommon architectures not obtainable with pyridyl appended ligands. Thus, imidazole-based supramolecular architectures are less explored because the outcome of the final architecture cannot be pre-determined during the design. Ruthenium p-cymene complexes have spurred much interest in the last two decades because they possess extremely stable octahedral geometry and has been extensively used in the construction of 2D and 3D supramolecular architectures. The recent search for viable alternatives to platinum drugs in cancer chemotherapy discovered ruthenium as an excellent alternative to platinum because of its low toxicity when compared to platinum. The robustness of the arene head on interaction with biomolecules and the accumulation of large molecular weight compounds specifically in cancer cells rather than in healthy cells also improved the activity of ruthenium supramolecular architectures in cancer therapy. This recent outcome has propelled significant research channelled towards synthesizing better ruthenium-based chemotherapeutics. Additionally, the presence of two different metals in a single self-assembled architecture may also impart an increased activity when compared to the individual activity of each metal. Thus, the heterometallic supramolecular architectures can open a new kind of chemotherapeutics which may give a distinct mechanistic pathway different from those reported in literature. Chapter 1 of this thesis describes the coordination-driven self-assembly strategy with specific emphasis on ruthenium p-cymene self-assembled architectures and their applications. A brief introduction on cancer and cancer therapy is discussed. The use of mononuclear and dinuclear metal-based chemotherapeutics is included while the use of heterometallic complexes as anticancer agents was also highlighted. Chapter 2 showcases the self-assembly of a series of 2D and 3D ruthenium(II) p-cymene architectures constructed from bidentate and tridentate rigid imidazole-based ligands and dinuclear ruthenium(II) building units. The influence of the rotational flexibility of the imidazole ligands on the final architecture was probed. In spite of the likelihood of the formation of different conformational isomeric architectures (syn and anti) and/or polymeric products due to free rotation on the donor sites of the imidazole ligands, the exclusive formation of a single conformational isomer (anti) as the only product turned out to be a noteworthy observation. This indicates that the coordination mode and flexibility of imidazole ligand can control and determine the geometry, topology and conformations of the final molecular architectures. Scheme 1: Self-assembly of 2D macrocycles [2 - 7](OTf)4 employing dinuclear ruthenium(II) building units [1a - 1c](OTf)2 and bidentate rigid imidazole ligands L1 - L2 in methanol at room temperature. Furthermore, the unexpected formation of a tetranuclear cationic macrocycle [8](OTf)4 was reported in the 2 + 3 self-assembly reaction of triazine-based tridentate imidazole ligand L3 and dinuclear ruthenium(II) building unit [1a](OTf)4 over the expected hexanuclear prismatic cage [8a](OTf)6 which is quite surprising. Scheme 2: Schematic representation of the formation of an unexpected tetranuclear macrocycle [8](OTf)4 over the expected hexanuclear prismatic cage [8a](OTf)6. Chapter 3 reports the synthesis of eight octanuclear cages via the coordination-driven self-assembly of two tetradentate pyridyl-based organic ligands and four dinuclear p-cymene Ru(II) acceptor clips. These octanuclear cages were explored in vitro as potential anticancer agents against human lung adenocarcinoma A549 and human cervical cancer HeLa cell lines. Four of the cages with polyaromatic spacers in their Ru(II) acceptor clip unit showed very low micromolar IC50 values and also possess higher anticancer activity than cisplatin against the tested cancer cell lines. The four dinuclear p-cymene Ru(II) acceptor clips A3 in OC-3 and OC-7 revealed some kind of synergy which is evident in their IC50 values against the tested cancer cell lines. In addition, OC-3 and OC-7 trigger both early and late apoptotic phases while OC-4 and OC-8 trigger majorly late apoptotic phase in the cancer cell lines tested. The mechanistic pathway by which cell death is progressing is through the generation of reactive oxygen species (ROS) which is of significant amount in OC-4 and OC-8. Scheme 3: Self-assembly of the discrete octanuclear cages (OC-1 - OC-8) in methanol at room temperature and the schematic illustration of the apoptosis mechanistic pathway. Chapter 4 describes the use of “metalloligands” as electron-rich building blocks and the subsequent use of the metalloligand for “one-pot” self-assembly reactions in the presence of electron-deficient metal acceptor building blocks. The pyridyl donors are the most preferred in metalloligands because of their predictable directionality in self-assembly. The introduction of a second metal into the ligand component of the self-assembled architecture is to bestow additional functionality as well as to construct elegantly designed discrete heterobimetallic supramolecular architectures. Four discrete Ru(II)-Pt(II) hexanuclear trigonal prismatic cages were synthesized employing a tritopic platinum(II) metalloligand and four p-cymene ruthenium(II) clips via coordination-driven self-assembly. The formation of these cages were confirmed by well-known spectroscopic techniques and their structural features was elucidated by geometry optimization. In vitro anticancer studies of these heterometallic cages failed because of solubility challenges in the culture media presumably due to their high molecular weights and many alkyl groups. Scheme 4: Energy minimized structures of the heterometallic trigonal prismatic cages 3a (left) and 3b (right). Hydrogen atoms have been removed for the sake of clarity [Ru: green, Pt: pink, O: red, N: blue, P: orange, C: grey]. Chapter 5 discusses the synthesis of two bidentate platinum(II) metalloligands as well as the self-assembly of six new heterometallic rectangles obtained from four Ru2(OOꓵOO)2(p-cymene)2Cl2 pillars and two bidentate pyridyl-based platinum(II) metalloligands. The Ru4Pt2 and Ru4Pt4 rectangles were structurally characterized and supported by geometry optimisation. Additionally, two Ru4Pt2 and two Ru4Pt4 rectangles were examined for their anticancer properties in eight human cancer cell lines with the aim of checking if the platinum metal centres in the metalloligands can enhance the anticancer activity of the rectangles. The results showed that these heterometallic rectangles are cytotoxic against the cancer cell lines tested but the incorporation of platinum(II) metal(s) into the metalloligand did not further enhance the cytotoxicity in the rectangles tested as hypothesized. The mechanism of cell death is via the generation of reactive oxygen species (ROS) and two Ru4Pt4 rectangles activates both early and late apoptosis. Cell cycle analysis showed that one of the Ru4Pt4 rectangles is a moderate inhibitor of cell cycle progression at the sub G1 phase similar to cisplatin while nuclear condensation and cell blebbing in the cells was also observed in the presence of the two Ru4Pt4 rectangles tested. The overall activity of the heterometallarectangles against the cancer cell lines tested was increased when they exist as a single entity thus reiterating the importance of heterobimetallic supramolecular architectures in cancer therapy. Scheme 5: Schematic diagram of the discrete Ru4Pt4 heterometallic rectangles and illustration of the cell death pathway. The results of the investigation reported in this thesis contribute to the rapidly developing field of organometallic ruthenium(II) self-assembled anticancer chemotherapeutics with specific evidences of the mechanistic pathway of cell death. This results can further guide the design and development of better chemotherapeutics for future use.

Made available in DSpace on 2017-07-10T18:13:27Z (GMT). No. of bitstreams: 1 Magali R S Orsi.pdf: 820994 bytes, checksum: ec0d061929d9701eac9c971bd40b8b8d (MD5) Previous issue date: 2011-08-02 / The sustainable use of natural resources, particularly in the case of fishery resources is a challenge that must be seen in terms of technical, political, economical and social, and Brazil is one of the few countries where inland fishery has a considerable economic value, which emphasizes the cultivation of fish in cages, allowing rivers and hydroelectric reservoirs been utilized not only for power generation. In this context fits Tekoha Ocoy, Ava-Guarani indigenous, allocated in São Miguel do Iguaçu at Paraná state and affected by dam construction for installation of the Itaipu Hydroelectric Plant. Thus, this work was characterized by a case study and survey data on fish farming in cages in this indigenous community, assisted by the Cultivando Água Boa Project, developed by Itaipu Binacional aims to promote social inclusion, recovery and enhancement of indigenous communities in the Bacia do Paraná 3 (BP3), providing better quality of life for these communities. It was found that the program, and its proposes, is not meeting the needs of the indigenous community, even showing its support to the implementation of the program, expressed no satisfaction over the results achieved and the manner of its execution, according to the data collected in the development of this research. The results obtained showed that fish culture in cages for this community in question can be a great lever of social, economic and cultural development, enabling the effective use of natural local resources, yet respecting the views of affected and the environment. For this, the activity should be planned considering the characteristics of community areas where it is deployed, been necessary to harmonize the production process with the local culture and environment, to become a viable alternative to sustainable development. / A utilização sustentável de recursos naturais, particularmente no caso de recursos pesqueiros, é um desafio que necessita ser considerado do ponto de vista técnico, político, econômico e social, e o Brasil é um dos poucos países em que a pesca em águas interiores possui um valor econômico apreciável, no qual se destaca o cultivo de peixes em tanques-rede, possibilitando que rios e reservatórios de usinas hidrelétricas sejam aproveitados não apenas para geração de energia. Neste contexto se insere a comunidade indígena Tekoha Ocoy, do ramo Avá-Guarani, alocada na cidade de São Miguel do Iguaçu PR e afetada pela construção da barragem para instalação da Usina Hidrelétrica de Itaipu. Assim, este trabalho caracterizou-se pelo estudo de caso e levantamento de dados sobre a piscicultura em tanques-rede nessa comunidade indígena, assistida pelo Programa Cultivando Água Boa, desenvolvido pela Itaipu Binacional, e que, na sua formatação, tem por objeto promover a inclusão social, o resgate e a valorização das comunidades indígenas na Bacia do Paraná 3 (BP3), de forma a proporcionar melhor qualidade de vida a essas comunidades. Evidenciou-se que o programa, pelo que propõe, não está atendendo às necessidades da comunidade indígena que, mesmo mostrando-se favorável à sua implantação, não demonstrou satisfação com relação aos resultados alcançados e à forma de sua execução, de acordo com os dados levantados no desenvolvimento desta pesquisa. A partir dos resultados obtidos, concluiu-se que a piscicultura em tanques-rede para essa comunidade em questão pode ser uma grande alavanca de desenvolvimento social, econômico e cultural, possibilitando o aproveitamento efetivo dos bens naturais locais, no entanto respeitando a opinião dos afetados e o meio ambiente. Para isso, a atividade deve ser planejada considerando-se as características da comunidade das áreas em que for implantada, sendo necessário harmonizar o processo produtivo com a cultura local e o ambiente, para tornar-se uma alternativa viável ao desenvolvimento sustentável.

Over the past few decades, supramolecular self-assembly has become an alternative synthetic tool for constructing targeted discrete molecular architectures. Among various interactions, metal-ligand coordination has attracted great attention owing to high bond enthalpy (15−50 Kcal/mol) and predictable directionality. The basic principle of metal-ligand directed self-assembly relies on the proper designing of information encoded rigid complementary building units (a transition metal based acceptor and a multidentate organic donor) that self-recognize themselves in a chemically reasonable way (depends on their bite angle and symmetry) during self-assembly process. As far as acceptor units are concerned, Pd(II) and Pt(II) metal-based cis-blocked 90° acceptors have so far been used greatly for the construction of a library of 2D/3D discrete supramolecular architectures due to their rigid square planar geometry and kinetic lability. However, in some cases the efforts to design finite supramolecular architectures using a cis-blocked 90° acceptor in combination with a bulky donor ligand were unsuccessful, which may be due to the steric demands of donor ligand. Moreover, the resulted assemblies from such cis-blocked 90° building unit are mostly non-fluorescent in nature and limit the possibility of using them as chemosensors for various practical applications. Unlike that of rigid square-planar Pt(II) and Pd(II)-metal based building blocks, the use of other transition metal-based building units for the construction of discrete nanoscopic molecular architectures are known to lesser extent, mainly because of their versatile coordination geometries. However, some of the half-sandwiched piano-stool complexes of late transition metals like Ru, Os, Ir and Rh are known to maintain the stable octahedral geometry under various reaction conditions. Moreover, the self-assembly using redox active transition metal-based building units may lead to redox active assemblies. On the other hand, symmetrical rigid donors have been widely used as the favorite choices for the purpose of constructing desired product mainly due to their predictable directionality. Flexible linkers are not predictable in their directionality during self-assembly process and thus results mostly in undesired polymeric products. Furthermore, metal-ligand directed self-assembly provides opportunity to introduce multifunctionality in a single step within/onto the final supramolecular architectures. Among various functional groups, the incorporation of unsaturated ethynyl functionality is expected to enrich the final assemblies to be π-electron-rich and the attachment of ethynyl functionality with heavy transition metal ions are known to be luminescent in nature due to the facile metal to ligand charge transfer (MLCT). Hence, the final supramolecular complexes can be used as potential fluorescence sensors for electron-deficient nitroaromatics, which are the chemical signature of most of the commercially available explosives. The main thrust of the present investigation is focused on the judicious design and syntheses of multifaceted 2D/3D supramolecular architectures of finite shapes, sizes and functionality using Pt(II)/Ru(II) based “shape-selective” organometallic building blocks and investigation of their application as chemosensors. CHAPTER 1 of the thesis presents a general review on the core concepts of self-assembly and supramolecular chemistry. In particular, it underlines the importance of metal-ligand directional bonding approach for designing a vast plethora of discrete 2D/3D supramolecular architectures with tremendous variation in topology. CHAPTER 2 describes the design and syntheses of a series of 2D metallamacrocycles using carbazole-functionalized shape-selective 90° building units. A new Pt2II organometallic 90° acceptor 3,6-bis[trans-Pt(PEt3)2(NO3)(ethynyl)]carbazole (M1) containing ethynyl functionality is synthesized via Sonagashira coupling reaction and characterized. The combination of M1 with three different flexible ditopic donors (L1−L3) afforded [2 + 2] self-assembled molecular squares (1−3), respectively [where L1 = 1,3-bis(4-pyridyl)isophthalamide; L2 = 1,3-bis(3-pyridyl)isophthalamide; L3 = 1,2-bis(4-pyridyl)ethane] (Scheme 1). Scheme 1: Schematic presentation of the formation of a series of [2 + 2] self-assembled molecular squares. An equimolar (1:1) combination of same acceptor M1 with rigid linear ditopic donors (L4-L5) yielded [4 + 4] self-assembled octanuclear molecular squares 4 and 5, respectively [L4 = 4,4’-bipyridine; L5 = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar reaction of M1 with an amide-based unsymmetrical linear flexible ditopic donor L6 resulted in the formation a [2 + 2] self-sorted molecular rhomboid (6a) as a single product [L6 = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboids, triangles and squares) due to different connectivity of the ambidentate linker, the formation of a single and symmetrical molecular rhomboid 6a as an exclusive product is an interesting observation. This chapter also presents the synthesis and characterization of a complementary 90° dipyridyl donor 3,6-bis(4-pyridylethynyl)carbazole (L7). Stoichiometric combination of L7 with several PdII/PtII-based 90° acceptors (M2−M4) yielded [2 + 2] self-assembled molecular “bowl” shaped macrocycles (7−9) respectively, in good yields [M2 = cis-(dppf)Pd(CF3SO3)2; M3 = cis-(dppf)Pt(CF3SO3)2; M4 = cis-(tmen)Pd(NO3)2]. All these newly synthesized macrocycles were characterized by various spectroscopic techniques and molecular structures of some of them were confirmed by single crystal X-ray diffraction analysis. In addition to their syntheses and characterization, fluorescence chemosensing ability for various analytes was investigated. Macrocycle 1 is a system composed of amide-based receptor units and carbazole-based fluorophore moieties. The fluorescence study of 1 elicited a dramatic enhancement in the fluorescence intensity upon gradual addition of P2O74- anion in DMF/H2O solvent mixture, whereas similar titration under identical condition with other anions like F-, ClO4-, and H2PO4- did not show such change. Hence, molecular square 1 can be used as selective fluorescence sensor for pyrophosphate (P2O74-) anion. Due to their extended π-conjugation, macrocycles 3-4 were used as fluorescence sensors for electron-deficient nitroaromatics, which are the chemical signatures of many commercially available explosives. The fluorescence study showed a marked quenching of initial fluorescence intensity of the macrocycles(3-4) upon gradual addition of picric acid (PA) and they exhibited large fluorescence quenching responses with high selectivity for nitroaromatics among various other electron deficient aromatic compounds tested. As macrocycle 7 has large concave aromatic surface, it was utilized as a suitable host for large convex guest such as fullerene C60. The fluorescence quenching titration study suggested that macrocycle 7 forms a stable ~1:1 host-guest complex with C60 and the calculated association constant (KSV) is 1.0 × 105 M-1. CHAPTER 3 presents two-component coordination-driven self-assembly of a series of [2 + 2] molecular rectangles and a [2 + 4] self-assembled molecular tetragonal prism. An equimolar combination of pre-designed linear PtII2-acceptors M5−M6 separately with three different “clip” donors (L2, L8−L9) led to the formation of [2 + 2] self-assembled tetranuclear cationic molecular rectangles (10−15), respectively [M5 = 1,4-bis[trans-Pt(PEt3)2(NO3)(ethynyl)] benzene; M6 = 4,4’-bis[trans-Pt(PEt3)2(CF3SO3)(ethynyl)]biphenyl; L8 = 1,3-bis(3-pyridyl)ethynylbenzene; L9 = 1,8-bis(4-pyridyl)ethynylanthracene]. Rectangles 10-15 showed strong fluorescence in solution owing to their extended π-conjugation. Amide-functionalized rectangle 10 was used as a macrocyclic receptor for dicarboxylic acids. Solution state fluorescence study showed that rectangle 10 selectively binds (KSV = 1.4 × 104 M-1) with maleic acid by subsequent enhancement in emission intensity and addition of other analogous aliphatic dicarboxylic acids such as fumaric, succinic, adipic, mesaconic and itaconic acids causes no change in the emission spectra; thereby demonstrated its potential use as macrocyclic receptor in sensor applications. Since rectangle 15 is enriched with π-conjugation, it was examined as a fluorescence sensor for electron-deficient nitroaromatics such as picric acid, which is often considered as a secondary chemical explosive. The fluorescence study of 15 showed a significant quenching of initial emission intensity upon titrating with picric acid (PA) and it exhibited the largest fluorescence quenching response with high selectivity for picric acid. Scheme 2: Schematic representation of formation of [2 + 4] self-assembled of molecular tetragonal prism. This chapter also describes two-component coordination [2 + 4] self-assembly of a pyrene-based PtII8 tetragonal prism (16) as shown in Scheme 2, using a newly designed tetratopic organometallic acceptor (M7; 1,3,6,8-tetrakis[trans-Pt(PEt3)2(NO3)(ethynyl)]pyrene) in combination with an amide-based “clip” donor (L2) and propensity of this prism (16) as a selective fluorescence sensor for nitroaromatic explosives has been examined both in solution as well as in thin-film. CHAPTER 4 reports the synthesis and structural characterization of a series of Ru(II)-based bi-and tetra-nuclear metallamacrocycles and hexanuclear trigonal prismatic cages. In principle, the self-assembly of a “clip” acceptor with an asymmetrical ditopic donor is expected to give two different linkage isomeric (head-to-tail and head-to-head) molecular rectangles because of different bond connectivity of the donor. However, the equimolar combination of half-sandwiched p-cymene binuclear Ru(II)-based “clip” acceptors (M8−M9) and an amide-based ambidentate donor (L6) resulted in the self-sorting of single linkage (head-to-tail) isomeric rectangles 17−18 as only products, respectively [M8 = [Ru2(μ-η4-C2O4)(MeOH)2(η 6-p-cymene)2](CF3SO3)2; M9 = [Ru2(μ- η4-C6H2O4)(MeOH)2(η 6-p-cymene)2](CF3SO3)2]. Molecular structures of these head-to-tail linkage isomeric rectangles were unambiguously proved by single crystal X-ray diffraction analysis. Likewise, the self-assembly of oxalato-bridged Ru(II) acceptor M8 with a rigid dipyridyl “clip” donor L8 yielded a tetranuclear cationic pincer complex 19, while a similar reaction of M8 with an anthracene-functionalized “clip” donor L9 having shorter distance (between their reactive sites) compared to L8 led to the formation of [1 + 1] self-assembled macrocycle 20. This chapter also represents the design and synthesis of two hexanuclear trigonal prismatic cages (21−22) from the self-assembly of a π-electron rich tripyridyl donor (L10; 1,3,5-tris(4-pyridylethynyl)benzene) in combination with binuclear acceptors M8 and M9, respectively (Scheme 3). Formation of these prismatic cages was initially characterized using various spectroscopic techniques and the molecular structure of oxalato-bridged prism 21 was confirmed by single crystal X-ray diffraction analysis. In addition to the structural characterization, the pincer complex 19 and trigonal prismatic cages 21−22 were used as fluorescence sensors for nitroaromatic explosives owing to their large internal porosity and their π-electron rich nature. Scheme 3: Schematic representation of the formation of [3 + 2] self-assembled trigonal prismatic cage. CHAPTER 5 covers the syntheses of a few discrete metallamacrocycles using flexible imidazole/carboxylate based donors instead of much widely employed polypyridyl donors. The metal-ligand directed self-assembly of oxalato-bridged acceptor M8 and an imidazole-based tetratopic donor (L11; 1,2,4,5-tetrakis(imidazol-1-yl)benzene) in methanol afforded [2 + 1] self-assembled tetranuclear macrocycle 23. Conversely, the similar combination of L11 with 2,5-dihydroxy-1,4-benzoquinonato-bridged binuclear complex (M9) in 1:2 molar ratio in methanol resulted in an octanuclear cage 24. Both the complexes (23−24) were isolated as their triflate salts in high yields and were characterized by various spectroscopic methods including single crystal X-ray diffraction analysis. Scheme 4: Schematic representation of formation of an octanuclear incomplete Ru(II) open prism via ruthenium-oxygen coordination driven self-assembly. This chapter also explains the self-sorting of an unusual octanuclear incomplete prism [Ru8(η6-p-cymene)8(tma)2(μ-η4-C2O4)2(OMe)4](CF3SO3)2 (25) via ruthenium-oxygen coordination driven self-assembly of building block M8 and sodium benzene-1,3,5-tricarboxylate (L12) (Scheme 4). Electronic absorption study indicated that prism 25 exhibited a remarkable shape-selective binding affinity for 1,3,5-trihydroxybenzene (phluoroglucinol) via multiple hydrogen bonding interactions and such shape-selective binding was confirmed by single crystal X-ray diffraction analysis. (For figures pl see the abstract file)

[EN] The present study was designed to evaluate in independent trials the effect of replace protein fishmeal (HP) by four plant sources, lupine (Lupinus mutabilis Sweet), corn gluten (CGM), amaranth (Amaranthus caudatus L.) and quinoa (Chenopodium quinoa) on the growth of juvenile shrimp Litopenaeus vannamei. For this four sets of diets were developed. The first two containing 35% protein and 11% lipids were prepared to replace the 0, 25, 50, 75 and 100% of the protein from HP by protein lupine (LKM) or CGM. The other two series of isoproteic (30%) and isolipidic (9.5%) diets were formulated to replace 0, 15, 25, 35 and 45% protein HP by protein amaranth and quinoa. Only the contents of corn starch and fish oil were varied to maintain constant levels of protein and lipid in all the experimental diets. All diets had squid meal to provide attractability. Depending on the test conducted eight (LKM and CGM) or seven (amaranth and quinoa) juveniles of about 1g were stocked randomly in aquariums (44 m-2 or 39 m-2) 50 L equipped with a flow-through water system using full-strength seawater. Six aquariums (replicates) were assigned to each of the treatments in a completely randomized design. The shrimp were fed ad libitum twice a day for about eight weeks. At the end of the growth trial, shrimp were fed experimental diets containing 0.5% of chromium oxide. Overall survival in the study was higher than 74% and did not change significantly (p>0.05) when HP was replaced partially or completely by each of the sources evaluated. The results of this study showed that LKM can replace 50% of the protein of HP without significantly (p>0.05) reducing growth (6.7-7.0 g final weight). LKM inclusion in any of the tested levels resulted in a significantly (p<0.05) reduced the apparent digestibility of dry matter (ADMS) and apparent digestibility of crude protein (ADPC) of the feed. The gradual increase of CGM in diets produced a significant (p<0.05) decrease of shrimp final weight (5.9 to 3.2 g) and growth rate (2.7 to 1.7% d-1) compared to those fed CGM 0 (7.1 g and 3.0% d-1). Feed Conversion Factor (FCA) was also significantly (p<0.05) affected by CGM level, diets CGM50, CGM75 and CGM100 had higher FCA than CGM0 and CGM25. The inclusion of CGM on any level tested resulted in a significant decrease in ADMS, from 77.9 to 66.0%, and ADPC, 80.5 to 52.0%, of the feed. The apparent digestibility of amino acids, except lysine, declined with the addition of CGM, reflecting the ADPC. While those shrimps fed diets based on amaranth showed that the diet with 15% replacement obtained a better growth (p<0.05) after the control diet. Diets with replacement 15% and 25% reported significantly (p<0.05) better DAMS (79.7% and 71.2%) and ADPC (88.4% and 81.1%) than the diet with 35% and 45% substitution. The replacement of quinoa in any of the assessed levels have not demonstrated performance (p<0.05) lower than the control diet. The DAMS and ADPC for quinoa diets were statistically superior (p<0.05) than control diet. These results show that lupine and quinoa have a very good potential as a protein source up to 50% and 45% respectively of the HP protein which is equivalent to a third of the total protein in the diet. The cost-benefit of including these ingredients needs to be evaluated. Lower values of corn gluten and amaranth on the HP could be due to low protein digestibility, imbalance of amino acids and / or the presence of antinutritional factors. / [ES] El presente estudio fue diseñado para evaluar en ensayos independientes el efecto de reemplazar la proteína de la harina de pescado (HP) por cuatro fuentes de origen vegetal, altramuz (Lupinus mutabilis Sweet), gluten de maíz (CGM), amaranto (Amaranthus caudatus L.) y quinua (Chenopodium quinoa) sobre el crecimiento de camarones juveniles Litopenaeus vannamei. Para esto se elaboraron cuatro series de dietas. Las dos primeras conteniendo 35% de proteína y 11% de lípidos fueron preparadas para sustituir el 0, 25, 50, 75 y 100% de la proteína proveniente de la HP por proteína de las harinas de altramuz (LKM) o CGM. Las otras dos series de dietas isoproteicas (30%) e isolipidicas (9,5%) fueron formuladas para reemplazar 0, 15, 25, 35 y 45% de la proteína de la HP por proteína de amaranto y quinua. Solamente los contenidos de almidón de maíz y aceite de pescado variaron para mantener constante los niveles de proteína y lípidos en todas las dietas experimentales. Todas las dietas tuvieron harina de calamar. Dependiendo del ensayo realizado ocho (LKM y CGM) o siete (amaranto y quinua) juveniles de alrededor de 1g fueron sembrados aleatoriamente en los acuarios (44 m-2 o 39 m-2) de 50 l equipados con un sistema de recambio de agua de mar de flujo continuo. Seis acuarios (réplicas) fueron asignadas a cada uno de los tratamientos en un diseño completamente aleatorizado. Los camarones fueron alimentados ad libitum dos veces al día por aproximadamente ocho semanas. Al final del ensayo de crecimiento, los camarones fueron alimentados con las dietas experimentales conteniendo 0,5% de óxido de cromo. La supervivencia en general del estudio fue superior a 74% y no varió significativamente (p>0,05) cuando la HP fue reemplazada parcial o totalmente por cada una de las fuentes evaluadas. Los resultados de este estudio mostraron que LKM puede reemplazar el 50% de la proteína de la HP sin disminuir significativamente (p>0,05) el crecimiento (6,7-7,0 g peso final). La inclusión de LKM en cualquiera de los niveles ensayados resultaron en una significativamente (p<0,05) reducción de la digestibilidad aparente de materia seca (DAMS) y la digestibilidad aparente de proteína cruda (DAPC) del alimento. El gradual incremento del CGM en las dietas produjo un significativo (p<0,05) decrecimiento del peso final (5,9 a 3,2 g) de los camarones y sus tasas de crecimiento (2,7 a 1,7% d-1) comparado a aquellos alimentados con 0 CGM (7,1 g y 3,0 % d-1). El Factor de Conversión Alimenticia (FCA) fue también significativamente (p<0,05) afectado por el nivel de CGM, las dietas CGM50, CGM75 y CGM100 tuvieron un más alto FCA que CGM0 y CGM25. La inclusión de CGM en cualquier nivel ensayado resultó en un significativo decrecimiento en DAMS, de 77,9 a 66,0%, y en DAPC, de 80,5 a 52,0%, del alimento. La digestibilidad aparente de aminoácidos, con la excepción de lisina, declinó con la incorporación de CGM, reflejando la ADPC. En tanto que los camarones alimentados con las dietas a base de amaranto mostraron (p<0,05) que la dieta con 15% de reemplazo obtuvo un mejor crecimiento después de la dieta control. Las dietas con reemplazo de 15% y 25% registraron significativamente (p<0,05) una mejor DAMS (79,70% y 71,21%) y DAPC (88,39% y 81,10%) que las dieta con 35% y 45% de sustitución. El reemplazo de la quinua en cualquiera de los niveles evaluados no demostraron tener un rendimiento (p<0,05) inferior a la dieta control. La DAMS y DAPC para las dietas con quinua fueron estadísticamente superiores (p<0,05) a la dieta control. Estos resultados muestran que el altramuz y quinua tienen un potencial muy bueno como fuente proteína hasta el 50% y 45% respectivamente de la proteína de la HP lo cual es equivalente a un tercio del total de la proteína presente en la dieta. Los valores más bajos del gluten de maíz y amaranto relativo a la HP podrían ser debido a la baja digestibilidad de la proteína, imbalance de aminoácidos y/o a la pres / [CAT] El present estudi va ser dissenyat per a avaluar en assajos independents l'efecte de reemplaçar la proteïna de la farina de peix (HP) per quatre fonts d'origen vegetal, tramús (Lupinus mutabilis Sweet), gluten de dacsa (CGM), amarant (Amaranthus caudatus L.) i quinoa (Chenopodium quinoa) sobre el creixement de gambetes juvenils Litopenaeus vannamei. Per a açò es van elaborar quatre sèries de dietes. Les dos primeres contenint 35% de proteïna i 11% de lípids van ser preparades per a substituir el 0, 25, 50, 75 i 100% de la proteïna provinent de la HP per proteïna de les farines de tramús (LKM) o CGM. Les altres dos sèries de dietes isoproteicas (30%) i isolipidicas (9,5%) van ser formulades per a reemplaçar 0, 15, 25, 35 i 45% de la proteïna de la HP per proteïna d'amarant i quinoa. Només els continguts de midó de dacsa i oli de peix van variar per a mantindre constant els nivells de proteïna i lípids en totes les dietes experimentals. Totes les dietes van tindre farina de calamar per a proveir atractabilidad. Depenent de l'assaig realitzat huit (LKM i CGM) o set (amarant i quinoa) juvenils d'al voltant de 1g van ser sembrats aleatòriament en els aquaris (44 m-2 o 39 m-2) de 50 l equipats amb un sistema de recanvi d'aigua de mar de flux continu. Sis aquaris (rèpliques) van ser assignades a cada un dels tractaments en un disseny completament aleatorizado. Les gambetes van ser alimentats ad libitum dos vegades al dia per aproximadament huit setmanes. Al final de l'assaig de creixement, les gambetes van ser alimentats amb les dietes experimentals contenint 0,5% d'òxid de crom. La supervivència en general de l'estudi va ser superior a 74% i no va variar significativament (p>0,05) quan la HP va ser reemplaçada parcial o totalment per cada una de les fonts avaluades. Els resultats d'este estudi van mostrar que LKM pot reemplaçar el 50% de la proteïna de la HP sense disminuir significativament (p>0,05) el creixement (6,7-7,0 g pes final). La inclusió de LKM en qualsevol dels nivells assajats van resultar en una significativament (p<0.05) reducció de la digestibilitat aparent de matèria seca (DAMS) i la digestibilitat aparent de proteïna crua (DAPC) de l'aliment. El gradual increment del CGM en les dietes va produir un significatiu decreixement del pes final (5,9 a 3,2 g) de les gambetes i les seues taxes de creixement (2,7 a 1,7% d-1) comparat a aquells alimentats amb 0 CGM (7,1 g i 3,0 % d-1). El Factor de Conversió Alimentària (FCA) va ser també significativament (p<0.05) afectat pel nivell de CGM, les dietes CGM50, CGM75 i CGM100 van tindre un més alt FCA que CGM0 i CGM25. La inclusió de CGM en qualsevol nivell assajat va resultar en un significatiu decreixement en DAMS, de 77,9 a 66,0%, i en DAPC, de 80,5 a 52,0%, de l'aliment. La digestibilitat aparent d'aminoàcids, amb l'excepció de lisina, va declinar amb la incorporació de CGM, reflectint l'ADPC. En tant que les gambetes alimentats amb les dietes a base d'amarant van mostrar que la dieta amb 15% de reemplaçament va obtindre un millor creixement després de la dieta control. Les dietes amb reemplaçament de 15% i 25% van registrar significativament una millor DAMS (79,70% i 71,21%) i DAPC (88,39% i 81,10%) que les dieta amb 35% i 45% de substitució. El reemplaçament de la quinoa en qualsevol dels nivells avaluats no van demostrar tindre un rendiment inferior a la dieta control. La DAMS i DAPC per a les dietes amb quinoa van ser estadísticament superiors a la dieta control. Estos resultats mostren que el tramús i quinoa tenen un potencial molt bo com a font proteïna fins al 50% i 45% respectivament de la proteïna de la HP la qual cosa és equivalent a un terç del total de la proteïna present en la dieta. El cost-benefici d'incloure estos ingredients necessita ser avaluat. Els valors més baixos del gluten de dacsa i amarant relatiu a la HP podrien ser degut a la baixa digestibilitat de la proteïna, imbalance d'aminoàcids y/o a / Molina Poveda, C. (2016). Evaluación de varias fuentes de proteína vegetal en dietas para camarón Litopenaeus vannamei [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63666 / TESIS

Made available in DSpace on 2017-07-10T18:13:32Z (GMT). No. of bitstreams: 1 Elaine C Rodrigues Bartozek.pdf: 1985797 bytes, checksum: a358025d50258b7eaddead48b3a3dc40 (MD5) Previous issue date: 2012-06-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In Brazil, hydroelectric powerplant reservoirs are used for multiple purposes, among them, fish farming in net cages. The present study aimed to evaluate spacial and temporal variations of the abiotic variables, nutrients concentration, trophic state and composition and structure of the phytoplankton community in an arm of Salto Caxias reservoir influenced by experimental fish cultivation in net cages. Samples were bimontly betweem September 2010 and July 2011 at the subsurface of the pelagic zone in four sampling stations, been two of them placed in the arm influenced by the cultivation of 30 net cages and the other two in the cagaless arm. No significant differences were observed for composition, diversity, density and phytoplankton biomass between the treatments. The results of the analisys performed showed only seasonal variations, separating the dry from the rainy period. The values of species richness and Shannon diversity were low during the entire study period. Evenness was high in the dry period and low in the rainy period. Both arms were classified as oligotrophic, possible demonstrating low influence of the net cages in the environment. Phytoplankton density and biomass were higher during the rainy period. The dry period was represented mainly for Bacillariophyceae taxa and the rainy period by Cyanobacteria and Chlorophyceae. Two functional groups (FG) were observed (FG F and K), both of them typical from shallow environments with high transparency water. Variations in the phytoplakton structure seem to have been influenced mainly by the seazonality. The effects of the net cages in the nutrients concentration and phytoplankton structure were probably low, possibly due to the low number of net cages and fishes emploied and environment dinamics, influenced by the inflows of the upstream rivers. / No Brasil, reservatórios de usinas hidrelétricas são utilizados para múltiplas propostas, entre elas, o cultivo de peixes em tanques-rede. O presente estudo objetivou avaliar as variações espaciais e temporais das variávies abióticas, concentração de nutrientes, estado trófico e da composição e estrutura da comunidade fitoplanctônica em um braço do reservatório de Salto Caxias influenciado pelo cultivo experimental de peixes em tanques-rede. Foram realizadas amostragens bimestrais, entre setembro de 2010 e julho de 2011, à subsuperfície da zona pelágica, em quatro estações de amostragem, sendo duas localizadas em um braço influenciado pelo cultivo em 30 tanques-rede e duas em um braço não influenciado. Não foram registradas diferenças significativas para a composição, diversidade, densidade e biomassa fitoplanctônica entre os tratamentos utilizados. Os resultados das análises realizadas evidenciaram apenas variações sazonais, separando o período seco do período chuvoso. Os valores de riqueza de espécies e diversidade de Shannon foram baixos durante todo o período de estudo. A equitabilidade foi elevada no período seco e baixa no período chuvoso. Ambos os braços foram classificados como oligotróficos, demonstrando possivelmente baixa influência dos tanques-rede sobre o ambiente. A densidade e biomassa fitoplanctônica foram maiores durante o período chuvoso. O período seco foi representado principalmente por táxons de Bacillariophyceae e o período chuvoso por Cyanobacteria e Chlorophyceae. Dois grupos funcionais (GF) fitoplanctônicos foram observados (GF F e K), ambos característicos de ambientes rasos e com elevada transparência da água. As variações da estrutura fitoplanctônica parecem ter sido influenciadas principalmente pela sazonalidade. Os efeitos dos tanques-rede sobre a concentração de nutrientes e estrutura da comunidade fitoplanctônica parecem ter sido pouco significativos, possivelmente devido ao pequeno número de tanques-rede e peixes utilizados e a hidrodinâmica dos ambientes estudados, influenciados pelos influxos dos rios à montante.