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DOE OSTI2021

Structural Color Production in Melanin-Based Disordered Colloidal Nanoparticle Assemblies in Spherical Confinement

Melanin is a ubiquitous natural pigment that exhibits broadband absorption and high refractive index. Despite its widespread use in structural color production, how the absorbing material, melanin, affects the generated color is unknown. Using a combined molecular dynamics and finite-difference time-domain computational approach, here we investigates structural color generation in one-component melanin nanoparticle-based supraparticles (called supraballs) as well as binary mixtures of melanin and silica (nonabsorbing) nanoparticle-based supraballs. Experimentally produced one-component melanin and one-component silica supraballs, with thoroughly characterized primary particle characteristics using neutron scattering, produce reflectance profiles similar to the computational analogs, confirming that the computational approach correctly simulates both absorption and multiple scattering from the self-assembled nanoparticles. These combined approaches demonstrate that melanin's broadband absorption increases the primary reflectance peak wavelength, increases saturation, and decreases lightness factor. Additionally, the dispersity of nanoparticle size more strongly influences the optical properties of supraballs than packing fraction, as evidenced by the production of a larger range of colors when size dispersity is varied versus packing fraction. For binary melanin and silica supraballs, the chemistry-based stratification allows for more diverse color generation and finer saturation tuning than does the degree of mixing/demixing between the two chemistries.

broadband absorption↗

DOE OSTI2019

Activity and Thermostability of GH5 Endoglucanase Chimeras from Mesophilic and Thermophilic Parents

Cellulases from glycoside hydrolase family 5 (GH5) are key endoglucanase enzymes in the degradation of diverse polysaccharide substrates and are used in industrial enzyme cocktails to break down biomass. The GH5 family shares a canonical (βα) 8 -barrel structure, where each (βα) module is essential for the enzyme’s stability and activity. Despite their shared topology, the thermostability of GH5 endoglucanase enzymes can vary significantly, and highly thermostable variants are often sought for industrial applications. Based on the previously characterized thermophilic GH5 endoglucanase Egl5A from Talaromyces emersonii ( Te Egl5A), which has an optimal temperature of 90°C, we created 10 hybrid enzymes with elements of the mesophilic endoglucanase Cel5 from Stegonsporium opalus ( So Cel5) to determine which elements are responsible for enhanced thermostability. Five of the expressed hybrid enzymes exhibit enzyme activity. Two of these hybrids exhibited pronounced increases in the temperature optimum (10 and 20°C), the temperature at which the protein lost 50% of its activity ( T 50 ) (15 and 19°C), and the melting temperature ( T m ) (16.5 and 22.9°C) and extended half-lives ( t 1/2 ) (~240- and 650-fold at 55°C) relative to the values for the mesophilic parent enzyme and demonstrated improved catalytic efficiency on selected substrates. The successful hybridization strategies were validated experimentally in another GH5 endoglucanase, Cel5 from Aspergillus niger ( An Cel5), which demonstrated a similar increase in thermostability. Based on molecular dynamics (MD) simulations of both the So Cel5 and Te Egl5A parent enzymes and their hybrids, we hypothesize that improved hydrophobic packing of the interface between α 2 and α 3 is the primary mechanism by which the hybrid enzymes increase their thermostability relative to that of the mesophilic parent So Cel5.Thermal stability is an essential property of enzymes in many industrial biotechnological applications, as high temperatures improve bioreactor throughput. Many protein engineering approaches, such as rational design and directed evolution, have been employed to improve the thermal properties of mesophilic enzymes. Structure-based recombination has also been used to fuse TIM barrel fragments, and even fragments from unrelated folds, to generate new structures. However, little research has been done on GH5 endoglucanases. In this study, two GH5 endoglucanases exhibiting TIM barrel structure, So Cel5 and Te Egl5A, with different thermal properties, were hybridized to study the roles of different (βα) motifs. This work illustrates the role that structure-guided recombination can play in helping to identify sequence function relationships within GH5 enzymes by supplementing natural diversity with synthetic diversity.

09 BIOMASS FUELS↗

DOE OSTI2020

Carbon Fiber and Syntactic Foam Hybrid Materials via Core–Shell Material Extrusion Additive Manufacturing

Abstract Biological materials often employ hybrid architectures, such as the core–shell (C–S) motif present in porcupine quills and plant stems, to achieve unique specific properties and performance. Drawing inspiration from these natural materials, a new method to fabricate lightweight and stiff C–S architected filaments is reported. Specifically, a C–S printhead conducive to printing highly loaded fiber‐filled inks, as well as a new low‐density syntactic foam ink, are utilized to 3D‐print C–S architectures consisting of a syntactic epoxy foam core surrounded by a stiff carbon fiber‐reinforced epoxy composite shell. Effective printing of test specimens and structures with controlled geometry, composition, and architecture is demonstrated. The new foam ink exhibits density as low as 0.68 g cm −3 and C–S structures exhibit up to 25% higher specific flexural stiffness ( E 1/3 /ρ) than either constituent alone. Finally, a new mechanical model is presented to predict this performance improvement while accounting for potential eccentricity of the core.

Pack, Robert C.↗

DOE OSTI2021

Towards synthetic L 1 0 -FeNi: Detecting the absence of cubic symmetry in Laser-Ablated Fe-Ni nanoparticles

The L 1 0 crystal structure underlines an important class of chemically ordered alloys that exhibits uniaxial magnetocrystalline anisotropy. The near-equiatomic L 1 0 -FeNi extracted from meteorites has demonstrated intriguing magnetic properties for permanent magnet applications. However, the synthesis of this chemically ordered non-cubic structure has been a longstanding challenge. Here, in this work, we demonstrate the absence of cubic symmetry in near-equiatomic Fe-Ni nanoparticles synthesized by picosecond-pulsed laser ablation in liquids. The non-cubic phase detected in these particles can only be L 1 0 -FeNi or hexagonal close-packed (HCP) FeNi, and the absence of cubic symmetry was unequivocal. The orientation relationship between the non-cubic phase and the adjacent cubic phase was characterized by a series of transmission electron microscopy (TEM) techniques, which consistently suggests that the formation of the non-cubic phase involves a martensitic transformation process.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Conceptual magnet design study for fusion nuclear science facility [Magnet design study for fusion nuclear science facility]

The Fusion Nuclear Science Facility (FNSF) is a nuclear confinement device to provide the integrated fusion environment with fusion reactor components. The FNSF is the stepping stone to bridge the technical gaps of burning plasma and nuclear science between the International Thermal Nuclear Experimental Reactor (ITER), currently under construction in the south of France, and the demonstration power plant (DEMO). For the next-step fusion reactors, resistive copper magnet cannot be a sustainable solution due to large power consumption in coils of large size needed. Both Low temperature superconductor (LTS) and high temperature superconductor (HTS) are considered for the FNSF magnet design based on the state-of-the-art fusion superconducting magnet technology. Input parameters to FNSF magnet design include magnetic field of 7.5 T at plasma center with a major radius of 4.8 m and minor radius of 1.2 m, and a peak field of over 16 T on the TF coils. The high magnetic field can be achieved by using the high performance ternary Restack Rod Process (RRP) Nb3Sn strands for toroidal field (TF) magnets and a high aspect ratio rectangular cable-in-conduit conductor (CICC) design. The conductor design concept and TF coil winding pack composition and dimension are discussed based on the horizontal maintenance scheme. Neutron radiation limits for the LTS and HTS conductors and electrical insulation materials are reviewed based on the available materials previously tested. The material radiation limits for FNSF magnets are defined as part of the conceptual design studies. In conclusion, the global structural analysis of FNSF magnets based on the radial build was performed to validate feasibility for the plant layout toward horizontal maintenance and global structural integrity of its magnet system.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2017

Functionalized Fullerenes for Highly Efficient Lithium Ion Storage: Structure-Property-Performance Correlation with Energy Implications

Here, we report that spherical C 60 derivatives with well-defined molecular structures hold great promise to be advanced anode materials for lithium-ion batteries (LIBs). We studied four C 60 molecules with various functional groups, including pristine C 60 , carboxyl C 60 , ester C 60 , and piperazine C 60 . The comparison of these C 60 s elucidated a strong correlation between functional group, overall packing (crystallinity), and the performance of C 60 -based LIBs. Specifically, carboxyl C 60 and neutral ester C 60 showed higher charge capacities than pristine C 60 , whereas positively-charged piperazine C 60 exhibited lower capacity. The highest charge capacity was achieved on the carboxyl C 60 0 (861 mAh g -1 at 100th cycle), which is five times higher than that of pristine C 60 (170 mAh g -1 ), more than double the theoretical capacity of commercial graphite (372 mAh g -1 ), and even higher than the theoretical capacity of graphene (744 mAh g -1 ). Carboxyl C 60 also showed a high capacity at a fast discharge-charge rate (370 mAh g -1 at 5 C). The exceptional performance of carboxyl C 60 can be attributed to multiple key factors. They include the complex formation between lithium ions and oxygen atoms on the carboxyl group, the improved lithium-binding capability of C 60 cage due to electron donating from carboxylate groups, the electrostatic attraction between carboxylate groups and lithium ions, and the large lattice void space and high specific area due to carboxyl functionalization. In conclusion, this study indicates that, while maintaining the basic C 60 electronic properties, functionalization with desired groups can achieve remarkably enhanced capacity and rate performance for lithium storage, thus holding great promise for future LIBs.

25 ENERGY STORAGE↗

DOE OSTI2017

Deuterium charge exchange recombination spectroscopy from the top of the pedestal to the scrape off layer in H-mode plasmas

Recent completion of the thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on DIII-D enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the edge, providing high resolution measurements of the pedestal and steep gradient edge region of H-mode plasmas. The complexities of the D α spectrum require fitting with a comprehensive model, as well as using iterative collisional radiative modeling to determine the underlying thermal deuterium ion properties. Large differences in the structure and magnitude of impurity (C 6+ ) and main-ion (D + ) toroidal rotation profiles are seen in the H-mode pedestal. Additionally the D + temperature can be half the value of the C 6+ temperature at the separatrix and shows more of a pedestal structure. Typically only the impurity properties are measured and the main-ion properties are either assumed to be the same, or inferred using neoclassical models, which require validation in the steep gradient region. Furthermore, these measured differences have implications for transport model validation, intrinsic rotation studies, pedestal stability, and the boundary conditions for scrape off layer and plasma material interactions studies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS2016

HIAD Advancements and Extension of Mission Applications

The Hypersonic Inflatable Aerodynamic Decelerator (HIAD) technology has made significant advancements over the last decade with flight test demonstrations and ground development campaigns. The first generation (Gen-1) design and materials were flight tested with the successful third Inflatable Reentry Vehicle Experiment flight test of a 3-m HIAD (IRVE-3). Ground development efforts incorporated materials with higher thermal capabilities for the inflatable structure (IS) and flexible thermal protection system (F-TPS) as a second generation (Gen-2) system. Current efforts and plans are focused on extending capabilities to improve overall system performance and reduce areal weight, as well as expand mission applicability. F-TPS materials that offer greater thermal resistance, and ability to be packed to greater density, for a given thickness are being tested to demonstrated thermal performance benefits and manufacturability at flight-relevant scale. IS materials and construction methods are being investigated to reduce mass, increase load capacities, and improve durability for packing. Previous HIAD systems focused on symmetric geometries using stacked torus construction. Flight simulations and trajectory analysis show that symmetrical HIADs may provide L/D up to 0.25 via movable center of gravity (CG) offsets. HIAD capabilities can be greatly expanded to suit a broader range of mission applications with asymmetric shapes and/or modulating L/D. Various HIAD concepts are being developed to provide greater control to improve landing accuracy and reduce dependency upon propulsion systems during descent and landing. Concepts being studied include a canted stack torus design, control surfaces, and morphing configurations that allow the shape to be actively manipulated for flight control. This paper provides a summary of recent HIAD development activities, and plans for future HIAD developments including advanced materials, improved construction techniques, and alternate geometry concepts that will greatly expand HIAD mission applications.

Johnson, R. Keith↗

NASA NTRSDate not supplied

Understanding Dynamic Challenges of In-Space Modular Assembly and Reconfiguration of Flexible Structures from Early Efforts

A review of 1980s to early 2010s research supporting and documenting successful missions for on-orbit assembly of large space structures was conducted to bring together flexible space structure dynamics challenges and progress toward solutions. Research in this period focused on issues ranging from ground validation via unique test beds to in-space modal characterization and model adjustment. The phased assembly of the International Space Station (ISS), along with its evolving structural loads and dynamics, provides the central example, with ground and on-orbit tests of other systems providing contributing and contrasting examples of potential value for researchers facing today’s challenges.

Modal Space Testing↗

DOE OSTI2016

Synthesis, electrochemistry, STM investigation of oligothiophene self-assemblies with superior structural order and electronic properties

Here, three oligothiophene (terthiophene, tetrathiophene and pentathiophene) derivatives are synthesized and their monolayer self-assemblies on gold (Au) are prepared via Au–S covalent bond. Our UV–Vis experimental characterization of solution reveals the dependence of the optical properties on the conjugation length of the oligothiophenes, which compares well with Time-Dependent Density Functional Theory (TDDFT) simulations of spectra of individual chromophores. Photoluminescent spectra of thin films show pronounced red shifts compared to that of solutions, suggesting strong inter-oligomer interactions. The comparative studies of cyclic voltammograms of tetrathiophene from solution, cast film and self-assembled monolayer (SAM) indicate presence of one, two, and three oxidized species in these samples, respectively, suggesting a very strong electronic coupling between tetrathiophene molecules in the SAM. Scanning tunneling microscopy (STM) imaging of SAMs of the tetrathiophene on an atomically flat Au surface exhibits formation of monolayer assemblies with molecular order, and the molecular packing appears to show an overlay of oligothiophene molecules on top of another one. In contrast, the trimer and pentamer images show only aggregated species lacking long-range order on the molecular level. Such trends in going from disordered–ordered–disordered monolayer assemblies are mainly due to a delicate balance between inter-chromophore π–π couplings, hydrophobic interaction and the propensity to form Au–S covalent bond. Such hypothesis has been validated by our computational results suggesting different interaction patterns of oligothiophenes with odd numbered and even numbered thiophene repeat units placed in a dimer configuration. Finally, observed correlations between oligomer geometry and structural order of monolayer assembly elucidate important structure–property relationships and have implications for these molecular structures in organic optoelectronic devices and energy devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Spontaneous formation of highly periodic nano-ripples in inclined deposition of Mo/Si multilayers

We investigated the growth of Mo/Si multilayers (ML) deposited using a highly collimated flux of ion-beam sputtered particles for a wide range of deposition angles. Growth of the multilayers at normal and moderately inclined deposition is dominated by surface relaxation resulting in smooth interfaces of the multilayer stack. The first signs of interface roughening are observed at a deposition angle of 45° with respect to the normal to the substrate surface. At an oblique angle of 55°, the ML interfaces undergo fast progressive roughening from the substrate to the top of the ML stack, leading to the formation of ripples which are perpendicular to the deposition flux direction. Deposition of the multilayer at an angle of 65° results in a highly periodic lateral ripple structure with a period of 10 nm. The mature ripple pattern forms during growth of only the first few layers and then stabilizes. The ripples propagate through the whole ML stack with almost no changes in frequency and amplitude, resulting in a highly periodic bulk array composed of silicon and molybdenum nano-rods closely packed in a 6-fold symmetric lattice. Here, we present a simple model for the ripple growth, which gives results that are in good agreement with experimental data.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Structural study of hcp and liquid iron under shock compression up to 275 GPa

Here we combine nanosecond laser shock compression with in situ picosecond x-ray diffraction to provide structural data on iron up to 275 GPa. We constrain the extent of hcp-liquid coexistence, the onset of total melt, and the structure within the liquid phase. Our results indicate that iron, under shock compression, melts completely by 258(8) GPa. A coordination number analysis indicates that iron is a simple liquid at these pressure-temperature conditions. We also perform texture analysis between the ambient body-centered-cubic (bcc) α, and the hexagonal-closed-packed (hcp) high-pressure ε-phase. We rule out the Rong-Dunlop orientation relationship (OR) between the α and ε - phase s. However, we cannot distinguish between three other closely related ORs: Burger's, Mao-Bassett-Takahashi, and Potter's OR. The solid-liquid coexistence region is constrained from a melt onset pressure of 225(3) GPa from previously published sound speed measurements and full melt [246.5(1.8)–258(8) GPa] from x-ray diffraction measurements, with an associated maximum latent heat of melting of 623 J/g. This value is lower than recently reported theoretical estimates and suggests that the contribution to the earth's geodynamo energy budget from heat release due to freezing of the inner core is smaller than previously thought. Melt pressures for these nanosecond shock experiments are consistent with gas gun shock experiments that last for microseconds, indicating that the melt transition occurs rapidly.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Synthesis, antityrosinase activity of curcumin analogues, and crystal structure of (1E,4E)-1,5-bis(4-ethoxyphenyl)penta-1,4-dien-3-one

Five derivatives of curcumin analogue (R = OCH{sub 2}CH{sub 3} (1), R = N(CH{sub 3}){sub 2} (2), R = 2,4,5-OCH{sub 3} (3), R = 2,4,6-OCH{sub 3} (4), and R = 3,4,5-OCH{sub 3} (5)) were synthesized and characterized by {sup 1}H NMR, FT-IR and UV–Vis spectroscopy. The synthesized derivatives were screened for antityrosinase activity, and found that 4 and 5 possess such activity. The crystal structure of 1 was determined by single crystal X-ray diffraction: monoclinic, sp. gr. P2{sub 1}/c, a = 17.5728(15) Å, b = 5.9121(5) Å, c = 19.8269(13) Å, β = 121.155(5)°, Z = 4. The molecule 1 is twisted with the dihedral angle between two phenyl rings being 15.68(10)°. In the crystal packing, the molecules 1 are linked into chains by C−H···π interactions and further stacked by π···π interactions with the centroid–centroid distance of 3.9311(13) Å.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2017

Spatial variation in microbial processes controlling carbon mineralization within soils and sediments

Soils have a defining role in global carbon cycling, having one of the largest dynamic stocks of C on earth—3300 Pg of C are stored in soils, which is three-times the amount stored in the atmosphere and more than the terrestrial land plants. An important control on soil organic matter (SOM) quantities is the mineralization rate. It is well recognized that the rate and extent of SOM mineralization is affected by climatic factors and mineral-organic matter associations. What remained elusive is to what extent constraints on microbial metabolism induced by the respiratory pathway, and specifically the electron acceptor in respiration, control overall rates of carbon mineralization in soils. Therefore, physical factors limiting oxygen diffusion such as soil texture and aggregate size (soil structure) may therefore be central controls on C mineralization rates. The goal of our research was therefore to determine if variations in microbial metabolic rates induced by anaerobic microsites in soils are a major control on SOM mineralization rates and thus storage. We performed a combination of laboratory experiments and field investigations will be performed to fulfill our research objectives. We used laboratory studies to examine fundamental factors of respiratory constraints (i.e., electron acceptor) on organic matter mineralization rates. We ground our laboratory studies with both manipulation of field samples and in-field measurements. Selection of the field sites is guided by variation in soil texture and structure while having (other environmental/soil factors constant. Our laboratory studies defined redox gradients and variations in microbial metabolism operating at the aggregate-scale (cm-scale) within soils using a novel constructed diffusion reactor. We further examined micro-scale variation in terminal electron accepting processes and resulting C mineralization rates within re-packed soils. A major outcome of our research is the ability to quantitatively place the importance of aggregate-based heterogeneity in microbial redox processes and the resulting lack of oxygen on the rate of carbon mineralization. Collectively, our research shows that anaerobic microsites are prevalent in soils and are important regulators of soil carbon persistence, shifting microbial metabolism to less efficient anaerobic respiration and selectively protecting otherwise bioavailable, reduced organic compounds such as lipids and waxes from decomposition. Further, shifting from anaerobic to aerobic conditions leads to a 10-fold increase in volume-specific mineralization rate, illustrating the sensitivity of anaerobically protected carbon to disturbance. Vulnerability of anaerobically protected carbon to future climate or land use change thus constitutes a yet unrecognized soil carbon-climate feedback that should be incorporated into terrestrial ecosystem models.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2017

Device for Temporal Measurement of Loads in Parachute Suspension Systems

In order to understand the distribution of loads in parachutes, the NASA Low Density Supersonic Decelerators (LDSD) project developed a wireless instrument to measure loads in the parachute suspension lines. The load cells are titanium links that are connected in the primary structural load path of the parachute system. Strain gages measure the elongation of the links and an onboard data acquisition system records the data to ash memory. The load cells have onboard power, and include a radio transceiver that is used to receive timing information. The load cells are designed to be interfaced with cordage, packed in a parachute bag, and deployed with a standard parachute deployment. The devices are triggered passively during the deployment of the parachute. Prototype devices with a mass of 100 grams and a load capability of 16,000 lbs were built as a proof of concept.

Brandeau, Erich J.↗

DOE OSTI2016

Origin of texture development in orthorhombic uranium

We study texture evolution of alpha-uranium (α-U) during plane strain compression and uniaxial compression to high strains at different temperatures. We combine a multiscale polycrystal constitutive model and detailed analysis of texture data to uncover the slip and twinning modes responsible for the formation of individual texture components. The analysis indicates that during plane strain compression, floor slip (001)[100] results in the formation of two pronounced {001}{001} texture peaks tilted 10–15° away from the normal toward the rolling direction. During both high-temperature (573 K) through-thickness compression and plane strain compression, the active slip modes are floor slip (001)[100] and chimney slip 1/2{110} <11¯0> with slightly different ratios. {130} <31¯0> deformation twinning is profuse during rolling and in-plane compression and decreases with increasing temperature, but is not as active for through-thickness compression. Lastly, we comment on some similarities between rolling textures of α-U, which has a c/a ratio of 1.734, and those that develop in hexagonal close packed metals with similarly high c/a ratios like Zn (1.856) and Cd (1.885) and are dominated by basal slip.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Proposed crystal structure of carbadox, C 11 H 10 N 4 O 4

A model for the crystal structure of carbadox has been generated and refined using synchrotron X-ray powder diffraction data and optimized using density functional theory techniques. Carbadox crystallizes in space groupP2 1 (#4) witha= 13.8155(3),b= 21.4662(1),c= 16.3297(3) Å,β= 110.0931(7)°,V= 4548.10(3) Å 3 , andZ= 16. The crystal structure is characterized by approximately parallel stacking of the eight independent carbadox molecules parallel to thebc-plane. There are two different molecular configurations of the eight carbadox molecules; five are in the lower-energy configuration and three are in a ~10% higher-energy configuration. This arrangement likely achieves the lowest-energy crystalline packing via hydrogen bonding. Hydrogen bonds link the molecules both within and between the planes. Each of the amino groups forms a N–H⋯O hydrogen bond to an oxygen atom of the 1,4-dioxidoquinoxaline ring system of another molecule. The result is four pairs of hydrogen-bonded molecules, which form rings with graph setR2,2(14). Variation in specimen preparation can affect the preferred orientation of particles considerably. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF®).

Materials Science↗

DOE OSTI2015

Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.

09 BIOMASS FUELS↗