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1.
Adv Mater ; : e2402431, 2024 May 08.
Artículo en Inglés | MEDLINE | ID: mdl-38718377

RESUMEN

With over 6 million tons produced annually, thermoplastic elastomers (TPEs) have become ubiquitous in modern society, due to their unique combination of elasticity, toughness, and reprocessability. Nevertheless, industrial TPEs display a tradeoff between softness and strength, along with low upper service temperatures, typically ≤100 °C. This limits their utility, such as in bio-interfacial applications where supersoft deformation is required in tandem with strength, in addition to applications that require thermal stability (e.g., encapsulation of electronics, seals/joints for aeronautics, protective clothing for firefighting, and biomedical devices that can be subjected to steam sterilization). Thus, combining softness, strength, and high thermal resistance into a single versatile TPE has remained an unmet opportunity. Through de novo design and synthesis of novel norbornene-based ABA triblock copolymers, this gap is filled. Ring-opening metathesis polymerization is employed to prepare TPEs with an unprecedented combination of properties, including skin-like moduli (<100 kPa), strength competitive with commercial TPEs (>5 MPa), and upper service temperatures akin to high-performance plastics (≈260 °C). Furthermore, the materials are elastic, tough, reprocessable, and shelf stable (≥2 months) without incorporation of plasticizer. Structure-property relationships identified herein inform development of next-generation TPEs that are both biologically soft yet thermomechanically durable.

2.
ACS Cent Sci ; 10(2): 272-282, 2024 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-38435512

RESUMEN

The rapid photochemical conversion of materials from liquid to solid (i.e., curing) has enabled the fabrication of modern plastics used in microelectronics, dentistry, and medicine. However, industrialized photocurables remain restricted to unimolecular bond homolysis reactions (Type I photoinitiations) that are driven by high-energy UV light. This narrow mechanistic scope both challenges the production of high-resolution objects and restricts the materials that can be produced using emergent manufacturing technologies (e.g., 3D printing). Herein we develop a photosystem based on triplet-triplet annihilation upconversion (TTA-UC) that efficiently drives a Type I photocuring process using green light at low power density (<10 mW/cm2) and in the presence of ambient oxygen. This system also exhibits a superlinear dependence of its cure depth on the light exposure intensity, which enhances spatial resolution. This enables for the first-time integration of TTA-UC in an inexpensive, rapid, and high-resolution manufacturing process, digital light processing (DLP) 3D printing. Moreover, relative to traditional Type I and Type II (photoredox) strategies, the present TTA-UC photoinitiation method results in improved cure depth confinement and resin shelf stability. This report provides a user-friendly avenue to utilize TTA-UC in ambient photochemical processes and paves the way toward fabrication of next-generation plastics with improved geometric precision and functionality.

3.
J Am Chem Soc ; 146(6): 4078-4086, 2024 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-38300153

RESUMEN

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization and their cobalt binding profiles were examined as a function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks with micrometer-level precision of geometry and nanometer-level pores were generated. Covalent integration of a methacrylate-functionalized bisdicyclohexyl acetamide (BDCA-MA) receptor enabled binding and release of cobalt(II) chloride (CoCl2) via a solvent polarity switch mechanism involving a change in solvent from ethanol to water. The present structures proved reusable as shown by sustained high binding efficiency over five bind and release cycles. This platform represents a "green" and energy conscious method for future electronic waste recycling.

4.
Chem Sci ; 14(39): 10736-10743, 2023 Oct 11.
Artículo en Inglés | MEDLINE | ID: mdl-37829029

RESUMEN

Photocages have enabled spatiotemporally governed organic materials synthesis with applications ranging from tissue engineering to soft robotics. However, the reliance on high energy UV light to drive an often inefficient uncaging process limits their utility. These hurdles are particularly evident for more reactive cargo, such as strong organobases, despite their attractive potential to catalyze a range of chemical transformations. Herein, two metal-free boron dipyrromethene (BODIPY) photocages bearing tetramethylguanidine (TMG) cargo are shown to induce rapid and efficient polymerizations upon exposure to a low intensity green LED. A suite of spectroscopic characterization tools were employed to identify the underlying uncaging and polymerization mechanisms, while also determining reaction quantum efficiencies. The results are directly compared to state-of-the-art TMG-bearing ortho-nitrobenzyl and coumainylmethyl photocages, finding that the present BODIPY derivatives enable step-growth polymerizations that are >10× faster than the next best performing photocage. As a final demonstration, the inherent multifunctionality of the present BODIPY platform in releasing radicals from one half of the molecule and TMG from the other is leveraged to prepare polymers with starkly disparate physical properties. The present findings are anticipated to enable new applications of photocages in both small-molecule photochemistry for medicine and advanced manufacturing of next generation soft materials.

5.
J Am Chem Soc ; 145(32): 17912-17918, 2023 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-37540781

RESUMEN

Unimolecular (Type I) radical photoinitiators (PIs) have transformed the chemical manufacturing industry by enabling (stereo)lithography for microelectronics and emergent 3D printing technologies. However, the reliance on high energy UV-violet light (≤420 nm) restricts the end-use applications. Herein, boron-methylated dipyrromethene (methylated-BODIPY) is shown to act as a highly efficient Type I radical PI upon irradiation with low energy green light. Using a low intensity (∼4 mW/cm2) light emitting diode centered at 530 nm and a low PI concentration (0.3 mol %), acrylic-based resins were polymerized to maximum conversion in ∼10 s. Under equivalent conditions (wavelength, intensity, and PI concentration), state-of-the-art visible light PIs Ivocerin and Irgacure 784 show no appreciable polymerization. Spectroscopic characterization suggests that homolytic ß-scission at the boron-carbon bond results in radical formation, which is further facilitated by accessing long-lived triplet excited states through installment of bromine. Alkylated-BODIPYs represent a new modular visible light PI platform with exciting potential to enable next generation manufacturing and biomedical applications where a spectrally discrete, low energy, and thus benign light source is required.

6.
bioRxiv ; 2023 Jul 06.
Artículo en Inglés | MEDLINE | ID: mdl-37461453

RESUMEN

While full-spectrum flow cytometry has increased antibody-based multiplexing, yet further increases remain potentially impactful. We recently proposed how fluorescence Multiplexing using Spectral Imaging and Combinatorics (MuSIC) could do so using tandem dyes and an oligo-based antibody labeling method. In this work, we found that such labeled antibodies had significantly lower signal intensity than conventionally-labeled antibodies in human cell experiments. To improve signal intensity, we tested moving the fluorophores from the original external (ext.) 5' or 3' end-labeled orientation to internal (int.) fluorophore modifications. Cell-free spectrophotometer measurements showed a ~6-fold signal intensity increase of the new int. configuration compared to the previous ext. configuration. Time-resolved fluorescence spectroscopy and fluorescence correlation spectroscopy showed that ~3-fold brightness difference is due to static quenching. Spectral flow cytometry experiments using peripheral blood mononuclear cells stained with anti-CD8 antibodies showed that int. MuSIC probe-labeled antibodies have signal intensity equal to or greater than conventionally-labeled antibodies with similar estimated proportion of CD8+ lymphocytes. The antibody labeling approach is general and can be broadly applied to many biological and diagnostic applications.

7.
ACS Appl Mater Interfaces ; 15(28): 34097-34107, 2023 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-37418641

RESUMEN

Multimaterial three-dimensional (3D) printing of objects with spatially tunable thermomechanical properties and shape-memory behavior provides an attractive approach toward programmable "smart" plastics with applications in soft robotics and electronics. To date, digital light processing 3D printing has emerged as one of the fastest manufacturing methods that maintains high precision and resolution. Despite the common utility of semicrystalline polymers in stimuli-responsive materials, few reports exist whereby such polymers have been produced via digital light processing (DLP) 3D printing. Herein, two commodity long-alkyl chain acrylates (C18, stearyl and C12, lauryl) and mixtures therefrom are systematically examined as neat resin components for DLP 3D printing of semicrystalline polymer networks. Tailoring the stearyl/lauryl acrylate ratio results in a wide breadth of thermomechanical properties, including tensile stiffness spanning three orders of magnitude and temperatures from below room temperature (2 °C) to above body temperature (50 °C). This breadth is attributed primarily to changes in the degree of crystallinity. Favorably, the relationship between resin composition and the degree of crystallinity is quadratic, making the thermomechanical properties reproducible and easily programmable. Furthermore, the shape-memory behavior of 3D-printed objects upon thermal cycling is characterized, showing good fatigue resistance and work output. Finally, multimaterial 3D-printed structures with vertical gradation in composition are demonstrated where concomitant localization of thermomechanical properties enables multistage shape-memory and strain-selective behavior. The present platform represents a promising route toward customizable actuators for biomedical applications.

8.
Chem Sci ; 14(15): 4120-4125, 2023 Apr 12.
Artículo en Inglés | MEDLINE | ID: mdl-37063794

RESUMEN

We report a copolymeric fluorescent sensor that is selective for lithium chloride. The two constituent polymers comprise pendent triphenylethylene (TPE) moieties for aggregate induced emission (AIE) along with either strapped-calix[4]pyrrole or secondary ammonium groups that drive aggregation via self-assembly upon polymer mixing. Addition of LiCl in acetonitrile disrupts the strapped-calix[4]pyrrole/secondary ammonium chloride salt host-guest crosslinks leading to disaggregation of the polymer chains and a decrease in TPE emission. The lack of AIE perturbation upon addition of NaCl, KCl, MgCl2 or CaCl2 provides for high selectivity for LiCl relative to potential interferants. This supramolecular dual polymer approach could serve as a complement to more traditional sensor systems.

9.
Phys Rev Lett ; 130(11): 115101, 2023 Mar 17.
Artículo en Inglés | MEDLINE | ID: mdl-37001109

RESUMEN

The linear growth and nonlinear energy transfer of the electron drift instability (EDI) are experimentally measured in the plume of a low-temperature, Hall effect discharge. A frequency-based bispectral analysis technique applied to fast ion density fluctuation measurements shows a growth rate function that is qualitatively similar to predictions from the linear instability dispersion relation, but an order of magnitude smaller. Calculation of the nonlinear transfer function indicates multiple three-wave interactions between high-frequency resonances of the instability in addition to an inverse energy cascade toward lower-frequency modes. These results are discussed in the context of recent theoretical, numerical, and experimental efforts on the EDI in Hall effect discharges and how the EDI may impact anomalous cross field transport.

10.
Angew Chem Int Ed Engl ; 62(22): e202219140, 2023 May 22.
Artículo en Inglés | MEDLINE | ID: mdl-36988076

RESUMEN

The use of visible light to drive polymerizations with spatiotemporal control offers a mild alternative to contemporary UV-light-based production of soft materials. In this spectral region, photoredox catalysis represents the most efficient polymerization method, yet it relies on the use of heavy-atoms, such as precious metals or toxic halogens. Herein, spin-orbit charge transfer intersystem crossing from boron dipyrromethene (BODIPY) dyads bearing twisted aromatic groups is shown to enable efficient visible light polymerizations in the absence of heavy-atoms. A ≈5-15× increase in polymerization rate and improved photostability was achieved for twisted BODIPYs relative to controls. Furthermore, monomer polarity had a distinct effect on polymerization rate, which was attributed to charge transfer stabilization based on ultrafast transient absorption and phosphorescence spectroscopies. Finally, rapid and high-resolution 3D printing with a green LED was demonstrated using the present photosystem.

11.
Adv Mater ; 35(9): e2210208, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36515127

RESUMEN

Access to multimaterial polymers with spatially localized properties and robust interfaces is anticipated to enable new capabilities in soft robotics, such as smooth actuation for advanced medical and manufacturing technologies. Here, orthogonal initiation is used to create interpenetrating polymer networks (IPNs) with spatial control over morphology and mechanical properties. Base catalyzes the formation of a stiff and strong polyurethane, while blue LEDs initiate the formation of a soft and elastic polyacrylate. IPN morphology is controlled by when the LED is turned "on", with large phase separation occurring for short time delays (≈1-2 min) and a mixed morphology for longer time delays (>5 min), which is supported by dynamic mechanical analysis, small angle X-ray scattering, and atomic force microscopy. Through tailoring morphology, tensile moduli and fracture toughness can be tuned across ≈1-2 orders of magnitude. Moreover, a simple spring model is used to explain the observed mechanical behavior. Photopatterning produces "multimorphic" materials, where morphology is spatially localized with fine precision (<100 µm), while maintaining a uniform chemical composition throughout to mitigate interfacial failure. As a final demonstration, the fabrication of hinges represents a possible use case for multimorphic materials in soft robotics.

12.
Phys Rev E ; 108(6-2): 065204, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-38243482

RESUMEN

The contribution of the electron drift instability to anomalous electron transport is experimentally assessed in a Hall effect discharge. The transport is represented by an anomalous collision frequency, which is related through quasilinear theory to the energy and growth rate of the instability. The wave energy is measured directly with ion saturation probes, while estimates of the growth rate are employed based on both linearized theory and direct measurement. The latter measurement is performed with a bispectral analysis method. The wave-driven collision frequency is compared to measurements of the actual collision frequency inferred from a method based on laser-induced fluorescence. It is found that estimates for transport using linearized theory for the growth differ by over an order of magnitude from the actual anomalous collision frequency in the plasma. The wave-driven anomalous collision frequency with measured growth, however, is shown to agree with the electron collision frequency in magnitude and capture aspects of the trends in spatial variation. This result demonstrates experimentally that wave-driven effects ultimately can explain the observed cross-field transport in these devices. The implications of this finding are discussed in the context of the key lengthscales that drive the transport as well as the implications identifying reduced fidelity models that could be used to predict anomalous collision frequency.

13.
Front Immunol ; 13: 1032618, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-36389679

RESUMEN

IL-9-producing CD4+ T helper cells, termed Th9 cells, differentiate from naïve precursor cells in response to a combination of cytokine and cell surface receptor signals that are elevated in inflamed tissues. After differentiation, Th9 cells accumulate in these tissues where they exacerbate allergic and intestinal disease or enhance anti-parasite and anti-tumor immunity. Previous work indicates that the differentiation of Th9 cells requires the inflammatory cytokines IL-4 and TGF-ß and is also dependent of the T cell growth factor IL-2. While the roles of IL-4 and TGF-ß-mediated signaling are relatively well understood, how IL-2 signaling contributes to Th9 cell differentiation outside of directly inducing the Il9 locus remains less clear. We show here that murine Th9 cells that differentiate in IL-2-limiting conditions exhibit reduced IL-9 production, diminished NF-kB activation and a reduced NF-kB-associated transcriptional signature, suggesting that IL-2 signaling is required for optimal NF-kB activation in Th9 cells. Interestingly, both IL-9 production and the NF-kB transcriptional signature could be rescued by addition of the NF-kB-activating cytokine IL-1ß to IL-2-limiting cultures. IL-1ß was unique among NF-kB-activating factors in its ability to rescue Th9 differentiation as IL-2 deprived Th9 cells selectively induced IL-1R expression and IL-1ß/IL-1R1 signaling enhanced the sensitivity of Th9 cells to limiting amounts of IL-2 by suppressing expression of the Th9 inhibitory factor BCL6. These data shed new light on the intertwined nature of IL-2 and NF-kB signaling pathways in differentiating Th cells and elucidate the potential mechanisms that promote Th9 inflammatory function in IL-2-limiting conditions.


Asunto(s)
Interleucina-4 , Interleucina-9 , Linfocitos T Colaboradores-Inductores , Animales , Ratones , Diferenciación Celular , Citocinas/metabolismo , Interleucina-2 , Interleucina-9/metabolismo , FN-kappa B , Proteínas Proto-Oncogénicas c-bcl-6/genética , Factor de Crecimiento Transformador beta/metabolismo , Interleucina-1beta/metabolismo
14.
Science ; 378(6616): 211-215, 2022 10 14.
Artículo en Inglés | MEDLINE | ID: mdl-36227995

RESUMEN

An organized combination of stiff and elastic domains within a single material can synergistically tailor bulk mechanical properties. However, synthetic methods to achieve such sophisticated architectures remain elusive. We report a rapid, facile, and environmentally benign method to pattern strong and stiff semicrystalline phases within soft and elastic matrices using stereo-controlled ring-opening metathesis polymerization of an industrial monomer, cis-cyclooctene. Dual polymerization catalysis dictates polyolefin backbone chemistry, which enables patterning of compositionally uniform materials with seamless stiff and elastic interfaces. Visible light-induced activation of a metathesis catalyst results in the formation of semicrystalline trans polyoctenamer rubber, outcompeting the formation of cis polyoctenamer rubber, which occurs at room temperature. This bottom-up approach provides a method for manufacturing polymeric materials with promising applications in soft optoelectronics and robotics.

15.
Biomacromolecules ; 23(9): 3743-3751, 2022 09 12.
Artículo en Inglés | MEDLINE | ID: mdl-35926160

RESUMEN

Multiangle light scattering (MALS) was used to determine the absolute molar mass of fluorescent macromolecules. It is standard protocol to install bandwidth filters before MALS detectors to suppress detection of fluorescent emissions. Fluorescence can introduce tremendous error in light scattering measurements and is a formidable challenge in accurately characterizing fluorescent macromolecules and particles. However, we show that for some systems, bandwidth filters alone are insufficient for blocking fluorescence in molar mass determinations. For these systems, we have devised a correction procedure to calculate the amount of fluorescence interference in the filtered signal. By determining the intensity of fluorescent emission not blocked by the bandwidth filters, we can correct the filtered signal accordingly and accurately determine the true molar mass. The transmission rates are calculated before MALS experimentation using emission data from standard fluorimetry techniques, allowing for the characterization of unknown samples. To validate the correction procedure, we synthesized fluorescent dye-conjugated proteins using an IR800CW (LI-COR) fluorophore and Bovine Serum Albumin protein. We successfully eliminated fluorescence interference in MALS measurements using this approach. This correction procedure has potential application toward more accurate molar mass characterizations of macromolecules with intrinsic fluorescence, such as lignins, fluorescent proteins, fluorescence-tagged proteins, and optically active nanoparticles.


Asunto(s)
Luz , Nanopartículas , Peso Molecular , Dispersión de Radiación , Albúmina Sérica Bovina
16.
Front Psychol ; 13: 846931, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35465485

RESUMEN

Much of our everyday, embodied action comes in the form of smooth coping. Smooth coping is skillful action that has become habituated and ingrained, generally placing less stress on cognitive load than considered and deliberative thought and action. When performed with skill and expertise, walking, driving, skiing, musical performances, and short-order cooking are all examples of the phenomenon. Smooth coping is characterized by its rapidity and relative lack of reflection, both being hallmarks of automatization. Deliberative and reflective actions provide the contrast case. In Dreyfus' classic view, smooth coping is "mindless" absorption into action, being in the flow, and any reflective thought will only interrupt this flow. Building on the pragmatist account of Dewey, others, such as Sutton, Montero, and Gallagher, insist on the intelligent flexibility built into smooth coping, suggesting that it is not equivalent to automatization. We seek to answer two complementary challenges in this article. First, how might we model smooth coping in autonomous agents (natural or artificial) at fine granularity? Second, we use this model of smooth coping to show how we might implement smooth coping in artificial intelligent agents. We develop a conceptual model of smooth coping in LIDA (Learning Intelligent Decision Agent). LIDA is an embodied cognitive architecture implementing the global workspace theory of consciousness, among other psychological theories. LIDA's implementation of consciousness enables us to account for the phenomenology of smooth coping, something that few cognitive architectures would be able to do. Through the fine granular analysis of LIDA, we argue that smooth coping is a sequence of automatized actions intermittently interspersed with consciously mediated action selection, supplemented by dorsal stream processes. In other words, non-conscious, automatized actions (whether learned or innate) often require occasional bursts of conscious cognition to achieve the skillful and flexible adjustments of smooth coping. In addition, never-conscious dorsal stream information and associated sensorimotor processes provide further online adjustments during smooth coping. To achieve smooth coping in LIDA we introduce a new module to the LIDA cognitive architecture the Automatized Action Selection sub-module. Our complex model of smooth coping borrows notions of "embodied intelligence" from enactivism and augments these by allowing representations and more detailed mechanisms of conscious control. We explore several extended examples of smooth coping, starting from basic activities like walking and scaling up to more complex tasks like driving and short-order cooking.

17.
Int J Cardiol ; 356: 73-78, 2022 06 01.
Artículo en Inglés | MEDLINE | ID: mdl-35296433

RESUMEN

BACKGROUND: Acute decompensated heart failure (ADHF) is a challenging medical emergency with high mortality and its prevalence is increasing in India. There is paucity of data on ADHF in the country. METHODS: Indian College of Cardiology National Heart Failure Registry (ICCNHFR) is an on-going observational registry on ADHF contributed by 22 hospitals across India; and we present the in-hospital and 30-day outcomes of ADHF patients enrolled from August 2018 to July 2019. Major objective included capturing demographics, comorbid conditions, aetiology, prescription patterns and assessing clinical outcomes. RESULTS: Of 5269 patients (mean age: 61.90 ± 13.85 years) enrolled in this study, males were predominant (67.09%). Mean duration of hospitalization was 5.74 ± 4.74 days. Ischemic heart disease was the most common (75.44%) aetiology. Abnormal electrocardiogram readings were found in most patients (89.86%). LVEF of ˂40% was found in 68.29% of patients. In-hospital mortality rates were 6.98%. The 30-day cumulative mortality was 12.35% and 30-day rehospitalization rate was 7.98%. At discharge, all guideline-based medical therapy (GDMT) were prescribed only to 24.99% of patients and 23.72% adhered to the prescription until 30 days. Older age, high serum creatinine levels and poor LVEF contributed to high mortality and rehospitalization. CONCLUSION: Patients with ADHF were younger and predominantly males. Usage of GDMT in ADHF patients was low (24.99%) and the in-hospital mortality was high. Older age, high serum creatinine levels, poor LVEF contributed for 30-day mortality and rehospitalization. This data on ADHF, could help in developing strategies to improve outcomes for HF patients in India.


Asunto(s)
Cardiología , Insuficiencia Cardíaca , Enfermedad Aguda , Anciano , Creatinina , Femenino , Insuficiencia Cardíaca/diagnóstico , Insuficiencia Cardíaca/epidemiología , Insuficiencia Cardíaca/terapia , Humanos , Masculino , Persona de Mediana Edad , Sistema de Registros , Volumen Sistólico
18.
ACS Cent Sci ; 8(1): 67-76, 2022 Jan 26.
Artículo en Inglés | MEDLINE | ID: mdl-35106374

RESUMEN

Patterning chemical reactivity with a high spatiotemporal resolution and chemical versatility is critically important for advancing revolutionary emergent technologies, including nanorobotics, bioprinting, and photopharmacology. Current methods are complex and costly, necessitating novel techniques that are easy to use and compatible with a wide range of chemical functionalities. This study reports the development of a digital light processing (DLP) fluorescence microscope that enables the structuring of visible light (465-625 nm) for high-resolution photochemical patterning and simultaneous fluorescence imaging of patterned samples. A range of visible-light-driven photochemical systems, including thiol-ene photoclick reactions, Wolff rearrangements of diazoketones, and photopolymerizations, are shown to be compatible with this system. Patterning the chemical functionality onto microscopic polymer beads and films is accomplished with photographic quality and resolutions as high as 2.1 µm for Wolff rearrangement chemistry and 5 µm for thiol-ene chemistry. Photoactivation of molecules in living cells is demonstrated with single-cell resolution, and microscale 3D printing is achieved using a polymer resin with a 20 µm xy-resolution and a 100 µm z-resolution. Altogether, this work debuts a powerful and easy-to-use platform that will facilitate next-generation nanorobotic, 3D printing, and metamaterial technologies.

19.
Artículo en Inglés | MEDLINE | ID: mdl-35080842

RESUMEN

The ability to 3D print structures with low-intensity, long-wavelength light will broaden the materials scope to facilitate inclusion of biological components and nanoparticles. Current materials limitations arise from the pervasive absorption, scattering, and/or degradation that occurs upon exposure to high-intensity, short-wavelength (ultraviolet) light, which is the present-day standard used in light-based 3D printers. State-of-the-art techniques have recently extended printability to orange/red light. However, as the wavelength of light increases, so do the inherent challenges to match the speed and resolution of traditional UV light-induced solidification processes (i.e., photocuring). Herein, a photosystem is demonstrated to enable low-intensity (<5 mW/cm2), long-wavelength (∼850 nm) near-infrared (NIR) light-driven 3D printing, "invisible" to the human eye. The combination of a NIR absorbing cyanine dye with electron-rich and -deficient redox pairs was required for rapid photocuring in a catalytic manner. The rate of polymerization and time to solidification upon exposure to NIR light were characterized via in situ spectroscopic and rheological monitoring. Translation to NIR digital light processing (projection-based) 3D printing was accomplished through rigorous optimization of resin composition and printing parameters to balance the speed (<60 s/layer) and resolution (<300 µm features). As a proof-of-concept, composite 3D printing with nanoparticle-infused resins was accomplished. Preliminary analysis showed improved feature fidelity for structures produced with NIR relative to UV light. The present report provides key insight that will inform next-generation light-based photocuring technology, such as wavelength-selective multimaterial 3D bio- and composite-printing.

20.
Cell Rep Phys Sci ; 3(12)2022 Dec 21.
Artículo en Inglés | MEDLINE | ID: mdl-37496708

RESUMEN

The formation of benign polymer scaffolds in water using green-light-reactive photocages is described. These efforts pave an avenue toward the fabrication of synthetic scaffolds that can facilitate the study of cellular events for disease diagnosis and treatment. First, a series of boron dipyrromethene (BODIPY) photocages with nitrogen-containing nucleophiles were examined to determine structure-reactivity relationships, which resulted in a >1,000× increase in uncaging yield. Subsequently, photoinduced hydrogel formation in 90 wt % water was accomplished via biorthogonal carbonyl condensation using hydrophilic polymer scaffolds separately containing BODIPY photocages and ortho-phthalaldehyde (OPA) moieties. Spatiotemporal control is demonstrated with light on/off experiments to modulate gel stiffness and masking to provide <100 µm features. Biocompatability of the method was shown through pre-/post-crosslinking cell viability studies. Short term, these studies are anticipated to guide translation to emergent additive manufacturing technology, which, longer term, will enable the development of 3D cell cultures for tissue engineering applications.

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