Improving the Performance of Photoactive Terpene-Based Resin Formulations for Light-Based Additive Manufacturing.

Photocurable liquid formulations have been a key research focus for the preparation of mechanically robust and thermally stable networks. However, the development of renewable resins to replace petroleum-based commodities presents a great challenge in the field. From this perspective, we disclose the design of photoactive resins based on terpenes and itaconic acid, both potentially naturally sourced, to prepare photosets with adjustable thermomechanical properties. Biobased perillyl itaconate (PerIt) was synthesized from renewable perillyl alcohol and itaconic anhydride via a scalable solvent-free method. Photoirradiation of PerIt in the presence of a multiarm thiol and photoinitiator led to the formation of networks over a range of compositions. Addition of nonmodified terpenes (perillyl alcohol, linalool, or limonene) as reactive diluents allowed for more facile preparation of photocured networks. Photosets within a wide range of properties were accessed, and these could be adjusted by varying diluent type and thiol stoichiometry. The resins showed rapid photocuring kinetics and the ability to form either brittle or elastic materials, with Young's modulus and strain at break ranging from 3.6 to 358 MPa and 15 to 367%, respectively, depending on the chemical composition of the resin. Glass transition temperatures (Tg) were influenced by thioether content, with temperatures ranging from 5 to 43 °C, and all photosets displayed good thermal resistance with Td,5% > 190 °C. Selected formulations containing PerIt and limonene demonstrated suitability for additive manufacturing technologies and high-resolution objects were printed via digital light processing (DLP). Overall, this work presents a simple and straightforward route to prepare renewable resins for rapid prototyping applications.

A renewably sourced, circular photopolymer resin for additive manufacturing.

The additive manufacturing of photopolymer resins by means of vat photopolymerization enables the rapid fabrication of bespoke 3D-printed parts. Advances in methodology have continually improved resolution and manufacturing speed, yet both the process design and resin technology have remained largely consistent since its inception in the 1980s1. Liquid resin formulations, which are composed of reactive monomers and/or oligomers containing (meth)acrylates and epoxides, rapidly photopolymerize to create crosslinked polymer networks on exposure to a light stimulus in the presence of a photoinitiator2. These resin components are mostly obtained from petroleum feedstocks, although recent progress has been made through the derivatization of renewable biomass3-6 and the introduction of hydrolytically degradable bonds7-9. However, the resulting materials are still akin to conventional crosslinked rubbers and thermosets, thus limiting the recyclability of printed parts. At present, no existing photopolymer resin can be depolymerized and directly re-used in a circular, closed-loop pathway. Here we describe a photopolymer resin platform derived entirely from renewable lipoates that can be 3D-printed into high-resolution parts, efficiently deconstructed and subsequently reprinted in a circular manner. Previous inefficiencies with methods using internal dynamic covalent bonds10-17 to recycle and reprint 3D-printed photopolymers are resolved by exchanging conventional (meth)acrylates for dynamic cyclic disulfide species in lipoates. The lipoate resin platform is highly modular, whereby the composition and network architecture can be tuned to access printed materials with varied thermal and mechanical properties that are comparable to several commercial acrylic resins.

Biopolymer-based nanocarriers for sustained release of agrochemicals: A review on materials and social science perspectives for a sustainable future of agri- and horticulture.

Devastating plant diseases and soil depletion rationalize an extensive use of agrochemicals to secure the food production worldwide. The sustained release of fertilizers and pesticides in agriculture is a promising solution to the eco-toxicological impacts and it might reduce the amount and increase the effectiveness of agrochemicals administration in the field. This review article focusses on carriers with diameters below 1 µm, such as capsules, spheres, tubes and micelles that promote the sustained release of actives. Biopolymer nanocarriers represent a potentially environmentally friendly alternative due to their renewable origin and biodegradability, which prevents the formation of microplastics. The social aspects, economic potential, and success of commercialization of biopolymer based nanocarriers are influenced by the controversial nature of nanotechnology and depend on the use case. Nanotechnology's enormous innovative power is only able to unfold its potential to limit the effects of climate change and to counteract current environmental developments if the perceived risks are understood and mitigated.

Cellulose nanocarriers via miniemulsion allow Pathogen-Specific agrochemical delivery.

The current spraying of agrochemicals is unselective and ineffective, consuming a high amount of fungicides, which endangers the environment and human health. Cellulose-based nanocarriers (NCs) are a promising tool in sustainable agriculture and suitable vehicles for stimuli-responsive release of agrochemicals to target cellulase-segregating fungi, which cause severe plant diseases such as Apple Canker. Herein, cellulose was modified with undec-10-enoic acid to a hydrophobic and cross-linkable derivative, from which NCs were prepared via thiol-ene addition in miniemulsion. During the crosslinking reaction, the NCs were loaded in situ with hydrophobic fungicides, Captan and Pyraclostrobin. NCs with average sizes ranging from 200 to 300 nm and an agrochemical-load of 20 wt% were obtained. Cellulose-degrading fungi, e.g. Neonectria. ditissima which is responsible for Apple Canker, lead to the release of fungicides from the aqueous NC dispersions suppressing fungal growth. In contrast, the non-cellulase segregating fungi, e.g. Cylindrocladium buxicola, do not degrade the agrochemical-loaded NCs. This selective action against Apple Canker fungi, N. ditissima, proves the efficacy of NC-mediated drug delivery triggered by degradation in the exclusive presence of cellulolytic fungi. Cellulose NCs represent a sustainable alternative to the current unselective spraying of agrochemicals that treats many crop diseases ineffectively.

Bio-Based Lignin Nanocarriers Loaded with Fungicides as a Versatile Platform for Drug Delivery in Plants.

Lignin-based nano- and microcarriers are a promising biodegradable drug delivery platform inside of plants. Many wood-decaying fungi are capable of degrading the wood component lignin by segregated lignases. These fungi are responsible for severe financial damage in agriculture, and many of these plant diseases cannot be treated today. However, enzymatic degradation is also an attractive handle to achieve a controlled release of drugs from artificial lignin vehicles. Herein, chemically cross-linked lignin nanocarriers (NCs) were prepared by aza-Michael addition in miniemulsion, followed by solvent evaporation. The cross-linking of lignin was achieved with the bio-based amines (spermine and spermidine). Several fungicides-namely, azoxystrobin, pyraclostrobin, tebuconazole, and boscalid-were encapsulated in situ during the miniemulsion polymerization, demonstrating the versatility of the method. Lignin NCs with diameters of 200-300 nm (determined by dynamic light scattering) were obtained, with high encapsulation efficiencies (70-99%, depending on the drug solubility). Lignin NCs successfully inhibited the growth of Phaeomoniella chlamydospora and Phaeoacremonium minimum, which are lignase-producing fungi associated with the worldwide occurring fungal grapevine trunk disease Esca. In planta studies proved their efficiency for at least 4 years after a single injection into Vitis vinifera ("Portugieser") plants on a test vineyard in Germany. The lignin NCs are of high interest as biodegradable delivery vehicles to be applied by trunk injection against the devastating fungal disease Esca but might also be promising against other fungal plant diseases.

Thiol-ene miniemulsion polymerization of a biobased monomer for biomedical applications.

Herein, we present the synthesis and characterization of poly(thioether-ester) nanoparticles via thiol-ene miniemulsion polymerization using a biobased α,ω-diene diester monomer, namely dianhydro-d-glucityl diundec-10-enoate (DGU), synthesized from 10-undecenoic acid (derived from castor oil) and isosorbide (derived from starch). DGU was copolymerized with 1,4-butanedithiol by thiol-ene miniemulsion polymerization resulting in waterborne poly(thioether-ester) particles with diameter around 200nm. Polymers with number average molecular weight up to 11kDa were obtained via miniemulsion polymerization. DSC and XRD analyses indicated a semi-crystalline polymer with a degree of crystallinity of at least 20% and Tm around 68°C. In addition, Coumarin 6 was encapsulated in the polymer particles with efficiency up to 98%. Nanoparticles presented biocompatibility in murine fibroblast (L929) and uterine colon cancer (HeLa) cells. The substantial cellular uptake of poly(thioether-ester) nanoparticles by HeLa cells suggests a potential use in uterine colon cancer treatment.