Hydrolytically degradable Poly (ß-amino ester) resins with tunable degradation for 3D printing by projection micro-stereolithography.

Applications of 3D printing that range from temporary medical devices to environmentally responsible manufacturing would benefit from printable resins that yield polymers with controllable material properties and degradation behavior. Towards this goal, poly(ß-amino ester) (PBAE)-diacrylate resins were investigated due to the wide range of available chemistries and tunable material properties. PBAE-diacrylate resins were synthesized from hydrophilic and hydrophobic chemistries and with varying electron densities on the ester bond to provide control over degradation. Hydrophilic PBAE-diacrylates led to degradation behaviors characteristic of bulk degradation while hydrophobic PBAE-diacrylates led to degradation behaviors dominated initially by surface degradation and then transitioned to bulk degradation. Depending on chemistry, the crosslinked PBAE-polymers exhibited a range of degradation times under accelerated conditions, from complete mass loss in 90 min to minimal mass loss at 45 days. Patterned features with 55 µm resolution were achieved across all resins, but their fidelity was dependent on PBAE-diacrylate molecular weight, reactivity, and printing parameters. In summary, simple chemical modifications in the PBAE-diacrylate resins coupled with projection microstereolithography enables high resolution 3D printed parts with similar architectures and initial properties, but widely different degradation rates and behaviors.

Local Optical Chirality Induced by Near-Field Mode Interference in Achiral Plasmonic Metamolecules.

When circularly polarized light interacts with a nanostructure, the optical response depends on the geometry of the structure. If the nanostructure is chiral (i.e., it cannot be superimposed on its mirror image), then its optical response, both in near-field and far-field, depends on the handedness of the incident light. In contrast, achiral structures exhibit identical far-field responses for left- and right-circular polarization. Here, we show that a perfectly achiral nanostructure, a plasmonic metamolecule with trigonal D3h symmetry, exhibits a near-field response that is sensitive to the handedness of light. This effect stems from the near-field interference between the different plasmonic modes sustained by the plasmonic metamolecule under circularly polarized light excitation. The local chirality in a plasmonic trimer is then experimentally evidenced with nanoscale resolution using a molecular probe. Our experiments demonstrate that the optical near-field chirality can be imprinted into the photosensitive polymer, turning an optical chirality into a geometrical chirality that can be imaged using atomic force microscopy. These results are of interest for the field of polarization-sensitive photochemistry.

Thiol-Anhydride Dynamic Reversible Networks.

The reaction of thiols and anhydrides to form ring opened thioester/acids is shown to be highly reversible and it is accordingly employed in the fabrication of covalent adaptable networks (CANs) that possess tunable dynamic covalent chemistry. Maleic, succinic, and phthalic anhydride derivatives were used as bifunctional reactants in systems with varied stoichiometries, catalyst, and loadings. Dynamic characteristics such as temperature-dependent stress relaxation, direct reprocessing and recycling abilities of a range of thiol-anhydride elastomers, glasses, composites and photopolymers are discussed. Depending on the catalyst strength, 100 % of externally imposed stresses were relaxed in the order of minutes to 2 hours at mild temperatures (80-120 °C). Pristine properties of the original materials were recovered following up to five cycles of a hot-press reprocessing technique (1 h/100 °C).

Modified Surface Relief Layer Created by Holographic Lithography: Application to Selective Sodium and Potassium Sensing.

Point-of-care diagnostics will rely upon the development of low-cost, noncomplex, and easily integrated systems in order to examine biological samples such as blood and urine obtained from the patient. The development of metal ion sensors is a subject of significant relevance for physiological samples. The level of different blood electrolytes, mainly H⁺, Na⁺, K⁺ and Cl- is considerably used to monitor irregular physiologies. The particular challenge in biosensing, and in fact for any other sensor, is signal differentiation between non-specifically bound material and the specific detecting of the target molecule/ion. The biosensors described in this paper are fabricated by a holographic recording of surface relief structures in a photopolymer material. The surface structures are modified by coating with either dibenzo-18-crown-6 (DC) or tetraethyl 4-tert-butylcalix[4]arene (TBC), which are embedded in a polymer matrix. Interrogation of these structures by light allows indirect measurement of the concentration of the analyte. The influence of polymer matrices with different porosities, plasticised polyvinyl chloride (PVC) and a sol-gel matrix, on the performance of the sensors for detection of K⁺ and Na⁺ is examined. Here we demonstrate a proof of concept that by using a matrix with higher porosity one can increase the sensitivity of the sensor. The results showed that the DC sensing layer provides a selective response to K⁺ over Na⁺ and the TBC modified grating is more responsive to Na⁺ over K⁺. The sensor responds to K⁺ and Na⁺ within the physiological concentration ranges.

New High-Power LEDs Open Photochemistry for Near-Infrared-Sensitized Radical and Cationic Photopolymerization.

Cyanines derived from heptamethines were investigated in combination with iodonium salts as initiators of the radical polymerization of tripropylene glycol diacrylate and epoxides derived from bisphenol-A-diglycidylether. A new near-infrared (NIR) LED prototype emitting at 805 nm with an exposure intensity of 1.2 W cm-2 facilitated initiation of both radical and cationic polymerization using sensitizers derived from cyanines. This new light-emitting device has brought new insight into the photochemistry of cyanines with the general structure 1 because a combination of photonic and thermal processes strongly influences reaction pathways. In particular, cationic cyanines comprising a cyclopentene moiety and diphenylamino group in the center initiated the cationic polymerization of epoxides. Selective oxidation of this unit explains why specifically these derivatives may function as initiators for cationic polymerization. In contrast, when the diphenylamino group was replaced by a barbital group at the meso-position cationic polymerization of epoxides was not initiated.

Photopolymerized Triazole-Based Glassy Polymer Networks with Superior Tensile Toughness.

Photopolymerization is a ubiquitous, indispensable technique widely applied in applications from coatings, inks, and adhesives to thermosetting restorative materials for medical implants, and the fabrication of complex macro-scale, microscale, and nanoscale 3D architectures via additive manufacturing. However, due to the brittleness inherent in the dominant acrylate-based photopolymerized networks, a significant need exists for higher performance resin/oligomer formulations to create tough, defect-free, mechanically ductile, thermally and chemically resistant, high modulus network polymers with rapid photocuring kinetics. This study presents densely cross-linked triazole-based glassy photopolymers capable of achieving preeminent toughness of ≈70 MJ m-3 and 200% strain at ambient temperature, comparable to conventional tough thermoplastics. Formed either via photoinitiated copper(I)-catalyzed cycloaddition of monomers containing azide and alkyne groups (CuAAC) or via photoinitiated thiol-ene reactions from monomers containing triazole rings, these triazole-containing thermosets completely recover their original dimensions and mechanical behavior after repeated deformations of 50% strain in the glassy state over multiple thermal recovery-strain cycles.

Exploring Network Formation of Tough and Biocompatible Thiol-yne Based Photopolymers.

This work deals with the in-depth investigation of thiol-yne based network formation and its effect on thermomechanical properties and impact strength. The results show that the bifunctional alkyne monomer di(but-1-yne-4-yl)carbonate (DBC) provides significantly lower cytotoxicity than the comparable acrylate, 1,4-butanediol diacrylate (BDA). Real-time near infrared photorheology measurements reveal that gel formation is shifted to higher conversions for DBC/thiol resins leading to lower shrinkage stress and higher overall monomer conversion than BDA. Glass transition temperature (Tg ), shrinkage stress, as well as network density determined by double quantum solid state NMR, increase proportionally with the thiol functionality. Most importantly, highly cross-linked DBC/dipentaerythritol hexa(3-mercaptopropionate) networks (Tg ≈ 61 °C) provide a 5.3 times higher impact strength than BDA, which is explained by the unique network homogeneity of thiol-yne photopolymers.

Adhesive, Flexible, and Fast Degradable 3D-Printed Wound Dressings with a Simple Composition.

3D printing technology has revolutionized the field of wound dressings, offering tailored solutions with mechanical support to facilitate wound closure. In addition to personalization, the intricate nature of the wound healing process requires wound dressing materials with diverse properties, such as moisturization, flexibility, adhesion, anti-oxidation and degradability. Unfortunately, current materials used in digital light processing (DLP) 3D printing have been inadequate in meeting these crucial criteria. This study introduces a novel DLP resin that is biocompatible and consists of only three commonly employed non-toxic compounds in biomaterials, that is, dopamine, poly(ethylene glycol) diacrylate, and N-vinylpyrrolidone. Simple as it is, this material system fulfills all essential functions for effective wound healing. Unlike most DLP resins that are non-degradable and rigid, this material exhibits tunable and rapid degradation kinetics, allowing for complete hydrolysis within a few hours. Furthermore, the high flexibility enables conformal application of complex dressings in challenging areas such as finger joints. Using a difficult-to-heal wound model, the manifold positive effects on wound healing in vivo, including granulation tissue formation, inflammation regulation, and vascularization are substantiated. The simplicity and versatility of this material make it a promising option for personalized wound care, holding significant potential for future translation.

Photopolymer Holographic Lenses for Solar Energy Applications: A Review.

Holographic lenses (HLs) are part of holographic optical elements (HOE), and are being applied to concentrate solar energy on a focal point or focal line. In this way, the concentrated energy can be converted into electrical or thermal energy by means of a photovoltaic cell or a thermal absorber tube. HLs are able to passively track the apparent motion of the sun with a high acceptance angle, allowing tracking motors to be replaced, thus reducing the cost of support structures. This article focuses on a review of the materials used in the recording of a holographic lens (HL) or multiple HLs in photovoltaic and/or concentrating solar collectors. This review shows that the use of photopolymers for the recording of HLs enables high-performance efficiency in physical systems designed for energy transformation, and presents some important elements to be taken into account for future designs, especially those related to the characteristics of the HL recording materials. Finally, the article outlines future recommendations, emphasizing potential research opportunities and challenges for researchers entering the field of HL-based concentrating solar photovoltaic and/or concentrating solar thermal collectors.

Multi-Material 3D Printing of Biobased Epoxy Resins.

Additive manufacturing (AM) has revolutionised the manufacturing industry, offering versatile capabilities for creating complex geometries directly from a digital design. Among the various 3D printing methods for polymers, vat photopolymerisation combines photochemistry and 3D printing. Despite the fact that single-epoxy 3D printing has been explored, the fabrication of multi-material bioderived epoxy thermosets remains unexplored. This study introduces the feasibility and potential of multi-material 3D printing by means of a dual-vat Digital Light Processing (DLP) technology, focusing on bioderived epoxy resins such as ELO (epoxidized linseed oil) and DGEVA (vanillin alcohol diglycidyl ether). By integrating different materials with different mechanical properties into one sample, this approach enhances sustainability and offers versatility for different applications. Through experimental characterisation, including mechanical and thermal analysis, the study demonstrates the ability to produce structures composed of different materials with tailored mechanical properties and shapes that change on demand. The findings underscore the promising technology of dual-vat DLP technology applied to sustainable bioderived epoxy monomers, allowing sustainable material production and complex structure fabrication.

Machine-Guided Discovery of Acrylate Photopolymer Compositions.

Additive manufacturing (AM) can be advanced by the diverse characteristics offered by thermoplastic and thermoset polymers and the further benefits of copolymerization. However, the availability of suitable polymeric materials for AM is limited and may not always be ideal for specific applications. Additionally, the extensive number of potential monomers and their combinations make experimental determination of resin compositions extremely time-consuming and costly. To overcome these challenges, we develop an active learning (AL) approach to effectively choose compositions in a ternary monomer space ranging from rigid to elastomeric. Our AL algorithm dynamically suggests monomer composition ratios for the subsequent round of testing, allowing us to efficiently build a robust machine learning (ML) model capable of predicting polymer properties, including Young's modulus, peak stress, ultimate strain, and Shore A hardness based on composition while minimizing the number of experiments. As a demonstration of the effectiveness of our approach, we use the ML model to drive material selection for a specific property, namely, Young's modulus. The results indicate that the ML model can be used to select material compositions within at least 10% of a targeted value of Young's modulus. We then use the materials designed by the ML model to 3D print a multimaterial "hand" with soft "skin" and rigid "bones". This work presents a promising tool for enabling informed AM material selection tailored to user specifications and accelerating material discovery using a limited monomer space.

High Refractive Index, Low Birefringence Holographic Materials via the Homopolymerization of 1,2-Dithiolanes.

High refractive index, low birefringence photopolymers were created via the radical-mediated, ring opening homopolymerization of 1,2-dithiolane functionalized monomers and were subsequently evaluated as holographic recording media. This investigation systematically characterized the reaction kinetics, thermodynamics, and volume shrinkage of the 1,2-dithiolane homopolymerization as well as the optical transparency, refractive index, birefringence, and holographic performance of multifunctional 1,2-dithiolane functionalized monomers and their resultant polymers. Real-time kinetic and thermodynamic analyses of a monofunctional 1,2-dithiolane monomer, lipoic acid methyl ester (LipOMe), indicated rapid monomer conversion, exceeding 90% in 60 s, with an overall enthalpy of reaction of 18 ± 1 kJ/mol. The ring-opening polymerization resulted in low shrinkage (10.6 ± 0.3 cm3/mol dithiolane) and a significant bulk refractive index increase (0.030 ± 0.003). The resulting photopolymers exhibited high optical transparency, minimal haze, and negligible birefringence, suggesting the potential of 1,2-homopolymers as optical materials. To further explore the specific capabilities for use as high-performance holographic recording applications, several multifunctional monomers were synthesized with the ethanedithiol lipoic acid monomer (EDT-Lip2) selected for experimentation. Holographic diffraction gratings written using this monomer achieved a peak-to-mean refractive index modulation of 0.008 with minimal haze and birefringence.

Optically Actuated Soft Microrobot Family for Single-Cell Manipulation.

Precisely controlled manipulation of nonadherent single cells is often a pre-requisite for their detailed investigation. Optical trapping provides a versatile means for positioning cells with submicrometer precision or measuring forces with femto-Newton resolution. A variant of the technique, called indirect optical trapping, enables single-cell manipulation with no photodamage and superior spatial control and stability by relying on optically trapped microtools biochemically bound to the cell. High-resolution 3D lithography enables to prepare such cell manipulators with any predefined shape, greatly extending the number of achievable manipulation tasks. Here, it is presented for the first time a novel family of cell manipulators that are deformable by optical tweezers and rely on their elasticity to hold cells. This provides a more straightforward approach to indirect optical trapping by avoiding biochemical functionalization for cell attachment, and consequently by enabling the manipulated cells to be released at any time. Using the photoresist Ormocomp, the deformations achievable with optical forces in the tens of pN range and present three modes of single-cell manipulation as examples to showcase the possible applications such soft microrobotic tools can offer are characterized. The applications describe here include cell collection, 3D cell imaging, and spatially and temporally controlled cell-cell interaction.

Dimensional Fidelity and Orientation Effects of PolyJet Technology in 3D Printing of Negative Features for Microfluidic Applications.

Negative features in microdevices find a wide range of applications. The process of 3D printing has revolutionized their fabrication due to the combination of good resolution and integration capability. Herein, we report on a systematic study of the effects of materials and print directions on the 3D printing of microfluidic channels as negative features under PolyJet technology. Specifically, the Statasys Objet500 printer was used for this study. We printed two sets of chips (n=10 each), each of which contains channel pairs of a high-contrast reference material and a sacrificial material, respectively. Both materials were embedded in a clear photopolymer resin. The channel pairs ranged in planned width from 64 to 992 µm. To explore the effect on print orientation, channels were printed either parallel or perpendicular with respect to the jetting head's movement. The width of each channel of a pair was compared for each planned width and each combination of materials. The effect of print orientation on channel morphology was also investigated. We found that reproducibility and accuracy were highest at a planned channel width of approximately ≥600 µm and that channel morphology was most suitable when the jetting head of the printer moved parallel to the channel's longitudinal axis. The results should be of interest to any users who wish to create negative features using PolyJet 3D technology.

Thermoresponsive Shape-Memory Biobased Photopolymers of Tetrahydrofurfuryl Acrylate and Tridecyl Methacrylate.

A series of thermoresponsive shape-memory photopolymers have been synthesized from the mixtures of two biobased monomers, tetrahydrofurfuryl acrylate and tridecyl methacrylate, with the addition of a small amount of 1,3-benzendithiol (molar ratio of monomers 0-10:0.5:0.03, respectively). Ethyl (2,4,6 trimethylbenzoyl) phenylphosphinate was used as photoinitiator. The calculated biorenewable carbon content of these photopolymers was in the range of (63.7-74.9)%. The increase in tetrahydrofurfuryl acrylate content in the photocurable resins resulted in a higher rate of photocuring, increased rigidity, as well as mechanical and thermal characteristics of the obtained polymers. All photopolymer samples showed thermoresponsive shape-memory behavior when reaching their glass transition temperature. The developed biobased photopolymers can replace petroleum-derived thermoresponsive shape-memory polymer analogues in a wide range of applications.

Effect of Geometry and Orientation on the Tensile Properties and Failure Mechanisms of Compliant Suture Joints.

Compliant sutures surrounded by stiff matrices are present in biological armors and carapaces, providing enhanced mechanical performance. Understanding the mechanisms through which these sutured composites achieve outstanding properties is key to developing engineering materials with improved strength and toughness. This article studies the impact of suture geometry and load direction on the performance of suture joints using a two-stage reactive polymer resin that enables facile photopatterning of mechanical heterogeneity within a single polymer network. Compliant sinusoidal sutures with varying geometries are photopatterned into stiff matrices, generating a modulus contrast of 2 orders of magnitude. Empirical relationships are developed connecting suture wavelength and amplitude to composite performance under parallel and perpendicular loading conditions. Results indicate that a greater suture interdigitation broadly improves composite performance when loading is applied perpendicular to suture joints but has deleterious effects when loading is applied parallel to the joint. Investigations into the failure mechanisms under perpendicular loading highlight the interplay between suture geometry and crack growth stability after damage initiation occurs. Our findings could enable a framework for engineering composites and bio-inspired structures in the future.

In Situ Observation of Micro-Patterned Elastomeric Surfaces: The Formation of the Area of Real Contact and the Influence on Its Friction and Deformation Behaviour.

Structured surfaces, which are the basis of the lotus blossom effect, have great potential to serve/operate as functionalised surfaces, i.e., surfaces with specific and/or adjustable properties. In the present study, the aim is to use micro-structured elastomeric surfaces to specifically influence the friction and deformation behaviours on the basis of the shape and arrangement of the structures. Thiol-acrylate-based photopolymers patterned via nanoimprint lithography were investigated by using an in situ tribological measurement set-up. A clear influence of the different structures on the surface's friction behaviour could be shown, and, furthermore, this could be brought into relation with the real area of contact. This finding provides an important contribution to further development steps, namely, to give the structures switchable properties in order to enable the control of friction properties in a targeted manner.

A printability study of multichannel nerve guidance conduits using projection-based three-dimensional printing.

Multichannel nerve guidance conduits (NGCs) replicating the native architecture of peripheral nerves have emerged as promising alternatives to autologous nerve grafts. However, manufacturing multichannel NGCs is challenging in terms of desired structural stability and resolution. In this study, we systematically investigated the effects of photopolymer properties, inner diameter dimensions, printing parameters, and different conditions on multichannel NGCs printability using projection-based three-dimensional printing. Low viscosity and rapid photocuring properties were essential requirements. A standard model was generated to evaluate multichannel NGC printed quality. The results showed that printing deviations decreased with increased mechanical strength and inner diameter. Subsequently, gelatin methacrylate (GelMA) NGCs was selected as a representative. It was found that printing conditions, including printing temperature, peeling, and shrinkage affected final NGC accuracy and quality. PC-12 cells cultured with the GelMA NGCs displayed non-toxic and promoted cell migration. Our research provides an effective, time-saving, and high-resolution technology for manufacturing multichannel NGCs with high fidelity, which may be used as reference templates for biomedical applications.

Development of Phantoms for Multimodal Magnetic Resonance Imaging and Magnetic Particle Imaging.

Phantoms are crucial for the development of imaging techniques based on magnetic nanoparticles (MNP). They serve as test objects to simulate application scenarios but are also used for quality assurance and interlaboratory comparisons. Magnetic particle imaging (MPI) is excellent for specifically detecting magnetic nanoparticles (MNP) without any background signals. To obtain information about the surrounding soft tissue, MPI is often used in combination with magnetic resonance imaging (MRI). For such application scenarios, this poses a challenge for phantom fabrication, as they need to accommodate MNP as well as provide MR visibility. Recently, layer-by-layer fabrication of parts using Additive Manufacturing (AM) has emerged as a powerful tool for creating complex and patient-specific phantoms, but these are characterized by poor MR visibility of the AM material. We present the systematic screening of AM materials as candidates for multimodal MRI/MPI imaging. Of all investigated materials, silicone (Dreve, Biotec) exhibited the best properties with sufficient MR-signal performance and the lowest absorption of MNP at the interface of AM materials. With the help of AM and the selection of appropriate materials, we have been able to produce suitable MRI/MPI phantoms.