Jarmo Ropponen

Bifunctional Dendronized Cellulose Surfaces as Biosensors

Well-defined dendronized cellulose substrates displaying multiple representations of dual-functionality were constructed by taking advantage of the efficiency of the click reaction combined with traditional anhydride chemistry. First, activated cellulose surfaces were decorated with several generations of dendrons, and their peripheral reactive groups were subsequently reacted with a trifunctional orthogonal monomer. The generated substrate tool box was successfully explored by accurately tuning the surface function using a versatile orthogonal dual postfunctionalization approach. In general, the reactions were monitored by using a click-dye reagent or a quartz crystal microbalance (QCM) technique, and the resulting surfaces were well-characterized using XPS, FT-IR, and contact angle measurements. Utilizing this approach two different surfaces have been obtained; that is, triethylenglycol oligomers and amoxicillin molecules were efficiently introduced to the dendritic surface. As a second example, mannose-decorated hydroxyl functional surfaces illustrated their potential as biosensors by multivalent detection of lectin protein at concentration as low as 5 nM.

Solvent extraction as a means of preparing homogeneous lignin fractions

Abstract Sequential extraction method was applied to lignins from hardwood and softwood isolated by kraft and VTT organosolv processes. Solvent extraction was found to fractionate lignin according to the molecular weight: small molecular weight lignin is dissolved in the organic solvents and the lignin with higher molecular weight is enriched into the residue. Isolated acetone fractions of lignin are more homogeneous with narrow molecular weight distributions. Based on the 31P NMR results, both total hydroxyl content and the content of phenolic hydroxyl units are higher in the acetone fraction than in the residue. Pyrolysis-GC/MS of all lignins showed that p-hydroxy phenols are enriched to the residues. Preferential dissolution of syringyl type lignin in acetone was observed for hardwood kraft lignin, whereas the opposite behavior was seen for the hardwood organosolv lignin. Glass transition temperatures of all acetone soluble fractions were notably low compared to starting and residue lignins, which gives possibilities for future applications as a material with specific properties.

Templating gold surfaces with function: a self-assembled dendritic monolayer methodology based on monodisperse polyester scaffolds.

The antibiotic resistance developed among several pathogenic bacterial strains has spurred interest in understanding bacterial adhesion down to a molecular level. Consequently, analytical methods that rely on bioactive and multivalent sensor surfaces are sought to detect and suppress infections. To deliver functional sensor surfaces with an optimized degree of molecular packaging, we explore a library of compact and monodisperse dendritic scaffolds based on the nontoxic 2,2-bis(methylol)propionic acid (bis-MPA). A self-assembled dendritic monolayer (SADM) methodology to gold surfaces capitalizes on the design of aqueous soluble dendritic structures that bear sulfur-containing core functionalities. The nature of sulfur (either disulfide or thiol), the size of the dendritic framework (generation 1-3), the distance between the sulfur and the dendritic wedge (4 or 14 Å), and the type of functional end group (hydroxyl or mannose) were key structural elements that were identified to affect the packaging densities assembled on the surfaces. Both surface plasmon resonance (SPR) and resonance-enhanced surface impedance (RESI) experiments revealed rapid formation of homogenously covered SADMs on gold surfaces. The array of dendritic structures enabled the fabrication of functional gold surfaces displaying molecular covering densities of 0.33-2.2 molecules·nm(-2) and functional availability of 0.95-5.5 groups·nm(-2). The cell scavenging ability of these sensor surfaces for Escherichia coli MS7fim+ bacteria revealed 2.5 times enhanced recognition for G3-mannosylated surfaces when compared to G3-hydroxylated SADM surfaces. This promising methodology delivers functional gold sensor surfaces and represents a facile route for probing surface interactions between multivalently presented motifs and cells in a controlled surface setting.

The effect of side-chain length of cellulose fatty acid esters on their thermal, barrier and mechanical properties

Abstract Currently, long-chain cellulose esters are not produced commercially because of high price, and since their preparation typically requires a large quantity of chemicals. To reduce the chemical consumption, cellulose reactivity needs to be increased without losing its quality. One way to increase the reactivity of cellulose is to decrease its molar mass in a controlled manner. In this study, we have synthesized cellulose esters with different side-chain length (C6–C18) in a homogeneous system using ozone molar mass-controlled cellulose. The target was to keep the degree of substitution as low as possible while still ensuring the suitability of cellulose esters for solvent casting. Thermal, barrier and mechanical properties were studied depending on cellulose fatty acid ester side-chain length. All our molar mass-controlled cellulose esters form optically transparent, flexible and heat-sealable films with good water barrier properties and are processable without the addition of an external plasticizer. Furthermore, the films have mechanical properties comparable to some generally used plastics. These good properties suggest that our molar mass-controlled cellulose esters could be potential candidates for various applications such as films and composites.

The effect of cellulose molar mass on the properties of palmitate esters.

Nowadays one of the growing trends is to replace oil-based products with cellulose-based materials. Currently most cellulose esters require a huge excess of chemicals and have therefore, not been broadly used in the industry. Here, we show that decreasing the molar mass of cellulose by ozone hydrolysis provides cellulose functionalization with less chemical consumption. To reveal the differences in reactivity and chemical consumption, we showed esterification of both native cellulose and ozone treated hydrolyzed cellulose. Based on the results, the molar mass of the starting cellulose has a significant effect on the end products degree of substitution and properties. Furthermore, molar mass controlled palmitate esters form mechanically strong, flexible and optically transparent films with excellent water barrier properties. We anticipate that molar mass controlled cellulose will provide a starting point for the greater use of cellulose based materials, in various application, such as films and composites.

Esterified lignin coating as water vapor and oxygen barrier for fiber-based packaging

Abstract Lignin, esterified with palmitic and lauric acid chloride, has been studied for the application as coating on fiber-based packaging material. The aim was to improve the barrier properties against water vapor and oxygen of paperboard. The esterification was followed by Fourier transform infrared spectroscopy, 31P nuclear magnetic resonance spectroscopy, and gel permeation chromatography measurements. The lignin esters were applied on paperboard and formed a continuous film. The moisture barrier property of the coated paperboards was characterized by the water vapor transmission rate (WVTR). A significant decrease in WVTR was observed, for example, 40 g m-2 (for 24 h) for a paperboard coated with 10.4 g m-2 hardwood kraft lignin palmitate. The contact angle of water on the lignin ester coatings was high and stable. For all paperboard samples coated with lignin esters, a significant decrease in oxygen transmission rate was observed. Accordingly, lignin palmitate and laurate have a high potential as a barrier materials in packaging applications.

Production of cellulose carbamate using urea-based deep eutectic solvents

Cellulose carbamate is a bio-based, biodegradable, and environmentally friendly material and thus an interesting alternative to petroleum-based polymers or fibers from cellulose produced using the viscose process for producing fibers from cellulose. In this study we described an efficient and green method to prepare cellulose carbamates by using deep eutectic solvents. Three different urea-based deep eutectic solvents were used with different molar ratios and cellulose consistency. Nitrogen content of cellulose carbamates increases when cellulose consistency increases from 5 to 20%. Also, the reaction temperature affects the nitrogen content. In addition, the cellulose crystallinity decreases during the carbamation reaction with 20% cellulose consistency using any of the three deep eutectic solvents studied, when the sample is processed in a high-consistency reactor. By selecting suitable parameters, the nitrogen content of cellulose carbamates can be easily adjusted to a desired level.

Hydrophobization and smoothing of cellulose nanofibril films by cellulose ester coatings

The Cellulose nanofibrils (CNF), also referred to as nanocellulose, is one of the most studied bio-based material in recent year, which has good potential in the future for packaging applications due to its excellent mechanical strength and oxygen barrier properties. In the future, CNF films may also find new applications for example in printed electronics, if the surface smoothness of CNF films can be improved. One way to improve surface smoothness is to use thin coating solutions with zero porosity, such as molar mass controlled cellulose ester coatings. In this study, we have coated CNF films using molar mass controlled cellulose esters with different side chain lengths forming 3-layer film (ester-CNF-ester). These coatings improved significantly the smoothness of CNF films. The 3-layer films have also good water vapor barrier and mechanical properties and the films are heat-sealable, which enable various new applications in the future.

The effect of oxyalkylation and application of polymer dispersions on the thermoformability and extensibility of paper

Wood fiber-based packaging materials, as renewable materials, have growing market potential due to their sustainability. A new breakthrough in cellulose-based packaging requires some improvement in the mechanical properties of paper. Bleached softwood kraft pulp was mechanically treated, in two stages, using high- and low-consistency refining, sequentially. Chemical treatment of pulp using the oxyalkylation method was applied to modify a portion of fiber material, especially the fiber surface, and its compatibility with polymer dispersions including one carbohydrate polymer. The results showed that the compatibility of the cellulosic fibers with some polymers could be improved with oxyalkylation. By adjusting mechanical and chemical treatments, and the thermoforming conditions, the formability of paper was improved, but simultaneously the strength and stiffness decreased. The results suggest that the formability of the paper is not a direct function of the extensibility of the applied polymer, but also depends on the fiber network structure and surface energy.

Polymerization of coniferyl alcohol by Mn3+-mediated (enzymatic) oxidation: Effects of H2O2 concentration, aqueous organic solvents, and pH

The objective of this study was to evaluate the ability of one versatile peroxidase and the biocatalytically generated complex Mn(III)‐malonate to polymerize coniferyl alcohol (CA) to obtain dehydrogenation polymers (DHPs) and to characterize how closely the structures of the formed DHPs resemble native lignin. Hydrogen peroxide was used as oxidant and Mn2+ as mediator. Based on the yields of the polymerized product, it was concluded that the enzymatic reaction should be performed in aqueous solution without organic solvents at 4.5 ≤ pH ≤ 6.0 and with 0.75 ≤ H2O2:CA ratio ≤ 1. The results obtained from the Mn3+‐malonate‐mediated polymerization showed that the yield was almost 100%. Reaction conditions had, however, effect on the structures of the formed DHPs, as detected by size exclusion chromatography and pyrolysis‐GC/MS. It can be concluded that from the structural point of view, the optimal pH for DHP formation using the presently studied system was 3 or 4.5. Low H2O2/CA ratio was beneficial to avoid oxidative side reactions. However, the high frequency of β–β linkages in all cases points to dimer formation between monomeric CA rather than endwise polymerization.