Sustainable Composite Materials Based on Carnauba Wax and Montmorillonite Nanoclay for Energy Storage.

Sustainable composite materials, including carnauba wax, can store energy in the form of latent heat, and containing the wax may allow form-stable melting and crystallization cycles to be performed. Here, it is shown that carnauba wax in the molten state and the abundant nanoclay montmorillonite form stable composites with mass ratios of 50-70% (w/w). Transmission electron microscopy analysis reveals the inhomogeneous distribution of the nanoclay in the wax matrix. Analyses with infrared and multinuclear solid-state nuclear magnetic resonance (NMR) spectroscopy prove the chemical inertness of the composite materials during preparation. No new phases are formed according to studies with powder X-ray diffraction. The addition of the nanoclay increases the thermal conductivity and prevents the leakage of the phase change material, as well as reducing the time intervals of the cycle of accumulation and the return of heat. The latent heat increases in the row 69.5 ± 3.7 J/g, 95.0 ± 2.5 J/g, and 107.9 ± 1.7 J/g for the composite materials containing resp. 50%, 60% and 70% carnauba wax. Analysis of temperature-dependent 13C cross-polarization solid-state NMR spectra reveal the enhanced amorphization and altered molecular dynamics of the carnauba wax constituents in the composite materials. The amorphization also defines changes in the thermal transport mechanism in the composites compared to pure wax at elevated temperatures.

Coupled reaction equilibria enable the light-driven formation of metal-functionalized molecular vanadium oxides.

The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di-metal-functionalization of a prototype molecular vanadium oxide cluster. Comprehensive mechanistic analyses show that coordination of a Mg2+ ion to the species {(NMe2H2)2[VV12O32Cl]}3- results in formation of the mono-functionalized {(NMe2H2)[(MgCl)VV12O32Cl]}3- with simultaneous release of a NMe2H2+ placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe2H2+ with Mg2+, and formation/crystallization of the di-metal-functionalized [(MgCl)2VIVVV11O32Cl]4-. Mechanistic studies show how stimuli such as light or competing cations affect the coupled equilibria. Transfer of this synthetic concept to other metal cations is also demonstrated, highlighting the versatility of the approach.

Lithium confinement and dynamics in hexagonal and monoclinic tungsten oxide nanocrystals: a 7Li solid state NMR study.

Mixed-valence tungsten bronzes AxWO3 (A = alkali metal, NH4+, etc.) are a series of compounds with adaptive structural and compositional features that make them a hot research topic in thermoelectrics, electrochromics, catalysis or energy applications in battery electrodes. The mixed hexagonal lithium ammonium bronze Lix(NH4)yWO3 is a new member of this structural family whose properties are compared to those of the pure hexagonal tungsten bronze (NH4)xWO3. Surface and structural (nanoconfined) Li+ cations were characterized by 7Li single pulse excitation and 1H-7Li cross-polarization (CP) NMR experiments. CP build-up curves and two-dimensional heteronuclear correlation solid-state NMR techniques provide information about the spatial connectivity between different proton and Li+ species. At 500 °C the bronze structurally transforms from the hexagonal to a monoclinic phase, and defects are formed that are characterized through the Li+ environment. 7Li exchange spectroscopy (EXSY) NMR experiments provide information about the chemical exchange between the lithium species. The measured 7Li T1 and T2 relaxation time constants and the T1/T2 ratio allow characterizing the local strength of Li+ binding.

Styryl dyes with N-Methylpiperazine and N-Phenylpiperazine Functionality: AT-DNA and G-quadruplex binding ligands and theranostic agents.

New monomethine, unsymmetrical styryl dyes consisting of benzothiazole and N-methylpiperazine or N-phenylpiperazine scaffolds were synthesized, and their binding affinities for different ds-polynucleotides and G-quadruplex were studied. Substitution of piperazine unit with methyl or phenyl group strongly influenced their binding modes, binding affinities, spectroscopic responses and antiproliferative activities. Compounds with N-methylpiperazine substituents showed a significant preference for AT-DNA polynucleotides and demonstrated AT-minor groove binding, which manifested in strong fluorescence increase, significant double helix stabilization, and positive induced circular dichroism spectra. These compounds formed complexes with G-quadruplex by π-π stacking interactions of dye with the top or bottom G-tetrad. Bulkier compounds with N-phenylpiperazine function are probably bound to ds-polynucleotide by partial intercalation between base pairs. On the other hand, they showed stronger stabilization of G-quadruplex compared to methyl-substituted compounds. Fluorimetric titrations pointed to possible mixed stoichiometry's: 1:1 complex with π-π stacking interactions of dye on the top or bottom G-tetrad and 1:2 complex with dye positioned between two G-quadruplex molecules. Bulkier dyes with N-phenylpiperazine fragments demonstrated micromolar and submicromolar antiproliferative activity that was especially pronounced for leukaemia and lymphoma. Flow cytometric assay shows dose- and time-dependent increase in SubG0/G1 phase. Furthermore, the compounds enter the cells readily and accumulate in the mitochondrial space, co-localize with the standard mitochondrial markers.

Generalized synthesis of NaCrO2 particles for high-rate sodium ion batteries prepared by microfluidic synthesis in segmented flow.

NaCrO2 particles for high-rate sodium ion batteries were prepared on a multigram scale in segmented flow from chromium nitrate and sodium nitrate using a segregated flow water-in-oil emulsion drying process. Microfluidic processing is an environmentally friendly and rapid synthetic method, which can produce large-scale industrial implementation for the production of materials with superior properties. The reaction time for NaCrO2 particles was reduced by almost one order of magnitude compared to a normal flask synthesis and by several orders of magntitude compared to a conventional solid-state reaction. In addition, it allows for an easy upscaling and was generalized for the synthesis of other layered oxides NaMO2 (M = Cr, Fe, Co, Al). The automated water-in-oil emulsion approach circumvents the diffusion limits of solid-state reactions by allowing a rapid intermixing of the components at a molecular level in submicrometer-sized micelles. A combination of Raman and nuclear magnetic resonance spectroscopy (1H, 23Na), thermal analysis, X-ray diffraction and high resolution transmission electron microscopy provided insight into the formation mechanism of NaCrO2 particles. The new synthesis method allows cathode materials of different types to be produced in a large scale, constant quality and in short reaction times in an automated manner.

Cell Adhesion on UV-Crosslinked Polyurethane Gels with Adjustable Mechanical Strength and Thermoresponsiveness.

Temperature-responsive polyurethane (PU) hydrogels represent a versatile material platform for modern tissue engineering and biomedical applications. However, besides intrinsic advantages such as high mechanical strength and a hydrolysable backbone composition, plain PU materials are generally lacking bio-adhesive properties. To overcome this shortcoming, the authors focus on the synthesis of thermoresponsive PU hydrogels with variable mechanical and cell adhesive properties obtained from linear precursor PUs based on poly(ethylene glycol)s (pEG) with different molar masses, isophorone diisocyanate, and a dimerizable dimethylmaleimide (DMMI)-diol. The cloud point temperatures of the dilute, aqueous PU solutions depend linearly on the amphiphilic balance. Rheological gelation experiments under UV-irradiation reveal the dependence of the gelation time on photosensitizer concentration and light intensity, while the finally obtained gel strength is determined by the polymer concentration and spacing of the crosslinks. The swelling ratios of these soft hydrogels show significant changes between 5 and 40 °C whereby the extent of this switch increases with the hydrophobicity of the precursor. Moreover, it is shown that the incorporation of a low amount of catechol groups into the networks through the DMMI dimerization reaction leads to strongly improved cell adhesive properties without significantly weakening the gels.

Magneli-type tungsten oxide nanorods as catalysts for the selective oxidation of organic sulfides.

Selective oxidation of thioethers is an important reaction to obtain sulfoxides as synthetic intermediates for applications in the chemical industry, medicinal chemistry and biology or the destruction of warfare agents. The reduced Magneli-type tungsten oxide WO3-x possesses a unique oxidase-like activity which facilitates the oxidation of thioethers to the corresponding sulfoxides. More than 90% of the model system methylphenylsulfide could be converted to the sulfoxide with a selectivity of 98% at room temperature within 30 minutes, whereas oxidation to the corresponding sulfone was on a time scale of days. The concentration of the catalyst had a significant impact on the reaction rate. Reasonable catalytic effects were also observed for the selective oxidation of various organic sulfides with different substituents. The WO3-x nanocatalysts could be recycled at least 5 times without decrease in activity. We propose a metal oxide-catalyzed route based on the clean oxidant hydrogen peroxide. Compared to other molecular or enzyme catalysts the WO3-x system is a more robust redox-nanocatalyst, which is not susceptible to decomposition or denaturation under standard conditions. The unique oxidase-like activity of WO3-x can be used for a wide range of applications in synthetic, environmental or medicinal chemistry.

Polycationic Monomeric and Homodimeric Asymmetric Monomethine Cyanine Dyes with Hydroxypropyl Functionality-Strong Affinity Nucleic Acids Binders.

New analogs of the commercial asymmetric monomethine cyanine dyes thiazole orange (TO) and thiazole orange homodimer (TOTO) with hydroxypropyl functionality were synthesized and their properties in the presence of different nucleic acids were studied. The novel compounds showed strong, micromolar and submicromolar affinities to all examined DNA ds-polynucleotides and poly rA-poly rU. The compounds studied showed selectivity towards GC-DNA base pairs over AT-DNA, which included both binding affinity and a strong fluorescence response. CD titrations showed aggregation along the polynucleotide with well-defined supramolecular chirality. The single dipyridinium-bridged dimer showed intercalation at low dye-DNA/RNA ratios. All new cyanine dyes showed potent micromolar antiproliferative activity against cancer cell lines, making them promising theranostic agents.

Rational Design of Thermoresponsive Microgel Templates with Polydopamine Surface Coating for Microtissue Applications.

Functional microgels provide a versatile basis for synthetic in vitro platforms as alternatives to animal experiments. The tuning of the physical, chemical, and biological properties of synthetic microgels can be achieved by blending suitable polymers and formulating them such to reflect the heterogenous and complex nature of biological tissues. Based on this premise, this paper introduces the development of volume-switchable core-shell microgels as 3D templates to enable cell growth for microtissue applications, using a systematic approach to tune the microgel properties based on a deep conceptual and practical understanding. Microscopic microgel design, such as the tailoring of the microgel size and spherical shape, is achieved by droplet-based microfluidics, while on a nanoscopic scale, a thermoresponsive polymer basis, poly(N-isopropylacrylamide) (PNIPAAm), is used to provide the microgel volume switchability. Since PNIPAAm has only limited cell-growth promoting properties, the cell adhesion on the microgel is further improved by surface modification with polydopamine, which only slightly affects the microgel properties, thereby simplifying the system. To further tune the microgel thermoresponsiveness, different amounts of N-hydroxyethylacrylamide are incorporated into the PNIPAAm network. In a final step, cell growth on the microgel surface is investigated, both at a single microgel platform and in spheroidal cell structures.

High-speed solid state fluorination of Nb2O5 yields NbO2F and Nb3O7F with photocatalytic activity for oxygen evolution from water.

Solid state reactions are slow because the diffusion of atoms or ions through the reactant, intermediate and crystalline product phases is the rate-limiting step. This requires days or even weeks of high temperature treatment, and consumption of large amounts of energy. We employed spark-plasma sintering, an engineering technique that is used for high-speed consolidation of powders with a pulsed electric current passing through the sample to carry out the fluorination of niobium oxide in minute intervals. The approach saves time and large amounts of waste energy. Moreover, it allows the preparation of fluorinated niobium oxides on a gram scale using poly(tetrafluoroethylene) (®Teflon) scrap and without toxic chemicals. The synthesis can be upscaled easily to the kg range with appropriate sintering equipment. Finally, NbO2F and Nb3O7F prepared by spark plasma sintering show significant photoelectrocatalytic (PEC) oxygen evolution from water in terms of photocurrent density and incident photon-to-current efficiency (% IPCE), whereas NbO2F and Nb3O7F prepared by conventional high temperature chemistry show little to no PEC response. Our study is a proof of concept for the quick, clean and energy saving production of valuable photocatalysts from plastic waste.

Gram-scale selective synthesis of WO3-x nanorods and (NH4)xWO3 ammonium tungsten bronzes with tunable plasmonic properties.

Localized surface plasmon resonance properties in unconventional materials like metal oxides or chalcogenide semiconductors have been studied for use in signal detection and analysis in biomedicine and photocatalysis. We devised a selective synthesis of the tungsten oxides WO3-x and (NH4)xWO3 with tunable plasmonic properties. We selectively synthesized WO3-x nanorods with different aspect ratios and hexagonal tungsten bronzes (NH4)xWO3 as truncated nanocubes starting from ammonium metatungstate (NH4)6H2W12O40·xH2O. Both particles form from the same nuclei at temperatures >200 °C; monomer concentration and surfactant ratio are essential variables for phase selection. (NH4)xWO3 was the preferred reaction product only for fast heating rates (25 K min-1), slow stirring speeds (∼150 rpm) and high precursor concentrations. A proton nuclear magnetic resonance (1H-NMR) spectroscopic study of the reaction mechanism revealed that oleyl oleamide, formed from oleic acid and oleylamine upon heating, is a key factor for the selective formation of WO3-x nanorods. Since oleic acid and oleylamine are standard surfactants for the wet chemical synthesis of many metal and oxide nanoparticles, the finding that oleyl oleamide acts as a chemically active reagent above 250 °C may have implications for many nanoparticle syntheses. Oriented attachment of polyoxotungstate anions is proposed as a model to rationalize phase selectivity. Magic angle spinning (MAS) 1H-NMR and powder X-ray diffraction (PXRD) studies of the bronze after annealing under (non)inert conditions revealed an oxidative phase transition. WO3-x and (NH4)xWO3 show a strong plasmon absorption for near infra-red light between 800 and 3300 nm. The maxima of the plasmon bands shift systematically with the nanocrystal aspect ratio.

A Generalized Method for High-Speed Fluorination of Metal Oxides by Spark Plasma Sintering Yields Ta3 O7 F and TaO2 F with High Photocatalytic Activity for Oxygen Evolution from Water.

A general method to carry out the fluorination of metal oxides with poly(tetrafluoroethylene) (PTFE, Teflon) waste by spark plasma sintering (SPS) on a minute scale with Teflon is reported. The potential of this new approach is highlighted by the following results. i) The tantalum oxyfluorides Ta3 O7 F and TaO2 F are obtained from plastic scrap without using toxic or caustic chemicals for fluorination. ii) Short reaction times (minutes rather than days) reduce the process time the energy costs by almost three orders of magnitude. iii) The oxyfluorides Ta3 O7 F and TaO2 F are produced in gram amounts of nanoparticles. Their synthesis can be upscaled to the kg range with industrial sintering equipment. iv) SPS processing changes the catalytic properties: while conventionally prepared Ta3 O7 F and TaO2 F show little catalytic activity, SPS-prepared Ta3 O7 F and TaO2 F exhibit high activity for photocatalytic oxygen evolution, reaching photoconversion efficiencies up to 24.7% and applied bias to photoconversion values of 0.86%. This study shows that the materials properties are dictated by the processing which poses new challenges to understand and predict the underlying factors.

Synthesis of Au, Ag, and Au-Ag Bimetallic Nanoparticles Using Pulicaria undulata Extract and Their Catalytic Activity for the Reduction of 4-Nitrophenol.

Plant extract of Pulicaria undulata (L.) was used as both reducing agent and stabilizing ligand for the rapid and green synthesis of gold (Au), silver (Ag), and gold-silver (Au-Ag) bimetallic (phase segregated/alloy) nanoparticles (NPs). These nanoparticles with different morphologies were prepared in two hours by stirring corresponding metal precursors in the aqueous solution of the plant extracts at ambient temperature. To infer the role of concentration of plant extract on the composition and morphology of NPs, we designed two different sets of experiments, namely (i) low concentration (LC) and (ii) high concentration (HC) of plant extract. In the case of using low concentration of the plant extract, irregular shaped Au, Ag, or phase segregated Au-Ag bimetallic NPs were obtained, whereas the use of higher concentrations of the plant extract resulted in the formation of spherical Au, Ag, and Au-Ag alloy NPs. The as-prepared Au, Ag, and Au-Ag bimetallic NPs showed morphology and composition dependent catalytic activity for the reduction of 4-nitrophenol (4-NPh) to 4-aminophenol (4-APh) in the presence of NaBH4. The bimetallic Au-Ag alloy NPs showed the highest catalytic activity compared to all other NPs.

Mixed Ligand Shell Formation upon Catechol Ligand Adsorption on Hydrophobic TiO2 Nanoparticles.

Modifying the surfaces of metal oxide nanoparticles (NPs) with monolayers of ligands provides a simple and direct method to generate multifunctional coatings by altering their surface properties. This works best if the composition of the monolayers can be controlled. Mussel-inspired, noninnocent catecholates stand out from other ligands like carboxylates and amines because they are redox-active and allow for highly efficient surface binding and enhanced electron transfer to the surface. However, a comprehensive understanding of their surface chemistry, including surface coverage and displacement of the native ligand, is still lacking. Here, we unravel the displacement of oleate (OA) ligands on hydrophobic, OA-stabilized TiO2 NPs by catecholate ligands using a combination of one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy techniques. Conclusive pictures of the ligand shells before and after surface modification with catecholate were obtained by 1H and 13C NMR spectroscopy (the 13C chemical shift being more sensitive and with a broader range). The data could be explained using a Langmuir-type approach. Gradual formation of a mixed ligand shell was observed, and the surface processes of catecholate adsorption and OA desorption were quantified. Contrary to the prevailing view, catecholate displaces only a minor fraction (∼20%) of the native OA ligand shell. At the same time, the total ligand density more than doubled from 2.3 nm-2 at native oleate coverage to 4.8 nm-2 at maximum catecholate loading. We conclude that the catecholate ligand adsorbs preferably to unoccupied Ti surface sites rather than replacing native OA ligands. This unexpected behavior, reminiscent of the Vroman effect for protein corona formation, appears to be a fundamental feature in the widely used surface modification of hydrophobic metal oxide NPs with catecholate ligands. Moreover, our findings show that ligand displacement on OA-capped TiO2 NPs is not suited for a full ligand shell refunctionalization because it produces only mixed ligand shells. Therefore, our results contribute to a better understanding and performance of photocatalytic applications based on catecholate ligand-sensitized TiO2 NPs.

Polymer-Functionalised Nanograins of Mg-Doped Amorphous Calcium Carbonate via a Flow-Chemistry Approach.

Calcareous biominerals typically feature a hybrid nanogranular structure consisting of calcium carbonate nanograins coated with organic matrices. This nanogranular organisation has a beneficial effect on the functionality of these bioceramics. In this feasibility study, we successfully employed a flow-chemistry approach to precipitate Mg-doped amorphous calcium carbonate particles functionalized by negatively charged polyelectrolytes-either polyacrylates (PAA) or polystyrene sulfonate (PSS). We demonstrate that the rate of Mg incorporation and, thus, the ratio of the Mg dopant to calcium in the precipitated amorphous calcium carbonate (ACC), is flow rate dependent. In the case of the PAA-functionalized Mg-doped ACC, we further observed a weak flow rate dependence concerning the hydration state of the precipitate, which we attribute to incorporated PAA acting as a water sorbent; a behaviour which is not present in experiments with PSS and without a polymer. Thus, polymer-dependent phenomena can affect flow-chemistry approaches, that is, in syntheses of functionally graded materials by layer-deposition processes.

Trapping Amorphous Intermediates of Carbonates - A Combined Total Scattering and NMR Study.

Crystallization via metastable phases plays an important role in chemical manufacturing, biomineralization, and protein crystallization, but the kinetic pathways leading from metastable phases to the stable crystalline modifications are not well understood. In particular, the fast crystallization of amorphous intermediates makes a detailed characterization challenging. To circumvent this problem, we devised a system that allows trapping and stabilizing the amorphous intermediates of representative carbonates (calcium, strontium, barium, manganese, and cadmium). The long-term stabilization of these transient species enabled a detailed investigation of their composition, structure, and morphology. Total scattering experiments with high-energy synchrotron radiation revealed a short-range order of several angstroms in all amorphous intermediates. From the synchrotron data, a structural model of amorphous calcium carbonate was derived that indicates a lower coordination number of calcium compared to the crystalline polymorphs. Our study shows that a multistep crystallization pathway via amorphous intermediates is open to many carbonates. We could isolate and characterize these transient species, thereby providing new insights into their crystallization mechanism.

Hydrogen Bonding in Amorphous Alkaline Earth Carbonates.

Amorphous intermediates play a crucial role during the crystallization of alkaline earth carbonates. We synthesized amorphous carbonates of magnesium, calcium, strontium, and barium from methanolic solution. The local environment of water and the strength of hydrogen bonding in these hydrated modifications were probed with Fourier transform IR spectroscopy, 1H NMR spectroscopy, and heteronuclear correlation experiments. Temperature-dependent spin-lattice (T1) relaxation experiments provided information about the water motion in the amorphous materials. The Pearson hardness of the respective divalent metal cation predominantly determines the strength of the internal hydrogen-bonding network. Amorphous magnesium carbonate deviates from the remaining carbonates, as it contains additional hydroxide ions, which act as strong hydrogen-bond acceptors. Amorphous calcium carbonate exhibits the weakest hydrogen bonds of all alkaline earth carbonates. Our study provides a coherent picture of the hydrogen bonding situation in these transient species and thereby contributes to a deeper understanding of the crystallization process of carbonates.

Calcium Sulfate Nanoparticles with Unusual Dispersibility in Organic Solvents for Transparent Film Processing.

Calcium sulfate is one of the most important construction materials. Today it is employed as high-performance compound in medical applications and cement mixtures. We report a synthesis for calcium sulfate nanoparticles with outstanding dispersibility properties in organic solvents without further functionalization. The nanoparticles (amorphous with small γ-anhydrite crystallites, 5-50 nm particle size) form long-term stable dispersions in acetone without any sign of precipitation. 1H NMR spectroscopic techniques and Fourier-transform infrared spectroscopy (FTIR) reveal absorbed 2-propanol on the particle surfaces that induce the unusual dispersibility. Adding water to the nanoparticle dispersion leads to immediate precipitation. A phase transformation to gypsum via bassanite was monitored by an in situ kinetic FT-IR spectroscopic study and transmission electron microscopy (TEM). The dispersibility in a volatile organic solvent and the crystallization upon contact with water open a broad field of applications for the CaSO4 nanoparticles, e.g., as nanogypsum for coatings or the fabrication of hybrid composites.

27Al NMR Study of the pH Dependent Hydrolysis Products of Al2(SO4)3 in Different Physiological Media.

Soluble inorganic aluminium compounds like aluminium sulfate or aluminium chloride have been challenged by the European Chemical Agency to induce germ cell mutagenicity. Before conducting mutagenicity tests, the hydrolysis products in water and in physiological solutions should be determined as a function of the concentration and pH. We used different 27Al NMR spectroscopic techniques (heteronuclear Overhauser effect spectroscopy (HOESY), exchange spectroscopy (EXSY), diffusion ordered (DOSY)) in this work to gain the information to study the aluminium species in solutions with Al2(SO4)3 concentrations of 50.0, 5.0, and 0.5 g/L and their pH and time dependent transformation. At low pH, three different species were present in all physiological solutions and water: [Al(OH)n(H2O)6 - n](3 - n)+ (n = 0-2), [Al(H2O)5SO4]⁺, and [Al2(OH)2(H2O)8]4+. Increasing pH reduced the amounts of the two monomer species, with a complete loss at pH 5 for solutions with a concentration of 50.0 g/L and at pH 4 for solutions with a concentration of 5.0 g/L. The dimer species [Al2(OH)2(H2O)8]4+ is present in a pH range between 3 and 6. Less symmetric oligomeric and probably asymmetric aluminium species are formed at pH of 5 and 6. The pH value is the driving force for the formation of aluminium species in all media, whereas the specific medium had only minor effect. No conclusive information could be obtained at pH 7 due to signal loss related to fast quadrupole relaxation of asymmetric aluminium species. A slight reduction of the content of the symmetric aluminium species due to the formation of oligomeric species was observed over a period of 6 weeks. Reference 27Al NMR experiments conducted on saturated water solutions of AlCl3 and those with a concentration of 50 g/L show that the type of salt/counter ion at the same concentration and pH influences the hydrolysis products formed.

Monitoring Thiol-Ligand Exchange on Au Nanoparticle Surfaces.

Surface functionalization of nanoparticles (NPs) plays a crucial role in particle solubility and reactivity. It is vital for particle nucleation and growth as well as for catalysis. This raises the quest for functionalization efficiency and new approaches to probe the degree of surface coverage. We present an (in situ) proton nuclear magnetic resonance (1H NMR) study on the ligand exchange of oleylamine by 1-octadecanethiol as a function of the particle size and repeated functionalization on Au NPs. Ligand exchange is an equilibrium reaction associated with Nernst distribution, which often leads to incomplete surface functionalization following "standard" literature protocols. Here, we show that the surface coverage with the ligand depends on the (i) repeated exchange reactions with large ligand excess, (ii) size of NPs, that is, the surface curvature and reactivity, and (iii) molecular size of the ligand. As resonance shifts and extensive line broadening during and after the ligand exchange impede the evaluation of 1H NMR spectra, one- and two-dimensional 19F NMR techniques (correlation spectroscopy and diffusion ordered spectroscopy) with 1H,1H,2H,2H-perfluorodecanthiol as the fluorinated thiol ligand were employed to study the reactions. The enhanced resolution associated with the spectral range of the 19F nucleus allowed carrying out a site-specific study of thiol chemisorption. The widths and shifts of the resonance signals of the different fluorinated carbon moieties were correlated with the distance to the thiol anchor group. In addition, the diffusion analysis revealed that moieties closer to the NP surface are characterized by a broader diffusion coefficient distribution as well as slower diffusion.