Thioxanthone-Based Siloxane Photosensitizer for Cationic/Radical Photopolymerization and Photoinduced Sol-Gel Reactions.

In this investigation, a multifunctional visible-light TX-based photosensitizer containing a siloxane moiety (TXS) was designed with a good overall yield of 54%. The addition of a siloxane moiety enabled the incorporation of a TX photosensitizer into a siloxane network by photoinduced sol-gel chemistry, thus avoiding its release. Both liquid 1H and solid-state 29Si NMR measurements undeniably confirmed the formation of photoacids resulting from the photolysis of the TXS/electron acceptor molecule (Iodonium salt), which promoted the photoinduced hydrolysis/condensation of the trimethoxysilane groups of TXS, with a high degree of condensation of its inorganic network. Notably, the laser flash photolysis, fluorescence, and electron paramagnetic resonance spin-trapping (EPR ST) experiments demonstrated that TXS could react with Iod through an electron transfer reaction through its excited states, leading to the formation of radical initiating species. Interestingly, the TXS/Iod was demonstrated to be an efficient photoinitiating system for free-radical (FRP) and cationic (CP) polymerization under LEDs@385, 405, and 455 nm. In particular, whatever the epoxy monomer mixtures used, remarkable final epoxy conversions were achieved up to 100% under air. In this latter case, we demonstrated that both the photoinduced sol-gel process (hydrolysis of trimethoxysilane groups) and the cationic photopolymerization occurred simultaneously.

Continuous-Flow Synthesis of Arylthio-Cyclopropyl Carbonyl Compounds.

The straightforward, continuous-flow synthesis of cyclopropyl carbaldehydes and ketones has been developed starting from 2-hydroxycyclobutanones and aryl thiols. This acid-catalyzed mediated procedure allows access to the multigram and easily scalable synthesis of cyclopropyl adducts under mild conditions, using reusable Amberlyst-35 as a catalyst. The resins, suitably ground and used for filling steel columns, have been characterized via TGA, ATR, SEM and BET analyses to describe the physical-chemical properties of the packed bed and the continuous-flow system in detail. To highlight the synthetic versatility of the arylthiocyclopropyl carbonyl compounds, a series of selective oxidation reactions have been performed to access sulfoxide and sulfone carbaldehyde cyclopropanes, oxiranes and carboxylic acid derivatives.

3D Printing of Cellulose Nanocrystal-Loaded Hydrogels through Rapid Fixation by Photopolymerization.

New ink compositions for direct ink writing (DIW) printing of hydrogels, combining superior rheological properties of cellulose nanocrystals (CNCs) and a water-compatible photoinitiator, are presented. Rapid fixation was achieved by photopolymerization induced immediately after the printing of each layer by 365 nm light for 5 s, which overcame the common height limitation in DIW printing of hydrogels, and enabled the fabrication of objects with a high aspect ratio. CNCs imparted a unique rheological behavior, which was expressed by orders of magnitude difference in viscosity between low and high shear rates and in rapid high shear recovery, without compromising ink printability. Compared to the literature, the presented printing compositions enable the use of low photoinitiator concentrations at a very short build time, 6.25 s/mm, and are also curable by 405 nm light, which is favorable for maintaining viability in bioinks.

Laser-Triggered Writing and Biofunctionalization of Thiol-Ene Networks.

The light responsivity of ortho-nitrobenzyl esters (o-NBE) is exploited to inscribe µ-scale 2.5D patterns in thiol-ene networks by direct laser writing. For this purpose, a multifunctional thiol and a photosensitive alkene with an o-NBE chromophore are cured upon visible light exposure without inducing a premature photocleavage of the o-NBE links. Once the network is formed, a laser beam source with a wavelength of 375 nm is used for selectively inducing the photocleavage reaction of the o-NBE groups. Positive tone patterns are directly inscribed onto the sample surface without the requirement of a subsequent development step (removing soluble species in an appropriate organic solvent). Along with the realization of dry-developable micropatterns, the chemical surface composition of the exposed areas can be conveniently adjusted since different domains with a tailored content of carboxylic groups are obtained simply by modulating the laser energy dose. In a following step, those are activated and exploited as anchor points for attaching an Alexa-546 conjugated Protein A. Thus, the laser writable thiol-ene networks do not only provide a convenient method for the fabrication of positive tone patterns but also open future prospectives for a wide range of biosensing applications.

All-in-One Cellulose Nanocrystals for 3D Printing of Nanocomposite Hydrogels.

Cellulose nanocrystals (CNCs) with >2000 photoactive groups on each can act as highly efficient initiators for radical polymerizations, cross-linkers, as well as covalently embedded nanofillers for nanocomposite hydrogels. This is achieved by a simple and reliable method for surface modification of CNCs with a photoactive bis(acyl)phosphane oxide derivative. Shape-persistent and free-standing 3D structured objects were printed with a mono-functional methacrylate, showing a superior swelling capacity and improved mechanical properties.

3D-Printed MEMS in Italy.

MEMS devices are more and more commonly used as sensors, actuators, and microfluidic devices in different fields like electronics, opto-electronics, and biomedical engineering. Traditional fabrication technologies cannot meet the growing demand for device miniaturisation and fabrication time reduction, especially when customised devices are required. That is why additive manufacturing technologies are increasingly applied to MEMS. In this review, attention is focused on the Italian scenario in regard to 3D-printed MEMS, studying the techniques and materials used for their fabrication. To this aim, research has been conducted as follows: first, the commonly applied 3D-printing technologies for MEMS manufacturing have been illustrated, then some examples of 3D-printed MEMS have been reported. After that, the typical materials for these technologies have been presented, and finally, some examples of their application in MEMS fabrication have been described. In conclusion, the application of 3D-printing techniques, instead of traditional processes, is a growing trend in Italy, where some exciting and promising results have already been obtained, due to these new selected technologies and the new materials involved.

Three-Dimensional Printing of Triboelectric Nanogenerators by Digital Light Processing Technique for Mechanical Energy Harvesting.

Triboelectric nanogenerators (TENGs) represent intriguing technology to harvest human mechanical movements for powering wearable and portable electronics. Differently, compared to conventional fabrication approaches, additive manufacturing can allow the fabrication of TENGs with good dimensional resolution, high reproducibility, and quick production processes and, in particular, the obtainment of complex and customized structures. Among 3D printing technologies, digital light processing (DLP) is well-known for being the most flexible to produce functional devices by controlling both the geometry and the different ingredients of printable resins. On the other hand, DLP was not exploited for TENG fabrication, and consequently, the knowledge of the performance of 3D printable materials as charge accumulators upon friction is limited. Here, the application of the DLP technique to the 3D printing of triboelectric nanogenerators is studied. First, several printable materials have been tested as triboelectric layers to define a triboelectric series of DLP 3D printable materials. Then, TENG devices with increased geometrical complexity were printed, showcasing the ability to harvest energy from human movement. The method presented in this work illustrates how the DLP may represent a valuable and flexible solution to fabricate triboelectric nanogenerators, also providing a triboelectric classification of the most common photocurable resins.

3D printable acrylate polydimethylsiloxane resins for cell culture and drug testing.

Nowadays, most of the microfluidic devices for biological applications are fabricated with only few well-established materials. Among these, polydimethylsiloxane (PDMS) is the most used and known. However, it has many limitations, like the operator dependent and time-consuming manufacturing technique and the high molecule retention. TEGORad or Acrylate PDMS is an acrylate polydimethylsiloxane copolymer that can be 3D printed through Digital Light Processing (DLP), a technology that can boast reduction of waste products and the possibility of low cost and rapid manufacturing of complex components. Here, we developed 3D printed Acrylate PDMS-based devices for cell culture and drug testing. Our in vitro study shows that Acrylate PDMS can sustain cell growth of lung and skin epithelium, both of great interest for in vitro drug testing, without causing any genotoxic effect. Moreover, flow experiments with a drug-like solution (Rhodamine 6G) show that Acrylate PDMS drug retention is negligible unlike the high signal shown by PDMS. In conclusion, the study demonstrates that this acrylate resin can be an excellent alternative to PDMS to design stretchable platforms for cell culture and drug testing.

Photocurable 3D-Printable Systems with Controlled Porosity towards CO2 Air Filtering Applications.

Porous organic polymers are versatile platforms, easily adaptable to a wide range of applications, from air filtering to energy devices. Their fabrication via vat photopolymerization enables them to control the geometry on a multiscale level, obtaining hierarchical porosity with enhanced surface-to-volume ratio. In this work, a photocurable ink based on 1,6 Hexanediol diacrylate and containing a high internal phase emulsion (HIPE) is presented, employing PLURONIC F-127 as a surfactant to generate stable micelles. Different parameters were studied to assess the effects on the morphology of the pores, the printability and the mechanical properties. The tests performed demonstrates that only water-in-oil emulsions were suitable for 3D printing. Afterwards, 3D complex porous objects were printed with a Digital Light Processing (DLP) system. Structures with large, interconnected, homogeneous porosity were fabricated with high printing precision (300 µm) and shape fidelity, due to the addition of a Radical Scavenger and a UV Absorber that improved the 3D printing process. The formulations were then used to build scaffolds with complex architecture to test its application as a filter for CO2 absorption and trapping from environmental air. This was obtained by surface decoration with NaOH nanoparticles. Depending on the surface coverage, tested specimens demonstrated long-lasting absorption efficiency.

Photocurable Thiol-yne Alginate Hydrogels for Regenerative Medicine Purposes.

Every year millions of people worldwide undergo surgical interventions, with the occurrence of mild or severe post-treatment consequences meaning that rehabilitation plays a key role in modern medicine. Considering the cases of burns and plastic surgery, the pressing need for new materials that can be used for wound patches or body fillers and are able to sustain tissue regeneration and promote cell adhesion and proliferation is clear. The challenges facing next-generation implant materials also include the need for improved structural properties for cellular organization and morphogenic guidance together with optimal mechanical, rheological, and topographical behavior. Herein, we propose for the first time a sodium alginate hydrogel obtained by a thiol-yne reaction, easily synthesized using carbodiimide chemistry in a two-step reaction. The hydrogels were formed in all cases within a few minutes of light irradiation, showing good self-standing properties under solicitation. The mechanical, rheological, topographical, and swelling properties of the gels were also tested and reported. Lastly, no cytotoxicity was detected among the hydrogels. Soluble extracts in culture media allowed cell proliferation, and no differences between samples were detected in terms of metabolic activity and DNA content. These results suggest the potential use of these cytocompatible hydrogels in tissue engineering and regenerative medicine.

Functional 3D printing: Approaches and bioapplications.

3D printing technology has become a mature manufacturing technique, widely used for its advantages over the traditional methods, such as the end-user customization and rapid prototyping, useful in different application fields, including the biomedical one. Indeed, it represents a helpful tool for the realization of biodevices (i.e. biosensors, microfluidic bioreactors, drug delivery systems and Lab-On-Chip). In this perspective, the development of 3D printable materials with intrinsic functionalities, through the so-called 4D printing, introduces novel opportunities for the fabrication of "smart" or stimuli-responsive devices. Indeed, functional 3D printable materials can modify their surfaces, structures, properties or even shape in response to specific stimuli (such as pressure, temperature or light radiation), adding to the printed object new interesting properties exploited after the fabrication process. In this context, by combining 3D printing technology with an accurate materials' design, functional 3D objects with built-in (bio)chemical functionalities, having biorecognition, biocatalytic and drug delivery capabilities are here reported.

3D Printing of PDMS-Like Polymer Nanocomposites with Enhanced Thermal Conductivity: Boron Nitride Based Photocuring System.

This study demonstrates the possibility of forming 3D structures with enhanced thermal conductivity (k) by vat printing a silicone-acrylate based nanocomposite. Polydimethylsiloxane (PDSM) represent a common silicone-based polymer used in several applications from electronics to microfluidics. Unfortunately, the k value of the polymer is low, so a composite is required to be formed in order to increase its thermal conductivity. Several types of fillers are available to reach this result. In this study, boron nitride (BN) nanoparticles were used to increase the thermal conductivity of a PDMS-like photocurable matrix. A digital light processing (DLP) system was employed to form complex structures. The viscosity of the formulation was firstly investigated; photorheology and attenuate total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) analyses were done to check the reactivity of the system that resulted as suitable for DLP printing. Mechanical and thermal analyses were performed on printed samples through dynamic mechanical thermal analysis (DMTA) and tensile tests, revealing a positive effect of the BN nanoparticles. Morphological characterization was performed by scanning electron microscopy (SEM). Finally, thermal analysis demonstrated that the thermal conductivity of the material was improved, maintaining the possibility of producing 3D printable formulations.

3D-printed self-healing hydrogels via Digital Light Processing.

Self-healing hydrogels may mimic the behavior of living tissues, which can autonomously repair minor damages, and therefore have a high potential for application in biomedicine. So far, such hydrogels have been processed only via extrusion-based additive manufacturing technology, limited in freedom of design and resolution. Herein, we present 3D-printed hydrogel with self-healing ability, fabricated using only commercially available materials and a commercial Digital Light Processing printer. These hydrogels are based on a semi-interpenetrated polymeric network, enabling self-repair of the printed objects. The autonomous restoration occurs rapidly, at room temperature, and without any external trigger. After rejoining, the samples can withstand deformation and recovered 72% of their initial strength after 12 hours. The proposed approach enables 3D printing of self-healing hydrogels objects with complex architecture, paving the way for future applications in diverse fields, ranging from soft robotics to energy storage.

Effects of the Manufacturing Methods on the Mechanical Properties of a Medical-Grade Copolymer Poly(L-lactide-co-D,L-lactide) and Poly(L-lactide-co-ε-caprolactone) Blend.

Biocompatible and biodegradable polymers represent the future in the manufacturing of medical implantable solutions. As of today, these are generally manufactured with metallic components which cannot be naturally absorbed within the human body. This requires performing an additional surgical procedure to remove the remnants after complete rehabilitation or to leave the devices in situ indefinitely. Nevertheless, the biomaterials used for this purpose must satisfy well-defined mechanical requirements. These are difficult to ascertain at the design phase since they depend not only on their physicochemical properties but also on the specific manufacturing methods used for the target application. Therefore, this research was focused on establishing the effects of the manufacturing methods on both the mechanical properties and the thermal behavior of a medical-grade copolymer blend. Specifically, Injection and Compression Molding were considered. A Poly(L-lactide-co-D,L-lactide)/Poly(L-lactide-co-ε-caprolactone) blend was considered for this investigation, with a ratio of 50/50 (w/w), aimed at the manufacturing of implantable devices for tendon repair. Interesting results were obtained.

Light Processable Starch Hydrogels.

Light processable hydrogels were successfully fabricated by utilizing maize starch as raw material. To render light processability, starch was gelatinized and methacrylated by simple reaction with methacrylic anhydride. The methacrylated starch was then evaluated for its photocuring reactivity and 3D printability by digital light processing (DLP). Hydrogels with good mechanical properties and biocompatibility were obtained by direct curing from aqueous solution containing lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP) as photo-initiator. The properties of the hydrogels were tunable by simply changing the concentration of starch in water. Photo-rheology showed that the formulations with 10 or 15 wt% starch started curing immediately and reached G' plateau after only 60 s, while it took 90 s for the 5 wt% formulation. The properties of the photocured hydrogels were further characterized by rheology, compressive tests, and swelling experiments. Increasing the starch content from 10 to 15 wt% increased the compressive stiffness from 13 to 20 kPa. This covers the stiffness of different body tissues giving promise for the use of the hydrogels in tissue engineering applications. Good cell viability with human fibroblast cells was confirmed for all three starch hydrogel formulations indicating no negative effects from the methacrylation or photo-crosslinking reaction. Finally, the light processability of methacrylated starch by digital light processing (DLP) 3D printing directly from aqueous solution was successfully demonstrated. Altogether the results are promising for future application of the hydrogels in tissue engineering and as cell carriers.

Tunable photo-responsive elastic metamaterials.

The metamaterial paradigm has allowed an unprecedented space-time control of various physical fields, including elastic and acoustic waves. Despite the wide variety of metamaterial configurations proposed so far, most of the existing solutions display a frequency response that cannot be tuned, once the structures are fabricated. Few exceptions include systems controlled by electric or magnetic fields, temperature, radio waves and mechanical stimuli, which may often be unpractical for real-world implementations. To overcome this limitation, we introduce here a polymeric 3D-printed elastic metamaterial whose transmission spectrum can be deterministically tuned by a light field. We demonstrate the reversible doubling of the width of an existing frequency band gap upon selective laser illumination. This feature is exploited to provide an elastic-switch functionality with a one-minute lag time, over one hundred cycles. In perspective, light-responsive components can bring substantial improvements to active devices for elastic wave control, such as beam-splitters, switches and filters.

Materials Testing for the Development of Biocompatible Devices through Vat-Polymerization 3D Printing.

Light-based 3D printing techniques could be a valuable instrument in the development of customized and affordable biomedical devices, basically for high precision and high flexibility in terms of materials of these technologies. However, more studies related to the biocompatibility of the printed objects are required to expand the use of these techniques in the health sector. In this work, 3D printed polymeric parts are produced in lab conditions using a commercial Digital Light Processing (DLP) 3D printer and then successfully tested to fabricate components suitable for biological studies. For this purpose, different 3D printable formulations based on commercially available resins are compared. The biocompatibility of the 3D printed objects toward A549 cell line is investigated by adjusting the composition of the resins and optimizing post-printing protocols; those include washing in common solvents and UV post-curing treatments for removing unreacted and cytotoxic products. It is noteworthy that not only the selection of suitable materials but also the development of an adequate post-printing protocol is necessary for the development of biocompatible devices.

DLP 3D Printing Meets Lignocellulosic Biopolymers: Carboxymethyl Cellulose Inks for 3D Biocompatible Hydrogels.

The development of new bio-based inks is a stringent request for the expansion of additive manufacturing towards the development of 3D-printed biocompatible hydrogels. Herein, methacrylated carboxymethyl cellulose (M-CMC) is investigated as a bio-based photocurable ink for digital light processing (DLP) 3D printing. CMC is chemically modified using methacrylic anhydride. Successful methacrylation is confirmed by 1H NMR and FTIR spectroscopy. Aqueous formulations based on M-CMC/lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP) photoinitiator and M-CMC/Dulbecco's Modified Eagle Medium (DMEM)/LAP show high photoreactivity upon UV irradiation as confirmed by photorheology and FTIR. The same formulations can be easily 3D-printed through a DLP apparatus to produce 3D shaped hydrogels with excellent swelling ability and mechanical properties. Envisaging the application of the hydrogels in the biomedical field, cytotoxicity is also evaluated. The light-induced printing of cellulose-based hydrogels represents a significant step forward in the production of new DLP inks suitable for biomedical applications.

Synthesis of γ-cyclodextrin substituted bis(acyl)phosphane oxide derivative (BAPO-γ-CyD) serving as multiple photoinitiator and crosslinking agent.

A new multi-photoactive γ-cyclodextrin substituted bis(acyl)phosphane oxide derivative (BAPO-γ-CyD) was successfully prepared via a convergent synthesis using a phospha-Michael-addition, as confirmed by 1H-, 13C-, 31P-NMR and IR spectroscopy and mass spectrometry. Kinetic studies carried out by photo-DSC and photo-rheology demonstrated its outstanding efficiency as a photoinitiator for free-radical polymerization. Remarkably, it is found that BAPO-γ-CyD also acts as a crosslinking agent to convert monofunctional methacrylate monomers into self-standing thermosetting networks with extensive swelling capability in water.

A modular 3D printed lab-on-a-chip for early cancer detection.

A functional polymeric 3D device is produced in a single step printing process using a stereolithography based 3D printer. The photocurable formulation is designed for introducing a controlled amount of carboxyl groups (-COOH), in order to perform a covalent immobilization of bioreceptors on the device. The effectiveness of the application is demonstrated by performing an immunoassay for the detection of protein biomarkers involved in angiogenesis, whose role is crucial in the onset of cancer and in the progressive metastatic behavior of tumors. The detection of angiogenesis biomarkers is necessary for an early diagnosis of the pathology, allowing the employment of a less invasive therapy for the patient. In particular, vascular endothelial growth factor and angiopoietin-2 biomarkers are detected with a limit of detection of 11 ng mL-1 and 0.8 ng mL-1, respectively. This study shows how 3D microfabrication techniques, material characterization, and device development could be combined to obtain an engineered polymeric chip with intrinsic tuned functionalities.