bluuebunny/crossref_metadata_2025 huggingface dataset:
Assessment of Genetic Variability to Contribute Yield and its Components Characters in Pigeonpea [Cajanus cajan (L.) Millsp.] Genotypes in Central Plain Agro-Climatic Region of Uttar Pradesh, India
Authors: Mourya Alok Kumar , Srivastava Arvind Kumar , Srivastava Aman , Nikhil . , Jaiswal Mallika , Kumar Anuj , Tiwari Utkarsh , Saini Ekta
Published: February 2023

The present investigation entitled “assessment of genetic variability to contribute yield and its components Characters in Pigeon pea [Cajanus cajan (L.) Millsp.]” genotypes in central plain agro-climatic region of uttar pradesh”was conducted at Oilseed Research Farm, Kalyanpur, C. S. Azad University of Agriculture and Technology, Kanpur- 208002 (U.P.) during kharif season 2021-22. Genetic variability studies were carried out for 34 pigeon pea genotypes during the years 2021-2022. The analysis of variance revealed that there was significant amount of variation for all the characters during these years. Days to maturity, plant height, number of secondary branches, days of 50% flowering, 100 seed weight, number of primary branches, biological yield, seed yield per plant, harvest index, number of pods per plant and number of seeds per pod was shown to have identified as high heritability value. High estimate of (phenotypic coefficient of variance and genotypic coefficient of variance) PCV and GCV were observed for the number of secondary branches, number of primary branches and days to maturity while moderate estimate of PCV and GCV were observed for plant height, 100 seed weight, days to 50% flowering, seed yield per plant, number of pods per plant and harvest index. The character association studies revealed that at genotypic and phenotypic level, seed yield per plant had positive and high significant correlation to harvest index, days to maturity, biological yield, 100 seed weight and number of pods per plant.
Impact of Tax Revenue and Infrastructural Development on Economic Growth in Nigeria
Authors: Akinola Oladapo Mathias , Akinrinola Olalekan
Published: February 2023

This study seeks to establish the impact of tax revenue and infrastructural development (through investment) on economic growth in Nigeria. It is expected that tax revenue should serve as an incentive for infrastructural development to strive and yield economic growth. The data used in the study was obtained majorly from World Development Indicator (WDI) Database 2022. Tax revenue was proxied as the actual total tax revenue collected from VAT, and CIT, and PPT. This formed the independent variables as well as Gross Capital formation (GCF) to represent infrastructural development. While the dependent variable is RGDP. The ARDL model was employed after variables were stationary at both levels and at first difference. The study found a significant long-run relationship among the variables. Specifically, PPT was found to be a strong contributor to economic growth in Nigeria. VAT was only positively significant at 15% accounting for economic growth. GCF and CIT were not significant in the study. The research employs a quantitative method of data analysis. These findings connote that GCF, VAT and CIT are yet to fully be additive components in the Nigerian economy. Government economic policy and financing henceforth should reflect good economic policy direction that will open up these components for economic growth in the country.
Mathematical Model and Simulation Based on ANSYS Maxwell of the Magnetic Fluid Differential Transformer Inclination Sensor
Authors: Xing Wang , Haitao Xu , Kuo Lu
Published: February 2023

A mathematical model of a mutual inductance magnetic fluid inclination sensor is established. The sensing element of the sensor is magnetic fluid. The composite magnetic core suspended in the magnetic fluid increases the permeability of the medium in the winding. The total magnetic induction intensity B in the winding is composed of two parts: the excitation magnetic induction intensity Bl and the additional magnetic induction intensity Ba generated by the magnetization of pure iron. The sensitivity S of the sensor and its influencing factors are derived. The output characteristics of the sensor are analyzed using ANSYS Maxwell simulation software. The results show that the variable resistance of the measuring circuit can eliminate the residual voltage at zero point, and the output voltage carrier after filtering and rectification is positive half cycle; The addition of pure iron to the magnetic core greatly increases the mutual inductance variation between the primary and secondary windings, and the inclination angle in a small range is linear with the mutual inductance variation; The recovery force of the composite core is proportional to the displacement.
Financing Health Care System Interventions Addressing Social Risks
Authors: Berkowitz Seth A. , Gottlieb Laura M. , Basu Sanjay
Published: February 2023

This Viewpoint discusses the benefits and drawbacks of health care involvement in social risk interventions and presents proposals to finance such involvement.
Estimation of Vaccine Effectiveness of CoronaVac and BNT162b2 Against Severe Outcomes Over Time Among Patients With SARS-CoV-2 Omicron
Authors: Wei Yuchen , Jia Katherine Min , Zhao Shi , Hung Chi Tim , Mok Chris Ka Pun , Poon Paul Kwok Ming , Man Leung Eman Yee , Wang Maggie Haitian , Yam Carrie Ho Kwan , Chow Tsz Yu , Guo Zihao , Yeoh Eng Kiong , Chong Ka Chun
Published: February 2023

Importance

Few studies have evaluated the waning of vaccine effectiveness against severe outcomes caused by SARS-CoV-2 Omicron infection. Hong Kong is providing inactivated and mRNA vaccines, but the population had limited protection from natural infections before the Omicron variant emerged.

Objective

To examine the change in vaccine effectiveness against hospitalization and mortality due to the Omicron variant over time.

Design, Setting, and Participants

This case-control study included adults with SARS-CoV-2 Omicron variant infection who died or were hospitalized in Hong Kong from January 1 to June 5, 2022 (ie, case participants), and adults with SARS-CoV-2 Omicron, sampled from the public health registry during the study period (ie, control participants), who were matched to case participants by propensity score.

Exposures

Vaccination status of the individuals.

Main Outcomes and Measures

Estimated vaccine effectiveness against death, death or hospitalization, and death among hospitalized patients. Vaccine effectiveness was calculated as 1 − adjusted odds ratio obtained by conditional logistic regression adjusted with covariates for each period following vaccination.

Results

There were 32 823 case participants (25 546 [77.8%] ≥65 years; 16 930 [47.4%] female) and 131 328 control participants (100 041 [76.2%] ≥65 years; 66 625 [46.6%] female) in the sample analyzed for the death or hospitalization outcome. Vaccine effectiveness against death or hospitalization was maintained for at least 6 months after the second dose of both CoronaVac (74.0%; 95% CI, 71.8%-75.8%) and BNT162b2 (77.4%; 95% CI, 75.5%-79.0%) vaccines. Vaccine effectiveness against death in those aged 18 to 49 years was 86.4% (95% CI, 85.8%-87.0%) and 92.9% (95% CI, 92.6%-93.2%) for those receiving 2 doses of CoronaVac and BNT162b2, respectively, while for patients aged 80 years or older, it dropped to 61.4% (95% CI, 59.8%-63.2%) and 52.7% (95% CI, 50.2%-55.6%) for CoronaVac and BNT162b2, respectively. Nevertheless, overall vaccine effectiveness against death at 4 to 6 months after the third dose was greater than 90% for CoronaVac, BNT162b2, and the mixed vaccine schedule (eg, mixed vaccines: vaccine effectiveness, 92.2%; 95% CI, 89.2%-95.1%).

Conclusions and Relevance

While vaccines were generally estimated to be effective against severe outcomes caused by SARS-CoV-2 Omicron infection, this analysis found that protection in older patients was more likely to wane 6 months after the second dose. Hence, a booster dose is recommended for older patients to restore immunity. This is especially critical in a setting like Hong Kong, where third-dose coverage is still insufficient among older residents.
Analysis of Psychiatric Disorders by Age Among Children Following a Mass Terrorist Attack in Nice, France, on Bastille Day, 2016
Authors: Askenazy Florence , Bodeau Nicolas , Nachon Ophélie , Gittard Mélanie , Battista Michèle , Fernandez Arnaud , Gindt Morgane
Published: February 2023

This cross-sectional study examines psychiatric disorders among children after a mass terrorist attack in Nice, France, in 2016.
Breast and Lung Cancer Screening Among Medicare Enrollees During the COVID-19 Pandemic
Authors: Doan Christopher , Li Shuang , Goodwin James S.
Published: February 2023

Importance

Several studies reported sharp decreases in screening mammography for breast cancer and low-dose computed tomographic screening for lung cancer in the early months of the COVID-19 pandemic, followed by a return to normal or near-normal levels in the summer of 2020.

Objective

To determine the observed vs expected mammography and low-dose computed tomographic scan rates from the beginning of the pandemic through April 2022.

Design, Setting, and Participants

In this retrospective cohort study assessing mammography and low-dose computed tomography rates from January 2017 through April 2022, data for January 2016 to February 2020 were used to generate expected rates for the period March 2020 to April 2022. The study included a 20% national sample of Medicare fee-for-service enrollees among women aged 50 to 74 years for mammography, and men and women aged 55 to 79 years for low-dose computed tomographic scan.

Main Outcomes and Measures

Receipt of screening mammography or low-dose computed tomographic scan.

Results

The yearly cohorts for the mammography rates included more than 1 600 000 women aged 50 to 74 years, and the cohorts for the low-dose computed tomographic scan rates included more than 3 700 000 men and women aged 55 to 79 years. From January 2017 through February 2020, monthly mammography rates were flat, whereas there was a monotonic increase in low-dose computed tomographic scan rates, from approximately 500 per million per month in early 2017 to 1100 per million per month by January 2020. Over the period from March 2020 to April 2022, there were episodic drops in both mammography and low-dose computed tomographic scan rates, coincident with increases in national COVID-19 infection rates. For the periods from March 2020 to February 2020 and March 2021 to February 2022, the observed low-dose computed tomographic scan rates were 24% (95% CI, 23%-24%) and 14% (95% CI, 13%-15%) below expected rates, whereas mammography rates were 17% (95% CI, 17%-18%) and 4% (95% CI, 4%-3%) below expected.

Conclusions and Relevance

In this cohort study, the decreases in cancer screening during the early phases of the COVID-19 pandemic did not resolve after the initial pandemic surges. Successful interventions to improve screening rates should address pandemic-specific reasons for low screening participation.
CO2 Adsorption in a Robust Iron(III) Pyrazolate‐Based MOF: Molecular‐Level Details and Frameworks Dynamics From Powder X‐ray Diffraction Adsorption Isotherms
Authors: Vismara Rebecca , Terruzzi Stephanie , Maspero Angelo , Grell Toni , Bossola Filippo , Sironi Angelo , Galli Simona , Navarro Jorge A. R. , Colombo Valentina
Published: February 2023

Understanding adsorption processes at the molecular level, with multi‐technique approaches, is nowadays at the frontier of porous materials research. In this work it is shown that with a proper data treatment, in situ high‐resolution powder X‐ray diffraction (HR‐PXRD) at variable temperature and gas pressure can reveal atomic details of the accommodation sites, the framework dynamics as well as thermodynamic information (isosteric heat of adsorption) of the CO2 adsorption process in the robust iron(III) pyrazolate‐based MOF Fe2(BDP)3 [H2BDP = 1,4‐bis(1H‐pyrazol‐4‐yl)benzene]. Highly reliable “HR‐PXRD adsorption isotherms” can be constructed from occupancy values of CO2 molecules. The “HR‐PXRD adsorption isotherms” accurately match the results of conventional static and dynamic gas sorption experiments and Monte Carlo simulations. These results are indicative of the impact of the molecular‐level behavior on the bulk properties of the system under study and of the potential of the presented multi‐technique approach to understand adsorption processes in metal–organic frameworks.
Smart Mitochondria‐Specific Anchored Gold‐based Nanosystem for Integration of Tumor Imaging and Treatment
Authors: Yin Xuelian , Zhan Lin , Ding Lin , Chen Xuerui , Zhang Junfeng , Li Chenchen , Zhang Yuxi , Khan Murad , Reis Rui L. , Wang Yanli
Published: February 2023

Although recent advances have been made in improving the efficacy of photodynamic therapy, efficient therapeutic approaches based on reactive oxygen species (ROS) are needed, particularly mitochondria‐specific targeting of nanomaterials that can alter the internal environment of organelles. Herein, we report the facile synthesis of mitochondria‐specific anchored nano‐complexes (AG‐CNP) comprised of a skeleton of gold and carbon atoms for cancer therapy. Compared to the effects of gold nanoclusters (Au NCs), AG‐CNP shows enhanced fluorescence imaging effects, which can be used for tumor monitoring. AG‐CNP targets the mitochondria and increases ROS damage in cancer cells. After treatment with AG‐CNP, the tumor inhibition rate reaches 70.94%, which is 25.98% and 36.91% higher than that of free doxorubicin (DOX) and gemcitabine (Gem), respectively. Studying the mechanism of AG‐CNP inhibiting cancer shows that AG‐CNP can promote tumor cells to produce excessive ROS by overexpressing P53 and increasing the number of apoptotic cancer cells, which is caused by overexpression of Caspase1 that was closely related to cell apoptosis. AG‐CNP is a promising anticancer drug that targets the mitochondria in vivo to trigger excessive ROS production in tumor cells and inhibit tumor growth.
AlGaN/GaN‐Based Optoelectronic Synaptic Devices for Neuromorphic Computing
Authors: Kai Cuihong , Wang Yue , Liu Xiaoping , Liu Xiao , Zhang Xuqing , Pi Xiaodong , Yang Deren
Published: February 2023

Neuromorphic computing promises to overcome the Von Neumann bottleneck of traditional computers. Optoelectronic synaptic devices are greatly desired given their potential applications in neuromorphic computing. In this work, optoelectronic synaptic devices with long‐term memory are fabricated. The devices are based on a GaN/AlGaN/AlN/GaN heterojunction and a SiNx charge trapping layer. Synaptic functionalities including excitatory postsynaptic current, paired pulse facilitation, and transition from short‐term memory to long‐term memory are realized. The retention time of long‐term memory may be more than 10 years, demonstrating the reliable charge storage of the devices. Logic functions are also realized by synergizing the photogating and electrical gating of the devices. The responsivity and specific detectivity are 2.64 × 105 A W−1 and 1.79 × 1016 Jones at the optical power density of 1.4 mW cm−2, respectively. In addition, the devices have a reconfigurable switch of 1000 cycles with working temperature up to 200 °C.
Enhanced Luminescent Performance via Passivation of Surface Undercoordinated Pb Atoms in a CsPbBr3 Microplate
Authors: Zhu Yizhi , Shi Linlin , Guo Heng , Chen Jinping , Lu Junfeng , Wang Weian , Xu Zhangsheng , Gao Naiwei , Han Xun , Peng Zhengchun , Cui Qiannan , Xu Chunxiang , Pan Caofeng
Published: February 2023

Perovskite materials are widely used in the fields of luminescence and light energy conversion with the advantages of low cost and outstanding optoelectronic properties. However, abundant surface lattice defects heavily affect the performances of perovskite optoelectronic devices. Here, by treating surface defects with oleylamine molecules in situ, the surface trap states are significantly decreased in a CsPbBr3 microplate, enabling photoluminescence intensity and carrier lifetimes to be dramatically enhanced and prolonged, respectively. These interesting phenomena can be attributed to the binding of undercoordinated Pb atoms with N atoms on the surface of perovskite microplate. The strong binding energy of lead‐halogen bonds inhibits the photodegraded reactions of the crystal, leading to the significant improvement of luminescent stability for the microplate correspondingly. The results not only provide experimental guidance for passivating lattice defects but also pave the way for improving the efficiency of wide materials and optoelectronic devices.
Multilevel Fully Integrated Electromechanical Property Modulation of Functionally Graded Graphene‐Reinforced Piezoelectric Actuators: Coupled Effect of Poling Orientation
Authors: Singh Kamalpreet , Shingare Kishor Balasaheb , Mukhopadhyay Tanmoy , Naskar Susmita
Published: February 2023

This article explores the coupled static and dynamic electromechanical responses of single and multilayered functionally graded (FG) graphene platelet (GPL)‐reinforced piezoelectric composite (GRPC) plates by developing a 3D finite‐element model. The bending and eigenfrequency of piezoelectric FG composite plates are investigated, wherein an active behavior is proposed to be exploited in terms of the functional design of poling angle for a more elementary level property modulation. The numerical results reveal that the mechanical behavior concerning deflection and resonance frequency of FG‐GRPC plates can be significantly enhanced and modulated due to the influence of piezoelectricity and a small fraction of GPLs along with the consideration of poling angle in a multiscale fully integrated computational framework. The notions of on‐demand property modulation, actuation, and active control are established here by undertaking a comprehensive numerical analysis considering the coupled influences of poling orientations, different distributions, patterns, and weight fractions of GPLs along with different electromechanical loadings. Against the backdrop of the recent advances in microscale manufacturing, the current computational work will provide necessary physical insights in modeling piezoelectric multifunctional FG composites for active control of mechanical properties and harvesting electromechanical energy in a range of devices and systems.
Carbon Dots Based Photoinduced Reactions: Advances and Perspective
Authors: Yu Yue , Zeng Qingsen , Tao Songyuan , Xia Chunlei , Liu Chongming , Liu Pengyuan , Yang Bai
Published: February 2023

Seeking clean energy as an alternative to traditional fossil fuels is the inevitable choice to realize the sustainable development of the society. Photocatalytic technique is considered a promising energy conversion approach to store the abundant solar energy into other wieldy energy carriers like chemical energy. Carbon dots, as a class of fascinating carbon nanomaterials, have already become the hotspots in numerous photoelectric researching fields and particularly drawn keen interests as metal‐free photocatalysts owing to strong UV–vis optical absorption, tunable energy‐level configuration, superior charge transfer ability, excellent physicochemical stability, facile fabrication, low toxicity, and high solubility. In this review, the classification, microstructures, general synthetic methods, optical and photoelectrical properties of carbon dots are systematically summarized. In addition, recent advances of carbon dots based photoinduced reactions including photodegradation, photocatalytic hydrogen generation, CO2 conversion, N2 fixation, and photochemical synthesis are highlighted in detail, deep insights into the roles of carbon dots in various systems combining with the photocatalytic mechanisms are provided. Finally, several critical issues remaining in photocatalysis field are also proposed.
In Situ Detection of Iron in Oxidation States ≥ IV in Cobalt‐Iron Oxyhydroxide Reconstructed during Oxygen Evolution Reaction
Authors: Reith Lukas , Hausmann Jan Niklas , Mebs Stefan , Mondal Indranil , Dau Holger , Driess Matthias , Menezes Prashanth W.
Published: February 2023

Cobalt‐iron oxyhydroxides (CoFeOOHx) are among the most active catalysts for the oxygen evolution reaction (OER). However, their redox behavior and the electronic and chemical structure of their active sites are still ambiguous. To shed more light on this, the complete and rapid reconstruction of four helical cobalt‐iron borophosphates with different Co:Fe ratios into disordered cobalt‐iron oxyhydroxides can be achieved, which are electrolyte‐penetrable and thus most transition metal sites can potentially participate in the OER. To track the redox behavior and to identify the active structure, quasi in situ X‐ray absorption spectroscopy is applied. Iron in high oxidation states ≥ IV (Fe4+) and its substantial redox behavior with an average oxidation state of around 2.8 to above 3.2 is detected. Furthermore, a 6% contraction of the Fe‐O bond length compared to Fe3+OOH references is observed during OER and a strong distortion of the [MO6] octahedra is identified. It is hypothesized that this bond contraction is caused by the presence of oxyl radicals and that di‐µ‐oxyl radical bridged cobalt‐iron centers are the active sites. It is anticipated that the detailed electronic and structural description can substantially contribute to the debate on the nature of the active site in bimetallic iron‐containing OER catalysts.
Pliocene seeds of Passiflora subgenus Decaloba (Gray Fossil Site, Tennessee) and the impact of the fossil record on understanding the diversification and biogeography of Passiflora
Authors: Hermsen Elizabeth J.
Published: February 2023

Premise

Passiflora is a diverse genus of ~570 extant species primarily distributed in the Americas, from the eastern United States to Argentina and Chile. Nevertheless, the known fossil record of Passiflora is small. To date, only two fossil seed species have been unequivocally assigned to the genus. In this contribution, rare sulcate seeds from Gray Fossil Site are described as a third fossil seed species of Passiflora.

Methods

Three partial seeds with sulcate sculpture from Gray Fossil Site, early Pliocene, Tennessee, USA, were examined, photographed, and measured. They were compared to samples of sulcate seeds from six extant Passiflora species in supersection Decaloba. A broader survey of sulcate seeds produced by modern species in the subgenera Decaloba, Deidamioides, and Tryphostemmatoides was done using published illustrations and descriptions.

Results

The Gray Fossil Site seeds are described as Passiflora sulcatasperma, sp. nov., and assigned to subgenus Decaloba, supersection Decaloba. They are characterized by their small size, elliptical shape, ridged‐and‐sulcate sculpture, rugulose ridges, and thin palisade seed coat.

Conclusions

The two largest subgenera of Passiflora can be identified from Neogene fossils. Subgenus Decaloba is represented by two fossil seed species, P. bulgarica (Miocene, Bulgaria) and P. sulcatasperma (Pliocene, USA). Subgenus Passiflora is represented by fossil pollen (Miocene, Argentina and Brazil) and P. appalachiana seeds (Pliocene, USA). The distributions of fossil and modern species suggest that Passiflora may have used both North Atlantic and Antarctic routes to expand into Europe and the Asian‐Oceanian Paleotropics, respectively.
Preferential Adsorption of Ethylene Oxide on Fe and Chlorine on Ni Enabled Scalable Electrosynthesis of Ethylene Chlorohydrin
Authors: Han Shuyan , Cheng Chuanqi , He Meng , Li Rui , Gao Ying , Yu Yifu , Zhang Bin , Liu Cuibo
Published: February 2023

Industrial manufacturing of ethylene chlorohydrin (ECH) critically requires excess corrosive hydrochloric acid or hypochlorous acid with dealing with massive by‐products and wastes. Here we report a green and efficient electrosynthesis of ECH from ethylene oxide (EO) with NaCl over a NiFe2O4nanosheet anode. Theoretical results suggest that EO and Cl preferentially adsorb on Fe and Ni sites, respectively, collaboratively promoting the ECH synthesis. A Cl radical‐mediated ring‐opening process is proposed and confirmed, and the key Cl and carbon radical species are identified by high‐resolution mass spectrometry. This strategy can enable scalable electrosynthesis of 185.1 mmol of ECH in 1 h with 92.5 % yield at a 55 mA cm−2current density. Furthermore, a series of other chloro‐ and bromoethanols with good to high yields and paired synthesis of ECH and 4‐amino‐3,6‐dichloropyridine‐2‐carboxylicacid via respectively loading and unloading Cl are achieved, showing the promising potential of this strategy.
Visible Helicity Induction and Memory in Polyallene toward Circularly Polarized Luminescence, Helicity Discrimination, and Enantiomer Separation
Authors: Xu Lei , Wu Yong‐Jie , Gao Run‐Tan , Li Shi‐Yi , Liu Na , Wu Zong‐Quan
Published: February 2023

Inspired by biological helices (e.g., DNA), artificial helical polymers have attracted intense attention. However, precise synthesis of one‐handed helices from achiral materials remains a formidable challenge. Herein, a series of achiral poly(biphenyl allene)s with controlled molar mass and low dispersity were prepared and induced into one‐handed helices using chiral amines and alcohols. The induced one‐handed helix was simultaneously memorized, even after the chiral inducer was removed. The switchable induction processes were visible to naked eye; the achiral polymers exhibited blue emission (irradiated at 365 nm), whereas the induced one‐handed helices exhibited cyan emission with clear circularly polarized luminescence. The induced helices formed stable gels in various solvents with helicity discrimination ability: the same‐handed helix gels were self‐healing, whereas the gels of opposite‐handed helicity were self‐sorted. Moreover, the induced helices could separate enantiomers via enantioselective crystallization with high efficiency and switchable enantioselectivity.
Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis
Authors: González‐Granda Sergio , Escot Lorena , Lavandera Iván , Gotor‐Fernández Vicente
Published: February 2023

The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse organic molecules in a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due to the possibility to assemble metal catalysis in C−C coupling, olefin metathesis, hydration and other reactions with the exquisite stereospecificity displayed by enzymes. Thus, this minireview is organized based on the action of the metal species (Pd, Ru, Au, Ir, Fe…) in combination with different enzymes. Special attention will be paid to the design of sequential processes and concurrent cascades, presenting solutions such as the use of surfactants or compartmentalization strategies for those cases where incompatibilities could hamper the overall process.
Mechanism‐Guided Design of Chain‐Growth Click Polymerization Based on a Thiol‐Michael Reaction
Authors: Jiang Suqiu , Huang Hanchu
Published: February 2023

The development of chain‐growth click polymerization is challenging yet desirable in modern polymer chemistry. In this work, we reported a novel chain‐growth click polymerization based on the thiol‐Michael reaction. This polymerization could be performed efficiently under ambient conditions and spatiotemporally regulated by ultraviolet light, allowing the synthesis of sulfur‐containing polymers in excellent yields and high molecular weights. Density functional theory calculations indicated that the thiolate addition to the Michael acceptor is the rate‐determining step, and introducing the phenyl group could facilitate the chain‐growth process. This polymerization is a new type of chain‐growth click polymerization, which will provide a unique approach to creating functional polymers.
Modulating the Differentiation of Kinetically Controlled Supramolecular Polymerizations through the Alkyl Bridge Length
Authors: Naranjo Cristina , Adalid Sergio , Gómez Rafael , Sánchez Luis
Published: February 2023

The synthesis and self‐assembling features of N‐annulated perylenebisimides (N‐PBIs) 2–4 are reported and compared with the complex self‐assembly of N‐PBI 1. The studies presented herein demonstrate that increasing the length of the alkyl spacer separating the central aromatic core of the dye and the peripheral side chains cancels the differentiation on the corresponding supramolecular polymerization. Thus, only 2 is able to form two different supramolecular polymorphs. The formation of kinetically trapped monomeric species is observed for all the N‐PBIs 2–4. These metastable species, constituted by intramolecularly H‐bonded pseudocycles of 7, 8, 9, or 10 members for compounds 1, 2, 3, and 4, respectively, provoke kinetically controlled supramolecular polymerizations that can be accelerated by the addition of seeds. The results presented herein shed light on the intricate process of differentiation in self‐assembly.
Facile Fabrication of a Continuous ZIF‐67 Membrane for Efficient Azeotropic Organic Solvent Mixture Separation
Authors: Sun Hao , Wang Fengkai , Li Xiaoting , Caro Jürgen , Meng Hong , Wang Naixin , An Quan‐Fu
Published: February 2023

Azeotropic organic solvent mixture separation is common in the chemical industry but extremely difficult. Zeolitic imidazolate framework‐67 (ZIF‐67) shows great potential in organic solvent mixture separation due to its rigid micropores and excellent stability. However, due to the fast nucleation rate, it is a great challenge to prepare continuous ZIF‐67 membrane layers with ultrathin thickness. In this study, a hydroxy salt layer with high inducible activity was synthesized as a precursor on different porous substrates to prepare ZIF‐67 membranes at room temperature. The precursor layer enables an intact ZIF‐67 membrane with an ultrathin thickness of 176±12 nm. The experimental and simulation results confirmed that the size sieving through the pore windows and the preferential adsorption of polar solvent molecules provide the ZIF‐67 membrane an unprecedented separation performance such as high separation factors and fluxes, for four types of azeotropic organic solvent mixtures.
Experimental Determination of an Isolated trans‐Dinitrosyl Manganese(II) Heme Analogue
Authors: Cao Hongli , Ding Wei , Li Jianfeng
Published: February 2023

The lack of direct proof in either natural or synthetic systems for trans‐dinitrosyl hemes, a key intermediate in the reactions of heme proteins (e.g. soluble guanylate cyclase (sGC), cytochrome c′ and So H‐NOX) with nitric oxide (NO), has hampered understanding of the exact reaction mechanisms, such as the formation of the five‐coordinate heme complex with NO at the proximal side (5c NOP). Herein, we report the first isolation of a dinitrosyl metalloporphyrin complex, the six‐coordinate, low‐spin {Mn(NO)2}7 species [Mn(TPP)(NO)2] (TPP2−=meso‐tetraphenylporphyrin dianion). The complex shows distinct features, such as an elongated axial bond (1.877(9) vs. 1.641(5) Å), a higher NO stretching bond position (1760 vs. 1735 cm−1) and an isotropic resonance at g = 2.0, in sharp contrast to those of five‐coordinate mononitrosyl analogues. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) and EPR studies provided deep insight into the reaction processes, demonstrating different responses of porphyrinates to NO.
Modular Metal‐Quinone Networks with Tunable Architecture and Functionality
Authors: Zhong Qi‐Zhi , Richardson Joseph J. , Tian Yuan , Tian Haijiang , Cui Jiwei , Mann Stephen , Caruso Frank
Published: February 2023

Nanostructured materials with tunable structures and functionality are of interest in diverse areas. Herein, metal ions are coordinated with quinones through metal‐acetylacetone coordination bonds to generate a class of structurally tunable, universally adhesive, hydrophilic, and pH‐degradable materials. A library of metal‐quinone networks (MQNs) is produced from five model quinone ligands paired with nine metal ions, leading to the assembly of particles, tubes, capsules, and films. Importantly, MQNs show bidirectional pH‐responsive disassembly in acidic and alkaline solutions, where the quinone ligands mediate the disassembly kinetics, enabling temporal and spatial control over the release of multiple components using multilayered MQNs. Leveraging this tunable release and the inherent medicinal properties of quinones, MQN prodrugs with a high drug loading (>89 wt %) are engineered using doxorubicin for anti‐cancer therapy and shikonin for the inhibition of the main protease in the SARS‐CoV‐2 virus.
Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts
Authors: Wang Sicong , Ding Tao , Liu Tong , Zhu Yanan , Tao Zhinan , Pang Beibei , Liu Xiaokang , Luo Qiquan , Sun Mei , Sheng Hongting , Zhu Manzhou , Yao Tao
Published: February 2023

The transformation from metal nanocluster catalysts to metal single‐atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single‐atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex‐situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low‐temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.
Elucidation of the Alternating Copolymerization Mechanism of Epoxides or Aziridines with Cyclic Anhydrides in the Presence of Halide Salts
Authors: Xu Jiaxi , Zhang Pengfei , Yuan Youyou , Hadjichristidis Nikos
Published: February 2023

Organic halide salts in combination with metal or organic compound are the most common and essential catalysts in ring‐opening copolymerizations (ROCOP). However, the role of organic halide salts was neglected. Here, we have uncovered the complex behavior of organic halides in ROCOP of epoxides or aziridine with cyclic anhydride. Coordination of the chain‐ends to cations, electron‐withdrawing effect, leaving ability of halide atoms, chain‐end basicity/nucleophilicity, and terminal steric hindrance cause three types of side reactions: single‐site transesterification, substitution, and elimination. Understanding the complex functions of organic halide salts in ROCOP led us to develop highly active and selective aminocyclopropenium chlorides as catalysts/initiators. Adjustable H‐bonding interactions of aminocyclopropenium with propagating anions and epoxides create chain‐end coordination process that generate highly reactive carboxylate and highly selective alkoxide chain‐ends.
NH4+ Deprotonation at Interfaces Induced Reversible H3O+/NH4+ Co‐insertion/Extraction
Authors: Huang Meng , He Qiu , Wang Junjun , Liu Xiong , Xiong Fangyu , Liu Yu , Guo Ruiting , Zhao Yan , Yang Jinlong , Mai Liqiang
Published: February 2023

Ion insertions always involve electrode‐electrolyte interface process, desolvation for instance, which determines the electrochemical kinetics. However, it′s still a challenge to achieve fast ion insertion and investigate ion transformation at interface. Herein, the interface deprotonation of NH4+ and the introduced dissociation of H2O molecules to provide sufficient H3O+ to insert into materials′ structure for fast energy storages are revealed. Lewis acidic ion‐NH4+ can, on one hand provide H3O+ itself via deprotonation, and on the other hand hydrolyze with H2O molecules to produce H3O+. In situ attenuated total reflection‐Fourier transform infrared ray method probed the interface accumulation and deprotonation of NH4+, and density functional theory calculations manifested that NH4+ tend to thermodynamically adsorb on the surface of monoclinic VO2, and deprotonate to provide H3O+. In addition, the inserted NH4+ has a positive effect for stabilizing the VO2(B) structure. Therefore, high specific capacity (>300 mAh g−1) and fast ionic insertion/extraction (<20 s) can be realized in VO2(B) anode. This interface derivation proposes a new path for designing proton ion insertion/extraction in mild electrolyte.
Plasmonic Cu Nanoparticles for the Low‐temperature Photo‐driven Water‐gas Shift Reaction
Authors: Zhao Jiaqi , Bai Ya , Li Zhenhua , Liu Jinjia , Wang Wei , Wang Pu , Yang Bei , Shi Run , Waterhouse Geoffrey I. N. , Wen Xiao‐Dong , Dai Qing , Zhang Tierui
Published: February 2023

The activation of water molecules in thermal catalysis typically requires high temperatures, representing an obstacle to catalyst development for the low‐temperature water‐gas shift reaction (WGSR). Plasmonic photocatalysis allows activation of water at low temperatures through the generation of light‐induced hot electrons. Herein, we report a layered double hydroxide‐derived copper catalyst (LD‐Cu) with outstanding performance for the low‐temperature photo‐driven WGSR. LD‐Cu offered a lower activation energy for WGSR to H2 under UV/Vis irradiation (1.4 W cm−2) compared to under dark conditions. Detailed experimental studies revealed that highly dispersed Cu nanoparticles created an abundance of hot electrons during light absorption, which promoted *H2O dissociation and *H combination via a carboxyl pathway, leading to the efficient production of H2. Results demonstrate the benefits of exploiting plasmonic phenomena in the development of photo‐driven low‐temperature WGSR catalysts.
Developing functional epoxy/graphene composites using facile in‐situ mechanochemical approach
Authors: Meng Qingshi , Feng Yuanyuan , Han Sensen , Yang Fei , Demiral Murat , Meng Fanze , Araby Sherif
Published: February 2023

The awareness of developing eco‐friendly polymer composites via green chemistry attract much attention in the recent years. In the current work, we explore preparing functional epoxy/ graphene nanocomposites using mechanochemical approach. Graphene platelets (GnPs) were modified with long‐chain surfactant via high‐energy ball milling. Modified‐GnPs (m‐GnPs) promote the dispersion quality and interface strength with epoxy matrix leading to higher mechanical properties, and better electrical and thermal conductivity compared to unmodified GnPs system. At 2.0 vol% m‐GnPs, elastic modulus, tensile strength, and thermal conductivity of epoxy were improved by 889%, 163%, and 105%, respectively. In addition, percolation threshold of electrical conductivity was observed at 0.71 vol% m‐GnPs. Halpin‐Tsai micromechanical model was able to predict the elastic modulus of the epoxy/GnP nanocomposites. The model results were compared experimental measurements. Furthermore, the measurements showed epoxy/m‐GnP film possess high sensitivity to mechanical strains and impact loads. The current work gives a step forward to use mechanochemistry approach in the production of functional epoxy/graphene composites.
Synthesis of molecularly imprinted polymer based on cooperative imprinting for enrichment of gallic acid in Puer tea
Authors: Zhang Li‐Ping , Zhu Fu‐Hua , Guo Yu , Yang Hui , Wang Lan , He Yi‐Fan , Li Shu‐Jing , Li Tian
Published: February 2023

The molecularly imprinted polymer (MIP) for gallic acid (GA) was prepared based on the cooperative imprinting of boronate affinity interactions and hydrogen bond. The fabricated MIP were designed by the polymerization of template with co‐functional monomer, 3‐acrylamidophenylboronic acid (AAPBA) and methacrylic acid (MAA). The characteristics of the resulting polymer (AAPBA‐co‐MAA MIP) were tested by scanning electron microscope (SEM), Fourier transform infrared spectra (FTIR) and nitrogen adsorption–desorption. Bonding performance demonstrated that the AAPBA‐co‐MAA MIP possessed the excellent recognition ability in the incubation solution with pH 7.4 and presented higher adsorption capacity, faster adsorption rate and satisfactory selectivity for GA. Additionally, the AAPBA‐co‐MAA MIP revealed the good applications in the separation and enrichment of GA from Puer tea, and the amount of GA enriched by them was determined to be 2.75 mg g−1. This work suggested that the integration of cooperative imprinting strategy between covalent and non‐covalent would be an effective way to improve the specific recognition performance of the MIP.
Mask or Enhance: Data Curation Aiding the Discovery of Piezoresponse Force Microscopy Contributors
Authors: Ligonde Gardy Kevin , Williams Kerisha N. , Gaponenko Iaroslav , Bassiri‐Gharb Nazanin
Published: February 2023

Piezoresponse force microscopy (PFM) is routinely used to probe the nanoscale electromechanical response of ferroelectric and piezoelectric materials. However, many challenges remain in the interpretation of the recovered signal. Specifically, many non‐ferroelectric contributions affect the measured response, ranging from electrostatics, to charge injection and trapping, and topographic cross‐talk. Recently, machine learning (ML) has been utilized to identify multiple contributors within complex data systems, such as PFM response. A substantial advancement in ML approaches for PFM techniques is offered by dimensional stacking, enabling encoding of physical and/or chemical correlations within the materials' response across different data dimensions spanning varying ranges. However, dimensional stacking requires appropriate scaling for each dimension (before ML analysis) to minimize undesired information loss. Here, the impact of clustering globally and locally scaled parameters in polarization switching experiments via resonant PFM (RPFM) are discussed. Specifically, dimensional stacking of scaled parameters can mask or enhance ferroelectric and non‐ferroelectric behaviors, and aid identification of various physical phenomena contributing to the measured RPFM response. This study highlights the importance of data curation for ML, and its role in identifying signal contributors to scanning probe microscopy (SPM)‐based techniques with multidimensional data, such as resonant and/or spectroscopic SPM.
Solid‐state NMR Spectroscopy of Iodine(I) Complexes
Authors: Ward Jas S. , Sievänen Elina I. , Rissanen Kari
Published: February 2023

Solid‐state NMR has been applied to a series of Barluenga‐type iodine(I) [L‐I‐L]PF6 (L=pyridine, 4‐ethylpyridine, 4‐dimethylaminopyridine, isoquinoline) complexes as their hexafluorophosphate salts, as well as their respective non‐liquid ligands (L), their precursor silver(I) complexes, and the respective N‐methylated pyridinium and quinolinium hexafluorophoshate salts. These results are compared and contrasted to the corresponding solution studies and single‐crystal X‐ray structures. As the first study of its kind on the solid‐state NMR behavior of halogen(I) complexes, practical considerations are also discussed to encourage wider utilization of this technique in the future.
Nickel(II) Complexes of Tripodal Ligands as Catalysts for Fixation of Atmospheric CO2 as Organic Carbonates
Authors: Muthuramalingam Sethuraman , Velusamy Marappan , Singh Rajput Swati , Alam Mehboob , Mayilmurugan Ramasamy
Published: February 2023

The fixation of atmospheric CO2 into value‐added products is a promising methodology. A series of novel nickel(II) complexes of the type [Ni(L)(CH3CN)2](BPh4)2 1–5, where L=N,N‐bis(2‐pyridylmethyl)‐N′, N′‐dimethylpropane‐1,3‐diamine (L1), N,N‐dimethyl‐N′‐(2‐(pyridin‐2‐yl)ethyl)‐N′‐(pyridin‐2‐ylmethyl) propane‐1,3‐diamine (L2), N,N‐bis((4‐methoxy‐3,5‐dimethylpyridin‐2‐ylmethyl)‐N′,N′‐dimethylpropane‐1,3‐diamine (L3), N‐(2‐(dimethylamino) benzyl)‐N′,N′‐dimethyl‐N‐(pyridin‐2‐ylmethyl) propane‐1,3‐diamine (L4) and N,N‐bis(2‐(dimethylamino)benzyl)‐N′, N′‐dimethylpropane‐1,3‐diamine (L5) have been synthesized and characterized as the catalysts for the conversion of atmospheric CO2 into organic cyclic carbonates. The single‐crystal X‐ray structure of 2 was determined and exhibited distorted octahedral coordination geometry with cis‐α configuration. The complexes have been used as a catalyst for converting CO2 and epoxides into five‐membered cyclic carbonates under 1 atmospheric (atm) pressure at room temperature in the presence of Bu4NBr. The catalyst containing electron‐releasing −Me and ‐OMe groups afforded the maximum yield of cyclic carbonates, 34% (TON, 680) under 1 atm air. It was drastically enhanced to 89% (TON, 1780) under pure CO2 gas at 1 atm. It is the highest catalytic efficiency known for CO2 fixation using nickel‐based catalysts at room temperature and 1 atm pressure. The electronic and steric factors of the ligands strongly influence the catalytic efficiency. Furthermore, all the catalysts can convert a wide range of epoxides (ten examples) into corresponding cyclic carbonate with excellent selectivity (>99%) under this mild condition.
A New Motif in Halogen Bonding: Cooperative Intermolecular S−Br⋅⋅⋅O, O⋅⋅⋅F, and F⋅⋅⋅F Associations in the Crystal Packing of α,ω‐Di(sulfonyl bromide) Perfluoroalkanes
Authors: Wacha Max , Helm David L. , Smart Megan M. , McMillen Colin D. , Casabianca Leah B. , Sachdeva Rakesh , Urick Catherine R. , Wilson London P. , Thrasher Joseph S.
Published: February 2023

We recently reported the first examples of S−Cl⋅⋅⋅O halogen bonding complemented by short F⋅⋅⋅F contacts between neighboring chains that resulted in stabilized crystals of ClSO2(CF2)4SO2Cl and ClSO2(CF2)6SO2Cl. More recently, other researchers studied our crystallographic data further using an Independent Gradient Model (IGM), and they suggested if one goes beyond IUPAC's proposed ‘less than the sum of the van der Waals radii’ criterion that even more noncovalent interactions between fluorine atoms on neighboring chains as well as Cl⋅⋅⋅Cl, Cl⋅⋅⋅S, O⋅⋅⋅F, and O⋅⋅⋅S attractive interactions can be found. With that said, we have prepared samples of the related BrSO2(CF2)nSO2Br derivatives (where n=4, 6, 8, and others), which give rise to even stronger S−Br⋅⋅⋅O halogen bonding interactions complemented minimally by O⋅⋅⋅F and F⋅⋅⋅F intermolecular interactions as shown by X‐ray crystallography and computational chemistry using IGM isosurface plots. Additional spectroscopic characterization (multinuclear NMR, FT‐IR, and MS) of the disulfonyl bromide derivatives BrSO2(CF2)4SO2Br, BrSO2(CF2)6SO2Br, and BrSO2(CF2)8SO2Br has also been obtained as well as some preliminary spectroscopic evidence for BrSO2(CF2)2SO2Br and BrSO2CF2O(CF2)2OCF2SO2Br. The implication of these results toward the preparation of the corresponding disulfonyl iodides is discussed.