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The present disclosure is directed to systems and methods for synthesizing a spidroin. In some embodiments, the methods comprise synthesizing a monomer in vivo in a heterologous host, the monomer comprising an N-terminus IntC domain and a C-terminus IntN domain, and post-translationally polymerizing the synthesized monomer via in vitro split-intein mediated polymerization.
The current embodiments include all-polymeric protective material for mitigating lightning strike damage. The protective material includes a hybrid matrix comprising PANI and MXene dispersed within a thermosetting epoxy resin. This hybrid matrix can be painted, printed, or applied as a conductive polymeric layer to a FRCP structure, for example an aircraft fuselage, wing, empennage, control surface (aileron, flap, slats, rudder, elevator) or a wind turbine blade. The protective material not only withstands lightning strikes, but also functions as shielding against electromagnetic interference and is corrosion-resistant and lightweight.
This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.
Polyolefins are by far the most ubiquitous industrially produced polymers and are primarily produced by early transition metal catalysts. These catalysts are not functional group tolerant, and copolymerization of ethylene and polar vinyl monomers is quite challenging. Furthermore, early metal catalysts convert ethylene to linear polyethylene, and introduction of branches requires addition of comonomers. In this Account, we describe our efforts in designing and implementing new Pd(II) and Ni(II) olefin polymerization catalysts based on mechanistic understanding of the chain growth process. Here, the original hindered nickel- and palladium-aryl-substituted diimine complexes were discovered in 1995. The key to the success of these now “classic” systems in generating high polymers rather than dimers or oligomers was realizing that incorporation of ortho-disubstituted aryl groups partially blocks the axial sites of the metal and thus retards the rate of chain transfer relative to propagation. Two key features of these late metal catalysts distinguish them from early metal complexes. First, they tolerate certain functional groups, which allows copolymerization of olefins with polar comonomers. Second, they can form a branched polymer from ethylene without the need to add α-olefin comonomers. Importantly, for nickel catalysts, branching levels can be modulated by changing reaction conditions, such as temperature and monomer pressure.
A well-defined palladium complex [(tBuXPhos)Pd(Me)(BAr f )] bearing a bulky monophosphine ligand was synthesized and fully characterized. X-ray diffraction analysis shows that the 1,3,5-triisopropylaryl group of the dialkylbiaryl phosphine ligand exhibits a weak η 6 -interaction with the Pd(II) center. This catalyst exhibits excellent functional group tolerance and polymerizes propargyl esters containing benzoyl and acetyl groups, propargyl methyl ether, propargyl alcohol, benzyl acetylene, and phenyl acetylene to yield polymers with M n values in the range of 5–15 kDa with monomodal molecular weight distributions between ca. 1.4 and 2.1.
This paper reviews research of silicone-based resins for vat polymerization printing (VPP). Silicone resins are used commonly in other 3D printing technologies because of their desirable properties. Silicones are chemically inert, oxidatively, and thermally stable, and have the lowest glass transition temperature of any polymer. Creating silicone resins processable by VPP is challenging because VPP requires low viscosity liquid resin that quickly photopolymerizes. This review will summarize VPP technologies, resin chemistries, and recent research of silicone VPP resins.
Two-photon polymerization (TPP) is widely used to create 3D micro- and nanoscale scaffolds for biological and mechanobiological studies, which often require the mechanical characterization of the TPP fabricated structures. To satisfy physiological requirements, most of the mechanical characterizations need to be conducted in liquid. However, previous characterizations of TPP fabricated structures are all conducted in air due to the limitation of conventional micro- and nanoscale mechanical testing methods. In this study, a new experimental method is reported for testing the mechanical properties of TPP-printed microfibers in liquid. The experiments show that the mechanical behaviors of the microfibers tested in liquid are significantly different from those tested in air. By controlling the TPP writing parameters, the mechanical properties of the microfibers can be tailored over a wide range to meet a variety of mechanobiology applications. In addition, it is found that, in water, the plasticly deformed microfibers can return to their predeformed shape after tensile strain is released. The shape recovery time is dependent on the size of microfibers. The experimental method represents a significant advancement in mechanical testing of TPP fabricated structures and may help release the full potential of TPP fabricated 3D tissue scaffolds for mechanobiological studies.
Since 2001, 3D microfabrication based on two‐photon polymerization (TPP) has drawn extensive attention and interest in biology, optics, photonics, material science, and high‐energy physics. The in‐volume fabrication capability due to the threshold behavior of two‐photon absorption enables TPP higher flexibility compared with other nanofabrication techniques. However, as determined by the in‐volume fabrication feature as well as various reaction dynamics, the writing characteristics of TPP, such as throughput, accuracy, surface quality, and fabrication capability, are still limited. Herein, a comprehensive study is performed on the spatiotemporal behavior of reaction dynamics during TPP fabrication, mainly focusing on spatiotemporal characteristics of radical diffusion, photothermal effect, microscale mechanics, and voxel stacking process. Based on the study, a nonsequential fabrication method is established to simultaneously improve key writing characteristics of TPP and realize sharp features, high speeds, large overhang structure, and smooth surfaces. The method established in this work can be applied to improve the performance of functional devices for various fields.
The chemoselectivity of molecular catalysts underpins much of modern synthetic organic chemistry. However, little is known about the selectivity of individual catalysts because this single-catalyst-level behavior is hidden by the bulk catalytic behavior. In this work, for the first time, the selectivity of individual molecular catalysts for two different reactions is imaged in real time at the single-catalyst level. This imaging is achieved through fluorescence microscopy paired with spectral probes that produce a snapshot of the instantaneous chemoselectivity of a single catalyst for either a single-chain-elongation or a single-chain-termination event during ruthenium-catalyzed polymerization. Superresolution imaging of multiple selectivity events, each at a different single-molecular ruthenium catalyst, indicates that catalyst selectivity may be unexpectedly spatially and time-variable.
The silylium-like surface species [ i Pr 3 Si][(R F O) 3 Al-OSi≡)] activates (N^N)Pd(CH 3 )Cl (N^N=Ar-N=CMeMeC=N-Ar, Ar=2,6-bis(diphenylmethyl)-4-methylbenzene) by chloride ion abstraction to form [(N^N)Pd-CH 3 ][(R F O) 3 Al-OSi≡)] ( 1 ). A combination of FTIR, solid-state NMR spectroscopy, and reactions with CO or vinyl chloride establish that 1 shows similar reactivity patterns as (N^N)Pd(CH 3 )Cl activated with Na[B(Ar F ) 4 ]. Multinuclear 13 C{ 27 Al} RESPDOR and 1 H{ 19 F} S-REDOR experiments are consistent with a weakly coordinated ion-pair between (N^N)Pd-CH 3 + and [(R F O) 3 Al-OSi≡)]. 1 catalyzes the polymerization of ethylene with similar activities as [(N^N)Pd-CH 3 ] + in solution and incorporates up to 0.4% methyl acrylate in copolymerization reactions. 1 produces polymers with significantly higher molecular weight than the solution catalyst, and generates the highest molecular weight polymers currently reported in copolymerization reactions of ethylene and methylacrylate.
Realizing efficient all-polymer solar cell (APSC) acceptors typically involves increased building block synthetic complexity, hence potentially unscalable syntheses and/or prohibitive costs. Here we report the synthesis, characterization, and implementation in APSCs of three new polymer acceptors P1–P3 using a scalable donor fragment, bis(2-octyldodecyl)anthra[1,2-b : 5,6-b’]dithiophene-4,10-dicarboxylate (ADT) co-polymerized with the high-efficiency acceptor units, NDI, Y6, and IDIC. Further, all three copolymers have comparable photophysics to known polymers; however, APSCs fabricated by blending P1, P2 and P3 with donor polymers PM5 and PM6 exhibit modest power conversion efficiencies (PCEs), with the champion P2-based APSC achieving PCE=5.64 %. Detailed morphological and microstructural analysis by AFM and GIWAXS reveal a non-optimal APSC active layer morphology, which suppresses charge transport. Despite the modest efficiencies, these APSCs demonstrate the feasibility of using ADT as a scalable and inexpensive electron rich/donor building block for APSCs.
Strained ring systems play an important role in synthesis and can be characterized by the ring strain energy (RSE). The RSE of 3, 4, 5, and 6 membered saturated and unsaturated ring systems containing N, O, P, and S heteroatoms and H, F, SiMe 3 , and SO 2 Me substituents were calculated at the G3(MP2) composite correlated molecular orbital theory level using up to 5 models to predict the RSE. Generally, the RSE decreased as ring size increased with a substantial decrease from 4 to 5 membered rings. Replacement of a ring CH 2 with P or S reduced the RSE, consistent with less angle strain. The RSE for unsaturated systems were generally greater than for saturated systems due to increased angle strain. No general trends were found with respect to substituent effects. In conclusion, the RSE values suggest that 3-pyrroline and 2-pyrroline and their derivatives may be able to support ring opening metathesis polymerization and warrant further study.
Two-photon polymerization (TPP) enables the fabrication of intricate 3D microstructures with submicron precision, offering significant potential in biomedical applications like tissue engineering. In such applications, to print materials and structures with defined mechanics, it is crucial to understand how TPP printing parameters impact the material properties in a physiologically relevant liquid environment. Herein, an experimental approach utilizing microscale tensile testing (μTT) for the systematic measurement of TPP-fabricated microfibers submerged in liquid as a function of printing parameters is introduced. Using a diurethane dimethacrylate-based resin, the influence of printing parameters on microfiber geometry is first explored, demonstrating cross-sectional areas ranging from 1 to 36 μm 2 . Tensile testing reveals Young's moduli between 0.5 and 1.5 GPa and yield strengths from 10 to 60 MPa. The experimental data show an excellent fit with the Ogden hyperelastic polymer model, which enables a detailed analysis of how variations in writing speed, laser power, and printing path influence the mechanical properties of TPP microfibers. The μTT method is also showcased for evaluating multiple commercial resins and for performing cyclic loading experiments. Collectively, this study builds a foundation toward a standardized microscale tensile testing framework to characterize the mechanical properties of TPP printed structures.
We previously reported a single-cell adhesion micro tensile tester (SCAμTT) fabricated from IP-S photoresin with two-photon polymerization (TPP) for investigating the mechanics of a single cell-cell junction under defined tensile loading. A major limitation of the platform is the autofluorescence of IP-S, the photoresin for TPP fabrication, which significantly increases background signal and makes fluorescent imaging of stretched cells difficult. In this study, we report the design and fabrication of a new SCAμTT platform that mitigates autofluorescence and demonstrate its capability in imaging a single cell pair as its mutual junction is stretched. By employing a two-material design using IP-S and IP-Visio, a photoresin with reduced autofluorescence, we show a significant reduction in autofluorescence of the platform. Further, by integrating apertures onto the substrate with a gold coating, the influence of autofluorescence on imaging is almost completely mitigated. With this new platform, we demonstrate the ability to image a pair of epithelial cells as they are stretched up to 250% strain, allowing us to observe junction rupture and F-actin retraction while simultaneously recording the accumulation of over 800 kPa of stress in the junction. In conclusion, the platform and methodology presented here can potentially enable detailed investigation of the mechanics of and mechanotransduction in cell-cell junctions and improve the design of other TPP platforms in mechanobiology applications.
Exercising direct control over the unusual electronic structures arising from quantum confinement effects in graphene nanoribbons (GNRs) is intimately linked to geometric boundary conditions imposed by the structure of the ribbon. Besides composition and position of substitutional dopant atoms, the symmetry of the unit cell, width, length, and termination of a GNR govern its electronic structure. Here, we present a rational design that integrates each of these interdependent variables within a modular bottom-up synthesis. Our hybrid chemical approach relies on a catalyst-transfer polymerization that establishes excellent control over length, width, and end groups. Complemented by a surface-assisted cyclodehydrogenation step, uniquely enabled by matrix-assisted direct (MAD) transfer protocols, geometry and functional handles encoded in a polymer template are faithfully mapped onto the structure of the corresponding GNR. Bond-resolved scanning tunneling microscopy (BRSTM) and spectroscopy (STS) validate the robust correlation between polymer template design and GNR electronic structure.
Copper(I) ions (Cu + ) are used in olefin separations due to their olefin complexing ability and low cost, but their instability in the presence of water and gases limits their widespread use. Ionic liquids (ILs) have emerged as stabilizers of Cu + ions and prevent their degradation, providing high olefin separation efficiency. There is limited understanding into the role that polymeric ionic liquids (PILs), which possess similar structural characteristics to ILs, have on Cu + ion-olefin interactions. Moreover, copper ions with diverse oxidation states, including Cu + and Cu 2+ ions, have been rarely employed for olefin separations. In this study, gas chromatography (GC) is used to investigate the interaction strength of olefins to stationary phases composed of the 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 6 MIM + ][NTf 2 – ]) IL and the poly(1-hexyl-3-vinylimidazolium [NTf 2 – ]) (poly([C 6 VIM + ][NTf 2 – ])) PIL containing monovalent and divalent copper salts (i.e., [Cu + ][NTf 2 – ] and [Cu 2+ ]2[NTf 2 – ]). The chromatographic retention of alkenes, alkynes, dienes, and aromatic compounds was examined. Incorporation of the [Cu 2+ ]2[NTf 2 – ] salt into a stationary phase comprised of poly(dimethylsiloxane) resulted in strong retention of olefins, while its addition to the [C 6 MIM + ][NTf 2 – ] IL and poly([C 6 VIM + ][NTf 2 – ]) PIL allowed for the interaction strength to be modulated. Olefins exhibited greater affinities toward IL and PIL stationary phases containing the [Cu 2+ ]2[NTf 2 – ] salt compared to those with the [Cu + ][NTf 2 – ] salt. Elimination of water from both copper salts was observed to be an important factor in promoting olefin interactions, as evidenced by increased olefin retention upon exposure of the stationary phases to high temperatures. Furthermore, to evaluate the long-term thermal stability of the stationary phase, chromatographic retention of probes was measured on the [Cu 2+ ]2[NTf 2 – ]/[C 6 MIM + ][NTf 2 – ] IL stationary phase after its exposure to helium at a temperature of 110°C.
The aim of this study was to examine the influence of pressure-assisted thermal sterilization (PATS) on properties of polymeric packaging and packaged avocado puree. High pressure of 600 MPa and initial vessel temperature of 90 °C were used over 5 min processing time. We used two high barrier film pouches: Film A-(PE/PA6//EVOH//PA6/PE) and film B-(AlO x -coated PET//AlO x -coated PET//PA//CPP). Oxygen transmission rates (OTR) changed from 0.16 ± 0.07 to 3.24 ± 0.52 cm 3 /m 2 .day for film A after processing while OTRs were not detected for film B. Water vapor transmission rates (WVTR) changed from 3.72 ± 0.06 to 4.97 ± 0.14 g/m 2 .day for film A and 0.11 ± 0.02 to 0.62 ± 0.0.6 g/m 2 .day for film B. The dissolved oxygen in packaged avocado puree reduced from 21% to 3% after PATS for both films. Reduced oxygen level in packaged avocado may help extend its shelf life. Dielectric properties and X-ray diffraction helped explain PATS induced changes in film barrier properties. The total chlorophyll, greenness, and lightness decreased significantly (p < 0.05) after PATS. The thiobarbituric acid activity reduced after PATS. PATS showed potential to produced shelf-stable avocado puree; however, shelf-life studies are needed to further develop PATS process.
Wearable electronic devices (WEDs) are receiving significant attention because of the increasing interest in soft robotics, electronic skin, and wearable sensors. Liquid metals (LMs) are compelling for WEDs owing to their metallic conductivity, fluidic nature, and low toxicity. For this study, we fabricated stretchable and soft WEDs using LM (eutectic gallium-indium alloy) wires (LMWs) patterned via force wetting through custom-made stencils on an elastic substrate. LMWs can generate thermal energy via Joule heating upon current application and deliver it to the substrate, resulting in wearable polymeric heaters. The LM mixed with carbonyl iron particles (CIPs) can also be patterned while preserving fluidic behavior. The degree of thermal energy generated through the LMWs can be manipulated as a function of the CIP concentration in the LM and geometrical factors of the electrode patterns, i.e., width and length. An elastic film patterned with LMWs attached to the human body exhibits changes in the effective electrical resistance depending on applied strain, demonstrating potential as a wearable strain sensor. This LM utilized WED that can generate thermal energy upon current application through the LMWs and detect the bodily motion has significant potential for application in wearable thermotherapy, electronic skin, and soft sensors.