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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

The Significant Differences in Solvation Thermodynamics of C1–C3 Oxygenates in Hydrophilic versus Hydrophobic Pores of a Hydrophilic Ti-FAU Zeolite Model

The rates of catalytic reactions have been observed to be dramatically different in zeolites, depending on if they are hydrophobic or hydrophilic. Hypotheses aimed at explaining this behavior have pointed to various solvent molecule and zeolite properties as having influence on entropy. Herein, the influence of various solvent and adsorbate properties on the solvation energies, entropies, and free energies of eleven C1-C3 oxygenates in hydrophobic and hydrophilic pores within a hydrophilic model of Ti-FAU zeolite are tested. The results indicate significant variation in the calculated solvation thermodynamics depending on the adsorbate type, as well as if it is bound within a hydrophobic or hydrophilic pore. Further, while solvation energies are related to solvent-adsorbate interactions, solvation entropies have multiple contributions, and these differ depending on if the adsorbate is in a hydrophobic or hydrophilic pore. Specifically, solvation entropies in hydrophobic pores are related to solvent structural properties, whereas solvation entropies in hydrophilic pores are related to adsorbate polarity. Here, the large range of results obtained from two different pores within one zeolite model with minimal unique adsorption sites suggests that solvation behavior in zeolites is complicated and that the phenomena that control observed performance depend on the zeolite, reaction, and solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mass spectrometry-based proteomics for analysis of hydrophilic phosphopeptides

Protein phosphorylation is a critical post-translational modification (PTM), with cell signaling networks being tightly regulated by protein phosphorylation. Despite recent technological advances in reversed-phase liquid chromatography (RPLC)-mass spectrometry (MS)-based proteomics, comprehensive phosphoproteomic coverage in complex biological systems remains challenging, especially for hydrophilic phosphopeptides that often have multiple phosphorylation sites. Herein we describe an MS-based phosphoproteomics protocol for effective quantitative analysis of hydrophilic phosphopeptides. This protocol was built upon a simple tandem mass tag (TMT)-labeling method for significantly increasing peptide hydrophobicity, thus effectively enhancing RPLC-MS analysis of hydrophilic peptides. Through phosphoproteomic analyses of MCF7 cells, this method was demonstrated to greatly increase the number of identified hydrophilic phosphopeptides and improve MS signal detection. With the TMT labeling method, we were able to identify a previously unreported phosphopeptide from the G protein-coupled receptor (GPCR) CXCR3, QPpSSSR, which is thought to be important in regulating receptor signaling. This protocol is easy to adopt and implement, and thus should have broad utility for effective RPLC-MS analysis of the hydrophilic phosphoproteome as well as other highly hydrophilic analytes.

Hydrophilic phosphopeptide, Phosphoproteomics, TMT↗
DOE OSTI2021

High-performance multiblock PEMs containing a highly acidic fluorinated-hydrophilic domain for water electrolysis

The present paper describes the design and evaluation of novel hydrophilic–hydrophobic poly(arylene ether sulfone) (PAES) multiblock copolymers for their synergistic effects upon transport properties and their potential use in proton exchange membrane water electrolysis. The multiblock copolymers are prepared via a coupling reaction between (i) a hydrophilic segment consisting of a disulfonated quinone fluorinated biphenyl group that contains fluorine moieties next to the sulfonated groups to increase the acidity, and (ii) hydrophobic segments composed of non-sulfonated biphenyl sulfone to provide dimensional stability. Two different lengths (molecular weights; 5k and 10k, where k represents 10 3 g mol -1 ) of hydrophobic segments are used to investigate the effects of the membrane properties compared with those of Nafion® and PAES random copolymer (i.e., BPSH40). Atomic force microscopy images of the BPSH40 and multiblock membranes are shown to agree closely with a mesoscale simulation, thus confirming the importance of the morphological effect upon the transport properties. Furthermore, the multiblock copolymer with a higher proportion of hydrophilic segments (10 k–5k) was shown to provide enhanced performance (3.41 A cm -2 at 1.9 V) compared to the multiblock copolymer with equal proportions of hydrophilic and hydrophobic segments (10 k–10 k) due to the greater continuity of nano-sized ionic channels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solution Structure and Hydration Forces between Mica and Hydrophilic Versus Hydrophobic Surfaces

Solid-liquid interfaces are central to a range of interesting phenomena including catalysis, heterogeneous nucleation, water desalination, and biomolecular assembly. While three-dimensional Fast Force Mapping (3D FFM) has emerged as a technique for resolving interfacial solution structure at the molecular scale, key challenges for data interpretation persist, most notably regarding the influence of the probe on the measured structure. Using the mica-water system as a case study, we investigate the effect of hydrophilic and hydrophobic probes on interfacial solution structure measured by 3D FFM. Data from hydrophilic silicon-based probes are in good agreement with molecular dynamics simulations, wherein the innermost water molecules adsorb preferentially at the surface ditrigonal cavity sites followed by two subsequent hydration layers. In contrast, the hydrophobic carbon-based probes detect vertical oscillatory features, but do not show lateral patterning that matches the underlying mica lattice. At high ionic strength, up to six of these oscillatory features are observed extending 2 nm into the solution phase with an average spacing of 0.29 ± (0.04) nm. Further, we also determine that the repulsive hydration force between mica and the hydrophilic probe depends on the nature and concentration of ions in solution. Specifically, solutions with stronger ion-water and ion-ion interactions increase the interfacial viscosity, which results in a stronger repulsive hydration force as the probe approaches the surface. Based on these observations, we present a scheme for controlling the outcomes of particle attachment and aggregation by varying the solution conditions to tune the hydration force.

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

Super‐Hydrophilic Microporous Ni(OH) x /Ni 3 S 2 Heterostructure Electrocatalyst for Large‐Current‐Density Hydrogen Evolution

Abstract Exploiting active and stable non‐precious metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at large current density plays a key role in realizing large‐scale industrial hydrogen generation. Herein, a self‐supported microporous Ni(OH) x /Ni 3 S 2 heterostructure electrocatalyst on nickel foam (Ni(OH) x /Ni 3 S 2 /NF) that possesses super‐hydrophilic property through an electrochemical process is rationally designed and fabricated. Benefiting from the super‐hydrophilic property, microporous feature, and self‐supported structure, the electrocatalyst exhibits an exceptional HER performance at large current density in 1.0 M KOH, only requiring low overpotential of 126, 193, and 238 mV to reach a current density of 100, 500, and 1000 mA cm −2 , respectively, and displaying a long‐term durability up to 1000 h, which is among the state‐of‐the‐art non‐precious metal electrocatalysts. Combining hard X‐rays absorption spectroscopy and first‐principles calculation, it also reveals that the strong electronic coupling at the interface of the heterostructure facilitates the dissociation of H 2 O molecular, accelerating the HER kinetics in alkaline electrolyte. This work sheds a light on developing advanced non‐precious metal electrocatalysts for industrial hydrogen production by means of constructing a super‐hydrophilic microporous heterostructure.

Chemistry↗
DOE OSTI2021

Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites

Ti-silicates activate H 2 O 2 to form Ti-hydroperoxo and Ti-peroxo intermediates that can react with alkenes to form epoxide products. Comparisons of kinetics for 1-octene epoxidation with H 2 O 2 on Ti-BEA and Ti-MFI catalysts with different hydrophilicities in methanol (CH 3 OH) or acetonitrile (CH 3 CN) solvents show the significance of the solvent for stabilizing catalytically-relevant species and the complex interdependencies between solvent, catalyst topology, and hydrophilicity. Epoxidation turnover rates are higher in CH 3 CN than CH 3 OH for Ti-BEA, but the opposite trend is observed for Ti-MFI. Ti-silicates with greater silanol densities, however, give greater epoxidation turnover rates than their hydrophobic counterparts in both solvents. Kinetic, spectroscopic, and thermodynamic analyses show that differences in turnover rates mainly arise from changes in the stabilization of reactive surface species by solvent mediated interactions, because the mechanism of the reaction and stability of the fluid-phase reactants remain similar in CH 3 CN and CH 3 OH. Specifically, apparent activation free energy values ($ΔG^{‡}_{App}$) indicate that surface intermediates responsible for alkene epoxidation are stabilized to a greater extent in CH 3 CN on Ti-BEA and in CH 3 OH on Ti-MFI. Hydrophilic Ti-silicates present lower ($ΔG^{‡}_{App}$) values regardless of solvent identity, which suggests that these differences correspond to the number of hydrogen-bonding solvent molecules found near reactive species bound to Ti active sites. Finally, taken together, these findings demonstrate the role of solvent molecules in allowing reactive intermediates to recognize the properties of active sites beyond the length-scale of covalent bonds, which carry implications for epoxidation but also other reactions within solvent-filled pores of microporous materials.

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

Simultaneously Enhanced Hydrophilicity and Stability of a Metal-Organic Framework via Post-Synthetic Modification for Water Vapor Sorption/Desorption

With increasing demands for high-performance water sorption materials, metal-organic frameworks (MOFs) have gained considerable attention due to their high maximum uptake capacities. In many cases, however, high overall capacity is not necessarily accomplishing high working capacity under operating conditions, due to insufficient hydrophilicity and/or water stability. Herein, we present a post-synthetic modification (PSM) of MOF-808, with di-sulfonic acids enhancing simultaneously its hydrophilicity and water stability without sacrificing its uptake capacity of ≈30 mmol g -1 . Further, di-sulfonic acid PSM enabled a shift of the relative humidity (RH) associated with a sharp step in water vapor sorption from 35–40 % RH in MOF-808 to below 25 % RH. While MOF-808 lost uptake capacity and crystallinity over multiple sorption/desorption cycles, the di-sulfonic acid PSM MOF-808 retained >80 % of the original capacity. PSM MOF-808 exhibited good hydrothermal stability up to 60 °C and high swing capacity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions

Molecular aggregates exhibit emergent properties, including the collective sharing of electronic excitation energy known as exciton delocalization, that can be leveraged in applications such as quantum computing, optical information processing, and light harvesting. In a previous study, we found unexpectedly large excitonic interactions (quantified by the excitonic hopping parameter J m,n ) in DNA-templated aggregates of squaraine (SQ) dyes with hydrophilic-imparting sulfo and butylsulfo substituents. Here, we characterize DNA Holliday junction (DNA-HJ) templated aggregates of an expanded set of SQs and evaluate their optical properties in the context of structural heterogeneity. Specifically, we characterized the orientation of and J m,n between dyes in dimer aggregates of non-chlorinated and chlorinated SQs. Here, three new chlorinated SQs that feature a varying number of butylsulfo substituents were synthesized and attached to a DNA-HJ via a covalent linker to form adjacent and transverse dimers. Various characteristics of the dye, including its hydrophilicity (in terms of log P o/w ) and surface area, and of the substituents, including their local bulkiness and electron withdrawing capacity, were quantified computationally.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Study of the water dynamics near hydrophilic, nanostructured CuO surfaces by quasielastic and inelastic neutron scattering

We have used quasielastic and inelastic neutron scattering to investigate the structure, dynamics, and phase transitions of water interacting with superhydrophilic CuO surfaces that not only possess a strong affinity for water but also a “grass-like” topography that is rough on both micro- and nanoscales. Here, we report quasielastic neutron scattering (QENS) measurements on two samples differing in water content at five temperatures below 280 K. The QENS spectra show water undergoing two different types of diffusive motion near the CuO surfaces: a “slow” translational diffusion occurring on a nanosecond time scale and a faster rotational motion. Further from the surfaces, there is “fast” translational diffusion comparable in rate to that of bulk supercooled water and the rotational motion occurring in the interfacial water. Analysis of the QENS spectra supports wetting of water to the CuO blades as seen in electron microscopy images. In addition, we observe an anomalous temperature dependence of the QENS spectra on cooling from 270 to 230 K with features consistent with a liquid–liquid phase transition. We suggest that the solvent-like properties of the coexisting bulk-like water in our CuO samples are a significant factor in determining the temperature dependence of the interfacial water’s dynamics. Our results are compared with those obtained from two well-studied substrate classes: (1) silicas that contain ordered cylindrical nanopores but have weaker hydrophilicity and (2) nanoparticles of other transition-metal oxides, such as TiO 2 , which share the strong hydrophilicity of our samples but lack their porosity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Simultaneously Enhanced Hydrophilicity and Stability of a Metal‐Organic Framework via Post‐Synthetic Modification for Water Vapor Sorption/Desorption

Abstract With increasing demands for high‐performance water sorption materials, metal‐organic frameworks (MOFs) have gained considerable attention due to their high maximum uptake capacities. In many cases, however, high overall capacity is not necessarily accomplishing high working capacity under operating conditions, due to insufficient hydrophilicity and/or water stability. Herein, we present a post‐synthetic modification (PSM) of MOF‐808, with di‐sulfonic acids enhancing simultaneously its hydrophilicity and water stability without sacrificing its uptake capacity of ≈30 mmol g −1 . Di‐sulfonic acid PSM enabled a shift of the relative humidity (RH) associated with a sharp step in water vapor sorption from 35–40 % RH in MOF‐808 to below 25 % RH. While MOF‐808 lost uptake capacity and crystallinity over multiple sorption/desorption cycles, the di‐sulfonic acid PSM MOF‐808 retained >80 % of the original capacity. PSM MOF‐808 exhibited good hydrothermal stability up to 60 °C and high swing capacity.

Luo, Tian‐Yi↗
DOE OSTI2023

Influence of ion-pairing reagents on the separation of intact glycoproteins using hydrophilic-interaction liquid chromatography - high-resolution mass spectrometry

Hydrophilic-interaction liquid chromatography (HILIC) of intact proteins offers high-resolution separations of glycoforms of glycoproteins differing in the number of (neutral) glycans. However, to obtain efficient separations it is essential that the positively charged sites of the proteins are shielded by acidic (negative) ion-pair reagents (IPRs), so as to enhance the contribution of the hydroxyl groups of the (neutral) sugars in the glycoprotein. Here, we studied the influence of various IPRs that differ in physico-chemical properties, such as hydrophobicity and acidity, on the capillary-scale HILIC separation of intact (glyco)proteins. We evaluated the use of fluoroacetic acid (MFA), difluoroacetic acid (DFA), trifluoroacetic acid (TFA), and heptafluorobutyric acid (HFBA) as diluents for sample preparation, as solvents for sample loading on a reversed-phase trap prior to the HILIC separation, and as mobile-phase components for HILIC and HILIC-MS. To reduce the contribution of ion-exchange interaction with the (silica-based) stationary phase, we used an acrylamide-based monolithic column. We studied the influence of the different IPRs on each step of the separation of a mixture of proteins of different size and hydrophilicity and on the separation of the five glycoforms of ribonuclease B. The content of IPR in the sample was shown not to affect the separation and the MS detection. However, a low content of TFA and DFA in the mobile phase is favourable, as it reduces adduct formation and leads to higher signal intensity. The optimized HILIC conditions successfully resolved nine major glycoforms groups of a ~40 kDa glycoprotein horseradish peroxidase (HRP), as an example of a complex glycoprotein.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Hydrophilic and Apolar Hydration in Densely Grafted Cationic Brushes and Counterions with Large Mobilities

We employ all-atom molecular dynamics (MD) simulation framework to unravel water microstructure and ion properties for cationic [Poly(2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC) brushes with chloride ions as counterions. First, we identify locally separate water domains (or first hydration shells) each around the {N(CH 3 ) 3 } + and the C=O functional groups of the PMETAC chain and one around the Cl - ion. These first hydration shells around the respective moieties overlap and the extent of the overlap depends on the nature of the species triggering it. Second, despite the overlap, the water molecules in these domains demonstrate disparate properties dictated by the properties of the atoms/groups around which they are located. For example, the presence of the methyl groups make the {N(CH 3 ) 3 } + group trigger apolar hydration as evidenced by the corresponding orientation of the dipole of the water molecules around the {N(CH 3 ) 3 } + moiety. These water molecules around the N(CH 3 ) 3 } + group also have enhanced tetrahedrality as compared to the water molecules constituting the hydration layer around the C=O group and the Cl - counterion. Our simulations also identify that there is an intervening water layer between the Cl - ion and {N(CH 3 ) 3 } + group: this layer prevents the Cl - ion from coming very close to the {N(CH 3 ) 3 } + group. As a consequence, there is a significantly large mobility of the Cl - ions inside the PMETAC brush layer. Furthermore, the C=O group of the PE chain, due to the partial negative charge on the oxygen atom and the specific structure of the PMETAC brush system, demonstrates strongly hydrophilic behavior and enforces a specific dipole response of water molecules analogous to that experienced by water around anionic species of high charge density. As a result, our findings confirm that PMETAC brushes undergo hydrophilic hydration at one site, apolar hydration at another site, and ensures large mobility of the supported Cl- counterions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Hydrophobic versus Hydrophilic Interfacial Coatings on Silicon Nanoparticles Teach Us How to Design the Solid Electrolyte Interphase in Silicon-Based Li-Ion Battery Anodes

Herein, we evaluate the effect of covalently attached molecular coating hydrophobicity on the surface of the silicon nanoparticle (Si NP) active anode material for Li-ion batteries. The experiments are a means to identify the interfacial properties that help minimize electrochemical side reactions during cycling. Preformed coatings on the Si NP surfaces prior to electrode fabrication mimic the ionically conducting and electronically insulating properties of the solid electrolyte interphase (SEI). Hydrophilic oligomers such as polyethylene oxide (PEO) and other related structures are commonly identified as Li+-conducting components of the SEI. Here, we study the effect of such hydrophilic PEO versus hydrophobic alkyl molecular coatings on Si NP anode electrochemical performance. We also study the effect of the PEO oligomer length and the resulting effective thickness of the interfacial coating on the electrochemical performance. We find that PEO oligomers electrochemically isolate Si NPs when the PEO coating thickness approaches the electron tunneling distance of ~2.5 nm. Surprisingly, the thickness of the PEO-based coatings has a negligible effect on their ability to minimize electrochemical side reactions as measured by Coulombic efficiency. These results reveal how the interfacial coating on silicon anode materials should differ from an operando-formed SEI layer and discuss design strategies for an ideal interfacial active material coating based on these results.

25 ENERGY STORAGE↗
DOE OSTI2022

Hydrophilic nanoparticles that kill bacteria while sparing mammalian cells reveal the antibiotic role of nanostructures

To dissect the antibiotic role of nanostructures from chemical moieties belligerent to both bacterial and mammalian cells, here we show the antimicrobial activity and cytotoxicity of nanoparticle-pinched polymer brushes (NPPBs) consisting of chemically inert silica nanospheres of systematically varied diameters covalently grafted with hydrophilic polymer brushes that are non-toxic and non-bactericidal. Assembly of the hydrophilic polymers into nanostructured NPPBs doesn’t alter their amicability with mammalian cells, but it incurs a transformation of their antimicrobial potential against bacteria, including clinical multidrug-resistant strains, that depends critically on the nanoparticle sizes. The acquired antimicrobial potency intensifies with small nanoparticles but subsides quickly with large ones. We identify a threshold size (d silica ~ 50 nm) only beneath which NPPBs remodel bacteria-mimicking membrane into 2D columnar phase, the epitome of membrane pore formation. This study illuminates nanoengineering as a viable approach to develop nanoantibiotics that kill bacteria upon contact yet remain nontoxic when engulfed by mammalian cells.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Hydrophilic and hydrophobic carboxamide pincers as anion hosts

Hydrophobic and hydrophilic, monotopic and ditopic carboxamide pincer hosts containing ethyl, hexyl, 2-hydroxyethyl and 2-hydroxyethyl ethyl ether pendant arms were synthesized. Solubility trends indicated that solubilities in water or hydrocarbon solvents varied depending on the nature of the pendant arms. Binding constants for hydrophilic pincers were larger in general than their hydrophobic analogs. Furthermore, significant synergistic binding effects for the ditopic hosts were not observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗