Carbon fiber (CF) is predominantly produced from fossil-based sources and is therefore an area of interest for further development towards a more sustainable society. The purpose of this thesis work was to investigate the possibility of producing precursor fibers (PFs) for CF production from a blend of renewable cellulose andlignin. Cellulose, which is used to some extent for CF production, was chosen, while the possibility of adding lignin was investigated in hope of increasing the gravimetric yield of the CF production. Blends of softwood kraft cellulose pulp (SKP) and softwood kraft lignin (SKL) were dissolved in an alkaline (NaOH) solvent system at different cellulose/lignin ratios. A total of eight dopes were prepared (SKP/SKL ratios of 100/0–60/40 wt./wt.) with total dope concentrations ranging from 4.5 wt.% to 9.2 wt.%. The addition of SKL resulted in dark colored dopes with viscosities of which mainly appeared to depend on the SKP concentration. The dopes were wet spun, resulting in continuously spun PFs. The PFs showed on an increasing pyrolysis yield with increased SKL content but decreasing mechanical properties. However, process optimization was not included in the work, subsequently leading to the assumption that greater values on mechanical properties can be achieved. A pure SKP PF and a SKP-SKL (70/30 wt./wt.) PF were successfully thermally converted into CFs by carbonization at 1000 °C. The PF containing SKL had a total gravimetric yield more than twice as high as the pure SKP PF, 28 wt.% and 12 wt.%, respectively. Thereby, the addition of SKL seems to have a positive impact on the CF yield when utilizing a NaOH(aq) solvent system. This thesis work has become a base for the future work towards the development of CFs from wet spun cellulose-lignin PFs in the NaOH(aq) solvent system.  

Biological pretreatment of wood chips by fungi is a well-known approach prior to mechanical- or chemical pulp production. For this biological approach, a limited number of white-rot fungi with an ability to colonize and selectively degrade lignin are used to pretreat wood chips allowing the remaining cellulose to be processed for further applications. Biopulping is an environmentally friendly technology that can reduce the energy consumption of traditional pulping processes. Fungal pretreatment also reduces the pitch content in the wood chips and improves the pulp quality in terms of brightness, strength, and bleachability. The bleached biopulps are easier to refine compared to pulps produced by conventional methodology. In the last decades, biopulping has been scaled up with pilot trials towards industrial level, with optimization of several intermediate steps and improvement of economic feasibility. Nevertheless, fundamental knowledge on the biochemical mechanisms involved in biopulping is still lacking. Overall, biopulping technology has advanced rapidly during recent decades and pilot mill trials have been implemented. The use of fungi as pretreatment for pulp production is in line with modern circular economy strategies and can be implemented in existing production plants. In this review, we discuss some recent advances in biopulping technology, which can improve mechanical-, chemical-, and organosolv pulping processes along with their mechanisms.

Molecularly imprinted polymers (MIPs) display intriguing recognition properties and can be used as sensor recognition elements or in separation. In this work, we investigated the formation of hierarchical porosity of compositionally varied MIPs using 129Xe Nuclear Magnetic Resonance (NMR) and 1H Time Domain Nuclear Magnetic Resonance (TD-NMR). Variable temperature 129Xe NMR established the morphological variation with respect to the degree of cross-linking, supported by 1H TDNMR determination of polymer chain mobility. Together, the results indicate that a high degree of cross-linking stabilizes the porous structure: highly cross-linked samples display a significant amount of accessible mesopores that instead collapse in less structured polymers. No significant differences can be detected due to the presence of templated pores in molecularly imprinted polymers: in the dry state, these specific shapes are too small to accommodate xenon atoms, which, instead, probe higher levels in the porous structure, allowing their study in detail. Additional resonances at a high chemical shift are detected in the 129Xe NMR spectra. Even though their chemical shifts are compatible with xenon dissolved in bulk polymers, variable temperature experiments rule out this possibility. The combination of 129Xe and TDNMR data allows attribution of these resonances to softer superficial regions probed by xenon in the NMR time scale. This can contribute to the understanding of the surface dynamics of polymers.

The hygroscopicity and thermodynamic properties of Pinus sylvestris L. wood from a coffin allegedly holding the remains of famous Spanish author Miguel de Cervantes Saavedra (1547–1616) were studied using the 15 °C and 35 °C isotherms fitted to the Guggenheim–Anderson–de Boer model and comparing them with the isotherms of recently felled wood of the same species. In addition, using infrared spectroscopy (FTIR-ATR) and X-ray diffractograms, the functional groups were determined and the crystallinity and organization of the cell wall components were analyzed. The absence of the 1740 cm⁻¹ group indicates hemicellulose degradation in the archaeological wood, and the X-ray diffractograms show a considerable decrease in cellulose crystallinity and disorganization of the cellulose crystallites. The greater availability of active –OH groups means that the archaeological wood isotherms are above the juvenile and mature wood isotherms, and therefore the thermodynamic balance in the sorption of the archaeological wood is greater.

The degradation states of archaeological white elm, with an age estimation of ~350 years, and poplar, with an age approximation of ~1000–1200 years, were studied by means of different chemical and microscopy analyses. Recently cut samples from the respective species were used for comparison reasons. The chemical composition analysis of the archaeological samples showed significantly low holocellulose values, while the lignin, extractive, and ash contents were considerably high, as compared with the recently cut samples. The Fourier-transform infrared (FTIR) spectroscopy also confirmed the changes in the chemical structure of the archaeological elm and poplar samples. The light and scanning electron microscopies illustrated that the erosion bacteria were the main degrading agent in both archaeological elm and poplar, although the hyphae of rot fungi were detected inside the vessel elements of the archaeological poplar sample.

The present study aims at characterization of freshly-cut and archaeological European white elm and poplar. The archaeological elm sample was buried at a depth of 8–10 m inside of soil with age approximation of ~1800–2000 years old, and the archaeological poplar sample was apart of a boat in a freshwater lake or river with age estimation of ~1000–1200 years. Alteration in the chemical structure of the elm and poplar samples due to the ageing process were confirmed by X-ray photoelectron spectroscopy (XPS). Both archaeological wood (AW) samples illustrated considerably lower cellulose crystallinity than the fresh samples as determined by X-ray diffraction. The sorption behavior of AW and fresh wood (FW) samples were evaluated by means of dynamic vapor sorption (DVS) analysis. Results exhibited a higher equilibrium moisture content (EMC) and sorption hysteresis values in archaeological elm and poplar as compared with the fresh samples. Higher hydrophilicity of the AW samples than the FW ones is attributed to their higher amorphous structure. The extensive degradation of AW samples were also confirmed by scanning electron microscopy (SEM) micrographs.

The biological deterioration of archaeological wood under oxygen-limited conditions varies due to the limited activities of microorganisms. It is essential to expand the knowledge of the degradation types and the status of archaeological monuments for selecting the proper consolidates. The physical, chemical, and anatomical properties of approximately 600–650 year old archaeological oak collected from an archaeological site in Iasi-Romania were analysed to assess the quality and to identify the degradation types. The results were compared with similar tests on recently-cut oak. X-ray photoelectron spectroscopy (XPS) revealed the presence of more lignin-related peaks in the archaeological oak, which likely reflected the degradation of the wood carbohydrates as evidenced by the decreased oxygen-to-carbon ratio Cox/Cnon-ox. The differences in cellulose crystallinity were not significant suggesting that any cellulose degradation occurred in the amorphous regions. This was also reflected in the dynamic water vapor sorption analysis where the differences in sorption isotherms and hysteresis of archaeological and recently-cut oaks were marginal. Microscopic analysis of the oak cells illustrated bacterial degradation patterns, while the field emission scanning electron microscopy (FESEM) showed the presence of erosion bacteria in the archaeological oak collected from the site with low oxygen conditions.

This research investigates the effect of plasma treatment with air, nitrogen (N2), and carbon dioxide (CO2) gases on the performance of waterborne (acrylic) and solvent-borne (polyester) coated fir (Abies alba M.) wood samples. The properties of the plasma-coated samples were analyzed before and after exposure to accelerated weathering and compared with those of untreated and solely treated ones. According to pull-off testing, the coating adhesion of the wood samples was considerably improved by plasma treatment, and obvious differences were observed between different plasma gases. The effect was more pronounced after the weathering test. Similar results were obtained for the abrasion resistance of the samples. The water contact angle measurement illustrated more hydrophilic character in the solely plasma-treated wood in comparison with the untreated wood. The application of coatings, however, strongly improved its hydrophobic character. The performances of waterborne and solvent-borne coatings on plasma-treated wood were comparable, although slightly better values were obtained by the waterborne system. Our results exhibit the positive effect of plasma treatment on coating performances and the increased weather resistance of the waterborne and solvent-borne coating systems on plasma-treated wood.

In this report, we have investigated factors contributing to the morphology and template recognition of bupivacaine-imprinted copolymers of methacrylic acid (MAA) and ethyleneglycol dimethacrylate (EGDMA). To this end, MAA, the most commonly used functional monomer in non-covalent molecular imprinting protocols, was compared and contrasted with the closely related acrylic acid (AA) in terms of polymer morphologies, recognition characteristics, and molecular level events in the corresponding pre-polymerization mixtures. Two series of analogous bupivacaine-imprinted EGDMA-copolymers containing increasing fractions of either AA or MAA were studied through all-component MD simulations in the pre-polymerization phase, equilibrium binding experiments on corresponding synthesized polymers and morphology characterization by N2-sorption measurements. A higher degree of hydrogen bonding frequency between respective functional monomer and bupivacaine was recorded for the mixtures containing AA compared to those containing MAA. In contrast, results from binding experiments demonstrated higher binding capacities for the polymers prepared with MAA than for those prepared with AA, which is explained by differences in polymer morphology. The surface areas and pore volumes of the AA-polymers were higher than for the MAA-polymers and the overall pore structure in the AA-polymers was ink-bottle shaped while the pores in the MAA-polymers were slit-shaped. We suggest that the methyl substituent of MAA contributes to differences in the reaction kinetics for AA and MAA during polymerization and resulted in different morphologies, in particular pore shape, which affected mass-transfer and consequently the binding qualities of the materials. © 2017 Elsevier Ltd

High volumes, fast production speed, and low material costs have been historically the driving factors of the particle- and fibreboard industries. However, in recent years the fossil-fuel dependency and health issues of the formaldehyde-containing adhesives used in the production have gained attention from both legislators and consumers. The latest example of legislation development is the change that the Federal Ministry for the Environment, Nature Conservation and Nuclear Safety of Germany  (Bundesministerium für Umwelt, Naturschutz und Nukleare Sicherheit) made to their testing method, effectively lowering the formaldehyde emission levels of wood-based panels in Germany from the European emission level of 0.1 ppm (E1, EN 717-1) to 0.05 ppm. As the emission levels of requirements decrease, market opportunities arise for formaldehyde-free bio-based adhesive systems. The aim of this thesis was thus to evaluate the different formaldehyde test methods at low emission levels (<0.05 ppm), and to explore new adhesive alternatives to the formaldehyde and petroleum-based systems used today.

As formaldehyde emissions decrease, choosing the right measurement method becomes increasingly important. Repeatability and correlation between the main European and American formaldehyde measurement chambers, described in EN 717-1 and ASTM D 6007 standards respectively, were determined. In addition, an alternative fast factory method based on emissions was evaluated, and the effect of reducing the conditioning time before emission measurements was investigated. A literature research was conducted on different bio-based raw materials in order to review their potential, from both scientific and industrial viewpoints, as alternatives to the current petroleum-derived and formaldehyde-based adhesives. Lignin residues from biorefinery processes were chosen for further testing due to their increasing volumes and potential to suit various pathways for adhesive making. Three different biorefinery lignins were compared, and ammonium lignosulfonate was chosen for making adhesives for particleboards by using one petroleum-based and one bio-based crosslinker.

The main conclusion of the formaldehyde emission part of the thesis was that formaldehyde emissions can be measured both accurately and quickly at low levels using chamber methods, even at factory environment. There was a good correlation between the American D 6007 and European EN 717-1 chamber methods at emission levels <0.05 ppm for both particleboards (r² = 0.9167) and fibreboards (r² = 0.9443). Further understanding on the effect of edge-sealing of boards and analytical methods described in the standards was obtained. It was confirmed that a fast chamber method with 1 day conditioning and 15 minutes measuring time could be used for factory formaldehyde control for most board types.

The bio-based adhesives’ literature review revealed a large amount of studies on different sustainable adhesive systems, some of which seem promising. Both soy protein and tannin were found to be partially commercialized, with certain pre-requisites. Kraft-lignin was especially well researched, but was found to be difficult to use for other applications than partial replacement of phenol in phenol-formaldehyde (PF) adhesives due to poor water solubility and purity. Lignin residues from biorefinery processes were found to be a less studied, growing raw-material source with a lot of potential. Thus, supercritical water hydrolysis lignin (SCWH) and two biorefinery lignosulfonates were chemically and thermally characterized, and evaluated as raw materials for value-added applications, including adhesives. SCWH lignin was found to have more β-R linkages and lower amount of impurities than the lignosulfonates. High amount of phenolic hydroxyl groups indicated that SCWH would be well suited for phenol replacement in PF adhesives. The two lignosulfonates had more aliphatic hydroxyl groups, which can be interesting for other crosslinking reactions than PF. Ammonium lignosulfonate (ALS) was chosen for further evaluation as having slightly better properties than sodium lignosulfonate (SLS). ALS was combined with one bio-based crosslinker, furfuryl alcohol (FOH), and one synthetic crosslinker, 4,4’-diphenylmethane diisocyanate (pMDI), and tested as particleboard adhesive. Although in veneer tensile shear strength testing the crosslinkers worked equally well, pMDI provided significantly better results in particleboards. In addition, higher emissions than what can be expected from wood particles alone were detected from the particleboard samples crosslinked with FOH, even though FOH can be classified as non-formaldehyde added adhesive system. Further research is needed to elucidate how much the lignin contributes to the final adhesion strength when it is used together with pMDI.

This thesis has provided new insights on formaldehyde emissions and bio-based adhesives towards healthier and more sustainable particle- and fibreboards. It has been proven that formaldehyde emissions can be measured accurately at emission levels of wood, enabling comparisons of formaldehyde-free systems. Formaldehyde-free adhesives based on a biorefinery lignin type and pMDI showed promising results for particleboards. However, these results need to be improved by different modifications of the lignin in order to bring the adhesive system to the economical and performance level required by the particleboard industry.

Wheat starch polymer was modified through the unequal reactivity of isocyanate groups in isophorone diisocyanate (IPDI) monomer. Fourier transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C NMR) confirmed the presence of both urethane and isocyanate functionalities in the modified polymer. Thermal stability and water vapor sorption properties of the modified polymer were evaluated by means of thermogravimetric analysis (TGA) and auto-dynamic vapor sorption (AVS) method, respectively. The results indicated that the modified starch polymer showed a better thermal stability (e.g. higher temperature at maximum weight loss) compared to the unmodified one. Water vapor sorption of starch polymer was considerably reduced after modification with IPDI monomer.

This study investigates the effect of proton acid pre-treatment and subsequent thermal modification at relatively low temperatures (up to 180 °C) on wood with respect to dimensional stability and water vapour sorption properties. The effects are compared to those of solely thermally-modified wood at higher temperatures (up to 250 °C). Scots pine sapwood (P. sylvestris L.) was impregnated with a proton acid or demineralised water, and subsequently, thermally modified to various mass losses (ML). Acid pre-treatment and thermal modification improved the dimensional stability and reduced the equilibrium moisture content (EMC) until certain ML. Excess surface work (ESW) obtained from vapour sorption studies indicated that, at comparable ML, the acid pre-treatment reduced the available sorption sites as compared to sole thermal treatment. Samples pre-treated with acid also showed stronger decreasing courses of EMC- and ESW-ratios than sole thermally modified ones. This was attributed to degradation of amorphous wood polymers and a stiffer matrix due to cross-linking of the cell wall polymers as a consequence of acid pre-treatment. Electron spin resonance (ESR) analysis indicated that acid pre-treatment did not enhance the concentration of phenoxy radicals, whereas thermally modified wood showed a considerably higher concentration of phenoxy radicals, suggesting that high radical density cannot be used as an indicator for high matrix stiffness.

Scots pine sapwood samples were pre-treated with a Lewis acid (AlCl₃) and a combination of Lewis and protonic acids (AlCl₃ and H₂SO₄), and were subsequently exposed to respective temperatures of 180 °C and 120 °C for establishing a comparable mass loss with those impregnated with demineralized water and solely thermally modified at 220 °C. Water impregnated samples dried at 120 °C also served as controls. The swelling behavior of all wood samples was examined with respect to maximum swelling in water, anti-swelling efficiency (ASE), shrinkage, and dynamic water vapor sorption at relative humidity ranges of 0% to 95%. The thermal modification at 220 °C diminished swelling and moisture adsorption, and also reduced moisture increment and decrement compared with the unmodified control. However, it was less obvious than both acid pre-treated samples. Excess surface work and Hailwood-Horrobin results calculated from water vapor sorption studies demonstrated that, at comparable mass loss, the available sorption sites were reduced to a greater extent by Lewis acid and combination of Lewis and protonic acids pre-treatment than the sole thermal treatment. This was attributed to more pronounced degradation of polysaccharides, mainly hemicelluloses and amorphous parts of cellulose, and to cross-linking of cell wall polymers due to the acid pre-treatments.

This study reports the fabrication and performance of sustainable polyurethane (PU) films based on wheat starch (native NS, modified MS), bio-polyols (1,3-propanediol PD, glycerol Gly), and polymeric diphenylmethane diisocyanate (pMDI). NS was successfully modified with isophorone diisocyanate, confirmed by Fourier transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance (13C NMR). Various PU films were prepared using NS, PD or Gly, MS and pMDI. For comparison, reference films were also synthesized without MS. PU films were analyzed from the viewpoint of their chemical, thermomechanical and flexural properties, and microstructural morphology. FTIR spectra demonstrated the total consumption of NCO groups, while the scanning electron microscopy micrographs of the films revealed that MS addition promoted the interactions between the compounds, enhancing in consequence their mechanical and thermomechanical performance. The study supported the suitability of functionalized carbohydrates to substitute petrochemical compounds in the synthesis of more environmentally-friendly PUs.

This study investigated the performance of polyurethane adhesives prepared with various combinations of wheat starch that had been modified by isophorone diisocyanate (MS), two polyol types (1,3-propanediol (PD) and glycerol (Gly)), native wheat starch (NS), and 4,4′-diphenylmethane diisocyanate (pMDI) at a NCO:OH weight ratio of 1:1. Two more adhesives were also synthesized with NS, PD, or Gly and pMDI blends and served as controls. The thermal behavior of the adhesives before and after the curing process, as well as their rheological performance and lap shear strength, were analyzed. Differential scanning calorimetry (DSC) showed a reduction in curing temperature and heat by adding MS. The thermal stability of the cured adhesives was slightly increased by MS addition. The viscosity of the adhesives that contained MS substantially increased at a linear ascendant ramp of shear, while the controls exhibited relatively low viscosity during the whole shear rate spectrum from 0.1 to 100 s−1. The tensile shear strength of wood veneers was also significantly increased by the incorporation of MS under both dry and wet measuring conditions. The maximum dry shear strength was obtained for the adhesive with Gly polyol and a higher content of MS and was comparable to the control adhesive with pMDI.

Pea starch and dextrin polymers were modified through the unequal reactivity of isocyanate groups in isophorone diisocyanate (IPDI) monomer. The presence of both urethane and isocyanate functionalities in starch and dextrin after modification were confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹³C nuclear magnetic resonance (¹³C NMR). The degree of substitution (DS) was calculated using elemental analysis data and showed higher DS values in modified dextrin than modified starch. The onsets of thermal degradation and temperatures at maximum mass losses were improved after modification of both starch and dextrin polymers compared to unmodified ones. Glass transition temperatures (T_g) of modified starch and dextrin were lower than unmodified control ones, and this was more pronounced in modified dextrin at a high molar ratio. Dynamic water vapor sorption of starch and dextrin polymers indicated a slight reduction in moisture sorption of modified starch, but considerably lower moisture sorption in modified dextrin as compared to that of unmodified ones.

Partial liquefaction of residual biomass shows good potential for developing new materials suitable for making bio-based composites. Three-layer particleboards were produced by replacing virgin wood particles with partially liquefied bark (PLB) in the core or surface layers. PLB was prepared by the acid-catalyzed liquefaction of industrial bark residues in polyhydric alcohol. The chemical and microscopic structure of bark and residues after liquefaction were evaluated by means of Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM), while the particleboards were tested for their mechanical and water-related properties, as well as their emission profiles. Through a partial liquefaction process, some FTIR absorption peaks of the bark residues were lower than those of raw bark, indicating hydrolysis of chemical compounds. The surface morphology of bark did not change considerably after partial liquefaction. Particleboards with PLB in the core layers showed overall lower densities and mechanical properties (modulus of elasticity, modulus of rupture, and internal bond strength), and were less water-resistant as compared to the ones with PLB used in the surface layers. Formaldehyde emissions from the particleboards were 0.284–0.382 mg/m2·h, and thus, below the E1 class limit required by European Standard EN 13986:2004. The major emissions of volatile organic compounds (VOCs) were carboxylic acids as oxidization and degradation products from hemicelluloses and lignin. The application of PLB in three-layer particleboards is more challenging than in single-layer boards as PLB has different effects on the core and surface layers.

Polyurethane (PU) adhesives were prepared with bio-polyols obtained via acid-catalyzedpolyhydric alcohol liquefaction of wood sawdust and polymeric diphenylmethane diisocyanate(pMDI). Two polyols, i.e., crude and purified liquefied wood (CLW and PLW), were obtained fromthe liquefaction process with a high yield of 99.7%. PU adhesives, namely CLWPU and PLWPU,were then prepared by reaction of CLW or PLW with pMDI at various isocyanate to hydroxyl group(NCO:OH) molar ratios of 0.5:1, 1:1, 1.5:1, and 2:1. The chemical structure and thermal behavior of thebio-polyols and the cured PU adhesives were analyzed by Fourier transform infrared spectroscopy(FTIR) and thermogravimetric analysis (TGA). Performance of the adhesives was evaluated by singlelap joint shear tests according to EN 302-1:2003, and by adhesive penetration. The highest shearstrength was found at the NCO:OH molar ratio of 1.5:1 as 4.82 ± 1.01 N/mm² and 4.80 ± 0.49 N/mm² for CLWPU and PLWPU, respectively. The chemical structure and thermal properties of the cured CLWPU and PLWPU adhesives were considerably influenced by the NCO:OH molar ratio. 

The use of liquid crystalline (LC) media as sacrificial templates during the polymer synthesis has been explored. The LC-media introduce morphological features into resultant polymers which when used together with molecular imprinting can produce materials with hierarchical architectures. Bupivacaine (1) imprinted co-polymers of 2-hydroxyethylmethacrylate (HEMA) (2a) and 1,4-divinylbenzene (DVB) (3a) were synthesized using photochemical initiation in lyotrophic liquid crystalline phases of AOT (5) in water/p-xylene and Triton X-100 (6) /water systems. SEM studies revealed the impact of the LC-media on polymer morphology, with polymer brush-like structures, with bristles of ≈30 nm diameter. The polymer morphology reflects that of the hexagonal phase of the LC medium. The rebinding characteristics of polymer films were evaluated quartz crystal microbalance (QCM, under FIA conditions). The influence of the presence of imprinting-derived recognition sites in AOT (5) in water/p-xylene polymer film induced brush-like features which provided a 25-fold enhancement of sensor sensitivity. This chemosensor was shown to be selective for the local anesthetic template, bupivacaine, through studies using the structural analogues ropivacaine and mepivacaine.

Herein, we report the use of the use of non-ionic deep eutectic solvents (ni-DESs) as porogens in polymer synthesis. Three ni-DES systems, acetamide-N-methylacetamide (AA-NMA), N-methylacetamide-N-methylurea (NMA-NMU) and N-methylacetamide-N,N'-dimethylurea (NMA-NN'DMU), were deployed in the synthesis of a series of cross-linked copolymer monoliths comprised of a functional monomer, methacrylic acid (MAA) or hydroxyethylmethacrylate (HEMA), and a cross-linking monomer, ethylene glycol dimethylacrylate (EGDMA) or divinylbenzene (DVB) or 1,4-bis(acryloyl)piperazine (BAP). Polymers were synthesized under thermally initiated conditions with 2,2'-azobis(2-methylpropionitrile) (AIBN) or 2,2'-azobis(2-amidinopropane) dihydrochloride (ABAH) as an initiator. The resulting polymer monoliths were ground and sieved to yield particles of 63-125 mu m. Corresponding polymers prepared in conventional porogens, acetonitrile, toluene and water were synthesized to serve as controls. The influence of the respective niDESs on polymer morphologies was examined by Brunauer-Emmett-Teller (BET) N2-adsorption, Fourier transform infrared spectroscopy (FT-IR), elemental analysis, scanning electron microscopy (SEM) and zeta potential measurements. The materials displayed surface areas, pore volumes and pore diameters of 115-532 m(2) g(-1), 0.1-1.4 cm(3) g(-1) and 5.2-12.5 nm, generally comparable with those of polymers obtained using conventional solvents, thus presenting these ni-DESs as viable alternatives to conventional organic solvents. The post-polymerization recovery of the ni-DESs (>80%) was demonstrated, highlighting the potential for using these novel liquids as alternatives to conventional, and often more expensive, toxic, flammable or volatile solvents in polymer synthesis.

In principle, molecularly imprinted polymer science and technology provides a means for ready access to nano-structured polymeric materials of predetermined selectivity. The versatility of the technique has brought it to the attention of many working with the development of nanomaterials with biological or biomimetic properties for use as therapeutics or in medical devices. Nonetheless, the further evolution of the field necessitates the development of robust predictive tools capable of handling the complexity of molecular imprinting systems. The rapid growth in computer power and software over the past decade has opened new possibilities for simulating aspects of the complex molecular imprinting process. We present here a survey of the current status of the use of in silico-based approaches to aspects of molecular imprinting. Finally, we highlight areas where ongoing and future efforts should yield information critical to our understanding of the underlying mechanisms sufficient to permit the rational design of molecularly imprinted polymers.

Significant enantioselective recognition has been achieved through the introduction of long range ordered and highly interconnected 300 nm diameter pores in molecularly imprinted polymer matrices.

This study reports the feasible use of chitosan as a thin film biosensor on the very sensitive quartz crystal micro balance system for detection of blends of multiple templates within a single matrix. The development of chitosan-based thin film materials with selectivity for nicotine derivatives is described. The molecular imprinting of a combination of nicotine derivatives in N-diacryloyl pipiradine-chitosan-methacrylic acid copolymer films on quartz crystal resonators was used to generate thin films with selectivity for nicotine and a range of nicotine analogues, particularly 3-phenylpyridine. The polymers were characterized by spectroscopic and microscopic evaluations; surface area, pore size, pore volume using Breuner-Emmet-Teller method. Temperature characteristics were also studied. The swelling and structure consistency of the Chitosan was achieved by grafting with methylmethacrylic acid and cross-linking with N-diacrylol pipiradine. A blend of 0.002 g (0.04 mmol) of Chitosan, 8.5 μL Methylmethacrylic Acid and 1.0 mg N-diacrylol pipradine (BAP) presented the best blend formulation. Detections were made within a time interval of 99 s, and blend templates were detected at a concentration of 0.5 mM from the Quartz crystal microbalance resonator analysis. The successful crosslinking of the biopolymers ensured successful control of the swelling and agglomeration of the chitosan, giving it the utility potential for use as thin film sensor. This successful crosslinking also created successful dual multiple templating on the chitosan matrix, even for aerosolized templates. The products can be used in environments with temperature ranges between 60 °C and 250 °C.

A series of molecular dynamics simulations of prepolymerization mixtures for phenylalanine anilide imprinted co-(ethylene glycol dimethacrylate-methacrylic acid) molecularly imprinted polymers have been employed to investigate the mechanistic basis for template selective recognition in these systems. This has provided new insights on the mechanisms underlying template recognition, in particular the significant role played by the crosslinking agent. Importantly, the study supports the occurrence of template self-association events that allows us to resolve debate between the two previously proposed models used to explain this system's underlying recognition mechanisms. Moreover, the complexity of the molecular level events underlying template complexation is highlighted by this study, a factor that should be considered in rational molecularly imprinted polymer design, especially with respect to recognition site heterogeneity.

Molecular dynamics (MD) simulations of prepolymerization mixtures can provide detailed insights concerning the molecular-level mechanisms underlying the performance of molecularly imprinted polymers (MIPs) and can be used for the in silico screening of candidate polymer systems. Here, we describe the use of MD simulations of all-atom, all-component MIP prepolymerization mixtures and procedures for the evaluation of the simulation data using the Amber simulation software suite.

In the present work we have performed classical molecular dynamics modelling to investigate the effects of different types of force-fields on the stress-strain and yielding behaviours in semi-crystalline lamellar stacked linear polyethylene. To this end, specifically the all-atomic optimized potential for liquid simulations (OPLS-AA) and the coarse-grained united-atom (UA) force-fields are used to simulate the yielding and tensile behaviour for the lamellar separation mode. Despite that the considered samples and their topologies are identical for both approaches, the results show that they predict widely different stress-strain and yielding behaviours. For all UA simulations we obtain oscillating stress-strain curves accompanied by repetitive chain transport to the amorphous region, along with substantial chain slip and crystal reorientation. For the OPLS-AA modelling primarily cavitation formation is observed, with small amounts of chain slip to reorient the crystal such that the chains align in the tensile direction. This force-field dependence is rooted in the lack of explicit H-H and C-H repulsion in the UA approach, which gives rise to underestimated ideal critical resolved shear stress. The computed critical resolved shear stress for the OPLS-AA approach is in good agreement with density functional theory calculations and the yielding mechanisms resemble those of the lamellar separation mode. The disparate energy and shear stress barriers for chain slip of the different models can be interpreted as differently predicted intrinsic activation rates for the mechanism, which ultimately are responsible for the observed diverse responses of the two modelling approaches.

We study the stability of twin boundaries and slip in crystalline orthorhombic polyethylene by means of density functional theory (DFT), using a nonempirical, truly nonlocal density function, and by means of classical molecular dynamics (MD). The results show that, in accordance with experimental observations, there is a clear preference to chain slip over transverse slip for all considered slip planes. The activation energy for pure chain slip lies in the range 10-20 mJ/m(2) while that for transverse slip corresponds to 40-280 mJ/m(2). For the (110)-slip plane the energy landscape is non-convex with multiple potential energy minima, indicating the presence of stable stacking faults. This suggests that dissociation of perfect dislocations into partials may occur. For the two low-energy twin boundaries considered in this work, {110} and {310}, we find that the former is more stable than the latter, with ground state energies corresponding to 8.9 and 28 mJ/m2, respectively. We have also evaluated how well the empirical MD simulations with the all-atom optimized potential for liquid MD simulations (OPLS-AA) and the coarsegrained united atom (UA) potential concur with the DFT results. It is found that an all-atom potential is necessary to partially capture the gamma-surface energy landscapes obtained from the DFT calculations. The OPLS-AA predicts chain slip activation energies comparable with DFT data, while the transverse slip energy thresholds are low in comparison, which is attributed to weak close ranged monomer repulsion. Finally, we find that the H-H interaction dominates the slip activation. While not explicitly represented in the UA potential, its key role is revealed by correlating the DFT energy landscape with changes in the electron distributions and by MD simulations in which components of the OPLS-AA intermolecular potential are selectively silenced. (C) 2017 Elsevier Ltd. All rights reserved.

Dynamic covalent polymers of different topology have been synthesized from an aromatic dialdehyde and alpha,omega-dinitroalkanes via the nitroaldol reaction. All dinitroalkanes yielded dynamers with the dialdehyde, where the length of the dinitroalkane chain played a vital role in determining the structure of the final products. For longer dinitroalkanes, linear dynamers were produced, where the degree of polymerization reached a plateau at higher feed concentrations. In the reactions involving 1,4-dinitrobutane and 1,5-dinitropentane, specific macrocycles were formed through depolymerization of the linear chains, further driven by precipitation. At lower temperature, the same systemic self-sorting effect was also observed for the 1,6-dinitrohexane-based dynamers. Moreover, the dynamers showed a clear adaptive behavior, displaying depolymerization and rearrangement of the dynamer chains in response to alternative building blocks as external stimuli.

Scots pine sapwood was pretreated with two levels of propanetriol (20% and 40% w/w glycerol), and then subjected to vacuum-heat treatment (VHT) at 180°C and 200°C. The treated samples were examined with respect to their weight and volumetric changes, mechanical properties, colour changes, and dynamic water vapour sorption. The weight of the samples after VHT did not change with increasing the temperature, but it was increased in glycerol pretreated samples. Combination of glycerol pretreatment and VHT decreased the maximum swelling. Total colour change was significantly higher during VHT at a higher temperature, while no obvious trend observed in the samples pretreated with glycerol. Modulus of elasticity (MOE) and modulus of rupture (MOR) were not affected by solely VHT, but strongly decreased after glycerol pretreatment. The equilibrium moisture content (EMC) of the samples decreased by VHT. The glycerol pretreatment caused a reduction in EMC values at a relative humidity (RH) below 60%, but considerably increased the moisture sorption in the RH above 75%. VHT slightly reduced the sorption hysteresis compared to untreated wood, but an apparent reduction in hysteresis observed by glycerol pretreatment. This indicates that the flexibility of the wood cell wall polymers increases due to glycerol pretreatment, which results in decreased MOE and sorption hysteresis values.

Hierarchically nanostructured chloramphenicol (CLP) imprinted thin polymer films have been developed using a renewable monomer, the antioxidant caffeic acid (CA), using sacrificial nanostructures to induce porosity into the films. The poly(caffeic acid) (PCA) films were synthesized on Au/quartz resonators via greener polymerization conditions (clean energy electropolymerization in aqueous buffer or a non-ionic deep eutectic solvent). The sacrificial nanostructures explored included zein-based protein nanobeads, anodized alumina membrane, and Tween 20-derived polysorbate micelles, where dissolution of the sacrificial nanostructure templates from the PCA films afforded uniform long-range hyperporous networks, nanowires and nanoparticles, respectively, as revealed by SEM studies. Selective extraction of the CLP template from PCA films, was monitored by XPS, and afforded CLP selective cavities. The CLP-imprinted PCA(zein) films demonstrated eight- to 25-fold higher sensitivity than the other nanostructures in a QCM-sensor format, the limit of detection (LOD) under optimized FIA conditions was 50 mM. Significant sensitivities for CLP in milk were observed (1.5 mu g/ml to 3 mg/ml), covering the clinically relevant concentration range. The PCA(zein) thin films selectively differentiate CLP from structurally related antibiotics and are robust. Their production from renewable feedstocks of biological origin highlights the potential of this class of nanostructured materials for applications utilizing thin films.

Controlled on-surface synthesis of polymer films using amide-based, environmentally friendly, nonionic deep eutectic solvents (ni-DESs) has been developed to regulate the porous features of the films. An appropriate combination of acetamide (A), urea (U), and their methyl derivatives (N-methylacetamide (NMA) and N-methylurea (NMU)) was used to prepare ni-DES. Polymer films were electrosynthesized using 4-aminobenzoic acid (4-ABA) and pyrrole as monomers in ni-DESs. We presumed that the flickering-cluster-like complexes and the extended H-bond networks in ni-DESs enhance the porosity of the polymer films, thus improving permeability features, as reflected in sensor performance. Electrosynthesized polymer films, imprinted with biotin templates (MIPs), have been tested as receptors for biotinylated targets. Molecular dynamics simulations of the prepolymerization mixture revealed the formed complexes between 4-ABA and biotin comprising high-frequency H-bonds. X-ray photoelectron spectroscopy (XPS) and reflection absorption infrared spectroscopy (RAIRS) studies revealed the structural integrity in the polymer films irrespective of the medium. Scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) measurements showed a highly corrugated and porous nature for MIPA-U and MIPNMU-U when prepared in A-U and NMU-U ni-DESs. Atomic force microscope (AFM) studies support these observations, displaying an enhancement in the surface roughness from 1.44 nm (MIPaqueous) to 23.6 nm (MIPNMU-U). QCM analysis demonstrated a remarkable improvement in sensitivity of MIPA-U (17.99 +/- 0.72 Hz/mM) and MIPNMU-U (18.40 +/- 0.81 Hz/mM) films toward the biotin methyl ester (BtOMe, biotin derivative) than the MIPaqueous film. The chemosensor devised with the above MIP recognition films selectively recognized BtOMe (LOD = 12.5 ng/mL) and biotinylated biomolecules, as shown by the stability constant K-s values (MIPA-U = 1442 and MIPNMU-U = 1502 M-1). The porous network generated in the polymer films by the flickering-cluster-like complexes present in the ni-DES facilitates the analyte diffusion and recognition. We propose this ni-DES as an economically advantageous and environmentally friendly alternative to conventional ionic liquids and organic solvents in polymer synthesis and to influence polymer morphology for developing hierarchical materials.

Wood is a natural renewable material with unique properties helping mankind to build and develop its communities since the genesis of human on the Earth. Moreover, wood/cellulosic composites provide the opportunity to utilize low-density wood species and agricultural materials that are basically not suitable for structural applications. Although wood is considered irreplaceable, it has some disadvantages narrowing its applications and limiting its service life. These disadvantages mainly include its susceptibility to water and water vapor, biological deteriorating fungi, insects, termites, and marine borers. The present chapter tries to summarize some main areas in which nanotechnology is being used to improve wood and lignocellulosic-based composite panels. Moreover, some new applications and capabilities of this precious natural material are also brought into perspective, areas such as transparent wood, self-cleaning coatings, and smart windows. Though some areas have been thoroughly studied, much potential still exists for further studies and commercialization.

A series of streptavidin-mimicking molecularly imprinted polymers has been developed and evaluated for their biotin binding characteristics. A combination of molecular dynamics and NMR spectroscopy was used to examine potential polymer systems, in particular with the functional monomers methacrylic acid and 2-acrylamidopyridine. The synthesis of copolymers of ethylene dimethacrylate and one or both of these functional monomers was performed. A combination of radioligand binding studies and surface area analyses demonstrated the presence of selectivity in polymers prepared using methacrylic acid as the functional monomer. This was predicted by the molecular dynamics studies showing the power of this methodology as a prognostic tool for predicting the behavior of molecularly imprinted polymers.