bluuebunny/crossref_metadata_2025 huggingface dataset:
Accessible Li Percolation and Extended Oxygen Oxidation Boundary in Rocksalt‐like Cathode Enabled by Initial Li‐deficient Nanostructure
Authors: Jiang Yun‐shan , Yu Fu‐da , Ke Wang , Deng Liang , Xia Yang , Li Xin‐yu , Que Lan‐fang , Zhang Nian , Zhao Lei , Wang Zhen‐bo
Published: April 2023

Disordered rocksalt cathodes have shown attractive electrochemical performance via oxygen redox, but are limited by a necessary Li‐excess level above the percolation threshold (x > 1.09 in LixTM2‐xO2, TM = transition metals) to obtain electrochemical activity. However, a relatively low‐Li content is essential to alleviate excessive oxygen charge compensation in rocksalt oxides. Herein, taking the homogeneous Li2MnO3 and LiMn2O4 as the starting point, disordered rocksalt‐like cathodes are prepared with initial Li‐deficient nanostructures, cation vacancies, and partial spinel‐type structures that provide a solution for the acquisition of fast Li+ percolation channels under Li‐deficient condition. As a result, the prepared sample exhibits high initial discharge capacity (363 mAh g−1) and energy density (1081 Wh kg−1). Advanced spectroscopy and in situ measurements observe highly reversible charge compensation during electrochemical process and assign coupled Mn‐ and O‐related redox contribution. Theoretical calculations also suggest the novel and chemical reversible trapped molecular O2 model in the rocksalt structure with vacancies, demonstrating a dual role of Li‐deficient structure in promoting cationic oxidation and extending reversible oxygen redox boundary. This work is expected to breakthrough the existing ideas of oxygen oxidation and opens up a higher degree of freedom in the design of disordered rocksalt structures.
Optimizing NaF‐Rich Solid Electrolyte Interphase for Stabilizing Sodium Metal Batteries by Electrolyte Additive
Authors: Zhu Chunlei , Wu Daxiong , Wang Zhongsheng , Wang Huaping , Liu Jiandong , Guo Kanglong , Liu Quanhui , Ma Jianmin
Published: April 2023

NaF‐rich electrode–electrolyte interphases play crucial roles in determining the cycling stability of sodium metal batteries (SMBs) because of their electronic insulation and mechanical stability. In this work, perfluorobenzene (PFB) is proposed as the additive to contribute the formation of NaF‐rich solid electrolyte interphases (SEI). PFB at the periphery of the solvation layer can pull out a part of the EC with the lowest solvation energy by Van der Waals forces, thus allowing more to participate in the Na+ solvation layer and form an anion‐aggregated solvation sheath, thus promoting the decomposition of to produce NaF. In addition, PFB has a higher highest occupied molecular orbital and lower lowest unoccupied molecular orbital energy level, which also preferentially decomposes to produce NaF at both electrodes. Benefiting from the intensified NaF ratio in SEI, the Na||Na symmetric cells with such an electrolyte achieves a superior cycling life over 350 h at 1 mA cm−2, and the Na||Na3V2(PO4)2O2F batteries also realize ultrahigh cycling performance with 88.8% capacity retention after 500 cycles.
Dynamically Tunable Subambient Daytime Radiative Cooling Metafabric with Janus Wettability
Authors: Fan Chonghui , Zhang Yuxin , Long Zhiwen , Mensah Alfred , Wang Qingqing , Lv Pengfei , Wei Qufu
Published: April 2023

Incorporating zero‐energy‐input cooling technology into personal thermal management (PTM) systems is a promising solution for preventing heat‐related illnesses while reducing energy consumption. Although concepts for passive radiative cooling materials are proposed, achieving subambient cooling performance while providing good wearing comfort remains a challenge. Here, a moisture‐wicking nonwoven metafabric is reported that assembles radiative cooling and evaporative heat dissipation to achieve high‐performance thermal and moisture comfort management. This metafabric demonstrates excellent spectral‐selectivity (sunlight reflection of ≈92%, atmospheric window thermal emissivity of ≈97%) and Janus wettability through large‐scale electrospinning and hierarchical design, and also inherits superior elasticity, air/moisture permeability of nonwoven fabric. Subambient temperature drops of ≈6.5 °C (≈750 W m−2solar intensity) for stand‐alone metafabric are observed. Thanks to the moisture‐wicking effect (water evaporation rate of 0.31 g h−1and water transport index of 1220%) of metafabric that enables fast evaporation of sweat, a maximum generation of 1 mL h−1of sweat can cool the skin, thus reducing the excessive sweating risk after intense exercise. Additionally, the cooling performance of metafabric can be regulated by applying various strains (0–100%). The cost‐efficiency and good wearability of metafabric provide an innovative way to sustainable energy, smart textiles, and thermal wet comfort applications.
Latest Innovations in 2D Flexible Nanoelectronics
Authors: Aftab Sikandar , Hussain Sajjad , Al‐Kahtani Abdullah A.
Published: April 2023

2D materials with dangling‐bond‐free surfaces and atomically thin layers have been shown to be capable of being incorporated into flexible electronic devices. The electronic and optical properties of 2D materials can be tuned or controlled in other ways by using the intriguing strain engineering method. The latest and encouraging techniques in regard to creating flexible 2D nanoelectronics are condensed in this review. These techniques have the potential to be used in a wider range of applications in the near and long term. It is possible to use ultrathin 2D materials (graphene, BP, WTe2, VSe2 etc.) and 2D transition metal dichalcogenides (2D TMDs) in order to enable the electrical behavior of the devices to be studied. A category of materials is produced on smaller scales by exfoliating bulk materials, whereas chemical vapor deposition (CVD) and epitaxial growth are employed on larger scales. This overview highlights two distinct requirements, which include from a single semiconductor or with van der Waals heterostructures of various nanomaterials. They include where strain must be avoided and where it is required, such as solutions to produce strain‐insensitive devices, and such as pressure‐sensitive outcomes, respectively. Finally, points‐of‐view about the current difficulties and possibilities in regard to using 2D materials in flexible electronics are provided.
Non‐Centrosymmetric 2D Nb3SeI7 with High In‐Plane Anisotropy and Optical Nonlinearity
Authors: Wang Jia‐Peng , Fang Yu‐Qiang , He Wen , Liu Quan , Fu Jie‐Rui , Li Xin‐Yu , Liu Yue , Gao Bo , Zhen Liang , Xu Cheng‐Yan , Huang Fu‐Qiang , Meixner Alfred J. , Zhang Dai , Li Yang
Published: April 2023

Integrating anisotropy and nonlinearity of physical properties in 2D materials is of great importance to the progress of nanoelectronic, nanophotonic, and nano‐optoelectronic applications. In this work, Nb3SeI7, a newly discovered ternary layered material with non‐centrosymmetric lattices, is introduced, which exhibits strong second harmonic generation (SHG), in‐plane anisotropic electricity, and light absorption. Symmetry breaking of 2D Nb3SeI7 induced by the polar off‐center displacement of niobium leads to a high nonlinear optical response with a second‐order susceptibility of 6.71 pm V−1 and a high anisotropic factor of photoresponsivity up to 4.6, which are higher than most of the 2D materials. These properties of 2D Nb3SeI7 create new possibilities for chip‐integrated nonlinear optics devices and future‐proof polarization‐sensitive optoelectronic systems.
Pyrene‐Based Polyimide Covalent Organic Framework with Temperature‐Dependent Fluorescence
Authors: Zadehnazari Amin , Khosropour Ahmadreza , Altaf Ataf Ali , Amirjalayer Saeed , Abbaspourrad Alireza
Published: April 2023

The synthesis of a fluorescent covalent organic framework (COF) using perylene and pyrene building blocks (PEPy‐COF), via a one‐pot condensation reaction is reported. PEPy‐COF is crystallized into 2D nanosheets with a cubic and prismatic crystalline morphology and demonstrates structural stability at temperatures up to 500 °C. The structural morphology is confirmed using X‐ray diffraction and atomic‐level simulations. These 2D porous polymer sheets form a tetragonal framework that is found to have a high specific surface area of 772 m2 g−1. Based on the definition of porous materials, the network is mesoporous with an observed pore size of 3.03 nm, which is in good agreement with the material's calculated pore size. The experimentally obtained HOMO‐LUMO band gap is 2.62 eV, confirming the semiconducting nature of PEPy‐COF. PEPy‐COF emits a shiny blue luminescence under UV and visible light. This luminescence intensity is temperature‐dependent in solvents with different polarities and dielectric constants demonstrating that the PEPy‐COF has potential use in a wide range of temperature‐sensing devices. The fluorescence intensity ratio is similar for different temperatures under ultra‐sound conditions and varying solvents.
High Performance Photorechargeable Li‐Ion Batteries Based on Nanoporous Fe2O3 Photocathodes
Authors: Chamola Shubham , Ahmad Shahab
Published: April 2023

In recent years, photorechargeable Li‐ion batteries (Li‐PRBs) are investigated as potential energy devices to supply continuous power to remote IoT or electronic devices. These Li‐PRBs, due to their lightweight and low‐cost, offers various advantages compared to conventional combination of solar cells and a battery. Single active material‐based PRBs have gained attention due to the use of multifunctional materials which perform both solar energy harvesting and storage, however most of the PRBs studied so far are based on ion intercalation. Herein, the use of conversion type active material α‐Fe2O3 for efficient and stable operation of Li‐PRBs is demonstrated. Cost‐effective solution processing method is used to synthesize α‐Fe2O3 nanorods (NRs), which form nanoporous morphology when blended with Multi‐walled carbon nanotubes / Phenyl‐C61 butyric acid methyl ester (MWCNT/PCBM) conducting additives to form photocathodes. α‐Fe2O3 NRs shown simultaneous solar energy harvesting in visible region of spectra, owing to its energy bandgap Eg ≈ 2.1 eV, and efficient Li‐ion storage via conversion reaction mechanism. Li‐PRB has shown photoconversion and storage efficiency of ≈1.988% when illuminated with blue LED (λex ≈ 470 nm) for large voltage window (0.8–2.57 V). The use of conversion type material like Fe2O3 in PRBs opens up new pathways to explore new materials and mechanisms for these emerging devices.
Giant Switchable Persistent Photoconductivity in Soft Chemistry Reduced SrTiO3
Authors: Gao Tianyi , Nian Leyan , Jin Li , Sun Haoying , Zhang Tingting , Yang Jiangfeng , Gu Zhengbin , Peng Luming , Nie Yuefeng
Published: April 2023

High tunability of photoconductivity is highly desired for applications in optical memories, sensors, and bioelectronics. Recently, room temperature persistent photoconductivity (PPC) in SrTiO3 (STO) has been revealed and has attracted great attention. However, reversible switching of the PPC in STO with a large on/off ratio remains challenging to date. Here, a giant switchable PPC in soft chemistry reduced STO is reported. An initial insulator‐to‐metal transition with on/off ratio up to 7 orders of magnitude is observed and about 5 orders of magnitude transition is found to be reversible. Via nuclear magnetic resonance measurements, it is uncovered that such unusual PPC is driven by the generation of excess carriers accompanied with a configuration evolution of the incorporated hydrogen from hydridic HO+ to protic Hi+ upon illumination. The work demonstrates giant switchable PPC transition in soft chemistry reduced perovskite oxides, providing a new platform for pursuing high performance sensors and nonvolatile optoelectronic memory devices.
Initial compatibility during a “Speed‐Dating” test predicts postpairing affiliation in titi monkeys (Plecturocebus cupreus)
Authors: Baxter Alexander , Lau Allison R. , Savidge Logan E. , Bales Karen L.
Published: April 2023

Behavioral compatibility plays a critical role in shaping how potential mates interact with and evaluate each other and whether they choose to pursue a relationship. Compatibility is especially important for mate choice and relationship quality in pair‐bonding species that form long‐term attachments between mates. Although this process has been studied in humans and birds, relatively few studies have investigated it in non‐human primates. In this study, we investigated whether pairing titi monkeys (Plecturocebus cupreus) based on initial compatibility increased postpairing affiliation between mates. Subjects were 12 unpaired adult titi monkeys (two cohorts of three males and three females). We determined each subject's initial interest in each opposite‐sex potential mate in their cohort across a series of six 30‐min interaction periods (i.e., “speed‐dates”). To determine initial compatibility, we used the Social Relations Model to calculate relationship effects in initial interest (how much each subject uniquely preferred each potential mate beyond their own affiliative disposition and their partner's popularity). We then paired monkeys in a way that maximized net relationship effects between pairs, and measured longitudinal pair affiliation (Proximity, Contact, Tail Twining, and Combined Affiliation) for 6 months postpairing using daily scan‐sample observations and monthly home‐cage video recordings. Multilevel models showed that, on average, the six speed‐dating pairs exhibited higher levels of Tail Twining (determined from scan‐sample observations; β = 0.31) compared to a group of 13 age‐matched colony pairs that were determined quasi‐randomly without quantifying compatibility. The degree of initial compatibility within speed‐dating pairs also predicted higher levels of Combined Affiliation (determined from video recordings) at earlier post‐pairing time points, with the association peaking at 2 months postpairing (β = 0.57). These findings suggest that initial compatibility facilitates pair bonding in titi monkeys. We conclude by discussing how the speed‐dating design can be used for colony management to inform pair‐housing decisions.
Associations of blood cell indices and anemia with risk of incident dementia: A prospective cohort study of 313,448 participants
Authors: Qiang Yi‐Xuan , Deng Yue‐Ting , Zhang Ya‐Ru , Wang Hui‐Fu , Zhang Wei , Dong Qiang , Feng Jian‐Feng , Cheng Wei , Yu Jin‐Tai
Published: April 2023

Introduction

Low hemoglobin and anemia are associated with cognitive impairment and Alzheimer's disease (AD). However, the associations of other blood cell indices with incident dementia risk and the underlined mechanisms are unknown.

Methods

Three hundred thirteen thousand four hundred forty‐eight participants from the UK Biobank were included. Cox and restricted cubic spline models were used to investigate linear and non‐linear longitudinal associations. Mendelian randomization analysis was used to identify causal associations. Linear regression models were used to explore potential mechanisms driven by brain structures.

Results

During a mean follow‐up of 9.03 years, 6833 participants developed dementia. Eighteen indices were associated with dementia risk regarding erythrocytes, immature erythrocytes, and leukocytes. Anemia was associated with a 56% higher risk of developing dementia. Hemoglobin and red blood cell distribution width were causally associated with AD. Extensive associations exist between most blood cell indices and brain structures.

Discussion

These findings consolidated associations between blood cells and dementia.

Highlight

Anemia was associated with 56% higher risk for all‐cause dementia.

Hematocrit percentage, mean corpuscular volume, platelet crit, and mean platelet volume had U‐shaped associations with incident dementia risk.

Hemoglobin (HGB) and red blood cell distribution width had causal effects on Alzheimer's risk.

HGB and anemia were associated with brain structure alterations.
Protein‐Targeted Glycan Editing on Living Cells Disrupts KRAS Signaling
Authors: Li Yiran , Huo Fan , Chen Liusheng , Wang Haiqi , Wu Jianzhuang , Zhang Peiwen , Feng Nan , Li Wei , Wang Lan , Wang Yichun , Wang Xiaojian , Yang Xiaoliang , Lu Zhiqiang , Mao Yang , Yan Chao , Ding Lin , Ju Huangxian
Published: April 2023

The frequent mutation of KRAS oncogene in some of the most lethal human cancers has spurred incredible efforts to develop KRAS inhibitors, yet only one covalent inhibitor for the KRASG12C mutant has been approved to date. New venues to interfere with KRAS signaling are desperately needed. Here, we report a “localized oxidation‐coupling” strategy to achieve protein‐specific glycan editing on living cells for disrupting KRAS signaling. This glycan remodeling method exhibits excellent protein and sugar specificity and is applicable to different donor sugars and cell types. Attachment of mannotriose to the terminal galactose/N‐acetyl‐D‐galactosamine epitopes of integrin αvβ3, a membrane receptor upstream of KRAS, blocks its binding to galectin‐3, suppresses the activation of KRAS and downstream effectors, and mitigates KRAS‐driven malignant phenotypes. Our work represents the first successful attempt to interfere with KRAS activity by manipulating membrane receptor glycosylation.
C−H Activation of Unbiased C(sp3)−H Bonds: Gold(I)‐Catalyzed Cycloisomerization of 1‐Bromoalkynes**
Authors: Miguélez Rubén , Semleit Nina , Rodríguez‐Arias Carlos , Mykhailiuk Pavel , González José M. , Haberhauer Gebhard , Barrio Pablo
Published: April 2023

Selective functionalization of non‐activated C(sp3)−H bonds is a major challenge in chemistry, so functional groups are often used to enhance reactivity. Here, we present a gold(I)‐catalyzed C(sp3)−H activation of 1‐bromoalkynes without any sort of electronic, or conformational bias. The reaction proceeds regiospecifically and stereospecifically to the corresponding bromocyclopentene derivatives. The latter can be readily modified, comprising an excellent library of diverse 3D scaffolds for medicinal chemistry. In addition, a mechanistic study has shown that the reaction proceeds via a so far unknown mechanism: a concerted [1,5]‐H shift / C−C bond formation involving a gold‐stabilized vinylcation‐like transition state.
Applications of ambient ionization mass spectrometry in 2022: An annual review
Authors: Rankin‐Turner Stephanie , Sears Patrick , Heaney Liam M
Published: April 2023

The development of ambient ionization mass spectrometry (AIMS) has transformed analytical science, providing the means of performing rapid analysis of samples in their native state, both in and out of the laboratory. The capacity to eliminate sample preparation and pre‐MS separation techniques, leading to true real‐time analysis, has led to AIMS naturally gaining a broad interest across the scientific community. Since the introduction of the first AIMS techniques in the mid‐2000s, the field has exploded with dozens of novel ion sources, an array of intriguing applications, and an evident growing interest across diverse areas of study. As the field continues to surge forward each year, ambient ionization techniques are increasingly becoming commonplace in laboratories around the world. This annual review provides an overview of AIMS techniques and applications throughout 2022, with a specific focus on some of the major fields of research, including forensic science, disease diagnostics, pharmaceuticals and food sciences. New techniques and methods are introduced, demonstrating the unwavering drive of the analytical community to further advance this exciting field and push the boundaries of what analytical chemistry can achieve.
Engineering Active Sites of 2D Materials for Active Hydrogen Evolution Reaction
Authors: Kim Jeong Hyo , Lee Da Yeon , Ling Ning , Lee Yongjoon , Yang Heejun , Cho Suyeon
Published: April 2023

Hydrogen evolution reaction (HER) is a promising clean and sustainable energy source with zero carbon emissions. Numerous studies have been conducted with versatile low dimensional materials, and the development of highly active electrochemical catalysts for HER is one of the most important applications of the materials in these studies. Despite such extensive research, the physical origin of the active catalytic performance of low dimensional materials remains unclear, and is distinguished from that of classical transition metal‐based catalysts. Here, recent studies on the intrinsic catalytic activity of 2D semimetals are reviewed, particularly among transition metal dichalcogenides (TMDs), highlighting promising strategies for the design of materials to further enhance their catalytic performance. One attractive approach for active HER involves fabricating single‐atom catalysts in the framework of TMDs. The electrochemical reaction at a catalytic atom for hydrogen evolution has typically been described by the Sabatier principle. Recent studies have focused on optimizing the Gibbs free energy for hydrogen adsorption via down‐sizing, alloying, hybridizing, hetero‐structuring, and phase boundary engineering, mostly with TMDs. The unique advantages of TMDs and their derivatives for HER are summarized, suggesting promising research directions for the design of low dimensional electrochemical catalysts for efficient HER and their energy applications.
Organismal form constrains the evolution of complex lever systems in Neotropical cichlid four‐bar linkages
Authors: Arbour Jessica , Rumpp Faith , López‐Fernández Hernán
Published: April 2023

The diversification of functional traits may be limited by the intrinsic constraints of organismal form (i.e., constructional constraints), owing to the differential investment in different anatomical structures. In this study, we test whether overall organismal form impacts the evolution of shape and function in complex lever systems. We examined the relationship between four‐bar shape and overall head shape in two four‐bar linkage systems: the oral‐jaw and hyoid‐neurocranium systems in Neotropical cichlids. We also investigated the strength of form‐function mapping in these four‐bar linkages and the impact of constraining head shape on these correlations. We quantified the shape of the head and two four‐bar linkages using geometric morphometrics and compared these with the kinematic transmission coefficient of each linkage system. The shapes of both linkages were strongly correlated with their mechanical properties, and head shape appears to constrain the shape of both four‐bar linkages. Head shape induced greater integration between the two linkages, was associated with stronger form‐function correlations and higher rates of evolution in biomechanically important features. Head shape constraints may also contribute to a weak but significant trade‐off in linkage kinematics. Elongation of the head and body, in particular, appears to minimize the impact of this trade‐off, possibly through maximizing anterior–posterior space availability. However, the strength of relationships between shape and function, and the impact of head shape differed between the two linkages, with the hyoid four‐bar in general showing stronger form‐function relationships despite being more independent from head shape constraints.
Management of point‐of‐use and point‐of‐entry for regulatory compliance: Survey of state administrators
Authors: Alfredo Katherine , Wilson Madelyn , Roberson Alan
Published: April 2023

The USEPA (United States Environmental Protection Agency) Lead and Copper Rule Revisions allow the use of distributed treatment approaches such as point‐of‐use (POU) and point‐of‐entry (POE) treatment for systems with 10,000 connections or less as a compliance strategy. However, this poses an opportunity for the USEPA to reevaluate system size recommendations for distributed treatment. The current research uses online surveys and semi‐structured interviews (SSIs) to highlight the general sentiment of state regulators managing POU/POE devices and inquiries. Analysis of the 43 survey responses and 13 SSIs revealed that most state regulators described systems of approximately 30–50 connections as the most successful. Resident cooperation, operation and maintenance, monitoring, and the actual implementation of distributed treatment approaches were repeatedly listed as the greatest concerns. As the use of distributed treatment continues to expand, the water sector must devote research efforts to quantitatively determining the drivers of success as well as highlighting clear indicators of potential failure.
What credentials are required for robotic‐assisted surgery in reconstructive and functional urology?
Authors: Harley Frances , Fong Eva , Yao Henry Han‐I , Hashim Hashim , O'Connell Helen E.
Published: April 2023

Introduction

The increasing popularity of robotic assisted surgery (RAS) as it is implemented in to sub specialities poses many challenges to ensuring standards in quality and safety. The area of Reconstructive and Functional Urology (RFU) has a wide range and largely complex heterogeneous procedures. In recent years RFU has started to incorporate RAS as the primary method to undertake these procedures due to improved vision, dexterity, and access to deep cavities. To ensure patient safety majority of institutions maintain minimal requirements to operate using RAS however across specialities and institutions these greatly vary.

Methods

A narrative review of all the relevant papers known to the author was conducted.

Results

Specific challenges facing RFU is the inability to rely on case numbers as a surrogate means to measure competency as well the ongoing consideration of how to differentiate between surgeons with robotic training and those with the clinical experience specific to RFU.

Conclusion

This review explores current models of training and credentialling and assess how it can be adapted to suggest a standardised guideline for RFU to ensure the highest standards of patient care.
Physiologically‐based pharmacokinetic/pharmacodynamic modeling to predict tumor growth inhibition and the efficacious dose of selective estrogen receptor degraders in humans
Authors: Ganti Anjani , Yu Sijia , Sharpnack Danielle , Ingalla Ellen , De Bruyn Tom
Published: April 2023

GDC‐9545 (giredestrant) is a highly potent, nonsteroidal, oral selective estrogen receptor antagonist and degrader that is being developed as a best‐in‐class drug candidate for early‐stage and advanced drug‐resistant breast cancer. GDC‐9545 was designed to improve the poor absorption and metabolism of its predecessor GDC‐0927, for which development was halted due to a high pill burden. This study aimed to develop physiologically‐based pharmacokinetic/pharmacodynamic (PBPK‐PD) models to characterize the relationships between oral exposure of GDC‐9545 and GDC‐0927 and tumor regression in HCI‐013 tumor‐bearing mice, and to translate these PK‐PD relationships to a projected human efficacious dose by integrating clinical PK data. PBPK and Simeoni tumor growth inhibition (TGI) models were developed using the animal and human Simcyp V20 Simulator (Certara) and adequately described each compound's systemic drug concentrations and antitumor activity in the dose‐ranging xenograft experiments in mice. The established PK‐PD relationship was translated to a human efficacious dose by substituting mouse PK for human PK. PBPK input values for human clearance were predicted using allometry and in vitro in vivo extrapolation approaches and human volume of distribution was predicted from simple allometry or tissue composition equations. The integrated human PBPK‐PD model was used to simulate TGI at clinically relevant doses. Translating the murine PBPK‐PD relationship to a human efficacious dose projected a much lower efficacious dose for GDC‐9545 than GDC‐0927. Additional sensitivity analysis of key parameters in the PK‐PD model demonstrated that the lower efficacious dose of GDC‐9545 is a result of improvements in clearance and absorption. The presented PBPK‐PD methodology can be applied to support lead optimization and clinical development of many drug candidates in discovery or early development programs.
[(η5‐CpR)Ge:]+[BArF4]−/O2 – A Sustainable and Efficient Catalytic System for the Hydrosilylation of Selected Olefins
Authors: Fritz‐Langhals Elke
Published: April 2023

The cationic Ge(II) borates [(η5‐CpR)Ge:]+[BArF4]− (CpR=substituted cyclopentadienyl) efficiently catalyze the anti‐Markovnikov hydrosilylation of alkenes in the presence of oxygen which is investigated using the examples of α‐methylstyrene and 1‐hexene. Full conversion is achieved with a minimal amount of 0.01 mol % of the cationic Ge(II) borate even at rt. The effect of oxygen is investigated and quantified by kinetic measurements which demonstrate that oxygen is an activator which interacts directly with the germanium complex. Solvent‐free hydrosilylation conditions are realized by the introduction of a more lipophilic silylated borate counteranion. Thus, the novel catalytic system is an efficient, sustainable and air‐stable catalyst alternative for the established hydrosilylation catalysts based on noble metal complexes.
Hydrolysis of Furfuryl Alcohol to Angelica Lactones and Levulinic Acid over Nb‐based Catalysts
Authors: Faria Vinícius W. , Santos Kryslaine M. A. , Calazans Alannah M. , Fraga Marco A.
Published: April 2023

Levulinic acid and angelica lactones are important building blocks obtained from hemicellulose. This process comprises multiple chemical reactions at which furfuryl alcohol is an intermediate, but only few studies have investigated its hydrolysis. This work studied the role played by the nature of acid sites and the impact of their strength and amount on furfuryl alcohol hydrolysis over Nb2O5 and NbOPO4. It was disclosed that production of levulinic acid is a two‐step cascade reaction at which angelica lactones are intermediates. These two hydrolysis steps were catalyzed by Brønsted acid sites with no contribution from Lewis centers. Brønsted acidity of Nb2O5 presented no activity while phosphate moieties on NbOPO4 were effective. Mixtures of organic solvent and water hindered side reactions, improving selectivity to valued bioproducts. 1,4‐dioxane was the most suitable organic solvent. This study shows that selectivity of 96 % of levulinic acid and angelica lactones can be accomplished over NbOPO4.
Antitumor Activity and Reductive Stress by Platinum(II) N‐Heterocyclic Carbenes based on Guanosine**
Authors: Leitão Maria Inês P. S. , Turos‐Cabal Maria , Sanchez‐Sanchez Ana Maria , Gomes Clara S. B. , Herrera Federico , Martin Vanesa , Petronilho Ana
Published: April 2023

Platinum(II) complexes bearing N‐heterocyclic carbenes based guanosine and caffeine have been synthesized by unassisted C−H oxidative addition, leading to the corresponding trans‐hydride complexes. Platinum guanosine derivatives bearing triflate as counterion or bromide instead of hydride as co‐ligand were also synthesized to facilitate correlation between structure and activity. The hydride compounds show high antiproliferative activity against all cell lines (TC‐71, MV‐4‐11, U‐937 and A‐172). Methyl Guanosine complex 3, bearing a hydride ligand, is up to 30 times more active than compound 4, with a bromide in the same position. Changing the counterion has no significant effect in antiproliferative activity. Increasing bulkiness at N7, with an isopropyl group (compound 6), allows to maintain the antiproliferative activity while decreasing toxicity for non‐cancer cells. Compound 6 leads to an increase in endoplasmic reticulum and autophagy markers on TC71 and MV‐4‐11 cancer cells, induces reductive stress and increases glutathione levels in cancer cells but not in non‐cancer cell line HEK‐293.
Ultralong Organic Phosphorescence of Triazatruxene Derivatives for Dynamic Data Encryption and Anti‐counterfeiting
Authors: Liang Baoshuai , An Wei , Liu Jie , Dong Yu , Feng Shiyu , Huang Weiguo
Published: April 2023

Comprehensive Summary

Organic luminogens with persistent room temperature phosphorescence (RTP) have drawn tremendous attentions due to their promising potentials in optoelectronic devices, information storage, biological imaging, and anti‐counterfeiting. In this work, six triazatruxene‐based lumiogens with different peripheral substituents and configurations are synthesized and systematically studied. The results show that their fluorescence quantum yields in solid states range from 15.73% to 37.58%. Dispersing the luminogens as guest into the host (PPh3) could turn on the persistent RTP, where PPh3 acts as not only a rigid matrix to suppress the non‐radiative transitions of the guest, but also provides energy transfer channels to the guest. The maximum phosphorescence efficiency and the longest lifetime could reach 29.35% and 0.99 s in co‐crystal films of 6‐TAT‐CN/PPh3 and 5‐TAT‐H/PPh3, respectively. Moreover, these host‐guest co‐crystalline films exhibit great potentials in advanced dynamic data encryption and anti‐counterfeiting. This work deepens the insight for low cost, halogen‐free, and facile fabrication of all‐organic persistent RTP materials.
Interaction of CO2 with MnOx/Pd(111) Reverse Model Catalytic Interfaces
Authors: Anil Arca , Sadak Omer Faruk , Karakurt Bartu , Kocak Yusuf , Lyubinetsky Igor , Ozensoy Emrah
Published: April 2023

Understanding the activation of CO2 on the surface of the heterogeneous catalysts comprised of metal/metal oxide interfaces is of critical importance since it is not only a prerequisite for converting CO2 to value‐added chemicals but also often, a rate‐limiting step. In this context, our current work focuses on the interaction of CO2 with heterogeneous bi‐component model catalysts consisting of small MnOx clusters supported on the Pd(111) single crystal surface. These metal oxide‐on‐metal ‘reverse’ model catalyst architectures were investigated via temperature programmed desorption (TPD) and x‐ray photoelectron spectroscopy (XPS) techniques under ultra‐high vacuum (UHV) conditions. Enhancement of CO2 activation was observed upon decreasing the size of MnOx nanoclusters by lowering the preparation temperature of the catalyst down to 85 K. Neither pristine Pd(111) single crystal surface nor thick (multilayer) MnOx overlayers on Pd(111) were not capable of activating CO2, while CO2 activation was detected at sub‐monolayer (∼0.7 ML) MnOx coverages on Pd(111), in correlation with the interfacial character of the active sites, involving both MnOx and adjacent Pd atoms.
Degradation of Polyvinyl Chloride by Sequential Dehydrochlorination and Olefin Metathesis
Authors: Skelly Patrick W. , Chang Chayo Fuentes , Braslau Rebecca
Published: April 2023

Polyvinyl chloride (PVC) is a problematic waste plastic with limited options for recycling or upcycling. Herein, we demonstrate preliminary results in breaking down the long carbon chains of PVC into oligomers and small organic molecules. First, treatment with a substoichiometric amount of alkali base effects elimination of HCl to form a salt and creates regions of conjugated carbon‐carbon double bonds, as determined by 1H NMR and UV‐Vis spectroscopy. Olefin cross metathesis with an added partner alkene then cleaves carbon‐carbon double bonds of the polymer backbone. Addition of allyl alcohol to the dehydrochlorination step introduces allyloxy groups by substitution of allylic chlorides. Subsequent metathesis of the pendant allyloxy groups provides a reactive terminal alkene to promote insertion of the metathesis catalyst onto the olefins in the all‐carbon backbone. The products obtained are a mixture of PVC oligomers with greatly reduced molecular weights and a small‐molecule diene corresponding to the substituents of the added alkene, as evidenced by 1H and DOSY NMR and GPC. This mild procedure provides a proof of concept towards harvesting carbon resources from PVC waste.
Multitrait selection in seedless grape hybrids in semiarid regions of Brazil
Authors: de Carvalho Jullyanna Nair , de Carvalho Pollyanna Aparecida , Pio Rafael , Barbosa Maria Angélica Guimarães , Leão Patrícia Coelho de Souza
Published: April 2023

The absence of seeds has been one of the most valued traits in grapes (Vitis spp.) for fresh consumption. However, the simultaneous selection of superior genotypes for multiple traits is complex. The objective of this study was to select genotypes of superior seedless table grapes in semiarid regions of Brazil. Multiple traits were considered by using the factor analysis and genotype–ideotype best linear unbiased prediction (FAI‐BLUP) selection index. A total of 110 grape progenies from 24 crosses were evaluated for traits of agronomic interest. Each hybrid was represented by a single vine plant, without experimental design or repetition. The mixed‐model methodology was used to predict the breeding values. The FAI‐BLUP index was used to select superior genotypes based on factor analysis and the genotype–ideotype distance. Four factors explained the 11 characteristics studied, with a variability of 81.84%. Desirable gains were observed for 10 of the 11 traits evaluated. The FAI‐BLUP index allowed the selection of superior seedless table grape hybrids, which can be used in the genetic improvement of grapevines. In conclusion, we report the selection of seedless table grape hybrids for our study to advance in the table grape breeding program in Brazilian semiarid regions.
The potential of trait data to increase the availability of bioindicators: A case study using plant conservatism values
Authors: Crisfield Varina E. , Ficken Cari D. , Allen Brandon E. , Jog Suneeti K. , Bried Jason T.
Published: April 2023

Biological indicators are commonly used to evaluate ecosystem condition. However, their use is often constrained by the availability of information with which to assign species‐specific indicator values, which reflect species' responses to the environmental conditions being evaluated by the indicator. As these responses are driven by underlying traits, and trait data for numerous species are available in publicly accessible databases, one possible approach to approximating missing bioindicator values is through traits. We used the Floristic Quality Assessment (FQA) framework and its component indicator of disturbance sensitivity, species‐specific ecological conservatism scores (C‐scores), as a study system to test the potential of this approach. We tested the consistency of relationships between trait values and expert‐assigned C‐scores and the trait‐based predictability of C‐scores across five regions. Furthermore, as a proof‐of‐concept exercise, we used a multi‐trait model to try to reconstruct C‐scores, and compared the model predictions to expert‐assigned scores. Out of 20 traits tested, there was evidence of regional consistency for germination rate, growth rate, propagation type, dispersal unit, and leaf nitrogen. However, the individual traits showed low predictability (R2 = 0.1–0.2) for C‐scores, and a multi‐trait model produced substantial classification errors; in many cases, >50% of species were misclassified. The mismatches may largely be explained by the inability to generalize regionally varying C‐scores from geographically neutral/naive trait data stored in databases, and the synthetic nature of C‐scores. Based on these results, we recommend possible next steps for expanding the availability of species‐based bioindication frameworks such as the FQA. These steps include increasing the availability of geographic and environmental data in trait databases, incorporating data about intraspecific trait variability into these databases, conducting hypothesis‐driven investigations into trait–indicator relationships, and having regional experts review our results to determine if there are patterns in the species that were correctly or incorrectly classified.
Projected northward shifts in eastern red‐backed salamanders due to changing climate
Authors: Hedrick Brandon P. , Estrada Alba , Sutherland Chris , Barbosa A. Márcia
Published: April 2023

Many species' distributions are being impacted by the acceleration of climate change. Amphibians in particular serve numerous ecosystem functions and are useful indicators of environmental change. Understanding how their distributions have been impacted by climate change and will continue to be impacted is thus important to overall ecosystem health. Plethodon cinereus (Eastern Red‐Backed Salamander) is a widespread species of lungless salamander (Plethodontidae) that ranges across northeastern North America. To better understand future potential lungless salamander range shifts, we quantify environmental favorability, the likelihood of membership in a set of sites where environmental conditions are favorable for a species, for P. cinereus in multiple time periods, and examine shifts in the species' distribution. First, utilizing a large data set of georeferenced records, we assessed which bioclimatic variables were associated with environmental favorability in P. cinereus. We then used species distribution modeling for two time periods (1961–1980 and 2001–2020) to determine whether there was a regional shift in environmental favorability in the past 60 years. Models were then used to project future distributions under eight climate change scenarios to quantify potential range shifts. Shifts were assessed using fuzzy logic, avoiding thresholds that oversimplify model predictions into artificial binary outputs. We found that P. cinereus presence is strongly associated with environmental stability. There has been a substantial northward shift in environmental favorability for P. cinereus between 1961–1980 and 2001–2020. This shift is predicted to continue by 2070, with larger shifts under higher greenhouse gas emission scenarios. As climate change accelerates, it is differentially impacting species but has especially strong impacts on dispersal‐limited species. Our results show substantial northward shifts in climatic favorability in the last 60 years for P. cinereus, which are likely to be exacerbated by ongoing climate change. Since P. cinereus is dispersal‐limited, these models may imply local extirpations along the southern modern range with limited northward dispersal. Continued monitoring of amphibians in the field will reveal microclimatic effects associated with climate change and the accuracy of the model predictions presented here.
Dynamics of circulating lymphocytes responding to human experimental enterotoxigenic Escherichia coli infection
Authors: Rim Sehee , Sakkestad Sunniva T. , Zhou Fan , Gullaksen Stein‐Erik , Skavland Jørn , Chauhan Sudhir K. , Steinsland Hans , Hanevik Kurt
Published: April 2023

Enterotoxigenic Escherichia coli (ETEC) is an important cause of children's and travelers’ diarrhea, with no licensed vaccine. This study aimed to explore the role of cellular immunity in protection against human ETEC infection. Nine volunteers were experimentally infected with ETEC, of which six developed diarrhea. Lymphocytes were collected from peripheral blood buffy coats, before and 3, 5, 6, 7, 10, and 28 days after dose ingestion, and 34 phenotypic and functional markers were examined by mass cytometry. Thirty‐three cell populations, derived by manually merging 139 cell clusters from the X‐shift unsupervised clustering algorithm, were analyzed. Initially, the diarrhea group responded with increased CD56dim CD16+ natural killer cells, dendritic cells tended to rise, and mucosal‐associated invariant T cells decreased. On day 5‐7, an increase in plasmablasts was paralleled by a consistent rise in CD4+ Th17‐like effector memory and regulatory cell subsets. CD4+ Th17‐like central memory cells peaked on day 10. All Th17‐like cell populations showed increased expression of activation, gut‐homing, and proliferation markers. Interestingly, in the nondiarrhea group, these same CD4+ Th17‐like cell populations expanded earlier, normalizing around day 7. Earlier development of these CD4+ Th17‐like cell populations in the nondiarrhea group may suggest a recall response and a potential role in controlling ETEC infections.
The Role of Sulfur in the S‐PtRe/Al2O3 Catalysts: The Endogenous Deposition Effect on the Metal/acid Micro‐environment
Authors: Miao Chenglin , Zhang Fengyu , Yang Yanpeng , Wang Tao , Zang Gaoshan , Wang Jieguang
Published: April 2023

Alumina is widely used as support in the industrial catalytic process. As a common impurity, the sulfur species, which are often considered a harmful component, play a positive role in some petrochemical reactions. Herein, the S‐modified catalysts were fabricated using the exogenous/endogenous deposition method to study the effect of the sulfur induced by introduction approaches. Series characterizations reveal that the exogenous sulfur from the sulfidation treatment affects the active metals by poisoning the low‐coordinated sites, leading to the active metal sites decrease. As for the endogenous deposition method, besides the poison effect, the removal of the endogenous sulfur from the S‐contain alumina support can produce oxygen vacancies, which can not only act as acid sites but work as an electron acceptor that optimizes the catalyst electronic structure. Benefits from the effect of endogenous sulfur, the catalyst with a suitable catalytic metal/acid micro‐environment exhibit the best dehydrocyclization performance.
Reactivity of a Free Aluminylene towards Boron Lewis Acids: Accessing Aluminum‐Boron‐Bonded Species
Authors: Zhang Xin , Liu Liu Leo
Published: April 2023

The reactivity of the free aluminylene [N]‐Al (1) ([N]=1,8‐bis(3,5‐di‐tert‐butylphenyl)‐3,6‐di‐tert‐butylcarbazolyl) towards boron Lewis acids is investigated. A facile oxidative addition reaction of 1 with Ph2BOBPh2 furnishes an exceedingly scarce example of the free alumaborane [N]‐Al(BPh2)(OBPh2) (2) with an Al−B electron‐sharing bond. By contrast, complexation of 1 with B(C6F5)3 and HB(C6F5)2 gives rise to the corresponding Lewis adducts [N]‐Al→B(C6F5)3 (3) and [N]‐Al→BH(C6F5)2 (4), respectively, with an Al→B dative bond. Crystallization of 4 in Et2O produces the adduct [N]‐Al(Et2O)→BH(C6F5)2 (5). Quantum chemical calculations are carried out to understand the formation of 2 as well as the bonding situation of 3 and 5.
Dihydroazulene‐Boron Subphthalocyanine Conjugates with Oligo(phenyleneethynylene) Bridging Unit: Photoswitchable Fluorophores
Authors: Bukuroshi Esmeralda , Ugleholdt Petersen Anne , Jensen Cecilie , Kirkholt Lund Mathias , Kühnel Martin , Nørgaard Kasper , Bender Timothy P. , Brøndsted Nielsen Mogens
Published: April 2023

In this work, we have linked the dihydroazulene (DHA)/vinylheptafulvene (VHF) photo‐/thermoswitch and the boron subphthalocyanine (BsubPc) fluorophore via an axial oligo(phenyleneethynylene) bridging unit into new DHA‐BsubPc conjugates. The objectives were to elucidate the influence of BsubPc on the DHA/VHF switching reactions and the influence of DHA/VHF on the BsubPc fluorescence in these conjugates for which the entire axial substituent connected to boron comprises one large, conjugated scaffold. We present the synthesis and properties of DHA‐BsubPc conjugates with varying peripheral substituents on the BsubPc core, being either unsubstituted (H12BsubPc) or partially fluorinated (F6BsubPc). Fluorination of the BsubPc core provided a remarkable increase in the reversibility of the DHA‐VHF interconversions promoted by light and heat, respectively, and accompanied by on/off switching of the BsubPc fluorescence. Synthetically, the units were connected using Sonogashira coupling reactions of suitable acetylenic building blocks.