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Dynamic entity formed by protein and its hydration water

The interaction between protein and water plays a pivotal role in shaping the structure, dynamics, and function of biomacromolecules. A comprehensive understanding of this intricate interplay necessitates a systematic evaluation of interaction strength and its consequential impact on the dynamics of proteins and water across diverse protein systems. Despite numerous works on understanding the dynamics of water and proteins and the coupling between them, there are still unanswered questions. Here, we combine neutron scattering and isotope labeling to probe the dynamics of proteins and their hydration water in a variety of protein systems. We consider proteins of different structures and varying thermostability as well as proteins within living cells with distinct growth temperatures. Simultaneous characterization of protein and hydration water dynamics across diverse systems was achieved. Moreover, we performed water sorption isothermal measurements on three representative proteins to correlate the observed dynamics with the strength of the interaction energies governing each system. The experimental results underscore that proteins manifesting stronger attractive interactions with water display diffusionlike dynamics with higher flexibility upon hydration, concomitant with a reduced mobility in hydration water. Significantly, our findings suggest that, in fact, it is the interaction between protein and its hydration water that facilitates the transfer of mobility from water to protein, with stronger interactions correlating to greater protein flexibility and slower hydration water diffusion. Published by the American Physical Society 2024

Ye, Yongfeng (ORCID:0009000792374198)↗

Study of Interfacial Interactions Using Thing Film Surface Modification: Radiation and Oxidation Effects in Materials

Interfaces play a key role in dictating the long-term stability of materials under the influence of radiation and high temperatures. For example, grain boundaries affect corrosion by way of providing kinetically favorable paths for elemental diffusion, but they can also act as sinks for defects and helium generated during irradiation. Likewise, the retention of high-temperature strength in nanostructured, oxide-dispersion strengthened steels depends strongly on the stoichiometric and physical stability of the (Y, Ti)-oxide particles/matrix interface under radiation and high temperatures. An understanding of these interfacial effects at a fundamental level is important for the development of materials for extreme environments of nuclear reactors. The goal of this project is to develop an understanding stability of interfaces by depositing thin films of materials on substrates followed by ion irradiation of the film-substrate system at elevated temperatures followed by post-irradiation oxidation treatments. Specifically, the research will be performed by depositing thin films of yttrium and titanium (~500 nm) on Fe-12%Cr binary alloy substrate. Y and Ti have been selected as thin-film materials because they form highly stable protective oxides layers. The Fe-12%Cr binary alloy has been selected because it is representative of ferritic steels that are widely used in nuclear systems. The absence of other alloying elements in this binary alloy would allow for a clearer examination of structures and compositions that evolve during high-temperature irradiations and oxidation treatments. The research is divided into four specific tasks: (1) sputter deposition of 500 nm thick films of Y and Ti on Fe-12%Cr alloy substrates, (2) ion irradiation of the film-substrate system with 2MeV protons to a dose of 2 dpa at temperatures of 300°C, 500°C, and 700°C, (3) oxidation of as-deposited and ion-irradiated samples in a controlled oxygen environment at 500°C and 700°C, (4) multi-scale computational modeling involving first- principle molecular dynamics (FPMD) and coarse-grained dissipative particle dynamics (DPD) approaches to develop theories underlying the evolution and stability of structures and phases. Samples from Tasks 1 to 3 (above) will be rigorously characterized and analyzed using scanning electron microscopy, Auger electron microscopy, x-ray diffraction, Rutherford back scatter spectroscopy, and transmission electron microscopy. Expected outcomes of the experimental work include a quantitative understanding film-substrate interface mixing, evolution of defects and other phases at the interface, interaction of interfaces with defects, and the ability of the Y and Ti films to mitigate irradiation-assisted oxidation.The aforementioned experimental work will be closely coupled with multi-scale molecular dynamics (MD) modeling to understand the reactions at the surface, the transport of oxidant through the thin film, and the stabilities of the deposited thin films under radiation and oxidation. Simulations of materials property changes under conditions of radiation and oxidation require multiple size domains and a different simulation scheme for each of these domains. This will be achieved by coupling the FPMD and coarse-grained kinetic Monte Carlo (KMC). This will enable the comparison of the results of each simulation approach with the experimental results.

36 MATERIALS SCIENCE↗

Quasielastic electromagnetic scattering cross sections and world data comparisons in the GENIE Monte Carlo event generator

The usage of Monte Carlo neutrino event generators (MC$\textit{ν}$EGs) is a norm within the high-energy $\textit{ν}$ scattering community. The relevance of quasielastic (QE) energy regimes to $\textit{ν}$ oscillation experiments implies that accurate calculations of $\textit{ν}$A cross sections in this regime will be a key contributor to reducing the systematic uncertainties affecting the extraction of oscillation parameters. In spite of this, many MC$\textit{ν}$EGs utilize highly phenomenological, parametrized models of QE scattering cross sections. Moreover, a culture of validation of MC$\textit{ν}$EGs against prolific electron ($\textit{e}$) scattering data has been historically lacking. In this work, we implement new eA cross sections obtained from nuclear ab initio approaches in GENIE, the primary MC$\textit{ν}$EG utilized by the FNAL community. In particular, we utilize results from quantum MC methods which solve the many-body nuclear problem in the short-time approximation (STA), allowing consistent retention of two-nucleon dynamics which are crucial to explain available nuclear electromagnetic (electroweak) data over a wide range of energy and momentum transfers. This new implementation in GENIE is fully tested against the world QE electromagnetic data, finding agreement with available data below ~2 GeV of beam energy with the aid of a scaling function formalism. The STA is currently limited to study $\textit{A}$ ≤ 12 nuclei, however, its semi-inclusive multibody identity components are exportable to other many-body computational techniques such as auxiliary field diffusion MC which can reach $\textit{A}$ ≤ 40 systems while continuing to realize the factorization contained within the STA’s multinucleon dynamics. Together, these developments promise to make future experiments such as DUNE more accurate in their assessment of MC$\textit{ν}$EG systematics, $\textit{ν}$ properties, and potentially empower the discovery of physics beyond the Standard Model.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Molecular Picture of the Transient Nature of Lipid Rafts

In biological membranes, lipid rafts are now thought to be transient and nanoscopic. However, the mechanism responsible for these nanoscopic assemblies remains poorly understood, even in the case of model membranes. Therefore, it has proven extremely challenging to probe the physicochemical properties of lipid rafts at the molecular level. Here, we use all-atom molecular dynamics (MD) simulations and inelastic X-ray scattering (IXS), an intrinsically nanoscale technique, to directly probe the energy transfer and collective short-wavelength dynamics (phonons) of biologically relevant model membranes. We show that the nanoscale propagation of stress in lipid rafts takes place in the form of collective motions made up of longitudinal (compression waves) and transverse (shear waves) molecular vibrations. Importantly, we provide a molecular picture for the so-called van der Waals mediated "force from lipid" [Anishkin, A. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 7898], a key parameter for the ionic channel mechano-transduction and the mechanism for the lipid transfer of molecular level stress [Aponte-Santamaría, C. et al. J. Am. Chem. Soc. 2017, 139, 13588]. Specifically, we describe how lipid rafts are formed and maintained through the propagation of molecular stress, lipid raft rattling dynamics, and a relaxation process. Eventually, the rafts dissipate through the self-diffusion of lipids making up the rafts. We also show that the molecular stress and viscoelastic properties of transient lipid rafts can be modulated through the use of hydrophobic biomolecules such as melatonin and tryptophan. Overall, the herein proposed mechanism describing the molecular interactions for the formation and dissolution of lipid rafts may offer insights as to how lipid rafts enable biological function.

36 MATERIALS SCIENCE↗

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?

There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of three Ruddlesden-Popper phases, general form A n-1 A 2 'BnO 3n+1 , A n-1 A 2 'BnX 3n+1 ; LaSrCo 0.5 Fe 0.5 O 4-δ (n = 1), La 0.3 Sr 2.7 CoFeO 7-δ (n = 2) and LaSr 3 Co 1.5 Fe 1.5 O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scattering of an exciton polariton by impurity centers in GaAs

Scattering of an exciton polariton by impurity centers at low temperatures has not been investigated comprehensively in spite of its significant role in processes accompanying Bose–Einstein condensation of an exciton polariton. For studying the peculiarities of the interaction of an exciton polariton with impurity centers, we have studied the integrated absorption of the ground state (n{sub 0} = 1) of the exciton in GaAs in thin (micrometer-thick) wafers with an appreciable optical transmission. Comparative analysis of the transmission in the vicinity of the exciton resonance performed on 15 samples of crystalline GaAs wafers with different concentrations N of impurity has revealed an unexpected regularity. The value of N increases by almost five decimal orders of magnitude, while the normalized spectrally integrated absorption of light exhibits a slight increase, following the power dependence N{sup m} on the concentration, where m = 1/6. It has been shown that this dependence indicates the diffusion mechanism of propagation of the exciton polaritons through the bulk of the semiconductor, which is present along with the ballistic propagation of light through the sample.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

X-RAY INVESTIGATION OF THE DIFFUSE EMISSION AROUND PLAUSIBLE {gamma}-RAY EMITTING PULSAR WIND NEBULAE IN KOOKABURRA REGION

We report on the results from Suzaku X-ray observations of the radio complex region called Kookaburra, which includes two adjacent TeV {gamma}-ray sources HESS J1418-609 and HESS J1420-607. The Suzaku observation revealed X-ray diffuse emission around a middle-aged pulsar PSR J1420-6048 and a plausible pulsar wind nebula (PWN) Rabbit with elongated sizes of {sigma}{sub X} = 1.'66 and {sigma}{sub X} = 1.'49, respectively. The peaks of the diffuse X-ray emission are located within the {gamma}-ray excess maps obtained by H.E.S.S. and the offsets from the {gamma}-ray peaks are 2.'8 for PSR J1420-6048 and 4.'5 for Rabbit. The X-ray spectra of the two sources were well reproduced by absorbed power-law models with {Gamma} = 1.7-2.3. The spectral shapes tend to become softer according to the distance from the X-ray peaks. Assuming the one-zone electron emission model as the first-order approximation, the ambient magnetic field strengths of HESS J1420-607 and HESS J1418-609 can be estimated as 3 {mu}G and 2.5 {mu}G, respectively. The X-ray spectral and spatial properties strongly support that both TeV sources are PWNe, in which electrons and positrons accelerated at termination shocks of the pulsar winds are losing their energies via the synchrotron radiation and inverse Compton scattering as they are transported outward.

79 ASTRONOMY AND ASTROPHYSICS↗

Search for Hydrogenated C{sub 60} (Fulleranes) in Circumstellar Envelopes

The recent detection of fullerene (C{sub 60}) in space and the positive assignment of five diffuse interstellar bands to C{sub 60}{sup +} reinforce the notion that fullerene-related compounds can be efficiently formed in circumstellar envelopes and be present in significant quantities in the interstellar medium. Experimental studies have shown that C{sub 60} can be readily hydrogenated, raising the possibility that hydrogenated fullerenes (or fulleranes, C{sub 60}H{sub m}, m = 1–60) may be abundant in space. In this paper, we present theoretical studies of the vibrational modes of isomers of C{sub 60}H{sub m}. Our results show that the four mid-infrared bands from the C{sub 60} skeletal vibrations remain prominent in slightly hydrogenated C{sub 60}, but their strengths diminish in different degrees with increasing hydrogenation. It is therefore possible that the observed infrared bands assigned to C{sub 60} could be due to a mixture of fullerenes and fulleranes. This provides a potential explanation for the observed scatter of the C{sub 60} band ratios. Our calculations suggest that a feature around 15 μm due to the breathing mode of heavily hydrogenated C{sub 60} may be detectable astronomically. A preliminary search for this feature in 35 C{sub 60} sources is reported.

79 ASTRONOMY AND ASTROPHYSICS↗

Computational approaches to model X-ray photon correlation spectroscopy from molecular dynamics

X-ray photon correlation spectroscopy (XPCS) allows for the resolution of dynamic processes within a material across a wide range of length and time scales. X-ray speckle visibility spectroscopy (XSVS) is a related method that uses a single diffraction pattern to probe ultrafast dynamics. Interpretation of the XPCS and XSVS data in terms of underlying physical processes is necessary to establish the connection between the macroscopic responses and the microstructural dynamics. To aid the interpretation of the XPCS and XSVS data, we present a computational framework to model these experiments by computing the X-ray scattering intensity directly from the atomic positions obtained from molecular dynamics simulations. We compare the efficiency and accuracy of two alternative computational methods: the direct method computing the intensity at each diffraction vector separately, and a method based on fast Fourier transform that computes the intensities at all diffraction vectors at once. Furthermore, the computed X-ray speckle patterns capture the density fluctuations over a range of length and time scales and are shown to reproduce the known properties and relations of experimental XPCS and XSVS for liquids.

36 MATERIALS SCIENCE↗

Modelling the thermal conductivity of (U x Th 1-x )O 2 and (U x Pu 1-x )O 2

The degradation of thermal conductivity due to the non-uniform cation lattice of (U x Th 1-x )O 2 and (U x Pu 1-x )O 2 solid solutions has been investigated by molecular dynamics, using the non-equilibrium method, from 300 to 2000 K. Degradation of thermal conductivity is predicted in (U x Th 1-x )O 2 and (U x Pu 1-x )O 2 as compositions deviate from the pure end members: UO 2 , PuO 2 and ThO 2 . The reduction in thermal conductivity is most apparent at low temperatures where phonon-defect scattering dominates over phonon-phonon interactions. The effect is greater for (U x Th 1-x )O 2 than U x Pu 1-x )O 2 due to the greater mismatch in cation size. Parameters for an analytical expressions have been developed that describe the predicted thermal conductivities over the full temperature and compositional ranges. Finally, these expressions may be used in higher level fuel performance codes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The Polarity of Co-solvents Regulates the Charge Storage Mechanisms in Supercapacitors with Concentrated Electrolytes

Developing better energy storage devices depends on comprehending the underlying mechanisms involved in charge storage. With the continuous conception of new electrolytes, this task becomes progressively more urgent and complex. An example is the utilization of co-solvated concentrated solutions. While these show promising electrochemical responses, their dynamic properties (especially under confinement) and their relationships with performance are not fully understood. Here, we combined modified step potential electrochemical spectroscopy and quasielastic neutron scattering to investigate systems composed of activated mesoporous carbon (AMC) and concentrated solutions of lithium bis(trifluoromethanesulfonyl)imide in acetonitrile co-solvated with either toluene or acetone. Further, we report that acetone does not impair surface-controlled mechanisms, contrary to the case with toluene, which competes with charged species to populate the AMC’s pores without contributing to charge storage. In turn, toluene promotes a greater overall capacitance owing to Faradaic processes, which may be related to changes in the solvation structures under confinement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lattice dynamics and broad-band dielectric properties of multiferroic Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} ceramics

Complex dielectric properties of Pb(Fe{sub 1/2}Nb{sub 1/2})O{sub 3} ceramics were investigated in a broad frequency range from 100 Hz up to 90 THz. A broad dielectric anomaly was observed near the temperature of the ferroelectric phase transition (T{sub C1} = 376 K). Below 1 MHz, the anomaly is strongly influenced by conductivity of the sample, but higher frequency data taken up to 81 MHz reveal a broad and frequency independent peak at T{sub C1} typical for a diffuse ferroelectric phase transition. Surprisingly, dielectric permittivity measured at 37 GHz exhibits a peak shifted by 25 K above T{sub C1}, which indicates polar nanoregions with dynamics in microwave frequency region. A dielectric relaxation, which appears in THz region below 700 K, slows down towards T{sub C1} and again hardens below T{sub C2} = 356 K. This central mode drives both phase transitions, so they belong to order–disorder type, although the polar phonons exhibit anomalies near both phase transitions. In the paraelectric phase, infrared reflectivity spectra correspond to local Fm3{sup ¯}m structure due to short-range chemical ordering of Fe and Nb cations on the B perovskite sites. Moreover, each polar phonon is split due to two different cations on the B sites. Recently, Manley et al. [Nat. Commun. 5, 3683 (2014)] proposed a new mechanism of creation of polar nanoregions in relaxor ferroelectrics. They argued, based on their inelastic neutron scattering studies of PMN–PT, that the TO1 phonon is split and interaction of both components gives rise to so called Anderson phonon localization, which can produce regions of trapped standing waves and these waves induce polar nanoregions in relaxors. We cannot exclude or confirm this mechanism, but we show that the splitting of polar phonons is a common feature for all complex perovskites with relaxor ferroelectric behavior and it can be also observed in canonical ferroelectric BaTiO{sub 3}, where the soft mode is split in paraelectric phase due to a strong lattice anharmonicity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

FCRD Advanced Reactor (Transmutation) Fuels Handbook

Transmutation of minor actinides such as Np, Am, and Cm in spent nuclear fuel is of international interest because of its potential for reducing the long-term health and safety hazards caused by the radioactivity of the spent fuel. One important approach to transmutation (currently being pursued by the DOE Fuel Cycle Research & Development Advanced Fuels Campaign) involves incorporating the minor actinides into U-Pu-Zr alloys, which can be used as fuel in fast reactors. U-Pu-Zr alloys are well suited for electrolytic refining, which leads to incorporation rare-earth fission products such as La, Ce, Pr, and Nd. It is, therefore, important to understand not only the properties of U-Pu-Zr alloys but also those of U-Pu-Zr alloys with concentrations of minor actinides (Np, Am) and rare-earth elements (La, Ce, Pr, and Nd) similar to those in reprocessed fuel. In addition to requiring extensive safety precautions, alloys containing U, Pu, and minor actinides (Np and Am) are difficult to study for numerous reasons, including their complex phase transformations, characteristically sluggish phasetransformation kinetics, tendency to produce experimental results that vary depending on the histories of individual samples, rapid oxidation, and sensitivity to contaminants such as oxygen in concentrations below a hundred parts per million. Although less toxic, rare-earth elements such as La, Ce, Pr, and Nd are also difficult to study for similar reasons. Many of the experimental measurements were made before 1980, and the level of documentation for experimental methods and results varies widely. It is, therefore, not surprising that little is known with certainty about U-Pu-Zr alloys, particularly those that also contain minor actinides and rare-earth elements. General acceptance of results commonly indicates that there is only a single measurement for a particular property. This handbook summarizes currently available information about U, Pu, Zr, Np, Am, La, Ce, Pr, and Nd and alloys of two or three of these elements. It contains information about phase diagrams and related information (including phases and phase transformations); heat capacity, entropy, and enthalpy; thermal expansion; and thermal conductivity and diffusivity. In addition to presenting information about materials properties, the handbook attempts to provide information about how well the property is known and how much variation exists between measurements. Although it includes some results from models, its primary focus is experimental data. The Handbook is organized in two sections: one with information about the U-Pu-Zr ternary and one with information about other elements and binary and vi ternary alloys in the U-Np-Pu-Am-La-Ce-Pr-Nd-Zr system. Within each section, information about elements is presented first, followed by information about binary alloys, then information about ternary alloys. The order in which the elements in each alloy are mentioned follows the order in the first sentence of this paragraph. Much of the information on the U-Pu-Zr system repeats information from the FCRD Transmutation Fuels Handbook 2015. Most of the other data has been published elsewhere (although scattered throughout numerous references, some quite obscure); however, some data from Idaho National Laboratory is presented here for the first time. As the FCRD programmatic mission evolves, future editions of this handbook will begin to include other advanced reactor fuel designs and compositions. Hence, the title of the handbook will transition to the Advanced Reactor Fuels Handbook.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Structure and Dynamics of Bimodal Colloidal Dispersions in a Low-Molecular-Weight Polymer Solution

We present an experimental study of the structural and dynamical properties of bimodal, micrometersized colloidal dispersions (size ratio ≈ 2) in an aqueous solution of low-molecular weight polymer (polyethylene glycol 2000) using synchrotron ultra-small angle X-ray scattering (USAXS) and USAXSbased X-ray photon correlation spectroscopy. We fixed the volume fraction of the large particles at 5 % and systematically increased the volume fraction of the small particles from 0 % to 5 % to evaluate its effect on the structure and dynamics. The bimodal dispersions were homogenous through the investigated parameter space. We found that the partial structure factors can be satisfactorily retrieved for the bimodal colloidal dispersions using a Percus-Yevick hard sphere potential when the particle size distributions of the particles were taken into account. We also found that the partial structure factor between the large particles does not exhibit significant variation with increasing volume fraction of small particles, whereas the isothermal compressibility of the binary mixture was found to decrease with increasing volume fraction of small particles. The dynamics of single-component large particle dispersion obey the principles of de Gennes narrowing, where the wave vector dependence of the interparticle diffusion coefficient is inversely proportional to the interparticle structure factor. The dynamics of the bimodal dispersions demonstrate strong dependence on the fraction of small particles. As a result, we also made a comparison between the experimental effective dynamic viscosity of the bimodal dispersion with theoretical predictions, which suggest that the complex mutual interactions between large and small particles have a strong effect on the dynamic behaviors of bimodal dispersions.

36 MATERIALS SCIENCE↗

Contribution of capillary electrophoresis to an integrated vision of humic substances size and charge characterizations

The physicochemical properties of three different humic substances (HS) are probed using capillary zone electrophoresis in alkaline carbonate buffers, pH 10. Special attention is drawn to the impact of the electrolyte ionic strength and counter-ion nature, chosen within the alkali-metal series, on HS electrophoretic mobility. Taylor-Aris dispersion analysis provides insights into the hydrodynamic radius (R-H) distributions of HS. The smallest characterized entities are of nano-metric dimensions, showing neither ionic strength- nor alkali-metal-induced aggregation. These results are compared with the entities evidenced in dynamic light scattering measurements, the size of which is two order of magnitude higher, ca. 100 nm. The extended Onsager model provides a reasonable description of measured electrophoretic mobilities in the ionic strength range 1-50 mM, thus allowing the estimation of limiting mobilities and ionic charge numbers for the different HS samples. An unexpected HS electrophoretic mobility increase (in absolute value) is observed in the order Li{sup +} ≤ Na{sup +} ≤ K{sup +} ≤ Cs{sup +} and discussed either in terms of retarding forces or in terms of ion-ion interactions. (authors)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methotrexate intercalated ZnAl-layered double hydroxide

The anticancerous drug methotrexate (MTX) has been intercalated into an ZnAl-layered double hydroxide (LDH) using an anion exchange technique to produce LDH-MTX hybrids having particle sizes in the range of 100-300 nm. X-ray diffraction studies revealed increases in the basal spacings of ZnAl-LDH-MTX hybrid on MTX intercalation. This was corroborated by the transmission electron micrographs, which showed an increase in average interlayer spacing from 8.9 A in pristine LDH to 21.3 A in LDH-MTX hybrid. Thermogravimetric analyses showed an increase in the decomposition temperature for the MTX molecule in the LDH-MTX hybrid indicating enhanced thermal stability of the drug molecule in the LDH nanovehicle. The cumulative release profile of MTX from ZnAl-LDH-MTX hybrids in phosphate buffer saline (PBS) at pH 7.4 was successfully sustained for 48 h following Rigter-Peppas model release kinetics via diffusion. - Graphical abstract: ZnAl-layered double hydroxide intercalated with methotrexate ({approx}34% loading) promises the possibility of use of ZnAl-LDH material as drug carrier and in controlled delivery. Highlights: > ZnAl-layered double hydroxide methotrexate nanohybrid has been synthesized. > XRD and TEM studies on nanohybrid revealed successful intercalation of methotrexate. > TG and CHN analyses showed {approx}34 wt% of methotrexate loading into the nanohybrid. > Possibility of use of ZnAl-LDH material as drug carrier and in delivery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling the core of fuel cell performance: engineering the ionomer/catalyst interface

The biggest obstacle to the widespread implementation of polymer electrolyte membrane fuel cells (PEMFCs) is their cost, primarily due to the use of platinum catalysts. The high intrinsic catalyst activity exhibited on a rotating disk electrode (RDE) is rarely realized in a membrane electrode assembly (MEA), which is a long-standing challenge for PEMFCs and a cause of low catalyst utilization. To translate the high RDE performance of a catalyst into a MEA, the design of an ideal ionomer/catalyst interface is proposed: a thin, conformal ionomer film covers the maximum surface of a Pt nanoparticle and thus simultaneously maximizes catalyst utilization, (i.e., high mass activity and electrochemically active surface area) and O 2 diffusion rate (i.e., high current density performance) without compromising proton conduction. Building such an interface is a long-standing challenge due to the lack of interaction between the ionomer and catalyst particles, resulting in large ionomer agglomerates and inhomogeneous ionomer coverage over the catalyst nanoparticle, with consequent poor fuel cell performance. In this work, this ionomer/catalyst interface has been engineered, utilizing the electrostatic attraction between positively charged catalyst and negatively charged ionomer particles in a catalyst ink and preserved in a solid catalyst layer. As a result, this interface leads to previously unachieved proton exchange membrane fuel cell performance in terms of both catalyst utilization (75% vs. 45%) and peak/rated power density (i.e., 1.430/0.930 W cm -2 , H 2 /air, cathode Pt loading: 0.1 mgPt cm -2 ) for pure Pt catalysts, even better than those of Pt alloy catalysts. This work demonstrates the formation of an interface in the liquid phase (using ultra-small-angle X-ray scattering in combination with cryo-TEM, isothermal–titration–calorimetry) and the preservation of the interface in the solid catalyst layer (using TEM) and estimates the effective coverage and thickness of the ionomer film (using limiting current density, RDE and fuel cell performance).

25 ENERGY STORAGE↗

Confocal Raman Microscopy for in Situ Measurement of Octanol–Water Partitioning within the Pores of Individual C 18 -Functionalized Chromatographic Particles

Octanol water partitioning is one of the most widely used predictors of hydrophobicity and lipophilicity. Traditional methods for measuring octanol water partition coefficients (K ow ), including shake flasks and generator columns, require hours for equilibration and milliliter quantities of sample solution. These challenges have led to development of smaller scale methods for measuring K ow . Recent advances in microfluidics have produced faster and smaller-volume approaches to measuring K ow . As flowing volumes are reduced, however, separation of water and octanol prior to measurement and detection in small volumes of octanol phase are especially challenging. In this work, we reduce the receiver volume of octanol water partitioning measurements from current practice by six-orders-of-magnitude, to the femtoliter scale, by using a single octanol filled reversed-phase, octadecylsilane-modified (C 18 -silica) chromatographic particle as a collector. The fluid handling challenges of working in such small volumes are circumvented by eliminating post equilibration phase separation. Partitioning is measured in situ within the pore confined octanol phase using confocal Raman microscopy, which is capable of detecting and quantifying a wide variety of molecular structures. Equilibration times are fast (less than a minute) because molecular diffusion is efficient over distance scales of micrometers. The demonstrated amount of analyte needed to carry out a measurement is very small, less than 50 fmol, which would be a useful attribute for drug screening applications or testing of small quantities of environmentally sensitive compounds. The method is tested for measurements of pH-dependent octanol-water partitioning of naphthoic acid, and the results are compared to both traditional shake-flask measurements and sorption onto C 18 -modified silica without octanol present within the pores.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗