Notes on the value function approach to multiobjective bilevel optimization. - In: Optimization, ISSN 1029-4945, Bd. 0 (2024), 0, S. 1-37
This paper is concerned with the value function approach to multiobjective bilevel optimization which exploits a lower-level frontier-type mapping in order to replace the hierarchical model of two interdependent multiobjective optimization problems by a single-level multiobjective optimization problem. As a starting point, different value-function-type reformulations are suggested and their relations are discussed. Here, we focus on the situations where the lower-level problem is solved up to efficiency or weak efficiency, and an intermediate solution concept is suggested as well. We study the graph-closedness of the associated efficiency-type and frontier-type mappings. These findings are then used for two purposes. First, we investigate existence results in multiobjective bilevel optimization. Second, for the derivation of necessary optimality conditions via the value function approach, it is inherent to differentiate frontier-type mappings in a generalized way. Here, we are concerned with the computation of upper coderivative estimates for the frontier-type mapping associated with the setting where the lower-level problem is solved up to weak efficiency. We proceed in two ways, relying, on the one hand, on a weak domination property and, on the other hand, on a scalarization approach. Illustrative examples visualize our findings and some flaws in the related literature.
https://doi.org/10.1080/02331934.2024.2323107
Sustainable harnessing of waste polycarbonate for synthesizing activated furans to generate Stenhouse adducts on polymer surface. - In: Chemistry, ISSN 1861-471X, Bd. 0 (2024), 0, e202400369, insges. 21 S.
Plastics are versatile materials, offering lightweight, durable, and affordable solutions across various industries. However, their non-degradable nature poses challenges by end of their life. This study presented an innovative carbonyl extraction method to utilize waste poly(bisphenol A carbonate) (PC) as reaction precursor to synthesis of activated furan as precursor for photoswitchable Stenhouse adducts. This innovative chemical strategy not only generated N,N’-functionalized barbiturates but also provided an eco-friendly and cost-effective alternative to traditional synthesis methods. The method presented hereby not only promotes sustainability by repurposing waste polycarbonate as carbonyl equivalent under green conditions but also yielded reusable bisphenol A (BPA). Furthermore, the derived activated furans exhibited their functionality by forming colored donor-acceptor Stenhouse adducts (DASAs) on aminated polymer surfaces. This work demonstrated a transition from a linear plastics economy toward a circular one, highlighting the potential of plastic waste as a resource for creating materials with improved properties.
https://doi.org/10.1002/asia.202400369
Toxicity of water-soluble D-g-PNIPAM polymers in a complex with chemotherapy drugs and mechanism of their action in vitro. - In: International journal of molecular sciences, ISSN 1422-0067, Bd. 25 (2024), 5, 3069, S. 1-15
The application of a biocompatible polymer nanocarrier can provide target delivery to tumor tissues, improved pharmacokinetics, controlled drug release, etc. Therefore, the proposed strategy was to use the water-soluble star-like copolymers with a Dextran core and Poly(N-isopropylacrylamide) grafts (D-g-PNIPAM) for conjugation with the widely used chemotherapy drugs in oncology-Cisplatin (Cis-Pt) and Doxorubicin (Dox). The molecular characteristics of the copolymer were received using size-exclusion chromatography. The physicochemical characterization of the D-g-PNIPAM-Cis-Pt (or Dox) nanosystem was conducted using dynamic light scattering and FTIR spectroscopy. Using traditional biochemical methods, a comparative analysis of the enhancement of the cytotoxic effect of free Cis-Pt and Dox in combination with D-g-PNIPAM copolymers was performed in cancer cells of the Lewis lung carcinoma line, which are both sensitive and resistant to Dox; in addition, the mechanism of their action in vitro was evaluated.
https://doi.org/10.3390/ijms25053069
Recent progress and future prospects of high-entropy materials for battery applications. - In: Journal of semiconductors, ISSN 2058-6140, Bd. 45 (2024), 3, 030202, S. 1-5
https://doi.org/10.1088/1674-4926/45/3/030202
The binding of the SARS-CoV-2 spike protein to platelet factor 4: a proposed mechanism for the generation of pathogenic antibodies. - In: Biomolecules, ISSN 2218-273X, Bd. 14 (2024), 3, 245, S. 1-14
Pathogenic platelet factor 4 (PF4) antibodies contributed to the abnormal coagulation profiles in COVID-19 and vaccinated patients. However, the mechanism of what triggers the body to produce these antibodies has not yet been clarified. Similar patterns and many comparable features between the COVID-19 virus and heparin-induced thrombocytopenia (HIT) have been reported. Previously, we identified a new mechanism of autoimmunity in HIT in which PF4-antibodies self-clustered PF4 and exposed binding epitopes for other pathogenic PF4/eparin antibodies. Here, we first proved that the SARS-CoV-2 spike protein (SP) also binds to PF4. The binding was evidenced by the increase in mass and optical intensity as observed through quartz crystal microbalance and immunosorbent assay, while the switching of the surface zeta potential caused by protein interactions and binding affinity of PF4-SP were evaluated by dynamic light scattering and isothermal spectral shift analysis. Based on our results, we proposed a mechanism for the generation of PF4 antibodies in COVID-19 patients. We further validated the changes in zeta potential and interaction affinity between PF4 and SP and found that their binding mechanism differs from ACE2-SP binding. Importantly, the PF4/SP complexes facilitate the binding of anti-PF4/Heparin antibodies. Our findings offer a fresh perspective on PF4 engagement with the SARS-CoV-2 SP, illuminating the role of PF4/SP complexes in severe thrombotic events.
https://doi.org/10.3390/biom14030245
Low abundant bacteria reflect soil specificity - analysis of bacterial communities from archaeological investigation of pre-industrial saline ash deposits of Bad Dürrenberg (Germany). - In: Environments, ISSN 2076-3298, Bd. 11 (2024), 3, 42, S. 1-20
Six soil samples from three layers of an archaeological investigation profile from a pre-industrial ash deposit place have been investigated by NGS analyses of 16 S rRNA. The three pairs of sample originate from top soil (internal reference), from an intermediate ash layer and from a lower ash layer, formed about two centuries ago. In addition to general abundant bacteria, special genera known as halophilic or alkaline-tolerant have been found as expected from the history of the place and from the measured pH-value and conductivity measurements. The close relations between samples of pairs and the differences between the three soil layers are clearly indicated by abundance correlation and PCA-diagrams. Comparative PCA correlation plots including samples from an archaeological excavation site dedicated to pre-industrial coal mining illustrate the high distinguishability of investigated soils. These relations are particular clearly shown when lower abundant bacteria are regarded. The investigations are a further example for the “ecological memory of soil” reflecting the strong human impact on this pre-industrial embossed place.
https://doi.org/10.3390/environments11030042
Boosting the energy density of bowl-like MnO2carbon through lithium-intercalation in a high-voltage asymmetric supercapacitor with “water-in-salt” electrolyte. - In: Small, ISSN 1613-6829, Bd. 0 (2024), 0, 2310037, S. 1-11
Highly concentrated “‘water-in-salt”’ (WIS) electrolytes are promising for high-performance energy storage devices due to their wide electrochemical stability window. However, the energy storage mechanism of MnO2 in WIS electrolytes-based supercapacitors remains unclear. Herein, MnO2 nanoflowers are successfully grown on mesoporous bowl-like carbon (MBC) particles to generate MnO2/MBC composites, which not only increase electroactive sites and inhibit the pulverization of MnO2 particles during the fast charging/discharging processes, but also facilitate the electron transfer and ion diffusion within the whole electrode, resulting in significant enhancement of the electrochemical performance. An asymmetric supercapacitor, assembled with MnO2/MBC and activated carbon (AC) and using 21 m LiTFSI solution as the WIS electrolyte, delivers an ultrahigh energy density of 70.2 Wh kg−1 at 700 W kg−1, and still retains 24.8 Wh kg−1 when the power density is increased to 28 kW kg−1. The ex situ XRD, Raman, and XPS measurements reveal that a reversible reaction of MnO2 + xLi+ + xe−↔LixMnO2 takes place during charging and discharging. Therefore, the asymmetric MnO2/MBC//AC supercapacitor with LiTFSI electrolyte is actually a lithium-ion hybrid supercapacitor, which can greatly boost the energy density of the assembled device and expand the voltage window.
https://doi.org/10.1002/smll.202310037
Integration of multijunction absorbers and catalysts for efficient solar-driven artificial leaf structures: a physical and materials science perspective. - In: Solar RRL, ISSN 2367-198X, Bd. 0 (2024), 0, 2301047, S. 1-88
Artificial leaves could be the breakthrough technology to overcome the limitations of storage and mobility through the synthesis of chemical fuels from sunlight, which will be an essential component of a sustainable future energy system. However, the realization of efficient solar-driven artificial leaf structures requires integrated specialized materials such as semiconductor absorbers, catalysts, interfacial passivation, and contact layers. To date, no competitive system has emerged due to a lack of scientific understanding, knowledge-based design rules, and scalable engineering strategies. Here, we will discuss competitive artificial leaf devices for water splitting, focusing on multi-absorber structures to achieve solar-to-hydrogen conversion efficiencies exceeding 15%. A key challenge is integrating photovoltaic and electrochemical functionalities in a single device. Additionally, optimal electrocatalysts for intermittent operation at photocurrent densities of 10-20 mA cm^-2 must be immobilized on the absorbers with specifically designed interfacial passivation and contact layers, so-called buried junctions. This minimizes voltage and current losses and prevents corrosive side reactions. Key challenges include understanding elementary steps, identifying suitable materials, and developing synthesis and processing techniques for all integrated components. This is crucial for efficient, robust, and scalable devices. Here, we discuss and report on corresponding research efforts to produce green hydrogen with unassisted solar-driven (photo-)electrochemical devices. This article is protected by copyright. All rights reserved.
https://doi.org/10.1002/solr.202301047
Error bounds for kernel-based approximations of the Koopman operator. - In: Applied and computational harmonic analysis, ISSN 1096-603X, Bd. 71 (2024), 101657, S. 1-25
We consider the data-driven approximation of the Koopman operator for stochastic differential equations on reproducing kernel Hilbert spaces (RKHS). Our focus is on the estimation error if the data are collected from long-term ergodic simulations. We derive both an exact expression for the variance of the kernel cross-covariance operator, measured in the Hilbert-Schmidt norm, and probabilistic bounds for the finite-data estimation error. Moreover, we derive a bound on the prediction error of observables in the RKHS using a finite Mercer series expansion. Further, assuming Koopman-invariance of the RKHS, we provide bounds on the full approximation error. Numerical experiments using the Ornstein-Uhlenbeck process illustrate our results.
https://doi.org/10.1016/j.acha.2024.101657
Bipolar membrane Electrolyzer for CO2 electro-reduction to CO in organic electrolyte with NaClO produced as byproduct. - In: Electrochimica acta, ISSN 1873-3859, Bd. 483 (2024), 144056, S. 1-8
A novel electrolyzer has been proposed for CO2 reduction to CO, concurrently generating NaClO as a byproduct at the anode. The cell is divided into two compartments by a bipolar membrane, which plays a pivotal role in the dissociation of H2O into H^+ and OH^−. In the cathode compartment, CO2 is reduced to CO within a neutral organic solution. Simultaneously, in the anode compartment, Cl^− undergoes oxidation to form ClO^− within a basic aqueous solution. The electrolyzer remains stable during 10 h of electrolysis, and the current density reaches 76.35 mA cm^−2 at a potential of -2.4 V (vs SHE), with the Faradaic efficiency of CO formation stable at 93 %. By increasing the product values, CO2 electro-reduction technology can be promoted to industrial applications.
https://doi.org/10.1016/j.electacta.2024.144056