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Thermoplastic, polysaccharide-based plastics are environmentally friendly. However, typical shortcomings include lack of water resistance and poor mechanical properties. Nanocomposite manufacturing using pure, highly linear, polysaccharides can overcome such limitations. Cast nanocomposites were fabricated with plant engineered pure amylose (AM), produced in bulk quantity in transgenic barley grain, and cellulose nanofibers (CNF), extracted from agrowaste sugar beet pulp. Morphology, crystallinity, chemical heterogeneity, mechanics, dynamic mechanical, gas and water permeability, and contact angle of the films were investigated. Blending CNF into the AM matrix significantly enhanced the crystallinity, mechanical properties and permeability, whereas glycerol increased elongation at break, mainly by plasticizing the AM. There was significant phase separation between AM and CNF. Dynamic plasticizing and anti-plasticizing effects of both CNF and glycerol were demonstrated by NMR demonstrating high molecular order, but also non-crystalline, and evenly distributed 20 nm-sized glycerol domains. This study demonstrates a new lead in functional polysaccharide-based bioplastic systems.

Covering: Up to 2019Phenolic cross-links and phenolic inter-unit linkages result from the oxidative coupling of two hydroxycinnamates or two molecules of tyrosine. Free dimers of hydroxycinnamates, lignans, play important roles in plant defence. Cross-linking of bound phenolics in the plant cell wall affects cell expansion, wall strength, digestibility, degradability, and pathogen resistance. Cross-links mediated by phenolic substituents are particularly important as they confer strength to the wall via the formation of new covalent bonds, and by excluding water from it. Four biopolymer classes are known to be involved in the formation of phenolic cross-links: lignins, extensins, glucuronoarabinoxylans, and side-chains of rhamnogalacturonan-I. Lignins and extensins are ubiquitous in streptophytes whereas aromatic substituents on xylan and pectic side-chains are commonly assumed to be particular features of Poales sensu lato and core Caryophyllales, respectively. Cross-linking of phenolic moieties proceeds via radical formation, is catalyzed by peroxidases and laccases, and involves monolignols, tyrosine in extensins, and ferulate esters on xylan and pectin. Ferulate substituents, on xylan in particular, are thought to be nucleation points for lignin polymerization and are, therefore, of paramount importance to wall architecture in grasses and for the development of technology for wall disassembly, e.g. for the use of grass biomass for production of 2nd generation biofuels. This review summarizes current knowledge on the intra- and extracellular acylation of polysaccharides, and inter- and intra-molecular cross-linking of different constituents. Enzyme mediated lignan in vitro synthesis for pharmaceutical uses are covered as are industrial exploitation of mutant and transgenic approaches to control cell wall cross-linking.

Corn bran is a major agro-industrial byproduct from corn starch processing. The bran is particularly rich in highly substituted feruloylated glucuronoarabinoxylan (FGAX). Yet, due to its recalcitrance to biocatalytic degradation, corn bran FGAX is currently not utilized in biorefinery processes. Here, we report selective enzymatic extraction of both single, and double-stranded high-molecular-weight FGAX molecules from corn bran using a bacterial, glucuronoyl-specific glycoside hydrolase family 30 endo-1,4-β-xylanase (EC 3.2.1.8) from Dickeya chrysanthemi (DcXyn30). The enzymatic extraction using DcXyn30 was optimized with respect to temperature, pH, and time to maximize yields of high-molecular-weight polysaccharides. Examination of the enzymatically extracted FGAX using SEC, HPAEC, LC-MS, and NMR analysis (after acid or alkaline hydrolysis) revealed that both single-stranded and double-stranded FGAX were extracted, since diferulate-linkages were present in the extracted FGAX. Furthermore, the NMR-analysis indicated presence of 1,5-linked arabinan dimers suggesting that some of the xylopyranosyl residues in the extracted FGAX contained arabinofuranosyl-arabinofuranosyl substitutions in addition to a significant amount of classical doubly-arabinose substitutions. Laccase treatment of the extracted FGAX produced strong hydrogels via oxidative, covalent feruloyl-cross-linking. At pH 6.5 the Myceliophthora thermophila derived laccase produced significantly faster cross-linking kinetics than the laccase from Pleurotus ostreatus as measured rheologically. The data reveal novel insight into corn bran FGAX chemistry and provide a new direction for enzyme-assisted upgrading of corn bran for valuable functional hydrogel applications.

Photobiocatalysis holds great promise toward the development of sustainable and environmentally friendly processes, harnessing light to drive biocatalytic reactions. However, photobiocatalysis at the interface of insoluble substrates, such as cellulose, has not been studied in much detail. In this context, the catalytic enhancement of lytic polysaccharide monooxygenases (LPMOs) by light is of great interest to the biorefinery field due to their capacity to oxidatively cleave such recalcitrant polysaccharides which can facilitate the degradation of lignocellulose. It has previously been reported that light-driven LPMO reactions have a huge catalytic potential, but effective continuous illumination in reactors may be challenging. Therefore, we investigated the impact of intermittent illumination. We show that illumination intervals as short as 1 s/min enable LPMO catalysis on phosphoric acid-swollen cellulose (PASC) to the same level as continuous illumination. Additionally, time-resolved measurements indicate that reductant depletion, and not enzyme inactivation, limits light-driven LPMO reactions. This study shows that a 60-fold reduction in illumination time enhances LPMO catalysis while protecting reaction elements, e.g. the reductant. Most importantly, the significant enhancement of LPMO catalysis with minimal and intermittent illumination is promising toward an application of photobiocatalytic depolymerization of lignocellulose where shading and light scattering minimize light availability and continuity., SCOPUS: ar.j, info:eu-repo/semantics/published

BACKGROUND: Crosslinked enzyme aggregates (CLEA) technology is a rapid and versatile method to produce immobilized enzymes via precipitation and cross-linking. A direct relationship between CLEA final activity and process parameters is however yet to be clarified. To address the issue, we have used a factorial design to test the formation and optimization of CLEA made from technical grade cellulase (EC 3.2.1.4). Three types of precipitant (ammonium sulfate, polyethylene glycol, tert-butyl alcohol) were used at varied levels of cross-linker concentration, cross-linking time, and temperature. RESULTS: It was found that the CLEAs produced with tert-butyl alcohol were inactive, whereas the polyethylene glycol- and ammonium sulfate-CLEA, recovered 29 and 17% of the free enzyme activity, respectively. Testing for re-usability, we observed that the polyethylene glycol-CLEA maintained 40% of the initial activity after four cycles, in contrast the ammonium sulfate-CLEA only maintained 10% of its activity after one cycle. CONCLUSION: Our study highlights the importance of evaluating the effect of the precipitant on final CLEA activity rather than re-solubilized enzyme activity. It was demonstrated that polyethylene glycol, despite not being able to precipitate the enzymes as readily as ammonium sulfate, resulted in better performing CLEA. (Less)

Cellulose fibers can be freed from the cell-wall skeleton via high-shear homogenization, to produce cellulose nanofibers (CNF) that can be used, for example, as the reinforcing phase in composite materials. Nanofiber production from agro-industrial byproducts normally involves harsh chemical-pretreatments and high temperatures to remove noncellulosic polysaccharides (20-70% of dry weight). However, this is expensive for large-scale processing and environmentally damaging. An enzyme-only pretreatment to obtain CNF from agro-industrial byproducts (potato and sugar beet) was developed with targeted commercial enzyme mixtures. It is hypothesized that cellulose can be isolated from the biomass, using enzymes only, due to the low lignin content, facilitating greater liberation of CNF via high-shear homogenization. Comprehensive Microarray Polymer Profiling (CoMPP) measured remaining extractable polysaccharides, showing that the enzyme-pretreatment was more successful at removing noncellulosic polysaccharides than alkaline- or acid-hydrolysis alone. While effective alone, the effect of the enzyme-pretreatment was bolstered via combination with a mild high-pH pretreatment. Dynamic rheology was used to estimate the proportion of CNF in resultant suspensions. Enzyme-pretreated suspensions showed 4-fold and 10-fold increases in the storage modulus for potato and sugar beet, respectively, compared to untreated samples. A greener yet facile method for producing CNF from vegetable waste is presented here.

Removal of non-cellulosic polymers from vegetable pulp to obtain cellulose nanofibers (CNF) is normally achieved by chemical pre-treatments which requires several washing steps. In the present study, it is demonstrated how incubation of sugar beet pulp at pH 9, followed by treatment with polysaccharide-degrading enzymes and subsequent bleaching can be done in a one-pot procedure to make CNF. The new method consumes 67% less water and removes non-cellulosic polysaccharides with similar efficiency as a chemical method. In addition, CNF produced by the new method contained slightly more pectin and formed gels with 2.7 times higher storage modulus. Nanopapers cast from chemically- and enzymatically produced CNF showed similar mechanical properties. However, without the pH 9 incubation step, the enzymes accessibility to cell-wall polymers was limited resulting in lower gel and paper strengths. In conclusion, the new method offers a sustainable route for producing high quality CNF from sugar beet waste.

Recently developed organic photovoltaics (OPVs) show distinct advantages over their inorganic counterparts due to their lighter weight, flexible shape, versatile materials synthesis and device fabr ...

Dissolving pulp was depolymerized with 2.5M HCl into cellulose fractions with decreasing molecular weight relative to acid treatment time. The cellulose fractions were dissolved at various concentrations in the ionic liquid 1-ethyl-3-methylimidazolium acetate (EmimAc) with co-solvent DMSO at ratio 1 : 1 (w/w) and electrospun. Size exclusion chromatography was used to evaluate the molecular weight distributions and the rheological properties were characterized with a cone-and-plate rheometer. Scanning electron microscope was used to evaluate the fiber morphology, and thereby spinnability. Zero shear viscosity as a function of cellulose concentration show that all the solutions in this study are in the entangled semi-dilute regime; where the polymer concentration is large enough for significant overlap necessary for chain entanglement. However, within the intervals studied, neither cellulose concentration nor molecular weight seems to be decisive for if a solution can be electrospun into fibers or not. It is rather the viscosity of the solution that is decisive for electrospinnability, even though the solution is in the entangled semi-dilute regime.

Cellulose was electrospun with various concentrations of ionic liquid and cosolvent. Three different cosolvents were used in this study; dimethylacetamide (DMAc), dimethyl formamide (DMF), and dimethyl sulfoxide (DMSO). The cosolvents were added to modify the viscosity, electrical conductivity, and surface tension of the solutions. The solubility of cellulose in ionic liquids is highly affected by changes in solvent properties on the molecular level in the binary solvent systems. The difference in molecular structure of the cosolvents and the interactions between cosolvent and ionic liquid can explain the difference in dissolution power of the cosolvents. Scanning electron microscope (SEM) was used to characterize electrospun cellulose fibers. For the systems tested the importance of having a rather high viscosity and high surface tension, and some degree of shear thinning to produce fibers is shown.

Oats are a new biofuel possible to use in modified residential wood pellet combustion appliances. The emissions of organic compounds from five sequential combustion stages; initial smouldering, early flaming, late flaming, after-flame smouldering and final glowing, for incomplete burning of oats on a laboratory scale were determined by gas chromatography and compared to those of softwood pellets. High concentrations of 1,6-anhydroglucose and furan-related compounds were released from the initial smouldering of oats, while high concentrations of methoxyphenols were released during the initial smouldering of wood pellets. The results indicate that oats are a biofuel with relatively low emissions during combustion, almost as low as those from wood pellets. After-flame smouldering of oats released lower concentrations of methane, alkenes and aromatic hydrocarbons than the after-flame smouldering of wood pellets. The large differences in emissions from the various combustion stages should be considered when evaluating the environmental aspects and health effects of residential burning of oats and wood pellets.

Four handling options for sewage sludge were studied from an environmental system's perspective using life cycle assessment. The studied options were restoration of mining areas, composting with other biomaterials for use on golf courses, hygienisation through storage for agricultural use, and supercritical water oxidation with phosphorus recovery. The results are discussed in terms of impact on global warming, acidification, eutrophication, and the use of finite resources and primary energy. A very large impact of including biogeochemical emissions from sludge handling and spreading on land can be seen. System expansions for replaced artificial fertilizers also had a major influence on the results. It is clear that it is important for the environmental outcome of sludge treatment options that biogeochemical emissions from sludge are minimized and that nutrients and other resources are utilized efficiently.

A conjugated polymer was prepd. based on 2-thia-1,3,5,8-tetraaza-cyclopenta[b]naphthalene central electron accepting unit and electron donating thiophene units on each side, LBPP-1, with unusually low band-gap (ca. 1.0 eV). Light absorption and photovoltaic response up to 1200 nm in composites with fullerene were demonstrated. The performance of solar cells contg. LBPP-1 is described and the suitability of LBPP-1 for photodetection in the IR region is discussed.

Charge transport in a near infrared absorbing polyfluorene copolymer (APFO-Green1) and its blends with methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM), and 3′-(3,5-bis-trifluorom ...

Low-bandgap alternating polyfluorenes with different donor-acceptor-donor moieties were synthesized. Electrochem. and optical absorption measurement show that onset bandgaps of these polymers range from 1.2 to 1.5 eV. These polymers, blended with a C70-deriv. as acceptor, are used for solar cell fabrication. Devices show promising photovoltaic properties, and the spectral response of photocurrent covers all visible and near-IR wavelength regions with its onset extended to 1 mm. The best data gives a photocurrent d. of 3.4 mA/cm2, open circuit voltage of 0.58 V and power conversion efficiency of 0.7% under illumination of AM1.5 (1000 W/m2) from a solar simulator. [on SciFinder (R)]

An alternating polyfluorene (APFO) with low band-gap segments. APFO-Green1, was synthesized for use in optoelectronic devices. The low band-gap segment consists of an electron acceptor (A), fenced by electron donors (D). This D-A-D configuration leads to partial charge transfer in the polymer backbone and a low band-gap of 1.3 eV. Characterization of APFO-Green1 include measurement of light absorption and emission at extended wavelengths and high hole mobility was found. Blends of the polymer with different fullerene derivs. exhibit unusually high photovoltaic performance at long wavelengths, making this type of conjugated polymers promising for application in plastic solar cells. [on SciFinder (R)]

Plastic solar cells have been fabricated using a low-bandgap alternating copolymer of fluorene and a donor-acceptor-donor moiety (APFO-Green1), blended with 3'-(3,5-bis-trifluoromethylphenyl)-1'-(4-nitrophenyl)pyrazolino fullerene (BTPF70) as electron acceptor. The polymer shows optical absorption in two wavelength ranges, l < 500 nm and 600 < l < 1000 nm. The BTPF70 absorbs light at l < 700 nm. A broad photocurrent spectral response in the wavelength range 300 < l < 1000 nm is obtained in solar cells. A photocurrent d. of 3.4 mA cm-2, open-circuit voltage of 0.58 V, and power-conversion efficiency of 0.7% are achieved under illumination of AM1.5 (1000 W m-2) from a solar simulator. Synthesis of BTPF70 is presented. Photoluminescence quenching and electrochem. studies are used to discuss photoinduced charge transfer. [on SciFinder (R)]

Two new alternating polyfluorene copolymers containing different low band gap segments have been designed and synthesized for use in optoelectronic devices. The low band gap segments consist of electron donating and accepting moieties which induce a partial charge transfer in the polymer backbone and thereby, a lower band gap. Results obtained from characterization of the new materials, called APFO-Green1 and APFO-Green2, include absorption and emission at extended wavelengths as well as high stability. Furthermore, blends of the new copolymers with different fullerene derivatives exhibit unprecedented photovoltaic behavior at long wavelengths.

Polymer solar cells were fabricated from a low band-gap alternating polyfluorene copolymer, APFO-Green2, combined with [6,6]-phenyl-C61-butyric acid Me ester (PCBM), from org. solns. External quantum efficiencies of the solar cells show an onset at 850 nm and a peak of >10% located at 650 nm, which corresponds to the extended absorption spectrum of the polymer. A photocurrent of 3.0 mA/cm2, photovoltage of 0.78 V, and power conversion efficiency of 0.9% were obtained with solar cells based on this new low-bandgap polymer under an illumination of AM 1.5 (1000 W/m2) from a solar simulator. [on SciFinder (R)]

We report on transistors and light-emitting diodes using a conjugated polymer consisting of alternated segments of fluorene units and low-band gap donor–acceptor–donor (D–A–D) units. The D–A–D segment includes two electron-donating thiophene rings combined with a thiadiazolo-quinoxaline unit, which is electron withdrawing to its nature. The resulting polymer is conjugated and has a band gap of around 1.27 eV. Here we present the corresponding electro- and photoluminescence spectra, which both peak at approximately 1 μm. Single layer light-emitting diodes demonstrated external quantum efficiencies from 0.03% to 0.05%. The polymer was employed as active material in thin film transistors, a field-effect mobility of 3 × 10−3 cm2/V s and current on/off ratio of 104 were achieved at ambient atmosphere.

Two new crescent-shaped unsymmetrical cyanine dyes have been synthesised and their interactions with DNA have been investigated by different spectroscopic methods. These dyes are analogues to a minor groove binding unsymmetrical cyanine dye, BEBO, recently reported by us. In this dye, the structure of the known intercalating cyanine dye BO was extended with a benzothiazole substituent. To investigate how the identity of the extending heterocycle affects the binding to DNA, the new dyes BETO and BOXTO have a benzothiazole group and a benzoxazole moiety, respectively. Whereas BEBO showed a heterogeneous binding to calf thymus DNA, linear and circular dichroism studies of BOXTO indicate a high preference for minor groove binding. BETO also binds in the minor groove to mixed sequence DNA but has a contribution of non-ordered and non-emissive species present. A non-intercalative binding mode of the new dyes, as well as for BEBO, is further supported by electrophoresis unwinding assays. These dyes, having comparable spectral properties as the intercalating cyanine dyes, but bind in the minor groove instead, might be useful complements for staining of DNA. In particular, the benzoxazole substituted dye BOXTO has attractive fluorescence properties with a quantum yield of 0.52 when bound to mixed sequence DNA and a 300-fold increase in fluorescence intensity upon binding.

In this study we report the synthesis, characterization, and photovoltaic properties of a series of six conjugated polymers based on donor-acceptor-donor (DAD) structure. The polymers are obtained via Suzuki polymerization of different alkoxy-substitutedDADmonomers together with a substituted fluorene or phenylene monomer. Application of polymers as light-harvesting and electron-donating materials in solar cells, in conjunction with both [60]PCBMand [70]PCBMas acceptors, show powerconversion efficiencies (PCEs) up to 2.9%, values obtained without extensive optimization work. Furthermore, atomic force microscopy and field-effect transistor (FET) mobility measurements of acceptor-polymer mixtures show that differences in substitution on the polymers affect morphology, mobility, and device performance. Within the series of polymers, all showing similar optical absorption and redox behavior, substituents play an important role in phase separation on a micrometer scale, which in turn has a large impact on device performance. The phase-separation behavior is clearly seen in [70]PCBM devices where the best-performing devices are obtained using the polymers with short alkoxy groups or no substituents together with a high speed of spin coating during device preparation. Refereed/Peer-reviewed

Solar cells based on organic molecules or conjugated polymers attract great attention due to their unique advantages, such as low cost, and their use in flexible devices, but are still limited by their low power conversion efficiency (PCE). To improve the PCEs of polymer solar cells, more efforts have been made to increase short-circuit current (Jsc) or open-circuit voltage (Voc). However, the trade-off between Jsc and Voc in bulk heterojunctions solar cells makes it tricky to find a polymer with a low band gap to efficiently absorb photons in the visible and near infrared region of the solar spectrum, while maintaining a high Voc in solar cells. Therefore, it is crucial to design and synthesize polymers with energy levels aligning with the LUMO (lowest unoccupied molecular orbital) of an electron acceptor to minimize the LUMO level difference between donor and acceptor to keep enough driving force for charge generation, thereby maximizing photovoltage in solar cells. Here a novel copolymer APFO-Green 9 was synthesized. Polymer solar cells based on APFO-Green 9 blended with a derivative of fullerene demonstrate high photovoltage by fine tuning the HOMO and LUMO level of APFO-Green 9. Solar cells based on APFO-Green 9 and [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM) present a photoresponse extended to 900 nm with Jsc of 6.5 mA cm 2, Voc of 0.81 V and PCE of 2.3% under illumination of AM1.5 with light intensity of 100 mW cm 2. As a low band gap polymer with a Voc bigger than 0.8 V, APFO-Green 9 is a promising candidate for efficient tandem solar cells. Refereed/Peer-reviewed

We report photo- and electroluminescence from an alternating conjugated polymer consisting of fluorene units and low-band gap donor-acceptor-donor (D–A–D) units. The D–A–D segment includes two elec ...

We report on transistors and light-emitting diodes using a conjugated polymer consisting of alternated segments of fluorene units and low-band gap donor-acceptor-donor (D-A-D) units. The D-A-D segment includes two electron-donating thiophene rings combined with a thiadiazolo-quinoxaline unit, which is electron withdrawing to its nature. The resulting polymer is conjugated and has a band gap of around 1.27 eV. Here we present the corresponding electro- and photoluminescence spectra, which both peak at approximately 1 micrometer. Single layer light-emitting diodes demonstrated external quantum efficiencies from 0.03% to 0.05%. The polymer was employed as active material in thin film transistors, a field-effect mobility of 0.003 cm 2 /Vs and current on/off ratio of 104 were achieved at ambient atmosphere.

The authors report polarized red, electroluminescence peak at 705 nm and near IR, electroluminescence peak at 950 nm, light emission from light emitting diodes based on two polyfluorene copolymers. The copolymers are synthesized from a fluorene monomer combined with donor-acceptor-donor comonomers and designed to have a low band gap and form birefringent liq. cryst. phases. Emission occurs from aligned thin films of polymer layers. The emissive layers are aligned by spin coating on a layer of rubbed conducting polymer poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) and thermally converted into glassy nematic liq. cryst. state. [on SciFinder (R)]

A conjugated polymer with a low band gap of 1.21 eV, i.e., absorbing infrared light, is demonstrated as active material in field-effect transistors (FETs). The material consists of alternating fluo ...