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Dissertations / Theses on the topic 'Complex solid solution'
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1
D'Aléo, Anthony. "From solution to solid state energy- and electron-transfer in complex materials /." [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2006. http://dare.uva.nl/document/89463.
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Petherick, Janice, University of Western Sydney, and School of Science. "Chiral discrimination associated with complex molecules." THESIS_XXXX_SS_Petherick_B.xml, 1999. http://handle.uws.edu.au:8081/1959.7/134.
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This thesis is a report on the design, synthesis and molecular structure of a set of chiral Co(III) metal complexes, in the solution and solid state. The complexes that have been synthesised will potentially intercalate between the base pairs of DNA. The structure of the bound tetradentate ligand, S,S-picchxnMe2 in the solid state was investigated to determine the flexibility of this seemingly rigid ligand. The bidentate ligands, R- and S-glu, were also bound to the Co complex and the differences in the tetradentate ligand were observed. The differences observed in the bonded tetradentate ligands were due to the chirality of the bonded amino acid. The aromatic amino acids, R- and S-phe, were used as bidentate ligands because of their ability to intercalate with DNA. Several scientific experiments were conducted and the results analysed in great depth<br>Doctor of Philosophy (PhD)
3
Pike, Sebastian David. "Investigating the chemistry of cationic rhodium bisphosphine complexes : comparing reactivity in the solid state with solution." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:413c8a57-0a5e-4e51-8874-e48db8079675.
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This thesis describes the synthesis and characterisation of a series of cationic rhodium bis-phosphine complexes. The reactivity of these new complexes in the solid-state and in solution is reported. In <b>Chapter 2</b> the synthesis of a series of rhodium bis-phosphine diene complexes is presented and the reactions of these complexes with hydrogen in the solid-state are investigated. Several examples of zwitterionic complexes coordinating the [BAr<sup>F</sup>4]<sup>─</sup> anion are produced by hydrogenation. A rare example of a sigma-alkane complex, [Rh(<sup>i</sup>Bu<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>P<sup>i</sup>Bu<sub>2</sub>)(eta<sup>2</sup>-<sub>CH</sub>-eta<sup>2</sup>-<sub>CH</sub>-NBA][BAr<sup>F</sup>4]<sup>─</sup], is also formed in the solid-state, by a single crystal to single crystal transition driven by hydrogen. This complex is crystallographically characterised and displays two short Rh∙∙∙H−C sigma-interactions. Deuteration studies indicate that the agostic complex [Rh(<sup>i</sup>Bu<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>P<sup>i</sup>Bu<sub>2</sub>)(eta<sup>2</sup>-<sub>CH</sub>-eta<sup>2</sup>-<sub>CH</sub>-NBE][BAr<sup>F</sup>4] may form as a short lived intermediate prior to the formation of the sigma-alkane complex. The temporal evolution of the solid-state hydrogenation reactions is monitored by powder X-ray diffraction methods. In <b>Chapter 3</b> the C−X activation of various aryl halides using the [Rh(<sup>i</sup>Bu<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>P<sup>i</sup>Bu<sub>2</sub>)]<sup>+</sup> fragment is reported. The 'ligand innocence' of the phosphine with respect to intramolecular C−H activation is also discussed. A rare example of C−X activation in the solid-state is presented, which shows the formation of an isomer that is not observed by analogous solution routes. <b>Chapter 4</b> investigates solid-state ligand exchange reactions using ethene, butadiene, CO and NH3 gases. A solid-state transfer dehydrogenation reaction is reported within single crystals of [Rh(<sup>i</sup>Bu<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>P<sup>i</sup>Bu<sub>2</sub>)(C<sub>2</sub>H<sub>4</sub>)<sub>2</sub>][BAr<sup>F</sup>4]. H/D exchange of NH3 can also occur in the solid state in the bis-ammonia complex [Rh(<sup>i</sup>Bu<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>P<sup>i</sup>Bu<sub>2</sub>)(NH<sub>3</sub>)<sub>2</sub>][BAr<sup>F</sup>4]. A variety of rhodium complexes are tested as heterogeneous catalysts for the hydrogenation of ethene and the isomerisation of butene. In <b>Chapter 5</b> the binding affinity of a variety of fluorinated arenes to rhodium bis-phosphine fragments is presented using ESI-MS methods. The dependence upon the arene substituents, phosphine substituents and phosphine bite angle are discussed.
4
Bufali, Simone. "Part 1 Chemical synthesis of biologically active glycolipids ; Part 2 Solution phase and automated solid phase synthesis of complex oligosaccharides /." Zürich : ETH, 2007. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17335.
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5
Petherick, Janice. "Chiral discrimination associated with complex molecules." Thesis, View thesis, 1999. http://handle.uws.edu.au:8081/1959.7/134.
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This thesis is a report on the design, synthesis and molecular structure of a set of chiral Co(III) metal complexes, in the solution and solid state. The complexes that have been synthesised will potentially intercalate between the base pairs of DNA. The structure of the bound tetradentate ligand, S,S-picchxnMe2 in the solid state was investigated to determine the flexibility of this seemingly rigid ligand. The bidentate ligands, R- and S-glu, were also bound to the Co complex and the differences in the tetradentate ligand were observed. The differences observed in the bonded tetradentate ligands were due to the chirality of the bonded amino acid. The aromatic amino acids, R- and S-phe, were used as bidentate ligands because of their ability to intercalate with DNA. Several scientific experiments were conducted and the results analysed in great depth
6
Behra, Philippe. "Etude du comportement d'un micropolluant metallique (le mercure) au cours de sa migration a travers un milieu poreux sature : identification experimentale des mecanismes d'echanges et modelisation des phenomenes." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13120.
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7
Jouanneaux, Alain. "Etude par r. P. E. De diffraction de neutrons des composes mixtes rb : :(x)(nh::(4))::(1-x)alf::(4), desordre chimique, transition de phase, ordre local, verre de spin structural." Nantes, 1987. http://www.theses.fr/1987NANT2044.
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Mise en evidence, a temperature ambiante, de la substitution de rb**(+) a toute concentration. Determination par diffraction de neutrons sur poudre de la structure moyenne des cristaux mixtes : resultats en accord avec les resultats rpe. Puis, etude a basse temperature de l'ordre du sous-reseau des ions nh::(4)**(+) pour 0 <ou= x >ou= 0,25. Mise en evidence de l'apparition de domaines antiphase et determination de la distance moyenne entre les discommensurations. Enfin, interpretation du comportement a basse temperature de ce systeme d'ising axial aleatoire dans le cadre du verre de "pseudo-spin" structural
8
Korenev, Vladimir Sergeevich. "Cluster complexes of polyoxometalates : synthesis, and solution and solid state studies." Versailles-St Quentin en Yvelines, 2011. http://www.theses.fr/2011VERS0044.
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Ce travail de thèse décrit la synthèse et les caractérisations de nouveaux composés Polyoxo(thio)métallates. Dans ce manuscrit sont étudiés la réactivité de clusters dinucléaires de type [Re2CI8]2-, [Rh2(CH3COO)4(H2O)2] et [Mo2O2S2(H20)6]2+ avec des POMs vacants tels que BW11, PW11et P8W48. Dans ce cadre, plusieurs architectures nouvelles ont été obtenues et caractérisées par RX sur monocristaux et en solution par RMN. Dans cette partie, une attention particulière est portée au composé [P8W48(Mo4O4s4(OH)2(H20))2]36-. Dans une seconde partie du manuscrit, la réactivité du cation [Mo2O2S2(H20)6]2+ vis-à-vis de molybdate est abordée. Cette étude a permis d’isoler 3 nouvelles espèces moléculaires spectaculaires de nucléarité Mo40, Mo63 et Mo132 suivant les conditions de synthèse. Les synthèses et les caractérisations de ces espèces sont présentées dans ce manuscrit et ces derniers résultats ouvrent de larges perspectives<br>This work describes the syntheses and the characterizations of some new Polyoxo(thio)metalates. In this manuscript are studied the reactivities of some dinuclear clusters as [Re2CI8]2-, [Rh2(CH3COO)4(H2O)2] and [Mo2O2S2(H20)6]2+ with vacant POMs like BW11, PW11et P8W48. Several new supramolecular architectures have been obtained and characterised by X-Ray diffraction in the solid state and by solution studies using Electronic spectroscopy and NMR. In this part, a particular attention was bring to the new compound [P8W48(Mo4O4s4(OH)2(H20))2]36-. The second part is devoted to the reactivity of the thiocation [Mo2O2S2(H20)6]2+ towards molybdates. This study allowed to isolate 3 new spectacular molecular architectures for which the nuclearity varies from Mo40 to Mo63 and Mo132 as a function of the synthesis conditions. The syntheses and the characterizations of these species are presented in this manuscript and these results open large interesting perspectives
9
Goodwin, Sarah L. "A solution and solid state study of polyiron complexes with carboxylate containing ligands." Thesis, University of East Anglia, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.318023.
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10
VILHENA, FELIPE DE SOUZA DIAS DOS SANTOS. "METAL COMPLEXES OF 2-PYRIDINEFORMAMIDE THIOSEMICARBAZONES: SOLUTION STUDIES, SOLID STATE STUDIES AND CYTOTOXIC ACTIVITY." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2008. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=11957@1.
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PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO<br>CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO<br>Tiossemicarbazonas e seus complexos metálicos apresentam um
amplo espectro de atividades biológicas. As
tiossemicarbazonas α(N)-heterocíclicas tem sido muito
estudadas em razão de sua comprovada ação antitumoral. O
mecanismo de ação antitumoral dessas drogas se dá pela
inibição da enzima ribonucleotídeo difosfato redutase
(RDR), que catalisa o ciclo de reações redox envolvido na
conversão de ribonucleotídeos a desoxirribonucleotídeos
durante a síntese do ADN. A forma ativa dessas drogas é o
complexo de ferro. Desse modo, a obtenção de novos
complexos de Fe de tiossemicarbazonas α(N)-heterocíclicas
constitui uma importante estratégia para a obtenção de
candidatos a antitumorais. Nesse trabalho investimos no
estudo, em solução aquosa, da interação entre 2-
piridinoformamida tiossemicarbazona (H2Am4DH) e seus
derivados N(4)-metil (H2Am4M), N(4)-etil (H2Am4E) e N(4)-
fenil (H2Am4Ph) e os íons Cu(II) e Fe(III). Esse estudo foi
monitorado por espectroscopia de absorção na região do
UV-vis. Para o cálculo das constantes de formação dos
complexos foram levados em consideração os valores das
constantes cumulativas calculadas inicialmente
para as tiossemicarbazonas livres ( β HL e β H2L+). Quatro
novos complexos de Fe(III) foram isolados e caracterizados:
[Fe(2Am4DH)2]Cl, [Fe(2Am4Me)2]Cl, [Fe(2Am4Et)2]Cl e [Fe
(2Am4Ph)Cl3]. Os valores de susceptibilidade magnética
para os complexos estão na faixa de 1,36-1,66 MB. Esses
valores são próximos do calculado (1,73 MB) para complexos
de Fe(III), octaédricos, spin baixo. Os dados
de infravermelho indicam que as tiossemicarbazonas estão
coordenadas ao ferro através do sistema quelante Npy-N-S. O
comportamento eletroquímico dos complexos é bastante
similar, sugerindo que suas estruturas em solução são
igualmente similares. A toxicidade das tiossemicarbazonas e
de seus complexos de ferro frente à Artemia salina foi
estudada como um pré-screening para sua ação
antitumoral. Os valores de LD50 obtidos indicam que esses
compostos têm atividade citotóxica, sugerindo que poderiam
igualmente apresentar ação antitumoral. Além disso, os
potenciais de redução FeIII/FeII observados para os
complexos estão dentro da faixa ideal dos redutores
celulares. Assim, se confirmada a atividade antitumoral o
mecanismo de ação poderia envolver a redução FeIII/FeII por
tiois celulares, como sugerido para outros complexos de
ferro de tiossemicarbazonas.<br>Thiosemicarbazones and their metal complexes present a wide
range of
bioactivities. It has been shown that the antitumoral
action of á(N)-heterocyclic
thiosemicarbazones occurs through the inhibition of
ribonucleotide diphosphate
reductase (RDR), a key enzyme involved in the conversion of
ribonucleotides into
deoxyribonucleotides during DNA syntheses. The active form
of the drugs are
their iron complexes. Hence the preparation of new iron
complexes with á(N)-
heterocyclic thiosemicarbazones constitutes an interesting
strategy in designing
antitumoral drug candidates. In the present work the
interactions of 2-
pyridineformamide thiosemicarbazone (H2Am4DH) and its N(4)-
methyl
(H2Am4Me), N(4)-ethyl (H2Am4Et) and N(4)-phenyl (H2Am4Ph)
derivatives
with Cu(II) as well as Fe(III) ions in aqueous solution
were studied, monitored in
the visible region by the variations of the absorption
spectrum. The cumulative
protonation constants â HL and â H2L+ were determined for
the ligands by a
potentiometric method and were used in the calculation of
the complex formation
constants. The iron(III) complexes [Fe(2Am4DH)2]Cl, [Fe
(2Am4Me)2]Cl,
[Fe(2Am4Et)2]Cl and [Fe(2Am4Ph)Cl3] were obtained and
characterized. The
values of magnetic moments in the 1.59-1.66 BM range are
close to the calculated
value of 1.73 BM, characteristic of the presence of one
unpaired electron as in low
spin iron(III) complexes. The infrared data for the
complexes indicate
coordination of the thiosemicarbazones through the Npy-N-S
chelating system.
The resemblance of electrochemical behaviors suggests that
the structures of the
complexes in solution are also very similar. The toxicity
of the
thiosemicarbazones and their metal complexes against
Artemia salina was assayed
as a prescreening of antitumoral action. The low values of
LD50 obtained for the
studied compounds in this assay indicate that they could
present antineoplastic
properties. Moreover, the determined values of FeIII/FeII
redox potentials for the complexes fall in the range of
cellular reductants. Therefore, if the complexes
present antitumoral activity, their biochemical pathway
could involve FeIII/FeII
reduction by cellular thiols, as suggested previously for
iron complexes of other
thiosemicarbazones.
11
Masschelein, C. A. "Etude photophysique de nouveaux complexes du ruthénium en solution et en matrice solide." Doctoral thesis, Universite Libre de Bruxelles, 1988. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/213341.
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Zapata-Ormachea, Mariel L. "Thermodynamic aspects of macrocycles and their metal-ion complexes in solution and in the solid state." Thesis, University of Surrey, 2000. http://epubs.surrey.ac.uk/843197/.
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This thesis concerns the thermodynamics of macrocycles and their metal cation complexes in non-aqueous media and these are discussed under two main headings, i) Thermodynamics of Alkali-Metal Cations and Macrocycles in Solution and in the Solid State. Thermodynamic parameters of complexation for alkali-metal cations and macrocycles (18-crown-6 and ethyl p-tert-butylcalix(6)arene hexanoate) in benzo-nitrile at 298.15 K are first reported. These data are compared with those previously reported for cryptand 222 and these cations in this solvent. A 'peak' selectivity for potassium is observed for the complexation of the calix(6)arene ester with alkali metal cations. The process is enthalpy controlled with an exothermic maximum for the potassium cation. Thermodynamic data of complexation are characterised by a lower enthalpic stability and a more favourable entropy (except for K+) than corresponding data involving cryptand 222 or indeed 18-crown-6. Standard enthalpies of solution, DeltasH0, of macrocycles and their sodium and potassium salts in benzonitrile measured calorimetrically are discussed in relation to (i) data for the uncomplexed salts and (ii) previously reported data for sodium and potassium cryptate salts in various solvents. Enthalpies of coordination, DeltacoordH0, for eighteen systems involving sodium and potassium coronates, cryptates and calix(6)arenates are derived and whenever possible these are discussed on the basis of (i) available X-ray crystallographic data and (ii) the anion effect on the coordination process. ii) Thermodynamics of Lower Rim Calix(4)arene Derivatives with the Silver Cation in Different Media at 298.15 K. The DeltasH0 values of p-tert-butyl(bis-diethylamine-bis-methysulphanyl) calix(4)arene (EATCalix4) in various solvents at 298.15 K are reported. Transfer parameters from acetonitrile to other solvents are calculated. The interaction of EATCalix4 and the silver cation was investigated by 1H NMR in deuterated acetonitrile at 298 K showing that the ligand hosts the metal cation through interaction with the different donor atoms (O, N, S). Conductimetric titrations indicate that the stoichiometry of the complex is 1:1. The thermodynamics of complexation of EATCalix4 and silver in six solvents at 298.15 K is reported. The DeltasH0 values of the free and the complex silver perchlorate salts have been also measured in various solvents and these have been combined with DeltacH0 data to derive the DeltacoordH0 of this system. A few representative examples about the use of coordination data are given. The medium effect on the complexation process is assessed in terms of DeltatG0, DeltatH0 and DeltatS0 of the reactants and the product from acetonitrile to the appropriate solvent. The relevance of analysing the solvation changes that these species undergo upon complexation is emphasised.
13
Dejean, de La Batie Anne. "Études structurales de complexes d'uranium avec des macrocycles, en phase solide et en solution." Paris 11, 1986. http://www.theses.fr/1986PA112254.
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Le but de cette étude sur la complexation de différents degrés d'oxydation de l'uranium par des ligands macrocycliques est de préciser la structure moléculaire de ces complexes en phase solide et en solution. La diffraction des rayons X a fourni cette structure dans le cas où des monocristaux ont été obtenus, la RMN paramagnétique a permis d'accéder à la structure des complexes en solution et l'EXAFS s'est avéré bien adapté à éclaircir ce problème structural à la fois en phase solide et en solution. Nous avons montré que l'EXAFS pouvait s'appliquer à l'uranium quelque soit le degré d'oxydation. Son application en solution a permis d'obtenir la structure de l'uranyle hydraté et de montrer une désinsertion de l'uranyle hors de la 18 - couronne - 6 dans l'acétronitrile. Nous avons mis en évidence la solubilisation des hydroxydes d'uranyle et d'uranium IV par les cyclodextrines. La RMN et la polarographie ont permis de montrer l'existence d'une complexation et de déterminer les fonctions complexantes de la cyclodextrine. Nous avons synthétisé le diamine - N - oxyde du cryptand [222]. La résolution de la structure de divers composés contenant ce macrocycle nous a révélé que cette molécule amphiphile possédait la propriété de « figer » par cristallisation la solution mère. Nous avons étudié des composés macrocycliques de l'uranium III. L’EXAFS a mis en évidence l'insertion de l'uranium III dans la 18 - couronne - 6 dans le complexe U₃ (BH₄)₉ (18-couronne-6)₂. La structure du complexe (U(BH₄)₂dccB)⁺₂ (UCl₅BH₄)²⁻ a été déterminée par diffraction des rayons X. L'uranium III est inséré dans dccB. La RMN a montré que la 18 - couronne- 6 et l'isomère B de la dicyclohexyle 18 - couronne- 6 stabilisaient le cation U(BH₄)⁺₂ dans le dichlorométhane et que le cryptand [222] stabilisait U(BH₄)₃ dans le 4nitrométhane.
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Dejean, de La Batie Anne. "Etudes structurales de complexes d'uranium avec des macrocycles en phase solide et en solution." Grenoble 2 : ANRT, 1986. http://catalogue.bnf.fr/ark:/12148/cb37597065b.
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Ma, Guibin. "On Thallium (III) and binuclear platinum-thallium complexes with N-donor ligands in solution and in solid." Doctoral thesis, Stockholm, 2001. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3129.
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de, Oliveira Gomes Eduardo. "Doping and phase transitions processes on semiconductors and vibrational properties in complex glasses: A theoretical and experimental investigation." Doctoral thesis, Universitat Jaume I, 2021. http://dx.doi.org/10.6035/14114.2021.779432.
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Bridging the gap between experimental and computational researchers by fostering close collaborations is mandatory for making a breakthrough in the investigation of materials. The combined forces of these two pillars, experiment and in-depth computational analyses are more powerful than ever and capable of quantitative predictions, though care must still be taken in comparing results from theory and experiment. It is the main strength of the present Ph. D, which cover a multidisciplinary field combining physics, chemistry, theoretical and computational chemistry, and materials science pushing the boundaries for find and understand the structure and properties, at atomic level, of two types of materials: glasses (Ba2SiO4, high-BaSiO3, Ba4Si6O16, Ba5Si8O21, Ba6Si10O26, high-BaSi2O5 and low-BaSi2O5) and semiconductors (PbMoO4, In2O3, ZrO2, CaWO4 and SnMoO4/SnWO4). We discuss and present recent advances for understanding, by the use of first-principles quantum-mechanical calculations, at DFT level, their structural, electronic, and optical properties. We also studied the doping processes, the formation of solid solution, and phase transitions induced by pressure, that play key roles in the further development of these materials for optoelectronic and photocatalytic applications. We hope that present results guide the synthesis for the most promising candidates of a particular application.<br>Programa de Doctorat en Química Teòrica i Modelització Computacional
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Shields, Dylan J. "Photochemistry of Organic Azides, Quinones, and Peroxides in Solution, Crystals, Super Molecular Complexes and Cryogenic Matrices." University of Cincinnati / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=ucin157441745178423.
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Darwich, Samer. "Colloidal Gold Nanoparticules : A study of their Drying-Mediated Assembly in Mesoscale Aggregation Patterns and of their AFM Assisted Nanomanipulation on Model Solid Surfaces." Phd thesis, Université de Haute Alsace - Mulhouse, 2011. http://tel.archives-ouvertes.fr/tel-00718640.
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This work deals with the study of the drying-mediated assembly of colloidal gold nanoparticles (Au NPs) in mesoscale aggregation patterns and their manipulation by atomic force microscopy (AFM) on model surfaces. The assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, NPs/biopolymers mixed solutions) on homogeneous and heterogeneous molecular surfaces was studied. This issue is important, both for understanding fundamental processes of self-organization, and for generating new functional mesostructures. The drying of complex fluids often leads to the emergence of highly complex aggregation structures as shown and discussed in this work. The richness and the aesthetics of these complex structures generated by these interfacial phenomena reflect not only the bulk properties of fluids (different sizes and lengths- scales, kinetic changes in state), but more importantly, the coupling between the fluid properties and those of the substrate surface (wetting interactions, confinement, hydrodynamics). In the case of two important heterogeneous fluids which are Au NPs and polysaccharide solutions, these drying-mediated structure formation lead to the genesis of unusually large and highly ramified dendrites aggregation patterns. The growth mechanism and the critical parameters that control the morphogenesis of these complexes structures are addressed in this work. In addition, the aging mechanisms and kinetics of these structures that are metastable and evolve either through direct dislocation via clusters NPs mobility on the surface, or through undulation-induced roughning of the dendrite branches. To better understanding this NPs mobility and thus the dislocation mechanism of the aging, a detailed study based on the manipulation of NPs by atomic force microscopy in tapping mode (AFM) was developed. The threshold dissipated energy to manipulate (move) the NPs can be quantified according to the intrinsic parameters of the particle (size, shape, and chemical nature), the chemical nature and topography of the substrate, and finally the operating and environment conditions. This work enabled us to understand the mechanisms and characterize the critical parameters that may intervene in the dislocation (aging) of NPs-based functional structures, depending on the nature of the environment liquid and the substrate. Finally, this work proposes an approch of evaluation and of monitoring the stability and the aging of these aggregation structures, in particular, those formed from the drying of films and drops of nano-particles solutions (metal nanoparticles, blood: proteins, viruses ...).
19
Roukos, Roy. "Transitions de phases dans des oxydes complexes de structure pérovskite : cas du système (1-x)Na0,5Bi0,5TiO3 - xCaTiO3." Thesis, Dijon, 2015. http://www.theses.fr/2015DIJOS020/document.
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Les solutions solides (1-x)Na0,5Bi0,5TiO3 (NBT) – xCaTiO3 (CT) ont été étudiées par diffraction des rayons X, spectroscopie Raman, microscopie électronique à balayage, spectroscopie d’impédance et DSC. Ce sont des matériaux présentant la structure cristalline pérovskite. L’étude révèle la complexité mais aussi la richesse des phénomènes physiques dans cette famille de composés : les séquences des transitions de phases, l’influence du dopant Ca2+ sur les propriétés physico-chimiques du matériau, la relation étroite entre propriétés diélectriques et caractéristiques structurales. Des solutions solides (1-x)NBT – xCT, avec 0 ≤ x ≤ 1,00, ont été synthétisées par voie solide classique puis frittées selon une procédure spécifique dans un milieu confiné pour éviter toute perte de sodium et de bismuth. Les caractéristiques cristallines des solides obtenus imposent clairement de distinguer trois domaines suivant les valeurs de x. En effet, pour les valeurs croissantes de x et à la température ambiante, on observe un premier domaine (Région I, pour x ≤ 0,07) dans lequel le solide obtenu est une solution solide de structure cristalline, de groupe d’espace R3c, identique à celle de NBT pur. Pour les valeurs les plus élevées de x (Région II, pour x ≥ 0,15), le solide obtenu est une solution solide de structure cristalline, de groupe d’espace Pnma, identique à celle de CT pur. Enfin, entre ces deux domaines (Région III, 0,09 ≤ x ≤ 0,13), les solides obtenus sont biphasés, R3c + Pnma, en se limitant aux appellations des groupes d’espacé des phases formées. Dans la région I, lors du chauffage, la séquence des transitions de phases R3c → P4bm → Pm3m est mise en évidence; les températures des transitions se déplacent vers les plus basses températures quand la concentration en Ca2+ augmente. Les solides sont ferroélectriques à l’ambiante puis développent un caractère relaxeur, par coexistence de deux phases, avec l’augmentation de la température. Dans la région II, les solides révèlent un comportement relaxeur dès l’ambiante. Une transition de phase diffuse au sein de la phase orthorhombique Pnma est toutefois mise en évidence ; le solide passe d’un état relaxeur à un état paraélectrique tout en conservant, a priori, la même structure cristalline. Le phénomène de relaxation dans ces composés est expliqué par la formation de micros ou nanorégions polaires. La région III, quant à elle, est caractérisée par l’apparition d’une hystérésis thermique mise en évidence pour la première fois ; elle est expliquée par la relation entre la microstructure cristalline et les propriétés diélectriques. Enfin, l’ensemble de nos résultats a été regroupé dans un diagramme de phase original en composition et en température<br>The solid solutions (1-x)Na0,5Bi0,5TiO3 (NBT) – xCaTiO3 (CT) were studied by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, impedance spectroscopy and DSC. These materials have a perovskite crystalline structure. This study reveals not only the complexity but also the richness of physical phenomena in these compounds: phases transitions sequences, the Ca2+ effect on the physical-chemistry properties and the relation between dielectric properties and crystalline structure. Thereby, (1-x)NBT – xCT solid solutions (0 ≤ x ≤ 1.00) were synthesized by chemical solid route, then they were sintered by a particular procedure in order to avoid sodium and bismuth volatilization. The solid crystalline characteristics obtained prove clearly the necessity to distinguish three fields as a function of x values. First of all, for increasing x at room temperature, there is a first region so called region I (x ≤ 0.07), wherein the crystalline structure of solid solutions obtained has a space group R3c identical to that of pure NBT. For the highest values of x, (Region II, x ≥ 0.15), the solid obtained has a space group Pnma, identical to that of pure CT. Finally, between these two regions, (0.09 ≤ x ≤ 0.13), the solid solutions obtained are biphasic, R3c + Pnma, limited to appellations of the space groups formed phases. In region I, upon heating, phase transition sequence R3c → R3c + Pnma → Pnma was determined; the corresponding transition temperatures move to low values with increasing Ca2+ concentration. These solids are ferroelectric at room temperature and then develop a relaxor character, by coexistence of two phases, with increasing temperature. In region II, these solids reveal a relaxor behavior at room temperature. However, a diffuse phase transition within the orthorhombic phase Pnma has been identified; the solid changes from relaxor to paraelectric while maintaining the same crystal structure. This phenomenon was explained by the formation of micro or nano-polar regions. Region III, demonstrated for the first time, is characterized by thermal hysteresis, and explained by the relation between crystalline microstructure and dielectric properties. Finally, all our results were assembled in an original phase diagram as a function of concentration of Ca2+ dopant and temperature
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Kowalska, Dorota. "Thermodynamic aspects of lower rim calix(4)arene ketone derivatives and their metal-ion complexes in solution and in the solid state." Thesis, University of Surrey, 2003. http://epubs.surrey.ac.uk/844564/.
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Following an introduction on calixarene chemistry and their metal-ion complexes including some of their applications, the aims of the work are described. Thus, this thesis concerns an investigation on the solution properties of p-tert-butylcalix(4)arene tetraketone derivatives and their metal-ion complexes. Macrocycles such as 5,11,17,23-tetra-terf-butyl-25,26,27,28-tetra(benzoyl)methoxycalix(4)arene and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra(acetoyl)methoxy calix(4) arene are structurally (1H NMR and X-ray crystallography) and thermodynamically (solubility, calorimetry) characterised. The complexing abilities of these ligands for metal cations are investigated by a variety of techniques. To obtain information about the active sites of the ligand in its interaction with metal cations, 1H NMR studies were performed. Conductance and UV spectrophotometric measurements were used to establish the composition of the metal-ion complexes in dipolar aprotic media. Potentiometric and calorimetric measurements were carried out to derive the thermodynamic parameters of complexation of p-tert-butylcalix(4)arene tetramethyl ketone and metal-ions in acetonitrile at 298.15 K. This ligand shows the highest affinity for calcium amongst all the investigated metal cations. The medium effect on the complexation process involving metal cations and calixarene derivatives is quantitatively assessed using as an illustrative example the interaction of p-terf-butylcalix(4)arene tetraphenyl ketone and the sodium cation. Thus, detailed thermodynamics of this system is reported taking into account the solution properties of the reactants and the product in various solvents and in acetonitrile / N,N- dimethylformamide solvent mixtures. In these mixtures a linear relationship is observed between the stability constant and the solvent composition. The strength of complexation decreases from MeCN through the mixtures to pure DMF. However in terms of the enthalpy of complexation, only small variations are found between the values in different mixtures. The complexation and solution data for the reactants and the product are used to calculate the standard co-ordination enthalpies as a means of checking the reliability of the data. Based on stability constant data, two metal-ion complexes were isolated. X-ray diffraction data shows that p-tert-butylcalix(4)arene tetraphenyl ketone hosts the sodium cation in its hydrophilic cavity where it is coordinated by four ethereal oxygen atoms and four carbonyl oxygen atoms. One molecule of acetonitrile is found in the hydrophobic cavity of the ligand with the CH3 end pointing inward. The crystal structure of the cadmium and acetonitrile p-tert-butylcalix(4)arene tetramethyl ketone complex shows that the metal ion is coordinated by four ethereal oxygen atoms of the ligand and only by three carbonyl oxygens. The eight coordination site is provided by the nitrogen atom of the molecule of acetonitrile which is present in the hydrophobic cavity of calixarene derivative with the CN end pointing inward. Conclusions and suggestions for further research in this area are given.
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Thomas, Fabien. "Mécanismes de rétention à l'interface alumine-solution aqueuse." Nancy 1, 1987. http://www.theses.fr/1987NAN10444.
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Le mécanisme d'adsorption à l'interface alimine-solution aqueuse a été étudié dans le cas de tensioactifs anioniques (alkylbenzènesulfonate de sodium) et de tensioactifs cationiques (chlorure d'alkyldiméthylbenzyl ammonium). Les propriétés structurales, texturales, superficielles des adsorbants ainsi que les propriétés électrochimiques ont été déterminées
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Ezzemouri, Khalid. "Etude des complexes entre quelques éthers : couronnes et le tetrahydruroaluminate de lithium LiAlH4 en solution dans le benzène et à l’état solide." Lyon, INSA, 1994. http://www.theses.fr/1994ISAL0038.
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L'étude est centrée sur la complexation du tétrahydruroaluminate de lithium LiAlH4 dans le benzène par l'intermédiaire de quelques éthers-couronnes. Dans un premier temps, six éthers couronnes (EC) ont été testés : 12-C-4, 15-C-5, benzo 15-C-5, 18-C6, dicyc/ohexano 18-C-6 et dibenzo 18-C-6. Il y a formation d'un complexe équimoléculaire EC/LiAIH4 (ou 1/1) dans tous les cas, sauf pour B 15-C-5 pour lequel la complexation ne se fait pas. Les espèces en solution ont été caractérisées par R. M. N. , spectroscopie I. R. Et conductimétrie pour les complexes les plus solubles (EC= 12-C-4, 15-C-5, 18-C-6 et DC 18-C-6). L'accent a été mis sur la complexation avec les deux 1 isomères cis-syn-cis et cis-anti-cis du dicyc/ohexano 18-C-6. La présence de l'anion (AIH4)- en solution dans un milieu non polaire est ainsi mise en évidence pour la première fois. Dans le cas des couronnes 18-C-6, le piégeage de l'ion Li+, de diamètre plus petit que celui de la cavité du macrocycle, entraîne une déformation de cette dernière. Le phénomène est accentué dans le cas du DC 18-C-6 isomère syn, pour lequel on observe un véritable effet de "pince coupante" vis-à-vis de la liaison cation-anion. Les mesures de conductivité électrique sur des solutions (à différentes concentrations) dans le benzène et le tétrahydrofuranne confirment ce point sans ambiguïté. Les mêmes complexes ont pu être isolés à l'état solide, par précipitation à l'hexane de leurs solutions benzéniques. L'étude de leur comportement thermique par analyse calorimétrique différentielle révèle pour la plupart d'entre eux l'existence d'une phase vitreuse après première fusion<br>The complexion of LiAlH4 with several crown-ethers (CE) has been studied in benzene solutions. Six CE were tested : 12-C-4, 15-C-5, benzo 15-C-5, 18-C6, dicyclohexano 18-C-6 and dibenzo 18-C-6. In allcases except for B 15-C-5 an equi-molar complex EC/LiAIH4 (or 1/1) is formed. Chemical species in solution were characterized by N. M. R. , I. R. Spectroscopy and conductimetry. A special attention was paid to the two isomers syn and anti of DC 18-C-6. The (AIH4)- anion is thus described for the first time as a dissolved species in a non-polar solvent. A drastic "nipper effect" against the cation-anion bond in LiAlH4 is observed in the case of the syn isomer of DC 18-C-6. Measurements of electrical conductivities in benzene confirm these results. EC/LiAIH4 complexes have been obtained in the solid state by precipitation with hexane from their solutions in benzene. D. S. C. Analysis have been performed in order to characterize the thermal behaviour. The existence of a glassy state is revealed in most cases
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Zarrouki, Mohamed. "Étude de l'adsorption dans un système liquide-solide : Solution d'ion dicyanoaurate-charbon actif." Phd thesis, Ecole Nationale Supérieure des Mines de Saint-Etienne, 1990. http://tel.archives-ouvertes.fr/tel-00845070.
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Ce travail a pour cadre l'étude de la récupération des métaux précieux complexes en solution grâce a du charbon actif. Il a permis de comprendre les mécanismes fondamentaux de l'adsorption dans un système modèle constitue d'une solution d'ion dicyanoaurate et de charbon actif. Les interactions entre cette solution et le solide ont été caractérisées par diverses techniques: la pHmétrie, la titrimétrie, la zetamétrie, la potentiométrie et la thermodésorption. Ces méthodes ont permis d'avoir des renseignements sur la nature des groupements fonctionnels à la surface du charbon, groupements constituant les sites responsables de l'adsorption des complexes. De même par une méthode de traitement originale gaz-liquide-solide, nous avons modifié la nature de ces sites et leur répartition à la surface du charbon, ce qui a permis d'améliorer la capacité d'adsorption du charbon. Cette modification dépend de la nature et de la pression du gaz utilise. L'étude thermodynamique a montré que l'adsorption de l'ion dicyanoaurate sur le charbon peut être représentée assez correctement par l'équation de Langmuir généralisée à plusieurs types de sites. L'adsorption s'effectue de façon plutôt localisée, avec interaction sur des sites d'énergie différente. La vitesse d'adsorption de l'ion dicyanoaurate sur le charbon actif a été étudiée en fonction de plusieurs paramètres physico-chimiques: la température, les conditions hydrodynamiques comme la vitesse d'agitation et le rapport solide/liquide, la concentration initiale en complexe, la nature des substances étrangères, et la nature du gaz en contact avec la solution. Le mécanisme d'adsorption se déroule en trois étapes. La réaction limitante est la diffusion à travers un film pendant le début de la réaction, puis la diffusion-adsorption dans la structure poreuse au voisinage de l'équilibre.
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Zahidi, Assou. "Etudes structurales et dynamiques de complexes macrocycliques par rmn heteronucleaire." Université Louis Pasteur (Strasbourg) (1971-2008), 1986. http://www.theses.fr/1986STR13171.
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Etude de la complexation de cations et d'anions par des ligands synthetiques a l'aide de la rmn heteronucleaire (**(6)li, **(7)li, **(13)c, **(14)n, **(15)n, **(19)f, **(31)p, **(35)cl et **(109)ag) et de mesures d'effet overhauser homo- et heteronuclaires
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Sizun, Christina. "Etude par rmn statique et dynamique en solution et en phase solide de complexes et de clusters comportant des noyaux quadrupolaires. Nouveaux domaines d'application de la rmn hrmas en chimie inorganique." Université Louis Pasteur (Strasbourg) (1971-2008), 2001. http://www.theses.fr/2001STR13072.
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Ce travail comporte deux parties. La premiere partie a ete consacree a l'etude d'echanges chimiques par rmn de noyaux quadrupolaires. La deuxieme partie explore de nouvelles possibilites d'application de la rmn hrmas. La premiere partie montre que les noyaux quadrupolaires, qui sont generalement difficiles a observer, constituent neanmoins une alternative interessante par rapport aux noyaux dipolaires pour apprehender la dynamique et les echanges chimiques en solution. Le noyau 1 3 3cs a ete utilise pour etudier l'echange multisite du cation cesium lie a des ligands calix-bis-couronnes, qui sont des candidats potentiels pour le traitement de dechets radioactifs. La dynamique des chaines polyethers et leur influence sur la decomplexation du cation ont ete analysees. La rmn mas 1 3 3cs, utilisee jusqu'a present sur des composes inorganiques, a ete appliquee a des complexes cristallises afin d'acceder aux parametres quadrupolaires. Ceux-ci ont valide les parametres obtenus pour la microdynamique. Le noyau 5 9co a permis de mieux caracteriser le comportement fluxionnel du cluster de cobalt co 4(co) 1 2. C'est le seul noyau present sur ce cluster qui permette de quantifier l'echange intramoleculaire des ligands carbonyles, si l'on tient compte de la relaxation quadrupolaire. Dans la deuxieme partie, l'exemple de tensioactifs inclus dans une silice mesoporeuse a montre que la rmn hrmas (high resolution magic angle spinning) permet d'obtenir des spectres 1h de haute resolution dans ces materiaux et que ces especes ont un comportement dynamique proche du solide. La rmn hrmas a egalement ete testee sur des clusters de cobalt greffes sur differentes resines avec les noyaux 1h, 1 3c, 3 1p et 5 9co. Les resultats obtenus montrent que la rmn hrmas est un outil d'investigation potentiel pour des molecules organometalliques et qu'un materiau mesoporeux peut etre utilise comme support solide. Ceci elargirait le domaine d'application d'une technique generalement utilisee en chimie combinatoire.
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Boulanger, Benoît. "Synthèse en flux et étude des propriétés optiques cristallines linéaires et non linéaires par la méthode de la sphère de KTiOPO et des nouveaux composés isotypes et solutions solides de formule générale (K, RB, CS) TIO (P,AS) O4." Nancy 1, 1989. http://www.theses.fr/1989NAN10043.
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La température de transition ferroélectrique est approchée par la mesure de la disparition de génération de second harmonique (SHG) sur des échantillons en poudres. Mesure de la susceptibilité électrique de rang trois. Mesure des angles de birefringence et détermination des axes optiques de KTiOPO::(4)
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El, Alaoui El Abdallaoui Habib. "Étude de la structure et de la dynamique de molécules phosphorylées et de leurs complexes métalliques par mesures du temps de relaxation spin-réseau des noyaux #3#1p, #1#3c et #1#7o en solution et RMN à l'état solide." Nancy 1, 1992. http://www.theses.fr/1992NAN10184.
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Le but de cette étude est d'essayer de mieux comprendre la nature de la liaison ion-ligand phosphoryle, généralement décrite dans la littérature comme une interaction de type purement électrostatique. Un des paramètres permettant d'obtenir des renseignements sur la perturbation induite par la coordination est la constante de couplage quadrupolaire du noyau #1#7o qui est sensible aux gradients de champ électrique, donc a la distribution électronique qui l'entoure. Dans un premier temps nous avons étudié la relaxation spin-réseau du noyau #3#1p pour onze produits organophosphorés (oxydes de phosphine, trialkylphosphates et phosphoramides), à trois fréquences différentes et en fonction de la température pour trois d'entre eux, ce qui nous a permis de déterminer et de comparer les contributions des différents mécanismes de relaxation possibles. La constante de couplage quadrupolaire du noyau #1#7o a été obtenue à partir des mesures du tenseur d'écran du noyau #3#1p, à l'état solide, et des spectres RMN #1#7o. Nous avons discuté la variation de ces paramètres, particulièrement entre l'oxyde de triphenylphosphine (tppo) libre et engagé dans les complexes zn(tppo)#4(bf#4)#2, mg(tppo)#4(cf#3)#2 et cd(tppo)#4(bf#4)#2. La corrélation entre l'étude RMN #3#1p à l'état solide du complexe zn(tppo)#4(bf#4)#2 et l'analyse radio-cristallographique, nous a fourni des informations structurales intéressantes. Grace à l'exploitation, des temps de relaxation spin-réseau et des effets Overhauser nucléaires des noyaux #1#3c des groupes phényles du TPPO et de ses complexes, les mouvements internes de rotation dans ces espèces ont pu être dénombrés et caractérisés par leur temps de corrélation. Enfin, nous avons étudié la cinétique d'échange entre le ligand (TPPO) libre et engage dans le complexe cd(TPPO)#4 (bf#4)#2
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Струтинський, Сергій Васильович. "Функціонально-оріентована елементна база проектування систем гідро- і пневмоприводів". Thesis, КПІ ім. Ігоря Сікорського, 2017. https://ela.kpi.ua/handle/123456789/19778.
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Виконано аналіз наявних елементних баз для проектування систем гідро- і пневмоприводів. Досліджено архітектуру і склад елементних баз та визначено їх вплив на формування функціональних можливостей систем гідро- і пневмоприводів.
Розроблена принципово нова елементна база систем гідро- і пневмоприводів, що включає комплектні гідро- і пневмоприводи агреговані із приводами мікропереміщень, пружно-деформовані приводи, гідростатичні та аеростатичні шарніри, в тому числі регульовані та магнітні шарніри та інерційні демпфери коливань. В запропонованій елементній базі використані нові матеріали та технології: кераміка, фото полімери, феромагнітні металполімерні композити. Застосовані комп’ютерно-інтегровані технології машинобудування, що включають лазерну обробку.
Досліджені робочі процеси в інноваційних елементах приводів, зокрема визначені характеристики течії в щілинах шарнірів, течії феромагнітної рідини та процеси в пневматичних пристроях. Досліджено динамічні властивості розроблених систем приводів. Інерційні характеристики приводів описані стохастичними тензорними полями тензорів моментів інерції із введенням тензора-градіента поля. Використані планарні та просторові лінійні та нелінійні динамічні моделі. Розроблені математичні моделі для розрахунку ланцюгових парціальних динамічних підсистем сферичного руху та встановлені особливості їх динамічних характеристик.
Основні результати досліджень апробовані виготовленням та дослідженням конкретних систем приводів, побудованих на новій елементній базі.<br>The analysis of existing elemental base for design of hydraulic and pneumatic drives was done. Architecture and structure of elemental bases was studied and their impact on the functional abilities of hydraulic and pneumatic drive systems were determined.
In this study a fundamentally new element base of hydraulic and pneumatic drive systems that include complex hydraulic and pneumatic drives aggregated with micromovement system, elastically-deformed drives, hydrostatic and aerostatic hinges, including adjustable and magnetic hinges and inertial fluctuations dampers was developed . In the proposed element base we used new materials and technologies: ceramics, photo polymers, metalpolymer and ferromagnetic composites. Computer integrated Manufacturing Engineering, including laser processing were applied.
The workflows in the innovative drives elements , including characteristics of flow in gaps of a hinges, ferromagnetic fluid flowing and processes in pneumatic devices were researched. The dynamic properties of the developed drive systems were investigated. The inertia characteristics of a drives were described using stochastic tensor fields of the moments of inertia with introducing tensor-gradient of a field. The planar and spatial linear and nonlinear dynamic models were used. The mathematical models for calculating the dynamic chain partial spherical motion subsystems were developed and the features of their dynamic characteristics were established.
The main results of research were tested by manufacturing of drive systems, built on new element base.<br>Выполнен анализ имеющихся элементных баз проектирования систем гидро- и пневмоприводов. Исследовано архитектуру и состав элементных баз и определено их влияние на формирование функциональных возможностей пространственных систем гидро- и пневмоприводов. Разработана принципиально новая элементная база систем гидро- и пневмоприводов, включающая комплектные гидро- и пневмоприводы агрегированные с приводами микроперемещений, упруго-деформированные приводы, гидростатические и аэростатические шарниры, в том числе регулируемые и магнитные шарниры. Предложены принципиально новые магнитные сферические шарниры, в том числе шарниры с ферромагнитной жидкостью в качестве рабочего тела.
Для улучшения динамических характеристик систем приводов предложены инерционные демпферы колебаний, в том числе эффективные демпферы с ферромагнитной жидкостью. В элементах устройств применены новые материалы и технологии: керамика, фотополимеры, ферромагнитные металполимерные композиты, мощные постоянные магниты (неодим), сплавы с памятью формы, композитная ферромагнитная жидкость. Для изготовления деталей шарниров рекомендованы компьютерно-интегрированные технологии машиностроения, включающих лазерную и гидроструйную обработку.
Исследованы рабочие процессы в инновационных элементах приводов. Установлены особенности течения жидкости и газа в малоразмерных щелях шарниров изготовленных из фотополимера методом лазерной стереолитографии и в шарнирах из ферромагнитного металполиметрного композита. Характеристики течения описаны тензорными величинами и нечетко определенными зависимостями.
Исследованы динамические характеристики разработанных пространственных систем приводов. Инерционные свойства приводов описаны стохастическими тензорными полями тензоров моментов инерции с введением характеристики поля в виде тензора-градиента. Динамика поводов описана моделями разного уровня сложности. Предложены упрощенные планарные модели на основе линейных зависимостей. В более сложных моделях учтены нелинейные характеристики предложенной элементной базы. Разработаны методы исследования динамики упругих систем, систем с распределенными параметрами и систем сферического движения.
Результаты исследований апробированы путем разработки систем приводов построенных на новой элементной базе. В том числе разработаны системы, которые перемещаются, изменяя свое положение путем кантования, системы с пластически-деформируемыми приводами изготовленными из сплава с памятью формы и системы, которые изменяют свою структуру в процессе работы (самоформирующиеся системы).
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"The studies of the hydrogen bonding interaction for the supramolecular complex series by the Cobalt-59 NMR in solution and solid state and their DFT calculation." 1997. http://library.cuhk.edu.hk/record=b6073044.
Full textAbstract:
by Zhou ping.<br>Thesis (Ph.D.)--Chinese University of Hong Kong, 1997.<br>Includes bibliographical references (p. 160-170).<br>Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web.<br>Mode of access: World Wide Web.
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Vieira, Vanessa Lourenco. "Linking solution and solid state studies of bismuth and cadmium complexes." Thesis, 2014. http://hdl.handle.net/10539/15106.
Full textAbstract:
In this project the link between species in solution and the solid state was considered.
This is relevant due to the many applications in life where there is this interchange
between solid and solution state, for example drug design, environmental metal
speciation and the manufacture of materials that are in contact with solution (such as
outdoor surface coatings, containers and so on). Complexation of two metal ions,
namely cadmium(II) and bismuth(III), was studied. With bismuth showing so much
promise in medicinal applications it was pertinent to investigate this interchange since
the intake of medication is generally in the solid form which then converts to solution
species as it dissolves in the body where it becomes active. For cadmium it is mainly
the environmental concerns which we are faced with that call for the examination of
speciation of complexes in solution, as well as their disposition upon precipitation or
crystallization.
A correlation was found between solution species and the complex that was isolated in
the crystalline form with regards to pH for a number of metal-ligand species. We show
how the results from solution experiments (achieved using direct current
polarography) and those of crystalline complexes can complement each other when
using species distribution diagrams as the intermediary. The distribution of species
can be varied by changing the concentration and ligand-to-metal ratio at which the
species distribution diagram is plotted. It is this characteristic which allows the
solution and crystalline complexes – which are achieved using differing experimental
conditions – to be correlated.
The speciation diagram for a metal-ligand system, calculated using formation
constants derived from solutions studies, was used in most instances to target specific
species for their growth in the solid state. In some cases the solid state structure was
used to confirm a suspected solution species, and in others the result was used to
identify minor solution species which cannot be detected by the techniques used in
determining formation constants. Further, we show that doing solution experiments
at a range of temperatures can also aid in elucidating these minor species.
The growth of crystalline species at low pH was important for this work because the pH
titrations used for solution experiments were conducted from below pH 2 where the
diffusion junction potential is large and changing. An in-situ witness ion was
incorporated into the experiment to monitor the shifts due to the diffusion junction
potential so that they could be compensated for. Additionally, for bismuth-ligand
systems, hydrolysis and complexation with nitrates occurs in this same pH region. The
formation constants and the species identified below pH 2 therefore do carry some
uncertainty, so obtaining crystalline complexes of these species provides further
confidence in their prediction in solution.
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Chang, Kuei-Hua, and 張桂華. "Reconition of Ru(II)/Re(I)-bipyridyl Complexes Toward Peptides in the Solid/Solution Systems, and Its Application to Other Biomolecular Recognition." Thesis, 2003. http://ndltd.ncl.edu.tw/handle/39341523679983543095.
Full textAbstract:
碩士<br>國立臺灣大學<br>化學研究所<br>91<br>Proteins play important roles in biological processes. They are not only essential for cellular metabolisms, but also have regulatory functions, such as emzymatic regulation, cellular recognition, and signal transduction. Artificial receptors can be designed in order to understand how to control these biological mechanisms in nature. We synthesized the artificial receptors for tripeptide recognition. The receptor was composed of Ru(II) or Re(I) bipyridyl moiety as a sensing unit and two arms of macrocyclic amides as the recognition unit for binding with specific sequences of tripeptides via hydrogen-bond interaction. D-Ala-Gly-D-Ala, L-Pro-L-Ser-D-Asn, and Gly-D-Ala-Gly showed the best binding affinity for the Ru(II) receptor from the result of solid-phase screening library. Thus the sequence of D-Ala-Gly-D-Ala and its diastereomers are first used for fluorescence titration studies in the solution system. A sequence of D-Ala-Gly-L-Val was set as the control because it was not selected from the solid-phase screening library. All of these tripeptides caused the fluorescent enhancement in the fluorescence titration experiments. It is suggested that the Ru(II)(bpy) receptor had both sequence- and stereo-selectivities toward tripeptides when the association constans were obtained from the titration curves respectively. Different solvent conditions and capping groups on tripeptides were main factors to determine the selectivity and affinity of the Ru(II) receptor toward tripeptides. Subsequently, the Ru(II) receptor and Re(I) receptor were applied to the detection of other biomolecules, such as sugars and anions.
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Saunders, Cheryl D. L. "Isolation of Lead-Amino Acid and Mercury-Amino Acid Complexes with Characterization in the Solid State, the Solution State, and the Gas Phase." 2009. http://hdl.handle.net/10222/12228.
Full textAbstract:
Although some physiological effects of toxic metal poisoning have been known for centuries, the specific chemical interactions between biological molecules and mercury(I), mercury(II) or lead(II) are not well understood. To date, only thirteen crystal structures of inorganic mercury-amino acid complexes and six crystal structures of lead-amino acid complexes have been reported with varying degrees of characterization. In order to improve our understanding of the coordination chemistry of mercury and lead in biological environments, a systematic method for the isolation of inorganic metal-amino acid complexes from acidic aqueous solutions has been developed. With this method we have prepared five new lead-amino acid complexes (with L-valine, L-isoleucine, L-phenylalanine, and L-arginine) and four new mercury-amino acid complexes (with L-alanine, D-alanine, L-proline, and N-methyl-L-alanine). These metal-amino acid complexes have been comprehensively characterized in the solid state, solution state and gas phase. The development of this isolation technique in conjunction with the exploration of a number of characterization techniques for studying metal-amino acid interactions greatly enhances the known methods by which metal-biological molecule systems are studied.