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.

We 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. These findings provide a unified framework for stereocontrol in chiral ion-pair radical catalysis and offer general strategies for designing asymmetric photoredox transformations.

One of the major features of the coastal zone is that part of its sea floor receives a significant amount of sunlight and can therefore sustain benthic primary production by seagrasses, macroalgae, microphytobenthos and corals. However, the contribution of benthic communities to the primary production of the global coastal ocean is not known, partly because the surface area where benthic primary production can proceed is poorly quantified. Here, we use a new analysis of satellite (SeaWiFS) data collected between 1998 and 2003 to estimate, for the first time at a nearly global scale, the irradiance reaching the bottom of the coastal ocean. The following cumulative functions provide the percentage of the surface (<i>S</i>) of the coastal zone receiving an irradiance greater than <i>E_z</i> (in mol photons m^&minus;2 d^&minus;1): <br><br> <i>S</i>_Non-polar = 29.61 &minus; 17.92 log₁₀(<i>E_z</i>) + 0.72 log₁₀²(<i>E_z</i>) + 0.90 log₁₀³(<i>E_z</i>) <br><br> <i>S</i>_Arctic = 15.99 &minus; 13.56 log₁₀(<i>E_z</i>) + 1.49 log₁₀²(<i>E_z</i>) + 0.70 log₁₀³(<i>E_z</i>) <br><br> Data on the constraint of light availability on the major benthic primary producers and net community production are reviewed. Some photosynthetic organisms can grow deeper than the nominal bottom limit of the coastal ocean (200 m). The minimum irradiance required varies from 0.4 to 5.1 mol photons m^&minus;2 d^&minus;1 depending on the group considered. The daily compensation irradiance of benthic communities ranges from 0.24 to 4.4 mol photons m^&minus;2 d^&minus;1. Data on benthic irradiance and light requirements are combined to estimate the surface area of the coastal ocean where (1) light does not limit the distribution of primary producers and (2) net community production (<i>NCP</i>, the balance between gross primary production and community respiration) is positive. Positive benthic <i>NCP</i> can occur over 33% of the global shelf area. The limitations of this approach, related to the spatial resolution of the satellite data, the parameterization used to convert reflectance data to irradiance, the lack of global information on the benthic nepheloid layer, and the relatively limited biological information available, are discussed.

In celebration of our 15th anniversary and some of our most popular articles, Mihail Atanasov and Frank Neese reflect on the modelling and examination of paramagnetic molecules, building on two papers in Chemical Science: https://doi.org/10.1039/C2SC20801F &amp; https://doi.org/10.1039/C2SC21394J.

International audience

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.

Abstract 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.

Blue 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.

5-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.

We 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.