Catalysts for chemical and electrochemical reactions underpin many aspects of modern technology and industry, from energy storage and conversion to toxic emissions abatement to chemical and materials ...synthesis. This role necessitates the design of highly active, stable, yet earth-abundant heterogeneous catalysts. In this Review, we present the perovskite oxide family as a basis for developing such catalysts for (electro)chemical conversions spanning carbon, nitrogen, and oxygen chemistries. A framework for rationalizing activity trends and guiding perovskite oxide catalyst design is described, followed by illustrations of how a robust understanding of perovskite electronic structure provides fundamental insights into activity, stability, and mechanism in oxygen electrocatalysis. We conclude by outlining how these insights open experimental and computational opportunities to expand the compositional and chemical reaction space for next-generation perovskite catalysts.
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BFBNIB, NMLJ, NUK, ODKLJ, PNG, SAZU, UL, UM, UPUK
Optical fiber gratings have developed into a mature technology with a wide range of applications in various areas, including physical sensing for temperature, strain, acoustic waves and pressure. All ...of these applications rely on the perturbation of the period or refractive index of a grating inscribed in the fiber core as a transducing mechanism between a quantity to be measured and the optical spectral response of the fiber grating. This paper presents a relatively recent variant of the fiber grating concept, whereby a small tilt of the grating fringes causes coupling of the optical power from the core mode into a multitude of cladding modes, each with its own wavevector and mode field shape. The main consequence of doing so is that the differential response of the modes can then be used to multiply the sensing modalities available for a single fiber grating and also to increase the sensor resolution by taking advantage of the large amount of data available. In particular, the temperature cross‐sensitivity and power source fluctuation noise inherent in all fiber grating designs can be completely eliminated by referencing all the spectral measurements to the wavelength and power level of the core mode back‐reflection. The mode resonances have a quality factor of 105, and they can be observed in reflection or transmission. A thorough review of experimental and theoretical results will show that tilted fiber Bragg gratings can be used for high resolution refractometry, surface plasmon resonance applications, and multiparameter physical sensing (strain, vibration, curvature, and temperature).
Optical fiber gratings have developed into a mature technology with a wide range of applications in various areas, including physical sensing for temperature, strain, acoustic waves and pressure. All of these applications rely on the perturbation of the period or refractive index of a grating inscribed in the fiber core as a transducing mechanism between a quantity to be measured and the optical spectral response of the fiber grating. This paper presents a relatively recent variant of the fiber grating concept, whereby a small tilt of the grating fringes causes coupling of the optical power from the core mode into a multitude of cladding modes, each with its own wavevector and mode field shape. The main consequence of doing so is that the differential response of the modes can then be used to multiply the sensing modalities available for a single fiber grating and also to increase the sensor resolution by taking advantage of the large amount of data available. In particular, the temperature cross‐sensitivity and power source fluctuation noise inherent in all fiber grating designs can be completely eliminated by referencing all the spectral measurements to the wavelength and power level of the core mode back‐reflection. The mode resonances have a quality factor of 105, and they can be observed in reflection or transmission. A thorough review of experimental and theoretical results will show that tilted fiber Bragg gratings can be used for high resolution refractometry, surface plasmon resonance applications, and multiparameter physical sensing (strain, vibration, curvature, and temperature).
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The absence of tumor antigens leads to a low response rate, which represents a major challenge in immune checkpoint blockade (ICB) therapy. Pyroptosis, which releases tumor antigens and ...damage‐associated molecular patterns (DAMPs) that induce antitumor immunity and boost ICB efficiency, potentially leads to injury when occurring in normal tissues. Therefore, a strategy and highly efficient agent to induce tumor‐specific pyroptosis but reduce pyroptosis in normal tissues is urgently required. Here, a smart tumor microenvironmental reactive oxygen species (ROS)/glutathione (GSH) dual‐responsive nano‐prodrug (denoted as MCPP) with high paclitaxel (PTX) and photosensitizer purpurin 18 (P18) loading is rationally designed. The ROS/GSH dual‐responsive system facilitates the nano‐prodrug response to high ROS/GSH in the tumor microenvironment and achieves optimal drug release in tumors. ROS generated by P18 after laser irradiation achieves controlled release and induces tumor cell pyroptosis with PTX by chemo‐photodynamic therapy. Pyroptotic tumor cells release DAMPs, thus initiating adaptive immunity, boosting ICB efficiency, achieving tumor regression, generating immunological memory, and preventing tumor recurrence. Mechanistically, chemo‐photodynamic therapy and control‐release PTX synergistically induce gasdermin E (GSDME)‐related pyroptosis. It is speculated that inspired chemo‐photodynamic therapy using the presented nano‐prodrug strategy can be a smart strategy to trigger pyroptosis and augment ICB efficiency.
A smart tumor microenvironmental reactive oxygen species/glutathione dual‐responsive nano‐prodrug (denoted as MCPP) with high paclitaxel and photosensitizer purpurin 18 loading is designed. Chemo‐photodynamic therapy using the presented nano‐prodrug strategy can be a smart strategy to trigger pyroptosis and augment the efficiency of immune checkpoint blockade therapy.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Exploring efficient and low‐cost electrocatalysts for the oxygen‐reduction reaction (ORR) and oxygen‐evolution reaction (OER) is critical for developing renewable energy technologies such as fuel ...cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition‐metal spinels, including MnxCo3−xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7, 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.
The eg occupancy of the active cation in octahedral sites is identified as the descriptor that governs the activity of the oxygen‐reduction reaction and the oxygen‐evolution reaction on transition‐metal spinel oxides.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The third-generation
tyrosine kinase inhibitor osimertinib is approved to treat patients with
T790M-positive non-small cell lung cancer (NSCLC) who have developed resistance to earlier-generation ...drugs. Acquired
C797S mutation has been reported to mediate osimertinib resistance in some patients. However, the remaining resistance mechanisms are largely unknown.
We performed mutation profiling using targeted next-generation sequencing (NGS) for 416 cancer-relevant genes on 93 osimertinib-resistant lung cancer patients' samples, mainly cell-free DNAs (cfDNAs), and matched pretreatment samples of 12 patients.
experiments were conducted to functionally study the secondary
mutations identified.
G796/C797, L792, and L718/G719 mutations were identified in 24.7%, 10.8%, and 9.7% of the cases, respectively, with certain mutations coexisting in one patient with different prevalence. L792 and L718 mutants markedly increased the half inhibitory concentration (IC
) of osimertinib
, among which the L718Q mutation conferred the greatest resistance to osimertinib, as well as gefitinib resistance when not coexisting with T790M. Further analysis of the 12 matched pretreatment samples confirmed that these
mutations were acquired during osimertinib treatment. Alterations in parallel or downstream oncogenes such as
, and
were also discovered, potentially contributing to the osimertinib-resistance in patients without
secondary mutations.
We present comprehensive mutation profiles of a large cohort of osimertinib-resistance lung cancer patients using mainly cfDNA. Besides C797 mutations, novel secondary mutations of
L718 and L792 residues confer osimertinib resistance, both
and
, and are of great clinical and pharmaceutical relevance.
.
In this Review, we discuss the state-of-the-art understanding of non-precious transition metal oxides that catalyze the oxygen reduction and evolution reactions. Understanding and mastering the ...kinetics of oxygen electrocatalysis is instrumental to making use of photosynthesis, advancing solar fuels, fuel cells, electrolyzers, and metal–air batteries. We first present key insights, assumptions and limitations of well-known activity descriptors and reaction mechanisms in the past four decades. The turnover frequency of crystalline oxides as promising catalysts is also put into perspective with amorphous oxides and photosystem II. Particular attention is paid to electronic structure parameters that can potentially govern the adsorbate binding strength and thus provide simple rationales and design principles to predict new catalyst chemistries with enhanced activity. We share new perspective synthesizing mechanism and electronic descriptors developed from both molecular orbital and solid state band structure principles. We conclude with an outlook on the opportunities in future research within this rapidly developing field.
Supercapacitor fibers, with short charging times, long cycle lifespans, and high power densities, hold promise for powering flexible fabric‐based electronics. To date, however, only short lengths of ...functioning fiber supercapacitors have been produced. The primary goal of this study is to introduce a supercapacitor fiber that addresses the remaining challenges of scalability, flexibility, cladding impermeability, and performance at length. This is achieved through a top‐down fabrication method in which a macroscale preform is thermally drawn into a fully functional energy‐storage fiber. The preform consists of five components: thermally reversible porous electrode and electrolyte gels; conductive polymer and copper microwire current collectors; and an encapsulating hermetic cladding. This process produces 100 m of continuous functional supercapacitor fiber, orders of magnitude longer than any previously reported. In addition to flexibility (5 mm radius of curvature), moisture resistance (100 washing cycles), and strength (68 MPa), these fibers have an energy density of 306 μWh cm−2 at 3.0 V and ≈100% capacitance retention over 13 000 cycles at 1.6 V. To demonstrate the utility of this fiber, it is machine‐woven and used as filament for 3D printing.
A flow‐based preform‐to‐fiber (top‐down) thermal drawing process is used in which a preform of macroscale dimensions, assembled with all the five component materials, is thermally drawn into 100 m lengths of fully functional supercapacitor fiber. The cell architecture is designed to address the mechanical, environmental, electrical, and storage requirements of a textile and 3D printed energy‐storage device.
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Hierarchical functionalized multiwalled carbon nanotube (MWNT)/graphene structures with thicknesses up to tens of micrometers and relatively high density (>1 g cm−3) are synthesized using vacuum ...filtration for the positive electrode of lithium batteries. These electrodes, which are self‐standing and free of binder and current collectors, utilize oxygen functional groups for Faradaic reactions in addition to double‐layer charging, which can impart high gravimetric (230 Wh kg−1 at 2.6 kW kg−1) and volumetric (450 Wh L−1 at 5 kW L−1) performance. It is demonstrated that the gravimetric and volumetric capacity, capacitance, and energy density can be tuned by selective removal of oxygen species from as‐prepared functionalized MWNT/graphene structures with heat treatments in H2/Ar, potentially opening new pathways for the design of electrodes with controlled surface chemistry.
Free‐standing electrodes of hierarchically structured oxygen‐functionalized multiwalled carbon nanotubes and graphene oxide are shown to deliver high volumetric energies up to 450 Wh L−1 at 5 kW L−1 in lithium cells, which are attributable to high mass densities (>1 g cm−3) and controllable utilization of surface oxygen species for Li+ Faradaic reactions.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Catalysts for oxygen electrochemical processes are critical for the commercial viability of renewable energy storage and conversion devices such as fuel cells, artificial photosynthesis, and ...metal-air batteries. Transition metal oxides are an excellent system for developing scalable, non-noble-metal-based catalysts, especially for the oxygen evolution reaction (OER). Central to the rational design of novel catalysts is the development of quantitative structure–activity relationships, which correlate the desired catalytic behavior to structural and/or elemental descriptors of materials. The ultimate goal is to use these relationships to guide materials design. In this study, 101 intrinsic OER activities of 51 perovskites were compiled from five studies in literature and additional measurements made for this work. We explored the behavior and performance of 14 descriptors of the metal–oxygen bond strength using a number of statistical approaches, including factor analysis and linear regression models. We found that these descriptors can be classified into five descriptor families and identify electron occupancy and metal–oxygen covalency as the dominant influences on the OER activity. However, multiple descriptors still need to be considered in order to develop strong predictive relationships, largely outperforming the use of only one or two descriptors (as conventionally done in the field). We confirmed that the number of d electrons, charge-transfer energy (covalency), and optimality of eg occupancy play the important roles, but found that structural factors such as M–O–M bond angle and tolerance factor are relevant as well. With these tools, we demonstrate how statistical learning can be used to draw novel physical insights and combined with data mining to rapidly screen OER electrocatalysts across a wide chemical space.
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Electrochemical energy storage by making H2 an energy carrier from water splitting relies on four elementary reactions, i.e., the hydrogen evolution reaction (HER), hydrogen oxidation reaction (HOR), ...oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Herein, the central objective is to recommend systematic protocols for activity measurements of these four reactions and benchmark activities for comparison, which is critical to facilitate the research and development of catalysts with high activity and stability. Details for the electrochemical cell setup, measurements, and data analysis used to quantify the kinetics of the HER, HOR, OER, and ORR in acidic and basic solutions are provided, and examples of state‐of‐the‐art specific and mass activity of catalysts to date are given. First, the experimental setup is discussed to provide common guidelines for these reactions, including the cell design, reference electrode selection, counter electrode concerns, and working electrode preparation. Second, experimental protocols, including data collection and processing such as ohmic‐ and background‐correction and catalyst surface area estimation, and practice for testing and comparing different classes of catalysts are recommended. Lastly, the specific and mass activity activities of some state‐of‐the‐art catalysts are benchmarked to facilitate the comparison of catalyst activity for these four reactions across different laboratories.
The rigorous protocols for activity measurements are the prerequisite of developing highly active electrocatalysts for water splitting and hydrogen fuel cell reactions. The electrochemical measurement and data analysis approaches to quantify the kinetics of these reactions are summarized, benchmarking the specific and mass activities of state‐of‐the‐art electrocatalysts.
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