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Item Band Engineering of ErAs:InGaAlBiAs Nanocomposite Materials for Terahertz Photoconductive Switches Pumped at 1550 nm(Advanced Functional Materials, 2024-04-18) Acuna, Wilder; Wu, Weipeng; Bork, James; Doty, Mathew F.; Jungfleisch, M. Benjamin; Gundlach, Lars; Zide, Joshua M. O.Terahertz technology has the potential to have a large impact in myriad fields, such as biomedical science, spectroscopy, and communications. Making these applications practical requires efficient, reliable, and low-cost devices. Photoconductive switches (PCS), devices capable of emitting and detecting terahertz pulses, are a technology that needs more efficiency when working at telecom wavelength excitation (1550 nm) to exploit the advantages this wavelength offers. ErAs:InGaAs is a semiconductor nanocomposite working at this energy; however, high dark resistivity is challenging due to a high electron concentration as the Fermi level lies in the conduction band. To increase dark resistivity, ErAs:InGaAlBiAs material is used as the active material in a PCS detecting Terahertz pulses. ErAs nanoparticles reduce the carrier lifetime to subpicosecond values required for short temporal resolution, while ErAs pins the effective Fermi level in the host material bandgap. Unlike InGaAs, InGaAlBiAs offers enough freedom for band engineering to have a material compatible with a 1550 nm pump and a Fermi level deep in the bandgap, meaning low carrier concentration and high dark resistivity. Band engineering is possible by incorporating aluminum to lift the conduction band edge to the Fermi level and bismuth to keep a bandgap compatible with 1550 nm excitation.Item A novel digital lifecycle for Material-Process-Microstructure-Performance relationships of thermoplastic olefins foams manufactured via supercritical fluid assisted foam injection molding(Polymer Engineering and Science, 2024-03-15) Pradeep, Sai Aditya; Deshpande, Amit M.; Lavertu, Pierre‐Yves; Zheng, Ting; Yerra, Veera Aditya; Shimabukuro, Yiro; Li, Gang; Pilla, SrikanthThis research significantly enhances the applicability of thermoplastic olefins (TPOs) in the automotive industry using supercritical N2 as a physical foaming agent, effectively addressing the limitations of traditional chemical agents. It merges experimental results with simulations to establish detailed material-process-microstructure-performance (MP2) relationships, targeting 5–20% weight reductions. This innovative approach labeled digital lifecycle (DLC) helps accurately predict tensile, flexural, and impact properties based on the foam microstructure, along with experimentally demonstrating improved paintability. The study combines process simulations with finite element models to develop a comprehensive digital model for accurately predicting mechanical properties. Our findings demonstrate a strong correlation between simulated and experimental data, with about a 5% error across various weight reduction targets, marking significant improvements over existing analytical models. This research highlights the efficacy of physical foaming agents in TPO enhancement and emphasizes the importance of integrating experimental and simulation methods to capture the underlying foaming mechanism to establish material-process-microstructure-performance (MP2) relationships. Highlights - Establishes a material-process-microstructure-performance (MP2) for TPO foams - Sustainably produces TPO foams using supercritical (ScF) N2 with 20% lightweighting - Shows enhanced paintability for TPO foam improved surface aesthetics - Digital lifecycle (DLC) that predicts both foam microstructure and properties - DLC maps process effects & microstructure onto FEA mesh for precise predictionItem Adhesion Characterization and Enhancement between Polyimide-Silica Composite and Nodulated Copper for Applications in Next-Generation Microelectronics(ACS Applied Materials & Interfaces, 2024-01-17) Doshi, Sagar M.; Barry, Alexander; Schneider, Alexander; Parambil, Nithin; Mulzer, Catherine; Yahyazadehfar, Mobin; Samadi-Dooki, Aref; Foltz, Benjamin; Warrington, Keith; Wessel, Richard; Zhang, Lei; Simone, Christopher; Blackman, Gregory S.; Lamontia, Mark A.; Gillespie, John W. Jr.As the need for high-speed electronics continues to rise rapidly, printed wiring board (PWB) requirements become ever-more demanding. A typical PWB is fabricated by bonding dielectric films such as polyimide to electrically conductive copper foil such as rolled annealed (RA) copper and is expected to become thinner, flexible, durable, and compatible with high-frequency 5G performance. Polyimide films inherently feature a higher coefficient of thermal expansion (CTE) than copper foils; this mismatch causes residual thermal stresses. To attenuate the mismatch, silica nanoparticles may be used to reduce the CTE of PI. A nodulated copper surface can be used to enhance the Cu/PI adhesion by additional bonding mechanisms that could include a type of mechanical bonding, which is a focus of this study. In this investigation, a 90° peel test was used to measure the peel strength in copper/polyimide/copper laminates containing nodulated copper and polyimide reinforced with 0, 20, and 40 wt % silica nanoparticles. The influence of silica nanoparticles on the peel strength was quantitatively evaluated. Laminates incorporating polyimide films lacking silica nanoparticles had a ∼3.75× higher peel strength compared with laminates reinforced with 40% silica. Their failure surfaces were analyzed by using scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and X-ray photoelectron spectroscopy to identify the mode of failure and to understand bonding mechanisms. The key bonding mechanism, mechanical interlocking, was achieved when the polyimide surrounded or engulfed the copper nodules when the laminate was created. Post-testing failure surface analysis revealed the presence of copper on the polyimide side and polyimide on the copper side, indicating mixed mode failure. An analytical model was developed to determine the impact of applied pressure, temperature, and time on the polyimide penetration and mechanical interlocking around the copper nodules. The model was validated by measuring the peel strength on another set of specimens fabricated using increased temperature and pressure that showed a 3× increase in peel strength compared to lower temperature/pressure processing conditions. This enhanced adhesion resulted from the lower polymer material viscosity at higher temperatures, which fosters deeper and more complete penetration around the copper nodules during processing at higher pressures for longer durations. The methodology of combining peel testing, viscosity and CTE measurement, SEM/EDX, surface chemical analysis, and penetration depth calculation developed herein enables the calculation of the desired processing parameters to enhance functionality and improve adhesion.Item Single-Mask Fabrication of Sharp SiOx Nanocones(IEEE Transactions on Semiconductor Manufacturing, 2023-11-28) Herrmann, Eric; Wang, XiThe patterning of silicon and silicon oxide nanocones onto the surfaces of devices introduces interesting phenomena such as anti-reflection and super-transmissivity. While silicon nanocone formation is well-documented, current techniques to fabricate silicon oxide nanocones either involve complex fabrication procedures, non-deterministic placement, or poor uniformity. Here, we introduce a single-mask dry etching procedure for the fabrication of sharp silicon oxide nanocones with smooth sidewalls and deterministic distribution using electron beam lithography. Silicon oxide films deposited using plasma-enhanced chemical vapor deposition are etched using a thin alumina hard mask of selectivity > 88, enabling high aspect ratio nanocones with smooth sidewalls and arbitrary distribution across the target substrate. We further introduce a novel multi-step dry etching technique to achieve ultra-sharp amorphous silicon oxide nanocones with tip diameters of ~10 nm. The processes presented in this work may have applications in the fabrication of amorphous nanocone arrays onto arbitrary substrates or as nanoscale probes.Item Growth factors and growth factor gene therapies for treating chronic wounds(Bioengineering and Translational Medicine, 2023-12-28) Mullin, James A.; Rahmani, Erfan; Kiick, Kristi L.; Sullivan, Millicent O.Chronic wounds are an unmet clinical need affecting millions of patients globally, and current standards of care fail to consistently promote complete wound closure and prevent recurrence. Disruptions in growth factor signaling, a hallmark of chronic wounds, have led researchers to pursue growth factor therapies as potential supplements to standards of care. Initial studies delivering growth factors in protein form showed promise, with a few formulations reaching clinical trials and one obtaining clinical approval. However, protein-form growth factors are limited by instability and off-target effects. Gene therapy offers an alternative approach to deliver growth factors to the chronic wound environment, but safety concerns surrounding gene therapy as well as efficacy challenges in the gene delivery process have prevented clinical translation. Current growth factor delivery and gene therapy approaches have primarily used single growth factor formulations, but recent efforts have aimed to develop multi-growth factor approaches that are better suited to address growth factor insufficiencies in the chronic wound environment, and these strategies have demonstrated improved efficacy in preclinical studies. This review provides an overview of chronic wound healing, emphasizing the need and potential for growth factor therapies. It includes a summary of current standards of care, recent advances in growth factor, cell-based, and gene therapy approaches, and future perspectives for multi-growth factor therapeutics. Translational Impact Statement Chronic wounds persist as a healthcare challenge despite extensive research on various treatments, including growth factors and gene therapies. Progress in translating these therapeutics to clinical use has been slow, with many growth factor approaches demonstrating promise in preclinical studies but providing limited benefits in clinical trials or clinical application. This review presents recent advances in growth factor therapies and growth factor gene therapies, discusses obstacles to regulatory approval, and offers perspectives on potential innovations for successful clinical translation.Item One Pot Photomediated Formation of Electrically Conductive Hydrogels(ACS Polymers Au, 2024-02-14) Nguyen, Dan My; Lo, Chun-Yuan; Guo, Tianzheng; Choi, Taewook; Sundar, Shalini; Swain, Zachary; Wu, Yuhang; Dhong, Charles; Kayser, Laure V.Electrically conductive hydrogels represent an innovative platform for the development of bioelectronic devices. While photolithography technologies have enabled the fabrication of complex architectures with high resolution, photoprinting conductive hydrogels is still a challenging task because the conductive polymer absorbs light which can outcompete photopolymerization of the insulating scaffold. In this study, we introduce an approach to synthesizing conductive hydrogels in one step. Our approach combines the simultaneous photo-cross-linking of a polymeric scaffold and the polymerization of 3,4-ethylene dioxythiophene (EDOT), without additional photocatalysts. This process involves the copolymerization of photo-cross-linkable coumarin-containing monomers with sodium styrenesulfonate to produce a water-soluble poly(styrenesulfonate-co-coumarin acrylate) (P(SS-co-CoumAc)) copolymer. Our findings reveal that optimizing the [SS]:[CoumAc] ratio at 100:5 results in hydrogels with the strain at break up to 16%. This mechanical resilience is coupled with an electronic conductivity of 9.2 S m–1 suitable for wearable electronics. Furthermore, the conductive hydrogels can be photopatterned to achieve micrometer-sized structures with high resolution. The photo-cross-linked hydrogels are used as electrodes to record stable and reliable surface electromyography (sEMG) signals. These novel photo-cross-linkable polymers combined with one-pot PEDOT (poly-EDOT) polymerization open possibilities for rapidly prototyping complex bioelectronic devices and creating custom-designed interfaces between electronics and biological systems.Item Unlocking Circularity Through the Chemical Recycling and Upcycling of Lignin-Derivable Polymethacrylates(Macromolecules, 2023-11-22) Christoff-Tempesta, Ty; O’Dea, Robert M.; Epps, Thomas H. IIIThe synthesis of polymers from lignin-derivable compounds can replace petrochemical building blocks with a renewable feedstock. However, the end-of-life management of bioderivable, nonbiodegradable polymers remains an outstanding challenge. Herein, the chemical recycling and upcycling of two higher-glass-transition temperature (>100 °C), lignin-derivable polymethacrylates, poly(syringyl methacrylate) (PSM) and poly(guaiacyl methacrylate) (PGM), is reported. Neat PSM and PGM were thermally depolymerized to quantitative conversions, producing their constituent monomers at high yields and purity. The deconstruction atmosphere influenced the depolymerization reaction order, and depolymerization was thermodynamically favored in air over N2. Further, monomer bulkiness and volatility impacted depolymerization activation energies. Notably, bulk depolymerization of PSM and PGM was performed without solvent or catalyst to high polymer conversions (89–90 wt %) and monomer yields (86–90 mol %) without byproduct formation. The resultant monomers were then upcycled to narrow-dispersity polymers and phase-separated block polymers. The findings herein offer a pathway to material circularity for higher-performance, lignin-derivable polymethacrylates.Item Peculiar bond length dependence in (Ag,Cu)GaSe2 alloys and its impact on the bandgap bowing(APL Materials, 2023-11-02) Falk, Hans H.; Eckner, Stefanie; Seifert, Michael; Ritter, Konrad; Levcenko, Sergiu; Pfeiffelmann, Timo; Welter, Edmund; Botti, Silvana; Shafarman, William N.; Schnohr, Claudia S.Contrary to other semiconductor alloys, incorporation of Ag into CuGaSe2 increases the bandgap, even though the lattice expands, and the Ga–Se bond length is theoretically predicted to decrease rather than increase. Herein, we experimentally confirm this peculiar bond length dependence of (Ag,Cu)GaSe2 using x-ray absorption spectroscopy. We further model the different anion displacements and estimate that their combined contribution to the bandgap bowing is close to zero. These findings differ from those for Cu(In,Ga)Se2 and demonstrate the diversity of chalcopyrite alloys and their properties.Item Surface Functionalization with (3-Glycidyloxypropyl)trimethoxysilane (GOPS) as an Alternative to Blending for Enhancing the Aqueous Stability and Electronic Performance of PEDOT:PSS Thin Films(ACS Applied Materials and Interfaces, 2023-11-29) Osazuwa, Peter O.; Lo, Chun-Yuan; Feng, Xu; Nolin, Abigail; Dhong, Charles; Kayser, Laure V.Organic mixed ionic–electronic conductors, such as poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), are essential materials for the fabrication of bioelectronic devices due to their unique ability to couple and transport ionic and electronic charges. The growing interest in bioelectronic devices has led to the development of organic electrochemical transistors (OECTs) that can operate in aqueous solutions and transduce ionic signals of biological origin into measurable electronic signals. A common challenge with OECTs is maintaining the stability and performance of the PEDOT:PSS films operating under aqueous conditions. Although the conventional approach of blending the PEDOT:PSS dispersions with a cross-linker such as (3-glycidyloxypropyl)trimethoxysilane (GOPS) helps to ensure strong adhesion of the films to device substrates, it also impacts the morphology and thus electrical properties of the PEDOT:PSS films, which leads to a significant reduction in the performance of OECTs. In this study, we instead functionalize only the surface of the device substrates with GOPS to introduce a silane monolayer before spin-coating the PEDOT:PSS dispersion on the substrate. In all cases, having a GOPS monolayer instead of a blend leads to increased electronic performance metrics, such as three times higher electronic conductivity, volumetric capacitance, and mobility–capacitance product [μC*] value in OECT devices, ultimately leading to a record value of 406 ± 39 F cm–1 V–1 s–1 for amorphous PEDOT:PSS. This increased performance does not come at the expense of operational stability, as both the blend and surface functionalization show similar performance when subjected to pulsed gate bias stress, long-term electrochemical cycling tests, and aging over 150 days. Overall, this study establishes a novel approach to using GOPS as a surface monolayer instead of a blended cross-linker, for achieving high-performance organic mixed ionic–electronic conductors that are stable in water for bioelectronics.Item Basement Membrane Mimetic Hydrogel Cooperates with Rho-Associated Protein Kinase Inhibitor to Promote the Development of Acini-Like Salivary Gland Spheroids(Advanced NanoBiomed Research, 2023-11-20) Fowler, Eric W.; Witt, Robert L.; Jia, XinqiaoSuccessful engineering of functional salivary glands necessitates the creation of cell-instructive environments for ex vivo expansion and lineage specification of primary human salivary gland stem cells (hS/PCs). Herein, basement membrane mimetic hydrogels are prepared using hyaluronic acid, cell adhesive peptides, and hyperbranched polyglycerol (HPG), with or without sulfate groups, to produce “hyperGel+” or “hyperGel”, respectively. Differential scanning fluorescence experiments confirm the ability of the sulfated HPG precursor to stabilize fibroblast growth factor 10. The hydrogels are nanoporous, cytocompatible, and cell-permissive, enabling the development of multicellular hS/PC spheroids in 14 days. The incorporation of sulfated HPG species in the hydrogel enhances cell proliferation. Culture of hS/PCs in hyperGel+ in the presence of a Rho kinase inhibitor Y-27632 (Y-27) leads to the development of spheroids with a central lumen, increases the expression of acinar marker aquaporin-3 at the transcript level (AQP3), and decreases the expression of ductal marker keratin 7 at both the transcript (KRT7) and the protein levels (K7). Reduced expression of transforming growth factor beta (TGF-β) targets SMAD2/3 is also observed in Y27-treated cultures, suggesting attenuation of TGF-β signaling. Thus, hyperGel+ cooperates with the Rho-associated protein kinase inhibitor to promote the development of lumened spheroids with enhanced expression of acinar markers.Item Combination cancer imaging and phototherapy mediated by membrane-wrapped nanoparticles(International Journal of Hyperthermia, 2023-10-30) Aboeleneena, Sara B.; Scully, Mackenzie A.; Kramarenko, George C.; Day, Emily S.Cancer is a devastating health problem with inadequate treatment options. Many conventional treatments for solid-tumor cancers lack tumor specificity, which results in low efficacy and off-target damage to healthy tissues. Nanoparticle (NP)-mediated photothermal therapy (PTT) is a promising minimally invasive treatment for solid-tumor cancers that has entered clinical trials. Traditionally, NPs used for PTT are coated with passivating agents and/or targeting ligands, but alternative coatings are being explored to enhance tumor specific delivery. In particular, cell-derived membranes have emerged as promising coatings that improve the biointerfacing of photoactive NPs, which reduces their immune recognition, prolongs their systemic circulation and increases their tumor accumulation, allowing for more effective PTT. To maximize treatment success, membrane-wrapped nanoparticles (MWNPs) that enable dual tumor imaging and PTT are being explored. These multifunctional theranostic NPs can be used to enhance tumor detection and/or ensure a sufficient quantity of NPs that have arrived in the tumor prior to laser irradiation. This review summarizes the current state-of-the-art in engineering MWNPs for combination cancer imaging and PTT and discusses considerations for the path toward clinical translation.Item Crystal structure and electrical and optical properties of two-dimensional group-IV monochalcogenides(Physical Review B, 2023-08-07) Querne, Mateus B. P.; Bracht, Jean M.; Da Silva, Juarez L. F.; Janotti, Anderson; Lima, Matheus P.Two-dimensional (2D) semiconductor materials offer a platform for unconventional applications such as valleytronics, flexible nanoelectronics, and hosts of quantum emitters. Many of these materials and their electronic properties remain to be explored. Using ab initio simulations based on the density functional theory, we investigate group-IV monochalcogenides MQ (M=Si, Ge,Sn and Q=S, Se, Te), an emerging class of 2D materials, with two competing crystal structures: (i) phosphorenelike (Pmn21), which has already been synthesized, and (ii) SiTe-type (P¯3m1), which has been much less explored. Except for Sn, we find that the SiTe type is the lowest-energy structure and has higher structural stability, motivating efforts to synthesize this less explored P¯3m1 phase. Regarding the optoelectronic properties of these two phases, in the P¯3m1 phase, MQ compounds have band gaps around the sunlight spectrum peak and show narrower variations in band gap with the composition and higher absorption coefficients for lighter chalcogens. In contrast, in the Pmn21 phase, MQ compounds have wider band gaps and show a band gap variation of up to 72% with composition, higher absorption coefficients with Te atoms, and potential for valleytronics. In particular, SiS shows interesting high optical anisotropy among all the investigated materials. Furthermore, the optical spectra present peaks that are particular to each phase or composition, making the refractive index a distinguishing parameter for identifying the different MQ compounds. Finally, a phase transition from monolayer to bulk due to an interaction between the layers is observed. Thus, the present results straighten out the role of the crystalline phase in the optoelectronic properties of these monochalcogenides.Item Modeling the Maturation of the Vocal Fold Lamina Propria Using a Bioorthogonally Tunable Hydrogel Platform(Advanced Healthcare Materials, 2023-08-02) Zou, Xiaoyu; Zhang, He; Benson, Jamie M.; Gao, Hanyuan; Burris, David L.; Fox, Joseph. M.; Jia, XinqiaoToward the goal of establishing an engineered model of the vocal fold lamina propria (LP), mesenchymal stem cells (MSCs) are encapsulated in hyaluronic acid (HA)-based hydrogels employing tetrazine ligation with strained alkenes. To mimic matrix stiffening during LP maturation, diffusion-controlled interfacial bioorthogonal crosslinking is carried out on the soft cellular construct using HA modified with a ferocious dienophile, trans-cyclooctene (TCO). Cultures are maintained in MSC growth media for 14 days to afford a model of a newborn LP that is homogeneously soft (nLP), a homogeneously stiffened construct zero (sLP0) or 7 days (sLP7) post cell encapsulation, and a mature LP model (mLP) with a stiff top layer and a soft bottom layer. Installation of additional HA crosslinks restricts cell spreading. Compared to the nLP controls, sLP7 conditions upregulate the expression of fibrous matrix proteins (Col I, DCN, and FN EDA), classic fibroblastic markers (TNC, FAP, and FSP1), and matrix remodeling enzymes (MMP2, TIMP1, and HAS3). Day 7 stiffening also upregulates the catabolic activities, enhances ECM turnover, and promotes YAP expression. Overall, in situ delayed matrix stiffening promotes a fibroblast transition from MSCs and enhances YAP-regulated mechanosensing.Item The Role of Optical Phonon Confinement in The Infrared Dielectric Response of III-V Superlattices(Advanced Materials, 2023-12-01) Matson, Joseph R.; Alam, Md Nazmul; Varnavides, Georgios; Sohr, Patrick; Knight, Sean; Darakchieva, Vanya; Stokey, Megan; Schubert, Mathias; Said, Ayman; Beechem, Thomas; Narang, Prineha; Law, Stephanie; Caldwell, Joshua D.Polar dielectrics are key materials of interest for infrared (IR) nanophotonic applications due to their ability to host phonon-polaritons (PhPs) that allow for low-loss, subdiffractional control of light. The properties of phonon-polaritons are limited by the characteristics of optical phonons, which are nominally fixed for most “bulk” materials. Superlattices composed of alternating atomically-thin materials offer control over crystal anisotropy through changes in composition, optical phonon confinement, and the emergence of new modes. In particular, the modified optical phonons in superlattices offer the potential for so-called crystalline hybrids whose IR properties cannot be described as a simple mixture of the bulk constituents. To date, however, studies have primarily focused on identifying the presence of new or modified optical phonon modes rather than assessing their impact on the IR response. This study focuses on assessing the impact of confined optical phonon modes on the hybrid IR dielectric function in superlattices of GaSb and AlSb. Using a combination of first principles theory, Raman, FTIR, and spectroscopic ellipsometry, the hybrid dielectric function is found to track with the confinement of optical phonons, leading to optical phonon spectral shifts of up to 20 cm−1. These results provide an alternative pathway towards designer IR optical materials.Item Sequence-Encoded Differences in Phase Separation Enable Formation of Resilin-like Polypeptide-Based Microstructured Hydrogels(Biomacromolecules, 2023-08-14) Patkar, Sai S.; Garcia, Cristobal Garcia; Palmese, Luisa L.; Kiick, Kristi L.Microstructured hydrogels are promising platforms to mimic structural and compositional heterogeneities of the native extracellular matrix (ECM). The current state-of-the-art soft matter patterning techniques for generating ECM mimics can be limited owing to their reliance on specialized equipment and multiple time- and energy-intensive steps. Here, a photocross-linking methodology that traps various morphologies of phase-separated multicomponent formulations of compositionally distinct resilin-like polypeptides (RLPs) is reported. Turbidimetry and quantitative 1H NMR spectroscopy were utilized to investigate the sequence-dependent liquid–liquid phase separation of multicomponent solutions of RLPs. Differences between the intermolecular interactions of two different photocross-linkable RLPs and a phase-separating templating RLP were exploited for producing microstructured hydrogels with tunable control over pore diameters (ranging from 1.5 to 150 μm) and shear storage moduli (ranging from 0.2 to 5 kPa). The culture of human mesenchymal stem cells demonstrated high viability and attachment on microstructured hydrogels, suggesting their potential for developing customizable platforms for regenerative medicine applications.Item Isocorrole-Loaded Polymer Nanoparticles for Photothermal Therapy under 980 nm Light Excitation(ACS Omega, 2022-10-18) Marek, Maximilian R. J.; Pham, Trong-Nhan; Wang, Jianxin; Cai, Qiuqi; Yap, Glenn P. A.; Day, Emily S.; Rosenthal, JoelPhotothermal therapy (PTT) is a promising treatment option for diseases, including cancer, arthritis, and periodontitis. Typical photothermal agents (PTAs) absorb light in the near-infrared (NIR)-I region of 650–900 nm with a predominant focus around 800 nm, as these wavelengths are minimally absorbed by water and blood in the tissue. Recently, interest has grown in developing nanomaterials that offer more efficient photothermal conversion and that can be excited by light close to or within the NIR-II window of 1000–1700 nm, which offers less absorption by melanin. Herein, we report on the development of 5,5-diphenyl isocorrole (5-DPIC) complexes containing either Zn(II) or Pd(II) (Zn[5-DPIC] and Pd[5-DPIC], respectively) that absorb strongly across the 850–1000 nm window. We also show that poly(lactic-co-glycolic acid) (PLGA) nanoparticles loaded with these designer isocorroles exhibit low toxicity toward triple-negative breast cancer (TNBC) cells in the dark but enable efficient heat production and photothermal cell ablation upon excitation with 980 nm light. These materials represent an exciting new platform for 980 nm activated PTT and demonstrate the potential for designer isocorroles to serve as effective PTAs.Item Matrix Degradability Contributes to the Development of Salivary Gland Progenitor Cells with Secretory Functions(ACS Applied Materials and Interfaces, 2023-07-12) Metkari, Apoorva S.; Fowler, Eric W.; Witt, Robert L.; Jia, XinqiaoSynthetic matrices that are cytocompatible, cell adhesive, and cell responsive are needed for the engineering of implantable, secretory salivary gland constructs to treat radiation induced xerostomia or dry mouth. Here, taking advantage of the bioorthogonality of the Michael-type addition reaction, hydrogels with comparable stiffness but varying degrees of degradability (100% degradable, 100DEG; 50% degradable, 50DEG; and nondegradable, 0DEG) by cell-secreted matrix metalloproteases (MMPs) were synthesized using thiolated HA (HA-SH), maleimide (MI)-conjugated integrin-binding peptide (RGD-MI), and MI-functionalized peptide cross-linkers that are protease degradable (GIW-bisMI) or nondegradable (GIQ-bisMI). Organized multicellular structures developed readily in all hydrogels from dispersed primary human salivary gland stem cells (hS/PCs). As the matrix became progressively degradable, cells proliferated more readily, and the multicellular structures became larger, less spherical, and more lobular. Immunocytochemical analysis showed positive staining for stem/progenitor cell markers CD44 and keratin 5 (K5) in all three types of cultures and positive staining for the acinar marker α-amylase under 50DEG and 100DEG conditions. Quantitatively at the mRNA level, the expression levels of key stem/progenitor markers KIT, KRT5, and ETV4/5 were significantly increased in the degradable gels as compared to the nondegradable counterparts. Western blot analyses revealed that imparting matrix degradation led to >3.8-fold increase in KIT expression by day 15. The MMP-degradable hydrogels also promoted the development of a secretary phenotype, as evidenced by the upregulation of acinar markers α-amylase (AMY), aquaporin-5 (AQP5), and sodium-potassium chloride cotransporter 1 (SLC12A2). Collectively, we show that cell-mediated matrix remodeling is necessary for the development of regenerative pro-acinar progenitor cells from hS/PCs.Item Assessment of Directionally Solidified Eutectic Sm–Fe(Co)–Ti Alloys as Permanent Magnet Materials(IEEE Transactions on Magnetics, 2023-05-29) Gabay, Alexander M.; Han, Chaoya; Ni, Chaoying; Hadjipanayis, George C.Sm–Fe–Ti and Sm–Fe 0.8 Co 0.2 –Ti alloys were prepared via arc-melting and directionally solidified on a water-cooled copper hearth. The as-solidified alloys featured cells of the Sm(Fe,Co,Ti) 12 –Ti(Fe,Co) 2+δ –(α-Fe) lamellar eutectic. The lamellae of Sm(Fe,Co,Ti) 12 phase with a crystal structure of the ThMn12 type were less than 0.2 μm thick, and had their [001] easy-magnetization directions oriented along the temperature gradient of the solidification. The eutectic microstructure led to an increased coercivity, especially in the Co-added alloys. Below 250 °C, this coercivity was found not to vary much with temperature with a temperature coefficient of -0.18 %/°C. However, the modest absolute values, reaching only 0.7 kOe, are insufficient for utilization of the directionally solidified alloys as anisotropic permanent magnets.Item Cholesterol-substituted 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and Poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol)(Giant, 2023-05-23) Wu, Yuhang; Nagane, Samadhan S.; Baugh, Quintin; Lo, Chun-Yuan; Chhatre, Shrirang S.; Lee, Junghyun; Sitarik, Peter; Kayser, Laure V.; Martin, David C.Cholesterol is a rigid, crystalline, non-polar natural substance that exists in animal blood and cell membranes. Some of its derivatives are known to form ordered liquid crystalline mesophases under suitable conditions. In this work, we carefully examined the influence of cholesterol substitution on the characteristics of 3,4-ethylenedioxythiophene (EDOT-MA-cholesterol) and its corresponding polymer poly(3,4-ethylenedioxythiophene) (PEDOT-MA-cholesterol) synthesized by both chemical and electrochemical polymerization. We found evidence for an ordered lamellar (smectic-like) structure in the EDOT-MA-cholesterol monomer by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X-ray diffraction techniques. The ordered phase was observed to form on cooling from the isotropic melt at about 80 °C. Due to the insulating and bulky cholesterol side group on the EDOT monomer, we found that there was a maximum charge density for electrodeposition at ∼ 0.155 C.cm−2. A series of electrodepositions were performed from 0 to 0.155 C.cm−2 for probing the change of the charge transport with more charges used for the electrodeposition. We found that the impedance increased in the high-frequency range (above 104 Hz) and decreased in the low-frequency range (below 102 Hz). Three equivalent circuit models were proposed for fitting impedance data at different charge densities for a better understanding of the film growth process. The suppressed cyclic voltammogram (CV) of PEDOT-MA-cholesterol showed that the charge storage capability was essentially eliminated in the thickest films. The limited doping of the films was corroborated by their diminished electrochromic behavior, polaron-dominating absorption in UV-vis, overoxidized S 2p X-ray Photoelectron Spectroscopy (XPS) signal of electrodeposited films, and proton Nuclear Magnetic Resonance (1H NMR) of chemically polymerized samples. Dense film morphologies were confirmed by scanning electron microscopy (SEM). Grazing incident X-ray diffraction (GIWAXS) indicated the disrupted stacking of conjugated chains, which correlated with the decreased conductivity of the PEDOT-MA-cholesterol films. The measurement of the electrical conductivity gave a value of around 3.30 × 10−6 S.cm−1 which is about six orders of magnitude lower than has been seen in PEDOT (∼3 S.cm-1). Graphical abstract available at: https://doi.org/10.1016/j.giant.2023.100163Item Carbon Additive Manufacturing with a Near-Replica “Green-to-Brown” Transformation(Advanced Materials, 2023-05-30) Zhang, Chunyan; Shi, Baohui; He, Jinlong; Zhou, Lyu; Park, Soyeon; Doshi, Sagar; Shang, Yuanyuan; Deng, Kaiyue; Giordano, Marc; Qi, Xiangjun; Cui, Shuang; Liu, Ling; Ni, Chaoying; Fu, Kun KelvinNanocomposites containing nanoscale materials offer exciting opportunities to encode nanoscale features into macroscale dimensions, which produces unprecedented impact in material design and application. However, conventional methods cannot process nanocomposites with a high particle loading, as well as nanocomposites with the ability to be tailored at multiple scales. A composite architected mesoscale process strategy that brings particle loading nanoscale materials combined with multiscale features including nanoscale manipulation, mesoscale architecture, and macroscale formation to create spatially programmed nanocomposites with high particle loading and multiscale tailorability is reported. The process features a low-shrinking (<10%) “green-to-brown” transformation, making a near-geometric replica of the 3D design to produce a “brown” part with full nanomaterials to allow further matrix infill. This demonstration includes additively manufactured carbon nanocomposites containing carbon nanotubes (CNTs) and thermoset epoxy, leading to multiscale CNTs tailorability, performance improvement, and 3D complex geometry feasibility. The process can produce nanomaterial-assembled architectures with 3D geometry and multiscale features and can incorporate a wide range of matrix materials, such as polymers, metals, and ceramics, to fabricate nanocomposites for new device structures and applications.