Smart Biomaterials

Ph.DDOCTOR OF PHILOSOPH

An adherent tissue-inspired hydrogel delivery vehicle utilised in primary human glioma models.

A physical hydrogel cross-linked via the host-guest interactions of cucurbit[8]uril and utilised as an implantable drug-delivery vehicle for the brain is described herein. Constructed from hyaluronic acid, this hydrogel is biocompatible and has a high water content of 98%. The mechanical properties have been characterised by rheology and compared with the modulus of human brain tissue demonstrating the production of a soft material that can be moulded into the cavity it is implanted into following surgical resection. Furthermore, effective delivery of therapeutic compounds and antibodies to primary human glioblastoma cell lines is showcased by a variety of in vitro and ex vivo viability and immunocytochemistry based assays.This work was supported by The Brain Tumour Charity (RG89672), the National Institute for Health Research Cambridge Biomedical Research Centre; the Higher Education Funding Council for England. We acknowledge the Human Research Tissue Bank and Biomedical Research Centre for the tissue being accessed through the Human Research Tissue Bank. The Human Research Tissue Bank is supported by the NIHR Cambridge Biomedical Research Centre. MJR thanks the University of Cambridge Chemical Biology and Molecular Medicine PhD Training Programme for funding. CCP is thankful for the support of the EPSRC and the Brain Tumour Charity for funding. JHM acknowledges the support of the Gates Cambridge Scholarship programme. AKK was supported by a studentship from the John and Lucille van Geest Foundation

Visible light-induced switching of soft matter materials properties based on thioindigo photoswitches

Thioindigos are visible light responsive photoswitches with excellent spatial control over the conformational change between their trans- and cis- isomers. However, they possess limited solubility in all conventional organic solvents and polymers, hindering their application in soft matter materials. Herein, we introduce a strategy for the covalent insertion of thioindigo units into polymer main chains, enabling thioindigos to function within crosslinked polymeric hydrogels. We overcome their solubility issue by developing a thioindigo bismethacrylate linker able to undergo radical initiated thiol-ene reaction for step-growth polymerization, generating indigo-containing polymers. The optimal wavelength for the reversible trans-/cis- isomerisation of thioindigo was elucidated by constructing a detailed photochemical action plot of their switching efficiencies at a wide range of monochromatic wavelengths. Critically, indigo-containing polymers display significant photoswitching of the materials’ optical and physical properties in organic solvents and water. Furthermore, the photoswitching of thioindigo within crosslinked structures enables visible light induced modulation of the hydrogel stiffness. Both the thioindigo-containing hydrogels and photoswitching processes are non-toxic to cells, thus offering opportunities for advanced applications in soft matter materials and biology-related research

Competition of electronic correlation and reconstruction in La1-xSrxTiO3/SrTiO3 heterostructures

Electronic correlation and reconstruction are two important factors that play a critical role in shaping the magnetic and electronic properties of correlated low-dimensional systems. Here, we report a competition between the electronic correlation and structural reconstruction in La1-xSrxTiO3/SrTiO3 heterostructures by modulating material polarity and interfacial strain, respectively. The heterostructures exhibit a critical thickness (tc) at which a metal-to-insulator transition (MIT) abruptly occurs at certain thickness, accompanied by the coexistence of two- and three-dimensional (2D and 3D) carriers. Intriguingly, the tc exhibits a V-shaped dependence on the doping concentration of Sr, with the smallest tc value at x = 0.5. We attribute this V-shaped dependence to the competition between the electronic reconstruction (modulated by the polarity) and the electronic correlation (modulated by strain), which are borne out by the experimental results, including strain-dependent electronic properties and the evolution of 2D and 3D carriers. Our findings underscore the significance of the interplay between electronic reconstruction and correlation in the realization and utilization of emergent electronic functionalities in low-dimensional correlated systems

The sustainable materials roadmap

Over the past 150 years, our ability to produce and transform engineered materials has been responsible for our current high standards of living, especially in developed economies. However, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of the economy, energy, and climate. We are at the point where something must drastically change, and it must change now. We must create more sustainable materials alternatives using natural raw materials and inspiration from nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments (LCAs) based on reliable and relevant data to quantify sustainability. We need to seriously start thinking of where our future materials will come from and how could we track them, given that we are confronted with resource scarcity and geographical constrains. This is particularly important for the development of new and sustainable energy technologies, key to our transition to net zero. Currently 'critical materials' are central components of sustainable energy systems because they are the best performing. A few examples include the permanent magnets based on rare earth metals (Dy, Nd, Pr) used in wind turbines, Li and Co in Li-ion batteries, Pt and Ir in fuel cells and electrolysers, Si in solar cells just to mention a few. These materials are classified as 'critical' by the European Union and Department of Energy. Except in sustainable energy, materials are also key components in packaging, construction, and textile industry along with many other industrial sectors. This roadmap authored by prominent researchers working across disciplines in the very important field of sustainable materials is intended to highlight the outstanding issues that must be addressed and provide an insight into the pathways towards solving them adopted by the sustainable materials community. In compiling this roadmap, we hope to aid the development of the wider sustainable materials research community, providing a guide for academia, industry, government, and funding agencies in this critically important and rapidly developing research space which is key to future sustainability.journal articl

Water soluble polyhydroxyalkanoates: Future materials for therapeutic applications

Chemical Society Reviews44102865-287

Stimuli-Responsive Cationic Hydrogels in Drug Delivery Applications

Stimuli-responsive, smart, intelligent, or environmentally sensitive polymers respond to changes in external stimuli such as pH, temperature, ionic strength, surfactants, pressure, light, biomolecules, and magnetic field. These materials are developed in various network architectures such as block copolymers, crosslinked hydrogels, nanogels, inter-penetrating networks, and dendrimers. Stimuli-responsive cationic polymers and hydrogels are an interesting class of “smart” materials that respond reversibly to changes in external pH. These materials have the ability to swell extensively in solutions of acidic pH and de-swell or shrink in solutions of alkaline pH. This reversible swelling-shrinking property brought about by changes in external pH conditions makes these materials useful in a wide range of applications such as drug delivery systems and chemical sensors. This article focuses mainly on the properties of these interesting materials and their applications in drug delivery systems

Sensors, Biosensors, and Analytical Technologies for Aquaculture Water Quality

In aquaculture industry, fish, shellfish, and aquatic plants are cultivated in fresh, salt, or brackish waters. The increasing demand of aquatic products has stimulated the rapid growth of aquaculture industries. How to effectively monitor and control water quality is one of the key concerns for aquaculture industry to ensure high productivity and high quality. There are four major categories of water quality concerns that affect aquaculture cultivations, namely, (1) physical parameters, e.g., pH, temperature, dissolved oxygen, and salinity, (2) organic contaminants, (3) biochemical hazards, e.g., cyanotoxins, and (4) biological contaminants, i.e., pathogens. While the physical parameters are affected by climate changes, the latter three are considered as environmental factors. In this review, we provide a comprehensive summary of sensors, biosensors, and analytical technologies available for monitoring aquaculture water quality. They include low-cost commercial sensors and sensor network setups for physical parameters. They also include chromatography, mass spectrometry, biochemistry, and molecular methods (e.g., immunoassays and polymerase chain reaction assays), culture-based method, and biophysical technologies (e.g., biosensors and nanosensors) for environmental contamination factors. According to the different levels of sophistication of various analytical techniques and the information they can provide (either fine fingerprint, highly accurate quantification, semiquantification, qualitative detection, or fast screening), we will comment on how they may be used as complementary tools, as well as their potential and gaps toward current demand of real-time, online, and/or onsite detection

Thermo-responsive hydrogels: From recent progress to biomedical applications

10.3390/gels7030077Gels737