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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Relaxation dynamics of water in the vicinity of cellulose nanocrystals

Water molecules near cellulose nanocrystals (CNCs; produced via the sulfuric acid-catalyzed hydrolysis of wood pulp) are believed to relax slower than those in the bulk liquid, which may result in unique properties of CNC aqueous dispersions. Herein this study analyzed the polarization behavior of water molecules in CNC aqueous dispersions and other reference samples using a dielectric relaxation spectroscopy (DRS) technique in the microwave frequency range (0.2–20 GHz). As the CNC concentration increases, two slow relaxation components become prominent. The comparison with DRS data of aqueous dispersions of nanoporous silica, polyvinyl alcohol (PVA), and hairy CNC (HCNC) with amorphous chains protruding from both ends suggested that these slow relaxation modes of water near CNC surfaces cannot be attributed to direct hydrogen bonding interactions with the hydroxyl (OH) groups exposed and immobilized at the solid surface. Instead, they are similar to the water molecules interacting with OH groups attached to flexible polymer chains. Molecular dynamics (MD) simulations of the polarization behavior of water near the (110) facet of cellulose Iβ crystals confirmed that the interactions of water molecules with the cellulose crystal surface do not cause slower relaxations in the frequency range studied via the DRS. These results indicated that the CNC surface cannot be depicted with the crystallographic facets of cellulose Iβ; instead, it resembles a polymer-brush surface on which the short glucan residues or fragments of the strong acid-catalyzed hydrolysis process are swollen and extended into the aqueous phase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Deciphering the non-linear impact of Al on chemical durability of silicate glass

The role of Al in aluminosilicate glasses remains somewhat a mystery: at low concentrations, it increases the resistance to hydrolysis of the glass, whereas at high concentrations an opposite effect is observed. To understand the origin of the phenomenon on a fundamental atomistic scale, we performed 577 MD simulations and applied potential mean force (PMF) calculations to estimate the activation barriers for hydrolysis and to statistically correlate them with local structural features of the glass. Models of pure silicate and aluminosilicate glasses are constructed and investigated. PMF simulation results are further validated by the experimental measurements and revealed that Al is very easy to dissociate, but it also increases the glass chemical durability through significantly increasing both the strength of Si and network connectivity of the glass. In contrast, at high Al concentration, preferential dissolution of Al weakens the silicate network, which it supposes to strengthen, and so the glass resistance becomes poor. Through PMF calculations, we evaluated the activation barriers for dissociating bonds around Al as 0.49 eV, which is less than a half of the energy to dissociate bonds around Si in pure silicate (1.22 eV) and around Si in aluminosilicate glass (1.34 eV), all these energy differences being statistically significant. Molecular structural level investigation revealed that Si with Al as a second neighbor in the glass network has a significantly higher activation energy for dissociation than Si in pure silicate glass. Furthermore, the proposed approach opens the way to the development of quantitative predictive models of glass durability.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Nitrogen derived from Combined Algal Processing supports algae cultivation for biofuels

Algae biomass, a biofuel feedstock with potential to reduce global CO 2 emissions, is currently too expensive Nitrogen, a significant input and life cycle cost, requires research on recycling and additional sources to reduce costs. Integral to nitrogen recycling is the knowledge of actual nitrogen requirements in outdoor ponds, thus data from the Unified Field Studies of the Algae Testbed Public-Private Partnership was analyzed. The data showed that Nannochloropsis oceanica used 14–24 mg/L NH 4 + per harvest cycle for robust growth. Nitrogen recycled directly from the algae conversion process will likely be the primary source of nitrogen for algae cultivation. Harvested algae can be fractionated via Combined Algal Processing (CAP), where algae are pretreated, fermented, and the fuel feedstocks (e. g. ethanol, lipids) are removed leaving a nitrogen rich slurry. Chlorella vulgaris grew robustly in nitrogen-free media supplemented with CAP residues through 4 harvest cycles with no inhibition. The amount of nitrogen as free ammonium available for recycling directly without further processing was insufficient (~4% of total needed), thus the nitrogen fixing bacteria, Azotobacter vinelandii, was investigated as a means for increasing ammonium concentration in CAP residues. This organism was shown to be proficient at growth on sugars liberated from algae biomass during pretreatment and sustained algae growth using A. vinelandii supernatants was also demonstrated. Using Azotobacter to increase ammonium concentrations on-site using an inexpensive biological process to generate the necessary ammonium for outdoor algae cultivation improves sustainability of algae biofuels by avoiding the energy intensive steps of typical ammonium production and transport. Furthermore, these results show that byproducts of algae conversion begin to close nitrogen demand and, with further supplementation by diazotrophic bacteria or protein hydrolysis, may completely replace current energyintensive and costly industrial nitrogen sources offering a path to increased economic feasibility and improved life cycle analysis of algae-based biofuels.

09 BIOMASS FUELS↗
DOE OSTI2023

Effect of pelleting on the enzymatic digestibility of corn stover

Pelleting of lignocellulosic biomass to improve its transportation, storage and handling impacts subsequent processing and conversion. Here, this work reports the role of high moisture pelleting in the enzymatic digestibility of corn stover prior to pretreatment, together with associated substrate characteristics. Pelleting increases the digestibility of unpretreated corn stover, from 8.2 to 15.5% glucan conversion, at 5% solid loading using 1 FPU Cellic® CTec2 per g solids. Compositional analysis indicates that loose and pelleted corn stover have similar non-dissolvable compositions, although their extractives are different. Enzymatic hydrolysis of corn stover after size reduction to normalize particle sizes and removal of extractives confirms that pelleting improves corn stover digestibility. Such differences may be explained by the decreased particle size, improved substrate accessibility, and hydrolysis of cross-linking structures induced by pelleting. These findings are useful for the development of processing schemes for sustainable and efficient use of lignocellulose.

09 BIOMASS FUELS↗
DOE OSTI2022

Coupling AFEX and steam-exploded sugarcane residue pellets with a room temperature CIIII-activation step lowered enzyme dosage requirements for sugar conversion

In this study, the potential integration of steam explosion (StEx) and ammonia fiber expansion (AFEX) with existing sugar/ethanol mills to form decentralized pre-processing depots was explored. Both StEx and AFEX pretreatment facilitated the production of sugarcane bagasse (SCB) and cane leaf matter (CLM) pellets with significantly higher bulk density, mechanical durability, and hydrophobicity relative to their untreated biomass pellet controls. However, ethanol production from standalone StEx and AFEX-treated SCB and CLM pellets required enzyme dosages greater than 21 mg/g glucan to achieve enzymatic hydrolysis sugar yields of 75% and ethanol titres greater than 40 g.L -1 . Coupling AFEX-treated SCB or CLM pellets with a room temperature CIII I -activation step using liquid ammonia lowered enzyme dosage requirements by more than 50% without affecting ethanol titers and production yields (greater than300 L per Mg residual dry matter raw dry biomass (RDM)). In contrast, treating StEx-treated pellets with CIIII-activation using liquid ammonia did not result in similar enzyme dosage reductions, due to pseudo-lignin formation, leading to enzyme deactivation and/or lignin blockage that retarded enzymatic hydrolysis at low enzyme dosages. A gross energy conversion assessment revealed that low enzyme dosage (3-4 mg enzyme/g RDM) ethanol and electricity co-production from AFEX and CIII I -activated SCB and CLM can recover up to 73% of the energy in the untreated biomass, compared to 54% recovered by StEx and CIII I -activation. The results from this work suggest that StEx or AFEX based pre-processing depots can produce dense and mechanically durable biomass pellets. The AFEX-treated pellets can be easily upgraded using a room temperature CIII I -activation step at the biorefinery to significantly reduce bioconversion enzymes.

42 ENGINEERING↗
DOE OSTI2026

Effect of H 2 O on the ethylene glycol/alkali dismantling of bagasse for high-value conversion

Using a high-boiling alcohol system to dismantle main components of biomass is a feasible technology. Reducing dismantle operating costs and improving dismantle efficiency are essential for promoting the green, economical, and sustainable development of biomass refining. Therefore, based on the low cost and chemical properties of H 2 O at high temperature, the effects of different H 2 O dosages in NaOH-catalyzed ethylene glycol (HBAA) system on the dismantling efficiency of bagasse, surface lignin coverage, recovered-lignin activity and enzymatic hydrolysis efficiency were investigated. Compared with the HBAA dismantling system without H 2 O, the HBAA system with 60% w/v H 2 O can obviously increase the removal rates of lignin and hemicellulose, while recovering up to 99% of cellulose and significantly declining surface lignin coverage, thus enhancing the enzymatic hydrolysis efficiency. Additionally, the results of density functional theory calculations and 2D HSQC NMR analysis prove that the synergy between H 2 O and ethylene glycol can promote the esterification reaction occurrence at the α-C carbon cation in β-O-4 structure of lignin, thereby protecting the β-O-4 aromatic ether bond. Simultaneously, when the H 2 O dosage increase from 0% to 60%, the enzymatic yield increases from 84.51% to 93.74% with an enzyme load of 10 FPU/g. Based on experimental results, this study conducted a techno-economic analysis of bagasse dismantling for ethanol and co-production of lignin, achieving a minimum ethanol selling price of $\$$1.07 per kg. Here, in this study, a green and economical solution for dismantling the main components of bagasse is developed, which is important for the high-value conversion of bagasse.

Ethylene glycol↗
DOE OSTI2025

Engineering PHL7 for Improved Poly(Ethylene Terephthalate) Depolymerization via Rational Design and Directed Evolution

Enzymatic depolymerization of poly(ethylene terephthalate) (PET) has emerged as a promising approach for polyester recycling, and, to date, many natural and engineered PET hydrolase enzymes have been reported. For industrial use, PET hydrolases must achieve high depolymerization extent and exhibit excellent thermostability. Here, we engineered a natural PET hydrolase, Polyester Hydrolase Leipzig #7 (PHL7), through rational design and directed evolution using a high-throughput screening platform. Four new enzymes were engineered with enhanced properties compared with the parent enzyme, wild-type PHL7 (PHL7-WT), and other benchmark PET hydrolases, under the tested conditions. In bioreactors, the exemplary engineered enzyme, PHL7-Jemez, exhibited improved ability to depolymerize amorphous PET film compared with PHL7-WT at 2.9% and 20% substrate loadings, with 37% and 270% higher hydrolysis, respectively, after 48 h. This study develops several state-of-the-art PET hydrolases and demonstrates a directed evolution platform to engineer high-performance enzymes, which can accelerate enzyme discovery toward improved biocatalytic recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Impact of non-irrigation on 1G and 2G bioethanol potential of oilcane feedstock: A field to fuel pipeline study

This study evaluates the bioethanol potential in response to irrigation (IR) and non-irrigation (NIR) of oilcane (OC) during a seasonal drought prior harvest. The juice was extracted through mechanical pressing of stems and fermented by Ethanol Red® yeast to produce first-generation bioethanol. Hydrothermal pretreatment followed by enzymatic hydrolysis of bagasse was performed to produce monomeric sugars from structural carbohydrates. The hydrolysates were fermented with engineered yeast for second-generation bioethanol production. The irrigated oilcane juice (276.3 ± 8.9 g/L) constitutes higher sugar concentrations than non-irrigated oilcane juice (236.5 ± 2.2 g/L). The enzymatic hydrolysis of IR-OC and NIR-OC pretreated bagasse yielded similar concentrations of 247.5 ± 2.22 and 249.7 ± 4.98 g/L fermentable sugars. Industry-relevant bioethanol titers of ≥99 g/L and ≥75 g/L were achieved from juice and hydrolysates, respectively. Therefore, the non-irrigation regime did not impact the 1G and 2G bioethanol titers. However, the overall bioethanol yield can be lower due to the reduction of stem yield (8 %) per hectare.

09 BIOMASS FUELS↗
DOE OSTI2020

Production of levulinic acid and biocarbon electrode material from corn stover through an integrated biorefinery process

To overcome the inefficient biomass conversion, waste generation, and lack of co-production in biorefineries, an integrated process was proposed for the conversion of corn stover into levulinic acid and biocarbon electrode material. Corn stover was pretreated through hydrothermal process using 0.45 wt% K 2 CO 3 which removed 76 wt% lignin and 85 wt% xylan while preserving 83 wt% glucan. This was followed by acid hydrolysis to produce levulinic acid at varying H 2 SO 4 concentrations and reaction time in a batch reactor at 190 °C. At a reaction time of 5 min in 2 wt% H 2 SO 4 , 35.8 wt% and 30 wt% glucan in raw and pretreated corn stover was converted to levulinic acid, respectively. The residue from acid hydrolysis was converted into biocarbon for supercapacitor electrodes via a two-step thermal activation process which showed a specific capacitance of 120 F g -1 . The proposed integrated biorefinery concept provides multiple value-added products for a greater financial and environmental sustainability.

09 BIOMASS FUELS↗
DOE OSTI2022

Land use-land cover gradient demonstrates the importance of perennial grasslands with intact soils for building soil carbon in the fertile Mollisols of the North Central US

The impact of land use change and agricultural management on the cycling of soil organic carbon (SOC) is not well understood, limiting our ability to manage for, and accurately model, soil carbon changes at both local and regional scales. To address this issue, here we combined long-term soil incubations with acid-hydrolysis and dry combustion to parse total SOC (C t ) into three operationally defined SOC pools (active, slow, and recalcitrant) from 9 long-term sites with varying land uses on current and former tallgrass prairie soil. Land uses represented a gradient of soil disturbance histories including remnant prairie, restored prairie, grazed pasture, annual crop rotations, and continuous maize. Dry combustion was used to estimate total carbon (C t , physical), while acid hydrolysis of both the active (C a ) and slow (C s ) pools was used to estimate a recalcitrant carbon pool (C r , chemical). Non-linear modeling of CO 2 efflux data from the long-term incubations was then used to estimate C a , and the decomposition rates of both C a and C s (k a and k r , biological). The size of the slow pools C s was then defined mathematically as C t- (C a + C r ). Remnant prairie had the highest C t , while cool-season pasture and a 35-y-old restored prairie had higher C t than the other agricultural systems. All agricultural systems, including pasture, had the highest fraction of C t as C r (~50%), whose mean residence time (MRT) in these soils is ≥500 years (Paul et al., 2001a) demonstrating that this fraction persists, while the more labile fractions were lost over the course of a few months (C a ) to a few decades (C s ) as a result of tillage-intensive agriculture. The two- to four-decade MRT time of C s indicated a pool likely to be more responsive to the 20 to 40 years of land-use practices used at some of the sites. The C s pool was largest in the remnant- and 35-y-old prairies indicating significant C accrual and stabilization compared to the agricultural ecosystems. Interestingly, the remnant prairie maintained the highest C a pool as well, demonstrating the strong connection between the quantity of fresh C inputs and the potential for long-term C stabilization and accrual. The accumulation of C in active (≈labile) pools as a first step toward long-term stabilization highlights the tenuous nature of early carbon gains, which can be quickly lost in response to climate change or poor management.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

The physiochemical alteration of flax fibers structuring components after different scouring and bleaching treatments

Scouring and bleaching are essential steps in flax yarn production; however, in many cases, these treatments have relatively low selectivity on non-cellulosic polysaccharides (NCPs) and lignin. Herein, the specific chemical properties of flax fibers through a variety of scouring and/or bleaching procedures are reviewed to understand their correlations with the mechanical and morphological characteristics. The hydrolysis behaviors of hemicellulose and lignin are different from those of cellulose during chlorine-alkali-oxygen (Cl-AO), enzyme-alkali-oxygen (EAO), and alkali-oxygen (AO) treatments, while the structural hemicellulose polysaccharides fractions were not affected by acid pretreatment followed by alkali scouring (AA) treatment. It was found that the unbleached AA treatment improved scouring efficiency to the greatest extent by decreasing 73.3 % of hemicellulose content and 59.8 % of lignin content compared to the untreated flax fibers and obtained the highest tensile strength (6.58 cN/dtex) and elongation (3.73 %). Delignification was more crucial on fiber tenacity and fineness than hemicellulose removal (R 2 = 0.71, 0.79 vs R 2 = 0.46, 0.61). Within the hemicellulose fractions, a corresponding beneficial relationship between the xylan (XYL) composition and flax fiber properties is presented. The correlation of GM and GGM contents in hemicellulose with flax fiber length was significant with R 2 value 0.97 and 0.99, respectively. This work provides insight into the hydrolysis behavior of hemicellulose and a basis for developing scouring and/or bleaching models that can predict fiber properties.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Development of an enzyme cocktail to bioconvert untapped starch in sweet sorghum processing by-products: Part II. Application and economic potential

Demand for bioethanol and other biochemicals produced from agricultural crops has increased. Sweet sorghum has been identified as a promising bioenergy crop as it can produce starch, sugar, and fibrous biomass. During processing, starch accumulates in the juice sediments and clarification mud. And, while currently not recovered, it can be made accessible for fermentation by enzymatic hydrolysis. The enzymatic hydrolysis of starch in sweet sorghum processing streams was investigated, followed by fermentation of the resulting glucose to ethanol. The juice sediment contained sufficient starch to increase fermentable sugars by 127%, allowing a final ethanol titer of 11.1 vol%. The economics for fermentation of only dissolved sugars (Scenario 1) versus dissolved sugars and hydrolyzed starch (Scenario 2) were compared using a technoeconomic model. Fixed capital cost was found to be similar for both scenarios. For a set harvest period, Scenario 2 could produce 20% more ethanol; however, if the distillation by-product was dried and marketed as animal feed, Scenario 1 was more cost effective. A plant producing 5.6–5.7 Mkg of fuel ethanol per year had a minimum selling price of $0.67/kg of ethanol with concurrent production of animal feed and zero cost sweet sorghum processing. Finally, even with these optimistic assumptions, the estimated production cost was higher than the current wholesale price of fuel ethanol.

09 BIOMASS FUELS↗
DOE OSTI2022

Beneficial effect of surfactant in adsorption/desorption of lignocellulose-degrading enzymes on/from lignin with different structure

Nonionic surfactant Tween 80 is effective in alleviating the adsorption of lignocellulose-degrading enzymes onto lignin. However, the impacts of lignin structural characteristics on this mitigation effect of Tween 80 were still not clear. Herein, effects of Tween 80 on cellulase and xylanase adsorption on different enzymatic residual lignins (ERLs) and poplar samples were investigated. Besides, effects of Tween 80 on desorption of the two enzyme preparations from different ERLs and poplar samples were also evaluated. By adding Tween 80, the inhibition of ERLs to cellulase hydrolysis was offset and the positive role of Tween 80 in Avicel hydrolysis with presence of ERLs was more effective. Binding strength of cellulase with ERLs was alleviated from 236.0 – 410.9 to 43.9 – 116.6 mL/g after adding 0.5 mg/mL Tween 80. When ERLs was more hydrophobic and had more condensed phenolic OH, the alleviation effect of Tween 80 on cellulase adsorption on ERLs was intensified but its positive effect on enhancing cellulase desorption was weakened. Tween 80 was effective in increasing xylanase activity and preventing xylanase deactivation. Further, with the increase of lignin content and phenolic OH in pretreated poplar, the effect of Tween 80 in alleviating xylanase adsorption on poplar samples was intensified but the effect in enhancing xylanase desorption from poplar samples was weakened. The results provided distinct findings to understand the interaction between Tween 80 and cellulase/xylanase in enzymatic saccharification of lignocelluloses.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Assessing microbial systems and process configurations for improved ethanol production from sugary stovers by integrating soluble sugars and holocellulose

Here, this study evaluated microbial systems and technological approaches to configure the whole slurry co-fermentation process for ethanol biosynthesis from a novel stover system rich in sugars. Two approaches, namely separate and simultaneous hydrolysis and co-fermentation (SHCF and SSCF, respectively), were investigated using Escherichia coli monoculture and E. coli-yeast coculture. The SSCF with E. coli monoculture produced 32.75 g/L ethanol, representing only 44.87% yield, which left 65.13 g/L of total sugars unconverted and exhibited limited xylose consumption. Subsequently, a coculture-based SHCF significantly enhanced sugar consumption, leading to increase in ethanol yield and concentration to 66.94% and 48.86 g/L, respectively. Nevertheless, xylose utilization remained minimal due to the preference for glucose and the inhibitory effects of certain compounds. Thereafter, modification of the medium composition by supplementing betaine and sodium metabisulfite improved ethanol production to 53.18 g/L by reducing the toxic effects of inhibitors. Finally, a dual-phase SSCF (DP-SSCF) was explored by allowing the consumption of sugars from the pretreated slurry in the first phase, followed by concurrent cellulose hydrolysis and utilization of the resulting glucose in the second phase. This strategy increased ethanol titer to 63.14 g/L, with 84.3% yield and 0.88 g/L/h productivity.

09 BIOMASS FUELS↗
DOE OSTI2021

Insights into the dual cleavage activity of the GH16 laminarinase enzyme class on β-1,3 and β-1,4 glycosidic bonds

Glycoside hydrolases (GH) are involved in the degradation of a wide diversity of carbohydrates and present several biotechnological applications. Many GH families are composed of enzymes with a single well-defined specificity. In contrast, enzymes from the GH16 family can act on a range of different polysaccharides, including β-glucans and galactans. SCLam, a GH16 member derived from a soil metagenome, an endo-β-1,3(4)-glucanase (EC 3.2.1.6), can cleave both β-1,3 and β-1,4 glycosidic bonds in glucans, such as laminarin, barley β-glucan, and cello-oligosaccharides. A similar cleavage pattern was previously reported for other GH16 family members. However, the molecular mechanisms for this dual cleavage activity on (1,3)- and (1,4)-β-D-glycosidic bonds by laminarinases have not been elucidated. In this sense, we determined the X-ray structure of a presumably inactive form of SCLam co-crystallized with different oligosaccharides. The solved structures revealed general bound products that are formed due to residual activities of hydrolysis and transglycosylation. Biochemical and biophysical analyses and molecular dynamics simulations help to rationalize differences in activity towards different substrates. Our results depicted a bulky aromatic residue near the catalytic site critical to select the preferable configuration of glycosidic bonds in the binding cleft. Altogether, these data contribute to understanding the structural basis of recognition and hydrolysis of β-1,3 and β-1,4 glycosidic linkages of the laminarinase enzyme class, which is valuable for future studies on the GH16 family members and applications related to biomass conversion into feedstocks and bioproducts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A fusion of the Bacteroides fragilis ferrous iron import proteins reveals a role for FeoA in stabilizing GTP-bound FeoB

Iron is an essential element for nearly all organisms, and under anoxic and/or reducing conditions, Fe 2+ is the dominant form of iron available to bacteria. The ferrous iron transport (Feo) system is the primary prokaryotic Fe 2+ import machinery, and two constituent proteins (FeoA and FeoB) are conserved across most bacterial species. However, how FeoA and FeoB function relative to one another remains enigmatic. In this work, we explored the distribution of feoAB operons encoding a fusion of FeoA tethered to the N-terminal, G-protein domain of FeoB via a connecting linker region. We hypothesized that this fusion poises FeoA to interact with FeoB to affect function. To test this hypothesis, we characterized the soluble NFeoAB fusion protein from Bacteroides fragilis, a commensal organism implicated in drug-resistant infections. Using X-ray crystallography, we determined the 1.50-Å resolution structure of BfFeoA, which adopts an SH3-like fold implicated in protein–protein interactions. Using a combination of structural modeling, small-angle X-ray scattering, and hydrogen–deuterium exchange mass spectrometry, we show that FeoA and NFeoB interact in a nucleotide-dependent manner, and we mapped the protein–protein interaction interface. Finally, using guanosine triphosphate (GTP) hydrolysis assays, we demonstrate that BfNFeoAB exhibits one of the slowest known rates of Feo-mediated GTP hydrolysis that is not potassium-stimulated. Importantly, truncation of FeoA from this fusion demonstrates that FeoA–NFeoB interactions function to stabilize the GTP-bound form of FeoB. Taken together, our work reveals a role for FeoA function in the fused FeoAB system and suggests a function for FeoA among prokaryotes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Medium controlled aggregative growth as a key step in mesoporous silica nanoparticle formation

Near monodisperse mesoporous silica nanoparticles (MSN) represent a promising and rapidly developing type of mesoporous silica materials; however, the vast data on their synthesis remains unorganized and ill-understood. We systematically studied the formation of MSN under basic and neutral conditions using various temperatures, CTAB concentrations, hydrolyzing agents (triethanolamine, ammonia, phosphate buffers), and media with different colloidal stabilization properties (with ethanol as a cosolvent and monovalent salts). In the typical conditions for the preparation of stable MSN colloids, the particle size was controlled by colloidal stabilization by the medium (solvent type, ionic strength, and surfactant concentration) in agreement with the “aggregative growth” mechanism, rather than by solely the hydrolysis and condensation rates conventionally used for data interpretation in the classical nucleation theory. Medium properties (pH, ion types and concentration, polarity) also defined the efficiency of silica-surfactant cooperative self-assembly, which directly affected the porosity, mesopore size and pore wall thickness. Interestingly, this traditional silica-surfactant route showed a limited effect on the particle size, emphasizing the dominating role of colloidal stabilization in the studied reaction conditions. In situ pH measurements showed that every reaction medium has unique pH evolution profiles depending on the buffer capacity, hydrolysis and condensation rates. Reaction systems that fail to maintain the working pH can lead to non-porous products or undesired particle morphology and size distribution. The established particle formation mechanism allowed us to formulate comprehensive guidelines for preparing relatively concentrated colloids of near monodisperse (PDI 5–15%) mesoporous 30–700 nm silica spheres with variable porosity and mesopore size. Here, these findings will be particularly useful in designing new mesoporous silica-containing materials for biomedical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Production of chitosan-based composite film reinforced with lignin-rich lignocellulose nanofibers from rice husk

Lignocellulosic nanofibers (LCNFs), implying lignin-containing cellulose fibers, maintain the properties of both lignin and cellulose, which are hydrophobic and hydrophilic, respectively. The presence of hydrophobic lignin in LCNFs is expected to be an economical and attractive option that can improve the thermal and mechanical properties of polymers. Thus, this study was conducted to produce lignin-rich LCNFs from sugar-rich waste obtained from rice husks after acidic pretreatment. The LCNFs were produced from the lignin-rich solid fractions obtained after pretreatment and enzymatic hydrolysis, which were then incorporated as an additive into a chitosan-based film. The variations in lignin content in the range of approximately 50.6%-66.8% in differently obtained LCNFs gave significantly different optical strengths and mechanical properties. These controllable processes may allow for customized film formation. Additionally, the glucose-rich liquid fractions obtained after pretreatment and enzymatic hydrolysis were used as a substrate for ethanol fermentation to achieve total utilization of rice husk biomass waste. In conclusion, the lignin-rich biomass fraction holds promise as a suitable material for chitosan-LCNF film and has the potential to increase the economic feasibility of the biomaterial industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗