Abstract
Catalytic-materials design requires predictive modeling of the interaction between catalyst and reactants. This is challenging due to the complexity and diversity of structure-property ...relationships across the chemical space. Here, we report a strategy for a rational design of catalytic materials using the artificial intelligence approach (AI) subgroup discovery. We identify catalyst
genes
(features) that correlate with mechanisms that trigger, facilitate, or hinder the activation of carbon dioxide (CO
2
) towards a chemical conversion. The AI model is trained on first-principles data for a broad family of oxides. We demonstrate that surfaces of experimentally identified good catalysts consistently exhibit combinations of
genes
resulting in a strong elongation of a C-O bond. The same combinations of
genes
also minimize the OCO-angle, the previously proposed indicator of activation, albeit under the constraint that the Sabatier principle is satisfied. Based on these findings, we propose a set of new promising catalyst materials for CO
2
conversion.
Catalysis by gold supported on reducible oxides has been extensively studied, yet issues such as the nature of the catalytic site and the role of the reducible support remain fiercely debated topics. ...Here we present ab initio molecular dynamics simulations of an unprecedented dynamic single-atom catalytic mechanism for the oxidation of carbon monoxide by ceria-supported gold clusters. The reported dynamic single-atom catalytic mechanism results from the ability of the gold cation to strongly couple with the redox properties of the ceria in a synergistic manner, thereby lowering the energy of redox reactions. The gold cation can break away from the gold nanoparticle to catalyse carbon monoxide oxidation, adjacent to the metal/oxide interface and subsequently reintegrate back into the nanoparticle after the reaction is completed. Our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in catalysis.
Gold (Au) catalysts exhibit a significant size effect, but its origin has been puzzling for a long time. It is generally believed that supported Au clusters are more or less rigid in working ...condition, which inevitably leads to the general speculation that the active sites are immobile. Here, by using atomic resolution in situ environmental transmission electron microscopy, we report size-dependent structure dynamics of single Au nanoparticles on ceria (CeO₂) in CO oxidation reaction condition at room temperature. While large Au nanoparticles remain rigid in the catalytic working condition, ultrasmall Au clusters lose their intrinsic structures and become disordered, featuring vigorous structural rearrangements and formation of dynamic low-coordinated atoms on surface. Ab initio molecular-dynamics simulations reveal that the interaction between ultrasmall Au cluster and CO molecules leads to the dynamic structural responses, demonstrating that the shape of the catalytic particle under the working condition may totally differ from the shape under the static condition. The present observation provides insight on the origin of superior catalytic properties of ultrasmall gold clusters.
In the present study, we perform systematic density functional investigations on the single-atom Pt catalysts dispersed on CeO2 (111), (110), and (100) surfaces. The structural and electronic ...properties of these SACs and their corresponding catalytic activity for CO oxidation are discussed. It is shown that the single-atom Pt substitution of a lattice Ce ion is thermodynamically stable on each ceria surface. On the (111) and (100) surfaces, the single Pt atom is found to exist at an oxidation state of +4 upon replacement of Ce4+, while, on the (110) surface, it exhibits a planar structure with a reduced oxidation state of +2 due to the spontaneous formation of surface peroxide O2 2– species. On all of the surfaces, CO oxidation is found to follow the Mars–van Krevelen mechanism. It is the single-atom Pt, rather than the lattice Ce, that acts as the electron acceptor/donor in the redox processes during the whole catalytic cycle. This work provides insights on the significant role of a single metal atom on reducible oxide of ceria and others.
A
bstract
Form factors, as quantities involving both local operators and asymptotic particle states, contain information of both the spectrum of operators and the on-shell amplitudes. So far the ...studies of form factors have been mostly focused on the large
N
c
planar limit, with a few exceptions of Sudakov form factors. In this paper, we discuss the systematical construction of full color dependent form factors with generic local operators. We study the color decomposition for form factors and discuss the general strategy of using on-shell unitarity cut method. As concrete applications, we compute the full two-loop non-planar minimal form factors for both half-BPS operators and non-BPS operators in the SU(2) sector in
N
= 4 SYM. Another important aspect is to investigate the color-kinematics (CK) duality for form factors of high-length operators. Explicit CK dual representation is found for the two-loop half-BPS minimal form factors with arbitrary number of external legs. The full-color two-loop form factor result provides an independent check of the infrared dipole formula for two-loop
n
-point amplitudes. By extracting the UV divergences, we also reproduce the known non-planar SU(2) dilatation operator at two loops. As for the finite remainder function, interestingly, the non-planar part is found to contain a new maximally transcendental part beyond the known planar result.
Conspectus Single atom electrocatalysts, with noble metal-free composition, maximal atom efficiency, and exceptional reactivity toward various energy and environmental applications, have become a ...research hot spot in the recent decade. Their simplicity and the isolated nature of the atomic structure of their active site have also made them an ideal model catalyst system for studying reaction mechanisms and activity trends. However, the state of the single atom active sites during electrochemical reactions may not be as simple as is usually assumed. To the contrary, the single atom electrocatalysts have been reported to be under greater influence from interfacial dynamics, with solvent and electrolyte ions perpetually interacting with the electrified active center under an applied electrode potential. These complexities render the activity trends and reaction mechanisms derived from simplistic models dubious. In this Account, with a few popular single atom electrocatalysis systems, we show how the change in electrochemical potential induces nontrivial variation in the free energy profile of elemental electrochemical reaction steps, demonstrate how the active centers with different electronic structure features can induce different solvation structures at the interface even for the same reaction intermediate of the simplest electrochemical reaction, and discuss the implication of the complexities on the kinetics and thermodynamics of the reaction system to better address the activity and selectivity trends. We also venture into more intriguing interfacial phenomena, such as alternative reaction pathways and intermediates that are favored and stabilized by solvation and polarization effects, long-range interfacial dynamics across the region far beyond the contact layer, and the dynamic activation or deactivation of single atom sites under operation conditions. We show the necessity of including realistic aspects (explicit solvent, electrolyte, and electrode potential) into the model to correctly capture the physics and chemistry at the electrochemical interface and to understand the reaction mechanisms and reactivity trends. We also demonstrate how the popular simplistic design principles fail and how they can be revised by including the kinetics and interfacial factors in the model. All of these rich dynamics and chemistry would remain hidden or overlooked otherwise. We believe that the complexity at an electrochemical interface is not a curse but a blessing in that it enables deeper understanding and finer control of the potential-dependent free energy landscape of electrochemical reactions, which opens up new dimensions for further design and optimization of single atom electrocatalysts and beyond. Limitations of current methods and challenges faced by the theoretical and experimental communities are discussed, along with the possible solutions awaiting development in the future.
Cisplatin resistance in tumor cells is known mainly due to the reduced accumulation of platinum ions by efflux, detoxification by intracellular GSH, and nucleotide excision repair machinery-mediated ...nuclear DNA repair. In this work, theranostic Pt(IV)-NPs, which are precisely self-assembled by biotin-labeled Pt(IV) prodrug derivative and cyclodextrin-functionalized IR780 in a 1:1 molecular ratio, have been developed for addressing all these hurdles via mitochondria-targeted chemotherapy solely or chemophotothermal therapy. In these nanoparticles, IR780 as a small-molecule dye acts as a mitochondria-targeting ligand to make Pt(IV)-NPs relocate finally in the mitochondria and release cisplatin. As demonstrated by in vitro and in vivo experiments, Pt(IV)-NPs can markedly facilitate cancer-specific mitochondrial targeting, inducing mitochondrial dysfunction and mitochondrial DNA (mtDNA) damage, thus greatly increasing the Pt accumulation, reducing the GSH levels, and avoiding DNA repair machinery in cisplatin-resistant cancer cells (A549R), finally resulting in significant inhibition of A549R tumor growth on animal models by chemotherapy solely. Upon near-infrared irradiation, mitochondria-targeted chemophotothermal synergistic therapy can be realized, further overcoming cisplatin resistance and even eliminating A549R tumors completely. Moreover, such novel Pt(IV)-NPs integrate multimodal targeting (cancer and mitochondria targeting), imaging (near-infrared imaging and photoacoustic imaging), and therapeutic (chemo- and photothermal therapy) moieties in a constant ratio (1:1:1) into a single, reproducible, and structurally homogeneous entity, avoiding nonuniform drug loading and premature leakage as well as the discrete steps of imaging and therapy, which thus is more beneficial for precise therapeutics and future clinical translation.
This paper studies a wireless-energy-transfer (WET) enabled massive multiple-input-multiple-output (MIMO) system (MM) consisting of a hybrid data-and-energy access point (H-AP) and multiple ...single-antenna users. In the WET-MM system, the H-AP is equipped with a large number M of antennas and functions like a conventional AP in receiving data from users, but additionally supplies wireless power to the users. We consider frame-based transmissions. Each frame is divided into three phases: the uplink channel estimation (CE) phase, the downlink WET phase, as well as the uplink wireless information transmission (WIT) phase. Firstly, users use a fraction of the previously harvested energy to send pilots, while the H-AP estimates the uplink channels and obtains the downlink channels by exploiting channel reciprocity. Next, the H-AP utilizes the channel estimates just obtained to transfer wireless energy to all users in the downlink via energy beamforming. Finally, the users use a portion of the harvested energy to send data to the H-AP simultaneously in the uplink (reserving some harvested energy for sending pilots in the next frame) . To optimize the throughput and ensure rate fairness, we consider the problem of maximizing the minimum rate among all users. In the large-M regime, we obtain the asymptotically optimal solutions and some interesting insights for the optimal design of WET-MM system.
Fully-heavy tetraquark states, i.e., cccc, bbbb, bbcc (ccbb), cbcc, cbbb, and cbcb, are systematically investigated by means of a nonrelativistic quark model based on lattice-QCD studies of the ...two-body QQ interaction, which exhibits a spin-independent Cornell potential along with a spin-spin term. The four-body problem is solved using the Gaussian expansion method; additionally, the so-called complex scaling technique is employed so that bound, resonance, and scattering states can be treated on the same footing. Moreover, a complete set of four-body configurations, including meson-meson, diquark-antidiquark, and K-type configurations, as well as their couplings, are considered for spin-parity quantum numbers JP(C) = 0+(+), 1+(±), and 2+(+) in the S -wave channel. Several narrow resonances, with two-meson strong decay widths less than 30 MeV, are found in all of the tetraquark systems studied. Particularly, the fully-charm resonances recently reported by the LHCb Collaboration, at the energy range between 6.2 and 7.2 GeV in the di- J/ψ invariant spectrum, can be well identified in our calculation. Focusing on the fully-bottom tetraquark spectrum, resonances with masses between 18.9 and 19.6 GeV are found. For the remaining charm-bottom cases, the masses are obtained within a energy region from 9.8 GeV to 16.4 GeV. All these predicted resonances can be further examined in future experiments.
Pancreatic cancer is a deadly disease with high mortality due to difficulties in its early diagnosis and metastasis. The tumor microenvironment induced by interactions between pancreatic ...epithelial/cancer cells and stromal cells is critical for pancreatic cancer progression and has been implicated in the failure of chemotherapy, radiation therapy and immunotherapy. Microenvironment formation requires interactions between pancreatic cancer cells and stromal cells. Components of the pancreatic cancer microenvironment that contribute to desmoplasia and immunosuppression are associated with poor patient prognosis. These components can facilitate desmoplasia and immunosuppression in primary and metastatic sites or can promote metastasis by stimulating angiogenesis/lymphangiogenesis, epithelial-mesenchymal transition, invasion/migration, and pre-metastatic niche formation. Some molecules participate in both microenvironment formation and metastasis. In this review, we focus on the mechanisms of pancreatic cancer microenvironment formation and discuss how the pancreatic cancer microenvironment participates in metastasis, representing a potential target for combination therapy to enhance overall survival.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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