The Young's modulus of multilayer films containing nanofibrillated cellulose (NFC) and polyethyleneimine (PEI) was determined using the strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) technique. (1) Multilayer films were built up on polydimethylsiloxane substrates using electrostatic layer-by-layer assembly. At 50% relative humidity, SIEBIMM gave a constant Young's modulus of 1.5 ± 0.2 GPa for 35-75 nm thick films. Conversely, in vacuum, the Young's modulus was 10 times larger, at 17.2 ± 1.2 GPa. A slight decrease in buckling wavelength with increasing strain was observed by scanning electron microscopy with in situ compression, and above 10% strain, extensive cracking parallel to the compressive direction occurred. We conclude that whereas PEI acts as a "glue" to hold multiple layers of NFC together, it prevents full development of hydrogen bonding and specific fibril-fibril interactions, and at high humidity, its hygroscopic nature decreases the elastic modulus when compared with pure NFC films.

Fluorescence enhancement of organic fluorophores shows tremendous potential to improve image contrast in fluorescence-based bioimaging. Here, we present an experimental study of the interaction of two cationic porphyrins, meso-tetrakis(1-methylpyridinium-4-yl)porphyrin chloride (TMPyP) and meso-tetrakis(4- N,N ,N-trimethylanilinium)porphyrin chloride (TMAP), with cationic surfactant-stabilized zinc oxide nanoparticles (ZnO NPs) based on several steady-state and time-resolved techniques. We show the first experimental measurements demonstrating a clear transition from pronounced fluorescence enhancement to charge transfer (CT) complex formation by simply changing the nature and location of the positive charge of the meso substituent of the cationic porphyrins. For TMPyP, we observe a sixfold increase in the fluorescence intensity of TMPyP upon addition of ZnO NPs. Our experimental results indicate that the electrostatic binding of TMPyP with the surface of ZnO NPs increases the symmetry of the porphyrin macrocycle. This electronic communication hinders the rotational relaxation of the meso unit and/or decreases the intramolecular CT character between the cavity and the meso substituent of the porphyrin, resulting in the enhancement of the intensity of the fluorescence. For TMAP, on the other hand, the different type and nature of the positive charge resulting in the development of the CT band arise from the interaction with the surface of ZnO NPs. This observation is confirmed by the femtosecond transient absorption spectroscopy, which provides clear spectroscopic signatures of photoinduced electron transfer from TMAP to ZnO NPs.

Novel features of the adsorption of humic acid on the surface of aluminium oxide were revealed by means of an in situ study by quartz crystal microbalance with dissipation (QCM-D). The adsorption of humic acid on the surface of aluminium oxide shows a special case at pH 3 where the adsorption takes place in two steps. Each step has characteristic thickness, kinetics and viscoelasticity. While the first step shows low thickness, fast kinetics and almost no viscoelastic character, indicating a rigidly adsorbed humic acid monolayer, the second step is of much higher thickness, slower kinetics and with significant viscoelastic character, indicating a large diffuse layer with significant bulk contributions. In contrast, adsorption at pH 5 and 6.8 was found to be limited to a monolayer which is more rigid at pH 5 than at pH 6.8. Ellipsometry and X-ray photoelectron spectroscopy (XPS) were used to prove and quantify the adsorption in the dry state. The monolayer thickness measured by ellipsometry is close to the Sauerbrey thickness obtained by QCM-D. Adsorption takes place at a dilute concentration of 1 mg L À1 , followed by saturation at a concentration of 10-20 mg L À1 . XPS spectra of the carbon 1s peak indicated almost no desorption of the adsorbed humic acid layer after immersion in water for 48 hours, implying irreversible adsorption based on a strong binding between humic acid and aluminium oxide.

Absorbent layers of semiconductor quantum dots (QDs) are now used as material platforms for low-cost, high-performance solar cells. The semiconductor metal oxide nanoparticles as an acceptor layer have become an integral part of the next generation solar cell. To achieve sufficient electron transfer and subsequently high conversion efficiency in these solar cells, however, energy-level alignment and interfacial contact between the donor and the acceptor units are needed. Here, the layer-by-layer (LbL) technique is used to assemble ZnO nanoparticles (NPs), providing adequate PbS QD uptake to achieve greater interfacial contact compared with traditional sputtering methods. Electron injection at the PbS QD and ZnO NP interface is investigated using broadband transient absorption spectroscopy with 120 femtosecond temporal resolution. The results indicate that electron injection from photoexcited PbS QDs to ZnO NPs occurs on a time scale of a few hundred femtoseconds. This observation is supported by the interfacial electronic-energy alignment between the donor and acceptor moieties. Finally, due to the combination of large interfacial contact and ultrafast electron injection, this proposed platform of assembled thin films holds promise for a variety of solar cell architectures and other settings that principally rely on interfacial contact, such as photocatalysis.

Thin UV-blocking films of poly(methyl methacrylate) (PMMA) and ZnO quantum dots (QDs) were built-up by spin-coating. Ellipsometry reveals average thicknesses of 9.5 and 8.6 nm per bilayer before and after heating at 100 °C for one hour, respectively. The surface roughness measured by Atomic force microscopy (AFM) was 3.6 and 8.4 nm for the one and ten bilayer films, respectively. The linear increase in thickness as well as the low surface roughness increment per bilayer indicates a stratified multilayer structure and a smooth interface without aggregation. The absorption of UV radiation increased with increasing number of bilayers. At the same time, transmission was damped at wavelengths shorter than 375 nm. The thin films had a high and constant transparency in the visible region. Green-light emitting QDs could be detected by confocal microscopy at a concentration of 20% in a single layer of PMMA/ZnO. PMMA/ZnO QDs thin films are hydrophobic, as indicated by contact angle measurements.