Laboratory Ozonolysis Using an Integrated Batch-DIY Flow System for Renewable Material Production.

Flow chemistry offers a solution for replacing batch methods in chemical preparation where intermediates or products may pose toxicity or instability hazards. Ozonolysis offers an ideal opportunity for flow chemistry solutions, but multiple barriers to entry exist for use of these methods, including equipment cost and performance optimization. To address these challenges, we developed a programmable DIY syringe pump system to use for a continuous flow multireactor process using 3D-printed parts, off-the-shelf stepper motors, and an Arduino microcontroller. Reaction kinetics of ozonide formation informed the use of an integrated batch-flow approach, where ozone addition to an olefin was timed to coincide with fluid movement of a single-syringe pump, followed by downstream Pinnick oxidation and reductive quench in flow. The system was demonstrated by continuous preparation of azelaic acid from ozonolysis of palmitoleic acid, a process limited to low production volumes via batch chemistry. High total production of azelaic acid with 80% yield was obtained from an algae oil sourced unsaturated fatty acid: a product with important applications in medicine, cosmetics, and polymers. This low-cost, scalable approach offers the potential for rapid prototyping and distributed chemical production.

Renewable Polyurethanes from Sustainable Biological Precursors.

Due to the depletion of fossil fuels, higher oil prices, and greenhouse gas emissions, the scientific community has been conducting an ongoing search for viable renewable alternatives to petroleum-based products, with the anticipation of increased adaptation in the coming years. New academic and industrial developments have encouraged the utilization of renewable resources for the development of ecofriendly and sustainable materials, and here, we focus on those advances that impact polyurethane (PU) materials. Vegetable oils, algae oils, and polysaccharides are included among the major renewable resources that have supported the development of sustainable PU precursors to date. Renewable feedstocks such as algae have the benefit of requiring only sunshine, carbon dioxide, and trace minerals to generate a sustainable biomass source, offering an improved carbon footprint to lessen environmental impacts. Incorporation of renewable content into commercially viable polymer materials, particularly PUs, has increasing and realistic potential. Biobased polyols can currently be purchased, and the potential to expand into new monomers offers exciting possibilities for new product development. This Review highlights the latest developments in PU chemistry from renewable raw materials, as well as the various biological precursors being employed in the synthesis of thermoset and thermoplastic PUs. We also provide an overview of literature reports that focus on biobased polyols and isocyanates, the two major precursors to PUs.

Fluorescence control of chitin and chitosan fabricated via surface functionalization using direct oxidative polymerization.

The copolymer of 3-hexylthiophene (3HT) and fluorene (F) was directly grafted onto chitin and chitosan using FeCl3 as an oxidant. The properties of the grafted chitin/chitosan were characterized by Fourier transform infrared (FT-IR) spectroscopy, UV-Vis spectroscopy, fluorescence spectroscopy, X-ray diffraction analysis, thermogravimetric analysis (TGA), transmission electron microscopy-energy dispersive X-ray spectroscopy, and quantum yield measurements. The UV-Vis absorption peaks of the chitin/chitosan grafted with 3-hexylthiophene and fluorene copolymer were increasingly blue-shifted upon increasing the fluorene content and the red-shifted emission of the grafted chitin/chitosan were controlled by varying the monomers feed of the 3HT/F units. The hypsochromic and bathochromic shifts of chitin/chitosan were ascribed to the (3HT/F) moieties grafted to their surface. The quantum yield of grafted chitin/chitosan increased upon increasing the fluorene content. The TGA and XRD analysis revealed that the thermal stability and crystallinity of chitin/chitosan decreased upon grafting the copolymer of fluorene and 3-hexylthiophene. This article represents a simple route towards the surface modification of chitin and chitosan using conducting copolymers, providing multicolor chitin and chitosan via a one-step reaction.

Photoluminescence Control of Cellulose via Surface Functionalization Using Oxidative Polymerization.

Control of the photoluminescence properties of cellulose is conducted by introduction of conducting polymers including fluorene (F) and 3-hexylthiophene (3HT) on cellulose surface through FeCl3 oxidative polymerization. The UV-vis absorption peak of cellulose grafted with the 3-hexylthiophene and fluorene copolymer was increasingly blue-shifted with increasing fluorene content and the shift in the peak position in photoluminescence spectra depend on the initial 3HT:F ratio of the copolymer. The crystallinity and thermal stability of cellulose decreased slightly upon graft polymerization with PF and P3HT, while the quantum yield, determined using absolute methods, increased from 3.1 to 9.7% with increasing fluorene content. The roles of the 3HT and F copolymers in improving the properties of cellulose were thoroughly studied by FT-IR, UV-vis, fluorescence, X-ray diffraction (XRD), thermogravimetric (TG), transmission electron microscopy-energy dispersive X-ray (TEM-EDX), and quantum yield measurements. Mechanistic insight into the grafting reaction is also provided.