Manganese-Catalyzed Synthesis of Polyketones Using Hydrogen-Borrowing Approach.

We report here a method of making polyketones from the coupling of diketones and diols using a manganese pincer complex. The methodology allows us to access various polyketones (polyarylalkylketone) containing aryl, alkyl, and ether functionalities, bridging the gap between the two classes of commercially available polyketones: aliphatic polyketones and polyaryletherketones. Using this methodology, 12 polyketones have been synthesized and characterized using various analytical techniques to understand their chemical, physical, morphological, and mechanical properties. Based on previous reports and our studies, we suggest that the polymerization occurs via a hydrogen-borrowing mechanism that involves the dehydrogenation of diols to dialdehyde followed by aldol condensation of dialdehyde with diketones to form chalcone derivatives and their subsequent hydrogenation to form polyarylalkylketones.

Characterising the HLA-I immunopeptidome of plasma-derived extracellular vesicles in patients with melanoma.

Extracellular vesicles (EVs) frequently express human leukocyte antigen class I (HLA-I) molecules. The immunopeptidomes presented on EV HLA-I are being mapped to provide key information on both specific cancer-related peptides, and for larger immunopeptidomic signatures associated with disease. Utilizing HLA-I immunoisolation and mass spectrometry, we characterised the HLA-I immunopeptidome of EVs derived from the melanoma cancer cell line, ESTDAB-026, and the plasma of 12 patients diagnosed with advanced stage melanoma, alongside 11 healthy controls. The EV HLA-I immunopeptidome derived from melanoma cells features T cell epitopes with known immunogenicity and peptides derived from known tumour associated antigens (TAAs). Both T cell epitopes with known immunogenicity and peptides derived from known TAAs were also identifiable in the melanoma patient samples. Patient stratification into two distinct groups with varying immunological profiles was also observed. The data obtained in this study suggests for the first time that the HLA-I immunopeptidome of EVs derived from blood may aid in the detection of important diagnostic or prognostic biomarkers and also provide new immunotherapy targets.

Synergistic growth of nickel and platinum nanoparticles via exsolution and surface reaction.

Bimetallic catalysts combining precious and earth-abundant metals in well designed nanoparticle architectures can enable cost efficient and stable heterogeneous catalysis. Here, we present an interaction-driven in-situ approach to engineer finely dispersed Ni decorated Pt nanoparticles (1-6 nm) on perovskite nanofibres via reduction at high temperatures (600-800 oC). Deposition of Pt (0.5 wt%) enhances the reducibility of the perovskite support and promotes the nucleation of Ni cations via metal-support interaction, thereafter the Ni species react with Pt forming alloy nanoparticles, with the combined processes yielding smaller nanoparticles that either of the contributing processes. Tuneable uniform Pt-Ni nanoparticles are produced on the perovskite surface, yielding reactivity and stability surpassing 1 wt.% Pt/γ-Al2O3 catalysts for CO oxidation. This approach heralds the possibility of in-situ fabrication of supported bimetallic nanoparticles with engineered compositional distributions and performance.

Improving the Oxygen Evolution Reaction: Exsolved Cobalt Nanoparticles on Titanate Perovskite Catalyst.

Perovskites are an important class of oxygen evolution reaction (OER) catalysts due to highly tunable compositions and adaptable characteristics. However, perovskite-based catalysts can have limited atom utilization efficiency due to large particle size, resulting in low mass activity. Herein, Cobalt nanoparticles are exsolved from La0.2+2x Ca0.7-2x Ti1-x Cox O3 perovskite and applied in OER. Upon reduction in the 5% H2 /N2 atmosphere at 800 °C for 2 h, the Co exsolved perovskite catalyst (R-LCTCo0.11) exhibits optimal OER performance. The mass activity of R-LCTCo0.11 reaches ≈1700 mA mg-1 at an overpotential of 450 mV, which is 17 times and 3 times higher than that of LCTCo0.11 (97 mA mg-1 ) and R-Mix (560 mA mg-1 ) catalysts respectively, surpassing the benchmark catalyst RuO2 (42.7 mA mg-1 of oxide at η = 470 mV). Electrochemical impedance spectroscopy (EIS) data reveals that R-LCTCo0.11 has the lowest charge transfer resistance (Rct  = 58 Ω), demonstrating the highest catalytic and kinetic activity for OER. Furthermore, this catalyst shows high stability during an accelerated durability test of 10 h electrolysis and 1000 cycles cyclic voltammetry (CV). This work demonstrates that nanoparticle exsolution from a doped perovskite is an effective strategy for improving the atom utilization efficiency in OER.

Enhanced CO2 Electrolysis Through Mn Substitution Coupled with Ni Exsolution in Lanthanum Calcium Titanate Electrodes.

In this study, perovskite oxides La0.3 Ca0.6 Ni0.05 Mnx Ti0.95- x O3- γ (x = 0, 0.05, 0.10) are investigated as potential solid oxide electrolysis cell cathode materials. The catalytic activity of these cathodes toward CO2 reduction reaction is significantly enhanced through the exsolution of highly active Ni nanoparticles, driven by applying a current of 1.2 A in 97% CO2 - 3% H2 O. The performance of La0.3 Ca0.6 Ni0.05 Ti0.95 O3-γ is notably improved by co-doping with Mn. Mn dopants enhance the reducibility of Ni, a crucial factor in promoting the in situ exsolution of metallic nanocatalysts in perovskite (ABO3 ) structures. This improvement is attributed to Mn dopants enabling more flexible coordination, resulting in higher oxygen vacancy concentration, and facilitating oxygen ion migration. Consequently, a higher density of Ni nanoparticles is formed. These oxygen vacancies also improve the adsorption, desorption, and dissociation of CO2 molecules. The dual doping strategy provides enhanced performance without degradation observed after 133 h of high-temperature operation, suggesting a reliable cathode material for CO2 electrolysis.

Manganese catalysed dehydrogenative synthesis of polyureas from diformamide and diamines.

We report here the synthesis of polyureas from the dehydrogenative coupling of diamines and diformamides. The reaction is catalysed by a manganese pincer complex and releases H2 gas as the only by-product making the process atom-economic and sustainable. The reported method is greener in comparison to the current state-of-the-art production routes that involve diisocyanate and phosgene feedstock. We also report here the physical, morphological, and mechanical properties of synthesized polyureas. Based on our mechanistic studies, we suggest that the reaction proceeds via isocyanate intermediates formed by the manganese catalysed dehydrogenation of formamides.

Ferrielectricity in the Archetypal Antiferroelectric, PbZrO3.

Antiferroelectric materials, where the transition between antipolar and polar phase is controlled by external electric fields, offer exceptional energy storage capacity with high efficiencies, giant electrocaloric effect, and superb electromechanical response. PbZrO3 is the first discovered and the archetypal antiferroelectric material. Nonetheless, substantial challenges in processing phase pure PbZrO3 have limited studies of the undoped composition, hindering understanding of the phase transitions in this material or unraveling the controversial origins of a low-field ferroelectric phase observed in lead zirconate thin films. Leveraging highly oriented PbZrO3 thin films, a room-temperature ferrielectric phase is observed in the absence of external electric fields, with modulations of amplitude and direction of the spontaneous polarization and large anisotropy for critical electric fields required for phase transition. The ferrielectric state observations are qualitatively consistent with theoretical predictions, and correlate with very high dielectric tunability, and ultrahigh strains (up to 1.1%). This work suggests a need for re-evaluation of the fundamental science of antiferroelectricity in this archetypal material.

Electrochemical Activation Applied to Perovskite Titanate Fibers to Yield Supported Alloy Nanoparticles for Electrocatalytic Application.

Active bi-metallic nanoparticles are of key importance in catalysis and renewable energy. Here, the in situ formation of bi-metallic nanoparticles is investigated by exsolution on 200 nm diameter perovskite fibers. The B-site co-doped perovskite fibers display a high degree of exsolution, decorated with NiCo or Ni3 Fe bi-metallic nanoparticles with average diameter about 29 and 35 nm, respectively. The perovskite fibers are utilized as cathode materials in pure CO2 electrolysis cells due to their redox stability in the CO/CO2 atmosphere. After in situ electrochemical switching, the nanoparticles exsolved from the perovskite fiber demonstrate an enhanced performance in pure CO2 electrolysis. At 900 °C, the current density of solid oxide electrolysis cell (SOEC) with 200 µm YSZ electrolyte supported NiFe doped perovskite fiber anode reaches 0.75 Acm-2 at 1.6 V superior to the NiCo doped perovskite fiber anode (about 1.5 times) in pure CO2 . According to DFT calculations (PBE-D3 level) the superior CO2 conversion on NiFe compared to NiCo bi-metallic species is related to an enhanced driving force for C-O cleavage under formation of CO chemisorbed on the nanoparticle and a reduced binding energy of CO required to release this product.

Atomic-scale imaging of emergent order at a magnetic field-induced Lifshitz transition.

The phenomenology and radical changes seen in material properties traversing a quantum phase transition have captivated condensed matter research over the past decades. Strong electronic correlations lead to exotic electronic ground states, including magnetic order, nematicity, and unconventional superconductivity. Providing a microscopic model for these requires detailed knowledge of the electronic structure in the vicinity of the Fermi energy, promising a complete understanding of the physics of the quantum critical point. Here, we demonstrate such a measurement at the surface of Sr3Ru2O7. Our results show that, even in zero field, the electronic structure is strongly C2 symmetric and that a magnetic field drives a Lifshitz transition and induces a charge-stripe order. We track the changes of the electronic structure as a function of field via quasiparticle interference imaging at ultralow temperatures. Our results provide a complete microscopic picture of the field-induced changes of the electronic structure across the Lifshitz transition.

Constitutionally Selective Dynamic Covalent Nanoparticle Assembly.

The future of materials chemistry will be defined by our ability to precisely arrange components that have considerably larger dimensions and more complex compositions than conventional molecular or macromolecular building blocks. However, exerting structural and constitutional control in the assembly of nanoscale entities presents a considerable challenge. Dynamic covalent nanoparticles are emerging as an attractive category of reaction-enabled solution-processable nanosized building block through which the rational principles of molecular synthetic chemistry can be extended into the nanoscale. From a mixture of two hydrazone-based dynamic covalent nanoparticles with complementary reactivity, specific molecular instructions trigger selective assembly of intimately mixed heteromaterial (Au-Pd) aggregates or materials highly enriched in either one of the two core materials. In much the same way as complementary reactivity is exploited in synthetic molecular chemistry, chemospecific nanoparticle-bound reactions dictate building block connectivity; meanwhile, kinetic regioselectivity on the nanoscale regulates the detailed composition of the materials produced. Selectivity, and hence aggregate composition, is sensitive to several system parameters. By characterizing the nanoparticle-bound reactions in isolation, kinetic models of the multiscale assembly network can be constructed. Despite ignoring heterogeneous physical processes such as aggregation and precipitation, these simple kinetic models successfully link the underlying molecular events with the nanoscale assembly outcome, guiding rational optimization to maximize selectivity for each of the three assembly pathways. With such predictive construction strategies, we can anticipate that reaction-enabled nanoparticles can become fully incorporated in the lexicon of synthetic chemistry, ultimately establishing a synthetic science that manipulates molecular and nanoscale components with equal proficiency.

Maximizing Information: A Machine Learning Approach for Analysis of Complex Nanoscale Electromechanical Behavior in Defect-Rich PZT Films.

Scanning Probe Microscopy (SPM) based techniques probe material properties over microscale regions with nanoscale resolution, ultimately resulting in investigation of mesoscale functionalities. Among SPM techniques, piezoresponse force microscopy (PFM) is a highly effective tool in exploring polarization switching in ferroelectric materials. However, its signal is also sensitive to sample-dependent electrostatic and chemo-electromechanical changes. Literature reports have often concentrated on the evaluation of the Off-field piezoresponse, compared to On-field piezoresponse, based on the latter's increased sensitivity to non-ferroelectric contributions. Using machine learning approaches incorporating both Off- and On-field piezoresponse response as well as Off-field resonance frequency to maximize information, switching piezoresponse in a defect-rich Pb(Zr,Ti)O3 thin film is investigated. As expected, one major contributor to the piezoresponse is mostly ferroelectric, coupled with electrostatic phenomena during On-field measurements. A second component is electrostatic in nature, while a third component is likely due to a superposition of multiple non-ferroelectric processes. The proposed approach will enable deeper understanding of switching phenomena in weakly ferroelectric samples and materials with large chemo-electromechanical response.

Elastic distortion determining conduction in BiFeO3 phase boundaries.

It is now well-established that boundaries separating tetragonal-like (T) and rhombohedral-like (R) phases in BiFeO3 thin films can show enhanced electrical conductivity. However, the origin of this conductivity remains elusive. Here, we study mixed-phase BiFeO3 thin films, where local populations of T and R can be readily altered using stress and electric fields. We observe that phase boundary electrical conductivity in regions which have undergone stress-writing is significantly greater than in the virgin microstructure. We use high-end electron microscopy techniques to identify key differences between the R-T boundaries present in stress-written and as-grown microstructures, to gain a better understanding of the mechanism responsible for electrical conduction. We find that point defects (and associated mixed valence states) are present in both electrically conducting and non-conducting regions; crucially, in both cases, the spatial distribution of defects is relatively homogeneous: there is no evidence of phase boundary defect aggregation. Atomic resolution imaging reveals that the only significant difference between non-conducting and conducting boundaries is the elastic distortion evident - detailed analysis of localised crystallography shows that the strain accommodation across the R-T boundaries is much more extensive in stress-written than in as-grown microstructures; this has a substantial effect on the straightening of local bonds within regions seen to electrically conduct. This work therefore offers distinct evidence that the elastic distortion is more important than point defect accumulation in determining the phase boundary conduction properties in mixed-phase BiFeO3.

Correction: Giant resistive switching in mixed phase BiFeO3via phase population control.

Correction for 'Giant resistive switching in mixed phase BiFeO3via phase population control' by David Edwards et al., Nanoscale, 2018, 10, 17629-17637.

Giant resistive switching in mixed phase BiFeO3via phase population control.

Highly-strained coherent interfaces, between rhombohedral-like (R) and tetragonal-like (T) phases in BiFeO3 thin films, often show enhanced electrical conductivity in comparison to non-interfacial regions. In principle, changing the population and distribution of these interfaces should therefore allow different resistance states to be created. However, doing this controllably has been challenging to date. Here, we show that local thin film phase microstructures (and hence R-T interface densities) can be changed in a thermodynamically predictable way (predictions made using atomistic simulations) by applying different combinations of mechanical stress and electric field. We use both pressure and electric field to reversibly generate metastable changes in microstructure that result in very large changes of resistance of up to 108%, comparable to those seen in Tunnelling Electro-Resistance (TER) devices.