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"Whittaker, Andrew"
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Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes
2022
Rechargeable batteries paired with sodium metal anodes are considered to be one of the most promising high-energy and low-cost energy-storage systems. However, the use of highly reactive sodium metal and the formation of sodium dendrites during battery operation have caused safety concerns, especially when highly flammable liquid electrolytes are used. Here we design and develop solvent-free solid polymer electrolytes (SPEs) based on a perfluoropolyether-terminated polyethylene oxide (PEO)-based block copolymer for safe and stable all-solid-state sodium metal batteries. Compared with traditional PEO SPEs, our results suggest that block copolymer design allows for the formation of self-assembled nanostructures leading to high storage modulus at elevated temperatures with the PEO domains providing transport channels even at high salt concentration (ethylene oxide/sodium = 8/2). Moreover, it is demonstrated that the incorporation of perfluoropolyether segments enhances the Na
+
transference number of the electrolyte to 0.46 at 80 °C and enables a stable solid electrolyte interface. The new SPE exhibits highly stable symmetric cell-cycling performance at high current density (0.5 mA cm
−2
and 1.0 mAh cm
−2
, up to 1,000 h). Finally, the assembled all-solid-state sodium metal batteries demonstrate outstanding capacity retention, long-term charge/discharge stability (Coulombic efficiency, 99.91%; >900 cycles with Na
3
V
2
(PO
4
)
3
cathode) and good capability with high loading NaFePO
4
cathode (>1 mAh cm
−2
).
Rechargeable batteries with sodium metal anodes are promising as energy-storage systems despite safety concerns related to reactivity and dendrite formation. Solvent-free perfluoropolyether-based electrolytes are now reported for safe and stable all-solid-state sodium metal batteries.
Journal Article
Minimum information reporting in bio–nano experimental literature
by
Whittaker, Andrew K
,
Thurecht, Kristofer J
,
Parton, Robert G
in
Bioengineering
,
Biological materials
,
Cancer
2018
Studying the interactions between nanoengineered materials and biological systems plays a vital role in the development of biological applications of nanotechnology and the improvement of our fundamental understanding of the bio–nano interface. A significant barrier to progress in this multidisciplinary area is the variability of published literature with regards to characterizations performed and experimental details reported. Here, we suggest a ‘minimum information standard’ for experimental literature investigating bio–nano interactions. This standard consists of specific components to be reported, divided into three categories: material characterization, biological characterization and details of experimental protocols. Our intention is for these proposed standards to improve reproducibility, increase quantitative comparisons of bio–nano materials, and facilitate meta analyses and in silico modelling.
Journal Article
Bioerodable PLGA-Based Microparticles for Producing Sustained-Release Drug Formulations and Strategies for Improving Drug Loading
by
Han, Felicity Y.
,
Smith, Maree T.
,
Thurecht, Kristofer J.
in
Acids
,
Alginic acid
,
Biocompatibility
2016
Poly(lactic-co-glycolic acid) (PLGA) is the most widely used biomaterial for microencapsulation and prolonged delivery of therapeutic drugs, proteins and antigens. PLGA has excellent biodegradability and biocompatibility and is generally recognized as safe by international regulatory agencies including the United States Food and Drug Administration and the European Medicines Agency. The physicochemical properties of PLGA may be varied systematically by changing the ratio of lactic acid to glycolic acid. This in turn alters the release rate of microencapsulated therapeutic molecules from PLGA microparticle formulations. The obstacles hindering more widespread use of PLGA for producing sustained-release formulations for clinical use include low drug loading, particularly of hydrophilic small molecules, high initial burst release and/or poor formulation stability. In this review, we address strategies aimed at overcoming these challenges. These include use of low-temperature double-emulsion methods to increase drug-loading by producing PLGA particles with a small volume for the inner water phase and a suitable pH of the external phase. Newer strategies for producing PLGA particles with high drug loading and the desired sustained-release profiles include fabrication of multi-layered microparticles, nanoparticles-in-microparticles, use of hydrogel templates, as well as coaxial electrospray, microfluidics, and supercritical carbon dioxide methods. Another recent strategy with promise for producing particles with well-controlled and reproducible sustained-release profiles involves complexation of PLGA with additives such as polyethylene glycol, poly(ortho esters), chitosan, alginate, caffeic acid, hyaluronic acid, and silicon dioxide.
Journal Article
Fluorination in advanced battery design
by
Hawker, Craig J.
,
Azad, Faezeh Makhlooghi
,
Wu, Zhenzhen
in
639/301/299/891
,
639/638/161
,
639/638/298
2024
The increasing demand for high-performance rechargeable batteries, particularly in energy storage applications such as electric vehicles, has driven the development of advanced battery technologies with improved energy density, safety and cycling stability. Fluorine has emerged as a crucial element in achieving these goals, owing to its hydrophobicity, robust bond strength and stability, exceptional dielectric properties and strong electronegativity and polarization. These attributes provide fluorinated battery components with high thermal and oxidative stability, chemical inertness and non-flammability. Importantly, fluorinated materials also facilitate the formation of a thin, protective film of corrosion products at the metal–electrolyte interface, which serves as a barrier against further chemical reactions with the electrolyte. Fluorinated species are now used in a wide range of battery components, including solid and liquid electrolytes, electrolyte additives, solvents, binders and protective layers for electrodes. This Review explores the design and utilization of fluorine-containing species in advanced batteries, focusing on the relationship between the chemical structure of the species and its impact on battery performance. Additionally, given the regulatory landscape surrounding the use of fluorinated compounds, we discuss the current challenges and future directions related to the responsible reuse and recycling of fluorinated materials in battery-related components.
Incorporating fluorine into battery components can improve the energy density, safety and cycling stability of rechargeable batteries. This Review explores the broad use of fluorinated compounds in battery design, examines the relationship between their chemical structure and battery performance and discusses the challenges and opportunities of fluorinated batteries within the present regulatory framework.
Journal Article
Polymer Electrode Materials for Sodium-ion Batteries
by
Zhao, Qinglan
,
Zhao, X. S.
,
Whittaker, Andrew K.
in
Alternative energy sources
,
Batteries
,
Carbon
2018
Sodium-ion batteries are promising alternative electrochemical energy storage devices due to the abundance of sodium resources. One of the challenges currently hindering the development of the sodium-ion battery technology is the lack of electrode materials suitable for reversibly storing/releasing sodium ions for a sufficiently long lifetime. Redox-active polymers provide opportunities for developing advanced electrode materials for sodium-ion batteries because of their structural diversity and flexibility, surface functionalities and tenability, and low cost. This review provides a short yet concise summary of recent developments in polymer electrode materials for sodium-ion batteries. Challenges facing polymer electrode materials for sodium-ion batteries are identified and analyzed. Strategies for improving polymer electrochemical performance are discussed. Future research perspectives in this important field are projected.
Journal Article
Fluoropolymer sorbent for efficient and selective capturing of per- and polyfluorinated compounds
2024
Per- and poly-fluoroalkyl substances (PFAS) have gained widespread attention due to their adverse effects on health and environment. Developing efficient technology to capture PFAS from contaminated sources remains a great challenge. In this study, we introduce a type of reusable polymeric sorbent (PFPE-IEX + ) for rapid, efficient, and selective removal of multiple PFAS impurities from various contaminated water sources. The resin achieves >98% removal efficiency ([PFPE-IEX + ] = 0.5–5 mg mL
−1
, [PFAS]
0
= 1–10 ppb in potable water and landfill leachate) and >500 mg g
−1
sorption capacity for the 11 types of examined PFAS. We achieve efficient PFAS removal without breakthrough and subsequent resin regeneration and demonstrate good PFAS recovery in a proof-of-concept cartridge setup. The outcomes of this study offer valuable guidance to the design of platforms for efficient and selective PFAS capture from contaminated water, such as drinking water and landfill leachate.
It is challenging to remove Per- and polyfluoroalkyl substances (PFAS) from water. Here, authors developed a polymer sorbent capable of selectively and efficiently removing PFAS from contaminated water sources to levels below detection limits.
Journal Article
Self-assembled protein-polymer nanoparticles via photoinitiated polymerization-induced self-assembly for targeted and enhanced drug delivery in cancer therapy
by
Yang, Wenting
,
Ediriweera, Gayathri R.
,
Chang, Yixin
in
Antineoplastic Agents - chemistry
,
Antineoplastic Agents - pharmacology
,
Aqueous solutions
2025
Protein–polymer bioconjugates offer numerous advantages in biomedical applications by integrating the benefits of functional proteins and tunable synthetic polymers. Developing drug-loaded protein–polymer nanoparticles, with a receptor-targeting protein forming the nanoparticle shell, would be ideal for the targeted delivery of drugs to cancer cells that overexpress specific receptors for more effective cancer therapy. In this study, we report the synthesis of reduction-responsive protein–polymer nanoparticles by a photoinitiated polymerization-induced self-assembly (photo-PISA) approach. Anti-cancer drugs can be efficiently encapsulated at high concentrations within the nanoparticles during the photo-PISA process. These protein–polymer nanoparticles present transferrin (Tf) on their surfaces, capable of targeting the overexpressed Tf receptors found on cancer cells. It was found that the nanoparticles demonstrate enhanced cellular uptake and delivery of the anti-cancer drug, curcumin, to cancer cells via Tf receptor-mediated endocytosis, compared to the control PEGylated nanoparticles that lack targeting capability. Moreover, the nanoparticles can release the encapsulated curcumin in response to a reducing environment, a characteristic of cancer cells compared to health cells. Consequently, the synthesized protein–polymer nanoparticles are more effective in inducing cancer cell death compared to the control nanoparticles, demonstrating their potential as an effective and targeted drug delivery system for cancer therapy.
Journal Article
Seismic Behavior of Low-Aspect-Ratio Reinforced Concrete Shear Walls
by
Luna, Bismarck N
,
Rivera, Jonathan P
,
Whittaker, Andrew S
in
Analysis
,
Concrete
,
Construction
2015
Twelve low-aspect-ratio reinforced concrete walls were constructed and tested at the University at Buffalo to develop validated equations for peak shear strength and hysteretic rules for nonlinear response-history analysis. The pretest analysis and construction of the walls are described. Global force-displacement relationships are presented. Currently used equations for peak nominal (in-plane) shear strength do not predict the measured resistance of the walls. Out-of-plane forces and deformations affected peak in-plane shear strength. The resistance of the 12 walls degraded quickly with repeated cycling at displacements greater than those associated with peak strength. The initial stiffnesses of the test specimens were substantially lower than calculated using equations in design standards.
Journal Article
One-step nanoarchitectonics of a multiple functional hydrogel based on cellulose nanocrystals for effective tumor therapy
by
Pan, Hui
,
Chen, Tianxing
,
Wang, Zhaoyang
in
Aldehydes
,
Animal research
,
Atomic/Molecular Structure and Spectra
2022
Hypoxia is a huge barrier for the development of photodynamic therapy (PDT). Chemodynamic therapy (CDT) could provide a possible solution to this dilemma. In this work, a controlled Schiff-base reaction was conducted between amido groups on the surface of carbon dots (CDs) and aldehyde groups on aldehyde-modified cellulose nanocrystals (mCNCs) as well as aldehyde-mCNCs decorated with Fe
3
O
4
nanoparticles. In this process, the mCNCs not only prevent the agglomeration of Fe
3
O
4
but also form hydrogels with CDs. The CDs act as both photothermal agent and photosensitizer. The hypoxia could be effectively relieved through the Fenton reaction due to the addition of Fe
3
O
4
, and the ·OH produced in the reaction further induces CDT and enhances tumor therapy efficiency. The therapy performance was further verified through
in vitro
cell experiments and
in vivo
animal experiments. This convenient method provides inspirations for the design and preparation of advanced biomaterials with multiple functions for cancer therapy.
Journal Article
In Situ Bonding Regulation of Surface Ligands for Efficient and Stable FAPbI3 Quantum Dot Solar Cells
2022
Quantum dots (QDs) of formamidinium lead triiodide (FAPbI3) perovskite hold great potential, outperforming their inorganic counterparts in terms of phase stability and carrier lifetime, for high‐performance solar cells. However, the highly dynamic nature of FAPbI3 QDs, which mainly originates from the proton exchange between oleic acid and oleylamine (OAm) surface ligands, is a key hurdle that impedes the fabrication of high‐efficiency solar cells. To tackle such an issue, here, protonated‐OAm in situ to strengthen the ligand binding at the surface of FAPbI3 QDs, which can effectively suppress the defect formation during QD synthesis and purification processes is selectively introduced. In addition, by forming a halide‐rich surface environment, the ligand density in a broader range for FAPbI3 QDs without compromising their structural integrity, which significantly improves their optoelectronic properties can be modulated. As a result, the power conversion efficiency of FAPbI3 QD solar cells (QDSCs) is enhanced from 7.4% to 13.8%, a record for FAPbI3 QDSCs. Furthermore, the suppressed proton exchange and reduced surface defects in FAPbI3 QDs also enhance the stability of QDSCs, which retain 80% of the initial efficiency upon exposure to ambient air for 3000 hours. An in situ surface ligand regulation strategy for deliberately controlling protonated‐oleylamine (OAm) dominated surface binding of formamidinium lead triiodide quantum dots (FAPbI3 QDs) is demonstrated. The QDs present reduced long‐chain insulating ligand density without compromising their structural integrity, leading to the corresponding QD solar cell a record power conversion efficiency of 13.8% for FAPbI3 QDSCs.
Journal Article