RESUMEN

The preparation of weblike titanium dioxide thin films by atomic layer deposition on cellulose biotemplates is reported. The method produces a TiO2 web, which is flexible and transferable from the deposition substrate to that of the end application. Removal of the cellulose template by calcination converts the amorphous titania to crystalline anatase and gives the structure a hollow morphology. The TiO2 webs are thoroughly characterized using electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy to give new insight into manufacturing of porous titanium dioxide structures by means of template-based methods. Functionality and integrity of the TiO2 hollow weblike thin films were successfully confirmed by applying them as electrodes in dye-sensitized solar cells.

RESUMEN

Cellulose fibres have poor reactivity and limited potential for surface engineering with advanced chemical functionalization in water. In this work, cellulose fibres were decorated with azide functions by charge-directed self-assembly of a novel water-soluble multifunctional cellulose derivative yielding reactive fibres. Propargylamine and 1-ethynylpyrene were utilized as a proof of concept that alkyne molecules may react with the azide functions of the reactive fibres via copper(I)-catalyzed azide-alkyne Huisgen cycloaddition (CuAAc) reaction in mild conditions. Chemical characterization of the fibres was carried out using classical techniques such as Raman-, fluorescence-, and UV-vis spectroscopy. Among other techniques, time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray spectroscopy (XPS), two-photon microscopy (TPM), and inductively coupled plasma mass spectrometry (ICP-MS) were useful tools for additional characterization of the fibres decorated with amino- or photoactive groups. The information gathered in this work might contribute to the basis for the preparation of reactive cellulose-based interfaces with potential application in CuAAc reactions.

Asunto(s)

RESUMEN

Eucalyptus bleached kraft pulp fibers were modified by adsorption of novel bio-based multifunctional cellulose derivatives in order to generate light responsive surfaces. The cellulose derivatives used were decorated with both cationic groups (degree of substitution, DS of 0.34) and photoactive groups (DS of 0.11 and 0.37). The adsorption was studied by UV-vis spectroscopy, surface plasmon resonance (SPR) and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). The adsorption isotherms followed the Freundlich model and it turned out that the main driving force for the adsorption was electrostatic interaction. Moreover, strong indications for hydrophobic interactions between the fibers and the derivatives and the derivatives themselves were found. ToF-SIMS imaging revealed an even distribution of the derivatives on the fiber surfaces. The modified fibers underwent fast photocrosslinking under UV-irradiation as demonstrated by light absorbance and fluorescence measurements. Thus, our results proved that the modified fibers exhibited light-responsive properties and can potentially be used for the manufacture of smart bio-based materials.

Asunto(s)

RESUMEN

Molecular assemblies, namely, polyelectrolyte complexes (PECs) composed of negatively charged xylan-based derivatives and a novel positively charged cellulose derivative (CN(+)), were used for interfacial modification of wood fibers by charge directed self-assembly. The adsorption process was studied using polyelectrolyte titration and elemental analysis. X-ray spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used as advanced techniques for the characterization of the modified fiber surfaces. The measurements revealed an intense interaction between the pulp fibers and PECs, and provided essential information for a better understanding of the adsorption process. The information gathered on this paper might contribute to the basis for the development of new value added products by the use of underutilized biomass.

Asunto(s)

RESUMEN

The photophysical and photochemical characteristics of nano-scaled particles obtained via solvent displacement from coumarin-modified dextrans were studied by means of absorption- and fluorescence-spectroscopy. The environment-dependent fluorescence emission of the pendant 4-methyl-7-alkoxy coumarin groups was exploited as a probe to gain information about the inner structure of the polysaccharide based nanoparticles. Time-resolved fluorescence measurements showed that the particles had two domains of different polarity and it could be confirmed that the core of the nano-assemblies contained water. Moreover, preliminary experiments were carried out demonstrating the possibility to control the morphology of the nanoparticles by the light induced 2π+2π cycloaddition of the coumarin substituents.

Asunto(s)

RESUMEN

Dextran alkyl carbonates were synthesized applying ethyl chloroformate, butyl chloroformate, butyl fluoroformate and 1H-imidazole-1-carboxylates. The influence of the reaction conditions on the reaction efficiency and the substitution pattern was studied in detail. The structure of the products obtained was clearly described by means of NMR- and IR-spectroscopy.

Asunto(s)

RESUMEN

We demonstrate that increasing the hydrophobic environment around the charge center of a polyelectrolyte (PE) not only decreases the water content of an adsorbed PE layer but can even dewater up to ~50% of an initially hydrated substrate. The results of this work are expected to yield new stratagies to dewater PE systems and have potential applications in mineral recovery, paper manufacturing, and biomedical materials. Adsorption of a series of cationically derivatized dextran polyelectrolytes onto sulfated nanocrystalline cellulose (SNC) has been studied using quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR). Synthesized samples of (N,N-dimethylamino)ethyldextran (DMAE-Dex), (N,N-diethylamino)ethyldextran (DEAE-Dex), and (N,N-diisopropylamino)ethyldextran (DIAE-Dex) had degrees of substitution (DS) ranging from 0.05 to 0.82. DMAE-Dex, DEAE-Dex, and DIAE-Dex all showed decreasing adsorption onto SNC and decreasing water content of the adsorbed film with increasing DS. Additionally, DEAE-Dex and DIAE-Dex films adsorbed onto SNC contained less water than DMAE-Dex films with the same DS. Interestingly, QCM-D results for high DS DIAE-Dex adsorbed onto SNC revealed mass loss, whereas SPR results clearly showed DIAE-Dex adsorbed. These observations were consistent with dehydration of the SNC substrate. This study indicates that the water content of the substrate could be tailored by controlling the DS and hydrophobic character of the adsorbed polyelectrolytes.

Asunto(s)

RESUMEN

Different types of photoactive dextran derivatives with high degree of substitution were prepared by an efficient and mild esterification of the biopolymer with 2-methoxycinnamic acid, [(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetic acid, and azobenzene-4-carboxylic acid via in situ activation of the carboxylic acid groups with N,N'-carbonyldiimidazole. The structures of the novel dextran esters were evaluated by means of NMR spectroscopy applying the perpropionylated samples. Perpropionylation yields samples soluble in chloroform and acetonitrile that are very useful solvents not only for NMR but also for UV-vis spectroscopic studies. The photochemistry was studied by NMR and UV-vis spectroscopy in the dissolved state and the changes observed may be used to control the properties. The photoactive dextran esters form spherical nanoparticles of a size below 200 nm that are of interest in the design of smart materials.

Asunto(s)