bluuebunny/crossref_metadata_2025_split huggingface dataset:
InP Low‐Dimensional Nanomaterials for Electronic and Optoelectronic Device Applications: A Review
Authors: Yue Lin‐Qing , Shi Yan‐Lei , Sun Nie‐Feng , Qiang Sheng , Qin Jing‐Kai , Zhen Liang , Xu Cheng‐Yan 
Published: March 2023

AbstractThe suitable direct bandgap, high carrier mobility, biologically nontoxicity, and size‐dependent physical properties of low‐dimensional indium phosphide InP (0D, 1D, and 2D) have attracted great interest from scientists. The appealing optical and electronic properties make them promising for the fabrication of state‐of‐the‐art nanoscale electronic and optoelectronic devices including photodiode, photodetector, and solar cells. This Review focuses on the recent development of low‐dimensional InP materials. The synthesis methods and growth mechanisms of high quality low‐dimensional InP are comprehensively recapped. The multifunctional applications in electronic and optoelectronic devices of low‐dimensional InP are discussed, and typical strategies to resolve the main challenges limiting the performance of low‐dimensional InP‐based application are then reviewed. Finally, a brief perspective on the challenges and opportunities of low‐dimensional InP in synthesis, electronics, and optoelectronics applications is also provided.
Frequency Reconfigurable and Multifunctional Metastructure Regulated by Nematic Liquid Crystal: Broadband Circular to Linear Polarization Converter
Authors: Qiao Zhen , Zhang Wei , Li Yu‐Peng , Li Bing‐Xiang , Zhang Hai‐Feng 
Published: March 2023

AbstractWith the tunability of the nematic liquid crystal (NLC), a broadband frequency reconfigurable and versatile metastructure (MS) is proposed and theoretically investigated in this paper, combining circular‐to‐linear (CTL) polarization conversion (PC) and circular‐to‐circular (CTC) PC simultaneously. The MS is composed of two via‐coupled modules, which can respond differently to the incident waves. Each module is connected utilizing a metal via a column, thus exceedingly enhancing the energy transmission and reducing the loss when transmitting. When the applied bias voltage (Vbias) is 0 V, the NCL molecules follow the initial orientation. The MS converts the incident right circular polarized (RCP) waves into linear polarized (LP) waves within 8.11–9.95 gigahertz (GHz) with a relative bandwidth of 20.38% and achieves the PC of left circular polarized (LCP) into RCP waves. As the Vbias reaches 20 V, the original operating interval reconfigures and shifts overall toward a lower frequency. The bandwidth of CTL is 7.66–9.02 GHz, and the CTC PC is broadened to 20.20%. Meanwhile, the structure justification is verified, and the inducing mechanism of PC is expounded. Possessing the merits of versatile collaborative processing and wide operating bands, such an MS is promising to be a polarization‐controlled application candidate and enrich multifunctional designs.
Photo‐Response with Radical Afterglow by Regulation of Spin Populations and Hole‐Electron Distributions
Authors: Yang Yujie , Wang Jiaqiang , Yang Jie , Tong Lihuan , Li Dan , Yang Yuqi , Fang Manman , Li Zhen 
Published: March 2023

AbstractNo matter photoinduced organic radicals have been reported frequently, they are usually non‐luminescent at ambient conditions. The internal mechanism on stability and electronic transitions of photoinduced radicals, is thus crucial for the development of relevant materials. Herein, a series of photoinduced radical emission systems were developed conveniently through doping benzoic acids into the hydrogen donor polyvinyl alcohol (PVA) matrix. Visual photoinduced radical emission and photochromism could be observed on Ph‐3COOH@PVA film with the formation of cyclohexadienyl‐type structure. For the first time, radical afterglow appeared with energy transfer from triplet state. The appropriate introduction of carboxylic groups to three nonadjacent carbon atoms on the benzene ring was the best for decreasing spin population and promoting electronic transitions of the radical. This study largely expands the radical emission property from both internal mechanism and practical application.
Non‐planar Nest‐like [Fe2S2] Cluster Sites for Efficient Oxygen Reduction Catalysis
Authors: Wang Ming , Zhang Zhong , Zhang Songlin , Liu Wei , Shang Wenzhe , Su Xiaofang , Liang Yan , Wang Furi , Ma Xujiao , Li Yadong , Liu Yiwei 
Published: March 2023

AbstractMetal‐nitrogen‐carbon catalysts, as promising alternative to platinum‐based catalysts for oxygen reduction reaction (ORR), are still highly expected to achieve better performance by modulating the composition and spatial structure of active site. Herein, we constructed the non‐planar nest‐like [Fe2S2] cluster sites in N‐doped carbon plane. Adjacent double Fe atoms effectively weaken the O−O bond by forming a peroxide bridge‐like adsorption configuration, and the introduction of S atoms breaks the planar coordination of Fe resulting in greater structural deformation tension, lower spin state, and downward shifted Fe d‐band center, which together facilitate the release of OH* intermediate. Hence, the non‐planar [Fe2S2] cluster catalyst, with a half‐wave potential of 0.92 V, displays superior ORR activity than that of planar [FeN4] or [Fe2N6]. This work provides insights into the co‐regulation of atomic composition and spatial configuration for efficient oxygen reduction catalysis.
A Modular Tubular Flow System with Replaceable Photocatalyst Membranes for Scalable Coupling and Hydrogenation
Authors: Li Yajiao , Zhang Dongsheng , Ye Jiani , Mai Yuanqiang , Wang Chao , Yang Yong , Li Yongwang , Besenbacher Flemming , Niemantsverdriet Hans , Rosei Federico , Pan Feng , Su Ren 
Published: March 2023

AbstractHeterogeneous photocatalysis is effective for the selective synthesis of value‐added chemicals at lab‐scale, yet falls short of requirements for mass production (low cost and user friendliness). Here we report the design and fabrication of a modular tubular flow system embedded with replaceable photocatalyst membranes for scalable photocatalytic C−C, C−N homocoupling and hydrogenation reactions, which can be operated in either circular and continuous flow mode with high performance. The photocatalyst membranes almost fully occupy the volume of the reactor, thus enabling optimal absorption of the incident light. Additionally, the porous structured photocatalyst membranes facilitate the mass transfer of the reactants to efficiently use the active sites, resulting in 0th‐order reaction kinetics and a high space‐time yield compared to the batch reaction system at practical application levels and prolonged reaction times.
Preparation and properties of cellulose acetate graft copolymer‐coated adsorbent resin for hemoperfusion device
Authors: Gao Xingtong , Liu Kai , Liu Peng , Bai Xiaoyu , Li Aixiang , Lyu Zijian , Li Qiuhong 
Published: March 2023

AbstractIn this paper, acrylic acid (AA) and sodium styrene sulfonate (SSS) were grafted onto the surface of cellulose acetate (CA) by free radical polymerization to obtain a heparin unit‐containing graft copolymer CA‐g‐P(AA/SSS). It was used to coat the adsorbent resin for disposable hemoperfusion devices to improve blood compatibility. The adsorption capacity of the modified CA‐coated adsorbent resin to creatinine, Vitamin B12, bilirubin, and imidacloprid was tested. The results showed that the modified CA‐coated adsorbent resin had a good adsorption effect on small and medium‐sized molecules. The hemolysis and coagulation tests showed that the CA‐g‐P(AA/SSS) coating could greatly improve the blood compatibility of the adsorbent resin. The hemolysis rate was 1.6%, which met the requirement of international standards for the hemolysis rate of blood contact equipment less than 5%. The coagulation index was higher than 1.55, which was comparable to the heparin‐preflashed HA130 currently in use. In addition, the CA‐g‐P(AA/SSS)‐coated adsorbent resin has good biocompatibility, no pyrogenic reaction, low vitro cytotoxicity, and no acute systemic toxicity. The resin has a good application prospect in uremia, hyperbilirubinemia, and rapid treatment of pesticide poisoning.
Separation, recovery and upgrading of 2,3‐butanediol from fermentation broth
Authors: Rajale Trideep , Yang Xiaokun , Judge Elizabeth J. , Moore Cameron M. , Martinez Abraham , Guo Mond F. , Ramasamy Karthikeyan K. , Elander Richard , Sutton Andrew D. 
Published: March 2023

Abstract2,3‐Butanediol (BDO) is a bio‐derived building block available from biomass through biochemical methods in high titers (>120 g L−1) making it an attractive target for production and further upgrading to chemical products and fuels such as sustainable aviation fuel. A key challenge to enable the adoption of BDO as a precursor is the effective separation and isolation of this molecule from the fermentation broth. 2,3‐Butanediol has a boiling point higher than that of water (177°C), and as a consequence, separation via distillation methods is an energy‐intensive and therefore costly approach. We have improved the BDO separation through conversion to a 1,3‐dioxolane directly in fermentation broth via reaction with bio‐derived aldehydes catalyzed by a solid acid catalyst. The resulting dioxolane phase separates from the fermentation broth, allowing for easy decantation and isolation in >90% isolated yield. Isolated dioxolane can be used directly as a compression iginition fuel, trans‐acetalized to recover high‐purity BDO or used directly in a catalytic process as a BDO synthon to produce methyl ethyl ketone with aldehyde recovery in near quantitative yield.
Tuning the Surface Wettability of Pd/COFs for Selective Hydrogenation
Authors: Li Xiang , Li He , Li Chunzhi , Wang Maodi , Yang Qihua 
Published: March 2023

AbstractCovalent organic frameworks (COFs) with imine linkage are promising solid supports to disperse ultra‐fine metal nanoparticles (NPs), but the modulation of their surface wettability, an important parameter affecting the catalytic performance of metal NPs, is still very challenging. Here, we report the preparation of two imine‐linked COFs with moderate and strong surface hydrophobicity by changing the carbon chain length of side oxyalkyl groups. Ultra‐small Pd NPs with an average size of ∼2.0 nm was successfully loaded on the two COFs, attributed to the strong interactions of Pd NPs and imine linkage as evidenced by the electron donating from imine linkage to Pd NPs by XPS characterizations. The TOF of Pd/COF is much higher than commercial Pd/C (714 h−1 vs 489 h−1) in the hydrogenation of nitrobenzene, which is attributed to the electron rich Pd, the hydrophobic surface and crystalline structure of COFs. Pd NPs on COFs with strong hydrophobicity are more active than those on COFs with moderate hydrophilicity in the hydrogenation of moderate lipophilic nitro compounds such as nitrobenzene, methyl nitrobenzene and nitronaphthalene. Reversed tendency was observed for the hydrogenation of moderate hydrophilic p‐amino‐nitrobenzene. The modulation of the surface wettability of COFs provides an efficient strategy to improve the catalytic performance of supported metal NPs.
Role of Titanium in Ti/SiO2‐Supported Metallocene‐based Olefin Polymerization Catalysts. Part 1: Genesis of Active Sites and Catalytic Performance
Authors: Zanoni Silvia , Welle Alexandre , Cirriez Virginie , Weckhuysen Bert M. 
Published: March 2023

AbstractPerformance enhancement of metallocene‐based olefin polymerization catalysts can be obtained, among others, by the chemical modification of their support. We investigated a titanated SiO2 (Ti/SiO2) as an improved support material for zirconocene catalysts, which lead to ∼35 % higher ethylene polymerization yields when compared to the unmodified SiO2‐supported metallocene. The improved catalytic performance of the modified catalyst was found to be related to the presence of a Ti‐based active site, second to the Zirconocene centers, as well as to a higher Lewis acidity in the titanated supported‐MAO, which improved the activation of the Zr‐based centers. The Ti active species were generated by reduction of the Ti/SiO2 support with the methylaluminoxane (MAO) co‐catalysts, which introduced oxygen vacancies (VO) and Ti3+ species, as confirmed by probe molecule Fourier Transform Infrared (FT‐IR) spectroscopy and UV‐Vis Diffuse Reflectance Spectroscopy (DRS). The higher Lewis acidity was linked to 5‐coordinated Ti4+, as detected by probe molecules FT‐IR spectroscopy.
N‐Doped Porous Carbon with Outstanding Pb2+ Adsorption Capacity in Wastewater
Authors: Hu Le , Chen Wenjie , Niu Yuxin , Wang Na , Liu Bin , Song Fuxiang 
Published: March 2023

AbstractAn N‐doped porous carbon (NPC) with porous structure was successfully prepared by a one‐step calcination method. The NPC with its abundant modified active functional groups was used in adsorption experiments, showing that the adsorption capacity of NPC for Pb2+ was up to 179.86 mg g−1 at pH 5. It displayed a fast kinetic adsorption rate and high selective adsorption and cyclic adsorption capacities. The Pb2+ adsorption mechanism consisted in cationic‐π interactions and electrostatic attraction. Thus, the developed NPC has a high potential for application in the removal of Pb2+ from wastewater, due to its excellent adsorption behavior and porous structure.
Assembling Artificial Photosynthetic Models in Water Using β‐Cyclodextrin‐Conjugated Phthalocyanines as Building Blocks
Authors: Chen Xiao‐Fei , Gobeze Habtom B. , D'Souza Francis , P. Ng Dennis K. 
Published: March 2023

AbstractTwo water‐soluble zinc(II) phthalocyanines substituted with two or four permethylated β‐cyclodextrin (β‐CD) moieties at the α positions have been utilized as building blocks for the construction of artificial photosynthetic models in water. The hydrophilic and bulky β‐CD moieties not only can increase the water solubility of the phthalocyanine core and prevent its stacking in water but can also bind with a tetrasulfonated zinc(II) porphyrin (ZnTPPS) and/or sodium 2‐anthraquinonesulfonate (AQ) in water through host–guest interactions. The binding interactions of these species have been studied spectroscopically, while the photoinduced processes of the resulting complexes have been investigated using steady‐state and time‐resolved spectroscopic methods. In the ternary complexes, the ZnTPPS units serve as light‐harvesting antennas to capture the light energy and transfer it to the phthalocyanine core via efficient excitation energy transfer. The excited phthalocyanine is subsequently quenched by the electron‐deficient AQ units through electron transfer. Femtosecond transient absorption spectroscopy provides clear evidence for the singlet‐singlet energy transfer from the photo‐excited ZnTPPS to the phthalocyanine core with a rate constant (kENT) in the order of 109 s−1. The population of phthalocyanine radical cations indicates the occurrence of electron transfer from the excited phthalocyanine to the AQ moieties, forming a charge‐separated state.
Circular dichroism of molecular aggregates: A tutorial
Authors: Bertocchi Francesco , Sissa Cristina , Painelli Anna 
Published: March 2023

AbstractIn this tutorial, we guide the reader through two alternative approaches to the calculation of circular dichroism (CD) spectra of chiral supramolecular assemblies of non‐chiral chromophores. The two seemingly different approaches rely on the same basic approximations and are therefore expected to lead to similar results. For a dimer, we obtain explicit analytic expressions for the CD responses in the two approaches and demonstrate the perfect equivalence of the two methods. Numerical results for larger systems further validate this result. We hope that this tutorial will help young students and scientists entering the field to approach the fascinating topic of supramolecular chirality.
Wassermanagement als Schlüsselparameter für die Skalierung eines CO2‐Elektrolyseurs
Authors: Hoof Lucas , Pellumbi Kevinjeorjios , Heuser Stephan , Siegmund Daniel , junge Puring Kai , Apfel Ulf-Peter 
Published: March 2023

AbstractEine der größten Herausforderungen der elektrochemischen Umwandlung von CO2 zu CO in Zero‐Gap‐Elektrolyseuren ist die Skalierung dieser Systeme in den industriellen Maßstab. Trotz der bemerkenswerten Ergebnisse der letzten Jahre, sind bisher nur wenige Fortschritte bei der Skalierung dieser Technologie erzielt worden. In diesem Beitrag wird gezeigt, wie die Steuerung des Wassergehalts an der Kathode es ermöglicht Flutungsprozesse zu minimieren und aussichtsreiche experimentelle Ergebnisse auf größere CO2 Elektrolysesysteme zu übertragen.
Oligomeric, phosphorylated, and truncated tau and spliceosome pathology within the entorhinal–hippocampal connectome across stages of Alzheimer's disease
Authors: Mahady Laura J. , Perez Sylvia E. , Malek‐Ahmadi Michael , Mufson Elliott J. 
Published: March 2023

AbstractNeurofibrillary tangles (NFTs) contain abnormally phosphorylated tau proteins, which spread within components of the medial temporal lobe (MTL) memory circuit in Alzheimer's disease (AD). Here, we used quantitative immunohistochemistry to determine the density of posttranslational oligomeric (TOC1 and TNT1), phosphorylated (AT8), and late truncated (TauC3) tau epitopes within the MTL subfields including entorhinal cortex (EC) layer II, subiculum, Cornu Ammonis (CA) subfields, and dentate gyrus (DG) in subjects who died with a clinical diagnosis of no cognitive impairment (NCI), mild cognitive impairment (MCI), and AD. We also examined whether alterations of the nuclear alternative splicing protein, SRSF2, are associated with tau pathology. Although a significant increase in TOC1, TNT1, and AT8 neuron density occurred in the EC in MCI and AD, subicular, DG granule cell, and CA1 and CA3 densities were only significantly higher in AD. TauC3 counts were not different between connectome regions and clinical groups. SRSF2 intensity in AT8‐positive cells decreased significantly in all regions independent of the clinical groups examined. CA1 and subicular AT8, TauC3, and oligomeric densities correlated across clinical groups. EC AT8 counts correlated with CA subfields and subicular and DG values across clinical groups. Oligomeric and AT8 CA1, EC, and subicular density correlated with Braak stage. Decreased nuclear SRSF2 in the presence of cytoplasmic phosphorylated tau suggests a dual‐hit process in NFT formation within the entorhinal hippocampal connectome during the onset of AD. Although oligomeric and phosphorylated tau follow a stereotypical pattern, clinical disease stage determined density of tau deposition and not anatomic location within the entorhinal–hippocampal connectome.
Utilization of a cell‐penetrating peptide‐adaptor for delivery of human papillomavirus proteinE2into cervical cancer cells to arrest cell growth and promote cell death
Authors: LeCher Julia C. , Didier Hope L. , Dickson Robert L. , Slaughter Lauren R. , Bejarano Juana C. , Ho Steven , Nowak Scott J. , Chrestensen Carol A. , McMurry Jonathan L. 
Published: March 2023

AbstractBackgroundHuman papillomavirus (HPV) is the causative agent of nearly all forms of cervical cancer, which can arise upon viral integration into the host genome and concurrent loss of viral regulatory gene E2. Gene‐based delivery approaches show that E2 reintroduction reduces proliferative capacity and promotes apoptosis in vitro.AimsThis work explored if our calcium‐dependent protein‐based delivery system, TAT‐CaM, could deliver functional E2 protein directly into cervical cancer cells to limit proliferative capacity and induce cell death.Materials and ResultsTAT‐CaM and the HPV16 E2 protein containing a CaM‐binding sequence (CBS‐E2) were expressed and purified fromEscherichia coli. Calcium‐dependent binding kinetics were verified by biolayer interferometry. Equimolar TAT‐CaM:CBS‐E2 constructs were delivered into the HPV16+SiHa cell line and uptake verified by confocal microscopy. Proliferative capacity was measured by MTS assay and cell death was measured by release of lactate dehydrogenase. As a control, human microvascular cells (HMECs) were used. As expected, TAT‐CaM bound CBS‐E2 with high affinity in the presence of calcium and rapidly disassociated upon its removal. After introduction by TAT‐CaM, fluorescently labeled CBS‐E2 was detected in cellular interiors by orthogonal projections taken at the depth of the nucleus. In dividing cells, E2 relocalized to regions associated with the mitotic spindle. Cells receiving a daily dose of CBS‐E2 for 4 days showed a significant reduction in metabolic activity at low doses and increased cell death at high doses compared to controls. This phenotype was retained for 7 days with no further treatments. When subcultured on day 12, treated cells regained their proliferative capacity.ConclusionsUsing the TAT‐CaM platform, bioactive E2 protein was delivered into living cervical cancer cells, inducing senescence and cell death in a time‐ and dose‐dependent manner. These results suggest that this nucleic acid and virus‐free delivery method could be harnessed to develop novel, effective protein therapeutics.
Can Li Atoms Anchored on Boron‐ and Nitrogen‐Doped Graphene Catalyze Dinitrogen Molecules to Ammonia? A DFT Study
Authors: Singh Verma Tushar , Paramita Samal Pragnya , Selvaraj Kaliaperumal , Krishnamurty Sailaja 
Published: March 2023

AbstractThe most successful electrochemical conversion of ammonia from dinitrogen molecule reported to date is through a Li mediated mechanism. In the framework of the above fact and that Li anchored graphene is an experimentally feasible system, the present work is a computational experiment to identify the potential of Li anchored graphene as a catalyst for N2 to NH3 conversion as a function of (a) minimum number of Li atoms needed for anchoring on graphene sheets and (b) the role of chemical modification of graphene surfaces. The studies bring forth an understanding that Li anchored graphene sheets are potential catalysts for ammonia conversion with preferential adsorption of N2 through end‐on configuration on Li atoms anchored on doped and pristine graphene surfaces. This mode of adsorption being characteristic of Nitrogen Reduction Reaction (NRR) through enzymatic pathway, examination of the same followed by analysis of electronic properties demonstrates that tri‐Li atoms (Tri Atom Catalysts, TACs) are more efficient as catalysts for NRR as compared to two Li atoms (Di Atom Catalysts, DACs). Either way, the rate determining step was found to be *NH2→*NH3 step (mixed pathway) with ΔGmax=1.02 eV and *NH2−*NH3→*NH2 step (enzymatic pathway) with ΔGmax=1.11 eV for 1B doped TAC and DAC on graphene sheet, respectively. Consequently, this work identifies the viability of Li anchored graphene based 2‐D sheets as hetero‐atom catalyst for NRR.