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At least 505 records · Page 28

Probing Hydrogen-Bond Anharmonicity in Cocrystals with Colossal Thermal Expansion

Organic cocrystals with sizable anisotropic thermal expansion (TE) are attractive building blocks for thermally responsive soft actuators. Such materials often display intermolecular H-bonding, whose thermal strength fluctuations are frequently overlooked if displacements and/or conformational changes are visible during TE. In this work, we employed variable-temperature single-crystal synchrotron diffraction to investigate the linear expansion coefficients of two organic cocrystals, 1 and 2, which exhibit colossal thermal expansivity exceeding 140 MK –1 . Despite such pronounced TE, solid-state 2 H and 13 C NMR experiments show no evidence of fast internal reorientations or large-amplitude molecular displacement during expansion. Although nondirectional π–π stacking dominates the colossal TE, our results indicate that hydrogen bonds play a non-negligible role in the anisotropic response. Molecular dynamics simulations reveal a temperature-dependent broadening of H-bond length distributions, which arises from the increased thermal sampling of an anharmonic potential energy surface. Our data support an expansion mechanism based on cooperativity in π-π interactions, accompanied by thermal softening and fluctuation-driven stretching of directional hydrogen bonds in these molecular solids. This mechanism underscores the significance of directional interactions in organic cocrystals, which is a key factor in the design of organic thermoresponsive crystalline materials.

Hernández-Morales, Ernesto A. [Univ. Nacional Auto↗

Origins of Electrostriction in Poly(vinylidene fluoride)-Based Ferroelectric Polymers

Although electrostriction is ubiquitous for dielectric polymers, giant electrostriction has not been observed until relaxor ferroelectric (RFE) poly(vinylidene fluoride) (PVDF)-based polymers are achieved. However, the exact origin for giant electrostriction in these polymers has not been fully understood. By studying the electrostriction in the uniaxially stretched films of a ferroelectric poly(VDF-co-trifluoroethylene) [P(VDF-TrFE)] random copolymer and an RFE poly(VDF-co-TrFE-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] random terpolymer in this work, we confirmed that ferroelectric switching with large hysteresis, such as in the case of P(VDF-TrFE), was not genuine electrostriction. By decreasing large ferroelectric domains to the nanometer scale (i.e., 2–3 nm), such as in the case of the P(VDF-TrFE-CTFE) terpolymer, electrostriction with low hysteresis could be achieved. Here, two origins of the large electrostriction in these polymers were identified. The first was the mechano-electrostriction due to the poling field-induced conformation transformation of oriented polymer chains. The second was the electric repulsion of electrically aligned nanodomains. These effects could occur in both crystals and the oriented amorphous fraction, which links between the nanocrystals and the isotropic amorphous fraction. When the poling field was relatively low (e.g., <40 MV/m), the mechano-electrostriction was the major contribution and the electric repulsion effect was a minor contribution to electrostriction. Meanwhile, a strong temperature dependence of the low-field electrostriction coefficient was observed. Finally, we found an empirical inverse relationship between the electrostriction coefficient and the product of Young’s modulus and dielectric constant. The knowledge obtained from this study provides an insightful understanding of the electrostriction mechanism in PVDF-based electroactive polymers, which will find potential applications in sensors and actuators for wearable electronics and soft robotics.

36 MATERIALS SCIENCE↗

Effects of Concentration, Salinity and Temperature on the Conformations of Zwitterionic Poly(2-Vinylpyridine- N -Oxide) Chains in Semidilute Solutions Probed by Small-Angle X-Ray and Neutron Scattering

Polyzwitterions, composed of repeating units with equal numbers of anionic and cationic groups, have drawn considerable interest for applications ranging from antimicrobial coatings and antifouling membranes to low-friction interfaces, energy storage media, and actuators. A characteristic feature of many polyzwitterions is the anti-polyelectrolyte effect salt-induced chain expansion in aqueous solution a phenomenon often implicated in their functional behavior. In this study, we investigated the conformational behavior of poly(2-vinylpyridine-N-oxide) (P2VPNO) using smallangle X-ray and neutron scattering (SAXS and SANS). Small-angle X-ray scattering (SAXS) revealed that, in salt-free aqueous solution, P2VPNO adopts an expanded wormlike conformation stabilized by hydration. With increasing concentration, the chains contract due to screening of intrachain excluded-volume interactions, qualitatively consistent with de Gennes’ scaling predictions for neutral polymers. Small-angle neutron scattering (SANS) further demonstrated that P2VPNO exhibits the characteristic anti-polyelectrolyte response to added salt, as observed in many other polyzwitterions. At elevated temperatures, chain flexibility increases, leading to a shorter Kuhn length and reduced radius of gyration. Notably, however, salt-induced chain expansion persists, indicating that the anti-polyelectrolyte effect remains operative under elevated thermal conditions. These findings provide the first experimental evidence of scaling behavior in polyzwitterions, as well as the first observation of their altered antipolyelectrolyte response at elevated temperatures, offering new insights into the solution physics of this important class of polymers.

Conformation↗

The Buckling Spectra of Nanoparticle Surfactant Assemblies

Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. In this study, we show that the bending modulus, B , of thin assemblies of nanoparticle surfactants (NPSs) at the oil–water interface can be varied continuously from sub- k B T to 10 6 k B T , by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Pseudoelasticity of SrNi2P2 Micropillar via Double Lattice Collapse and Expansion

The maximum recoverable strain of most crystalline solids is less than 1% because plastic deformation or fracture usually occurs at a small strain. In this work, we show that a SrNi 2 P 2 micropillar exhibits pseudoelasticity with a large maximum recoverable strain of ~14% under uniaxial compression via unique reversible structural transformation, double lattice collapse–expansion that is repeatable under cyclic loading. Its high yield strength (~3.8 ± 0.5 GPa) and large maximum recoverable strain bring out the ultrahigh modulus of resilience (~146 ± 19 MJ/m 3 ), a few orders of magnitude higher than that of most engineering materials. The double lattice collapse–expansion mechanism shows stress–strain behaviors similar to that of conventional shape-memory alloys, such as hysteresis and thermo-mechanical actuation, even though the structural changes involved are completely different. Our work suggests that the discovery of a new class of high-performance ThCr 2 Si 2 -structured materials will open new research opportunities in the field of pseudoelasticity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Probing the In Situ Pseudocapacitive Charge Storage in Ti 3 C 2 MXene Thin Films with X-ray Reflectivity

MXenes are a large family of two-dimensional materials that are attractive for energy storage due to their high-rate charging capabilities as well as for electrochemical actuators, water purification, and many other technologies. Ion intercalation during electrochemically driven charge and discharge processes is the fundamental process associated with MXene functionality, which we have characterized here using in situ and operando X-ray reflectivity (XRR). Experiments performed at the Advanced Photon Source at Argonne National Laboratory monitored the changes in the structure of a Ti 3 C 2 MXene film on a platinum current collector as a function of static applied potential between 0.3 and –0.7 V vs Ag/AgCl in an aqueous 0.1 M Li 2 SO 4 electrolyte. Negative potential sweeps lead to a contraction of 1.2 Å in the interlayer spacing and a loss of electron density between the layers, likely due to Li + ion insertion and water removal. The change in lattice spacing includes a continuous variation vs potential as well as an additional discrete contraction that occurs near –0.35 V that has the characteristics of a first-order transition. The continuous change in the MXene interlayer spacing is associated with the capacitive charge, while the discrete change in structure correlated to the weak feature in the cyclic voltammogram at –0.35 V can be interpreted as either a pseudocapacitive charging process or a potential-dependent change in capacity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Functionalization of Established 3D-Printed Aza-Michael Liquid Crystal Elastomers with Donor–Acceptor Stenhouse Adducts

Extrusion 3D printing has advanced the manufacturing of complex liquid crystal elastomer (LCE) architectures. In parallel, donor–acceptor Stenhouse adducts (DASAs), a class of white-light-responsive photoswitches, have enabled both photochemical and photothermal LCE actuation. However, DASA–LCEs have yet to be extruded and 3D-printed. Two key challenges exist: DASA’s inherent sensitivity to heat and radicals can lead to degradation during ink preparation and printing, and small changes in the concentration of the added DASA component impact the properties of the extrudable ink, requiring reoptimization of well-established 3D-printing protocols. To overcome these challenges, we present a post-printing functionalization strategy that circumvents these limitations. Residual secondary amines, inherent to inks synthesized via standard aza-Michael addition, serve as active sites for covalent attachment of DASA photoresponsive groups following printing and cross-linking. Our method means that DASAs can be directly grafted onto 3D-printed aza-Michael LCEs without modifying the ink formulation or processing. The resulting DASA–LCEs exhibit wavelength tunability within the visible range and a variety of photothermal and photochemical responses. The post-functionalization can occur within 2 min and enables spatial control of the DASA concentration, producing films with tunable color gradients and locally varied photothermal and photochemical responses under visible light. In conclusion, this approach enables the rapid fabrication of DASA-based light-responsive LCEs using established ink formulations with the potential for the design of complex 3D architectures.

3D printing↗

Liquid Crystal Films as Active Substrates for Nanoparticle Control

Organizing nanoparticles in a controlled way allows us to monitor their optical properties. It is particularly interesting to organize them on top of liquid crystal films to take advantage, in a second step, of the easy actuation of liquid crystals with external parameters such as temperature, electric fields, and so forth. We show that despite their fluidity, nematic and smectic films allow the formation of well-ordered hexagonal domains of gold spherical nanoparticles (AuNPs) at their surface, but we also show that both nematic films and AuNP domains impact each other. Using optical microscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), and spectrophotometry, we compare nematic, polymer-stabilized nematic, and smectic films with AuNP domains made of NPs of diameter 6 nm. On the liquid crystal films, depressions are revealed below the AuNP domains, whereas the AuNP domains appear well-organized but with a hexagonal period shortened with respect to AuNP monolayers formed on hard substrates. We interpret these features by the anchoring tilt imposed by the AuNP domains on the liquid crystal molecules. The smectic-A layers characteristic of the nematic surface transform into smecticC layers, which induce the formation of depression. Here, the energy penalty associated with the local smectic-A/smectic-C transition induces the shortening of the AuNP domain period in order to decrease the AuNP domain surface. The observed large depth of the polymer-stabilized nematic depressions below AuNP domains may be explained either by an increased size of the polymer-stabilized smectic layers close to the surface or by an increased number of polymer-stabilized smectic liquid crystal smectic layers close to the surface with respect to pure nematic films.

36 MATERIALS SCIENCE↗

Operando X-ray Reflectivity Reveals the Dynamical Response of Ti 3 C 2 MXene Film Structure during Electrochemical Cycling

The dynamical structural response of MXenes during electrochemical ion intercalation is critical for their functionality in fast chemical actuation and high-power electrical energy storage but has yet to be observed. Here, the dynamically evolving layer spacing of a Ti 3 C 2 T $x$ MXene film was observed using time-resolved operando X-ray reflectivity during cyclic voltammetry for applied potentials between +0.3 and -0.7 V (vs Ag/AgCl) at sweep rates 1 ≤ $v$ ≤ 500 mV/s. The pseudocapacitive electrochemical MXene response in the aqueous 0.1 M Li 2 SO 4 electrolyte, including both capacitive and redox characteristics, is characterized by kinetically limited lithium intercalation and layer contraction. In conclusion, two types of dynamical responses were observed: slow and fast lattice contraction regimes versus applied potential are correlated with the capacitive and redox features, respectively, with structural relaxation rates that scale as ~$v$ 1/2 and ~$v$, revealing two distinct dynamical structural responses during electrochemical ion intercalation.

25 ENERGY STORAGE↗

Radical Polymer-Based Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are an emerging platform for bioelectronic applications. Significant effort has been placed in designing advanced polymers that simultaneously transport both charge and ions (i.e., macromolecules that are mixed conductors). Furthermore, the considerations for mixed organic conductors are often different from the established principles that are well-known in the solid-state organic electronics field; thus, the discovery of new OECT macromolecular systems is highly desired. Here, we demonstrate a new materials system by blending a radical polymer (i.e., a macromolecule with a nonconjugated backbone and with stable open-shell sites at its pendant group) with a frequently used conjugated polymer. Specifically, poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO) was blended with poly(3-hexylthiophene) (P 3 HT) to create thin films with distinct closed-shell and open-shell domains. Importantly, the sharp and unique oxidation–reduction (redox) potential associated with the radical moieties of the PTEO chain provided a distinct actuation feature to the blended films that modulated the ionic transport of the OECT devices. In turn, this led to controlled regulation of the doping of the P 3 HT phase in the composite film. By decoupling the ionic and electronic transport into two distinct phases and by using an ion transport phase with well-controlled redox activity, never-before-seen performance for a P3HT-based OECT was observed. That is, at loadings as low as 5% PTEO (by weight) OECTs achieved figure-of-merit (i.e., μC*) values >150 F V –1 cm –1 s –1 , which place the performance on the same order as state-of-the-art conjugated polymers despite the relatively common conjugated macromolecular moiety implemented. As such, this effort presents a design platform by which to readily create a tailored OECT response through strategic macromolecular selection and polymer processing.

36 MATERIALS SCIENCE↗

Titanium Carbide MXene Shows an Electrochemical Anomaly in Water-in-Salt Electrolytes

Identifying and understanding charge storage mechanisms is important for advancing energy storage. Well-separated peaks in cyclic voltammograms (CVs) are considered key indicators of diffusion-controlled electrochemical processes with distinct Faradaic charge transfer. Herein, we report on an electrochemical system with separated CV peaks, accompanied by surface-controlled partial charge transfer, in 2D Ti 3 C 2 T x MXene in water-in-salt electrolytes. The process involves the insertion/desertion of desolvation-free cations, leading to an abrupt change of the interlayer spacing between MXene sheets. This unusual behavior increases charge storage at positive potentials, thereby increasing the amount of energy stored. This also demonstrates opportunities for the development of high-rate aqueous energy storage devices and electrochemical actuators using safe and inexpensive aqueous electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled Assembly of Upconverting Nanoparticles for Low-Threshold Microlasers and Their Imaging in Scattering Media

Micron-sized lasers fabricated from upconverting nanoparticles (UCNP) coupled to whispering gallery mode (WGM) microresonators can exhibit continuous-wave anti-Stokes lasing useful for tracking cells, environmental sensing, and coherent stimulation of biological activity. The integration of these microlasers into organisms and microelectronics requires even smaller diameters, however, which raises threshold pump powers beyond practical limits for biological applications. To meet the need for low lasing thresholds and high fidelity fabrication methods, we use correlative optical and electron microscopy to uncover the nanoparticle assembly process and structural factors that determine efficient upconverted lasing. We show that 5 μm microspheres with controlled submonolayer UCNP coatings exhibit, on average, 25-fold lower laser thresholds (1.7 ± 0.7 kW/cm 2 ) compared to the mean values of the lowest threshold UCNP lasers, and variability is reduced 30-fold. WGMs are observed in the upconversion spectra for TiO 2 -coated microspheres as small as 3 μm, a size at which optical losses had previously prevented such observations. Finally, we demonstrate that the WGM signatures of these upconverting microlasers can be imaged and distinguished through tissue-mimicking phantoms. These advances will enable the fabrication of more efficient upconverting lasers for imaging, sensing, and actuation in optically complex environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Compensation Challenges in Processing Antiferroelectric PbZrO 3 Thin Films

The electric field-induced antipolar-to-polar phase transition in antiferroelectric materials is accompanied by large changes in the structural and functional response, making them attractive for many applications ranging from pulsed energy capacitors to high-strain-high (blocking-)force actuators, solid-state heating and cooling systems, and optoelectronic devices. PbZrO 3 , as an end member of the PZT, (x)PbZr 1–x Ti x O 3 , solid solution, has been the subject of many studies. However, processing of perovskite PbZrO 3 is extremely challenging due to phase instabilities induced by Pb loss at the temperatures necessary for perovskite crystallization. Here, we discuss the challenges associated with Pb loss, as well as its compensation through bulk Pb overstoichiometry and interfacial PbO additions, in chemical solution processed, highly oriented PbZrO 3 thin films. For both 042 o - and 001 o -oriented (o-orthorhombic distortion) PbZrO 3 thin films, the crystallization interfaces are the most important contributors to Pb loss and off-stoichiometric outcomes, and no single approach was sufficient to address these challenges. Pb-rich and Pb-deficient nonperovskite phases including ZrO x were only observable through microscopic characterization, and X-ray diffraction alone could not rule out the presence of such secondary phases. “Ideal” macroscopic antiferroelectric polarization-electric field double hysteresis curves were observed despite (at times) the large presence of secondary phases. However, reduced saturation polarization and increased phase transition electric fields were observed concomitantly with the presence of secondary phase(s) and tentatively assigned to the voltage drop across the ZrO x nanocrystals. Based on these results, it is imperative that the presence of secondary phases always be addressed (beyond X-ray diffraction spectra) in order to correctly evaluate the properties of antiferroelectric films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light-Driven Expansion of Spiropyran Hydrogels

The incorporation of molecular switches in organic structures is of great interest in the chemical design of stimuli-responsive materials that mimic the complex functions of living systems. Merocyanine dyes that convert to spiropyran moieties upon exposure to visible light have been extensively studied as they can be incorporated in hydrated covalent networks that will expel water when this conversion occurs and induce a volumetric shrinkage. We report here on a sulfonatebased water soluble photoswitch that in contrast to the well-known system triggers a volumetric expansion in hydrogels upon exposure to photons. Contraction is in turn observed under dark conditions in a highly reversible manner. The novel behavior of the photoswitch incorporated in the covalent network was also predicted by coarse grain simulations of the system’s chemical structure. Using pH control and polymeric structures that differ in lower critical solution temperature we were able to develop hydrogels with highly tunable volumetric expansion. Furthermore, the novel molecular function of the systems developed here led to materials with the negative phototaxis observed in plants, and can expand the potential use of hydrogels as sensors, soft robots, and actuators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering microscale systems for fully autonomous intracellular neural interfaces

Conventional electrodes and associated positioning systems for intracellular recording from single neurons in vitro and in vivo are large and bulky, which has largely limited their scalability. Further, acquiring successful intracellular recordings is very tedious, requiring a high degree of skill not readily achieved in a typical laboratory. We report here a robotic, MEMS-based intracellular recording system to overcome the above limitations associated with form-factor, scalability and highly skilled and tedious manual operations required for intracellular recordings. This system combines three distinct technologies: 1) novel microscale, glass-polysilicon penetrating electrode for intracellular recording, 2) electrothermal microactuators for precise microscale movement of each electrode and 3) closed-loop control algorithm for autonomous positioning of electrode inside single neurons. Here, we demonstrate the novel, fully integrated system of glass-polysilicon microelectrode, microscale actuators and controller for autonomous intracellular recordings from single neurons in the abdominal ganglion of Aplysia Californica (n = 5 cells). Consistent resting potentials (< –35 mV) and action potentials (> 60 mV) were recorded after each successful penetration attempt with the controller and microactuated glass-polysilicon microelectrodes. The success rate of penetration and quality of intracellular recordings achieved using electrothermal microactuators were comparable to that of conventional positioning systems. The MEMS-based system offers significant advantages: 1) reduction in overall size for potential use in behaving animals, 2) scalable approach to potentially realize multi-channel recordings and 3) a viable method to fully automate measurement of intracellular recordings. Furthermore, this system will be evaluated in vivo in future rodent studies.

42 ENGINEERING↗

Scalable and automated CRISPR-based strain engineering using droplet microfluidics

Abstract We present a droplet-based microfluidic system that enables CRISPR-based gene editing and high-throughput screening on a chip. The microfluidic device contains a 10 × 10 element array, and each element contains sets of electrodes for two electric field-actuated operations: electrowetting for merging droplets to mix reagents and electroporation for transformation. This device can perform up to 100 genetic modification reactions in parallel, providing a scalable platform for generating the large number of engineered strains required for the combinatorial optimization of genetic pathways and predictable bioengineering. We demonstrate the system’s capabilities through the CRISPR-based engineering of two test cases: (1) disruption of the function of the enzyme galactokinase ( galK ) in E. coli and (2) targeted engineering of the glutamine synthetase gene ( glnA ) and the blue-pigment synthetase gene ( bpsA ) to improve indigoidine production in E. coli .

42 ENGINEERING↗

Mercury methylation by metabolically versatile and cosmopolitan marine bacteria

Microbes transform aqueous mercury (Hg) into methylmercury (MeHg), a potent neurotoxin that accumulates in terrestrial and marine food webs, with potential impacts on human health. This process requires the gene pair hgcAB, which encodes for proteins that actuate Hg methylation, and has been well described for anoxic environments. However, recent studies report potential MeHg formation in suboxic seawater, although the microorganisms involved remain poorly understood. In this study, we conducted large-scale multi-omic analyses to search for putative microbial Hg methylators along defined redox gradients in Saanich Inlet, British Columbia, a model natural ecosystem with previously measured Hg and MeHg concentration profiles. Analysis of gene expression profiles along the redoxcline identified several putative Hg methylating microbial groups, including Calditrichaeota, SAR324 and Marinimicrobia, with the last the most active based on hgc transcription levels. Marinimicrobia hgc genes were identified from multiple publicly available marine metagenomes, consistent with a potential key role in marine Hg methylation. Computational homology modelling predicts that Marinimicrobia HgcAB proteins contain the highly conserved amino acid sites and folding structures required for functional Hg methylation. Furthermore, a number of terminal oxidases from aerobic respiratory chains were associated with several putative novel Hg methylators. Our findings thus reveal potential novel marine Hg-methylating microorganisms with a greater oxygen tolerance and broader habitat range than previously recognized.

59 BASIC BIOLOGICAL SCIENCES↗

Structural and electronic switching of a single crystal 2D metal-organic framework prepared by chemical vapor deposition

The incorporation of metal-organic frameworks into advanced devices remains a desirable goal, but progress is hindered by difficulties in preparing large crystalline metal-organic framework films with suitable electronic performance. We demonstrate the direct growth of large-area, high quality, and phase pure single metal-organic framework crystals through chemical vapor deposition of a dimolybdenum paddlewheel precursor, Mo 2 (INA) 4 . These exceptionally uniform, high quality crystals cover areas up to 8600 µm 2 and can be grown down to thicknesses of 30 nm. Moreover, scanning tunneling microscopy indicates that the Mo 2 (INA) 4 clusters assemble into a two-dimensional, single-layer framework. Devices are readily fabricated from single vapor-phase grown crystals and exhibit reversible 8-fold changes in conductivity upon illumination at modest powers. Moreover, we identify vapor-induced single crystal transitions that are reversible and responsible for 30-fold changes in conductivity of the metal-organic framework as monitored by in situ device measurements. Gas-phase methods, including chemical vapor deposition, show broader promise for the preparation of high-quality molecular frameworks, and may enable their integration into devices, including detectors and actuators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗