RESUMO
The lack of chemical diversity in light-driven reactions for 3D printing poses challenges in the production of structures with long-term ambient stability, recyclability, and breadth in properties (mechanical, optical, etc.). Herein we expand the scope of photochemistries compatible with 3D printing by introducing onium photocages for the rapid formation of poly(thiourethanes) (PTUs). Efficient nonsensitized visible-light photolysis releases organophosphine and -amine derivatives that catalyze thiol-isocyanate polyaddition reactions with excellent temporal control. Two resin formulations comprising commercial isocyanates and thiols were developed for digital light processing (DLP) 3D printing to showcase the fast production of high-resolution PTU objects with disparate mechanical properties. Onium photocages represent valuable tools to advance light-driven manufacturing of next-generation high-performance sustainable materials.
RESUMO
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.
RESUMO
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 (â¼4 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 â¼10 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.
RESUMO
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.
RESUMO
Reported herein are two functionalized crown ether strapped calix[4]pyrroles, H1 and H2. As inferred from competitive salt binding experiments carried out in nitrobenzene-d5 and acetonitrile-d3, these hosts capture LiCl selectively over four other test salts, viz. NaCl, KCl, MgCl2, and CaCl2. Support for the selectivity came from density functional theory (DFT) calculations carried out in a solvent continuum. These theoretical analyses revealed a higher innate affinity for LiCl in the case of H1, but a greater selectivity relative to NaCl in the case of H2, recapitulating that observed experimentally. Receptors H1 and H2 were outfitted with methacrylate handles and subject to copolymerization with acrylate monomers and cross-linkers to yield gels, G1 and G2, respectively. These two gels were found to adsorb lithium chloride preferentially from an acetonitrile solution containing a mixture of LiCl, NaCl, KCl, MgCl2, and CaCl2 and then release the lithium chloride in methanol. The gels could then be recycled for reuse in the selective adsorption of LiCl. As such, the present study highlights the use of solvent polarity switching to drive separations with potential applications in lithium purification and recycling.
RESUMO
The driving of rapid polymerizations with visible to near-infrared light will enable nascent technologies in the emerging fields of bio- and composite-printing. However, current photopolymerization strategies are limited by long reaction times, high light intensities, and/or large catalyst loadings. The improvement of efficiency remains elusive without a comprehensive, mechanistic evaluation of photocatalysis to better understand how composition relates to polymerization metrics. With this objective in mind, a series of methine- and aza-bridged boron dipyrromethene (BODIPY) derivatives were synthesized and systematically characterized to elucidate key structure-property relationships that facilitate efficient photopolymerization driven by visible to far-red light. For both BODIPY scaffolds, halogenation was shown as a general method to increase polymerization rate, quantitatively characterized using a custom real-time infrared spectroscopy setup. Furthermore, a combination of steady-state emission quenching experiments, electronic structure calculations, and ultrafast transient absorption revealed that efficient intersystem crossing to the lowest excited triplet state upon halogenation was a key mechanistic step to achieving rapid photopolymerization reactions. Unprecedented polymerization rates were achieved with extremely low light intensities (<1 mW/cm2) and catalyst loadings (<50 µM), exemplified by reaction completion within 60 s of irradiation using green, red, and far-red light-emitting diodes. Halogenated BODIPY photoredox catalysts were additionally employed to produce complex 3D structures using high-resolution visible light 3D printing, demonstrating the broad utility of these catalysts in additive manufacturing.
RESUMO
Access to clean drinking water is a recognized societal need that touches on the health and livelihood of millions of people worldwide. This is providing an incentive to develop new water-treatment technologies. Traditional technologies, while widespread, are usually inefficient at removing organic pollutants from sewage or so-called grey water. Macrocycle-containing covalent polymer networks have begun to attract attention in the context of water treatment owing to the inherent stability provided by the polymer backbones and their ability to capture micropollutant guests as the result of tunable macrocycle-based host-guest interactions. In this Minireview, we summarize recent advances (from 2016 to mid-2020) involving the removal of organic micropollutants from water using macrocycle-containing covalent polymer networks. An overview of future challenges within this subfield is also provided.
Assuntos
Polímeros/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Água/químicaRESUMO
A novel library of tunable negative photochromic compounds, donor-acceptor Stenhouse adducts (DASAs), is reported. Tailoring the electron deficient "acceptor" moiety yielded DASAs that can be activated with mild visible and far red light. The effect of acceptor composition on reactivity, absorption, equilibrium, and cyclability is exploited for the design of high performance photoswitches. The structural changes to the carbon acid acceptor also provide access to new, more structurally diverse DASA derivatives by facilitating the ring-opening reaction with electron deficient amine donors.
RESUMO
The fabrication of well-defined, multifunctional polymer brushes under ambient conditions is described. This facile method uses light-mediated, metal-free atom-transfer radical polymerization (ATRP) to grow polymer brushes with only microliter volumes required. Key to the success of this strategy is the dual action of N-phenylphenothiazine (PTH) as both an oxygen scavenger and polymerization catalyst. Use of simple glass cover slips results in a high degree of spatial and temporal control and allows for multiple polymer brushes to be grown simultaneously. The preparation of arbitrary 3D patterns and functional/emissive polymer brushes demonstrates the practicality and versatility of this novel strategy.
RESUMO
Conjugated polymer zwitterions (CPZs) are neutral, hydrophilic, polymer semiconductors. The pendent zwitterions, viewed as side chain dipoles, impart solubility in polar solvents for solution processing, and open opportunities as interfacial components of optoelectronic devices, for example, between metal electrodes and organic semiconductor active layers. Such interlayers are crucial for defining the performance of organic electronic devices, e.g., field-effect transistors (OFETs), light-emitting diodes (OLEDs), and photovoltaics (OPVs), all of which consist of multilayer structures. The interlayers reduce the Schottky barrier height and thus improve charge injection in OFETs and OLEDs. In OPVs, the interlayers serve to increase the built-in electric potential difference (Vbi) across the active layer, ensuring efficient extraction of photogenerated charge carriers. In general, polar and even charged electronically active polymers have gained recognition for their ability to modify metal/semiconductor interfaces to the benefit of organic electronics. While conjugated polyelectrolytes (CPEs) as interlayer materials are well-documented, open questions remain about the role of mobile counterions in CPE-containing devices. CPZs possess the processing advantages of CPEs, but as neutral molecules lack any potential complications associated with counterions. The electronic implications of CPZs on metal electrodes stem from the orientation of the zwitterion dipole moment in close proximity to the metal surface, and the resultant surface-induced polarization. This generates an interfacial dipole (Δ) at the CPZ/metal interface, altering the work function of the electrode, as confirmed by ultraviolet photoelectron spectroscopy (UPS), and improving device performance. An ideal cathode interlayer would reduce electrode work function, have orthogonal processability to the active layer, exhibit good film forming properties (i.e., wettability/uniformity), prevent exciton quenching, possess optimal electron affinity that neither limits the work function reduction nor impedes the charge extraction, transport electrons selectively, and exhibit long-term stability. Our recent discoveries show that CPZs achieve many of these attributes, and are poised for further expansion and development in the interfacial science of organic electronics. This Account reviews a recent collaboration that began with the synthesis of CPZs and a study of their structural and electronic properties on metals, then extended to their application as interlayer materials for OPVs. We discuss CPZ structure-property relationships based on several material platforms, ranging from homopolymers to copolymers, and from materials with intrinsic p-type conjugated backbones to those with intrinsic n-type conjugated backbones. We discuss key components of such interlayers, including (i) the origin of work function reduction of CPZ interlayers on metals; (ii) the role of the frontier molecular orbital energy levels and their trade-offs in optimizing electronic and device properties; and (iii) the role of polymer conductivity type and the magnitude of charge carrier mobility. Our motivation is to present our prior use and current understanding of CPZs as interlayer materials in organic electronics, and describe outstanding issues and future potential directions.
RESUMO
The utility of Meldrum's activated furan (MAF) for the colorimetric detection of sub ppm levels of amines in solution, on solid supports, and as vapors is reported. MAF is synthesized in one step from inexpensive and commercially available starting materials and exhibits high selectivity for primary and secondary amines in the presence of competing nucleophiles. The reaction between activated furans and amines results in a distinct color change, discernable by the naked eye. UV/Vis absorption spectroscopy was utilized to monitor reactions in solution and determine detection limits. Additionally, solutions of MAF were useful as stains for thin layer chromatography and for monitoring solid-phase synthesis of peptides and peptidomimetics. Finally, MAF was used to detect volatile amines released from fish samples, demonstrating potential for food spoilage applications.
RESUMO
A class of tunable visible and near-infrared donor-acceptor Stenhouse adduct (DASA) photoswitches were efficiently synthesized in two to four steps from commercially available starting materials with minimal purification. Using either Meldrum's or barbituric acid "acceptors" in combination with aniline-based "donors", an absorption range spanning from 450 to 750 nm is obtained. Additionally, photoisomerization results in complete decoloration for all adducts, yielding fully transparent, colorless solutions and films. Detailed investigations using density functional theory, nuclear magnetic resonance, and visible absorption spectroscopies provide valuable insight into the unique structure-property relationships for this novel class of photoswitches. As a final demonstration, selective photochromism is accomplished in a variety of solvents and polymer matrices, a significant advantage for applications of this new generation of DASAs.
RESUMO
Three conjugated polymer zwitterions (CPZs), containing thiophene-, diketopyrrolopyrrole- (DPP), and naphthalene diimide (NDI) backbones, were synthesized with pendant zwitterions, specifically sulfobetaine groups. Diboronate-ester-functionalized bithiophene and benzothiadiazole monomers were copolymerized with zwitterion-substituted dibromothiophene, DPP, and NDI monomers by A2 + B2 Suzuki polymerization. The CPZs were incorporated into polymer solar cells (PSCs) as interlayers between the photoactive layer and Ag cathode. The thiophene-based CPZs gave power conversion efficiencies (PCEs) of about 5%, while the narrow-energy-gap DPP- and NDI-based CPZs performed exceptionally well, giving PCEs of 9.49% and 10.19%, respectively. The interlayer thickness had only a minor impact on the device performance for the DPP- and NDI-CPZs, a finding attributed to their electron-transport properties. Ultraviolet photoelectron and reflectance spectroscopies, combined with external quantum efficiency measurements, provided structure-property relationships that lend insight into the function of CPZ interlayers in PSCs. NDI-based CPZ interlayers provide some of the best performing organic solar cells reported to date, and prove useful in conjunction with high-performing polymer-active layers and stable, high-work-function, metal cathodes.
RESUMO
Drawing inspiration from nature's own intricate designs, synthetic multimaterial structures have the potential to offer properties and functionality that exceed those of the individual components. However, several contemporary hurdles, from a lack of efficient chemistries to processing constraints, preclude the rapid and precise manufacturing of such materials. Herein, the development of a photocurable resin comprising color-selective initiators is reported, triggering disparate polymerization mechanisms between acrylate and thiol functionality. Exposure of the resin to UV light (365 nm) leads to the formation of a rigid, highly crosslinked network via a radical chain-growth mechanism, while violet light (405 nm) forms a soft, lightly crosslinked network via an anionic step-growth mechanism. The efficient photocurable resin is employed in multicolor digital light processing 3D printing to provide structures with moduli spanning over two orders of magnitude. Furthermore, local intensity (i.e., grayscale) control enables the formation of programmable stiffness gradients with ≈150× change in modulus occurring across sharp (≈200 µm) and shallow (≈9 mm) interfaces, mimetic of the human knee entheses and squid beaks, respectively. This study provides composition-processing-property relationships to inform advanced manufacturing of next-generation multimaterial objects having a myriad of applications from healthcare to education.
RESUMO
Imagine if it were possible to create 3D objects in the palm of your hand within seconds using only a single photonic chip. Although 3D printing has revolutionized the way we create in nearly every aspect of modern society, current 3D printers rely on large and complex mechanical systems to enable layer-by-layer addition of material. This limits print speed, resolution, portability, form factor, and material complexity. Although there have been recent efforts in developing novel photocuring-based 3D printers that utilize light to transform matter from liquid resins to solid objects using advanced methods, they remain reliant on bulky and complex mechanical systems. To address these limitations, we combine the fields of silicon photonics and photochemistry to propose the first chip-based 3D printer. The proposed system consists of only a single millimeter-scale photonic chip without any moving parts that emits reconfigurable visible-light holograms up into a simple stationary resin well to enable non-mechanical 3D printing. Furthermore, we experimentally demonstrate a stereolithography-inspired proof-of-concept version of the chip-based 3D printer using a visible-light beam-steering integrated optical phased array and visible-light-curable resin, showing 3D printing using a chip-based system for the first time. This work demonstrates the first steps towards a highly-compact, portable, and low-cost solution for the next generation of 3D printers.
RESUMO
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.
RESUMO
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.
RESUMO
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.
RESUMO
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.