Synthesis of water-soluble surfactants using catalysed condensation polymerisation in green reaction media.

Sustainable and biobased surfactants are required for a wide range of everyday applications. Key drivers are cost, activity and efficiency of production. Polycondensation is an excellent route to build surfactant chains from bio-sourced monomers, but this typically requires high processing temperatures (≥200 °C) to remove the condensate and to lower viscosity of the polymer melt. In addition, high temperatures also increase the degree of branching and cause discolouration through the degradation of sensitive co-initiators and monomers. Here we report the synthesis of novel surface-active polymers from temperature sensitive renewable building blocks such as dicarboxylic acids, polyols (d-sorbitol) and fatty acids. We demonstrate that the products have the potential to be key components in renewable surfactant design, but only if the syntheses are optimised to ensure linear chains with hydrophilic character. The choice of catalyst is key to this control and we have assessed three different approaches. Additionally, we also demonstrate that use of supercritical carbon dioxide (scCO2) can dramatically improve conversion by reducing reaction viscosity, lowering reaction temperature, and driving condensate removal. We also evaluate the performance of the new biobased surfactants, focussing upon surface tension, and critical micelle concentration.

Facile Dye-Initiated Polymerization of Lactide-Glycolide Generates Highly Fluorescent Poly(lactic-co-glycolic Acid) for Enhanced Characterization of Cellular Delivery.

Poly(lactic-co-glycolic acid) (PLGA) is a versatile synthetic copolymer that is widely used in pharmaceutical applications. This is because it is well-tolerated in the body, and copolymers of varying physicochemical properties are readily available via ring-opening polymerization. However, native PLGA polymers are hard to track as drug delivery carriers when delivered to subcellular spaces, due to the absence of an easily accessible "handle" for fluorescent labeling. Here we show a one-step, scalable, solvent-free, synthetic route to fluorescent blue (2-aminoanthracene), green (5-aminofluorescein), and red (rhodamine-6G) PLGA, in which every polymer chain in the sample is fluorescently labeled. The utility of initiator-labeled PLGA was demonstrated through the preparation of nanoparticles, capable of therapeutic subcellular delivery to T-helper-precursor-1 (THP-1) macrophages, a model cell line for determining in vitro biocompatibility and particle uptake. Super resolution confocal fluorescence microscopy imaging showed that dye-initiated PLGA nanoparticles were internalized to punctate regions and retained bright fluorescence over at least 24 h. In comparison, PLGA nanoparticles with 5-aminofluorescein introduced by conventional nanoprecipitation/encapsulation showed diffuse and much lower fluorescence intensity in the same cells and over the same time periods. The utility of this approach for in vitro drug delivery experiments was demonstrated through the concurrent imaging of the fluorescent drug doxorubicin (λex = 480 nm, λem = 590 nm) with carrier 5-aminofluorescein PLGA, also in THP-1 cells, in which the intracellular locations of the drug and the polymer could be clearly visualized. Finally, the dye-labeled particles were evaluated in an in vivo model, via delivery to the nematode Caenorhabditis elegans, with bright fluorescence again apparent in the internal tract after 3 h. The results presented in this manuscript highlight the ease of synthesis of highly fluorescent PLGA, which could be used to augment tracking of future therapeutics and accelerate in vitro and in vivo characterization of delivery systems prior to clinical translation.

Bio-Inspired Polymersome Nanoreactors.

Two key concepts in living organisms are that biochemical reactions are sequestered into reaction compartments such as cells and organelles, and that many of the complex biological reaction cascades involve transient activation of reactions in response to external triggers. Here we review our efforts to implement these concepts into artificial nanoreactors. Block copolymer vesicles (polymersomes) for laccase-catalyzed oxidations as well as a generally applicable permeabilization method for polymersome membranes are highlighted. Moreover, polymersome nanoreactors that can be switched on by visible light and that immediately return to their off state in the dark are reviewed. These systems have the potential to create bio-inspired catalytic systems, e.g. to orchestrate reaction cascades.

Self-Reporting Fiber-Reinforced Composites That Mimic the Ability of Biological Materials to Sense and Report Damage.

Sensing of damage, deformation, and mechanical forces is of vital importance in many applications of fiber-reinforced polymer composites, as it allows the structural health and integrity of composite components to be monitored and microdamage to be detected before it leads to catastrophic material failure. Bioinspired and biomimetic approaches to self-sensing and self-reporting materials are reviewed. Examples include bruising coatings and bleeding composites based on dye-filled microcapsules, hollow fibers, and vascular networks. Force-induced changes in color, fluorescence, or luminescence are achieved by mechanochromic epoxy resins, or by mechanophores and force-responsive proteins located at the interface of glass/carbon fibers and polymers. Composites can also feel strain, stress, and damage through embedded optical and electrical sensors, such as fiber Bragg grating sensors, or by resistance measurements of dispersed carbon fibers and carbon nanotubes. Bioinspired composites with the ability to show autonomously if and where they have been damaged lead to a multitude of opportunities for aerospace, automotive, civil engineering, and wind-turbine applications. They range from safety features for the detection of barely visible impact damage, to the real-time monitoring of deformation of load-bearing components.