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Radiolabeling and nuclear imaging techniques are used to investigate the biodistribution patterns of the soft and hard protein corona around poly (lactic-co-glycolic acid) nanoparticles (PLGA NPs) after administration to healthy mice. Soft and hard protein coronas of 131I-labeled BSA or 131I-labeled serum are formed on PLGA NPs functionalized with either polyehtylenimine (PEI) or bovine serum albumin (BSA). The exchangeability of hard and soft corona is assessed in vitro by gamma counting exposing PLGA NPs with corona to non-labeled BSA, serum, or simulated body fluid. PEI PLGA NPs form larger and more stable coronas than BSA PLGA NPs. Soft coronas are more exchangeable than hard ones. The in vivo fate of PEI PLGA NPs coated with preformed 18F-labeled BSA hard and soft coronas is assessed by positron emission tomography (PET) following intravenous administration. While the soft corona shows a biodistribution similar to free 18F BSA with high activity in blood and kidney, the hard corona follows patterns characteristic of nanoparticles, accumulating in the lungs, liver, and spleen. These results show that in vivo fates of soft and hard corona are different, and that soft corona is more easily exchanged with proteins from the body, while hard corona is largely retained on the nanoparticle surface.
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The Cu-glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF-8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single-atom Cu(I) catalyst. Synergy between Cu(I) and ZIF-8, revealed by catalytic experiments and DFT calculation, affords CO2 conversion into high-value-added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10â times without significant decrease in catalytic efficiency.
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Polyamine-based vectors offer many advantages for gene therapy, but they are hampered by a limited knowledge on their biological fate and efficacy for nucleic acid delivery. The 18 F radiolabeled siRNA is complexed with poly(allyl amine) hydrochloride (PAH), PEGylated PAH (PAHPEG ), or oleic acid-modified PAH (PAHOleic ) to form polyplexes, and injected them intravenously into healthy rodents. The biodistribution patterns obtained by positron emission tomography (PET) imaging vary according to the polymer used for complexation. Free siRNA is quickly eliminated through the bladder. PAH and oleic acid modify PAH polyplexes accumulate in the lungs and liver. No elimination through the bladder is observed for PAH and PAHOleic within 2 h after administration. PAHPEG polyplexes accumulate in kidneys and are eliminated through the bladder. Polyplexes prepared with 18 F-labeled oleic acid-modified PAH and non-labeled siRNA show similar biodistribution to those prepared with labeled siRNA, but with more accumulation in the lungs due to the presence of non-complexed polymer. Intravenous administration of PAHOleic polyplexes in tumor models results in a limited availability of siRNA. When PAHOleic polyplexes are administered intratumorally in tumor bearing rodents, ≈40% of the radioactivity is retained in the tumor after 180 min while free siRNA is completely eliminated.
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Neoplasias , Ácido Oléico , Humanos , ARN Interferente Pequeño , Distribución Tisular , Tomografía de Emisión de Positrones , Polímeros , PoliaminasRESUMEN
An electrochemical exfoliation method for the production of graphene oxide and its characterization by electrochemical techniques are presented here. Graphite rods are used as working electrode in a three-electrode electrochemical cell, and electro-exfoliation is achieved by applying anodic polarization in a sulfuric acid solution. The electrochemical process involved two steps characterized by an intercalation at lower potential and an exfoliation at higher potential. The electrochemical behavior of the produced GO is studied through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). X ray Photoelectronic Spectroscopy (XPS), Raman spectroscopy, Transmission Electron Microscopy (TEM), and Atomic Force Microscopy (AFM) are employed to characterize the structural and chemical properties of the exfoliated GO. The results demonstrate that the electrochemical exfoliation method yields GO materials with varying degrees of oxidation, defect density, and crystallite size, depending on the applied potential and acid concentration. The graphene oxide samples exhibited distinct electrochemical properties, including charge transfer resistance, interfacial capacitance, and relaxation times for the charge transfer, as revealed by CV and EIS measurements with a specifically selected redox probe. The comprehensive characterization performed provides valuable insights into the structure-property relationships of the GO materials synthesized through electrochemical exfoliation of graphite.
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N-Acetylgalactosamine-6-sulfatase (GALNS) is an enzyme whose deficiency is related to the lysosomal storage disease Morquio A. For the development of effective therapeutic approaches against this disease, the design of suitable enzyme enhancers (i.e. pharmacological chaperones) is fundamental. The natural substrates of GALNS are the glycosaminoglycans keratan sulfate and chondroitin 6-sulfate, which mainly display repeating units of sulfated carbohydrates. With a biomimetic approach, gold nanoparticles (AuNPs) decorated with simple monosaccharides, sulfated ligands (homoligand AuNPs), or both monosaccharides and sulfated ligands (mixed-ligand AuNPs) were designed here as multivalent inhibitors of GALNS. Among the homoligand AuNPs, the most effective inhibitors of GALNS activity are the ß-D-galactoside-coated AuNPs. In the case of mixed-ligand AuNPs, ß-D-galactosides/sulfated ligands do not show better inhibition than the ß-D-galactoside-coated AuNPs. However, a synergistic effect is observed for α-D-mannosides in a mixed-ligand coating with sulfated ligands that reduced IC50 by one order of magnitude with respect to the homoligand α-D-mannoside-coated AuNPs. SAXS experiments corroborated the association of GALNS with ß-D-galactoside AuNPs. These AuNPs are able to restore the enzyme activity by almost 2-fold after thermal denaturation, indicating a potential chaperoning activity towards GALNS. This information could be exploited for future development of nanomedicines for Morquio A. The recent implications of GALNS in cancer and neuropathic pain make these kinds of multivalent bionanomaterials of great interest towards multiple therapies.
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Condroitinsulfatasas , Nanopartículas del Metal , Oro , Acetilgalactosamina , Monosacáridos , Ligandos , Sulfatos , Dispersión del Ángulo Pequeño , Difracción de Rayos X , LisosomasRESUMEN
Multiple sclerosis (MS) is a chronic and demyelinating disease with an autoimmune origin, which leads to neurodegeneration and progressive disability. Approximately 30 to 50% of patients do not respond optimally to disease-modifying therapies (DMTs), and therapeutic response may be influenced by genetic factors such as genetic variants. Therefore, our study aimed to investigate the association of the HLA-DRB1*0403 genetic variant and therapeutic response to DMTs in MS. We included 105 patients with MS diagnosis. No evidence of disease activity based on the absence of clinical relapse, disability progression or radiological activity (NEDA-3) was used to classify the therapeutic response. Patients were classified as follows: (a) controls: patients who achieved NEDA-3; (b) cases: patients who did not achieve NEDA-3. DNA was extracted from peripheral blood leukocytes. HLA-DRB1*0403 genetic variant was analyzed by quantitative polymerase chain reaction (qPCR) using TaqMan probes. NEDA-3 was achieved in 86.7% of MS patients treated with DMTs. Genotype frequencies were GG 50.5%, GA 34.3%, and AA 15.2%. No differences were observed in the genetic variant AA between patients who achieved NEDA-3 versus patients who did not achieve NEDA-3 (48.7% vs. 43.1%, p = 0.6). We concluded that in Mexican patients with MS, HLA-DRB1*0403 was not associated with the therapeutic response to DMTs.
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Esclerosis Múltiple , Humanos , Esclerosis Múltiple/tratamiento farmacológico , Esclerosis Múltiple/genética , Cadenas HLA-DRB1/genética , Predisposición Genética a la Enfermedad , Estudios de Casos y Controles , GenotipoRESUMEN
In this work, monodisperse silica-coated gold nanoparticles (NPs) were synthesized and used for obtaining aqueous colloidal dispersions with an optimum relationship between colloidal stability and photothermal activity. The idea behind this design was to produce systems with the advantages of the presence of a silica shell (biocompatibility, potential for surface modification, and protecting effect) with a minimal loss of optical and thermal properties. With this aim, the photothermal properties of NPs with silica shells of different thicknesses were analyzed under conditions of high radiation extinction. By using amorphous, gel-like silica coatings, thicknesses higher than 40 nm could be obtained without an important loss of the light absorption capacity of the colloids and with a significant photothermal response even at low NP concentrations. The effects produced by changes in the solvent and in the NP concentration were also analyzed. The results show that the characteristics of the shell control both, the photothermal effect and the optical properties of the colloidal dispersions. As the presence of a silica shell strongly enhances the possibilities of adding cargo molecules or probes, these colloids can be considered of high interest for biomedical therapies, sensing applications, remote actuation, and other technological applications.
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Nanopartículas del Metal , Nanocáscaras , Coloides/química , Oro/química , Nanopartículas del Metal/química , Dióxido de Silicio/química , SuspensionesRESUMEN
Anthracycline doxorubicin hydrochloride (DX) is a positively charged fluorescent drug, which in water self-associates into non-fluorescent antiparallel dimers upon increasing concentration and/or ionic strength. The positive charge of DX allows for complexation with negatively charged polymers and drug carriers. The fluorescence of DX following complexation with polyanion polystyrene sulfonate (PSS) is studied here. The fluorescence emission of DX decreases in the presence of PSS, being almost completely quenched when the ratio (R) of PSS monomers-to-DX molecules is larger than 10. Increasing R values over 30 results in a progressive recovery of fluorescence. The circular dichroism of PSS-DX complexes shows inverted characteristic bands of DX dimers suggesting the presence of parallel dimers at a concentration of DX below dimerization in water. Molecular dynamics studies corroborate a preferential orientation of DX into parallel dimers when interacting with PSS and show that DX molecules interact with a binding pocket of PSS monomers rather than with one single monomer. Increasing the ionic strength results in a recovery of fluorescence without an apparent release of DX from the PSS-DX complex as shown by DOSY NMR. PSS acts as a template for concentrating DX, triggering dimerisation and orienting DX molecules with their charged groups facing the negatively charged PSS monomers.
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Doxorrubicina , Poliestirenos , Dimerización , Poliestirenos/química , Doxorrubicina/química , Polímeros/química , Agua/químicaRESUMEN
While mesoporous silica nanoparticles (MSNs) are extensively studied as high-potential drug delivery platforms, the successful clinical translation of these nanocarriers strongly depends on their biodistribution, biodegradation, and elimination patterns in vivo. Here, a novel method is reported to follow the in vivo degradation of MSNs by tracking a radioactive label embedded in the silica structure. Core-shell silica nanoparticles (NPs) with a dense core and a mesoporous shell are labeled with low quantities of the positron emitter 89 Zr, either in the dense core or in the mesoporous shell. In vivo positron emission tomography imaging and ex vivo organ measurements reveal a remarkable difference in the 89 Zr biodistribution between the shell-labeled and the core-labeled NPs. Release of the radiotracer from shell-labeled NPs is used as a probe of the extent of silica dissolution, and a prompt release of the radioisotope is observed, with partial excretion already in the first 2 h post injection, and a slower accumulation in bones over time. On the other hand, when 89 Zr is embedded in the nanoparticle core, the biodistribution remains largely unchanged during the first 6 h. These findings indicate that MSNs have fast, hour-scale, degradation kinetics in vivo.
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Nanopartículas , Dióxido de Silicio , Sistemas de Liberación de Medicamentos , Porosidad , Distribución TisularRESUMEN
An approach for reducing toxicity and enhancing therapeutic potential of supramolecular polyamine phosphate nanoparticles (PANs) through PEGylation of polyamines before their assembly into nanoparticles is presented here. It is shown that the number of polyethylene glycol (PEG) chains for polyamine largely influence physico-chemical properties of PANs and their biological endpoints. Poly(allylamine hydrochloride) (PAH) are functionalized through carbodiimide chemistry with three ratios of PEG molecules per PAH chain: 0.1, 1, and 10. PEGylated PAH is then assembled into PANs by exposing the polymer to phosphate buffer solution. PANs decrease size and surface charge with increasing PEG ratios as evidenced by dynamic light scattering and zeta potential measurements, with the ten PEG/PAH ratio PANs having practically zero charge. Small angle X-ray scattering (SAXS) proves that PEG chains form a shell around a polyamine core, which is responsible for the screening of positive charges. MTT experiments show that the screening of amine groups decreases nanoparticle toxicity, with the lowest toxicity for the 10 PEG/PAH ratio. Fluorescence correlation spectroscopy (FCS) proves less interaction with proteins for PEGylated PANs. Positron emission tomography (PET) imaging of 18 F labelled PANs shows longer circulation time in healthy mice for PEGylated PANs than non-PEGylated ones.
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Nanopartículas , Fosfatos , Animales , Ratones , Nanopartículas/toxicidad , Poliaminas/toxicidad , Polietilenglicoles , Dispersión del Ángulo Pequeño , Difracción de Rayos XRESUMEN
Among carbohydrate-processing enzymes, Jack bean α-mannosidase (JBα-man) is the glycosidase with the best responsiveness to the multivalent presentation of iminosugar inhitopes. We report, in this work, the preparation of water dispersible gold nanoparticles simultaneously coated with the iminosugar deoxynojirimycin (DNJ) inhitope and simple monosaccharides (ß-d-gluco- or α-d-mannosides). The display of DNJ at the gold surface has been modulated (i) by using an amphiphilic linker longer than the aliphatic chain used for the monosaccharides and (ii) by presenting the inhitope, not only in monomeric form, but also in a trimeric fashion through combination of a dendron approach with glyconanotechnology. The latter strategy resulted in a strong enhancement of the inhibitory activity towards JBα-man, with a Ki in the nanomolar range (Ki = 84 nM), i.e., more than three orders of magnitude higher than the monovalent reference compound.
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1-Desoxinojirimicina/administración & dosificación , Canavalia/enzimología , Inhibidores Enzimáticos/administración & dosificación , Oro/química , Nanopartículas del Metal/administración & dosificación , alfa-Manosidasa/antagonistas & inhibidores , 1-Desoxinojirimicina/química , Inhibidores Enzimáticos/química , Nanopartículas del Metal/químicaRESUMEN
By combining surface plasmon resonance (SPR) and electrolyte gated field-effect transistor (EG-FET) methods in a single analytical device we introduce a novel tool for surface investigations, enabling simultaneous measurements of the surface mass and charge density changes in real time. This is realized using a gold sensor surface that simultaneously serves as a gate electrode of the EG-FET and as the SPR active interface. This novel platform has the potential to provide new insights into (bio)adsorption processes on planar solid surfaces by directly relating complementary measurement principles based on (i) detuning of SPR as a result of the modification of the interfacial refractive index profile by surface adsorption processes and (ii) change of output current as a result of the emanating effective gate voltage modulations. Furthermore, combination of the two complementary sensing concepts allows for the comparison and respective validation of both analytical techniques. A theoretical model is derived describing the mass uptake and evolution of surface charge density during polyelectrolyte multilayer formation. We demonstrate the potential of this combined platform through the observation of layer-by-layer assembly of PDADMAC and PSS. These simultaneous label-free and real-time measurements allow new insights into complex processes at the solid-liquid interface (like non-Fickian ion diffusion), which are beyond the scope of each individual tool.
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This work reports on a novel and versatile approach to control the structure of metal-organic framework (MOFs) films by using polymeric brushes as 3D primers, suitable for triggering heterogeneous MOF nucleation. As a proof-of-concept, this work explores the use of poly(1-vinylimidazole) brushes primer obtained via surface-initiated atom transfer radical polymerization (SI-ATRP) for the synthesis of Zn-based ZIF-8 MOF films. By modifying the grafting density of the brushes, smooth porous films were obtained featuring inherently hydrophobic microporosity arising from ZIF-8 structure, and an additional constructional interparticle mesoporosity, which can be employed for differential adsorption of targeted adsorbates. It was found that the grafting density modulates the constructional porosity of the films obtained; higher grafting densities result in more compact structures, while lower grafting density generates increasingly inhomogeneous films with a higher proportion of interparticle constructional porosity.
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Negatively charged poly(N-isopropylacrylamide-co-methacrylic acid) (P(NIPAm-co-MAA)) microgels undergo size changes in response to changes in temperature and pH. Complexation of these microgels with positively charged polyelectrolytes can greatly affect their physical properties and their capacity for encapsulating active molecules. Here we study the interaction between (P(NIPAm-co-MAA)) microgels and a model positively charged polyelectrolyte, poly allylamine hydrochloride (PAH), with different molecular weights. Experiments were conducted at temperatures below and above the lower critical solution temperature (LCST) of the microgel (30-32 °C), at 20 and 40 °C, respectively, and for PAH at molecular weights of 15, 50, and 140 kDa. Below the LCST, dynamic light scattering and zeta potential measurements with molecular simulation show that for the 15 kDa PAH there is preferential accumulation of PAH inside the microgel, whereas for the higher molecular weight PAH, the polyelectrolyte deposits mainly on the microgel surface. Above the LCST, PAH is preferentially located on the surface of the microgels for all molecular weights studied as a result of charge segregation in the hydrogels. Confocal scanning laser microscopy and flow cytometry were used to quantify rhodamine labelled PAH associated with the microgel. Isothermal titration calorimetry studies give insight into the thermodynamics of the interaction of PAH with the hydrogels, and how this interaction is affected by the molecular weight of PAH. Finally, microgels with encapsulated doxorubicin were exposed to PAH, revealing that the drug is displaced from the microgel by the PAH chains.
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Mechanochemistry is an emerging and reliable alternative to conventional solution (batch) synthesis of complex molecules under green and solvent-free conditions. In this regard, we report here on the conjugation of a dextran polysaccharide with a fluorescent probe, a phenylboronic acid (PBA)-functionalized boron dipyrromethene (BODIPY) applying the ball milling approach. The ball milling formation of boron esters between PBA BODIPY and dextran proved to be more efficient in terms of reaction time, amount of reactants, and labelling degree compared to the corresponding solution-based synthetic route. PBA-BODIPY dextran assembles into nanoparticles of around 200 nm by hydrophobic interactions. The resulting PBA-BODIPY dextran nanoparticles retain an apolar interior as proved by pyrene fluorescence, suitable for the encapsulation of hydrophobic drugs with high biocompatibility while remaining fluorescent.
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The interaction of polyamine poly(allylamine hydrochloride) with Na3PO4, Na4P2O7, Na5P3O10, Na6P6O18, and (NaPO3)26 salts and the formation of polyamine phosphate nanoparticles (PANs) are studied here. Dynamic light scattering, isothermal titration calorimetry (ITC), electrophoretical mobility measurements, atomic force microscopy, and transmission electron microscopy are used to explore the formation, stability, and pH sensitivity of PANs. An optimal concentration for PAN formation is found for each phosphate salt in terms of the most stable size and lowest polydispersity index of the nanoparticles. The minimal concentration of phosphate ions for PAN formation decreases with the increasing number of phosphate groups per phosphate salt. ITC measurements show that all polyphosphates display a characteristic endothermic peak, which is not present when monophosphates are used for PAN formation. pH stability of PANs depends on the type of phosphate salt. PANs formed with small phosphates show a small window of stability with pH from 8 to 9, while those formed with long phosphates are stable in more acidic pH environments. Our findings open multiple possibilities for fine-tuning the pH sensitivity of PANs by varying phosphate salts for potential applications in drug delivery.
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Ammonia borane hydrolysis is considered as a potential means of safe and fast method of H2 production if it is efficiently catalyzed. Here a series of nearly monodispersed alloyed bimetallic nanoparticle catalysts are introduced, optimized among transition metals, and found to be extremely efficient and highly selective with sharp positive synergy between 2/3 Ni and 1/3 Pt embedded inside a zeolitic imidazolate framework (ZIF-8) support. These catalysts are much more efficient for H2 release than either Ni or Pt analogues alone on this support, and for instance the best catalyst Ni2Pt@ZiF-8 achieves a TOF of 600 molH2·molcatal-1·min-1 and 2222 molH2·molPt-1·min-1 under ambient conditions, which overtakes performances of previous Pt-base catalysts. The presence of NaOH boosts H2 evolution that becomes 87 times faster than in its absence with Ni2Pt@ZiF-8, whereas NaOH decreases H2 evolution on the related Pt@ZiF-8 catalyst. The ZIF-8 support appears outstanding and much more efficient than other supports including graphene oxide, active carbon and SBA-15 with these nanoparticles. Mechanistic studies especially involving kinetic isotope effects using D2O show that cleavage by oxidative addition of an O-H bond of water onto the catalyst surface is the rate-determining step of this reaction. The remarkable catalyst activity of Ni2Pt@ZiF-8 has been exploited for successful tandem catalytic hydrogenation reactions using ammonia borane as H2 source. In conclusion the selective and remarkable synergy disclosed here together with the mechanistic results should allow significant progress in catalyst design toward convenient H2 generation from hydrogen-rich substrates in the close future.
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Click ferrocenyl-terminal dentromers, a family of arene-cored dendrimers with triple branching (9-Fc, 27-Fc, 81-Fc, and 243-Fc), reduce AuIII to ferricinium dentromer-stabilized Au nanoparticles (AuNPs). Cyclic voltammetry studies in CH2 Cl2 show reversible CV waves with some adsorption for the 243-Fc dentromer and the number of redox groups found, 255±25, by using the Bard-Anson method, is close to the theoretical number of 243. The dentromers reduce aqueous HAuCl4 to water-soluble ferricinium chloride dentromer-stabilized AuNPs with core sizes between 30 and 47â nm. These triazolylferricinium dentromer-stabilized AuNPs are reduced by cobaltocene to cobalticinium chloride and ferrocene dentromer weakly stabilized AuNPs together with a redshift of the AuNP plasmon. The weakness of the AuNP stabilization is characterized by dentromer extraction with CH2 Cl2 along with irreversible AuNP agglomeration for the 9, 27, and 81-ferrocenyl dentromer, with only the 243-ferrocenyl dentromer-AuNP withstanding this process. Altogether, this demonstrates the electronic switching of the dentromer-mediated AuNP stabilization.
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Nanoparticles (NPs) are actively investigated for their efficient use in catalysis, but their means of synthesis is a key factor influencing their catalytic properties owing to surface coverage with byproducts. Here, neutral electron- and hydride-rich late transition metal organometallics are compared for the synthesis of late transition metal NPs in the presence of poly(vinylpirolidone) (PVP). In particular, the effect of electron-reservoir donors, hydride-reservoir donors, and electron-rich dimers yielding NPs electrostatically stabilized by cationic organometallics are compared in terms of NP size and catalytic efficiency. The catalytic reactions scrutinized with excellent results include 4-nitrophenol reduction to 4-aminophenol by NaBH4 for the AuNPs and PdNPs, and Suzuki-Miyaura reactions for the PdNPs. The nature of the reductant has more influence on the NP size in the case of AuNPs than PdNPs, and the best NP catalysts are obtained with hydride-reservoir complexes as reductants. The less bulky hydride donors are superior, with the complex [CoCp(Å4 -C5 H6 )] (Cp=Å5 -C5 H5 ) giving the NPs with the best catalyst efficiencies for both reactions. Protection of the NP cores by the organometallic sandwich salt is found to be the key to catalytic efficiency.
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Interfacial supramolecular architectures displaying mesoscale organized components are of fundamental importance for developing materials with novel or optimized properties. Nevertheless, engineering the multilayer assembly of different building blocks onto a surface and exerting control over the internal mesostructure of the resulting film is still a challenging task in materials science. In the present work we demonstrate that the integration of surfactants (as mesogenic agents) into layer-by-layer (LbL) assembled polyelectrolyte multilayers offers a straightforward approach to control the internal film organization at the mesoscale level. The mesostructure of films constituted of hexadecyltrimethylammonium bromide, CTAB, and polyacrylic acid, PAA (of different molecular weights), was characterized as a function of the number of assembled layers. Structural characterization of the multilayered films by grazing-incidence small-angle X-ray scattering (GISAXS), showed the formation of mesostructured composite polyelectrolyte assemblies. Interestingly, the (PAA/CTA)n assemblies prepared with low PAA molecular weight presented different mesostructural regimes which were dependent on the number of assembled layers: a lamellar mesophase for the first bilayers, and a hexagonal circular mesophase for n ≥ 7. This interesting observation was explained in terms of the strong interaction between the substrate and the first layers leading to a particular mesophase. As the film increases its thickness, the prevalence of this strong interaction decreases and the supramolecular architecture exhibits a "bulk" mesophase. Finally, we demonstrated that the molecular weight of the polyelectrolyte has a considerable impact on the meso-organization for the (PAA/CTA)n assemblies. We consider that these studies open a path to new rational methodologies to construct "nanoarchitectured" polyelectrolyte multilayers.