Cellulosic Substrates Research Articles

Enhancing the attraction of positively charged precursors of conductive polymer poly(3,4-ethylenedioxythiophene) by anchoring sulfonate groups in cellulose fibres

Interfacial interactions are key to the development of high-performance coatings such as conductive polymer layers on fibrous materials. In this work, we present an approach of strengthening the interaction by forming ionic bonds between cellulose fibres and the conductive polymer layer by introducing a sulfonate group on cellulose fibres. The ionic bonds are formed between anchored sulfonate group and the positively charged precursor 3,4-ethylenedioxythiophene (EDOT), followed by the deposition and polymerisation of poly(3,4-ethylenedioxythiophene):sulfate (PEDOT:SO4) on the fibrous substrate surface. The conductance of the PEDOT:SO4 coated substrate with anchored sulfonate groups coated may be 1.7 times higher compared to the conductance of the unmodified cellulose substrate depending on experimental conditions. EDX measurements confirm the presence of sulfur and a shift of zeta potential at lower pH supports the evidence of the anionic anchored groups on the fibre surface. Our study therefore provides a new way to enhance the affinity of fibrous cellulose materials towards polymer conductive coatings.

Specific features of enzymatic hydrolysis of cellulose

In this article, the features of enzymatic hydrolysis of cellulose samples with different structural characteristics were studied. It was discovered that outer paracrystalline layers of crystallites are accessible and susceptible to hydrolysis along with the poorly ordered amorphous domains of cellulose. The thermodynamic analysis showed that the hydrolysis process of cellulose samples at 298 K is exothermic. Since reaction enthalpy is negative and the temperature-entropy factor is positive, the Gibbs potential of this process becomes negative, which contributes to the implementation of enzymatic hydrolysis of cellulose. Moderate enhancement in temperature to optimal value, 323 K, increases the negative value of Gibbs potential and thereby promotes the hydrolysis of cellulose substrates. The most negative Gibbs potential was observed for the hydrolysis of the most accessible amorphous cellulose. Thus, amorphization of cellulose substrates facilitates enzymatic hydrolysis. On the other hand, the enzymatic hydrolysis of high-ordered crystalline domains of cellulose cannot be performed even at optimal temperature since the Gibbs potential of this process is close to zero.

Ecofriendly Cellulose Substrate‐Based Flexible Transparent Electrode for Flexible Organic Solar Cells with Efficiency Over 18%

Flexibility is a key advantage of organic solar cells (OSCs), and the power conversion efficiencies (PCEs) of flexible OSCs (FOSCs) are primarily constrained by flexible transparent electrodes (FTEs). While much attention has been devoted to the study of conductive layers on FTEs, the importance of flexible substrates in influencing the properties of FTEs and the performance of FOSCs is often overlooked. In this study, an FTE is developed using an eco‐friendly ethyl cellulose (EC) substrate and silver nanowires (AgNWs) as the conductive electrode. The FTE exhibits a high transmittance of up to 88% at 550 nm and a low sheet resistance of 17.65 Ω/□. Consequently, FOSCs based on the EC/PI FTEs achieve a remarkable PCE of 18.05%, comparable to that on the rigid ITO substrate. The flexible devices also demonstrate excellent bending and peeling durability even under extreme bending conditions.

Insights into the action of phylogenetically diverse microbial expansins on the structure of cellulose microfibrils

BackgroundMicrobial expansins (EXLXs) are non-lytic proteins homologous to plant expansins involved in plant cell wall formation. Due to their non-lytic cell wall loosening properties and potential to disaggregate cellulosic structures, there is considerable interest in exploring the ability of microbial expansins (EXLX) to assist the processing of cellulosic biomass for broader biotechnological applications. Herein, EXLXs with different modular structure and from diverse phylogenetic origin were compared in terms of ability to bind cellulosic, xylosic, and chitinous substrates, to structurally modify cellulosic fibrils, and to boost enzymatic deconstruction of hardwood pulp.ResultsFive heterogeneously produced EXLXs (Clavibacter michiganensis; CmiEXLX2, Dickeya aquatica; DaqEXLX1, Xanthomonas sacchari; XsaEXLX1, Nothophytophthora sp.; NspEXLX1 and Phytophthora cactorum; PcaEXLX1) were shown to bind xylan and hardwood pulp at pH 5.5 and CmiEXLX2 (harboring a family-2 carbohydrate-binding module) also bound well to crystalline cellulose. Small-angle X-ray scattering revealed a 20–25% increase in interfibrillar distance between neighboring cellulose microfibrils following treatment with CmiEXLX2, DaqEXLX1, or NspEXLX1. Correspondingly, combining xylanase with CmiEXLX2 and DaqEXLX1 increased product yield from hardwood pulp by ~ 25%, while supplementing the TrAA9A LPMO from Trichoderma reesei with CmiEXLX2, DaqEXLX1, and NspEXLX1 increased total product yield by over 35%.ConclusionThis direct comparison of diverse EXLXs revealed consistent impacts on interfibrillar spacing of cellulose microfibers and performance of carbohydrate-active enzymes predicted to act on fiber surfaces. These findings uncover new possibilities to employ EXLXs in the creation of value-added materials from cellulosic biomass.

Modification of cellulose substrate by in situ synthesis of metal-organic framework-5 for thin film microextraction of some non-steroidal anti-inflammatory drugs and their measurement by high-performance liquid chromatography-ultraviolet detector

This work, reports the successful preparation a thin film by a simple and inexpensive process for quantification of a model analytes in the urine sample using HPLC-UV. To this end, cellulose paper was employed as a substrate for the in-situ synthesis of MOF-5, to increase the resistance of the prepared film. The prepared film can be reused 26 times with no reduction in its performance. The thin film prepared by MOF-5 modified cellulose substrate was utilized in thin film microextraction (TFME) method for the extraction and preconcentration of naproxen, aspirin, tolmetin, and celecoxib. Under optimal conditions, the linear dynamic range of the target analytes was 2–500 µg L−1 with correlation coefficients (R2) ranging from 0.9961 to 0.9990. Also, the limits of detection (LODs), the limits of quantification (LOQs) and relative standard deviation (RSD%) of the proposed method for selected analytes ranged between 0.57 and 0.77 µg L−1, 1.7 to 2.3 and 3.5 % to 6.2 %, respectively. Moreover, relative recoveries varied from of 94 % to 108 %, indicating the absence of matrices effect in the proposed method. Eventually, the TFME was successfully used for the extraction of selected analytes from urine samples.

Parasitic dodder expresses an arsenal of secreted cellulases with multi-substrate specificity during host invasion

Cuscuta campestris is a common and problematic parasitic plant which relies on haustoria to connect to and siphon nutrients from host plants. Glycoside hydrolase family 9 (GH9) cellulases (EC 3.2.1.4) play critical roles in plant cell wall biosynthesis and disassembly, but their roles during Cuscuta host invasion remains underexplored. In this study, we identified 22 full-length GH9 cellulase genes in C. campestris genome, which encoded fifteen secreted and seven membrane-anchored cellulases that showed distinct phylogenetic relationships. Expression profiles suggested that some of the genes are involved in biosynthesis and remodeling of the parasite's cell wall during haustoriogenesis, while other genes encoding secreted B- and C-type cellulases are tentatively associated with degrading host cell walls during invasion. Transcriptomic data in a host-free system and in the presence of susceptible or partially resistant tomato hosts, showed for especially GH9B7, GH9B11 and GH9B12 a shift in expression profiles in the presence of hosts, being more highly expressed during host attachment, indicating that Cuscuta can tune cellulase expression in response to a host. Functional analyses of recombinant B- and C-type cellulases showed endoglucanase activities over wide pH and temperature conditions, and activities towards multiple cellulose and hemicellulose substrates. These findings improve our understanding of host cell wall disassembly by Cuscuta, and cellulase activity towards broad substrate range potentially explain its wide host range. This is the first study to provide a broad biochemical insight into Cuscuta GH9 cellulases, which based on our study may have potential applications in industrial bioprocessing.

A graphene oxide-modified biosensor for non-invasive glucose monitoring in college athletes

The study aims to address the need for accurate and real-time monitoring of glucose levels in college athletes during physical activities. This work reports on the development of an electrochemical sensor that uses glucose oxidase (GOx) immobilized on PdO nanoparticles to reduce graphene oxide (rGO) nanocomposite printed on a cellulose substrate (GOx/PdO-rGO/C-PE). The successful reduction of GO to rGO, the production of the PdO-rGO nanocomposite, and the electropolymerization of GOx on the PdO-rGO nanocomposite were all validated by the material characterization. The biosensor's electrochemical response investigation showed that its detection limit was 0.046 μM and its sensitivity was 0.03239 μA/μM. Excellent stability, reproducibility, and glucose selectivity were shown by the GOx/PdO-rGO/C-PE, which makes it a viable option for consistent and dependable glucose sensing in real-world applications. The real sample analysis assessed how well the combination of GOx/PdO-rGO/C-PE could identify glucose in human serum. Furthermore, under a variety of real-world conditions, such as during various physical activities and at different times of the day, the sensor demonstrated outstanding performance in real-time glucose monitoring. These findings imply that the GOx/PdO-rGO/C-PE offers accurate and dependable readings in the field of non-invasive glucose monitoring, which will be especially helpful for college and professional athletes.

Precise electronically modulated Mn doped nickel iron phosphate with P, N codoped carbon decorated P-doped carbonized bacterial cellulose for efficient electrocatalytic glucose conversion coupled with H2 generation

Biomass electrocatalytic-conversion coupled with hydrogen generation exhibits low energy consumption, efficient hydrogen production and green syntheses of value-added chemicals. However, constructing electrocatalysts with precise electronic modulation and structures for efficient biomass electrocatalytic conversion coupled hydrogen production remains challenging. Herein, a bacterial cellulose substrate was combined in situ with a Mn-doped NiFe Prussian blue analogue (PBA) precursor, and one-step carbonization-phosphorylation was developed for the preparation of Mn-doped nickel iron phosphate (MNFP) embedded in a P, N codoped carbon (PNC) substrate grown directly on P-doped carbonized bacterial cellulose (MNFP-PNC/PCBC). Benefiting from the three-dimensional network structure of P-doped carbonized bacterial cellulose (PCBC) and atomic doping, MNFP-PNC/PCBC exhibited an optimized electronic structure, abundant active sites and excellent electrical conductivity. Therefore, the voltages required with hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and glucose electrocatalytic-conversion (GCR) to drive a current density of 50 mA cm−2 were 0.214, 1.5, and 1.34 V, respectively. Moreover, the required cell voltage of the novel electrolyser containing MNFP-PNC/PCBC as electrodes can be further reduced to 1.55 V at 50 mA cm−2 compared to overall water splitting, resulting in more than 8-time improvement in hydrogen production efficiency and production of value-added formate. This work provides a unique approach for electrocatalytic-conversion of biomass coupled with electrocatalytic hydrogen generation.

Silica-Containing Phosphorus-Based Sol-Gel Finishing to Improve Flame Retardant Performance of Cotton Fabrics

In this paper, the sol-gel technique was used to design hybrid phosphorus-doped silica structures for improving the thermal stability and flame retardancy of cotton fabrics. To this aim, diethylphosphatoethyltriethoxysilane (DPTS) was employed as phosphate alkoxysilane in a multistep procedure that involved multiple layers (from 1 to 6) depositions. The multi-layer coatings were applied by padding using sols containing appropriate molar ratios of the precursor, anhydrous ethanol, catalyst, and hydrochloric acid. Moreover, the synergism P-N on flame retardancy of cotton was assessed by introducing 3-aminopropyltriethoxysilane (APTES) as an N-donor precursor in DPTS sols. The effects of the catalyst during the alkoxide reaction and the silica amount applied by sol-gel treatment on the thermo-oxidative behavior of the treated fabrics were deeply studied. The creation of the silica skeleton on the cotton surface and the interactions between the cellulosic fibres and the doped layer were investigated using FT-IR ATR spectroscopy. Moreover, thermal and thermo-oxidative stability, flammability properties, and combustion behavior of the sol-gel treated cotton fabrics were also studied, proving the effectiveness of the sol-gel coating in the fire protection of the cellulosic substrate.

A cellulose derived nanofibrous nitrogen-doped carbon/TiO2/SnO2/carbon composite anodic material for lithium storage

SnO2 with high theoretical specific capacity is regarded as a desirable anodic material for lithium storage. However, the serious volume variation during discharge/charge cycling and poor conductivity significantly constrain the electrochemical performance. Herein, nanofibrous nitrogen-doped carbon (NC)/TiO2/SnO2/carbon composite was fabricated through layer-by-layer assembly of SnO2 and TiO2-gel layers alternately using cellulosic filter paper as the structural scaffold, followed by deposition of polypyrrole on the surface by chemical polymerization method, and subsequent calcination of the as-obtained matter in inert atmosphere. The achieved composite possesses a typical three-dimensional fibrous porous network structure inherited from the cellulosic substrate, and complete NC nanolayer coating on each nanofiber by adjusting the amount of pyrrole, which can alleviate the volume change and increase the conductivity of SnO2. Furthermore, the interlaced TiO2 multilayer can enhance the cycling stability during cycling, as well as facilitate the lithium-ion transfer through abundant interface. The optimal NC/TiO2/SnO2/carbon composite delivers an initial discharge capacity of 1492.6 mAh g−1 at a current density of 100 mA g−1, and retains a reversible capacity of 680.8 mAh g−1 after 200 discharge/charge cycles. This work provides an efficient strategy for design and construction of metal-oxides/carbon composite anodic materials with hierarchical microstructure that hold great potential in lithium storage.

Fibrous morphological cellulose-derived ternary composite filter for immobilizing heavy metal ions from wastewater

Sewage containing heavy metal ions (HMIs) has caused serious damage to ecological environment and human health when discharged without treatment. In this work, a practical filter has been made with cellulose/zinc oxide/magnesium hydroxide (CelZnMg) ternary composite prepared via a simple hydrothermal method. The characterizations show that granular ZnO and lamellar Mg(OH)2 evenly distribute on cellulose. The electrostatic attraction drives the coupling of cellulose and ZnO/Mg(OH)2, and the formed CelZnMg is significantly stabilized by interfacial hydrogen bonds and dative bonds. On the other hand, the cellulose substrate also immobilizes the recovered HMIs and completely and easily separates them from wastewater. The ternary composite has outstanding bifunctional performance. Its Mg(OH)2 component offers high HMIs-removing capability; for instance, qmax of Cd2+ and Cu2+ in 400 mL 500 mg·L–1 solution reaches 693.2 and 764.6 mg·g–1 respectively. The ZnO moiety endows the antibacterial property, which inhibits the growth of Staphylococcus aureus and Escherichia coli. The inhibition effect indicates that cellulose in the composite is stable during application. Due to its multiple merits, the CelZnMg filter would be a perspective candidate for the use as water treatment agent.

Cellulose derived fibrous vanadium-sulfide/carbon composite with enhanced lithium storage properties

Vanadium-sulfides are considered as promising anodic materials for lithium-ion batteries (LIBs) due to their unique layered structures and high theoretical capacities. However, the main challenge of vanadium-sulfide as an electrode material is still faced with slow Li-ion diffusion kinetics and inevitable structural damage during charging/discharging processes. Herein, a series of bio-inspired hierarchical fibrous VS4/C composites were designed based on cellulose substance as the scaffold and carbon source via simple hydrothermal method. The resultant fibrous VS4/C composites possessed a three-dimensional porous network structure consisting of carbon fibers coated with VS4 nanosheets. As a consequence, the optimized VS4/C anodic materials exhibit high reversible capacities (953 mAh g−1 at 0.1 A g−1), good rate features (420 mAh g−1 at 2 A g−1), and fast diffusion kinetics. The superior electrochemical properties of the VS4/C composites are mainly attributed to the three-dimensional porous network structures combined with the carbon fibers matrix, which promotes the contact between the electrode and electrolyte, alleviates the structural damage of VS4, as well as facilitates the electron transfer and Li-ion diffusion during the cycling processes.

Simulation and experimental evaluation of laser-induced graphene on the cellulose and lignin substrates

In this article, the formation of laser-induced graphene on the two natural polymers, cellulose, and lignin, as precursors was investigated with molecular dynamics simulations and some experiments. These eco-friendly polymers provide significant industrial advantages due to their low cost, biodegradability, and recyclable aspects. It was discovered during the simulation that LIG has numerous defects and a porous structure. Carbon monoxide, H2, and water vapor are gases released by cellulose and lignin substrates. H2O and CO are released when the polymer transforms into an amorphous structure. Later on, as the amorphous structure changes into an ordered graphitic structure, H2 is released continuously. Since cellulose monomer has a higher mass proportion of oxygen (49%) than lignin monomer (29%), it emits more CO. The LIG structure contains many 5- and 7-carbon rings, which cause the structure to have bends and undulations that go out of the plane. In addition, to verify the molecular dynamics simulation results with experimental tests, we used a carbon dioxide laser to transform filter paper, as a cellulose material, and coconut shell, as a lignin material, into graphene. Surprisingly, empirical experiments confirmed the simulation results.

High-Molecular-Weight Xylanase from B. pumilus US570 Strain: Purification, Characterization and Application in Banana and Orange Peels Hydrolysis and Breadmaking.

New xylanase (XylUS570) was purified from the Bacillus pumilus US570 strain. It has a molecular mass of about 232kDa. This is the first report on the highest molecular weight monomeric xylanase produced by bacteria. The optimum pH and temperature recorded for enzyme activity were 7 and 55°C, respectively with a half-life time of 10min at 60°C. At 37°C, the enzyme retains more than 50% of its activity at a pH ranging from 6 to 9.5 for 24h. The XylUS570 exhibited a high activity on xylan, but no activity was detected for cellulosic substrates. The Vmax and Km values exhibited by the purified enzyme on beechwood xylan were 37.05 U mL-1 and 4.189mg mL-1, respectively. The XylUS570 was used in banana and orange peels hydrolysis and showed potential efficiency to liberate reducing sugars. It could be a good candidate for bio-ethanol production from fruit waste. The purified enzyme was used also as an additive in breadmaking. A decrease in water absorption, an increase in dough rising and improvements in volume and specific volume of the bread were recorded.

Characterization of Thermostable Cellulase Enzyme Isolated from a Hot Spring Bacterium: Bacillus sp.

Cellulase is a complex of enzymes which consists of β-1,4-endoglucanase, cellobiohydrolase, and β-glucosidase. Cellulase contributes a significant share to the world enzyme market and is used in number of industries viz; paper and pulp, food and beverage, bioethanol, detergent and textile. The harsh industrial conditions such as high temperature, extreme pH levels and high substrate concentration etc. which is used in such industries adversely effect on structure and activity of enzymes. Therefore, huge amount of chemical catalysts which cause chemical wastes are used in industrial settings instead of enzymes. Since the chemical wastes adversely affect the ecosystem, isolation and characterization of thermostable cellulase enzyme-producing bacteria and exploring the industrial perspective of thermostable enzymes is a better approach towards green chemistry. The present study focused on characterization of cellulase enzyme produced by Bacillus sp., which shows optimum activity at 60 C under neutral conditions, isolated from Gomarankadavala hot spring in Sri Lanka. The effect of different Carbon sources: glucose and lactose, Nitrogen sources: peptone, tryptone, yeast extract and urea on enzyme production and different Carboxymethylcellulose (CMC) concentrations; 0.5%, 1.5% and 2%, on enzyme activity were measured using the DNS method. Under the optimum conditions, cellulase enzyme activity on different substrates: corn cob, rice bran and raw leaves were measured. The highest enzyme production was recorded in the culture medium which added tryptone as the nitrogen source and adding carbon sources to the culture medium showed an increase of cellulase enzyme production. The optimum CMC concentration for the enzyme activity was recorded as 1% and from all the optimized parameters, the substrate; raw leaves showed the highest enzyme activity of 11.305 U/ml. Further, a considerable amount of enzyme activity was recorded on corn cobs and rice bran as well. Thus, the thermostable cellulase enzyme produced by bacterium identified as Bacillus cereus isolated from Gomarankadavala hot spring could be successfully used in industrial settings such as kitchen/industrial waste management, bioethanol production, paper and pulp industry and textile industry which use high temperatures and cellulosic substrates as raw materials. 
 Keywords: Thermostable enzymes, Cellulase, Industrial applications, Hot springs

Assessing the role of redox partners in TthLPMO9G and its mutants: focus on H2O2 production and interaction with cellulose

BackgroundThe field of enzymology has been profoundly transformed by the discovery of lytic polysaccharide monooxygenases (LPMOs). LPMOs hold a unique role in the natural breakdown of recalcitrant polymers like cellulose and chitin. They are characterized by a “histidine brace” in their active site, known to operate via an O2/H2O2 mechanism and require an electron source for catalytic activity. Although significant research has been conducted in the field, the relationship between these enzymes, their electron donors, and H2O2 production remains complex and multifaceted.ResultsThis study examines TthLPMO9G activity, focusing on its interactions with various electron donors, H2O2, and cellulose substrate interactions. Moreover, the introduction of catalase effectively eliminates H2O2 interference, enabling an accurate evaluation of each donor’s efficacy based on electron delivery to the LPMO active site. The introduction of catalase enhances TthLPMO9G’s catalytic efficiency, leading to increased cellulose oxidation. The current study provides deeper insights into specific point mutations, illuminating the crucial role of the second coordination sphere histidine at position 140. Significantly, the H140A mutation not only impacted the enzyme’s ability to oxidize cellulose, but also altered its interaction with H2O2. This change was manifested in the observed decrease in both oxidase and peroxidase activities. Furthermore, the S28A substitution, selected for potential engagement within the His1–electron donor–cellulose interaction triad, displayed electron donor-dependent alterations in cellulose product patterns.ConclusionThe interaction of an LPMO with H2O2, electron donors, and cellulose substrate, alongside the impact of catalase, offers deep insights into the intricate interactions occurring at the molecular level within the enzyme. Through rational alterations and substitutions that affect both the first and second coordination spheres of the active site, this study illuminates the enzyme’s function. These insights enhance our understanding of the enzyme’s mechanisms, providing valuable guidance for future research and potential applications in enzymology and biochemistry.

Exploring the use of supercritical carbon dioxide in enzymatic hydrolysis of cellulosic substrate

Enzymes are critical components for production of fermentable sugars in lignocellulosic biorefineries. Their activity could be influenced by various reaction parameters. Herein, a formulated cellulolytic enzyme cocktail was immobilized into mesoporous aerogel material and used under high pressure environment of supercritical CO2 (scCO2). The cocktail was immobilized at different enzyme loads (36.0 to 144.0 mg enzyme/g aerogel) using sol-gel entrapment method and scCO2 drying. The immobilized cocktail at 144.0 mg/g aerogel enzyme load retained a residual yield of >50.0 % after fourth cycle of reuse compared to first cycle under atmospheric pressure. Sugar yield by the cocktail aerogel was below 10 wt% in second cycle under scCO2 due to enzyme leaching. Additionally, surface area and porous volume of reused aerogels was decreased over the reuse cycles. The study suggests that scCO2 could be employed for aerogel preparation after optimizing the immobilization process for pure enzymes rather than crude enzymes.

Elucidating fungal decomposition of organic matter at sub-micrometer spatial scales using optical photothermal infrared (O-PTIR) microspectroscopy.

In microbiological studies, a common goal is to link environmental factors to microbial activities. Both environmental factors and microbial activities are typically derived from bulk samples. It is becoming increasingly clear that such bulk environmental parameters poorly represent the microscale environments microorganisms experience. Using infrared (IR) microspectroscopy, the spatial distribution of chemical compound classes can be visualized, making it a useful tool for studying the interactions between microbial cells and their microenvironments. The spatial resolution of conventional IR microspectroscopy has been limited by the diffraction limit of IR light. The recent development of optical photothermal infrared (O-PTIR) microspectroscopy has pushed the spatial resolution of IR microspectroscopy beyond this diffraction limit, allowing the distribution of chemical compound classes to be visualized at sub-micrometer spatial scales. To examine the potential and limitations of O-PTIR microspectroscopy to probe the interactions between fungal cells and their immediate environments, we imaged the decomposition of cellulose films by cells of the ectomycorrhizal fungus Paxillus involutus and compared O-PTIR results using conventional IR microspectroscopy. Whereas the data collected with conventional IR microspectroscopy indicated that P. involutus has only a very limited ability to decompose cellulose films, O-PTIR data suggested that the ability of P. involutus to decompose cellulose was substantial. Moreover, the O-PTIR method enabled the identification of a zone located outside the fungal hyphae where the cellulose was decomposed by oxidation. We conclude that O-PTIR can provide valuable new insights into the abilities and mechanisms by which microorganisms interact with their surrounding environments.IMPORTANCEInfrared (IR) microspectroscopy allows the spatial distribution of chemical compound classes to be visualized. The use of conventional IR microspectroscopy in microbiological studies has been restricted by limited spatial resolution. Recent developments in laser technology have enabled a new class of IR microspectroscopy instruments to be developed, pushing the spatial resolution beyond the diffraction limit of IR light to approximately 500 nm. This improved spatial resolution now allows microscopic observations of changes in chemical compounds to be made, making IR microspectroscopy a useful tool to investigate microscale changes in chemistry that are caused by microbial activity. We show these new possibilities using optical photothermal infrared microspectroscopy to visualize the changes in cellulose substrates caused by oxidation by the ectomycorrhizal fungus Paxillus involutus at the interface between individual fungal hyphae and cellulose substrates.

Natural Deep Eutectic Solvents as Rust Removal Agents from Lithic and Cellulosic Substrates.

The peculiar physicochemical features of deep eutectic solvents (DESs), in particular their tunability, make them ideal media for various applications. Despite their ability to solubilize metal oxides, their use as rust removers from valuable substrates has not yet been thoroughly investigated. In this study, we chose three known DESs, consisting of choline chloride and acetic, oxalic or citric acid for evaluating their ability to remove corrosion products from a cellulose-based material as linen fabric and two different lithotypes, as travertine and granite. The artificial staining was achieved by placing a rusty iron grid on their surfaces. The DESs were applied by means of cellulose poultice on the linen fabrics, while on the rusted stone surfaces with a cotton swab. Macro- and microscopic observations, colorimetry and SEM/EDS analysis were employed to ascertain the cleaning effectiveness and the absence of side effects on the samples after treatment. Oxalic acid-based DES was capable of removing rust stains from both stone and cellulose-based samples, while choline chloride/citric acid DES was effective only on stone specimens. The results suggest a new practical application of DESs for the elimination of rust from lithic and cellulosic substrates of precious and artistic value.

A detailed sensitivity analysis identifies the key factors influencing the enzymatic saccharification of lignocellulosic biomass

Corn stover is the most abundant form of crop residue that can serve as a source of lignocellulosic biomass in biorefinery approaches, for instance for the production of bioethanol. In such biorefinery processes, the constituent polysaccharide biopolymers are typically broken down into simple monomeric sugars by enzymatic saccharification, for further downstream fermentation into bioethanol. However, the recalcitrance of this material to enzymatic saccharification invokes the need for innovative pre-treatment methods to increase sugar conversion yield. Here, we focus on experimental glucose conversion time-courses for corn stover lignocellulose that has been pre-treated with different acid-catalysed processes and intensities. We identify the key parameters that determine enzymatic saccharification dynamics by performing a Sobol's sensitivity analysis on the comparison between the simulation results from our complex stochastic biophysical model, and the experimental data that we accurately reproduce. We find that the parameters relating to cellulose crystallinity and those associated with the cellobiohydrolase activity are predominantly driving the enzymatic saccharification dynamics. We confirm our computational results using mathematical calculations for a purely cellulosic substrate. On the one hand, having identified that only five parameters drastically influence the saccharification dynamics allows us to reduce the dimensionality of the parameter space (from nineteen to five parameters), which we expect will significantly speed up our fitting algorithm for comparison of experimental and simulated saccharification time-courses. On the other hand, these parameters directly highlight key targets for experimental endeavours in the optimisation of pre-treatment and saccharification conditions. Finally, this systematic and two-fold theoretical study, based on both mathematical and computational approaches, provides experimentalists with key insights that will support them in rationalising their complex experimental results.