bluuebunny/crossref_metadata_2025 huggingface dataset:
Controlling the Fate of Roxarsone and Inorganic Arsenic in Poultry Litter
Authors: Makris Konstantinos C. , Salazar Jason , Quazi Shahida , Andra Syam S. , Sarkar Dibyendu , Bach Stephan B. H. , Datta Rupali
Published: May 2008

A growing body of literature reports 3‐nitro‐4‐hydroxyphenylarsonic acid (roxarsone) degradation in poultry litter (PL) to the more toxic inorganic arsenic (As). Aluminum‐based drinking‐water treatment residuals (WTR) present a low‐cost amendment technology to reduce As availability in PL, similar to the use of alum to reduce phosphorus availability. Batch experiments investigated the effectiveness of WTR in removing roxarsone and inorganic As species from PL aqueous suspensions. Incubation experiments with WTR‐amended PL evaluated the effects of WTR application rates (2.5–15% by weight) and incubation time (up to 32 d) at two incubation temperatures (23 and 35°C) on As availability in PL. Batch PL aqueous experiments showed the high affinity of As(V), As(III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), and roxarsone for the WTR. The 10% WTR amendment rate decreased As availability in PL by half of that of the unamended (no WTR) PL‐incubated samples. The reduction in dissolved As concentrations during incubation of WTR‐amended PL samples was kinetically limited, being complete within 13 d. Parallel reductions in roxarsone, As(V), and DMA concentrations were observed with liquid chromatography–inductively coupled plasma mass spectrometry, whereas As(III) and MMA concentrations were always <5% of dissolved As. Incubation temperature did not significantly (p > 0.05) influence dissolved As concentrations in the WTR‐amended PL. Potential formation of a copper‐containing roxarsone metabolite was considered in PL aqueous suspensions with the aid of electrospray mass spectrometry. Further experiments in the field are necessary to ensure that sorbed As is stable in WTR‐amended PL.
Effect of Land Cover Data on Nitrous Oxide Inventory in Fen Meadows
Authors: Nol Linda , Verburg Peter H. , Heuvelink Gerard B. M. , Molenaar Karin
Published: May 2008

Landscape representations based on land cover databases differ significantly from the real landscape. Using a land cover database with high uncertainty as input for emission inventory analyses can cause propagation of systematic and random errors. The objective of this study was to analyze how different land cover representations introduce systematic errors into the results of regional N2O emission inventories. Surface areas of grassland, ditches, and ditch banks were estimated for two polders in the Dutch fen meadow landscape using five land cover representations: four commonly used databases and a detailed field map, which most closely resembles the real landscape. These estimated surface areas were scaled up to the Dutch western fen meadow landscape. Based on the estimated surface areas agricultural N2O emissions were estimated using different inventory techniques. All four common databases overestimated the grassland area when compared to the field map. This caused a considerable overestimation of agricultural N2O emissions, ranging from 9% for more detailed databases to 11% for the coarsest database. The effect of poor land cover representation was larger for an inventory method based on a process model than for inventory methods based on simple emission factors. Although the effect of errors in land cover representations may be small compared to the effect of uncertainties in emission factors, these effects are systematic (i.e., cause bias) and do not cancel out by spatial upscaling. Moreover, bias in land cover representations can be quantified or reduced by careful selection of the land cover database.
Extraction of copper ions using silica gel with chemically modified surface
Authors: Rykowska Iwona , Wasiak Wiesław , Byra Joanna
Published: May 2008

The applicability of silica gels for the application in solid-phase extraction was tested. Silica was modified with ketoimine groups. Surface characteristics of the modified silica were determined by elemental analysis, NMR spectra of solid phases (29Si CP MAS NMR), analysis of pore size distribution of the silica support, and nitrogen adsorption-desorption. Newly proposed sorbents with ketoimine groups were applied in the preconcentration of trace amounts of the Cu (II) ions from lake water, post-industrial water, and demineralized water unburdened back to the lake.
Efficient cyclodehydration of diethylene glycol in Brønsted acidic ionic liquids
Authors: Wang Yuan-Yuan , Li Wei , Dai Li-Yi
Published: May 2008

Cyclodehydration of diethylene glycol using various Brønsted acidic ionic liquids as dual solvent-catalysts has been studied for the first time. Better results were obtained in the presence of 1-butyl-3-methylimidazolium hydrogen sulfate ([PSmim]HSO4) compared with other Brønsted acidic ionic liquids. Effects of the reaction conditions such as reaction temperature, reaction time and molar ratio of ionic liquid to diethylene glycol have been investigated. High diethylene glycol conversion, 97.0 %, and high 1,4-dioxane selectivity, 89.3 %, were obtained in [PSmim]HSO4 under optimum conditions. Hammett method was used to determine the acidity order of these ionic liquids and the results were consistent with the catalytic activities observed in the cyclodehydration reaction. Utilization of Brønsted acidic ionic liquids as dual solvent-catalysts has some advantages, e.g. high conversion of DEG, easy preparation and reuse of ionic liquids, avoiding toxic catalysts and solvents.
Strengthening the Role of the NIH in the Firearm Violence Epidemic
Authors: Richmond Therese S. , Hargarten Stephen W. , Rivara Frederick P.
Published: April 2024

This Viewpoint discusses the potential for the National Institutes of Health (NIH), the premier research entity in the world, to significantly strengthen its investment in preventing and reducing firearm-related harms.
Treatment centers increasingly open to adding mental health operations
Authors: Enos Gary
Published: April 2024

A growing number of traditionally addiction‐only treatment organizations are at least discussing if not implementing the addition of mental health treatment services, in some cases for individuals without a substance use disorder (SUD) diagnosis. In doing so, they find themselves needing to grapple with numerous challenges around staffing, assessment, payment and the ideal structure under which to add mental health care.
To achieve drug abstinence, all patients stopped drinking alcohol
Authors: Knopf Alison
Published: April 2024

A combination of residential treatment for substance use disorders (SUDs) and the cessation of drinking resulted in increased abstinence rates from drugs in general, a recent study of “situational factors” linked to abstinence from drugs has found. In addition, even for patients not in residential treatment, employment and the cessation of drinking were linked to increased abstinence rates. The patients in the study excluded those with alcohol use disorders (AUD). The study was conducted in Japan, where drug use is illegal and strictly enforced.
Exceptional Alignment in a Donor–Acceptor Conjugated Polymer via a Previously Unobserved Liquid Crystal Mesophase
Authors: Schrickx Harry M. , Kashani Somayeh , Buck Lauren , Ding Kan , Rech Jeromy J. , Flagg Lucas Q. , Li Ruipeng , Kudenov Michael W. , You Wei , Richter Lee J. , Ade Harald , O'Connor Brendan T.
Published: April 2024

Orienting polymer semiconductors is desirable to optimize device characteristics, provide insight into microstructure, and magnify subtle phase behavior. Here, a combination of uniaxial strain and subsequent heating of the donor–acceptor (DA) polymer PBnDT‐FTAZ is discovered to lead to exceptional optical dichroic ratios of up to 38 (and close to 50 near the polymer's absorption edge). This alignment is achieved due to the existence of a previously undetected thermotropic liquid crystal (LC) mesophase. The LC transition, not discernable through calorimetry, is uncovered through a combination of in situ UV–vis spectroscopy, X‐ray scattering, and dynamic mechanical analysis (DMA). Comparing PBnDT‐FTAZ to the non‐fluorinated PBnDT‐HTAZ and the homo polymer PBnDT, all of which show similar thermal transitions, reveals that exceptional alignment is only found in PBnDT‐FTAZ. This is attributed to the PBnDT‐FTAZ film having two distinct liquid crystal populations, and the polymer templating to a highly aligned, high‐clearing temperature population when heated. The DMA thermal relaxation behavior observed here is also seen in other DA conjugated polymers suggesting that such thermotropic LC mesophases may be common in these materials. These findings demonstrate a polymer semiconductor with remarkable alignment and uncover phase behavior with broad implications for process‐structure‐property relationships in polymer semiconductors.
Visualizing Structure, Growth, and Dynamics of Li Dendrite in Batteries: From Atomic to Device Scales
Authors: Li Yonghe , Xu Hui , Ning Qiaoru , Li Shiting , Wang Jing , Wang Jiexin , Hu Zhongting , Tian Jinshu , Li Xiaonian , Han Yu , Zhu Yihan
Published: April 2024

The growth of lithium (Li) dendrites, characterized by construction of internal Li substrate and surface solid electrolyte interphase (SEI), represents a significant hurdle for both liquid‐state and solid‐state Li batteries. To better understand the growth behaviors of these dendrites at atomic to device scale, advanced electron microscopy techniques have emerged as a valuable tool, providing high temporal and spatial resolutions for real‐time observations. In this review, the mechanistic aspects of growth of Li dendrites are delved first from both thermodynamic and kinetic perspectives. Then, a systematic overview of the state‐of‐the‐art in‐situ devices is provided that is developed for integration into electron microscopes, detailing the corresponding static and dynamic structures of Li dendrites. Additionally, the utilization of the non‐destructive cryogenic TEM technique is explored to classify and compare the local fine structure information of as‐formed Li deposits, which are influenced by various factors such as current density, temperature, electrolyte composition, solvents, and additives. Overall, this review article offers a comprehensive understanding of the physical origins associated with Li dendrites, spanning from atomic to device scales and encompassing both liquid and all‐solid‐state battery scenarios, then envisioning fundamental principles and strategies for optimizing batteries and overcoming the critical challenges posed by Li dendrites.
Evolutionary Games‐Assisted Synchronization Metasurface for Simultaneous Multisource Invisibility Cloaking
Authors: Huang Min , Zheng Bin , Li Ruichen , Shen Lian , Li Xiaofeng , Lu Huan , Zhu Rongrong , Cai Tong , Chen Hongsheng
Published: April 2024

The realization of a metasurface cloak for the simultaneous invisibility of multiple sources presents a long‐standing scientific challenge. Ideally, for the establishment of a simultaneous multisource invisibility cloak, the metasurface must provide a wide phase coverage and angular stability in a single architecture, especially for broadband, wide‐angle, and even omnidirectional scenarios. However, achieving this goal has proven to be elusive thus far. Current approaches for implementing metasurface‐based invisibility cloak involve both active and passive metasurface. These approaches often rely on phase‐compensation mechanisms, which inevitably encounter issues related to limited incidence angles or narrow working bands. Here, a novel paradigm of synchronization metasurface optimized through an evolution‐optimization strategy, enabling the realization of simultaneous multisource invisibility cloaking, is proposed. The underlying physics of the synchronization metasurface relies on an evolution‐optimization strategy (an evolutionary game algorithm), which is used to get rid of the entanglement between incident directions, frequencies, and metasurface phase gradients. Consequently, the synchronization metasurface is capable of manipulating simultaneous incoming waves at any angle over a wide range (cloak). In experimental validation, the synchronization metasurface demonstrates an impressive capability to cloak both single and simultaneous double sources in any direction, highly resembling background fields.
A Superhuman Sensing Triboelectric Nanogenerator with Boosted Power Density and Durability via a Bio‐Inspired Janus Structure
Authors: Jin Chun , Zhang Chen , Yan Pengfei , Jiang Mengqi , Yin Rui , Li Kang , Zhao Weiwei , Bai Ziqian
Published: April 2024

Triboelectric nanogenerators (TENG) not only enable sustainable self‐powered sensing of devices, but also have superhuman noncontact/contact identification capabilities, which are propelling humanity toward the intelligent era. However, the inherently low dielectric constant of triboelectric materials as well as the mechanical mismatch between electrodes and dielectric materials severely limited their efficient and stable output performance. Taking inspiration from the asymmetric structure and function of human skin, a novel single‐electrode TENG is developed, whose electrode and dielectric layer are integrated in a Janus architecture. By tuning the balance between gravity and the internal noncovalent interactions, gradient dispersion of carbon nanotubes in waterborne polyurethane networks can be feasibly achieved, which can boost the device performance by reinforcement in both the charge trapping capacity of the dielectric layer and the charge transfer of the electrode layer. As a proof‐of‐concept, triboelectric sensing and deep learning are integrated to realize the evolution from perception to identification under both noncontact (motion prediction) and contact (material identification) modes. The bionic design strategy of gradient Janus film can offer valuable insights into improving the output performance and durability of TENG. Additionally, the proximal prediction and tactile identification functions are also desirable attempts for future human‐machine interfaces.
Correlating Graphite Surface with Interphase for Fast‐Charging and Low‐Temperature Operation
Authors: Yin Yue , Peng Yu , Chen Jiawei , Wang Yonggang , Dong Xiaoli , Xia Yongyao
Published: April 2024

The properties of graphite surface can not only affect the interaction between graphite and electrolyte but also induce the formation of solid electrolyte interphase (SEI) film. Herein, the graphite surface is purposely treated to incorporate oxygen‐containing functional groups, which facilitates a desired Li2CO3‐rich SEI with high ionic conductivity and good mechanical stability. The modified graphite electrodes exhibit significant enhancement in electrochemical performance during rapid charging at the rate of 15 C, where an impressive capacity of 225 mAh g−1 is still maintained, corresponding to a capacity retention of 60.8%. Moreover, the modified electrodes showcase outstanding performance under wide temperature ranging from −50 to +65 °C, with an amazing capacity retention of 97.6% under −20 °C, the conceivable capacity of 105 mAh g−1 at −50 °C as well as excellent stability at both −20 °C and +65 °C. These findings offer valuable insights into the design of a thin and robust Li2CO3‐rich SEI layer via a facile chemical treatment of the graphite surface.
A Novel Coacervate Embolic Agent for Tumor Chemoembolization
Authors: Liu Menghui , Sun Yang , Zhou Yitong , Chen Yanlv , Yu Meng , Li Liujun , Yan Leye , Yuan Yajun , Chen Jiayao , Zhou Kaixiang , Shan Hong , Peng Xin
Published: April 2024

Transcatheter arterial chemoembolization (TACE) has proven effective in blocking tumor‐supplied arteries and delivering localized chemotherapeutic treatment to combat tumors. However, traditional embolic TACE agents exhibit certain limitations, including insufficient chemotherapeutic drug‐loading and sustained‐release capabilities, non‐biodegradability, susceptibility to aggregation, and unstable mechanical properties. This study introduces a novel approach to address these shortcomings by utilizing a complex coacervate as a liquid embolic agent for tumor chemoembolization. By mixing oppositely charged quaternized chitosan (QCS) and gum arabic (GA), a QCS/GA polymer complex coacervate with shear‐thinning property is obtained. Furthermore, the incorporation of the contrast agent Iohexol (I) and the chemotherapeutic doxorubicin (DOX) into the coacervate leads to the development of an X‐ray‐opaque QCS/GA/I/DOX coacervate embolic agent capable of carrying drugs. This innovative formulation effectively embolizes the renal arteries without recanalization. More importantly, the QCS/GA/I/DOX coacervate can successfully embolize the supplying arteries of the VX2 tumors in rabbit ear and liver. Coacervates can locally release DOX to enhance its therapeutic effects, resulting in excellent antitumor efficacy. This coacervate embolic agent exhibits substantial potential for tumor chemoembolization due to its shear‐thinning performance, excellent drug‐loading and sustained‐release capabilities, good biocompatibility, thrombogenicity, biodegradability, safe and effective embolic performance, and user‐friendly application.
pH‐Triggered Transformable Peptide Nanocarriers Extend Drug Retention for Breast Cancer Combination Therapy
Authors: Yuan Xiaomeng , Liu Xiaoying , Li Hongjie , Peng Shan , Huang Haiqin , Yu Zhe , Chen Limei , Liu Xinlu , Bai Jingkun
Published: April 2024

Increasing the penetration and accumulation of antitumor drugs at the tumor site are crucial in chemotherapy. Smaller drug‐loaded nanoparticles (NPs) typically exhibit increased tumor penetration and more effective permeation through the nuclear membrane, whereas larger drug‐loaded NPs show extended retention at the tumor site. In addition, cancer stem cells (CSCs) have unlimited proliferative potential and are crucial for the onset, progression, and metastasis of cancer. Therefore, a drug‐loaded amphiphilic peptide, DDP‐ and ATRA‐loaded Pep1 (DA/Pep1), is designed that self‐assembles into spherical NPs upon the encapsulation of cis‐diamminedichloroplatinum (DDP) and all‐trans retinoic acid (ATRA). In an acidic environment, DA/Pep1 transforms into aggregates containing sheet‐like structures, which significantly increases drug accumulation at the tumor site, thereby increasing antitumor effects and inhibiting metastasis. Moreover, although DDP treatment can increase the number of CSCs present, ATRA can induce the differentiation of CSCs in breast cancer to increase the therapeutic effect of DDP. In conclusion, this peptide nanodelivery system that transforms in response to the acidic tumor microenvironment is an extremely promising nanoplatform that suggests a new idea for the combined treatment of tumors.
Flexible Electromagnetic Tactile Sensor Based on Double‐Layer High‐Density MEMS Coils and Tilted Magnetic Column Array
Authors: Liu Jianjun , Hou Xiaojuan , Liu Juan , Bi Xiaoxue , Wu Hui , Zhang Jie , Niu Lixin , Chen Wei , He Jian , Chou Xiujian
Published: April 2024

With the rapid development of wearable devices, tactile sensors have received extensive attention as supplements to vision and hearing. However, it remains challenging for a single tactile sensor to generate distinguishable electrical signals when receiving mechanical stimuli in different directions. Herein, a novel flexible electromagnetic tactile sensor (FETS) prepared by combining flexible double‐layer coils and a flexible tilted magnetic column array (TMCA) is presented. Flexible double‐layer high‐density coils are fabricated using the micro‐electromechanical system (MEMS) technology. The turns of the coil (1 × 1 cm) are 100, while both the line width and spacing of turns are 40 µm. TMCA is prepared using a template and magnetized along the axis direction. When a pulling force or pressure is applied to the TMCA, the magnetic flux decreases or increases correspondingly, allowing the FETS to accurately distinguish stimuli and produce different signals (−/+ or +/−). The FETS presents a sensitivity of up to 21.7 µV kPa−1 (0.05–10 kPa), a minimal magnetic field detection limit of 10 mT, a low‐pressure detection limit of 5 g, and good repeatability (5000 cycles). Additionally, the FETS is applied in robotic tactile testing, Morse code, and noncontact magnetic field recognition. It has potential applications in the Internet of Things (IoT) and information communication.
Reviews on Flexible Force Sensors Based on Fiber Assemblies with Mass Production Efficiency
Authors: Wu Liwei , Jin Yuting , Xia Zhaopeng , Han Jing , Han Wei , Dong Kai , Tang Youhong , Jiang Qian
Published: April 2024

Flexible force sensors show great potential applications in smart wearable devices based on their softness and ease of deformation. Textiles are extremely compatible with the human body, where mechanical forces generated by human movements and physiological activities create rich application scenarios for flexible force sensors. Currently, the bottleneck in the development of flexible sensors depends on the breakthrough of mass production efficiency, which has been a research focus in recent years to accelerate the application of smart textiles in various fields. This work reviews the research progress of flexible force sensors based on fiber assemblies with mass production efficiency, which is discussed in four aspects: sensing mechanisms, structure design, preparation methods, and application. Finally, the challenges faced by mass production of flexible force sensors are analyzed and summarized, and a few inspirations for their future development direction are provided.
Programmable Meta‐Reflector for Multiple Tasks in Intelligent Connected Environments
Authors: Meftah Nawel , Ratni Badreddine , El Korso Mohammed Nabil , Burokur Shah Nawaz
Published: April 2024

In the face of the challenges posed by the advent of 5G, Internet of Things (IoT) and requirements of future communication generations, the urgent need for cutting‐edge technologies capable of adapting their operation to a variety of dynamic tasks for efficient signal propagation management is clear. Connected intelligent metasurfaces, distinguished by their ability to dynamically and autonomously adapt their responses, and able to interact with an external uncontrollable and fast‐changing communication environment to benefit from collective intelligence so as to determine the required action, are emerging as an innovative solution in this field. Herein, an intelligent connected system based on a programmable metasurface reflector, is presented and assessed in two scenarios simulating dynamic uplink and downlink communications. For the uplink configuration, the metasurface is exploited for the estimation of the direction of arrival (DOA) of an incoming wave, while for the downlink scenario, it enables the automated tracking of mobile targets using global positioning system (GPS) data updated from a real‐time database. Experimental results highlight the responsiveness of the metasurface and demonstrate efficiency in wave focusing and mobile target tracking.
The Emerging Heteroepitaxial NiSe2/Nb2C: A Two‐In‐One Bi‐Functional Material Architecture for Electrocatalytic and Supercapattery Application
Authors: Arunkumar Murugesan , Nasrin Kabeer , Allwyn Nadar , Kavinkumar Parthasarathy , Sivashanmugam Arumugam , Sathish Marappan
Published: April 2024

The rational design of electrode materials is pivotal for optimizing the performance of energy storage and conversion systems such as supercapattery and electrocatalysis. In this study, a one‐step supercritical fluid synthesis is presented to craft a unique heteroepitaxial composite, incorporating nickel di‐selenide nanoparticles on niobium carbide MXene nanosheets in various ratios. The integration of 2D nanosheets enhances the kinetics of the electrode reaction process, while NiSe2 facilitates efficient charge transport in MXene. The composite demonstrated superior performance with the 1:2 ratio of NiSe2/Nb2CTx demonstrates an impressive specific capacitance of 1309 C g−1 at 2 A g−1 current density in a three‐electrode system. Furthermore, the asymmetric supercapattery, featuring NiSe2/Nb2CTx 1:2 (positive electrode) and bio‐derived activated carbon (AC) (negative electrode) achieves a gravimetric capacitance of 205 C/g at 0.5 A g−1 current density, a power density of 10,800 W kg−1 at the energy density of 64 Wh kg−1, with 90% retention after 12 000 cycles. As a catalyst for water oxidation, the NiSe2/Nb2CTx 1:2 exhibits the lowest over potential of 359 mV at the current density 10 mA cm−2 and Tafel slope of 105 mV dec−1. This investigation introduces an innovative approach for developing high‐performance supercapattery electrode materials and electrocatalysts using MXene.
Hydrogel‐Reactive‐Microenvironment Powering Reconfiguration of Polymer Architectures
Authors: Liu Pengchao , Mao Zhengyi , Zhao Yan , Yin Jian'an , Chu Chengshengze , Chen Xuliang , Lu Jian
Published: April 2024

Reconfiguration of architected structures has great significance for achieving new topologies and functions of engineering materials. Existing reconfigurable strategies have been reported, including approaches based on heat, mechanical instability, swelling, origami/kirigami designs, and electromagnetic actuation. However, these approaches mainly involve physical interactions between the host materials and the relevant stimuli. Herein, a novel, easy‐manipulated, and controllable reconfiguration strategy for polymer architectures is proposed by using a chemical reaction of host material within a hydrogel reactive microenvironment. 3D printed polycaprolactone (PCL) lattices transformed in an aqueous polyacrylamide (PAAm) hydrogel precursor solution, in which ultraviolet (UV) light triggered heterogeneous grafting polymerization between PCL and AAm. In situ microscopy shows that PCL beams go through volumetric expansion and cooperative buckling, resulting in transformation of PCL lattices into sinusoidal patterns. The transformation process can be tuned easily and patterned through the adjustment of the PCL beam diameter, unit cell width, and UV light on–off state. Controlling domain formation is achieved by using UV masks. This framework enables the design, fabrication, and programming of architected materials and inspires the development of novel 4D printing approaches.
Effect of risk and incentives on contracts: The case of farm operators in Iowa
Authors: Lee Jun Yeong
Published: April 2024

Longitudinal data on Iowa landowner–operator contracts are used to examine how the mean, variance, and skewness of expected farmland returns affected contract terms from 2008 to 2019. To control for unobserved operator risk preferences and ability as a fixed effect, the sample includes operators with multiple contracts. Our empirical work shows that farmland with lower variance is more likely to be rented for cash, whereas land with highly variable returns is more likely to be custom contracted. [EconLit Citations: L14, Q15]
Spin modulation of single Fe atoms with thiolate‐poisoned Pd nanoclusters for highly efficient ammonia synthesis
Authors: Zhang Bin , Yang Chen , Jia Yunjiao , Nie Guohui , Yang Guidong
Published: April 2024

Nitrate reduction toward ammonia is pivotal in energy and environmental domains but faces challenges in achieving simultaneous high selectivity and activity. Manipulating interactions between intermediates and metal species is deemed effective for catalytic enhancement. In this study, a uniformly configured Fe1‐N4 single‐atom catalyst with four‐coordination was synthesized. Subsequent deposition of thiol‐poisoned Pd nanoclusters provided a platform to investigate the neighboring effect of Pd nanoclusters, excluding activity influences from Pd catalysts. Through this neighbor engineering, the Fe 3d electron spin configuration shifted from low spin to medium spin (MS). Experimental and theoretical analyses affirmed that MS Fe species optimized nitrate reduction by enhancing the *NO desorption process. This spin‐modulated Fe single‐atom catalyst demonstrated superior activity (392.16 mmol−1 gcat−1 h−1, ~40 mol−1 gFe−1 h−1) and a Faraday efficiency of 98.6% at −0.5 V vs. RHE, surpassing reported values. This study presents a promising strategy for nitrogen‐chemistry transition metal catalysts.
3D Radiation Mapping Using Gaussian Process Regression with Intensity Projection
Authors: Jung Jihoon , You Donggil , Lee Kooksun , Oh Junghyun
Published: April 2024

This article presents a novel approach for generating a three‐dimensional radiation map using data collected by mobile robots, aimed at monitoring radiation distribution in environments such as nuclear power plants. The proposed approach leverages Gaussian process regression with a novel adaptation of the inverse square law as a kernel function, which accurately reflects the physical characteristics of radiation, enabling precise mapping from uncertain data. Additionally, a method is proposed for constructing a comprehensive radiation map in 3D environments by estimating the radiation source and project the radiation data from sparse data. The effectiveness of the methodology is validated through simulations and experiments. Utilizing Octomap, a 3D spatial mapping tool, the study not only successfully visualizes radiation distribution in complex settings with multiple sources but also quantitatively demonstrates the enhanced accuracy of our approach compared to other existing methods. This research offers contributions in managing radiation risks, providing essential insights into the field.
Strategies to Diversification of the Mechanical Properties of Organic Crystals
Authors: Dai Shuting , Zhong Jiangbin , Yang Xiqiao , Chen Chao , Zhou Liping , Liu Xinyu , Sun Jingbo , Ye Kaiqi , Zhang Hongyu , Li Liang , Naumov Panče , Lu Ran
Published: April 2024

Structurally ordered soft materials that respond to complementary stimuli are susceptible to control over their spatial and temporal morphostructural configurations by intersectional or combined effects such as gating, feedback, shape‐memory, or programming. In the absence of general and robust design and prediction strategies for their mechanical properties, at present, combined chemical and crystal engineering approaches could provide useful guidelines to identify effectors that determine both the magnitude and time of their response. Here, we capitalize on the purported ability of soft intermolecular interactions to instigate mechanical compliance by using halogenation to elicit both mechanical and photochemical activity of organic crystals. Starting from (E)‐1,4‐diphenylbut‐2‐ene‐1,4‐dione, whose crystals are brittle and photoinert, we use double and quadruple halogenation to introduce halogen‐bonded planes that become interfaces for molecular gliding, rendering the material mechanically and photochemically plastic. Fluorination diversifies the mechanical effects further, and crystals of the tetrafluoro derivative are not only elastic but also motile, displaying the rare photosalient effect.
Enantioselective Nickel‐Catalyzed Denitrogenative Transannulation En Route to N−N Atropisomers
Authors: Ge Fang‐Bei , Lu Chuan‐Jun , Chen Xiao , Yao Wang , An Mei , Jiang Yu‐Kun , Xu Li‐Ping , Liu Ren‐Rong
Published: April 2024

Nickel‐catalyzed transannulation reactions triggered by the extrusion of small gaseous molecules have emerged as a powerful strategy for the efficient construction of heterocyclic compounds. However, their use in asymmetric synthesis remains challenging because of the difficulty in controlling stereo‐ and regioselectivity. Herein, we report the first nickel‐catalyzed asymmetric synthesis of N−N atropisomers by the denitrogenative transannulation of benzotriazones with alkynes. A broad range of N−N atropisomers was obtained with excellent regio‐ and enantioselectivity under mild conditions. Moreover, density functional theory (DFT) calculations provided insights into the nickel‐catalyzed reaction mechanism and enantioselectivity control.
Stereoselective Synthesis of Polysubstituted Conjugated Dienes Enabled by Photo‐Driven Sequential Sigmatropic Rearrangement
Authors: Ji Xin , Shen Chaoren , Ni Yuhao , Si Zhi‐Yao , Wang Yuzhu , Zhi Xinrong , Zhao Yuting , Peng Huiling , Liu Lu
Published: April 2024

We here reported a highly stereoselective method for the synthesis of polysubstituted conjugated dienes from α‐aryl α‐diazo alkynyl ketones and pyrazole‐substituted unsymmetric aminals under mild conditions, which was promoted by photo‐irridation and involved with 1,6‐dipolar intermediate and quadruple sigmatropic rearrangements, was successfully developed. In this transformation, the cleavage of four bonds and the recombination of five bonds were implemented in one operational step. This protocol provided a modular tool for constructing dienes from amines, pyrazoles and α‐alkynyl‐α‐diazoketones in one‐pot manner. The results of mechanistic investigation indicated that the plausible reaction path underwent the 1,6‐sigmatropic rearrangement instead of the 1,5‐sigmatropic rearrangement.
Novel Photocatalyst Based on Through‐Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low‐Power Excitation Light
Authors: Liang Hui , Zhang Xue , Lu Manlin , Chen Xi , Li Weiqiang , Li Shangru , Li Ming‐De , Zhao Jianzhang , Huo Yanping , Ji Shaomin
Published: April 2024

Currently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (<50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm.
Preserving Mesoporosity in Type III Porous Liquids through Dual‐layer Surface Weaving
Authors: Li Siqi , Wang Dongxu , Lee Yongjin , Li Tao
Published: April 2024

The fundamental limitation for pore preservation in a Type III porous liquid (T3PL) is the need for a small aperture from the porous filler to realize size exclusion of a bulky solvent. We present a dual‐layer surface weaving strategy that can disregard this limitation and achieve micro‐ and mesoporous metal–organic framework (MOF)‐based T3PLs even with apertures much larger than the solvent molecules. By first weaving a tight network of poly(tert‐butyl methacrylate) on the MOF surface, the poly(dimethylsiloxane) (PDMS) solvent can be effectively excluded from the pores while smaller guest molecules such as CO2, C2H4, and H2O can freely access the interior, as confirmed by low‐pressure adsorption isotherms. Further application of a PDMS‐containing polymer coating helps lower the viscosity of the PL due to increased particle dispersibility. This strategy has resulted in the successful construction of T3PLs with aperture sizes up to 3.1 nm.
Recent Advances in Environmentally Friendly Dual‐crosslinking Polymer Networks
Authors: Zhang Mingyue , Choi Woosung , Kim Minju , Choi Jinyoung , Zang Xuerui , Ren Yujing , Chen Han , Tsukruk Vladimir , Peng Juan , Liu Yijiang , Kim Dong Ha , Lin Zhiqun
Published: April 2024

Environmentally friendly crosslinked polymer networks feature degradable covalent or non‐covalent bonds, with many of them manifesting dynamic characteristics. These attributes enable convenient degradation, facile reprocessibility, and self‐healing capabilities. However, the inherent instability of these crosslinking bonds often compromises the mechanical properties of polymer networks, limiting their practical applications. In this context, environmentally friendly dual‐crosslinking polymer networks (denoted EF‐DCPNs) have emerged as promising alternatives to address this challenge. These materials effectively balance the need for high mechanical properties with the ability to degrade, recycle, and/or self‐heal. Despite their promising potential, investigations into EF‐DCPNs remain in their nascent stages, and several gaps and limitations persist. This Review provides a comprehensive overview of the synthesis, properties, and applications of recent progress in EF‐DCPNs. Firstly, synthetic routes to a rich variety of EF‐DCPNs possessing two distinct types of dynamic bonds (i.e., imine, disulfide, ester, hydrogen bond, coordination bond, and other bonds) are introduced. Subsequently, complex structure‐ and dynamic nature‐dependent mechanical, thermal, and electrical properties of EF‐DCPNs are discussed, followed by their exemplary applications in electronics and biotechnology. Finally, future research directions in this rapidly evolving field are outlined.
Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites
Authors: Zhao Yonggui , Wan Wenchao , Erni Rolf , Pan Long , Patzke Greta R.
Published: April 2024

Metal‐based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X‐ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure–activity relationships of low‐crystalline cobalt sulfide (L−CoS) catalysts toward overall water splitting. The operando results for L−CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S−Co−Co−S moieties as the true catalytically active species. In comparison, during the acidic HER, L−CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co−S−Co configurations. Further operando characterizations highlight the crucial formation of high‐valent Co4+ species in L−CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co‐LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.
Selective Defluorination of Trifluoromethyl Substituents by Conformationally Induced Remote Substitution
Authors: Jesani Mehul H. , Schwarz Maria , Kim Shiwhu , Evans Finlay L. , White Alexander , Browning Alex , Abrams Roman , Clayden Jonathan
Published: April 2024

The selective reduction of an aromatic trifluoromethyl substituent to a difluoromethyl substituent may be achieved by base‐promoted elimination to form a difluoro‐p‐quinomethide which is trapped by an intramolecular nucleophile. High yields are obtained when the nucleophilic trap entails the conformationally favoured cyclisation of an aminoisobutyric acid (Aib) derivative. The resulting cyclised difluoromethyl‐substituted arylimidazolidinone products are readily converted to versatile difluoromethyl‐substituted aldehydes by reduction and hydrolysis. Defluorination is successful on a range of benzenoid (both para and ortho CF3‐substituted) and heterocyclic substrates. Double defluorination may likewise be achieved sequentially, or in a single step, from an Aib dipeptide derivative.
Structural Insights Into the Terpene Cyclization Domains of Two Fungal Sesterterpene Synthases and Enzymatic Engineering for Sesterterpene Diversification
Authors: Xu Meng , Xu Houchao , Lei Zhenyu , Xing Baiying , Dickschat Jeroen S. , Yang Donghui , Ma Ming
Published: April 2024

Little is known about the structures and catalytic mechanisms of sesterterpene synthases (StTSs), which greatly hinders the structure‐based engineering of StTSs for structural diversity expansion of sesterterpenes. We here report on the crystal structures of the terpene cyclization (TC) domains of two fungal StTSs: sesterfisherol synthase (NfSS) and sesterbrasiliatriene synthase (PbSS). Both TC structures contain benzyltriethylammonium chloride (BTAC), pyrophosphate (PPi), and magnesium ions (Mg2+), clearly defining the catalytic active sites. A combination of theory and experiments including carbocationic intermediates modeling, site‐directed mutagenesis, and isotope labeling provided detailed insights into the structural basis for their catalytic mechanisms. Structure‐based engineering of NfSS and PbSS resulted in the formation of 20 sesterterpenes including 13 new compounds and four pairs of epimers with different configurations at C18. These results expand the structural diversity of sesterterpenes and provide important insights for future synthetic biology research.
Design, synthesize, physicochemical characterization, nonlinear optical properties structural elucidation, biomedical studies, and DNA interaction of some new mixed ligand complexes incorporating 4,6‐dimethylpyrimidine derivative and imidazole ligand
Authors: Abu‐Dief Ahmed M. , El‐Khatib Rafat M. , El‐Dabea Tarek , Abdel‐Latif Samir A. , Barnawi Ibrahim Omar , Aljohani Faizah S. , Al‐Ghamdi Khalaf , El‐Remaily Mahmoud Abd El Aleem Ali Ali
Published: April 2024

This study was planned to prepare new mixed ligand chelates derived from N‐(4,6‐dimethylpyrimidin‐2‐yl)‐3a,4,5,6,7,7a‐hexahydro‐1H‐benzimidazol‐2‐amine (BIP), and imidazole (I). They identified through CHN study, spectroscopic (NMR, FT‐IR, and UV–Vis), conductivity, magnetic susceptibility, mass analysis, and thermal analysis. Correlation between all results exposed that the BIP ligand performed as a bi‐dentate ligand through NN donation locations, where the co‐ligand shows as N–H monodentate. The optimization for the studied chelates led to the formation of distorted octahedral geometry for BIPICu and BIPIVO chelates, distorted (tetrahedral and square planar) geometry for BIPIAg and BIPIPd chelates, respectively, around the metal salt. The B3LYP level, B3LYP/6‐311G** level for the free ligand, and B3LYP/6–311G**‐LANL2DZ functional level for the solid chelates were used in density functional theory (DFT) calculations. The findings showed that DFT calculations produce conclusions that are consistent with those of the experiments. The resulting compounds' nonlinear optical properties were examined by calculating the hyperpolarizability (β) and molecular polarizability (α) parameters, which gave rise to several unexpected optical properties for the synthesized compounds. Using the agar well diffusion method, the antimicrobial activity of the produced compounds was experimentally confirmed against a subset of G+ and G− bacteria. To ascertain how these substances attach to the targeted protein binding sites, a molecular docking mechanism between the microbially resistant chelates and their suppressed microbial protein pocket receptors was investigated. Also, DNA binding estimated for studied structures was tested by electronic absorption spectrum, viscosity estimation, and gel electrophoresis. Data proposed that all tested compounds link with DNA using an intercalation, electrostatic, and covalent binding mechanism. Moreover, antioxidant performance for studied compounds was governed by radical scavenging techniques in vitro. In addition, an MTT assay has been worked out to explore in vitro cytotoxic impending. All the tested chelates assumed antimicrobial, antitumor, and antioxidant performances that cause them to suggest drugs.
Impact of olive leaves powder addition on extra virgin olive oil: Sensory, quality, nutritional and volatile compounds implications
Authors: Álvares Andressa Anelo , Silva Lucas Tolio , Cavalcante Luana Souza , Pires Dafne Marcelle Alves , Machado Isabel Cristina Kasper , Aboy Ana Lúcia , Mello Wendell , Scheid Camila , Merib Josias , Garavaglia Juliano
Published: April 2024

Olive leaves currently represent a waste from olive oil industry that can be reused as source of polyphenols and other compounds. The objective of this study was to test whether incorporation of olive leaf powder directly in olive oils can enhance and modify its chemical‐sensory quality. Thus, leaves from cultivar “Koroneiki” were washed, sanitized, dried (37–40°C for 48 h) and milled until obtaining a powder that was added to “Arbequina” and “Koroneiki” extra virgin olive oils, at 1% and 3%. The oils were stored in dark conditions at room temperature and samples were checked after 0, 3, 6 and 12 months. The quality parameters, sensory properties, and nutrition quality (total phenolics, antioxidant, oleuropein and alpha‐tocopherol) were evaluated. The olive leaves affected quality and chemical composition, mainly increasing resistance to oxidation, which was not verified in samples without leaves addition. The incorporation of leaves powder significantly increased the contents of C6‐C5 alcohols/aldehydes, intensity of the green fruity and bitter, also artichoke, herbs, tomato leaf, olive leaves and banana peels sensations.
Determination of hydroxyl value of vegetable oils‐based polyols through ring‐preopening, solvent‐extraction, and acetylation method
Authors: Li Jun , Li Wenlong , Ye Zihan , Sun Yuewen , Gong Weijian , Wang Yiming , Bi Yanlan
Published: April 2024

Vegetable oils‐based polyols prepared by epoxidation‐hydroxylation often have the phenomenon of the coexistence of epoxy and hydroxyl groups due to different ring‐opening degrees. The acylation method recommended by the American Society of Testing Materials (ASTM) standard (D1957‐86) and the Association of Official Analytical Chemists (AOAC) standard (965.32) is applicable only to fatty alcohols in oils and fats and their derivatives but not to vegetable oils‐based polyols since the residual epoxy groups in vegetable oils‐based polyols lead the tested hydroxyl value (OHV) to be higher than the actual OHV. A method combining ring‐preopening of residual epoxy groups, ether extraction of ring‐preopened vegetable oils‐based polyols, and subsequent acetylation by acetic anhydride‐acetic acid was established for OHV determination of vegetable oils‐based polyols. The accuracy of the method was verified by the known theoretical OHVs of short‐chain alcohols and simulated vegetable oils‐based polyols. The absolute values of relative deviations for OHVs of short‐chain alcohols and simulated vegetable oils‐based polyols were within 1.0% and 3.1%, respectively, which indicates the feasibility of the established method in eliminating the negative effects of residual epoxy groups in vegetable oils‐based polyols on OHV determination as well as accurately determining and evaluating the OHV of vegetable oils‐based polyols. The method can broaden the range of OHV determination up to 1800 mg KOH/g. The ratio of acetic anhydride and acetic acid and reaction time are key factors affecting the complete degree of acetylation, which can be regulated mutually in accurately determining the OHV of vegetable oils‐based polyols according to the practice. It is the first time, to our best knowledge, to establish a method to eliminate the negative effects of residual epoxy groups in vegetable oils‐based polyols on OHV determination. The established method provides a feasible method for polyol industry to accurately evaluate the product quality of vegetable oils‐based polyols.