The organometallic-mediated radical polymerization (OMRP) of vinylidene fluoride (VDF) using an alkyl cobalt(III) compound as initiator was recently proven successful for the controlled synthesis of PVDF (Angew.
Multifunctional,
stimuli-responsive block copolymers have been
prepared via the sequential atom transfer radical polymerization (ATRP)
of 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the in-house synthesized
1′-(2-methacryloxyethyl)-3′,3′-dimethyl-6-nitrospiro-(2H-1-benzopyran-2,2′-indoline) (SPMA) monomer. Two
PDMAEMA-b-PSPMA diblock copolymers, containing 3
and 14 mol % SPMA, were synthesized. The amphiphilic nature of the
PDMAEMA-b-PSPMA diblock copolymers led to the formation
of well-defined spherical micelles, comprising a hydrophobic PSPMA
core and a hydrophilic PDMAEMA shell, in water. The combination of
the pH- and temperature-responsive character of PDMAEMA with the pH-,
temperature-, and light-sensitive properties of the PSPMA block has
resulted in a complex responsive behavior of the copolymer micelles
in aqueous solution, when applying three different external stimuli
(i.e., light irradiation, pH, and temperature). More importantly,
the synergistic response of the block copolymer micelles when varying
simultaneously the solution pH and temperature is reported for the
first time. Such multisensitive self-assembled nanostructures pave
the way for the on-demand controlled capture and release of actives
under complex environmental cues.
A study of the copolymerization kinetics of vinylidene fluoride with tert-butyl 2-trifluoromethyl acrylate: a suitable pair for the synthesis of alternating fluorinated copolymers.
The synthesis of fluorinated dual-responsive block terpolymers via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization is presented. The resulting block terpolymers consist of a hydrophobic block which comprises an alternating...
Aims
Our understanding of the rhizosphere is limited by the lack of techniques for in situ live microscopy. Current techniques are either destructive or unsuitable for observing chemical changes within the pore space. To address this limitation, we have developed artificial substrates, termed smart soils, that enable the acquisition and 3D reconstruction of chemical sensors attached to soil particles.
Methods
The transparency of smart soils was achieved using polymer particles with refractive index matching that of water. The surface of the particles was modified both to retain water and act as a local sensor to report on pore space pH via fluorescence emissions. Multispectral signals were acquired from the particles using a light sheet microscope, and machine learning algorithms predicted the changes and spatial distribution in pH at the surface of the smart soil particles.
Results
The technique was able to predict pH live and in situ within ± 0.5 units of the true pH value. pH distribution could be reconstructed across a volume of several cubic centimetres around plant roots at 10 μm resolution. Using smart soils of different composition, we revealed how root exudation and pore structure create variability in chemical properties.
Conclusion
Smart soils captured the pH gradients forming around a growing plant root. Future developments of the technology could include the fine tuning of soil physicochemical properties, the addition of chemical sensors and improved data processing. Hence, this technology could play a critical role in advancing our understanding of complex rhizosphere processes.
SummaryAgriculture must reduce green-house gas emission and pollution, produce safer and healthier food, closer to home, reducing waste whilst delivering more diverse diets to a growing world population. Soils could enable this transformation, but unfortunately, they have a hugely complex and opaque structure and studies of its myriad of mechanisms are difficult. Here, the fabrication of smart soils for the screening of below-ground bio-processes is demonstrated. Particles were generated from fluoropolymer waste with functionalisation converting them into sensors able to report on key chemical dynamics. Tailored functionalization was obtained by radical terpolymerisation to improve growth conditions and sensing capabilities. The study demonstrates the potential for the development of accelerated genetic or agrochemical screens and could pave the way for controlled indoor soil bio-production systems.
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