Photopolymerization Technique Research Articles

KH571 construct interfacial molecular bridge in calcium silicate/TMPTA/HDDA scaffolds for improving mechanical properties, biodegradability and photopolymerization

Digital Light Processing (DLP) offers the potential for personalized bone implants. Within this method, the interfacial bonding capacity of inorganic/organic materials and the solid-phase content of the slurry emerge as primary factors influencing scaffolds mechanical properties. In this research, KH571 was applied to establish an interfacial “molecular bridge”, adopting in situ coupling technology to forge stable covalent bonds between calcium silicate (CSi) and KH571. Chemical grafting, surface photografting, and photopolymerization techniques were then utilized to construct a photo-crosslinked network by CSi-KH571-TMPTA/HDDA slurry, thereby transforming the weak physical connections at the interface into strong chemical bonds. Consequently, the curing capacity and mechanical properties of the scaffolds were enhanced. Further control grain size, crystal phase transition, and shrinkage of CSi-KH571 scaffolds, post-treatment sintering processes were employed, resulting in scaffolds with a high content of β-CSi. Moreover, the optimal process parameters were selected concerning grafting rate, chemical composition, microscopic morphology, crystalline transformation, dimensional accuracy, mechanical properties, biodegradability and biocompatibility of CSi-KH571. The elastic modulus and compressive properties of CSi25-55 scaffolds exhibited a notable improvement of 29.71 % and 59.30 %, respectively, compared to CSi-50 scaffolds. By regulating the phase composition of CSi, CSi25-55 scaffolds were designed to possess a controllable degradation. In vitro cell culture experiments validated its excellent biocompatibility and promoted the proliferation and differentiation of bone marrow mesenchymal stem cells (BMSCs) as well as the deposition of bone matrix. Herein, a novel and sustainable approach has been promoted for enhancing the interfacial bonding capacity of inorganic/organic materials and the solid-phase content of printing slurry, which lays the foundation for the printing of high-resolution degradable bioceramic scaffolds.

Micro-fluidic covalent immobilization of multi-gradient RGD peptides on a gelatin surface for studying endothelial cell migration.

Collective endothelial migration is a hallmark of wound healing, which is regulated by spatial concentration gradients of extracellular biochemical factors. Arginine-glycine-aspartate (RGD) peptides play a vital role in regulating cell migration through specific binding to integrins. In this study, a micro-fluidic technology combined with a photopolymerization technique is developed to create gelatin methacryloyl (GelMA)-based substrates with various concentration gradients of RGD peptides. The capability of generating linear and nonlinear RGD concentration gradients was quantitatively verified through numerical simulation and immunohistochemical quantitative experiments. The results of the concentration gradients show a strong concurrence between the immunohistochemical quantification experiments and numerical simulations. Furthermore, endothelial migration experiments were conducted with various concentration gradients of RGD peptides. We have observed that endothelial cells on the surface of gels with a linear concentration gradient exhibit a larger cell area, a longer cell perimeter, and more stress fiber density. Furthermore, the cells demonstrate directional alignment and migration towards regions with a higher RGD concentration. High concentration gradients significantly enhance endothelial cell migration, consistent with observations on surfaces of gels with nonlinear concentration gradients. In brief, we proposed a simple and effective micro-fluidic photopolymerization technique capable of generating diverse concentration gradients of RGD and probing their effects on cell migration. The results suggest that regulating the RGD peptide concentration gradients can alter the migration of endothelial cells, showing potential for promoting wound healing.

Diatomaceous Earth‐Containing Linseed Oil‐Based Environmentally Friendly Hydrophobic Coatings

AbstractThe use of bio‐based building blocks for the synthesis of polymers is increasing day by day. Coatings prepared by modifying bio‐based building blocks such as linseed oil (LO) and diatomaceous earth (DE) are very promising. In this study, bio‐based hydrophobic coatings were prepared by cationic photopolymerization technique using epoxidized linseed oil (ELO) and dimer diamine‐modified diatomaceous earth. The bio‐based coatings with hydrophobic properties were prepared by using the spin coating method. ELO was characterized by Fourier transform infrared spectroscopy (FTIR) and proton nuclear magnetic resonance (1H‐NMR). The thermal properties of the prepared coatings were determined by thermogravimetric analysis (TGA). The pendulum hardness, pencil hardness, and gel content of the prepared coatings were examined. Also, the hydrophobicity of the obtained bio‐based coatings was determined by contact angle measurements. The highest contact angle among the investigated compositions was found to be 110°.

Additive Manufacturing of Tough Silicone Via Large-Scale, High-Viscosity Vat Photopolymerization

Abstract In this work, a large-scale, high-viscosity vat photopolymerization additive manufacturing system is designed and fabricated to print 3D structures as large as 370 × 300 × 370 mm3 out of high-viscosity, low-reactivity elastomeric resins. A detailed overview is presented of the printer's design and capabilities, including a resin processing sub-system that stores and spreads high-viscosity resin; a roll-to-roll variable tensioning system to mitigate the separation forces after printing each layer; and a light patterning system that generates high-intensity light patterns across an area of 370 × 300 mm2 with a resolution of 3840 × 4320 pixels. The ability to print with both high-viscosity and low-reactivity resins and resins that require high-intensity light enables additive manufacturing of new classes of materials that could not be printed previously using vat photopolymerization techniques. These materials include highly reinforced silica nanoparticle composites, high-molecular-weight polymers such as silicones and acrylate or methacrylate resins, and low-reactivity resins such as photocurable platinum-catalyzed liquid silicone rubber.

Flexible FPI sensor fabricated by fiber end photopolymerization and integration for high sensitivity gas pressure sensing

This work presents a new design framework for highly sensitive fiber gas pressure sensor. We construct a Flexible Fabry–Perot Interferometer (F-FPI), which consists of three polymer pillars and an end cap, on a fiber end face. A unique fiber-end photopolymerization and integration (FEPI) technique is adopted for fabricating the device. The varied gas pressure in the enclosed space not only changes the refractive index (RI) of the gas but also the length of the pillars. Therefore the difference in the optical path length of the FPI is more sensitive to pressure changes. Experimental results indicate that the F-FPI realizes a gas pressure sensitivity up to 79.0 pm/kPa in the range of 0–200 kPa. In addition, the Vernier effect is introduced to amplify the sensitivity to −409.7 pm/kPa. The temperature compensation is achieved by cascading a Fiber Bragg Grating (FBG) behind the F-FPI. Such a design framework provides a new idea for highly sensitivity gas pressure sensing.

Insights into morphology and mechanical properties of architected interpenetrating aluminum-alumina composites

Additive manufacturing (AM) technologies are unleashing the restrictions imposed by conventional manufacturing, allowing the production of innovative designs tailored to improve properties or performance. AM techniques in ceramic production allow the application of novel designs to ceramic parts, opening new opportunities for combining technologies aiming to obtain architected interpenetrating phase composites (IPCs). In this study, alumina structures with different architectures and Computer Aided Design (CAD) structure porosity oriented unidirectionally or bidirectionally, were fabricated by vat photopolymerization technique, namely Digital Light Processing. Afterwards, these structures were infiltrated with an aluminum alloy through investment casting, thus obtaining aluminum-alumina IPCs. Under compression, the IPCs presented a ductile behavior, conversely to the fragile ceramic counterparts. The IPCs compressive strength and absorbed energy were expressively higher than their ceramic counterparts. Comparing the bidirectional IPCs with the unidirectional ones, a significant increase in compressive strength and absorbed energy was observed, from 36.2% to 42.3% and from 164.8% to 358.1%, respectively, due to the greater amount and interconnection of the metal inside the ceramic structure. This study demonstrates the feasibility of this manufacturing route, combining two distinctive technologies, for the fabrication of metal-ceramic architected IPCs, allowing to tailor their mechanical properties and energy absorption capacity for a given application.

Printing of low-viscosity materials using tomographic additive manufacturing

Tomographic volumetric additive manufacturing (VAM) is a high-speed 3D printing technique that overcomes many of the challenges faced by conventional layer-by-layer based approaches. However, unlike other vat photopolymerization techniques, VAM must use much higher viscosity resins prohibiting the use of more commonly available lower-viscosity materials. Low-viscosity poly(ethylene glycol) diacrylate (PEGDA) has seen wide usage in bioprinting techniques but has eluded printing in VAM. Using a VAM printer with a high angular dose delivery rate, as well as tomographic projections optimized for low-viscosity printing conditions, we demonstrate high-fidelity VAM printing in PEGDA with viscosities as low as 12 cP. Micro-computed tomography imaging of printed parts reveal close-to voxel resolution limited performance. Furthermore, we have demonstrated the first direct printing of a low-viscosity hydrogel in VAM. The proposed method expands the viscosity range, and in turn the catalogue of materials accessible to VAM, giving this printing modality the broadest viscosity range of any vat photopolymerization technique.

ZrO2 reinforced porous Si3N4-based ceramics with improved mechanical properties fabricated via vat photopolymerization (VPP)

Porous Si3N4 ceramics are widely applied in many fields owing to their excellent properties such as high electromagnetic wave permeability, oxidation resistance, and wear resistance. Besides, the vat photopolymerization (VPP) technique can fabricate porous Si3N4-based ceramics with complex shapes and high precision. Nevertheless, The high absorptivity and refractive index of Si3N4 to ultraviolet light make it difficult to form porous Si3N4-based ceramics with the VPP technique. In this work, the addition of ZrO2 simultaneously improved the printability of Si3N4 slurries and the performance of Si3N4 ceramics via VPP technology. Rheological behavior and curing properties of the slurries were investigated, and the influence of ZrO2 content on the mechanical properties of printed Si3N4-based ceramics was investigated systematically. The addition of ZrO2 decreased the UV absorptivity of composite powder, thus improving the curing depth from 25.2 ± 2.6 μm to 64.8 ± 3.7 μm. XRD analysis revealed that ZrO2 in the composite ceramics mainly exists as the phase of yttria-stabilized tetragonal zirconia (Zr0.92Y0.08O1.96), which could ensure the effect of phase transformation toughening. With the increase of ZrO2 content, flexural strength and fracture toughness of porous Si3N4-based ceramics exhibited a trend of increase first and then decrease. As ZrO2 content increased to 10 wt%, the flexural strength and fracture toughness of porous Si3N4-based ceramics were improved from 214.7 MPa and 4.23 MPa·m1/2 to 345.0 MPa and 5.69 MPa·m1/2, respectively. Therefore, this work provided an important reference for the fabrication of high-performance porous Si3N4-based ceramic components with complex structures.

Vat photopolymerization printing of functionalized hydrogels on commercial contact lenses

Contact lenses are widely used for vision correction and cosmetic purposes. Smart contact lenses offer further opportunities as functionalized non-invasive devices capable of simultaneous vision correction, real-time health monitoring and patient specific drug delivery. Herein, a low-cost vat photopolymerization technique is developed for directly 3D printing functionalized structures on commercially available contact lenses. The process enables controlled deposition of functionalized hydrogels, in customizable patterns, on the commercial contact lens surface with negligible optical losses. Multi-functional contact lenses can also be 3D printed with multiple materials deposited at different regions of the contact lens. Herein, the functionalities of colour blindness correction and real-time UV monitoring are demonstrated, by employing three suitable dyes incorporated into 2-hydroxyethyl methacrylate (HEMA) hydrogel structures printed on contact lenses. The results suggest that 3D printing can pave the way towards simple production of low-cost patient specific smart contact lenses.

Laser-induced micro-cavity on a fiber end with a harmonic-Vernier effect for salinity sensing

In this paper, a fiber optic salinity sensor based on Fabry–Perot interference (FPI) with a harmonic-Vernier effect is suggested. An open cavity and a resin solid cavity are grown at the end of the fiber by a unique fiber-end photopolymerization and integration (FEPI) technique. When seawater fills the open cavity, it changes the optical path length (OPL) of the interferometer directly. While the OPL of the reference interferometer is hardly impacted by the seawater. The insertion of the harmonic envelope shifts greatly with salinity. Tunable sensing performances are achieved by adjusting the cavity length ratio(CLR) according to a theoretical model. The maximum sensitivity of 6.53 nm/‰is attained in the range of 25 ‰to 45 ‰when its CLR approaches 1.18. In addition, the measuring accuracy, consistency, and temperature compensation method are also experimentally investigated. The suggested sensor is a prospective competitor in the field of measuring the salinity of seawater due to the advantages of high sensitivity, compact size, large dynamic range, and adjustable capabilities.

High-efficiency laminated luminescent solar concentrators based on carbon dots and nanorings

Creation of novel fluorescent nanomaterials with high photoluminescence quantum yield (PLQY) will lead to high-efficiency luminescent solar concentrators (LSCs). Herein, two kinds of carbon dots (CDs), e.g., blue and green emissive CDs and one novel carbon nanorings (NRs) with yellow emission are synthesized by the solvothermal method. Diaminobenzenesulfonic acid is used as one main precursor to create blue, green emission carbon dots (B/GCDs) and yellow emission carbon nanorings (YCNRs). Importantly, the PLQYs of B/GCDs and YCNRs are 59.8±3.2 %, 12.2±0.7 % and 63.2±1.5 %, respectively. Moreover, B/GCDs and YCNRs are used as fluorescent nanomaterials to construct laminated LSCs with single-layer and double-layer through one-step photopolymerization technique. For single-layer laminated LSCs, YCNRs-based LSCs have the maximum external optical efficiency (ηopt), up to 3.05 %. Furthermore, for double-layer laminated LSCs, the LSCs based on BCDs and YCNRs achieve the highest ηopt of 4.09 %. Compared to single-layer laminated LSCs, the double-layer laminated LSCs show an increase of 34 % in ηopt. Their internal quantum efficiency (ηint) of 29.88 % and external quantum efficiency (ηext) of 25.18 % are obtained, respectively. The presented values are just for single-wavelength excitation. Thus, the synthesis of novel YCNRs with high PLQYs contributes to the optical performances at a large level. Remarkably, the optimal double-layer laminated LSCs show good transparency.

Injectable dECM-enhanced hyaluronic microgels with spatiotemporal release of cartilage-specific molecules to improve osteoarthritic chondrocyte’s function

The interior environment of articular cartilage in osteoarthritis (OA) presents substantial hurdles, leading to the malfunction of chondrocytes and the breakdown of collagen II-enriched hyaline cartilage matrix. Despite this, most clinical treatments primarily provide temporary relief from OA discomfort without arresting OA progression. This study aimed to alleviate OA by developing intra-articular injectable dECM-enhanced hyaluronic (HE) microgels. The HE hydrogel was engineered and shaped into uniformly sized microgels using microfluidics and photopolymerization techniques. These microgels provided a spatiotemporal cascade effect, facilitating the rapid release of growth factors and a slower release of ECM macromolecules and proteins. This process assisted in the recovery of OA chondrocytes’ function, promoting cell proliferation, matrix synthesis, and cartilage-specific gene expression in vitro. It also effectively aided repair of the collagen II-enriched hyaline cartilage and significantly reduced the severity of OA, as demonstrated by radiological observation, gross appearance, histological/immunohistochemical staining, and analysis in an OA rat model in vivo. Collectively, the HE injectable microgels with spatiotemporal release of cartilage-specific molecules have shown promise as a potential candidate for a cell-free OA therapy approach.Graphical

Selective and Sensitive MIP-Based Electrochemical Sensor for the Analytical Determination of Lanreotide

Lanreotide (LAN) is an analog of somatostatin used to treat acromegaly and neuroendocrine tumors. Considering drug toxicity and the lack of sensitive techniques in drug analysis, the development of sensitive analytical methods is of great importance. During this research, a molecular imprinted polymer (MIP) based film [P(HEMA-MAGA)@MIP/GCE] was prepared by photopolymerization technique for electrochemical determination of LAN for the first time. N-methacryloyl-L-glutamic acid (MAGA) and hydroxyethyl methacrylate (HEMA) were used as functional and basic monomers, respectively. The surface alterations were investigated using scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) and the chemical composition of the MIP-based sensor. Theelectrochemical characterization of the modifiedelectrodes was assessed using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Using differential pulse voltammetry (DPV) in standard solution and spiked serum sample of LAN, the linear response range for LAN was obtained as 1.0x10 − 14 M – 1.0x10 − 13 M. The limit of detection (LOD) values were 1.76x10 − 15 M and 1.82x10 − 15 M in water and commercial human serum, respectively. The limit of quantitation(LOQ) values for these were 5.85x10 − 15 M and 6.07x10 − 15 M, respectively. The P(HEMA-MAGA)@MIP/GCE sensor also showed excellent recovery in pharmaceutical preparation and commercial human serum form with of 99.37 % and 99.27 %, respectively, with a good RSD value (0.51–0.73), confirming the accuracy and precision of the sensor. As a control, the non-imprinted polymer (NIP) was also prepared to serve in the same way but without the template. The selectivity experiments were conducted using somatostatin (SOM) and octreotide (OC) as potential competitors to demonstrate the selectivity of the proposed sensor against LAN molecules.

Volumetric Additive Manufacturing of SiOC by Xolography.

Additive manufacturing (AM) of ceramics has significantly contributed to advancements in ceramic fabrication, solving some of the difficulties of conventional ceramic processing and providing additional possibilities for the structure and function of components. However, defects induced by the layer-by-layer approach on which traditional AM techniques are based still constitute a challenge to address. This study presents the volumetric AM of a SiOC ceramic from a preceramic polymer using xolography, a linear volumetric AM process that allows to avoid the staircase effect typical of other vat photopolymerization techniques. Besides optimizing the trade-off between preceramic polymer content and transmittance, a pore generator is introduced to create transient channels for gas release before decomposition of the organic constituents and moieties, resulting in crack-free solid ceramic structures even at low ceramic yield. Formulation optimization alleviated sinking of printed parts during printing and prevented shape distortion. Complexsolid and porous ceramic structures with a smooth surface and sharp features are fabricated under the optimized parameters. This work provides a new method for the AM of ceramics at µm/mm scale with high surface quality and large geometry variety in an efficient way, opening the possibility for applications in fields such as micromechanical systems and microelectronic components.

Robust Miniemulsion PhotoATRP Driven by Red and Near-Infrared Light.

Photoinduced polymerization techniques have gathered significant attention due to their mild conditions, spatiotemporal control, and simple setup. In addition to homogeneous media, efforts have been made to implement photopolymerization in emulsions as a practical and greener process. However, previous photoinduced reversible deactivation radical polymerization (RDRP) in heterogeneous media has relied on short-wavelength lights, which have limited penetration depth, resulting in slow polymerization and relatively poor control. In this study, we demonstrate the first example of a highly efficient photoinduced miniemulsion ATRP in the open air driven by red or near-infrared (NIR) light. This was facilitated by the utilization of a water-soluble photocatalyst, methylene blue (MB+). Irradiation by red/NIR light allowed for efficient excitation of MB+ and subsequent photoreduction of the ATRP deactivator in the presence of water-soluble electron donors to initiate and mediate the polymerization process. The NIR light-driven miniemulsion photoATRP provided a successful synthesis of polymers with low dispersity (1.09 ≤ Đ ≤ 1.29) and quantitative conversion within an hour. This study further explored the impact of light penetration on polymerization kinetics in reactors of varying sizes and a large-scale reaction (250 mL), highlighting the advantages of longer-wavelength light, particularly NIR light, for large-scale polymerization in dispersed media owing to its superior penetration. This work opens new avenues for robust emulsion photopolymerization techniques, offering a greener and more practical approach with improved control and efficiency.

Deep eutectic supramolecular polymer functionalized MXene for enhancing mechanical properties, photothermal conversion, and bacterial inactivation of cellulose textiles

Two-dimensional (2D) transition metal carbides (Ti3C2Tx MXene) have gained significant attention for their potential in constructing diverse functional materials, However, MXene is easily oxidized and weakly bound to the cellulose matrix, which pose challenges in developing MXene-decorated non-woven fabric with strong bonding and stable thermal management properties. Herein, we successfully prepared deep eutectic supramolecular polymer (DESP) functionalized MXene to address these issues. MXene can be wrapped with DESP to be insulated from water and protected from being oxidized. Subsequently, we achieved an efficient in-situ deposition of DESP-functionalized MXene onto fibers through a combination of dip coating and photopolymerization technique. The resulting nonwoven fabric (CNs-DESP@M) exhibited excellent photothermal conversion properties along with rapid thermal response and functional stability. Interestingly, the interface bonding between MXene and the fiber surface was significantly enhanced due to the abundant pyrogallol groups in DESP, resulting in the composite textile exhibiting commendable mechanical properties (2.68 MPa). Moreover, the as-prepared textile demonstrates outstanding bactericidal efficacy against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The multifunctional textile, created through a facile and efficient approach, demonstrates remarkable potential for applications in smart textiles, catering to the diverse needs of individuals in the future.

High pressure salt water and low temperature effects on the material performance characteristics of additive manufacturing polymers

The effects of salt water exposure at deep ocean depth pressures when coupled with low temperatures on the material characteristics of three unique additively manufactured polymers has been investigated through a detailed experimental approach. The polymers in the study were manufactured utilizing both Vat Photopolymerization and Material Extrusion printing techniques. The Material Extrusion process was utilized to produce material specimens of Stratasys ULTEM 9085 and Markforged Onyx while the Vat Photopolymerization process was used to produce specimens of Accura ClearVue. The ULTEM 9085 and Markforged Onyx are filament based polymers and the ClearVue is a liquid based resin. The specimens were first submerged in a high pressure, salt water bath of 3.5% NaCl solution at 34.5 MPa (5000 lb/in2) for a total exposure time of 60 days to determine the water absorption characteristics. Subsequent to the salt water exposure at high pressure, the specimens were evaluated to determine changes in tension, compression, flexure, and in-plane fracture properties. To determine the effects of water saturation and low temperature coupling, the mechanical testing was performed at temperatures of 20 °C, 0 °C and −20 °C in both dry and saturated conditions. Additionally, non-destructive testing in the form of TeraHertz and FIRT imaging was conducted to analyze the physical material changes through the thickness of the material due to the saline water absorption. To quantify the change in material storage and loss moduli properties, Dynamic Mechanical Analysis (DMA) characterization was performed on each of the AM polymers in dry and saturated states. The DMA testing also quantified changes in the Glass Transition Temperature because of salt water exposure. In summary, The current study investigates the effects of coupled long term/high pressure salt water exposure with low temperatures on the mechanical and material characteristics of three unique AM polymers by: (1) immersing the materials in a salt water solution at 34.5 MPa for 60 days, (2) Conducting post exposure mechanical testing on the materials at 0 °C and −20 °C with comparisons to 20 °C testing on dry specimens, and quantifies changes in material properties through DMA experiments. The results from all testing in the study show that high pressure salt water exposure when coupled with low temperatures has unique effects on each of the materials considered in the study and careful consideration to each parameter must be given based on the material type when components will be employed in marine operations.

Vat photopolymerization of large-aperture high performance SiC mirror through multiphase carbon infiltration modification

Vat photopolymerization technique (VPP) shows advantages in rapidly preparation of complex structure silicon carbide matrix composites (Si/SiC). However, compared with traditional preparation technology, the properties of Si/SiC prepared via VPP are insufficient due to the presence of residual Si and carbon. Herein, the reaction mechanism of Si and carbon were systematically studied. Multiphase carbon was introduced into porous SiC preform via carbon precursor infiltration pyrolysis (CPIP) and graphitization methods. The content of residual Si was significantly decreased after reactive melt infiltration (RMI), and the residual carbon was eliminated through partial graphitization of the carbon. The influence mechanism of the carbon content and crystallinity on the reaction process of Si and carbon was studied. It suggested that the diameter of capillary channel and crystallinity of carbon are the main factors affecting residual carbon content in the final body after RMI. The sample with multiphase carbon achieved the best performance after RMI. The residual Si content, bulk density, flexural strength and elastic modulus are 11.58%, 3.04 g/cm3, 280.09 MPa and 355.48 GPa. In addition, the lowest coefficient of linear expansion was 2.39×10−6 K−1. Finally, a large-aperture SiC mirror with a diameter of 500 mm was prepared. Therefore, this research lays a foundation for promoting the application of large-aperture Si/SiC prepared via 3D printing.

Progress in photocontrolled radical polymerization for the synthesis of nonlinear polymer architectures

AbstractControlled radical polymerization (CRP) techniques enable the preparation of diverse, chemically tailored polymers with a variety of chain architectures. Separately, light‐mediated polymerization reactions offer a number of advantages over thermal polymerizations in terms of energy efficiency, sustainability, and versatility. Recent work has combined photopolymerization and CRP techniques to advance the synthesis of polymers with nonlinear architectures, including bottlebrush polymers, star polymers, hyperbranched polymers, and cyclic polymers. These photoCRP methods offer novel routes to nonlinear polymers using mild reaction conditions. In this review, we provide an overview of photoCRP techniques for the synthesis of nonlinear polymers. We start with a discussion of photoCRP applied to the synthesis of linear polymers and discuss the underlying reaction mechanisms. Then, we discuss photoCRP applied to the synthesis of bottlebrush, star, hyperbranched, cyclic, and surface‐initiated polymer brushes. For each case, we discuss the synthetic strategy and the unique properties and characteristics of the resulting polymers, and we provide a perspective on potential future directions for research.

A 3D-MICROPRINTED COAXIAL NOZZLE FOR FABRICATING LONG, FLEXIBLE MICROFLUIDIC TUBING.

A variety of emerging applications, particularly those in medical and soft robotics fields, are predicated on the ability to fabricate long, flexible meso/microfluidic tubing with high customization. To address this need, here we present a hybrid additive manufacturing (or "three-dimensional (3D) printing") strategy that involves three key steps: (i) using the "Vat Photopolymerization (VPP) technique, "Liquid-Crystal Display (LCD)" 3D printing to print a bulk microfluidic device with three inlets and three concentric outlets; (ii) using "Two-Photon Direct Laser Writing (DLW)" to 3D microprint a coaxial nozzle directly atop the concentric outlets of the bulk microdevice, and then (iii) extruding paraffin oil and a liquid-phase photocurable resin through the coaxial nozzle and into a polydimethylsiloxane (PDMS) channel for UV exposure, ultimately producing the desired tubing. In addition to fabricating the resulting tubing-composed of polymerized photomaterial-at arbitrary lengths (e.g., > 10 cm), the distinct input pressures can be adjusted to tune the inner diameter (ID) and outer diameter (OD) of the fabricated tubing. For example, experimental results revealed that increasing the driving pressure of the liquid-phase photomaterial from 50 kPa to 100 kPa led to fluidic tubing with IDs and ODs of 291±99 μm and 546±76 μm up to 741±31 μm and 888±39 μm, respectively. Furthermore, preliminary results for DLW-printing a microfluidic "M" structure directly atop the tubing suggest that the tubing could be used for "ex situ DLW (esDLW)" fabrication, which would further enhance the utility of the tubing.