In exploring the toxicity of micro- and nanoplastics, molecular simulations of plastic nanoparticles have been gaining traction recently. Modeling of nanoplastics involves the folding of multiple polymeric chains into an entangled particle, which is a challenging process, necessitating thorough optimization of the folding procedure. In this contribution, we use the simulated annealing procedure in a systematic workflow for preparing stable nanoplastic structures for the first time, based on the CHARMM36 force field. On the structures prepared with the fine-tuned protocol, we carry out quantum chemical geometry optimizations with the GFN2-xTB method, followed by benchmarking single-point calculations with GGA and hybrid DFT functionals. We further demonstrate the applicability of this approach through four plastic systems, including polyethylene, polypropylene, polystyrene, and nylon-66. Remarkably, the geometry of the resulting most stable assemblies show similarities to features observed earlier theoretically and experimentally for such systems. For polyethylene, a highly ordered, crystalline structure is obtained, in which the polymer chains possess long sections with all C–C–C–C units in trans configuration. For polypropylene and polystyrene, helical structures are observed, formed by alternating gauche and trans configurations along the backbone. For nylon-66, the structure-directing effect of the hydrogen bonds between amide moieties complicates the folding, resulting in parallelly arranged hydrogen bonding chains throughout the particle. Especially, we make the whole set of optimized structures available for the community in an online repository, with hopes of advancing simulation studies in the field, even making ensemble simulations accessible.
The Supplementary material contains additional theory (derivation of CP-SCF equations, additional contributions which arise from ECPs and point charges), figures and tables supporting conclusions drawn in the main text.
In this work, a systematic computational investigation of the optical band gap (BG) problem of Co 3 O 4 is carried out on the basis of the embedded cluster approach in combination with a series of particle/hole and wavefunction-based approaches.
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Abstract Background Conventional time-to-first event analyses for composite endpoints consider only the first event, whereas win ratio analyses account for event severity and recurrence. Methods We performed a win ratio analysis of the 1-year composite endpoint in the LANDMARK trial, a multicentre, non-inferiority study that randomized patients with severe native aortic valve stenosis to receive either the Myval transcatheter heart valve (THV) series (n = 384) or contemporary THVs (n = 384), consisting of the Sapien and Evolut series (n = 192 each). The 1-year composite endpoint included the following components, ranked in hierarchical order: all-cause death, disabling stroke, non-disabling stroke, and procedure- or valve-related hospitalization. For death and stroke events, wins or losses were determined according to the time-to-first-event principle. For procedure- or valve-related hospitalizations, the total number of events was compared. Win ratio analysis was also conducted for an extended composite endpoint that also included quality-of-life outcomes. Results Among 147 456 (384 × 384) unmatched patient pairs, the win ratio for the primary composite endpoint was 1.02 (95% CI: 0.68–1.51; P = .94), with 17 870 (12.1%) wins for the Myval group and 17 599 (11.9%) for the contemporary group. For the extended composite endpoint, the win ratio was 1.13 (95% CI: 0.82–1.55; P = .45), with 27 007 (18.3%) wins for the Myval group and 23 920 (16.2%) for the contemporary group. Comparisons between the Myval and Sapien groups, and between the Myval and Evolut groups, were also not statistically significant. Conclusions Win ratio analysis did not demonstrate a significant difference between Myval and contemporary THVs, consistent with the primary time-to-first event analysis of the LANDMARK trial.
ABSTRACT Although triboelectric nanogenerators (TENGs) are regarded as a promising technology for wave energy utilization, most present devices are only effective at relative high frequency with a narrow range, seriously incompatible with actual wave spectrum of energy distribution. Here, we present a wave‐adaptive triboelectric nanogenerator based on device‐anchor‐water synergistic effect, achieving ultrawide frequency range highly compatible with actual wave spectrum via a simple structure. Specifically, the device adopts a novel partial Ferris wheel design, featuring revolution‐spin coupling motion of planet TENGs under agitations, and the potential energy landscape of the wheel can be tuned for unique non‐linear behavior, which imparts the device supreme adaptation capability to real capricious waves of varying frequencies and amplitudes, maximizing power take‐off. Based on the high‐performance generator, an autonomous smart ocean platform for customizable marine sensing applications is developed. A prototype for smart marine ranch using the platform can collect and transmit local data automatically to the base station 1.24 km away, surpassing present record and ready for practical application. The work provides not only a general multifunctional architecture for self‐powered marine Internet‐of‐Things, but also a paradigm shift for solving the wave‐adaptation and spectrum‐matching challenges in wave energy harvesting, greatly enhancing practical performance.
. showcase that interferons (IFNs) trigger a functional reprogramming of tumor-associated macrophages (TAMs) by downregulating NADH dehydrogenase (ubiquinone) 1 alpha subcomplex 4 (NDUFA4), a key subunit of mitochondrial complex Ⅳ. This drives a transition from protumor TAMs to antitumor IFN-associated TAMs (IFN-TAMs) through activation of the cyclic GMP-AMP synthase-stimulator of interferon genes (cGAS-STING) pathway. This mechanism can be leveraged to boost antitumor immunity and improve responses to immune checkpoint blockade.
Read moreAbstract Die Kinetik der Zersetzung wäßriger (′103‐ Lösungen wird unter den Bedingungen der Chlorbleiche von Pulpe (40‐80°C, pH 2‐7), jedoch in Abwesenheit von Pulpe untersucht.
Read moreIn this study, we consider the extended Brinkman's-Darcy model for a triple diffusive convection system which consists of some parameters such as Taylor number (Ta), Solutal Rayleigh numbers (RC1 , RC2 ), and Prandtl number (Pr). To investigate the range of these parameters, a dynamical system of the Ginzburg-Landau equation is developed. The parametric analysis and comparative study of the model for the three Rayleigh numbers which leads to the clear fluid layer, sparsely packed porous layer, and densely packed porous layer is done with the help of bifurcation maps and the Lyapunov exponents. It is found that for a certain range of parameters, the system exhibits a chaotic behaviour.
Read moreGraphene is an ideal sample support for electron microscopy experiments. Its crystalline nature and single atomic thickness make it easy for any objects placed on graphene to be identified and studied. At the same time, these advantages can easily be negated by contamination of the graphene surface, which often occurs during growth and transfer procedures. In this study, we present a new polymer-free transfer method by direct adhesion, which produces contamination-free graphene for sample support in transmission electron microscopy studies. High-angle annular dark-field scanning transmission electron microscopy and convergent beam electron diffraction images of the samples obtained using the new graphene transfer protocol show the absence of any contamination originating from the transfer procedure, and only soft contamination due to hydrocarbons is observed. These observations are supported by simulations of graphene with hydrocarbons. We also compare the new dry transfer method against two other procedures known from the previous literature. The samples prepared using the new direct polymer-free adhesion method demonstrate superior quality when compared to the samples prepared by the two other procedures.
Read moreWe investigate the origin of stereocontrol in asymmetric counteranion-directed photoredox catalysis (ACPC) using a representative [2+2] cycloaddition mediated by a chiral IDPi counteranion (Science 2023, 379, 494–499). Combining extensive conformational sampling, high-level DFT calculations, and multiscale modeling, we elucidate the mechanism and stereochemical landscape of this transformation. Both enantio- and diastereoselectivity are established in the first C–C bond-forming step: diastereoselectivity arises from intrinsic aryl–aryl interactions within the radical cation–styrene pair, whereas enantioselectivity is imposed by the confined chiral environment of the IDPi counteranion. Although electronically silent during the initial photoinduced single-electron transfer, the counteranion anchors the radical cation and organizes its cycloaddition with styrene. Atomic decomposition of the London dispersion (ADLD) and molecular dispersion potential (MDP) analyses reveal that attractive van der Waals forces, shaped by the steric and electronic architecture of the counteranion, promote reactive prealignment of the substrates and selectively stabilize the transition state leading to the major product. Extension to substituted styrenes shows that ring substitution reconfigures the noncovalent contact map within the catalyst pocket, reshaping the energetic balance between competing pathways in line with experiment. These findings provide a unified framework for stereocontrol in chiral ion-pair radical catalysis and offer general strategies for designing asymmetric photoredox transformations.
Read moreBlue natural capital (BNC) markets have the potential to address global environmental crises such as biodiversity and climate emergencies by contributing to the conservation and restoration of marine ecosystems while providing economic benefits to the owners of these ecosystems and the buyers of their services.Philanthropic and official aid fall short of the funding needed to protect and restore BNC.The resulting finance gap for nature, now approaching USD $1 trillion annually, cannot be closed without mobilizing private capital at scale.However, developing nature markets face significant challenges, including the absence of the visible hand (i.e., policy and regulation) and global coordination, along with issues related to market design, valuation, credibility, governance, and social equity.This paper recognizes and explores the complexities of establishing equitable and nature-positive BNC markets that integrate environmental, social, cultural, and economic dimensions to support market development that is both sustainable and inclusive.
Read more5-Hydroxymethylfurfural (HMF) has been efficiently hydrogenated into the highly valuable 5-hydroxymethyltetrahydrofurfural (HMTHF) through the selective hydrogenation of the furan ring using Pd supported on pure silica ITQ-2 zeolite functionalized with amino groups (Pd-NITQ-2). Highly dispersed nanosized Pd nanoparticles were generated on the amino functionalized support, which exhibits high activity and selectivity to HMTHF. Yields up to 97% (99% selectivity) of HMTHF were achieved by working at room temperature under 10 bar hydrogen using ethanol as a solvent. Comparatively, Pd supported over nonfunctionalized ITQ-2 (Pd-ITQ-2) showed 17 times lower activity than Pd-NITQ-2. The IR of CO titration studies showed that on Pd-ITQ-2, catalyst oxophilic Pd species (Pdδ+) are generated, which is related to their lower activity in H2 activation and therefore their lower activity in the hydrogenation of the furan ring with respect to the Pd-NITQ-2 sample. The effect of Pd loading on NITQ-2, as well as the solvent effect, was studied. The optimized catalyst ((1%)-Pd-NITQ-2) was stable and could be reused for seven consecutive cycles, practically maintaining activity and selectivity. Finally, the optimized catalyst was applied to three different two-step cascade processes to obtain tetrahydrofuran substituted Knoevenagel adducts, N-substituted tetrahydrofurfurylamines, and tetrahydrofuran-substituted benzimidazole derivatives.
Read moreWhile existing photovoltaic technologies continue to advance, there are still many exciting opportunities in the area of novel materials. These opportunities arise because there is a substantial need for reducing the costs associated with the preparation and processing of photovoltaics, and because the theoretically possible photovoltaic efficiencies have yet to be achieved in practical devices. Thus it remains reasonable to continue photovoltaic research activity aimed at entirely new approaches to processing and at entirely new materials as the active media. This group identified three areas for further consideration: (a) Nano/molecular composites and hierarchical structures; (b) Organic semiconductors; and (c) Hot carrier devices.
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