, Synthèse des différentes particules zwitterioniques
, Synthèse des polymères zwitterioniques et caractérisations, p.62
Synthèse des polymères dibloc zwitterion-imidazole, p.62 ,
, Échange de ligands à la surface des Quantum Dots, p.65
Comparaison des différentes chimies de surface, p.67 ,
Quantification des interactions non spécifiques, p.69 ,
, Mesures in vitro de la couronne dure de protéines : dosage à la fluorescamine
, Mesures in vitro de la couronne dynamique de protéines : mesures par FCS
, Mesures dans des cellules vivantes de la couronne de protéines : suivi de QD unique dans le cytoplasme
Comparaison des différents QD-zwitterions, p.75 ,
, Influence de l'ajout de fonctions chimiques chargées, p.81
, Influence de la fonction d'ancrage des polymères à la surface des QD, vol.84
, Importance de la pureté des polymères
, Imagerie in vivo dans les cellules et marquage biologique, p.88
, III.1.1 Études réalisées sur des copolymères sulfadimethoxines (SDM), p.98
Études réalisées sur des copolymères sulfamethazine (SMZ), p.103 ,
Nano-sonde de pH avec des QD visibles, p.107 ,
, Assemblage de la nano-sonde de pH
, III.3 Nano-sonde de pH dans l'infrarouge court, p.117
, Synthèse de la nano-sonde SWIR
Comparaison entre la théorie et l'expérience, p.123 ,
Échange de ligands sensibles au pH sur les NP, p.138 ,
, Synthèse des polymères pDPA et pDPA/LA sensibles au pH, p.138
Caractérisations des polymères sensibles au pH, p.140 ,
Échange de ligands sur des AuNP sphériques, p.142 ,
, IV.1.4 Échange de ligands sur des QD visibles et, p.143
, Micelles de copolymère pDPA-b-SB sensibles au pH, p.145
Synthèse des copolymères surfactants pDPA-b-SB, p.145 ,
Caractérisations des polymères surfactants pDPA-b-SB, p.147 ,
, Analyse des micelles avec du pyrène
Auto-assemblage des micelles autour des NP-pDPA, p.155 ,
, IV.3.1 Micelles encapsulant les AuG-pDPA, p.155
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Micelles encapsulant les QD-pDPA, p.156 ,
, Micelles encapsulant les AuNP-pDPA/LA et les QD-pDPA/LA, p.157
, Micelles fluorescentes sensibles au pH
Influence de la présence du surfactant pH-labile, p.158 ,
Influence de la quantité du surfactant pH-labile, p.160 ,
, Influence de la taille du polymère surfactant pH-labile, p.160
, Influence de la taille et de la quantité des AuNP, p.161
, Résultats préliminaires avec des sondes visibles et SWIR en mesures ratiométriques
, Le produit a été dissous dans de l'eau et passé sur une résine échangeuse d'ions Amberlyst@A-26(OH) afin d'hydrolyser la fonction terminale ester. L'eau a été éliminée sous vide. Rendement = 80-90%, opération a été répétée deux fois
, 32 (C10), 22 (C6), vol.63, p.36
, Monomère lipoamide méthacrylamide : LA Figure VII.4 -Synthèse du monomère LA
Une extraction liquide-liquide est ensuite effectuée. Le milieu réactionnel est lavée avec une solution aqueuse à 0,1 M de HCl (2 x 50 ml), de l'eau désionisée (1 x 50 ml) et une solution basique de NaOH à 0,2 M (2 x 50 ml). La phase organique a été séparée, séchée sur MgS0 4 , filtrée et concentrée sous pression réduite, ,5 ml, 17,9 mmol) a été ajoutée à une suspension de APMA-HCl (2 g, 11,2 mmol) dans du dichlorométhane (20 mL) ,
, 03 (s, 1H), vol.7
,
, Cette synthèse a été effectuée en deux étapes. La première est un couplage peptidique entre l'acide lipoïque et le DMED (N,N-diméthylethylenediamine). Typiquement, l'acide lipoïque (20 mmol) et le CDI (1,1-carbonyldiimidazole) (26 mmol) sont dissous dans du chloroforme VII, p.17
,
, Varian Cary-5E équipé d'une lampe halogène pour la gamme 350-3300 nm et d'une lampe au deutérium pour la gamme 175-350 nm. Les échantillons sont placés dans une cuve en quartz : 3 mL pour les échantillons pour lesquels la quantité est suffisante ou 600 µL pour les autres. Ces cuves présentent une absorption limitée sur la gamme UV-Vis-NIR. Les spectres sont acquis avec un pas d'un nanomètre. Pour l'acquisition des spectres, les NPs sont en suspension dans un solvant et la référence se, Absorption Les mesures d'absorbance ont été réalisées sur un spectrophotomètre ultraviolet (UV)-visible (Vis)-proche infrarouge (NIR)
, Il est équipé d'une lampe blanche continue qui, combinée avec un monochromateur de largeur variable, permet de choisir la longueur d'onde d'excitation. Ce spectrofluorimètre possède quatre détecteurs mais seulement trois ont été utilisés : l'un, très sensible, couvre la gamme du visible (400-800 nm), un autre, un peu moins sensible, couvre une gamme spectrale plus large (500-1000 nm) et le troisième permet de travailler dans le SWIR (900-1600 nm). Ce spectromètre est également équipé d'une diode laser pulsée émettant à 376 nm avec une fréquence de pulse variable entre 50 ns et 50 µs qui
, Microscopie Electronique à Transmission (TEM)
, Les particules sont déposées (deux ou trois gouttes) sur des grilles de TEM en cuivre (200 lignes par pouce). Ces grilles sont ensuite mises à dégazer toute la nuit sous un vide secondaire. Les images sont acquises avec différents grandissements au moyen d'un microscope JEOL, Pour les images de TEM, les nanoparticules sont lavées puis dispersées dans un solvant à des concentrations de l'ordre du µM, 2010.
, Exclusion Stérique (SEC) Les masses molaires moyennes en nombre (Mn) et en poids (Mw) ainsi que l'indice de polydispersité (Ip = Mw/Mn) des différents polymères ont été déterminés par chromatographie d'exclusion stérique, vol.18
,
Sigma Aldrich), biotine (Sigma), 2,2-Bis(2,5-dioxo-3-sulfo-1-pyrrolidinyl)octanedioate (BS3, C 16 H 18 N 2 Na 2 O 14 S 2 , Thermofisher), chloroforme (CHCl 3 ,VWR), chlorure de sodium (NaCl, Sigma-Aldrich), décahydrate de carbonate de sodium (Na 2 CO 3 .10H 2 O, Prolabo), 2,2'-[1,2-diazènediyl]bis(2-méthylpropanimidamide)chlorohydrate (V50, 97%, (NC(CH 3 ) 2 C(NH)NH 2 ) 2 .2HCl, Aldrich), hydroxysuccinimide ester, N-(3-aminopropyl)méthacrylamide chlorhydrate (APMA.HCl, C 7 H 14 N 2 O.HCl), ammoniaque (NH 4 OH, 28-30%, Aldrich), bicarbonate de sodium, vol.14 ,
,
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