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At least 163 records · Page 9

Influence of the molecular weight and size distribution of PSS on mixed ionic-electronic transport in PEDOT:PSS

The commercially available polyelectrolyte complex poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is ubiquitous in organic and hybrid electronics. As such, it has often been used as a benchmark material for fundamental studies and the development of new electronic devices. Yet, most studies on PEDOT:PSS have focused on its electronic conductivity in dry environments, with less consideration given to its ion transport, coupled ionic-electronic transport, and charge storage properties in aqueous environments. These properties are essential for applications in bioelectronics (sensors, actuators), charge storage devices, and electrochromic displays. Importantly, past studies on mixed ionic-electronic transport in PEDOT:PSS neglected to consider how the molecular structure of PSS affects mixed ionic-electronic transport. Herein, we therefore investigated the effect of the molecular weight and size distribution of PSS on the electronic properties and morphology of PEDOT:PSS both in dry and aqueous environments, and overall performance in organic electrochemical transistors (OECTs). Using reversible addition–fragmentation chain transfer (RAFT) polymerization with two different chain transfer agents, six PSS samples with monomodal, narrow (D = 1.1) and broad (D = 1.7) size distributions and varying molecular weights were synthesized and used as matrices for PEDOT. We found that using higher molecular weight of PSS (Mn = 145 kg mol –1 ) and broad dispersity led to OECTs with the highest transconductance (up to 16 mS) and [μC*] values (~140 F cm –1 V –1 s –1 ) in PEDOT:PSS, despite having a lower volumetric capacitance (C* = 35 ± 4 F cm –3 ). The differences were best explained by studying the microstructure of the films by atomic force microscopy (AFM). We found that heterogeneities in the PEDOT:PSS films (interconnected and large PEDOT- and PSS-rich domains) obtained from high molecular weight and high dispersity PSS led to higher charge mobility (μOECT ~4 cm 2 V –1 s –1 ) and hence transconductance. Furthermore, these studies highlight the importance of considering molecular weight and size distribution in organic mixed ionic-electronic conductor, and could pave the way to designing high performance organic electronics for biological interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vertical van der Waals heterojunction diodes comprising 2D semiconductors on 3D β-Ga 2 O 3

Wide bandgap semiconductors such as gallium oxide (Ga 2 O 3 ) have attracted much attention for their use in next-generation high-power electronics. Although single-crystal Ga 2 O 3 substrates can be routinely grown from melt along various orientations, the influence of such orientations has been seldom reported. Further, making rectifying p–n diodes from Ga 2 O 3 has been difficult due to lack of p-type doping. In this study, we fabricated and optimized 2D/3D vertical diodes on β-Ga 2 O 3 by varying the following three factors: substrate planar orientation, choice of 2D material and metal contacts. Furthermore, the quality of our devices was validated using high-temperature dependent measurements, atomic-force microscopy (AFM) techniques and technology computer-aided design (TCAD) simulations. Our findings suggest that 2D/3D β-Ga 2 O 3 vertical heterojunctions are optimized by substrate planar orientation (–201), combined with 2D WS 2 exfoliated layers and Ti contacts, and show record rectification ratios (>10 6 ) concurrently with ON-Current density (>10 3 A cm –2 ) for application in power rectifiers.

36 MATERIALS SCIENCE↗

The effect of low temperature on poly(3-methyl- N -vinylcaprolactam)- b -poly( N -vinylpyrrolidone) diblock copolymer nanovesicles assembled from all-aqueous media

Nanosized polymeric vesicles (polymersomes) self-assembled from double hydrophilic copolymers of poly(3-methyl-N-vinylcaprolactam) n -b-poly(N-vinylpyrrolidone) m (PMVC n -b-PVPON m ) using all aqueous media are a promising platform for biomedical applications, because of their superior stability over liposomes in vivo and high loading capacity. Herein, we explored the temperature-sensitive behavior of PMVC 58 -b-PVPON 65 vesicles using transmission electron microscopy (TEM), dynamic light scattering (DLS), atomic force microscopy (AFM), and small-angle neutron scattering (SANS) in response to lowering the solution temperature from 37 to 25, 20, 14 and 4 °C. The copolymer vesicles with an average size of 350 nm at 37 °C were assembled from the diblock copolymer dissolved in aqueous solution at 4 °C. We show that while the polymersome's size gradually decreases upon the temperature decrease from 37 to 4 °C, the average shell thickness increases from 17 nm to 25 nm, respectively. SANS study revealed that the PMVC 58 -b-PVPON 65 vesicle undergoes a gradual structure evolution from a dense-shell vesicle at 37–25 °C to a highly-hydrated shell vesicle at 20–14 °C to molecular chain aggregates at 4 °C. From SANS contrast matching study, this vesicle behavior is found to be driven by the gradual rehydration of PMVC block at 37–14 °C. The shell hydration at 20–14 °C also correlated with the 4.4-fold decrease in the relative fluorescence intensity from vesicle-encapsulated fluorescent dye, indicating ~80% of the dye release within 12 hours after the vesicle exposure to 14 °C. No significant (<5%) dye release was observed for the vesicle solutions at 37–20 °C, indicating excellent cargo retention inside the vesicles. Our study provides new fundamental insights on temperature-sensitive polymer vesicles and demonstrates that the copolymer assembly into polymersomes can be achieved by decreasing a copolymer aqueous solution temperature below 14 °C followed by solution exposure to ≥20 °C. This type of all-aqueous assembly, instead of nanoprecipitation from organic solvents or solvent exchange, can be highly desirable for encapsulating a wide range of biological molecules, including proteins, peptides, and nucleic acids, into stable polymer vesicles without a need for organic solvents for dissolution of the copolymers that are amphiphilic at physiologically relevant temperatures of 20–37 °C.

36 MATERIALS SCIENCE↗

Expanding the Zinc Precursor Toolbox: A Comparative Study of Precursors for Thermal ALD of ZnO Thin Films

Atomic layer deposition (ALD) of zinc oxide (ZnO) has been widely researched using diethyl zinc (DEZ)-based methods. The significant importance of thin films of ZnO as transparent conductive oxides (TCO) in optoelectronic devices and photovoltaics warrants examining alternative Zn precursors for ZnO ALD as potential replacements for the pyrophoric DEZ. In this study, we investigated three alternative Zn precursors: Zn(EEKI)2, Zn(DMP)2, ZnEt(HMDS), in the process development for high-quality ZnO thin films and compared them to DEZ. The ALD processes were studied using in situ spectroscopic ellipsometry. The properties of the ALD ZnO films were characterized using ex situ X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry and nuclear reaction analysis (RBS/NRA), X-ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and ultraviolet-visible (UV/Vis) spectrophotometry. These measurements confirmed the formation of pure, stoichiometric, and polycrystalline ZnO films using all four Zn precursors. Although the selected precursors are chemically diverse Zn compounds, they all yielded saturating ALD processes and high-quality ZnO thin films at 200 °C. This study highlights the potential benefits of alternative zinc precursors in designing ALD processes for ZnO thin films.

Obenlüneschloß, Jorit↗

Excitation energy transfer in proteoliposomes reconstituted with LH2 and RC-LH1 complexes from Rhodobacter sphaeroides

Abstract Light-harvesting 2 (LH2) and reaction-centre light-harvesting 1 (RC-LH1) complexes purified from the photosynthetic bacterium Rhodobacter (Rba.) sphaeroides were reconstituted into proteoliposomes either separately, or together at three different LH2:RC-LH1 ratios, for excitation energy transfer studies. Atomic force microscopy (AFM) was used to investigate the distribution and association of the complexes within the proteoliposome membranes. Absorption and fluorescence emission spectra were similar for LH2 complexes in detergent and liposomes, indicating that reconstitution retains the structural and optical properties of the LH2 complexes. Analysis of fluorescence emission shows that when LH2 forms an extensive series of contacts with other such complexes, fluorescence is quenched by 52.6 ± 1.4%. In mixed proteoliposomes, specific excitation of carotenoids in LH2 donor complexes resulted in emission of fluorescence from acceptor RC-LH1 complexes engineered to assemble with no carotenoids. Extents of energy transfer were measured by fluorescence lifetime microscopy; the 0.72 ± 0.08 ns lifetime in LH2-only membranes decreases to 0.43 ± 0.04 ns with a ratio of 2:1 LH2 to RC-LH1, and to 0.35 ± 0.05 ns for a 1:1 ratio, corresponding to energy transfer efficiencies of 40 ± 14% and 51 ± 18%, respectively. No further improvement is seen with a 0.5:1 LH2 to RC-LH1 ratio. Thus, LH2 and RC-LH1 complexes perform their light harvesting and energy transfer roles when reconstituted into proteoliposomes, providing a way to integrate native, non-native, engineered and de novo designed light-harvesting complexes into functional photosynthetic systems.

59 BASIC BIOLOGICAL SCIENCES↗

Nanoindentation-Enhanced Tip-Enhanced Raman Spectroscopy

We combine nanoindentation, herein achieved using atomic force microscopy (AFM)-based pulsed-force lithography, with tip-enhanced Raman spectroscopy (TERS) and imaging. Our approach entails indentation and multimodal characterization of otherwise flat Au substrates, followed by chemical functionalization and TERS spectral imaging of the indented nanostructures. We find that the resulting structures, which vary in shape and size depending on the tip used to produce them, may sustain nano-confined and significantly enhanced local fields. We take advantage of the latter and illustrate TERS-based ultrasensitive detection/chemical fingerprinting as well as chemical reaction imaging – all using a single platform for nano-lithography, topographic imaging, hyperspectral dark field optical microscopy, and TERS.

Wang, Chih-Feng↗

Mixed-flow design for microfluidic printing of two-component polymer semiconductor systems

The rational creation of two-component conjugated polymer systems with high levels of phase purity in each component is challenging but crucial for realizing printed soft-matter electronics. Here, we report a mixed-flow microfluidic printing (MFMP) approach for two-component π -polymer systems that significantly elevates phase purity in bulk-heterojunction solar cells and thin-film transistors. MFMP integrates laminar and extensional flows using a specially microstructured shear blade, designed with fluid flow simulation tools to tune the flow patterns and induce shear, stretch, and pushout effects. This optimizes polymer conformation and semiconducting blend order as assessed by atomic force microscopy (AFM), transmission electron microscopy (TEM), grazing incidence wide-angle X-ray scattering (GIWAXS), resonant soft X-ray scattering (R-SoXS), photovoltaic response, and field effect mobility. For printed all-polymer (poly[(5,6-difluoro-2-octyl-2H-benzotriazole-4,7-diyl)-2,5-thiophenediyl[4,8-bis[5-(2-hexyldecyl)-2-thienyl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl]-2,5-thiophenediyl]) [J51]:(poly{[N,N′-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-bithiophene)}) [N2200]) solar cells, this approach enhances short-circuit currents and fill factors, with power conversion efficiency increasing from 5.20% for conventional blade coating to 7.80% for MFMP. Moreover, the performance of mixed polymer ambipolar [poly(3-hexylthiophene-2,5-diyl) (P3HT):N2200] and semiconducting:insulating polymer unipolar (N2200:polystyrene) transistors is similarly enhanced, underscoring versatility for two-component π -polymer systems. Mixed-flow designs offer modalities for achieving high-performance organic optoelectronics via innovative printing methodologies.

42 ENGINEERING↗

Laser interference structuring of Cu for adhesive joining of HVAC equipment

Due to potential energy and cost savings benefits, adhesive joining has been recently considered for heating, ventilation, air conditioning, and refrigeration (HVAC&R) systems. HVAC adhesive bonding requires cost-effective and adequate surface preparations of adherents. Here, this article investigates the use of abrasion, traditional single-beam laser, and a laser-interference technique as surface preparations of copper surfaces. Surface morphology is characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Effective submicrometer peak-to-valley structuring with a periodicity of ∼2.7μ⁢m was demonstrated for laser-interference processing. Single-lap shear tests were conducted for 89 joints made with bondline thicknesses of 0.15 and 0.3 mm. Data on process variables and measured variables included open-time, bond length, maximum load, displacement at failure, shear lap strength, and failure mode. A statistical analysis was conducted on each lot to determine the lower limit with 95% confidence intervals for displacements at failure and shear lap strengths. A comparison is presented between the properties of laser-structured joints with respect to those prepared by abrasion, which is considered the baseline surface preparation technique. Based on this comparison, one single-beam laser technique and two laser-interference techniques were shown to exhibit vastly superior performance over the joints made with abraded specimens.

Sabau, Adrian S. [Oak Ridge National Laboratory (O↗

Effect of layer thickness on structural, morphological and superconducting properties of Nb 3 Sn films fabricated by multilayer sequential sputtering

Superconducting Nb3Sn films can be synthesized by controlling atomic concentration of Sn. Multilayer sequential sputtering of Nb and Sn thin films followed by high temperature annealing is considered as a method to fabricate Nb3Sn films where Sn composition of deposited films can be controlled by controlling the thickness of alternating Nb and Sn layers. We report on the structural, morphological and superconducting properties of Nb3Sn films fabricated by multilayer sequential sputtering of Nb and Sn films on sapphire substrates with ex-situ annealing at 950 °C for 3 h. We have investigated the effect of Nb and Sn layer thickness on the properties of Nb3Sn films. The thicknesses of Nb and Sn layers were varied in two ways: (1) varied Nb:Sn thickness ratio (1:1, 2:1, 3:1, 4:1), and (2) varied layer thickness of both Nb and Sn layers, while keeping constant Nb:Sn thickness ratio of 2:1. The crystal structure, surface morphology, topography, and film composition were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and energy dispersive X-ray spectroscopy (EDS) respectively. The results showed Sn loss from the surface due to evaporation during annealing. Superconducting Nb3Sn films of critical temperature up to 17.93 K have been achieved.

Sayeed, M. N.↗

Direct evidence that tumor cells soften when navigating confined spaces.

The mechanical properties of cells strongly regulate many physiological and pathological processes. For example, in cancer, invasive and metastatic tumor cells have often been reported to be softer than nontumor cells, raising speculation that cancer cells might adaptively soften to facilitate migration through narrow tissue spaces. Despite growing interest in targeting cell softening to impede invasion and metastasis, it remains to be directly demonstrated that tumor cells soften as they migrate through confined spaces. Here, we address this open question by combining topographically patterned substrates with atomic force microscopy (AFM). Using a polydimethylsiloxane open-roof microdevice featuring tapered, fibronectin-coated channels, we followed the migration of U2OS cells through various stages of confinement while simultaneously performing AFM indentation. As cells progress from unconfined migration to fully confined migration, cells soften and exclude Yes-associated protein from the nucleus. Superresolution imaging reveals that confinement induces remodeling of actomyosin stress fiber architecture. Companion studies with flat one-dimensional microlines indicate that the changes in cytoarchitecture and mechanics are intrinsically driven by topographical confinement rather than changes in cellular aspect ratio. Our studies represent among the most direct evidence to date that tumor cells soften during confined migration and support cell softening as a mechanoadaptive mechanism during invasion.

59 BASIC BIOLOGICAL SCIENCES↗

Formation of niobium hydride precipitates in superconducting qubits

We report evidence for the formation of niobium hydride phase within niobium films on silicon substrates in superconducting qubits fabricated at Rigetti Computing. For this study, we combined complementary techniques—including room-temperature and cryogenic atomic force microscopy (AFM), synchrotron x-ray diffraction, and time-of-flight secondary ion mass spectroscopy (ToF-SIMS)—to directly reveal the existence of niobium hydride precipitates on the surface of superconducting qubits. Upon cryogenic cooling, we observed variation in the size and morphology of the hydrides, ranging from small (∼5 nm) irregular shapes to large (∼10–100 nm) domains within the Nb grains, which were fully converted to niobium hydrides. Since niobium hydrides are nonsuperconducting and can easily change in size and location upon different cooldowns to cryogenic temperature, our finding highlights a previously unknown source of decoherence in superconducting qubits. This contributes to quasiparticle losses, offering a potential explanation for changes in qubit performance upon cooldowns. Finally, by leveraging the RF performance of a 3D bulk Nb resonator, we quantify RF dissipation in a superconducting qubit caused by hydrogen concentration variation, and propose a practical engineering pathway to mitigate the formation of Nb hydrides for superconducting qubit applications.

Sung, Zuhawn [Fermi National Accelerator Laborator↗

The effect of longer-range waviness on X-ray reflectivity measurements

A model for calculating the X-ray reflectivity (XRR) of surfaces to extract both roughness and waviness features is presented. Expressions of reflectivity intensity are derived as a function of root-mean-square (RMS) roughness σ, RMS waviness σ L , and the cut-off frequency between the features ω 0 . Experiments were conducted at the Advanced Light Source at Lawrence Berkeley National Laboratory, beamline 8.3.2, on BK7 glass manufactured with a multi-step polishing process to validate the model, and were compared with atomic force microscopy (AFM), Fizeau interferometry and surface profilometry measurements. Here, the parameter results and their deviations for XRR measurements were σ = 2.9 ± 0.2 nm and σ L = 14.6 ± 0.5 nm with a wavelength cut-off of 1/(18 ± 2) µm –1 , while the results from the AFM, Fizeau and profilometry measurements were σ AFM = 3.4 ± 0.4 nm, σ L,Fizeau = 21.6 nm, σ prof = 4.0 ± 0.1 nm, and σ L,prof = 21.4 ± 0.1 nm with cut-offs for the profilometry and Fizeau measurements limited to frequencies of (1/16) µm –1 to (1/4) mm –1 .

42 ENGINEERING↗

The mechanism driving a solid–solid phase transition in a biomacromolecular crystal

A solid-solid phase transition (SSPT) occurs between distinguishable crystalline forms. Because of its importance in application and theory in material science and condensed matter physics, SSPT has been studied most extensively in metallic alloys, inorganic salt or small organic molecular crystals, but much less so in biomacromolecular crystals. In general, the mechanism of SSPT at atomic and molecular levels is not well understood. Here, we describe the ordered molecular rearrangements in biomacromolecular crystals of the adenine riboswitch (riboA) aptamer using real-time serial crystallography and solution atomic force microscopy (AFM). The large, ligand-induced conformational changes drive the initial phase transition from the apo unit cell (AUC) to the trans unit cell 1 (TUC1). During this transition, coaxial stacking of P1 duplexes becomes the dominant packing interface, whereas P2-P2 interactions are almost completely disrupted, resulting in “floating” layers of molecules. The coupling points in TUC1 and their local conformational flexibility allow the molecules to reorganize to achieve the more densely packed and energetically favorable bound unit cell (BUC). Our study thus reveals the interplay between the conformational changes and the crystal phases—the underlying mechanism that drives the phase transition. Using polarized video microscopy (PVM) to monitor the SSPT in small crystals at high ligand concentration, we have identified the time window during which the major conformational changes take place, and simulated the in crystallo kinetics. Together, these results provide the spatiotemporal information necessary for informing time-resolved crystallography (TRX) experiments. Moreover, this study illustrates a practical approach to characterize SSPT in transparent crystals.

36 MATERIALS SCIENCE↗

The evolution of grain boundary energy in textured and untextured Ca–doped alumina during grain growth

The role of anisotropic grain boundary energy in grain growth is investigated using textured microstructures that contain a high proportion of special grain boundaries. Textured and untextured Ca–doped alumina was prepared by slip casting inside and outside a high magnetic field, respectively. At 1600°C, the textured microstructure exhibits faster growth than the untextured microstructure and its population of low–angle boundaries increases. Atomic force microscopy (AFM) is employed to measure the geometry of thermal grooves to assess the relative grain boundary energy of these systems before and after growth. In the textured microstructure, the grain boundary energy distribution narrows and shifts to a lower average energy. Conversely, the energy distribution broadens for the untextured microstructure as it grows and exhibits abnormal grain growth. Further analysis of the boundary networks neighboring abnormal grains reveals an energy incentive that facilitates their growth. These results suggest that coarsening is not the only dominant grain growth mechanism and that the system can lower its energy effectively by replacing high energy boundaries with those of low energy. The faster growth of lower energy boundaries suggests that isotropic simulations do not adequately account for anisotropic grain growth mechanisms or anisotropic mobility.

36 MATERIALS SCIENCE↗

Predictive Modeling of Electrodeposition in a Single Pore Flow-Through Electrode: From Electronucleation to Coating Thickness Uniformity

The emergence of advanced manufacturing methods capable of producing porous three-dimensional structures has expanded the design space for next-generation functional components. The ability to fabricate ordered 3D foams for use in electrocatalysis reactors has increased the need for controlled deposition of catalytic metals onto porous support materials, such as carbon. However, there is a lack of clear design guidelines for electrodeposition onto 3D substrates, due to the geometric complexity and multi-scale nature of the problem. Furthermore, electro-nucleation phenomena are often overlooked in macro-scale models of current distribution during deposition. Here, a graphite flow-through electrode (FTE) is used as a model system for copper deposition within a single pore. Potential distributions and electro-nucleation phenomena are coupled in a continuum level model by incorporating nucleation size and density as a function of overpotential, determined experimentally using in situ atomic force microscopy (AFM). The model predictions are validated by measuring the coating uniformity in the pore using micro-computed X-ray tomography (μCT). A scaling analysis comprising dimensionless parameters such as the Wagner number is presented. The simplified scaling relationship framework can guide the electrodeposition process and electrode design to optimize plating of porous substrates under fluid flow conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation of Ta 2 O 5 / SiO 2 dielectric cavity mirrors in ultra-high vacuum

In order for optical cavities to enable strong light-matter interactions for quantum metrology, networking, and scalability in quantum computing systems, their mirrors must have minimal losses. However, high-finesse dielectric cavity mirrors can degrade in ultra-high vacuum (UHV), increasing the challenges of upgrading to cavity-coupled quantum systems. We observe the optical degradation of high-finesse dielectric optical cavity mirrors after high-temperature UHV bake in the form of a substantial increase in surface roughness. We provide an explanation of the degradation through atomic force microscopy (AFM), X-ray fluorescence (XRF), selective wet etching, and optical measurements. We find the degradation is explained by oxygen reduction in Ta 2 O 5 followed by growth of tantalum sub-oxide defects with height to width aspect ratios near ten. We discuss the dependence of mirror loss on surface roughness and finally give recommendations to avoid degradation to allow for quick adoption of cavity-coupled systems.

Optics↗

Wafer-scale waveguide sidewall roughness scattering loss characterization by image processing

Photonic integrated circuits (PICs) are vital for developing affordable, high-performance optoelectronic devices that can be manufactured at an industrial scale, driving innovation and efficiency in various applications. Optical loss of modes in thin film waveguides and devices is a critical measure of their performance. Thin film growth, lithography, masking, and etching processes are imperfect processes that introduce significant sidewall and top-surface roughness and cause dominating optical losses in waveguides and photonic structures. This roughness, as perturbations couple light from guided to far-field radiation modes, leads to scattering losses that can be estimated from theoretical models. Typically, with UV-based lithography, sidewall roughness is significantly larger than wafer-top surface roughness. Atomic force microscopy (AFM) imaging measurement gives a 3D and high-resolution roughness profile, but the measurement is inconvenient, costly, and unscalable for large-scale PICs and at wafer-scale. Here, we evaluate the sidewall roughness profile based on 2D high-resolution scanning electron microscope (SEM) imaging. We characterized the loss on two homemade nitride and oxide films on 3-inch silicon wafers with 12 waveguide devices on each and correlated the scattering loss estimated from a 2D image-based sidewall profile and theoretical Payne model. The lowest loss of guided fundamental transverse electric (TE 0 ) mode is found at 0.075 dB/cm at 633 nm across 24 devices, a record at visible wavelength. Our work shows 100% success (edge continuity span exceeding 95% of image width/height) in edge detection in image processing of all images to estimate autocorrelation function and optical mode loss. These demonstrations offer valuable insights into waveguide sidewall roughness and a comparison of experimental and 2D SEM image processing based loss estimations with applications in loss characterization at wafer-scale PICs.

Khurana, Mohit (ORCID:0000000207898672)↗

Modulating ion-binding at macromolecular interfaces during (bio)mineralization: A snapshot review for calcium carbonate and calcium phosphate systems

Abstract Local environments have strict influence over (bio)mineralization in calcifying systems. This snapshot review discusses recent insights into the roles of Ca 2+ -macromolecule interactions on the nucleation of calcium carbonate and calcium phosphate minerals. Experimental findings combined with simulations/modeling are providing breakthrough information and raising important questions for future studies. The emerging picture is that both nucleation and growth are driven by local ordering of ions and water about the macromolecule interface, rather than broader properties or molecular class. Tuning macromolecular properties at the atomic scale thus provides opportunities for highly specific controls on mineralization; however, many limitations and challenges remain. We highlight studies employing in-situ atomic force microscopy (AFM) and transmission electron microscopy (TEM) to observe crystallization processes on or near macromolecular substrates. As the distribution and ability of these techniques increases, fundamental studies integrating experimental and computational methods will be crucial to inform a broad range of applications. Graphical abstract

Knight, Brenna M. (ORCID:0000000244000067)↗