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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,765 records · Page 98
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Anion effect on the topological frameworks of a series of manganese coordination polymers based on 1,4-bis(imidazol-1-yl)-benzene: Syntheses, crystal structures and magnetic properties

In this work, the rod-like ligand 1,4-bis(imidazol-1-yl)-benzene (bib) has been utilized as a building block to perform counterion researches on the structural diversities of coordination polymers. A series of new manganese compounds, ([Mn(bib){sub 3}(ClO{sub 4}){sub 2}](CHCl{sub 3}){sub 2}){sub n} (1), [Mn(bib){sub 2}(N{sub 3}){sub 2}]{sub n} (2), [Mn(bib){sub 2}(HCO{sub 2}){sub 2}]{sub n} (3), [Mn(bib){sub 2}(Ac){sub 2}]{sub n} (4), ([Mn(bib){sub 2}(CF{sub 3}SO{sub 3}){sub 2}](CH{sub 2}Cl{sub 2}){sub 4}){sub n} (5), and [Mn(bib){sub 2}(SO{sub 4})]{sub n} (6) have been successfully synthesized. Compound 1 shows a 3D interpenetrating α-Po network only based on the bib linker. Compounds 2 and 3 exhibit a 2D (4,4) layer with parallel and incline interpenetration, respectively. Compounds 4 and 5 display a parallel-packing 2D (4,4) layer with the porosity of 23.4% and 61.4%, respectively. Compound 6 furnishes a 3D α-Po framework with a 2D (4,4) layer pillared by the μ{sub 2}-SO{sub 4}{sup 2−} ion. The structural diversities among 1–6 have been carefully discussed, and the roles of counterions (from coordination affinity and molecular size) in the self-assembly of coordination polymers have also been well documented. Furthermore, magnetic properties of 6 have been carefully studied. - Graphical abstract: Six new compounds have been successfully synthesized. Structural studies reveal that the topology, entanglement and porosity are tunable by the counterion. Furthermore, the weak ferromagnetic coupling is conducted in 6. - Highlights: • Six new Mn{sup II} compounds have been synthesized. • Compounds 1–3 exhibit diverse interpenetrating frameworks. • Compounds 4 and 5 exhibit 3D packing porous architectures. • The tunable effect of counterion has been documented. • Magnetic properties of 6 have been studied by fitting the data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Ancillary ligand-assisted assembly of C{sub 3}-symmetric 4,4′,4″-nitrilotribenzoic acid with divalent Zn{sup 2+} ions: Syntheses, topological structures, and photoluminescence properties

4,4′,4″-nitrilotribenzoic acid (H{sub 3}L), a C{sub 3}-symmetric ligand, was found to self-assemble into two polymorphs driven by intermolecular hydrogen-bonding interactions. Reactions of this ligand with Zn{sup 2+} under solvothermal conditions resulted in four new coordination polymers bearing interesting structural motifs: [Zn{sub 2}(L){sub 2}(py){sub 2}]·2(H{sub 2}NMe{sub 2}){sup +}·DMF·2H{sub 2}O (1), [Zn{sub 2}(L)(H{sub 2}L)(bipy)]·1.5H{sub 2}O·Guest (2), [Zn{sub 2}(L){sub 2}(bipy)]·2(H{sub 2}NMe{sub 2}){sup +}·2DMF (3), and [Zn{sub 3}(L){sub 2}(bpa)]·2H{sub 2}O·Guest (4) (H{sub 3}L=4,4′,4′′-nitrilotribenzoic acid, DMF=dimethylformamide, py=pyridine, bipy=4,4′-bipyridine, bpa=1,2-bis(4-pyridyl)diazene). Single-crystal structural analysis revealed that compound 1 exhibits a rare example of twofold interpenetrating anionic 3D (3,3)-net framework containing helical channels, whereas in 2, the 3D pillar-layer structure generated from bipy-pillared Zn{sub 2}(L)(H{sub 2}L) layer is further reinforced by intermolecular hydrogen bonding among pairs of free –COOH units. Compound 3 shows an interesting entangled architecture of 2D→3D parallel polycatenation consisting five-coordinated Zn{sup 2+} ions. Compound 4 displays a 3D pillar-layer framework with trimeric Zn{sub 3}(CO{sub 2}){sub 6} serving as secondary building unit (SBU). The syntheses, structures, thermal stabilities, powder X-ray diffractions and solid-state photoluminescence properties for these crystalline materials have been carried out. In addition, supramolecular assembly of H{sub 3}L under solvothermal conditions will also be addressed. - Graphical abstract: Supramolecular assembly of 4,4′,4′′-nitrilotribenzoic acid and its ligand behavior toward Zn{sup 2+} were investigated, which exhibit two polymorphs of the free acid and four metal coordination polymers bearing interesting structural motifs. - Highlights: • Two polymorphs of H{sub 3}L showing different hydrogen-bonded network were obtained. • Tune over the structure of MOFs was achieved. • 1 has a 2-fold interpenetrating anionic 3D network containing helical channels. • Structures bearing free carboxylic acid (–COOH) unit are constructed in 2. • 3 represents a rare 2D+2D→3D catenation array containing five-coordinated Zn{sup 2+}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Carboxylate ligands induced structural diversity of zinc(II) coordination polymers based on 3,6-bis(imidazol-1-yl)carbazole: Syntheses, structures and photocatalytic properties

Solvothermal reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with 3,6-bis(1-imidazolyl)carbazole (3,6-bmcz) and 1,4-benzenedicarboxylic acid (1,4-H{sub 2}bdc), p-phenylenediacetic acid (p-H{sub 2}pda), benzophenone-4,4-dicarboxylic acid (H{sub 2}bpda) afforded three coordination polymers [Zn(1,4-bdc)(3,6-bmcz)]{sub n} (1), {[Zn(p-pda)(3,6-bmcz)]·1.5H_2O}{sub n} (2) and {[Zn(bpda)(3,6-bmcz)]·0.25H_2O}{sub n} (3). Complexes 1–3 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. Complex 1 shows 3D structure with 2D nets inclined polycatenation. Complexes 2 and 3 possess an extended 3D supramolecular architecture based on their respective 2D layers through hydrogen-bonding interactions and the π···π stacking interactions. The solid state luminescent and optical properties of 1–3 at ambient temperature were also investigated. A comparative study on their photocatalytic activity toward the degradation of methylene blue in polluted water was explored. - Graphical abstract: Reactions of Zn(NO{sub 3}){sub 2} and 3,6-(1-imidazolyl)carbazole with 1,4-benzenedicarboxylic acid, p-phenylenediacetic acid or benzophenone-4,4-dicarboxylic acid afforded three coordination polymers with different topologies and photocatalytic activity. - Highlights: • Reactions of 1,4-H{sub 2}bdc, p-H{sub 2}pda or H{sub 2}bpda with 3,6-bmcz and Zn(II) gave three CPs. • Complex 1 is a 3D entanglement. • Complex 2 or 3 is a 3D supramolecular structure based on different 2D layers. • Complex 2 exhibited good catalytic activity of methylene blue photodegradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

The effect of phase interface on the synthesis of SnS{sub 2}-Cu{sub 2}S

Highlights: • Opto-crystalline character of the composition of Cu{sub 2}S and S{sub 2}Sn was considered. • The formation Cu{sub 2}SnS{sub 3} is strongly related to phase separation at interface. • The entanglement of phases is strongly due to the chemical bond competition. • The suggested fluctuation region is approved by PL spectra. • Reconstruction and cluster formation is evident by formation of flat-spiral flowers. - Abstract: Optical character of crystal structure of the composition of two different semiconducting metallic sulfides, Cu{sub 2}S and S{sub 2}Sn, in pure phase formation of the ternary chalcogenide Cu{sub 2}SnS{sub 3} was considered. Because of the difficulties related to the phase separation at the definite Eutectic temperature for the composite formation, which is evident in optical absorption fluctuations, solvothermal synthesis in the intermediate temperature range 180–220 °C seems convenient where tetragonal crystal structure is investigated by XRD. Absorption fluctuations below E = E{sub g} were more pronounced for the lower limit case (180 °C) reflected in a sharp peak located at 1.48 eV on S1 as seen in UV-PL measurement. The characteristic behavior of the interface, resulting in the reconstruction and cluster formation due to the offset of bond rupturing displacement of atomic positions, is in favor of aggregation instead of agglomeration, which is evident by formation of small flat-spiral flowers in SEM images.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Optimization of the CVD parameters for ZnO nanorods growth: Its photoluminescence and field emission properties

Highlights: • Home-made CVD reactor fabricated and successfully used for growing ZnO nanorods. • Growth of nanostructures depends on several CVD process parameters. • CVD parameters, flow rate of carrier gas, substrate temperature, Au catalyst droplet size, growth time duration, etc. optimized. • The mechanism of crystal growth understood by studying FESEM/TEM/XRD. • Photoluminescence and Field emission studies done for defects and applications. - Abstract: Vertically aligned single crystalline ZnO nanorods arrays were grown on a silicon substrate in a CVD reactor using Au as a catalyst. The CVD parameters such as substrate temperature, catalyst layer thickness/morphology and reaction time play a crucial role in the synthesis of nanostructures by the vapor-liquid-solid process. By optimizing these various CVD parameters, highly controlled guided growth of ZnO nanorods was achieved. The structural and morphological properties of resultant ZnO nanorods were studied by means of X-ray diffraction, high-resolution transmission electron microscopy, selected area electron diffraction and field emission scanning electron microscopy. The photoluminescence spectroscopy was also done to investigate the defects in grown ZnO nanorods. The field emission results of nanorods array indicated that the properties of the field emission follow Fowler–Nordheim law. The nanorods (grown for 20 min) are vertically aligned on the substrate surface without entanglements and with good crystal quality as well which is very important for several applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Designing complex concentrated alloys with quantum machine learning and language modeling

Designing novel complex concentrated alloys (CCAs) is an essential topic in materials science. However, due to the complicated high-dimensional component-property relationship, tuning material properties by researchers’ experience is challenging, even when guided by physical or empirical rules. Here, we adopt quantum computing (QC) technology and machine learning models to provide a proof-of-concept application of QC in physical metallurgy. We propose a quantum support vector machine (QSVM) model to predict single-phase CCAs. We show that fine-tuned quantum kernels with entanglement deliver promising performance, with a maximum accuracy of 89.4%. The QSVM model is then used to identify 1,741 lightweight CCAs jointly with a new text-mining-based method. Meanwhile, we devise a controllable approach to study the effect of noise on model performance and find that the noise level needs to be minimized for high-performance QSVM models. Finally, this study provides a practical and general approach to designing CCAs based on quantum technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Extracting physics through deep data analysis

In recent decades humankind has become very apt at generating and recording enormous amounts of data, ranging from tweets and selfies on social networks, to financial transactions in banks and stores. The scientific community has not shunned this popular trend and now routinely produces hundreds of petabytes of data per year [1]. This is because materials and phenomena in the world around us exist in an interweaved, entangled form, which gives rise to the complexity of the Universe and determines the size and complexity of the data that describes it. Science and technology endeavor to unravel this convolution and extract pure components from the mixtures, be it in ore mining and metal smelting or separation of thermal conductivity into the electronic and phononic contributions. Decomposition of complex behavior is the key to understanding manifestations of Nature. However, tools to carry out this task are not readily available, and therefore, intricate systems often remain well-characterized experimentally, but still not well understood due to intricacy of the collected data. Lastly, in materials science, understanding and ultimately designing new materials with complex properties will require the ability to integrate and analyze data from multiple instruments, including computational models, designed to probe complementary ranges of space, time, and energy.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Exploring pressure-dependent inelastic deformation and failure in bonded granular composites: An energetic materials perspective

In polymer-filled granular composites, damage may develop in mechanical loading prior to material failure. Damage mechanisms such as microcracking or plastic deformation in the binder phase can substantially alter the material’s mesostructure. For energetic materials, such as solid propellants and plastic bonded explosives, these mesostructural changes can have far reaching effects including degraded mechanical properties, potentially increased sensitivity to further insults, and changes in expected performance. Unfortunately, predicting damage is nontrivial due to the complex nature of these composites and the entangled interactions between inelastic mechanisms. In this work, we assess the current literature of experimental knowledge, focusing on the pressure-dependent shear response, and propose a simple simulation framework of bonded particles to study four limiting-case material formulations at both meso- and macro-scales. Further, to construct the four cases, we systematically vary the relative interfacial strength between the polymer binder and granular filler phase and also vary the polymer’s glass transition temperature relative to operating temperature which determines how much the binder can plastically deform. These simulations identify key trends in global mechanical response, such as the emergence of strain hardening or softening regimes with increasing pressure which qualitatively resemble experimental results. By quantifying the activation of different inelastic mechanisms, such as bonds breaking and plastically straining, we identify when each mechanism becomes relevant and provide insight into potential origins for changes in mechanical responses. The locations of broken bonds are also used to define larger, mesoscopic cracks to test various metrics of damage. We primarily focus on triaxial compression, but also test the opposite case of triaxial extension to highlight the impact of Lode angle on mechanical behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Efficient and mechanically-robust organic solar cells based on vertical stratification modulation through sequential blade-coating

Mechanically durable organic solar cells (OSCs) with high efficiency are deemed as the ideal candidate for the power source of the next generation wearable electronic devices. However, the brittle nature of small molecules in most high-efficiency OSCs consisting of polymer and small molecule encourages easy formation of cracks in the photoactive film under deformation. Here, the vertical composition distribution of the active layer has been well optimized through sequential blade coating to realize highly deformable while efficient OSC. The optimized morphology exhibits distinct donor-rich and homogenous region distributed along the vertical direction in the bulk. The donor-rich region provides sufficient chain entanglements and strong interfaces beneficial for mechanical robustness of film, while homogeneously mixed region offers continuous interpenetrating network to maintain high device through-put, resulting in superior efficiency of 14.4% with high crack-onset strain (COS) of 30.5%. This efficiency versus COS combination is much higher than the best combination reported in all polymer systems (COS of 15.9% and efficiency of 11.1%). To the best of our knowledge, it is the highest COS value achieved in polymer-small molecule systems. As a result, the rational control over vertical stratification demonstrated here would guide researchers in the development of innovative wearable electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Time-reversed Young’s experiment: Deterministic, diffractionless second-order interference effect

The classic Young’s double-slit experiment exhibits first-order interference, producing alternating bright and dark fringes shaped by the diffraction effect of the slits. In contrast, here we demonstrate that its time-reversed configuration generates an ideal, deterministic second-order ‘ghost’ interference pattern free from diffraction and first-order effects with the use of only a position-fixed detector. The pattern’s size is governed by the dimensions of the ‘effectively extended light source’ formed by point emitter(s). Beyond highlighting the nonreciprocal physics between the two configurations, this system unlocks a range of novel phenomena inaccessible in traditional double-slit experiments. These include fully programmable, digitized interference fringe formations and the ability to align the pattern plane with the source plane on the same side of the setup. Remarkably, our proposed experiment achieves these outcomes without relying on nonclassical correlations or quantum entanglement. Here, by restoring time-reversal symmetry and eliminating diffraction, our theoretical analysis reveals that this approach offers exciting potential for advancing optical imaging and sensing technologies with improved transverse and longitudinal phase-shift sensitivity and resolution limit beyond current limitations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2017

Computing with a single qubit faster than the computation quantum speed limit

Here, the possibility to save and process information in fundamentally indistinguishable states is the quantum mechanical resource that is not encountered in classical computing. I demonstrate that, if energy constraints are imposed, this resource can be used to accelerate information-processing without relying on entanglement or any other type of quantum correlations. In fact, there are computational problems that can be solved much faster, in comparison to currently used classical schemes, by saving intermediate information in nonorthogonal states of just a single qubit. There are also error correction strategies that protect such computations.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Do atoms age?

Time evolution generically entangles a quantum state with environmental degrees of freedom. The resulting increase in entropy changes the properties of that quantum system leading to “aging”. It is interesting to ask if this familiar property also applies to simple, single particle quantum systems such as the decay of a radioactive particle. We propose a test of such aging in an ion clock setup where we probe for temporal changes to the energies of the electronic state of an ion containing a radioactive nucleus. Such effects are absent in standard quantum mechanics and this test is thus a potent null test for violations of quantum mechanics. As a proof of principle, we show that these effects exist in causal non-linear modifications of quantum mechanics.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

Implications of styrenic triblock copolymer gel mechanics on midblock bridging fraction

Triblock copolymer gels have garnered considerable scientific interest over the past few decades and are used in a variety of applications including consumer cushioning, pressure-sensitive adhesives, and ballistics gels. While many of their applications rely upon understanding mechanical properties, mechanical studies of block copolymer gels are relatively disjointed with each focusing on specific copolymers, which inherently have a fixed molecular weight and composition. Here, the present study examines the quasistatic mechanical response of styrenic triblock copolymer gels composed of seven unique triblock copolymers at various concentrations. Resultant stress-extension data is fitted with the slip-tube network (STN) theory that describes gel mechanics based upon crosslinked network (G c ) and chain entanglement (G e ) modulus contributions. Collectively, modulus contributions imply that midblock bridging is independent of copolymer identity (i.e., molecular weight and block fraction) and dependent on triblock copolymer concentration via F b ∝ φ ABA 0.91±0.39 over the concentration range examined (φ ABA = 0.05–0.39). Gels composed of a complementary diblock-triblock copolymer pair were subsequently analyzed to explore the influence of interlocking loop-loop and loop-bridge pairs within the effective midblock bridging population. These results point to the presence of a physically significant quantity of interlocked loops, but quantitative analysis was inconclusive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hyperfine structures and isotopic shifts of uranium transitions using tunable laser spectroscopy of laser ablation plumes

We report isotopic shifts and hyperfine structures of selected U transitions employing tunable spectroscopy viz: laser-induced fluorescence and laser absorption spectroscopy of laser ablation plumes. The laser-produced plasmas were produced during ns laser ablation on a natural U metal which contains 0.7% 235U. Our results show that isotopic shifts between 238U and 235U are entangled with hyperfine structures of 235U. The isotopic ratio obtained using laser-induced fluorescence is affected by optical saturation effect. Time-resolved laser absorption spectroscopy is carried out for evaluating the optical absorption and estimating the hyperfine constants.

(020.3260) Isotope shifts↗
DOE OSTI2017

Quantum phase transition and destruction of Kondo effect in pressurized SmB 6

SmB 6 has been a well-known Kondo insulator for decades, but recently attracts extensive new attention as a candidate topological system. Studying SmB 6 under pressure provides an opportunity to acquire the much-needed understanding about the effect of electron correlations on both the metallic surface state and bulk insulating state. Here we do so by studying the evolution of two transport gaps (low temperature gap E l and high temperature gap E h ) associated with the Kondo effect by measuring the electrical resistivity under high pressure and low temperature (0.3 K) conditions. We associate the gaps with the bulk Kondo hybridization, and from their evolution with pressure we demonstrate an insulator-to-metal transition at ~4 GPa. At the transition pressure, a large change in the Hall number and a divergence tendency of the electron-electron scattering coefficient provide evidence for a destruction of the Kondo entanglement in the ground state. In conclusion, our results raise the new prospect for studying topological electronic states in quantum critical materials settings.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Shining light on nanoscale ‘vine-on-stick’ eutectic structures in the Al-Ce-Ni system

Multiphase eutectics often comprise entangled solid phases with nanoscale periodicity, making it difficult to unravel their 3D connectivity using conventional 2D techniques. Among such systems, the three-phase eutectic Al-Al 11 Ce 3 -Al 3 Ni stands out for its ultrafine (∼100 nm) interphase spacing and promising creep resistance, yet its microstructure remains relatively unexplored despite its potential for high-temperature applications. Here, we use scanning hard X-ray microscopy with an unprecedented ∼10 nm pixel size to resolve its 3D morphology. Reconstructions reveal a novel “vine-on-stick” motif, wherein Al 11 Ce 3 wraps around Al 3 Ni pillars. Analysis of phase tortuosities confirms that Al 11 Ce 3 exhibits more convoluted morphologies than Al 3 Ni. No orientation relationship was observed between the two intermetallics, suggesting that growth is controlled by local solute gradients rather than epitaxy. Fragmentation of intermetallics along their longitudinal axis suggests a Rayleigh-type breakup mechanism in solid state. The “vine-on-stick” pattern may generalize to other alloy systems with variable interfacial anisotropies and low mutual solubilities.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Changes in cholesterol homeostasis and acute phase response link pulmonary exposure to multi-walled carbon nanotubes to risk of cardiovascular disease

Adverse lung effects following pulmonary exposure to multi-walled carbon nanotubes (MWCNTs) are well documented in rodents. However, systemic effects are less understood. Epidemiological studies have shown increased cardiovascular disease risk after pulmonary exposure to airborne particles, which has led to concerns that inhalation exposure to MWCNTs might pose similar risks. We analyzed parameters related to cardiovascular disease, including plasma acute phase response (APR) proteins and plasma lipids, in female C57BL/6 mice exposed to a single intratracheal instillation of 0, 18, 54 or 162 μg/mouse of small, entangled (CNT{sub Small}, 0.8 ± 0.1 μm long) or large, thick MWCNTs (CNT{sub Large}, 4 ± 0.4 μm long). Liver tissues and plasma were harvested 1, 3 and 28 days post-exposure. In addition, global hepatic gene expression, hepatic cholesterol content and liver histology were used to assess hepatic effects. The two MWCNTs induced similar systemic responses despite their different physicochemical properties. APR proteins SAA3 and haptoglobin, plasma total cholesterol and low-density/very low-density lipoprotein were significantly increased following exposure to either MWCNTs. Plasma SAA3 levels correlated strongly with pulmonary Saa3 levels. Analysis of global gene expression revealed perturbation of the same biological processes and pathways in liver, including the HMG-CoA reductase pathway. Both MWCNTs induced similar histological hepatic changes, with a tendency towards greater response following CNT{sub Large} exposure. Overall, we show that pulmonary exposure to two different MWCNTs induces similar systemic and hepatic responses, including changes in plasma APR, lipid composition, hepatic gene expression and liver morphology. The results link pulmonary exposure to MWCNTs with risk of cardiovascular disease. - Highlights: • Systemic and hepatic alterations were evaluated in female mice following MWCNT instillation. • Despite being physicochemically different, the two MWCNTs induced a similar systemic acute phase response. • We found a close correlation between plasma SAA levels and pulmonary Saa3 transcription levels. • Similar changes in plasma lipid levels and in the hepatic transcriptome were observed. • Our results indicate a link between pulmonary exposure to MWCNTs with risk of cardiovascular disease.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2019

Predicting Protein–Polymer Block Copolymer Self-Assembly from Protein Properties

Protein–polymer bioconjugate self-assembly has attracted a great deal of attention as a method to fabricate protein nanomaterials in solution and the solid state. To identify protein properties that affect phase behavior in protein–polymer block copolymers, a library of 15 unique protein- b -poly(N-isopropylacrylamide) (PNIPAM) copolymers comprising 11 different proteins was compiled and analyzed. Many attributes of phase behavior are found to be similar among all studied bioconjugates regardless of protein properties, such as formation of micellar phases at high temperature and low concentration, lamellar ordering with increasing temperature, and disordering at high concentration, but several key protein-dependent trends are also observed. In particular, hexagonal phases are only observed for proteins within the molar mass range 20–36 kDa, where ordering quality is also significantly enhanced. While ordering is generally found to improve with increasing molecular weight outside of this range, most large bioconjugates exhibited weaker than predicted assembly, which is attributed to chain entanglement with increasing polymer molecular weight. Additionally, order–disorder transition boundaries are found to be largely uncorrelated to protein size and quality of ordering. However, the primary finding is that bioconjugate ordering can be accurately predicted using only protein molecular weight and percentage of residues contained within β sheets. This model provides a basis for designing protein–PNIPAM bioconjugates that exhibit well-defined self-assembly and a modeling framework that can generalize to other bioconjugate chemistries.

59 BASIC BIOLOGICAL SCIENCES↗