Chemical Circularity in 3D Printing with Biobased Δ-Valerolactone.

Digital Light Processing (DLP) is a vat photopolymerization-based 3D printing technology that fabricates parts typically made of chemically crosslinked polymers. The rapidly growing DLP market has an increasing demand for polymer raw materials, along with growing environmental concerns. Therefore, circular DLP printing with a closed-loop recyclable ink is of great importance for sustainability. The low-ceiling temperature alkyl-substituted δ-valerolactone (VL) is an industrially accessible biorenewable feedstock for developing recyclable polymers. In this work, acrylate-functionalized poly(δ-valerolactone) (PVLA), synthesized through the ring-opening transesterification polymerization of VL, is used as a platform photoprecursor to improve the chemical circularity in DLP printing. A small portion of photocurable reactive diluent (RD) turns the unprintable PVLA into DLP printable ink. Various photocurable monomers can serve as RDs to modulate the properties of printed structures for applications like sacrificial molds, soft actuators, sensors, etc. The intrinsic depolymerizability of PVLA is well preserved, regardless of whether the printed polymer is a thermoplastic or thermoset. The recovery yield of virgin quality VL monomer is 93% through direct bulk thermolysis of the printed structures. This work proposes the utilization of depolymerizable photoprecursors and highlights the feasibility of biorenewable VL as a versatile material platform toward circular DLP printing.

Applicability of UV-Curable Binders in High Solid Suspensions for Direct-Ink-Write 3D Printing in Extremely Cold Temperatures.

Leveraging material extrusion 3D printing of high solid suspensions for rapid manufacturing in future space missions requires materials compatible with the unique environments found on the Lunar surface. However, there is currently a lack of selection criteria for materials processable in the harsh environmental conditions on the Moon without significantly altering the 3D printers. Here, we provide valuable insights into the behavior of high solid suspensions at low temperatures to guide informed decision-making for manufacturing in subzero environments. We investigate the effects of direct-ink-write (DIW) printing at -30 °C on the structure-property relationships of UV-curable high solid inks of glass microspheres. We analyze the inks based on extrudability and curability at subzero temperatures to verify extrusion, shape retention, and sufficient solidification, culminating in successful printing at -30 °C. Preferential polymerization among monomers is observed at -30 °C and results in a lower cross-linking density in the final print, with a reduced tensile modulus. However, lower ratios of highly mobile monomers result in the retention of mechanical properties, demonstrating the selection criteria for binder design. Through this work, we highlight the importance of binder formulations used for 3D printing in uncommon environmental conditions that are emerging as tomorrow's manufacturing challenge.

Processability of Thermoelectric Ultrafine Fibers via Electrospinning for Wearable Electronics.

Polymer-based thermoelectric generators hold great appeal in the realm of wearable electronics as they enable the utilization of body heat for power generation. Fibers produced from conducting polymers for use in thermoelectric generators have high porosity and good flexibility, providing comfort-based performance advantages over thin films for wearable electronics. Some fiber processing techniques have been explored to produce textile-based thermoelectric generators; however, they fail to approach the conductivities of polymeric thin films. Ultrafine fibers solution processed through electrospinning yield fiber diameters on the nanoscale, allowing for high surface area to volume ratios and thus low thermal conductivity; however, a number of processing challenges in electrospinning conducting polymers limit the success of preparing high performing thermoelectric textiles. In this work, the specific processing challenges inherent to electrospinning conducting polymers are addressed for both n- and p-type materials. For the p-type polymer, 63 wt % PEDOT:PSS fibers are fabricated through solution formulation improvements yielding a conductivity of 3 S/cm and a power factor of 0.1 µW/mK2. The first of their kind n-type poly(NiETT)/PVA electrospun fibers were created yielding a conductivity of 0.11 S/cm and a power factor of 0.0036 µW/mK2. These nonwoven ultrafine fiber mats show progress toward achieving textile-based thermoelectric materials with equivalent performance of comparable polymeric thin films. This work shows the feasibility of creating ultrafine fibers for use in thermoelectric generators through electrospinning including the first demonstration of poly(NiETT)/PVA fibers.

Material extrusion additive manufacturing of dense pastes consisting of macroscopic particles.

Additive manufacturing of dense pastes, those with greater than 50 vol% particles, via material extrusion direct ink write is a promising method to produce customized structures for high-performance materials, such as energetic materials and pharmaceuticals, as well as to enable the use of waste or other locally available particles. However, the high volume fraction and the large sizes of the particles for these applications lead to significant challenges in developing inks and processing methods to prepare quality parts. In this prospective, we analyze challenges in managing particle characteristics, stabilizing the suspensions, mixing the particles and binder, and 3D printing the pastes.

Solvent selection for polymers enabled by generalized chemical fingerprinting and machine learning.

We present machine learning models trained on experimental data to predict room-temperature solubility for any polymer-solvent pair. The new models are a significant advancement over past data-driven work, in terms of protocol, validity, and versatility. A generalizable fingerprinting method is used for the polymers and solvents, making it possible, in principle, to handle any polymer-solvent combination. Our data-driven approach achieves high accuracy when either both the polymer and solvent or just the polymer has been seen during the training phase. Model performance is modest though when a solvent (in a newly queried polymer-solvent pair) is not part of the training set. This is likely because the number of unique solvents in our data set is small (much smaller than the number of polymers). Nevertheless, as the data set increases in size, especially as the solvent set becomes more diverse, the overall predictive performance is expected to improve.

Solvent Effects on the Elasticity of Electrospinnable Polymer Solutions.

Ultrafine fibers manufactured through electrospinning are a frontrunner for advanced fiber applications, but transitioning from potential to commercial applications for ultrafine fibers requires a better understanding of the behavior of polymer solutions in electrospinning to enable the design of more complex spinning dopes. In complex fluids, there are viscoelastic stresses and microstructural transitions that alter free surface flows. These may not be seen in shear rheology; therefore, an in-depth analysis of the extensional rheological behavior must be performed. In this work, we use dripping-onto-substrate rheometry to characterize the extensional viscosities of electrospinning dopes from four polymer solutions commonly used in electrospinning (low- and high-molecular-weight polyvinylpyrrolidone in methanol and water as well as poly(ethylene oxide) and poly(vinyl alcohol) in water). We link the electrospinnability, characterized through fiber morphology, to the extensional rheological properties for semidilute and entangled polymer solutions and show that high-surface-tension solvents require higher extensional viscosities and relaxation times to form smooth fibers and that the Deborah and Ohnesorge numbers are a promising method of determining electrospinnability. Through this tie between solvent characteristics, viscoelasticity, and electrospinnability, we will enable the design of more complex spinning dopes amenable to applications in wearable electronics, pharmaceuticals, and more.

Stabilization of Metastable Indomethacin α in Cellulose Nanocrystal Aerogel Scaffolds.

Indomethacin (IM) is a small molecule active pharmaceutical ingredient (API) that exhibits polymorphism with the γ-form being the most thermodynamically stable form of the drug. The α-form is metastable, but it exhibits higher solubility, making it a more attractive form for drug delivery. As with other metastable polymorphs, α-IM undergoes interconversion to the stable form when subjected to certain stimuli, such as solvent, heat, pH, or exposure to seed crystals of the stable form. In this study, IM was crystallized into cellulose nanocrystal aerogel scaffolds as a mixture of the two polymorphic forms, α-IM and γ-IM. Differential scanning calorimetry (DSC) and Raman spectroscopy were used to quantitatively determine the amount of each form. Our investigation found that the metastable α-IM could be stabilized within the aerogel without phase transformation, even in the presence of external stimuli, including heat and γ-IM seed crystals. Because interconversion is often a concern during production of metastable forms of APIs, this approach has important implications in being able to produce and stabilize metastable drug forms. While IM was used as a model drug in this study, this approach could be expanded to additional drugs and provide access to other metastable API forms.

Tailoring Optical Properties of Luminescent Semiconducting Nanocrystals through Hydrostatic, Anisotropic Static, and Dynamic Pressures.

Luminescent semiconductor nanocrystals are a fascinating class of materials because of their size-dependent emissions. Numerous past studies have demonstrated that semiconductor nanoparticles with radii smaller than their Bohr radius experience quantum confinement and thus size-dependent emissions. Exerting pressure on these nanoparticles represents an additional, more dynamic, strategy to alter their size and shift their emission. The application of pressure results in the lattices becoming strained and the electronic structure altered. In this Minireview, colloidal semiconductor nanocrystals are first introduced. The effects of uniform hydrostatic pressure on the optical properties of metal halide perovskite (ABX3 ), II-VI, III-V, and IV-VI semiconductor nanocrystals are then examined. The optical properties of semiconductor nanocrystals under static and dynamic anisotropic pressure are then summarized. Finally, future research directions and applications utilizing the pressure-dependent optical properties of semiconductor nanocrystals are discussed.

Combining Surface Templating and Confinement for Controlling Pharmaceutical Crystallization.

Poor water solubility is one of the major challenges to the development of oral dosage forms containing active pharmaceutical ingredients (APIs). Polymorphism in APIs leads to crystals with different surface wettabilities and free energies, which can lead to different dissolution properties. Crystal size and habit further contribute to this variability. An important focus in pharmaceutical research has been on controlling the drug form to improve the solubility and thus bioavailability of APIs. In this regard, heterogeneous crystallization on surfaces and crystallization under confinement have become prominent forms of controlling polymorphism and drug crystal size and habits; however there has not been a thorough review into the emerging field of combining these approaches to control crystallization. This tutorial-style review addresses the major advances that have been made in controlling API forms using combined crystallization methods. By designing templates that not only control the surface functionality but also enable confinement of particles within a porous structure, these combined systems have the potential to provide better control over drug polymorph formation and crystal size and habit. This review further provides a perspective on the future of using a combined crystallization approach and suggests that combining surface templating with confinement provides the advantage of both techniques to rationally design systems for API nucleation.

Polyelectrolyte Complex Coacervate Assembly with Cellulose Nanofibers.

Polyelectrolytes are used in paper manufacturing to increase flocculation and water drainage and improve mechanical properties. In this study, we examine the interaction between charged cellulosic nanomaterials and polyelectrolyte complex coacervates of weak polyelectrolytes, polyacrylic acid salt, and polyallylamine hydrochloride. We observe that by changing the order of addition of the polyelectrolytes to cellulose nanofibers (CNFs), we can tune the interactions between the materials, which in turn changes the degree of association of the coacervates to the CNFs and the rate at which they aggregate. Importantly for the papermaking process, when adding the polyelectrolytes sequentially to the CNFs, we found faster aggregation to the fibers and lower water retention values compared to those when preformed coacervates or CNFs by themselves were used. Coarse-grain molecular dynamic simulations further support the fundamental mechanism of aggregation by taking into consideration the interaction between cellulose and the complexes at the molecular level. The simulations corroborate the experimental observations by showing the importance of strong electrostatic interactions in aggregate formation.

Giant Hyaluronan Polymer Brushes Display Polyelectrolyte Brush Polymer Physics Behavior.

Polyelectrolyte brushes are important stimuli-responsive materials in a variety of technological applications as well as in biological systems. Their small size, however, introduces characterization challenges, particularly in studying 3D structure and time-dependent behavior. In this Letter, we report on the polyelectrolyte brush behavior of extra-large hyaluronan brushes (∼15 µm) recently developed using an enzyme-mediated growth process. In response to increasing ionic strength, the brush displays the osmotic brush regime and the salted brush regime. We also show a collapse of 96% when the brush is placed in a poor solvent. This collapse is rapid when changing from a good to poor solvent, but re-expansion is slow when changing back to a good solvent. The observed brush behavior described in this Letter is similar to that seen for smaller polyelectrolyte brushes, indicating that these larger brushes may serve as model systems to study more complex phenomena through confocal microscopy.

Pharmaceutical crystallization in surface-modified nanocellulose organogels.

A significant research focus in the pharmaceutical industry is on methods to improve drug uptake into the body by increased dissolution of poorly water soluble active pharmaceutical ingredients (APIs) or sustained drug release behavior, which results in higher overall uptake. Production of higher energy, higher solubility polymorphs is one approach to address this problem. Here we utilize natural materials, cellulose nanocrystals (CNCs), that have a high surface area covered with readily-modified hydroxyl groups to form organogels that promote API crystallization into polymorphs that differ from the as-received materials. We form the gels by oxidizing the CNCs and mixing them with an amine-containing surfactant, octadecylamine (ODA) in dimethylsulfoxide (DMSO) and we optimize the composition and preparation conditions for these gels. The APIs, sulfamethoxazole, sulfapyridine, and sulfamerazine, are added to the mixture prior to the gelation step and are expected to localize in the solvophobic regions of the physical gel and crystallize. We found that sulfamethoxazle recovered from the gels is in the amorphous state, while sulfapyridine crystallizes into a mixture of forms I, III and IV, and sulfamerazine crystallizes into forms I and II, which are different from the as-received materials. This system shows promise for rational design of nanocellulose organogel supports for heterogeneous crystallization of pharmaceutical materials with desired polymorphs.

Intermolecular Interactions in Polyelectrolyte and Surfactant Complexes in Solution.

Polyelectrolytes are an important class of polymeric materials and are increasingly used in complex industrial formulations. A core use of these materials is in mixtures with surfactants, where a combination of hydrophobic and electrostatic interactions drives unique solution behavior and structure formation. In this review, we apply a molecular level perspective to the broad literature on polyelectrolyte-surfactant complexes, discussing explicitly the hydrophobic and electrostatic interaction contributions to polyelectrolyte surfactant complexes (PESCs), as well as the interplay between the two molecular interaction types. These interactions are sensitive to a variety of solution conditions, such as pH, ionic strength, mixing procedure, charge density, etc. and these parameters can readily be used to control the concentration at which structures form as well as the type of structure in the bulk solution.

Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes.

Subtle details about a polyelectrolyte's surrounding environment can dictate its structural features and potential applications. Atomic force microscopy (AFM), surface forces apparatus (SFA) measurements, and coarse-grained molecular dynamics simulations are combined to study the structure of planar polyelectrolyte brushes [poly(styrenesulfonate), PSS] in a variety of solvent conditions. More specifically, AFM images provide a first direct visualization of lateral inhomogeneities on the surface of polyelectrolyte brushes collapsed in solutions containing trivalent counterions. These images are interpreted in the context of a coarse-grained molecular model and are corroborated by accompanying interaction force measurements with the SFA. Our findings indicate that lateral inhomogeneities are absent from PSS brush layers collapsed in a poor solvent without multivalent ions. Together, AFM, SFA, and our molecular model present a detailed picture in which solvophobic and multivalent ion-induced effects work in concert to drive strong phase separation, with electrostatic bridging of polyelectrolyte chains playing an essential role in the collapsed structure formation.

Comparing Solvophobic and Multivalent Induced Collapse in Polyelectrolyte Brushes.

Coarse-grained molecular dynamics enhanced by free-energy sampling methods is used to examine the roles of solvophobicity and multivalent salts on polyelectrolyte brush collapse. Specifically, we demonstrate that while ostensibly similar, solvophobic collapsed brushes and multivalent-ion collapsed brushes exhibit distinct mechanistic and structural features. Notably, multivalent-induced heterogeneous brush collapse is observed under good solvent polymer backbone conditions, demonstrating that the mechanism of multivalent collapse is not contingent upon a solvophobic backbone. Umbrella sampling of the potential of mean-force (PMF) between two individual brush strands confirms this analysis, revealing starkly different PMFs under solvophobic and multivalent conditions, suggesting the role of multivalent "bridging" as the discriminating feature in trivalent collapse. Structurally, multivalent ions show a propensity for nucleating order within collapsed brushes, whereas poor-solvent collapsed brushes are more disordered; this difference is traced to the existence of a metastable PMF minimum for poor solvent conditions, and a global PMF minimum for trivalent systems, under experimentally relevant conditions.

Bulk and nanoscale polypeptide based polyelectrolyte complexes.

Polyelectrolyte complexes (PECs) formed using polypeptides have great potential for developing new self-assembled materials, in particular for the development of drug and gene delivery vehicles. This review discusses the latest advancements in PECs formed using polypeptides as the polyanion and/or the polycation in both polyelectrolyte complexes that form bulk materials and block copolymer complexes that form nanoscale assemblies such as PEC micelles and other self-assembled structures. We highlight the importance of secondary structure formation between homogeneous polypeptide complexes, which, unlike PECs formed using other polymers, introduces additional intermolecular interactions in the form of hydrogen bonding, which may influence precipitation over coacervation. However, we still include heterogeneous complexes consisting of polypeptides and other polymers such as nucleic acids, sugars, and other synthetic polyelectrolytes. Special attention is given to complexes formed using nucleic acids as polyanions and polypeptides as polycations and their potential for delivery applications.

Templated nucleation of acetaminophen on spherical excipient agglomerates.

We investigated the effect of spherical agglomeration of heterogeneous crystalline substrates on the nucleation of acetaminophen (AAP). Optical and electron microscopy showed that the surface morphologies of single crystal triclinic lactose and D-mannitol differed significantly from their counterparts formed via spherical agglomeration. Spherical agglomerates of lactose were shown to enhance the nucleation rate of acetaminophen (AAP) by a factor of 11 compared to single crystal lactose; however, no such enhancement was observed for D-mannitol. X-ray powder diffraction identified the presence of new crystal faces of lactose present only in the spherical agglomerates However, D-mannitol did not show any significant change in crystal morphology. The new crystal faces of triclinic lactose were analyzed using geometric lattice matching software and molecular dynamics simulations to establish any new and significant epitaxial matches between lactose and AAP. A coincident lattice match and a large favorable energy interaction from hydrogen bonding were observed between the (141¯) and (001) crystal faces of lactose and AAP, respectively. The enhanced nucleation kinetics, X-ray data, and computational studies indicated that the spherical crystallization of lactose exposed the (141¯) face on the surface of the agglomerates, which subsequently enhanced the nucleation rate of AAP through geometric lattice matching and molecular functionality. This study highlights the importance of exploring different heterogeneous substrate morphologies for enhancing nucleation kinetics.

Electrospun formulations containing crystalline active pharmaceutical ingredients.

PURPOSE: To investigate the use of electrospinning for forming solid dispersions containing crystalline active pharmaceutical ingredients (API) and understand the relevant properties of the resulting materials. METHOD: Free surface electrospinning was used to prepare nanofiber mats of poly(vinyl pyrrolidone) (PVP) and crystalline albendazole (ABZ) or famotidine (FAM) from a suspension of the drug crystals in a polymer solution. SEM and DSC were used to characterize the dispersion, XRD was used to determine the crystalline polymorph, and dissolution studies were performed to determine the influence of the preparation method on the dissolution rate. RESULTS: The electrospun fibers contained 31 wt% ABZ and 26 wt% FAM for the 1:2 ABZ:PVP and 1:2 FAM:PVP formulations, respectively, and both APIs retained their crystalline polymorphs throughout processing. The crystals had an average size of about 10 µm and were well-dispersed throughout the fibers, resulting in a higher dissolution rate for electrospun tablets than for powder tablets. CONCLUSIONS: Previously used to produce amorphous formulations, electrospinning has now been demonstrated to be a viable option for producing fibers containing crystalline API. Due to the dispersion of the crystals in the polymer, tablets made from the fiber mats may also exhibit improved dissolution properties over traditional powder compression.

Free surface electrospinning of fibers containing microparticles.

Many materials have been fabricated using electrospinning, including pharmaceutical formulations, superhydrophobic surfaces, catalysis supports, filters, and tissue engineering scaffolds. Often these materials can benefit from microparticles included within the electrospun fibers. In this work, we evaluate a high-throughput free surface electrospinning technique to prepare fibers containing microparticles. We investigate the spinnability of polyvinylpyrrolidone (PVP) solutions containing suspended polystyrene (PS) beads of 1, 3, 5, and 10 µm diameter in order to better understand free surface electrospinning of particle suspensions. PS bead suspensions with both 55 kDa PVP and 1.3 MDa PVP were spinnable at 1:10, 1:5, and 1:2 PS:PVP mass loadings for all particle sizes studied. The final average fiber diameters ranged from 0.47 to 1.2 µm and were independent of the particle size and particle loading, indicating that the fiber diameter can be smaller than the particles entrained and can furthermore be adjusted based on solution properties and electrospinning parameters, as is the case for electrospinning of solutions without particles.

Solid-state nuclear magnetic resonance study of the physical stability of electrospun drug and polymer solid solutions.

A major challenge in utilizing the amorphous form of an active pharmaceutical ingredient (API) in a final oral dosage form is preventing crystallization over time and ensuring stability. One method to improve stability is lowering the mobility of an API by formulating as a solid solution with an excipient. In this work, we use electrospinning to prepare solid solutions of API, aliskiren (SPP) or indomethacin (IND), and a polymer, polyvinylpyrrolidone (PVP). The stability of the solid solutions over 6-month storage in a desiccator at 40 °C was investigated. Using X-ray diffraction and differential scanning calorimetry, it was determined that no crystals were present in the four formulations tested--1:1 SPP-PVP, 4:1 SPP-PVP, 1:1 IND-PVP, and 2:1 IND-PVP at any time. Solid-state nuclear magnetic resonance relaxation time measurements were used to determine whether phase separation of the API and polymer occurred during the study period. It was found that all formulations remained homogeneous down to at least a 2-10 nm length scale, indicating that for these APIs, electrospinning is an acceptable method for forming stable amorphous solid solutions.