bluuebunny/crossref_metadata_2025 huggingface dataset:
Single Component Organic Photosensitizer with NIR‐I Emission Realizing Type‐I Photodynamic and GSH‐Depletion Caused Ferroptosis Synergistic Theranostics
Authors: Fang Laiping , Han Mingda , Zhang Yuan , Song Yue , Liu Botong , Cai Minmin , Jiang Mengpei , Hu Liyun , Zheng Ran , Lian Xin , Yan Fei , Huang Keke , Feng Shouhua
Published: April 2023

Phototheranostic agents have thrived as prominent tools for tumor luminescence imaging and therapies. Herein, a series of organic photosensitizers (PSs) with donor‐acceptors (D‐A) are elaborately designed and synthesized. In particular, PPR‐2CN exhibits stable near infrared‐I (NIR‐I) emission, excellent free radicals generation and phototoxicity. Experimental analysis and calculations imply that a small singlet‐triplet energy gap (ΔES1−T1) and large spin‐orbit coupling (SOC) constant boost the intersystem crossing (ISC), leading to type‐I photodynamic therapy (PDT). Additionally, the specific glutamate (Glu) and glutathione (GSH) consumption abilities of PPR‐2CN inhibit the intracellular biosynthesis of GSH, resulting in redox dyshomeostasis and GSH‐depletion causing ferroptosis. This work first realizes that single component organic PS could be simultaneously used as a type‐I photodynamic agent and metal‐free ferroptosis inducer for NIR‐I imaging‐guided multimodal synergistic therapy.
Recent Developments of Inorganic Nanosensitizers for Sonodynamic Therapy
Authors: He Zongyan , Du Jun , Miao Yuqing , Li Yuhao
Published: April 2023

As a noninvasive treatment, sonodynamic therapy (SDT) has been widely used in the treatment of tumors because of its ability to penetrate deep tissue with few side effects. As the key factor of SDT, it is meaningful to design and synthesize efficient sonosensitizers. Compared with organic sonosensitizers, inorganic sonosensitizers can be easily excited by ultrasound. In addition, inorganic sonosensitizers with stable properties, good dispersion, and long blood circulation time, have great development potential in SDT. This review summarizes possible mechanisms of SDT (sonoexcitation and ultrasonic cavitation) in detail. Based on these mechanisms, the design and synthesis of inorganic nanosonosensitizers can be divided into three categories: traditional inorganic semiconductor sonosensitizers, enhanced inorganic semiconductor sonosensitizers, and cavitation‐enhanced sonosensitizers. Subsequently, the current efficient construction methods of sonosensitizers are summarized including accelerated semiconductor charge separation and enhanced production of reactive oxygen species through ultrasonic cavitation. Furthermore, the advantages and disadvantages of different inorganic sonosensitizers and detailed strategies are systematically discussed on how to enhance SDT. Hopefully, this review could provide new insights into the design and synthesis of efficient inorganic nano‐sonosensitizers for SDT.
Preparation and Properties of Shape Memory PEG/IEM Resin and Its Composite Designed for Ureter Stent
Authors: Li Ce , Zhang Fenghua , Zhao Wei , Wang Linlin , Liu Yanju , Leng Jinsong
Published: April 2023

In this paper, isocyanoethyl methacrylate (IEM) is used to functionalize the two ends of poly(ethylene glycol) (PEG) diol with acrylic acid groups through an urethanization reaction. The synthesized PEG/IEM resin is then photo‐cured with a 405 nm ultraviolet lamp. Ttrans of the PEG/IEM resin can be regulated by the different molecular weights of PEG and the use of plasticizer Triacetin to reach 44 °C, which is closer to the human body temperature. Cytotoxicity assay and DMA shape memory cycling testing show that the PEG/IEM resin has excellent biocompatibility and shape memory properties. The flower structure is prepared and its shape recovery process is demonstrated. The performance of 10wt% nano Fe3O4/PEG4000/IEM resin and its composite spring stent structure satisfy the requirement of the stent properties in vivo, and can quickly recover to the original shape under magnetically driven. This work provides a material option for developing new biological application devices such as ureter stents.
Hierarchically Ordered Macro–Mesoporous Electrocatalyst with Hydrophilic Surface for Efficient Oxygen Reduction Reaction
Authors: Yao Wen , Hu Anqian , Ding Jieting , Wang Nanshu , Qin Ze , Yang Xianfeng , Shen Kui , Chen Liyu , Li Yingwei
Published: April 2023

Metal–organic frameworks (MOFs) offer versatile templates/precursors to prepare supported metal catalysts. However, the afforded catalysts usually exhibit microporous structures and unsuitable wettability, which will restrict the accessibility of active sites in liquid‐phase reactions. Herein, an etching–functionalization strategy is developed for the construction of a tannic‐acid‐functionalized MOF with a unique hollow‐wall and 3D‐ordered macroporous (H‐3DOM) structure. The functional MOF can be further employed as an ideal precursor for the synthesis of cobalt supported on oxygen/nitrogen‐co‐doped carbon composites with H‐3DOM structures, and hydrophilic surface. The H‐3DOM structure can improve the external surface area to maximize the exposure of active sites. Moreover, the oxygen‐containing functional groups can enhance the surface wettability to guarantee the external active sites to be more electrochemically accessible in aqueous electrolyte. Benefitting from these outstanding characteristics, H‐3DOM‐Co/ONC exhibits high electrocatalytic activity in the oxygen reduction reaction, superior to its counterparts without the hierarchically ordered structure and surface functionalization.
Surface‐Functionalized Nanoparticles as Catalysts for Artificial Photosynthesis
Authors: Martí Gerard , Mallón Laura , Romero Nuria , Francàs Laia , Bofill Roger , Philippot Karine , García‐Antón Jordi , Sala Xavier
Published: April 2023

Analogously to enzymatic catalysis, where the active metal sites and their environment are controlled by protein residues, the catalytic properties of metal nanoparticles (NPs) can be tuned by carefully selecting their surface‐coordinated species. In artificial photosynthesis, surface‐functionalization emerged in the last decade, grounded on the development of reliable methods for tailored synthesis, advanced characterization and theoretical modeling of metal NPs, altogether with the aim of transferring to the nanoscale the mechanistic knowledge acquired from molecular complexes. Metal NPs surface‐functionalization modulates the energetics of key catalytic intermediates, introduces second coordination sphere effects, influences the catalyst‐electrolyte interface, and determines the metal NPs surface coverage and, accordingly, the number of accessible active sites. In photoactivated systems, metal NPs surface‐functionalization may play a key role in modulating the charge transfers and recombination processes between the light absorber and the active sites and in the light absorber itself. Thus, after a presentation of the most relevant synthetic methods to produce well‐defined surface‐functionalized metal NPs, a critical analysis of why the above effects are the cornerstone in enhancing their catalytic performance in the key processes of artificial photosynthesis, namely the oxygen evolution reaction, the hydrogen evolution reaction, and the CO2 reduction reaction, is given.
New insights on regional differences of the farmland price structure: An extended replication study on the parcel size–price relationship
Authors: Schaak Henning , Meissner Luise , Musshoff Oliver
Published: April 2023

This study adds insights about the nonlinear effect of parcel sizes on farmland prices. Therefore, replications of Ritter et al. (2020, Land Use Policy, DOI: j.landusepol.2020.104771) are performed in four ways. The study contributes to the literature within two dimensions: (i) the geographical scope, which allows insights into regional differences in the price structure for farmland and (ii) the role of assumptions regarding the functional form for the size–price relationship. The results of the extended replication show that the size–price relationship differs between federal states. Further, the results highlight the importance of assumptions imposed on functional forms of nonlinear relationships in hedonic regression studies.
MicroRNA expression in extracellular vesicles as a novel blood‐based biomarker for Alzheimer's disease
Authors: Kumar Ashish , Su Yixin , Sharma Mitu , Singh Sangeeta , Kim Susy , Peavey Jeremy J. , Suerken Cynthia K. , Lockhart Samuel N. , Whitlow Christopher T. , Craft Suzanne , Hughes Timothy M. , Deep Gagan
Published: April 2023

INTRODUCTION

Brain cell–derived small extracellular vesicles (sEVs) in blood offer unique cellular and molecular information related to the onset and progression of Alzheimer's disease (AD). We simultaneously enriched six specific sEV subtypes from the plasma and analyzed a selected panel of microRNAs (miRNAs) in older adults with/without cognitive impairment.

METHODS

Total sEVs were isolated from the plasma of participants with normal cognition (CN; n = 11), mild cognitive impairment (MCI; n = 11), MCI conversion to AD dementia (MCI‐AD; n = 6), and AD dementia (n = 11). Various brain cell–derived sEVs (from neurons, astrocytes, microglia, oligodendrocytes, pericytes, and endothelial cells) were enriched and analyzed for specific miRNAs.

RESULTS

miRNAs in sEV subtypes differentially expressed in MCI, MCI‐AD, and AD dementia compared to the CN group clearly distinguished dementia status, with an area under the curve (AUC) > 0.90 and correlated with the temporal cortical region thickness on magnetic resonance imaging (MRI).

DISCUSSION

miRNA analyses in specific sEVs could serve as a novel blood‐based molecular biomarker for AD.

Highlights

Multiple brain cell–derived small extracellular vesicles (sEVs) could be isolated simultaneously from blood.

MicroRNA (miRNA) expression in sEVs could detect Alzheimer's disease (AD) with high specificity and sensitivity.

miRNA expression in sEVs correlated with cortical region thickness on magnetic resonance imaging (MRI).

Altered expression of miRNAs in sEVCD31 and sEVPDGFRβ suggested vascular dysfunction.

miRNA expression in sEVs could predict the activation state of specific brain cell types.
Altered limbic functional connectivity in individuals with subjective cognitive decline: Converging and diverging findings across Chinese and German cohorts
Authors: Jiang Xueyan , Hu Xiaochen , Daamen Marcel , Wang Xiaoqi , Fan Chunqiu , Meiberth Dix , Spottke Annika , Roeske Sandra , Fliessbach Klaus , Spruth Eike Jakob , Altenstein Slawek , Lohse Andrea , Hansen Niels , Glanz Wenzel , Incesoy Enise I. , Dobisch Laura , Janowitz Daniel , Rauchmann Boris‐Stephan , Ramirez Alfredo , Kilimann Ingo , Munk Matthias H. , Wang Xiao , Schneider Luisa‐Sophie , Gabelin Tatjana , Roy Nina , Wolfsgruber Steffen , Kleineidam Luca , Hetzer Stefan , Dechent Peter , Ewers Michael , Scheffler Klaus , Amthauer Holger , Buchert Ralph , Essler Markus , Drzezga Alexander , Rominger Axel , Krause Bernd J. , Reimold Matthias , Priller Josef , Schneider Anja , Wiltfang Jens , Buerger Katharina , Perneczky Robert , Teipel Stefan , Laske Christoph , Peters Oliver , Düzel Emrah , Wagner Michael , Jiang Jiehui , Jessen Frank , Boecker Henning , Han Ying
Published: April 2023

INTRODUCTION

It remains unclear whether functional brain networks are consistently altered in individuals with subjective cognitive decline (SCD) of diverse ethnic and cultural backgrounds and whether the network alterations are associated with an amyloid burden.

METHODS

Cross‐sectional resting‐state functional magnetic resonance imaging connectivity (FC) and amyloid‐positron emission tomography (PET) data from the Chinese Sino Longitudinal Study on Cognitive Decline and German DZNE Longitudinal Cognitive Impairment and Dementia cohorts were analyzed.

RESULTS

Limbic FC, particularly hippocampal connectivity with right insula, was consistently higher in SCD than in controls, and correlated with SCD‐plus features. Smaller SCD subcohorts with PET showed inconsistent amyloid positivity rates and FC–amyloid associations across cohorts.

DISCUSSION

Our results suggest an early adaptation of the limbic network in SCD, which may reflect increased awareness of cognitive decline, irrespective of amyloid pathology. Different amyloid positivity rates may indicate a heterogeneous underlying etiology in Eastern and Western SCD cohorts when applying current research criteria. Future studies should identify culture‐specific features to enrich preclinical Alzheimer's disease in non‐Western populations.

Highlights

Common limbic hyperconnectivity across Chinese and German subjective cognitive decline (SCD) cohorts was observed.

Limbic hyperconnectivity may reflect awareness of cognition, irrespective of amyloid load.

Further cross‐cultural harmonization of SCD regarding Alzheimer's disease pathology is required.
Evolutionary Algorithm Directed Synthesis of Mixed Anion Compounds LaF2X (X=Br, I) and LaFI2
Authors: Kato Daichi , Song Peng , Ubukata Hiroki , Taguro Haruki , Tassel Cédric , Miyazaki Kohei , Abe Takeshi , Nakano Kousuke , Hongo Kenta , Maezono Ryo , Kageyama Hiroshi
Published: April 2023

Mixed‐anion compounds have attracted growing attentions, but their synthesis is challenging, making a rational search desirable. Here, we explored LaF3‐LaX3 (X=Cl, Br, I) system using ab initio structure searches based on evolutionary algorithms, and predicted LaF2X and LaFX2 (X=Br, I), which are respectively isostructural with LaHBr2 and YH2I, consisting of layered La‐F blocks with single and double ordered honeycomb lattices, separated by van der Waals gaps. We successfully synthesized these compounds: LaF2Br and LaFI2 crystallize in the predicted structure, while LaF2I is similar to the predicted one but with different layer stacking. LaF2I exhibits fluoride ion conductivity comparable to that of non‐doped LaF3, and has the potential to show better ionic conductivity upon appropriate doping, given the theoretically lower diffusion energy barrier and the presence of soft iodine anions. This study shows the structure prediction using evolutionary algorithms will accelerate the discovery of mixed‐anion compounds in future, in particular those with an ordered anion arrangement.
NIR‐Absorbing B,N‐Heteroarene as Photosensitizer for High‐Performance NIR‐to‐Blue Triplet‐Triplet Annihilation Upconversion
Authors: Li Ji‐Kun , Zhang Ming‐Yu , Zeng Le , Huang Ling , Wang Xiao‐Ye
Published: April 2023

Triplet‐triplet annihilation upconversion (TTA‐UC) with near‐infrared (NIR) photosensitizers is highly desirable for a variety of emerging applications. However, the development of NIR‐to‐blue TTA‐UC with a large anti‐Stokes shift is extremely challenging because of the energy loss during the intersystem crossing (ISC). Here, we develop the first NIR‐absorbing B,N‐heteroarene‐based sensitizer (BNS) with multi‐resonance thermally activated delayed fluorescence (MR‐TADF) characters to achieve efficient NIR‐to‐blue TTA‐UC. The small energy gap between the singlet and triplet excited states (0.14 eV) of BNS suppresses the ISC energy loss, and its long‐delayed fluorescence lifetime (115 μs) contributes to efficient triplet energy transfer. As a result, the largest anti‐Stokes shift (1.03 eV) among all heavy‐atom‐free NIR‐activatable TTA‐UC systems is obtained with a high TTA‐UC quantum yield of 2.9 % (upper limit 50 %).
Preserving Macroporosity in Type III Porous Liquids
Authors: Dai Dejun , Luo Lianshun , Zhu Qinlin , Wang Dongxu , Li Tao
Published: April 2023

Preserving large permanent pore structures in a fluid may endow conventional liquids with emergent physical properties. However, such materials are challenging to make because of the tendency of the pores to be filled and occupied by the solvent molecules. Here, we report the design and synthesis of the first Type III porous liquid (PL) containing uniform yet stable 480 nm cavities. This was achieved by first constructing a single crystalline hollow metal–organic framework (MOF), UiO‐66‐NH2, through chemical etching. The thin yet defect‐free MOF shell effectively excludes the bulky poly(dimethylsiloxane) solvent molecules from entering the cavity through its 4 Å aperture, resulting in the preservation of both micro‐ and macroporosity in the PL. These enormous void spaces allow the PL to reversibly host and release up to 27 wt % water for up to 10 cycles. The switching between the “dry” state and the “wet” state led to a large changes of the thermal conductivity of the PL from 0.140 to 0.256 W m−1 K−1, affording a guest‐responsive liquid thermal switch with a switching ratio of 1.8.
Modulation of Colloidal Assembly Behavior Enables Printable Low‐Dimensional Perovskite Photovoltaics
Authors: Xing Zhi , Meng Xiangchuan , Li Dengxue , Zhang Yanyan , Fan Baojin , Huang Zengqi , Wang Fuyi , Hu Xiaotian , Hu Ting , Chen Yiwang
Published: April 2023

The multiple quantum wells (QWs) distribution in low‐dimensional perovskite films hinders charge transport due to the fundamental difficulty of controlling crystal growth from precursor solutions, yielding poorly homogeneous low‐dimensional perovskite solar cells (PSCs), especially in upscaling fabrication. Here, efficient low‐dimensional PSCs are realized by modulating the colloidal assembly behavior in the precursor solution to induce intermediate structures. In combination with in situ liquid time‐of‐flight secondary ion mass spectrometry, the assembly behavior of organic cations involved lead iodide‐dominated colloidal soft framework is visualized by investigating the precursor species differences under hydrogen bonding interactions. Subsequently, solid‐state reactions emerge and the formamidine (FA)‐based perovskite films exhibit significantly suppressed multiple QWs distribution. Encouragingly, the FA device (n=9, by meniscus‐assisted coating) achieves a power conversion efficiency (PCE) of 20.28 % for a size of 0.04 cm2 and a PCE of 15.35 % for a mini‐module of 16.94 cm2 with superior stability.
Fluorescence Enhancement of a Metal‐Organic Framework for Ultra‐Efficient Detection of Trace Benzene Vapor
Authors: Li Wen‐Bin , Wu Ying , Zhong Xiao‐Feng , Chen Xiong‐Hai , Liang Gang , Ye Jia‐Wen , Mo Zong‐Wen , Chen Xiao‐Ming
Published: April 2023

Indoor detection of volatile organic compounds (VOCs) concentration is necessary due to the serious toxicity hazards even at trace level. However, physisorbents usually exhibit weak interactions especially in the presence of trace concentrations of VOCs, thus exhibiting poor responsive signal. Herein, we report a new flexible metal–organic framework (MOF) that exhibits interesting pore‐opening behavior after immersing in H2O. The pore‐opening phase shows significant (≈116 folds) and extremely fast (<1 minute) fluorescence enhancement after being exposed to saturated benzene vapor. The limit of detection concentration for benzene vapor can be calculated as 0.133 mg L−1. Thus this material represents the first MOF to achieve visual detection of trace benzene vapor by the naked eyes. Theoretical calculations and single‐crystal structure reveal that the special “bilateral π–π stacking” interactions between the host and guest, which facilitate electron transfer and greatly enhance the intensity of fluorescence.
Levocetirizin‐Dihydrochlorid: Die Aufklärung einer lang verborgenen Struktur mittels Elektronenbeugung
Authors: Karothu Durga Prasad , Alhaddad Zainab , Göb Christian R. , Schürmann Christian J. , Bücker Robert , Naumov Panče
Published: April 2023

Levocetirizin ist ein oral verabreichtes Antihistaminikum der zweiten Generation, dass seit über 25 Jahren zur Behandlung von Allergiesymptomen und langanhaltender Nesselsucht eingesetzt wird. Trotz der weiten Verbreitung dieser Verbindung war ihre Kristallstruktur bisher unbekannt. Hier berichten wir über die Anwendung der 3D‐Elektronenbeugung (3D ED)/Mikrokristallbeugung (MicroED) zur Bestimmung der Kristallstruktur von Levocetirizindihydrochlorid direkt aus kristallinen Pulvern, handelsüblicher Tabletten, die diese Verbindung enthalten. Weiterhin zeigen wir auch den Nutzen der dynamischen Verfeinerung zur eindeutigen Zuordnung der absoluten Konfiguration. Die Ergebnisse unterstreichen das immense Potenzial der 3D‐ED/MicroED für die Strukturaufklärung von Komponenten mikrokristalliner Gemische, wodurch sich die Züchtung großer Einkristalle und der Einsatz ergänzender Analysetechniken erübrigt. Dies wird nicht nur dazu beitragen, dass die Methode für die Identifizierung, sondern auch für die primäre strukturelle Charakterisierung neuer Verbindungen in Zukunft an Bedeutung gewinnt.
Realizing Abundant Chirality Inversion of Supramolecular Nanohelices by Multiply Manipulating the Binding Sites in Molecular Blocks
Authors: Gao Laiben , Dou Xiaoqiu , Xing Chao , Gao Fengli , Jiang Zichao , Yang Kaikai , Zhao Changli , Feng Chuanliang
Published: April 2023

The induction of diverse chirality regulation in nature by multiple binding sites of biomolecules is ubiquitous and plays an essential role in determining the biofunction of biosystems. However, mimicking this biological phenomenon and understanding at a molecular level its mechanism with the multiple binding sites by establishing an artificial system still remains a challenge. Herein, abundant chirality inversion is achieved by precisely and multiply manipulating the co‐assembled binding sites of phenylalanine derivatives (D/LPPF) with different naphthalene derivatives (NA, NC, NP, NF). The amide and hydroxy group of naphthalene derivatives prefer to bind with the carboxy group of LPPF, while carboxylic groups and fluoride atoms tend to bind with the amide moiety of LPPF. All these diverse interaction modes can precisely trigger helicity inversion of LPPF nanofibers. In addition, synergistically manipulating the carboxy and amide binding sites from a single LPPF molecule to simultaneously interact with different naphthalene derivatives leads to chirality regulation. Typically, varying the solvent may switch the interaction modes and the switched new interaction modes can be employed to further regulate the chirality of the LPPF nanofibers. This study may provide a novel approach to explore chirality diversity in artificial systems by regulating the intermolecular binding sites.
Sculpting In‐plane Fractal Porous Patterns in Two‐Dimensional MOF Nanocrystals for Photoelectrocatalytic CO2 Reduction
Authors: Dutta Soumen , Gurumoorthi Akshay , Lee Shinbi , Jang Sun Woo , Kumari Nitee , Hong Yu‐Rim , Choi Wonyong , Son Chang Yun , Lee In Su
Published: April 2023

Herein, by choosing few‐nm‐thin two‐dimensional (2D) nanocrystals of MOF‐5 containing in‐planner square lattices as a modular platform, a crystal lattice‐guided wet‐chemical etching has been rationally accomplished. As a result, two attractive pore patterns carrying Euclidean curvatures; precisely, plus(+)‐shaped and fractal‐patterned pores via ⟨100⟩ and ⟨110⟩ directional etching, respectively, are regulated in contrast to habitually formed spherical‐shaped random etches on MOF surface. In agreement with the theoretical calculations, a diffusion‐limited etching process has been optimized to devise high‐yield of size‐tunable fractal‐pores on the MOF surface that tenders for a compatibly high payload of catalytic ReI‐complexes using the existing large edge area once modified into a free amine‐group‐exposed inner pore surface. Finally, on benefiting from the long‐range fractal opening in 2D MOF support structure, while loaded on an electrode surface, a facilitated cross‐interface charge‐transportation and well‐exposure of immobilized ReI‐catalysts are anticipated, thus realizing enhanced activity and stability of the supported catalyst in photoelectrochemical CO2‐to‐CO reduction.
Bifunctional Interphase with Target‐Distributed Desolvation Sites and Directionally Depositional Ion Flux for Sustainable Zinc Anode
Authors: Zhang Ruochen , Feng Yang , Ni Youxuan , Zhong Beidou , Peng Maoyu , Sun Tianjiang , Chen Shan , Wang Huan , Tao Zhanliang , Zhang Kai
Published: April 2023

Aqueous zinc batteries (AZBs) feature high safety and low cost, but intricate anodic side reactions and dendrite growth severely restrict their commercialization. Herein, ethylenediaminetetraacetic acid (EDTA) grafted metal organic framework (MOF‐E) is proposed as a dually‐functional anodic interphase for sustainable Zn anode. Specifically, the target‐distributed EDTA serves as an ion‐trapped tentacle to accelerate the desolvation and ionic transport by powerful chemical coordination, while the MOFs offer suitable ionic channels to induce oriented deposition. As a result, MOF‐E interphase fundamentally suppresses side reactions and guides horizontally arranged Zn deposition with (002) preferred orientations. The Zn|MOF‐E@Cu cell exhibits a markedly improved Coulombic efficiency of 99.7 % over 2500 cycles, and the MOF‐E@Zn|KVOH (KV12O30‐y ⋅ nH2O) cell yields a steady circulation of 5000 cycles@90.47 % at 8 A g−1.
Thioethers as Dichotomous Electrophiles for Site‐Selective Silylation via C−S Bond Cleavage
Authors: Chen Shuai , Guo Xueying , Hou Haoran , Geng Shasha , Liu Zhengli , He Yun , Xue Xiao‐Song , Feng Zhang
Published: April 2023

The development of aryl alkyl sulfides as dichotomous electrophiles for site‐selective silylation via C−S bond cleavage has been achieved. Iron‐catalyzed selective cleavage of C(aryl)−S bonds can occur in the presence of β‐diketimine ligands, and the cleavage of C(alkyl)−S bonds can be achieved by t‐BuONa without the use of transition metals, resulting in the corresponding silylated products in moderate to excellent yields. Mechanistic studies suggest that Fe−Si species may undergo metathesis reactions during the cleavage of C(aryl)−S bonds, while silyl radicals are involved during the cleavage of C(alkyl)−S bonds.
Vibrational Circular Dichroism Spectroscopy of Chiral Molecular Crystals: Insights from Theory
Authors: Jähnigen Sascha
Published: April 2023

Chirality is a curious phenomenon that appears in various forms. While the concept of molecular (RS‐)chirality is ubiquitous in chemistry, there are also more intricate forms of structural chirality. One of them is the enantiomorphism of crystals, especially molecular crystals, that describes the lack of mirror symmetry in the unit cell. Its relation to molecular chirality is not obvious, but still an open question, which can be addressed with chiroptical tools. Vibrational circular dichroism (VCD) denotes chiral infrared (IR) spectroscopy that is susceptible to both, the molecular as well as the intermolecular space by means of vibrational transitions. When carried out in the solid state, VCD delivers a very rich set of non‐local contributions that are determined by crystal packing and collective motion. Since its discovery in the 1970s, VCD has become the method of choice for the determination of absolute configurations, but its applicability reaches beyond towards the study of different crystal forms and polymorphism. This brief review summarises the theoretical concepts of crystal chirality and how computations of solid‐state VCD can shed light into the intimate connection of chiral structure and vibrational optical activity.
The Elusive Structure of Levocetirizine Dihydrochloride Determined by Electron Diffraction
Authors: Karothu Durga Prasad , Alhaddad Zainab , Göb Christian R. , Schürmann Christian J. , Bücker Robert , Naumov Panče
Published: April 2023

Levocetirizine is an orally administrated, second‐generation antihistaminic active pharmaceutical ingredient that has been used to treat symptoms of allergy and long‐term hives for over 25 years. Despite the wide use of this compound, its crystal structure has remained unknown. Here we report the application of 3D electron diffraction (3D ED)/Micro‐crystal electron diffraction (MicroED) to determine the crystal structure of Levocetirizine dihydrochloride directly from crystalline powders that were extracted from commercially available tablets containing the compound. We also showcase the utility of dynamical refinement to unambiguously assign absolute configuration. The results highlight the immense potential of 3D ED/MicroED for structure elucidation of components of microcrystalline mixtures that obviates the need to grow large‐size single crystals and the use of complementary analytical techniques, which could be important for identification as well as for primary structural characterization.
Synthesis and properties of water‐dispersible polyurethanes based on various diisocyanates and PEG as the hard segment
Authors: Oprea Stefan , Potolinca Violeta Otilia
Published: April 2023

Water‐dispersible polyurethanes are a greener alternative to polyurethane solutions in organic solvents. Various polyurethane materials were prepared by a two‐step polymerization procedure of polypropylene glycol with Mn of 2000, polyethylene glycol with Mn of 1500, and diisocyanates with different chemical structures, aliphatic, cycloaliphatic and aromatic. It was investigated how the diisocyanate structure affected the molecular morphology, contact angle measurements, and physical characteristics of water‐dispersible polyurethanes. FTIR and NMR measurements showed a close relationship between the intermolecular connections and the hard segment structure, mainly of the diisocyanate used. Also, the polarized light method showed that the presence of the PEG in the hard domain improved aggregation through physical interactions due to its structural flexibility and mobility. These water‐dispersible polyurethanes can assure the use of these polyurethane materials in a broad range of applications with increased environmental protection.
Synthesis and performance evaluation of water‐absorbing resin coated with polymethyl methacrylate as a lost circulation material
Authors: Bai Xiaodong , Deng Licheng , Yan Yancheng , Hu Hua , Luo Yumei , Cai Xuetong
Published: April 2023

Lost circulation will cause huge economic losses every year. In order to effectively reduce the harm of lost circulation to drilling, it is particularly important to use reasonable and efficient lost circulation materials (LCM). As a kind of water‐absorbing, expandable and deformable LCM, water‐absorbing resin can adapt to holes and cracks of different sizes. In this study, a kind of encapsulated water‐absorbing resin LCM (PMMA/PNAD) was proposed. The water‐absorbing resin is synthesized by acrylamide (AM), 2‐acrylamide‐2‐methyl‐propane sulfonic acid (APMS) and diallyl dimethyl ammonium chloride (DMDAAC) as reaction monomers through aqueous solution polymerization. The shell material is polymethylmethacrylate (PMMA), which is coated on the surface of the water‐absorbing resin by oil phase separation method. The results of the experimental evaluation indicate that the water‐absorbing resin possesses robust water‐absorbing and swelling properties, which significantly affect the rheological properties of the drilling fluid. However, the coated shell can effectively mitigate the impact of the absorbent resin on the drilling fluid. Under the formation environment of 100°C or 2 Mpa, the shell can soften or break to release the absorbent resin. The lost circulation control performance test results show that PMMA/PNAD has good pressure bearing capacity, and can still maintain good lost circulation control at 6.9 Mpa.
Characterization of the STA1600 CCD for the high‐resolution spectrograph PEPSI
Authors: Ilyin Ilya
Published: April 2023

Characterization of the STA1600 CCD for the high‐resolution spectrograph Potsdam Echelle Polarimetric and Spectroscopic Instrument (PEPSI) is presented. We tested the fixed‐pattern noise reduction efficiency with sufficient number of master flat fields and show that the noise reduction follows the expected value. The lateral charge diffusion is measured with photon transfer technique versus CCD binning factor and by measuring the change of spectral lines width versus their amplitude. The charge diffusion effect versus wavelength follows the behavior of the back‐illuminated CCD while also showing a strong positional dependence on the CCD.
Spoken language outcomes in limited language preschoolers with autism and global developmental delay: RCT of early intervention approaches
Authors: Kasari Connie , Shire Stephanie , Shih Wendy , Landa Rebecca , Levato Lynne , Smith Tristram
Published: April 2023

Preschool autistic children with significant global developmental delays and very limited language skills are at high risk for remaining minimally verbal at entry into primary school. This study compared two early intervention models for improving social communication and spoken language outcomes in 164 children who received intervention in their community preschool program for 6 months, with a six‐month follow‐up. The primary outcome measure was a standardized language assessment, and secondary measures focused on social communication. Results indicated children on average made 6 months gain in language development in the active 6 months of intervention with no difference between intervention models. Children who initiated joint attention more frequently, or who had higher receptive language at baseline made more progress if assigned to receive JASPER, a naturalistic developmental behavioral intervention. Children who received Discrete Trial Training made greater spoken language progress from exit to follow‐up. These findings suggest that progress can be made in autistic children who have very little spoken language and who receive targeted early interventions. Individual trajectories vary and depend in part on initial abilities in social communication and receptive language. Future research might consider methods to systematically personalize approaches to fit child characteristics and family preference.

Lay Summary

This study compared two different early intervention approaches for teaching spoken language to minimally verbal, globally delayed autistic preschoolers. Children were given an hour of therapy daily for 6 months and then reassessed 6 months later. The majority of the 164 participants were from historically excluded populations (low income and minority), and therapy was delivered in school community settings by expert clinicians. Results indicated that the participants made significant progress regardless of intervention approach: 6 months gain in standardized language scores over 6 months, but slower progress during the period after therapy ended. Children who initiated joint attention more frequently, or who had higher language understanding at baseline made more progress if assigned to receive JASPER, a naturalistic developmental behavioral intervention. Children who received Discrete Trial Training made greater language progress during 6‐month period after therapy ended. These findings suggest that progress can be made in children with ASD who have very little spoken language and who receive targeted early interventions.
Evaluation of in vitro effect, molecular docking, and molecular dynamics simulations of some dihydropyridine‐class calcium channel blockers on human serum paraoxonase 1 (hPON1) enzyme activity
Authors: Gökçe Başak , Muhammed Muhammed Tilahun
Published: April 2023

Paraoxonase 1 (PON1) was purified 148.80‐fold in 37.92% yield by hydrophobic interaction chromatography technique. The purity of PON1 was checked by sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS‐PAGE) with a single band of 43 kDa. The in vitro effects of nine different calcium channel blockers on PON1 activity were evaluated. All drugs strongly decreased PON1 activity, and IC50 levels were between 13.987 ± 0.59 and 238.104 ± 2.14 μM, Ki values between 8.58 ± 0.36 and 111 ± 1.27 μM. The drugs with the strongest inhibitory effect were nisoldipine with 13.987 ± 0.59 μM and nicardipine with 20.158 ± 0.43 μM. The mechanism of action for the inhibition of the enzyme by nisoldipine and nicardipine was investigated through molecular docking. The stability of enzyme–ligand complexes obtained from the docking was explored through molecular dynamics simulation. The binding affinity of the ligands toward the enzyme was also investigated through MMPBSA (molecular mechanics Poisson–Boltzmann surface area method). The computational analysis demonstrated these compounds could inhibit the enzyme. Nisoldipine had the strongest binding, and its complex was the most stable one. Furthermore, nicardipine was found to have the highest affinity toward the enzyme.
Bipolar Isoindoline Nitroxide for Nonaqueous Symmetrical Redox Flow Battery
Authors: Loomans Benjamin I. , Bottle Steven E. , Blinco James P.
Published: April 2023

Crossover in non‐aqueous redox flow batteries remains a critical challenge to the cycle stability of these devices. The use of bipolar redox‐active organic materials (ROM) is an emerging strategy for mitigating crossover. Herein we report the first example of a bipolar ROM derived from an isoindoline nitroxide, a ring class which gives a number of advantages over the more commonly employed piperidines, including greater stability and a 200 mV higher oxidation potential. Through facile synthetic transformation, the unsubstituted isoindoline nitroxide was nitrated to give a novel bipolar molecule, 5‐nitro‐1,1,3,3‐tetramethylisoindoline‐2‐yloxyl (NTMIO). This material was investigated electrochemically, revealing a reversible oxidation and quasi‐reversible reduction giving a cell potential of 2.07 V. NTMIO was then assessed as an active material in both a static and flow battery model, where cycling was observed for both oxidative and reductive redox couples for over 70 and 20 cycles respectively.
The Effects of Uniform and Nonuniform Magnetic Fields in Plant Growth: A Meta‐Analysis Approach
Authors: Tapia‐Belmonte Francisco , Concha Andrés , Poupin María J.
Published: April 2023

Magnetic field (MF) effects have been reported in plants' growth, seed germination, gene expression, and water consumption. Accordingly, magnetic treatments have been proposed as a sustainable alternative to improve yields. Nevertheless, a comprehensive quantitative assessment is needed to understand whether their effects are general, species‐specific, or dependent on the experimental setting. We conducted a multilevel meta‐analysis of 45 articles that studied 29 different plant species. A positive and neutral effect of a nonuniform MF was found on fresh weight and germination rate, respectively. A significant association was found between a uniform MF and germination. These results suggest that MFs improve plant growth. However, the effects are highly dependent on the experimental setting. This opens exciting questions about the biophysical mechanisms underlying the perception and transduction of this environmental cue and about the possible translation to agricultural practices. © 2023 Bioelectromagnetics Society.
Stilbene ligand‐based metal–organic frameworks for efficient dye adsorption and nitrobenzene detection
Authors: Kim Jiyun , Na Chanju , Son Younghu , Prabu Mani , Yoon Minyoung
Published: April 2023

The technological developments of metal–organic framework (MOF) for selective adsorption and sensing have been achieved in recent years. Herein, we report two stilbene‐based MOFs, denoted as Zn3(SDC)3(bpy) (1) and Zn(SDC)(bpy)·2DMF (2). MOFs 1 and 2 were synthesized in pure form by controlling the organic linker ratio and were used for the adsorptive removal of dye molecules. Despite their low adsorption capacities, the MOFs were more selective toward cationic dye (methylene blue) than anionic dye (methyl orange). The unique fluorescent property of the MOFs was harnessed for the sensing of harmful organic molecules. Interestingly, the fluorescence of 1′ was quenched by aromatic analytes containing amine and nitro functional groups. However, 2′ only showed modest fluorescence quenching by nitrobenzene. The quenching efficiency of nitrobenzene had a low detection limit for 1′ and 2′ (14.28 and 25.42 μM, respectively). These MOFs can be used as adsorbents and highly sensitive chemical sensors.
A comparative metabolomics study on dried and processed Rehmannia Radix
Authors: Liu Tong , Zhou Ning , Bai Zhiyao , Cao Yumin , Zhang Jinying , Wang Yongxiang , Zheng Xiaoke , Feng Weisheng
Published: April 2023

The efficacy of Rehmannia Radix changes after processing. However, the precise effect of processing on the properties of Rehmannia Radix is an intricate topic, as this effect cannot be explained by traditional methods. The purpose of this study was to investigate how processing methods influence the properties of Rehmannia Radix, as well as the changes in body function after administering dried Rehmannia Radix (RR) and processed Rehmannia Radix (PR) using a metabolomics approach. In addition, principal component analysis and orthogonal partial least‐squares discriminant analysis models were generated using SIMCA‐P 14.0 to evaluate the properties of RR and PR. Potential biomarkers were identified, and associated metabolic networks were established to clarify differences in the properties and efficacies of RR and PR. The results showed that RR and PR have cold and hot properties, respectively. RR can exert a hypolipidaemic effect by regulating nicotinate and nicotinamide metabolism. PR exerts a tonic effect and regulates the body’s reproductive function through the regulation of alanine, aspartate and glutamate metabolism, arachidonic acid, pentose and glucuronate metabolism, respectively. Ultra‐high‐performance liquid chromatography–quadrupole time‐of‐flight mass spectrometry‐based metabolomics is a promising approach to determine the cold/hot properties of traditional Chinese medicine formulations.
Immersive virtual reality in AECO/FM to enhance education: Systematic literature review and future directions
Authors: Tastan Hasan , Tong Togan
Published: April 2023

Immersive virtual reality (IVR) is considered as an effective and efficient instructional tool for architecture, engineering, construction, operation, and facility management (AECO/FM) education. However, it is essential to systematically evaluate them to obtain consolidated evidence on the impact of IVR applications. Thus, the aim of this article is to present the state‐of‐the‐art on all AECO/FM use cases, including learning theories/models, all key factors, and experimental design, and to suggest future directions for IVR research. This review follows a systematic literature review methodology to analyze 79 papers between 2013 and 2022. The results show that learning theories/models are not sufficiently applied. There is consensus that IVR influences affective factors positively. It is necessary to consider task type, task complexity, virtual environment design, and ergonomics of IVR tools in terms of cognitive factors. Cognitive/affective factors associated with learning performance should be examined in depth to develop more effective learning methods. Future studies should design and conduct experimental procedures with more scientific rigor.
An educational tool for understanding MPEG‐2 video compression and coding techniques
Authors: Fernández‐Plazaola Unai , Gómez Gerardo , López‐Martínez F. Javier
Published: April 2023

The understanding of the video encoding/decoding processes is a key skill for students of computer science, engineering, or telecommunications, especially those specialized in multimedia. The special characteristics of the video signals, and how such features are leveraged to compress the video frames using coding theory, are hard to understand for engineering students. In this paper, we describe MPEG‐2 analyzer, an educational tool designed to provide a comprehensive and interactive way to understand MPEG‐2 video compression and encoding techniques. We have used our tool to evaluate its usefulness in reinforcing the knowledge about the MPEG‐2 video (de)coding process to Telecommunication Engineering students. Results show that the evaluation of the tool is very positive, and it has helped them to understand many of the complex concepts covered in the course.
Discovery of Potent Pyrazoline‐Based Covalent SARS‐CoV‐2 Main Protease Inhibitors**
Authors: Moon Patrick , Zammit Charlotte M. , Shao Qian , Dovala Dustin , Boike Lydia , Henning Nathaniel J. , Knapp Mark , Spradlin Jessica N. , Ward Carl C. , Wolleb Helene , Fuller Daniel , Blake Gabrielle , Murphy Jason P. , Wang Feng , Lu Yipin , Moquin Stephanie A. , Tandeske Laura , Hesse Matthew J. , McKenna Jeffrey M. , Tallarico John A. , Schirle Markus , Toste F. Dean , Nomura Daniel K.
Published: April 2023

While vaccines and antivirals are now being deployed for the current SARS‐CoV‐2 pandemic, we require additional antiviral therapeutics to not only effectively combat SARS‐CoV‐2 and its variants, but also future coronaviruses. All coronaviruses have relatively similar genomes that provide a potential exploitable opening to develop antiviral therapies that will be effective against all coronaviruses. Among the various genes and proteins encoded by all coronaviruses, one particularly “druggable” or relatively easy‐to‐drug target is the coronavirus Main Protease (3CLpro or Mpro), an enzyme that is involved in cleaving a long peptide translated by the viral genome into its individual protein components that are then assembled into the virus to enable viral replication in the cell. Inhibiting Mpro with a small‐molecule antiviral would effectively stop the ability of the virus to replicate, providing therapeutic benefit. In this study, we have utilized activity‐based protein profiling (ABPP)‐based chemoproteomic approaches to discover and further optimize cysteine‐reactive pyrazoline‐based covalent inhibitors for the SARS‐CoV‐2 Mpro. Structure‐guided medicinal chemistry and modular synthesis of di‐ and tri‐substituted pyrazolines bearing either chloroacetamide or vinyl sulfonamide cysteine‐reactive warheads enabled the expedient exploration of structure‐activity relationships (SAR), yielding nanomolar potency inhibitors against Mpro from not only SARS‐CoV‐2, but across many other coronaviruses. Our studies highlight promising chemical scaffolds that may contribute to future pan‐coronavirus inhibitors.
Phospholipid‐Coated Boronic Oxide Nanoparticles as Boron Agents for Boron Neutron Capture Therapy
Authors: Kawasaki Riku , Hirano Hidetoshi , Yamana Keita , Oshige Ayano , Nishimura Kotaro , Kono Nanami , Sanada Yu , Bando Kaori , Tabata Anri , Yasukawa Naoki , Azuma Hideki , Takata Takushi , Sakurai Yoshinori , Tanaka Hiroki , Suzuki Minoru , Tarutani Naoki , Katagiri Kiyofumi , Nagasaki Takeshi , Ikeda Atsushi
Published: April 2023

Minimally invasive boron neutron capture therapy (BNCT) is an elegant approach for cancer treatment. The highly selective and efficient deliverability of boron agents to cancer cells is the key to maximizing the therapeutic benefits of BNCT. In addition, enhancement of the frequencies to achieve boron neutron capture reaction is also significant in improving therapeutic efficacy by providing a highly concentrated boron agent in each boron nanoparticle. As the density of the thermal neutron beam remains low, it is unable to induce high‐efficiency cell destruction. Herein, we report phospholipid‐coated boronic oxide nanoparticles as agents for BNCT that can provide a highly concentrated boron atom in each nanoparticle. The current system exhibited in vitro BNCT activity seven times higher than that of commercial boron agents. Furthermore, the system could penetrate cancer spheroids deeply, efficiently suppressing thermal neutron irradiation‐induced growth.
Precise and Controlled Modification of Proteins using Multifunctional Chemical Constructs
Authors: Albada Bauke
Published: April 2023

Bioconjugation of chemical entities to biologically active proteins has increased our insight in the inner workings of a cell and resulted in novel therapeutic agents. A current challenge is the efficient generation of homogeneous conjugates of native proteins, not only when isolated, but also when still present in their native environment. To do this, various features of protein‐modifying enzymes have been combined in artificial constructs. In this concept, the current status of this approach is evaluated, and the interplay between designs and protein modification will be discussed. Particular focus is directed on the protein‐binding anchor, the chemistry that is used for the modification, and the linker that connects these two units. Suggestions how to include additional elements such as a trigger‐responsive switch that regulated protein modification are also presented.