bluuebunny/crossref_metadata_2025 huggingface dataset:
Zero‐Bias Long‐Wave Infrared Nanoantenna‐Mediated Graphene Photodetector for Polarimetric and Spectroscopic Sensing
Authors: Xie Junsheng , Ren Zhihao , Wei Jingxuan , Liu Weixin , Zhou Jingkai , Lee Chengkuo
Published: February 2023

Graphene has attracted great interest for integrated photonic platforms in the long‐wave infrared (LWIR) for spectroscopic and polarimetric sensing due to the capability of on‐chip integration, fast response, and broadband operation. However, graphene suffers from low photoresponsivity and thus poor sensing performance due to weak absorption. Polarization detection using graphene is hindered by its small in‐plane anisotropy. Here, nanoantenna‐mediated graphene photodetectors (NMGPDs) are proposed to enhance responsivity by tailoring the nanoantenna near‐field distribution to generate a strong photoresponse. The devices demonstrate a high responsivity of 6.3 V W−1 under zero bias at room temperature with low noise‐equivalent power of 1.6 nW Hz−1/2. Furthermore, polarization detection is enabled by artificial near‐field anisotropy enabled by double L‐shaped nanoantennas. The proposed LWIR NMGPDs achieve subtle polarization‐angle detection down to 0.05° thanks to the unusual negative polarization ratio of −1. To demonstrate the advances of LWIR NMGPDs for molecule detection, acetone is chosen as an analyte for spectroscopic sensing. The devices show a low limit of detection of 115 ppm, and fast dynamic gas sensing response of 6 s for real‐time monitoring. These results reveal the potential of the device as a multi‐functional on‐chip miniaturized optoelectronic platform for polarimetric and spectroscopic sensing toward real‐time environmental monitoring and biomedical screening.
Enhanced Ultra‐Long Room Temperature Phosphorescence by Intermolecular Donor–Acceptor Interaction in Polymer Network
Authors: Zhao Xiaoya , Wu Bo , Xu Xingtang , Wang Guojie
Published: February 2023

Ultra‐long room temperature phosphorescence (URTP) is an attractive phenomenon in organic photonics. However, most of the reported strategies for enhancing URTP require complicated synthesis processes. Herein, a novel strategy is reported, two birds with one stone, for enhancing URTP by doping the ground‐state intermolecular donor–acceptor complexes into a dense polymer network: i) The dense network ensures the formation of intermolecular donor–acceptor complexes, which provide a smaller singlet‐triplet energy difference (ΔEST) and more intersystem crossing (ISC) channels than the individual donor or acceptor molecules; ii) The dense network adequately suppresses the non‐radiative relaxation caused by molecular vibrations and oxygen quenching. The URTP intensities of the intermolecular donor–acceptor complexes doped film are 20 times higher than that of the film only doped with acceptor molecules, and the phosphorescence lifetime is up to 200 ms. The theoretical calculation reveals the electronic interaction between donor and acceptor and the increased ISC channel, which elucidates the photophysical mechanism of the strategy and confirms its rationality. An advanced encryption application is developed based on enhanced URTP films. This work opens a new direction for URTP materials through the intermolecular donor–acceptor interaction.
Broadband Photoconductive Sampling in Gallium Phosphide
Authors: Altwaijry Najd , Qasim Muhammad , Mamaikin Mikhail , Schötz Johannes , Golyari Keyhan , Heynck Michael , Ridente Enrico , Yakovlev Vladislav S. , Karpowicz Nicholas , Kling Matthias F.
Published: February 2023

Direct measurements of the electric field of light enable new observations of light–matter interactions. In the near‐infrared and visible spectral ranges, this typically relies on techniques that exploit nonlinearities in gases or solids, which limits their sensitivity. Here, a method for the detection of broadband near‐infrared fields spanning more than one octave from 110 to 220 THz based on linear absorption in a semiconductor is demonstrated. This technique, which avoids complex vacuum setups and works under ambient conditions, employs linear photoconductive sampling (LPS) in gallium phosphide. Simulations reveal that the response function of LPS is concerned with the intensity envelope of the gate field, in contrast to electro‐optic sampling, relaxing the stringent temporal requirements on the gate pulse.
Coronary Au@Bi Nanospheres for Highly Impedance‐Sensitive Immunosensing toward CEA
Authors: Wang Caihong , Ouyang Ruizhuo , Liu Jinyao , Zhao Yuefeng , Li Yuhao , Guo Ning , Liu Baolin , Miao Yuqing
Published: February 2023

Novel coronary Au@Bi nanospheres (NSs) are simply synthesized by sparkling gold nanoparticles (Au NPs) on the surface of bismuth (Bi) NSs and successfully used as highly impedance‐sensitive immunosensing platform to develop a new label‐free electrochemical immunosensor for the detection of carcinoembryonic antigen (CEA). Firstly, Bi NSs are prepared by one‐pot hydrothermal method, showing uniform sphere morphology with a dense oxide film formed outside Bi NSs due to the easy oxidation of Bi in the air. The oxide film significantly hinders the transmission of electrons and effectively improves the sensitivity of the proposed electrochemical impedance immunosensor. The surface functionalization of Bi NSs with Au NPs enhances the biocompatibility, stability, as well as active surface area of the produced Au@Bi NSs, preferable for the efficient loading of antibody molecules. The electrochemical impedance spectroscopy (EIS) is selected as the optical technique to measure CEA with the constructed immunosensor based on Au@Bi NSs. Because of the excellent impedance‐responsive performance, this new immunosensor displays highly sensitive detection toward CEA in a linear range of 50 fg mL−1–100 ng mL−1 with an extremely low detection limit of 9.83 fg mL−1 and could be potentially used in early clinical detection of cancer.
Designing Single‐Atom Active Sites on sp2‐Carbon Linked Covalent Organic Frameworks to Induce Bacterial Ferroptosis‐Like for Robust Anti‐Infection Therapy
Authors: Sun Baohong , Wang Xinye , Ye Ziqiu , Zhang Juyang , Chen Xiong , Zhou Ninglin , Zhang Ming , Yao Cheng , Wu Fan , Shen Jian
Published: February 2023

With the threat posed by drug‐resistant pathogenic bacteria, developing non‐antibiotic strategies for eradicating clinically prevalent superbugs remains challenging. Ferroptosis is a newly discovered form of regulated cell death that can overcome drug resistance. Emerging evidence shows the potential of triggering ferroptosis‐like for antibacterial therapy, but the direct delivery of iron species is inefficient and may cause detrimental effects. Herein, an effective strategy to induce bacterial nonferrous ferroptosis‐like by coordinating single‐atom metal sites (e.g., Ir and Ru) into the sp2‐carbon‐linked covalent organic framework (sp2c‐COF‐Ir‐ppy2and sp2c‐COF‐Ru‐bpy2) is reported. Upon activating by light irradiation or hydrogen peroxide, the as‐constructed Ir and Ru single‐atom catalysts (SACs) can significantly expedite intracellular reactive oxygen species burst, enhance glutathione depletion‐related glutathione peroxidase 4 deactivation, and disturb the nitrogen and respiratory metabolisms, leading to lipid peroxidation‐driven ferroptotic damage. Both SAC inducers show potent antibacterial activity against Gram‐positive bacteria, Gram‐negative bacteria, clinically isolated methicillin‐resistantStaphylococcus aureus(MRSA), and biofilms, as well as excellent biocompatibility and strong therapeutic and preventive potential in MRSA‐infected wounds and abscesses. This delicate nonferrous ferroptosis‐like strategy may open up new insights into the therapy of drug‐resistant pathogen infection.
Cardiac Arrest and Neurologic Recovery: Insights from the Case of Mr. Damar Hamlin
Authors: Geocadin Romergryko G. , Agarwal Sachin , Goss Adeline L. , Callaway Clifton W. , Richie Megan
Published: February 2023

The association between brain injury after cardiac arrest and poor survival outcomes has led to longstanding pessimism. However, the publicly witnessed cardiac arrest, resuscitation, and acute management of Mr. Damar Hamlin and his favorable neurologic recovery provides some optimism. Mr. Hamlin's case highlights the neurologic advances of the last 2 decades and presents the opportunity to improve outcomes for all cardiac arrest patients in key areas: (1) effectively implementing the American Heart Association “Chain of Survival” to prevent initial brain injury and promote neuroprotection; (2) revisiting the process of neurologic prognostication and re‐defining the brain recovery during the early periods, and (3) incorporating neurorehabilitation into existing cardiac rehabilitation models to support holistic recovery. ANN NEUROL 2023;93:871–876
Gold Complexes in Anticancer Therapy: From New Design Principles to Particle‐Based Delivery Systems
Authors: Moreno‐Alcántar Guillermo , Picchetti Pierre , Casini Angela
Published: February 2023

The discovery of the medicinal properties of gold complexes has fuelled the design and synthesis of new anticancer metallodrugs, which have received special attention due to their unique modes of action. Current research in the development of gold compounds with therapeutic properties is predominantly focused on the molecular design of drug leads with superior pharmacological activities, e.g., by introducing targeting features. Moreover, intensive research aims at improving the physicochemical properties of gold compounds, such as chemical stability and solubility in the physiological environment. In this regard, the encapsulation of gold compounds in nanocarriers or their chemical grafting onto targeted delivery vectors could lead to new nanomedicines that eventually reach clinical applications. Herein, we provide an overview of the state‐of‐the‐art progress of gold anticancer compounds, andmore importantly we thoroughly revise the development of nanoparticle‐based delivery systems for gold chemotherapeutics.
Bestimmung der physikalisch‐chemischen Zusammensetzung von biomolekularen Kondensaten durch räumlich aufgelöste NMR
Authors: Pantoja Christian F. , Ibáñez de Opakua Alain , Cima‐Omori Maria‐Sol , Zweckstetter Markus
Published: February 2023

Die Flüssig‐Flüssig‐Phasentrennung hat sich als grundlegender Prozess bei der Bildung biomolekularer Kondensate erwiesen. Einblicke in die Zusammensetzung und Struktur biomolekularer Kondensate werden jedoch durch deren molekulare Komplexität und Dynamik erschwert. Hier stellen wir ein verbessertes räumlich aufgelöstes NMR‐Experiment vor, das eine quantitative Analyse der physikalisch‐chemischen Zusammensetzung von biomolekularen Mehrkomponenten‐Kondensaten im Gleichgewicht und ohne Markierung ermöglicht. Die Anwendung der ortsaufgelösten NMR auf Kondensate, die durch das mit der Alzheimer‐Krankheit assoziierte Protein Tau gebildet werden, zeigt einen verringerten Wassergehalt, den Ausschluss des molekularen Verdrängungsmittels Dextran, das Vorhandensein einer spezifischen chemischen Umgebung des kleinen Moleküls DSS und eine ≈150‐fach erhöhte Konzentration von Tau im Kondensat. Die Ergebnisse deuten darauf hin, dass die ortsaufgelöste NMR einen großen Einfluss auf das Verständnis der Zusammensetzung und der physikalischen Chemie von biomolekularen Kondensaten haben kann.
Charge Makes a Difference: Molecular Ionic Bismuth Compounds
Authors: Heine Johanna , Peerless Benjamin , Dehnen Stefanie , Lichtenberg Crispin
Published: February 2023

Key challenges in modern synthetic chemistry include the design of reliable, selective, and more sustainable synthetic methods, as well as the development of promising candidates for new materials. Molecular bismuth compounds offer valuable opportunities as they show an intriguing spectrum of properties that is yet to be fully exploited: a soft character, a rich coordination chemistry, the availability of a broad variety of oxidation states (at least +V to −I) and formal charges (at least +3 to −3) at the Bi atoms, and reversible switching between multiple oxidation states. All this is paired with the status of a non‐precious (semi−)metal of good availability and a tendency towards low toxicity. Recent findings show that some of these properties only come into reach, or can be substantially optimized, when charged compounds are specifically addressed. In this review, essential contributions to the synthesis, analyses, and utilization of ionic bismuth compounds are highlighted.
1,2‐Difunctionalization of Acetylene Enabled by Light
Authors: Lü Shiwei , Wang Zipeng , Gao Xiang , Chen Kai , Zhu Shifa
Published: February 2023

Although the direct conversion of gaseous acetylene into value‐added liquid commodity chemicals is becoming increasingly attractive, the majority of the established methodologies are focused on cross‐coupling, hydro‐functionalization, and polymerization. Herein, we describe a 1,2‐difunctionalization method that inserts acetylene directly into readily available bifunctional reagents. This method provides access to diverse C2‐linked 1,2‐bis‐heteroatom products in high regio‐ and stereoselectivity along with opening up previously unexplored synthetic directions. In addition, we demonstrate this method's synthetic potential by converting the obtained products into diverse functionalized molecules and chiral sulfoxide‐containing bidentate ligands. Using a combination of experimental and theoretical methods, the mechanism for this insertion reaction was investigated.
Spontaneous Proton Chemistry Enables Ultralow‐temperature and Long‐life Aqueous Copper Metal Batteries
Authors: Yan Changyuan , Chen Zixuan , Huang Hao , Deng Xianyu
Published: February 2023

Aqueous copper metal batteries with acidic electrolytes are regarded as promising candidates for low‐temperature energy storage, benefiting from fast kinetics of protons and acid resistance of copper. Here, a Cu(BF4)2 electrolyte that spontaneously generates protons is developed for ultralow‐temperature copper metal batteries. Systematic studies demonstrate that the hydrolysis of BF4− generates more protons, rendering the Cu(BF4)2 among the most effective aqueous electrolyte capable of breaking hydrogen bonds in water molecules. This electrolyte endows a polyaniline/Cu battery to deliver a short charging time of 21 s and a charge/discharge capability of up to 10 A g−1 at −30 °C, along with a high discharge specific capacity of 70 mAh g−1 and a supercapacitor‐comparable power density of 3000 W kg−1. Furthermore, it can exhibit a long and stable cycling lifespan over 10 000 cycles at −50 °C and works well at −70 °C. This work provides an opportunity for intrinsically acidic electrolytes.
Transition Metal‐Free Activation of Carbon Monoxide: Ketenyl Anions by PPh3/CO Exchange
Authors: Hansmann Max M.
Published: February 2023

Ketenes (R2C=C=O) are important reactive intermediates in organic chemistry which are often challenging to access in stable form due to their polarized cumulenic structure and inherent high reactivity. Ketenyl anions (R(M)C=C=O) or metal ynolates (R−C≡C−OM) represent alternative, highly attractive synthetic targets, but are typically prepared in situ and their structure and synthetic access are little investigated. Now, a fundamentally new strategy utilizing an exchange reaction of a phosphine with carbon monoxide at a metalated ylide gives rise to a series of novel ketenyl anions. These compounds are flexible reagents and can easily be transferred with electrophiles into more complex building blocks for synthetic applications. Since carbon monoxide is an inexpensive C1 building block, the new exchange strategy is an elegant concept and a valuable new entry in the synthetic toolbox of organic synthesis.
Reduktive Eliminierung in geschlossener Schale und radikalische Kopplung in offener Schale für regioselektive Ruthenium‐katalysierte C−H‐Aktivierungen anhand von Berechnungen und Experimenten
Authors: Chen Xinran , Gülen Hasret Can , Wu Jun , Zhang Zi‐Jing , Hong Xin , Ackermann Lutz
Published: February 2023

Die meta C–H‐Funktionalisierung durch Ruthenium‐katalysierte σ‐Bindungsaktivierung hat sich als nützliches Werkzeug zum Knüpfen distaler C–C‐Bindungen erwiesen. Aufgrund der begrenzten Anzahl von mechanistischen Studien ist jedoch kein klares Verständnis des Hintergrunds der Regioselektivität und des vollständigen Reaktionsmusters vorhanden. Hier präsentieren wir systematische computerchemische Studien zur Ruthenium‐katalysierten C–H‐Funktionalisierung mit primären, sekundären und tertiären Alkyl‐ sowie Arylbromiden. Die C–H‐Aktivierung und die C–C‐Bindungsbildung wurden sorgfältig untersucht. Monocyclometallierte Ruthenium(II)‐Komplexe wurden als aktive Spezies identifiziert, welche anschließend über einen Innersphären‐Elektronentransfer (ISET) Organobromide aktivieren. Die Regioselektivität ergibt sich aus der Konkurrenz zwischen der geschlossen schaligen reduktiven Eliminierung und der offen schaligen radikalischen Kopplung. Auf Grundlage dieses mechanistischen Verständnisses wurde ein multilineares Regressionsmodell zur Vorhersage der Regioselektivität erstellt, das durch Experimente bestätigt wurde.
Manganese‐Catalyzed Chemoselective Coupling of Secondary Alcohols, Primary Alcohols and Methanol
Authors: Tang Jun , He Jingxi , Zhao Sheng‐Yin , Liu Weiping
Published: February 2023

Herein, we report a manganese‐catalyzed three‐component coupling of secondary alcohols, primary alcohols and methanol for the synthesis of β,β‐methylated/alkylated secondary alcohols. Using our method, a series of 1‐arylethanol, benzyl alcohol derivatives, and methanol undergo sequential coupling efficiently to construct assembled alcohols with high chemoselectivity in moderate to good yields. Mechanistic studies suggest that the reaction proceeds via methylation of a benzylated secondary alcohol intermediate to generate the final product.
Determining the Physico‐Chemical Composition of Biomolecular Condensates from Spatially‐Resolved NMR
Authors: Pantoja Christian F. , Ibáñez de Opakua Alain , Cima‐Omori Maria‐Sol , Zweckstetter Markus
Published: February 2023

Liquid‐Liquid phase separation has emerged as fundamental process underlying the formation of biomolecular condensates. Insights into the composition and structure of biomolecular condensates is, however, complicated by their molecular complexity and dynamics. Here, we introduce an improved spatially‐resolved NMR experiment that enables quantitative analysis of the physico‐chemical composition of multi‐component biomolecular condensates in equilibrium and label‐free. Application of spatially‐resolved NMR to condensates formed by the Alzheimer's disease‐associated protein Tau demonstrates decreased water content, exclusion of the molecular crowding agent dextran, presence of a specific chemical environment of the small molecule DSS, and ≈150‐fold increased concentration of Tau inside the condensate. The results suggest that spatially‐resolved NMR can have a major impact in understanding the composition and physical chemistry of biomolecular condensates.
Organocatalytic Synthesis of Triflones Bearing Two Non‐Adjacent Stereogenic Centers
Authors: Budinská Alena , Wennemers Helma
Published: February 2023

Trifluoromethylsulfones (triflones) are useful compounds for synthesis and beyond. Yet, methods to access chiral triflones are scarce. Here, we present a mild and efficient organocatalytic method for the stereoselective synthesis of chiral triflones using α‐aryl vinyl triflones, building blocks previously unexplored in asymmetric synthesis. The peptide‐catalyzed reaction gives rise to a broad range of γ‐triflylaldehydes with two non‐adjacent stereogenic centers in high yields and stereoselectivities. A catalyst‐controlled stereoselective protonation following a C−C bond formation is key to control over the absolute and relative configuration. Straightforward derivatization of the products into, e.g., disubstituted δ‐sultones, γ‐lactones, and pyrrolidine heterocycles highlights the synthetic versatility of the products.
Cobalt‐Catalyzed Enantioselective Hydrogenation of Trisubstituted Carbocyclic Olefins: An Access to Chiral Cyclic Amides
Authors: Chakrabortty Soumyadeep , Konieczny Katharina , de Zwart Felix J. , Bobylev Eduard. O. , Baráth Eszter , Tin Sergey , Müller Bernd H. , Reek Joost N. H. , de Bruin Bas , de Vries Johannes G.
Published: February 2023

The enantioselective hydrogenation of cyclic enamides has been achieved using an earth‐abundant cobalt‐bisphosphine catalyst. Using CoCl2/(S,S)‐Ph‐BPE, several trisubstituted carbocyclic enamides were reduced with high activity and excellent enantioselectivity (up to 99 %) to the corresponding saturated amides. The methodology can be extended to the synthesis of chiral amines by base hydrolysis of the hydrogenation products. Preliminary mechanistic investigations reveal the presence of a high spin cobalt (II) species in the catalytic cycle. We propose that the hydrogenation of the carbon‐carbon double bond proceeds via a sigma‐bond‐metathesis pathway.
The First UV Nonlinear Optical Selenite Material: Fluorination Control in CaYF(SeO3)2 and Y3F(SeO3)4
Authors: Li Peng‐Fei , Hu Chun‐Li , Kong Fang , Mao Jiang‐Gao
Published: February 2023

It is a great challenge to develop UV nonlinear optical (NLO) material due to the demanding conditions of strong second harmonic generation (SHG) intensity and wide band gap. The first ultraviolet NLO selenite material, Y3F(SeO3)4, has been obtained by control of the fluorine content in a centrosymmetric CaYF(SeO3)2. The two new compounds represent similar 3D structures composed of 3D yttrium open frameworks strengthened by selenite groups. CaYF(SeO3)2 has a large birefringence (0.138@532 nm and 0.127@1064 nm) and a wide optical band gap (5.06 eV). The non‐centrosymmetric Y3F(SeO3)4 can exhibit strong SHG intensity (5.5×KDP@1064 nm), wide band gap (5.03 eV), short UV cut‐off edge (204 nm) and high thermal stability (690 °C). So, Y3F(SeO3)4 is a new UV NLO material with excellent comprehensive properties. Our work shows that it is an effective method to develop new UV NLO selenite material by fluorination control of the centrosymmetric compounds.
Close‐Shell Reductive Elimination versus Open‐Shell Radical Coupling for Site‐Selective Ruthenium‐Catalyzed C−H Activations by Computation and Experiments
Authors: Chen Xinran , Gülen Hasret Can , Wu Jun , Zhang Zi‐Jing , Hong Xin , Ackermann Lutz
Published: February 2023

Ruthenium‐catalyzed σ‐bond activation‐assisted meta‐C−H functionalization has emerged as a useful tool to forge distal C−C bonds. However, given the limited number of mechanistic studies, a clear understanding of the origin of the site‐selectivity and the complete reaction pattern is not available. Here, we present systematic computational studies on ruthenium‐catalyzed C−H functionalization with primary, secondary, tertiary alkyl bromides and aryl bromides. The C−H scission and the C−C formation were carefully examined. Monocyclometalated ruthenium(II) complexes were identified as the active species, which then underwent inner‐sphere single electron transfer (ISET) to activate the organic bromides. The site‐selectivity results from the competition between the close‐shell reductive elimination and the open‐shell radical coupling. Based on this mechanistic understanding, a multilinear regression model was built to predict the site‐selectivity, which was further validated by experiments.
Syntheses and structures of magnetic nanodendrimers and their catalytic application in organic synthesis
Authors: Kalantari Fatemeh , Rezayati Sobhan , Ramazani Ali , Poor Heravi MohammadReza
Published: February 2023

Magnetic nanoparticles have been proved as a tremendously powerful synthetic tool to achieve a milder process for the organic transformations and also suggested many potentialities in biomedical applications. They have an important role in the human health, environment protection, and energy resource management. Excellent reusability, easy separation of nanosized catalysts, and stability are the significant advantages of these catalysts. Hence, detailed studies on their synthesis mechanism for both chemical transformations and biomedical applications are crucial. In this review, we described a brief introduction of the dendrimers and various methods that are used for their synthesis, followed by the discussion of the syntheses and structures of magnetic nanodendrimers and their catalytic application in organic synthesis. We accordingly embarked on the studies on their synthesis mechanism for chemical transformations especially their surface modification since 2001.
The femora ofDrepanosauromorpha(Reptilia:Diapsida): Implications for the functional evolution of the thigh ofSauropsida
Authors: Pritchard Adam C. , Irmis Randall B. , Olori Jennifer C. , Nesbitt Sterling J. , Smith Nathan D. , Stocker Michelle R. , Turner Alan H.
Published: February 2023

The femora of diapsids have undergone morphological changes related to shifts in postural and locomotor modes, such as the transition from plesiomorphic amniote and diapsid taxa to the apomorphic conditions related to a more erect posture within Archosauriformes. One remarkable clade of Triassic diapsids is the chameleon‐like Drepanosauromorpha. This group is known from numerous articulated but heavily compressed skeletons that have the potential to further inform early reptile femoral evolution. For the first time, we describe the three‐dimensional osteology of the femora of Drepanosauromorpha, based on undistorted fossils from the Upper Triassic Chinle Formation and Dockum Group of North America. We identify apomorphies and a combination of character states that link these femora to those in crushed specimens of drepanosauromorphs and compare our sample with a range of amniote taxa. Several characteristics of drepanosauromorph femora, including a hemispherical proximal articular surface, prominent asymmetry in the proximodistal length of the tibial condyles, and a deep intercondylar sulcus, are plesiomorphies shared with early diapsids. The femora contrast with those of most diapsids in lacking a crest‐like, distally tapering internal trochanter. They bear a ventrolaterally positioned tuberosity on the femoral shaft, resembling the fourth trochanter in Archosauriformes. The reduction of an internal trochanter parallels independent reductions in therapsids and archosauriforms. The presence of a ventrolaterally positioned trochanter is also similar to that of chameleonid squamates. Collectively, these features demonstrate a unique femoral morphology for drepanosauromorphs, and suggest an increased capacity for femoral adduction and protraction relative to most other Permo‐Triassic diapsids.
Base‐catalyzed Effective C2‐Amidation of Azolium Salts Using Isocyanates under Mild Conditions
Authors: Bauri Somnath , Ramachandran Arya , Rit Arnab
Published: February 2023

An unprecedented base‐catalyzed hydroarylation of isocyanates with azolium salts was developed, which follows a simple reaction pathway and provided facile access to diverse C2‐amidated azolium salts under mild conditions. Importantly, this methodology can also be applied for the successive C2‐amidation of a bisimidazolium salt with two different isocyanates to provide the corresponding unsymmetrically substituted bisamide derivatives. Notably, the obtained amidated salts can also serve as a prominent carbene surrogate for the synthesis of metal‐NHC complexes.
Die Orthoverbundplatte – Aktuelles aus Praxis und Forschung
Authors: Mansperger Tobias
Published: February 2023

Bei Großbrücken spielt das Eigengewicht der Fahrbahnplatte eine sehr wichtige Rolle. Orthotrope Stahlfahrbahnplatten sind leicht, jedoch sehr ermüdungsanfällig. Deswegen werden orthotrope Platten heute nur noch in Ausnahmefällen geplant. Stahlbetonfahrbahnplatten von Verbundbrücken sind robust, jedoch für große Spannweiten zu schwer. Die Orthoverbundplatte kombiniert die Vorteile der orthotropen Fahrbahnplatte mit der Stahlbetonfahrbahnplatte von Verbundbrücken auf ideale Weise. Das Grundprinzip von leichten Verbundfahrbahnplatten existiert schon seit den 1930er‐Jahren und wurde bei einigen Großbrücken erfolgreich eingesetzt. Die Orthoverbundplatte ist eine Kombination aus einer orthotropen Stahlplatte und einer im Verbund stehenden, bewehrten Aufbetonschicht. Sie vereint die positiven Eigenschaften beider Bauweisen. Sie ist leicht, aber dennoch robust, dauerhaft und widerstandsfähig gegenüber Materialermüdung. Sie kann mit einem sehr hohen Vorfertigungsgrad schnell, präzise und wirtschaftlich hergestellt werden. Die Orthoverbundplatte ist unanfällig bei extremen thermischen Ereignissen wie Blitzeisbildung und Zwangsbeanspruchungen infolge Heißeinbau von Gussasphalt.
Decreased plasma exposure of clopidogrel active metabolite in rats after long‐term treatment with clopidogrel
Authors: Wang Yani , Liu Yingrui , Yao Hongwei , Chen Xue , Sun Yantong , Guo Yingjie
Published: February 2023

Clopidogrel (Clop) is oxidized by cytochrome P450s (CYPs) to an active thiol metabolite, Clop‐AM, to inhibit platelet activation and aggregation. As an irreversible inhibitor of CYP2B6 and CYP2C19, clopidogrel may inhibit its own metabolism after long‐term administration. The study compared the pharmacokinetic profiles of clopidogrel and its metabolites in rats receiving a single or a 2 week administration of Clop. The mRNA and protein levels of hepatic clopidogrel‐metabolizing enzymes and their enzymatic activities were analyzed to explore their contribution to any altered plasma exposure of Clop and its metabolites. The results showed that long‐term treatment with clopidogrel significantly decreased the AUC(0‐t) and Cmax values of Clop‐AM in rats, accompanied with markedly impaired catalytic activities of Clop‐metabolizing CYPs including CYP1A2, CYP2B6, CYP2C9, CYP2C19, and CYP3A4. It suggests that consecutive administration of Clop to rats decreases hepatic CYPs activities, which may, in turn, inhibit clopidogrel metabolism and then reduce Clop‐AM plasma exposure. Therefore, long‐term treatment with clopidogrel has the potential to reduce its anti‐platelet activity and to increase the risk of drug–drug interaction.
Comparison of cohort and nested case‐control designs for estimating the effect of time‐varying drug exposure on the risk of adverse event in the presence of ties
Authors: Manitchoko Liliane , Abrahamowicz Michal , Tubert‐Bitter Pascale , Benichou Jacques , Thiébaut Anne C. M.
Published: February 2023

Cohort and nested case‐control (NCC) designs are frequently used in pharmacoepidemiology to assess the associations of drug exposure that can vary over time with the risk of an adverse event. Although it is typically expected that estimates from NCC analyses are similar to those from the full cohort analysis, with moderate loss of precision, only few studies have actually compared their respective performance for estimating the effects of time‐varying exposures (TVE). We used simulations to compare the properties of the resulting estimators of these designs for both time‐invariant exposure and TVE. We varied exposure prevalence, proportion of subjects experiencing the event, hazard ratio, and control‐to‐case ratio and considered matching on confounders. Using both designs, we also estimated the real‐world associations of time‐invariant ever use of menopausal hormone therapy (MHT) at baseline and updated, time‐varying MHT use with breast cancer incidence. In all simulated scenarios, the cohort‐based estimates had small relative bias and greater precision than the NCC design. NCC estimates displayed bias to the null that decreased with a greater number of controls per case. This bias markedly increased with higher proportion of events. Bias was seen with Breslow's and Efron's approximations for handling tied event times but was greatly reduced with the exact method or when NCC analyses were matched on confounders. When analyzing the MHT‐breast cancer association, differences between the two designs were consistent with simulated data. Once ties were taken correctly into account, NCC estimates were very similar to those of the full cohort analysis.
Neuropsychiatric manifestations of monkeypox: A clinically oriented comprehensive review
Authors: Sethi Yashendra , Agarwal Pratik , Murli Hamsa , Waheed Summaiya , Matar Sajeda Ghassan , Baklola Mohamed , Chopra Hitesh , Emran Talha Bin , Hasabo Elfatih A.
Published: February 2023

Monkeypox (MPX) has emerged as a threatening outbreak in recent months. The understanding of disease pathogenesis and its systemic involvement has evolved with time. Both the virus and its vaccine, like other members of the Orthopoxvirus family, were always expected to have neuropsychiatric consequences. Several neurological complications have been reported with MPX and its vaccines that include but not limited to headaches, myalgia, encephalitis, and coma. Psychiatric complications like anxiety and depression have also been reported; however, we lack evidence to present a direct causality. We conducted a literature review to compile recent evidence on neuropsychiatric manifestations and underline the importance of evolving aspects and complications of MPX. We advocate for better reporting of cases and adverse events, to enhance our understanding of the disease, aiding physicians to make more informed decisions, thus facilitating timely diagnosis and treatment.
Green innovation in emerging economies: The role of managerial ties and market learning
Authors: Ushie Adadu Michael , Jiang Xu , Ali Adnan , Nwoba Arinze Christian , Hossain Syed Far Abid
Published: February 2023

This study adopts the social capital and organizational learning perspectives to examine (i) how managerial business and political ties drive green product and process innovation, respectively, and (ii) the roles that explorative and exploitative market learning play in moderating the effects of managerial business and political ties on green product and process innovation. Findings from a survey of 283 Chinese firms show that managerial business and political ties distinctively drive green product and process innovation. Explorative and exploitative market learning strengthens the positive effects of managerial business and political ties on green product and process innovation for sustainable development. These findings advance the green innovation literature by clarifying how firms convert top‐level managers' network ties and market‐learning capabilities to strengthen corporate green innovation practices.
Five‐year survival post hepatectomy for colorectal liver metastases in a real‐world Chinese cohort: Recurrence patterns and prediction for potential cure
Authors: Su Yu‐Ming , Liu Wei , Yan Xiao‐Luan , Wang Li‐Jun , Liu Ming , Wang Hong‐Wei , Jin Ke‐Min , Bao Quan , Wang Kun , Li Juan , Xu Da , Xing Bao‐Cai
Published: February 2023

Background

Patients with a 5‐year recurrence‐free survival post liver resection for colorectal cancer liver metastases (CRLM) are considered to be potentially cured. However, there is a deficit of data on long‐term follow‐up and the recurrence status among these patients in the Chinese population. We analyzed real‐world follow‐up data of patients with CRLM who underwent hepatectomy, explored the recurrence patterns, and established a prediction model for a potential cure scenario.

Methods

Patients who underwent radical hepatic resection for CRLM during 2000–2016, with actual follow‐up data for at least 5 years, were enrolled. The observed survival rate was calculated and compared among the groups with different recurrence patterns. The predictive factors for 5‐year non‐recurrence were determined using logistic regression analysis; a recurrence‐free survival model was developed to predict long‐term survival.

Results

A total of 433 patients were included, of whom 113 patients were found non‐recurrence after 5 years follow‐up, with a potential cure rate of 26.1%. Patients with late recurrence (>5 months) and lung relapse showed significantly superior survival. Repeated localized treatment significantly improved the long‐term survival of patients with intrahepatic or extrahepatic recurrences. Multivariate analysis showed that RAS wild‐type CRC, preoperative CEA <10 ng/ml, and liver metastases ≤3 were independent factors for a 5‐year disease‐free recurrence. A cure model was developed based on the above factors, achieving good performance in predicting long‐term survival.

Conclusions

About one quarter patients with CRLM could achieve potential cure with non‐recurrence at 5‐year after surgery. The recurrence‐free cure model could well distinguish the long‐term survival, which would aid clinicians in determining the treatment strategy.
Potential Anti‐Inflammatory Components of Rhododendron molle G. Don Leaf Extracts in LPS‐Induced RAW 264.7
Authors: Luo Yuqiang , Wu Decai , Zong Luye , Shen Yu , Dai Liangfang , Luo Xiangdong
Published: February 2023

As a traditional Chinese medicine, Rhododendron molle G. Don has a long history of treating rheumatoid arthritis. In this study, RAW 264.7 cells induced by lipopolysaccharide (LPS) were established as cell inflammatory model to evaluate the anti‐inflammatory activity of chloroform extract from R. molle leaves (CERL), ethyl acetate extract from R. molle leaves (EERL) and butanol extract from R. molle leaves (BERL) and analyze the potential anti‐inflammatory components of R. molle. Potential anti‐inflammatory components analysis of CERL were performed by HPLC and UHPLC‐Q‐TOF‐MS. Prediction of potential anti‐inflammatory components by molecular docking experiments. Compared with negative control group, 25 μg/mL CERL could reduce the release level of NO by 62 %, and the mRNA expression levels of COX‐2, IL‐6, IL‐1β and TNF‐α were reduced by 69.74 %, 86.25 %, 77.94 % and 56.80 %, respectively. Western‐Blot showed similar results. CERL, EERL and BERL exerted their inhibitory activity in dose‐dependent manner. All results showed that the higher the concentration, the better the anti‐inflammatory activity. CERL showed the best inhibitory activity, the second was EERL, and then was BERL. 21 terpenoids and 4 flavonoids were identified in CERL by UHPLC‐Q‐TOF‐MS. Molecular docking results showed that triterpenoids in CERL had better interaction with target proteins (TNF‐α, IL‐1β). It indicated that triterpenoids may be potential anti‐inflammatory components of R. molle leaves. This study explored the anti‐inflammatory activities of CERL, EERL, BERL, which laid a foundation for further promoting the clinical application of R. molle.
Inhibition of CD73 expression or A2AR blockade reduces MRP1 expression and increases the sensitivity of cervical cancer cells to cisplatin
Authors: Carrera‐Martínez Monserrat , Mora‐García María de L. , García‐Rocha Rosario , Weiss‐Steider Benny , Montesinos‐Montesinos Juan J. , Hernández‐Montes Jorge , Don‐López Christian A. , Monroy‐García Alberto
Published: February 2023

Recently, a link between the biological activity of CD73 in solid tumors and multidrug resistance protein (MRP) has been proposed. Cisplatin (CP) is the most widely used anticancer agent to treat advanced and recurrent cervical cancer (CC). However, multidrug resistance protein‐1 (MRP1) is overexpressed in approximately 85% of these tumors and has been strongly associated with cisplatin resistance (CPR). In this study, we examine the involvement of CD73 and the interaction of adenosine (ADO) with its receptors (ARs) in MRP1 expression in CC cells. We found that ADO positively modulates MRP1 expression in CC cells in a dose‐dependent manner. The inhibition of CD73 expression with a CD73‐targeted siRNA and A2AR blockade with the selective antagonist ZM241385 significantly decreased MRP1 expression and the extrusive capacity of CC cells, making them significantly more sensitive to CP treatment than cancer cells treated with MK‐751, a specific MRP1 inhibitor. These results suggest CD73 inhibition or blocking ADO signaling through A2AR could be strategies to reverse CPR in patients with advanced or recurrent CC, which is characterized by very low response rates to CP (10%–20%).
A case of hemorrhagic shock in a patient with neurofibromatosis type 1
Authors: Sakaguchi Yutaro , Okano Hiromu , Furuya Ryosuke , Otsuka Tsuyoshi , Miyazaki Hiroshi
Published: February 2023

Complications of neurofibromatosis type 1 include fatal bleeding events due to vascular fragility. In this case of hemorrhagic shock due to a neurofibroma, the bleeding was controlled using an occlusion balloon and endovascular treatment which stabilized the patient. Systemic vascular investigation for bleeding sites is important to prevent fatal outcomes.
Structure Elucidation of Lithium Compounds Using 7Li Residual Quadrupolar Couplings
Authors: Rüttger Franziska , Patten Tim , Kretsch Johannes , Krawczuk Anna , Stalke Dietmar , John Michael
Published: February 2023

A new NMR method for the structure elucidation of lithium compounds under solution‐like conditions is presented. It is based on the measurement of 7Li residual quadrupolar couplings (RQCs) in a stretched polystyrene (PS) gel, and comparison to RQCs predicted from crystal or DFT‐derived model structures in combination with alignment tensors derived from one‐bond 1H,13C residual dipolar couplings (RDCs). The method was applied to five lithium model complexes containing monoanionic, bidentate bis(benzoxazole‐2‐yl)methanide, bis(benzothiazole‐2‐yl)methanide and bis(pyridyl)methanide ligands, of which two are first introduced in this work. In agreement with the crystalline state, four complexes are monomeric with Li coordinated fourfold by two additional THF molecules, whereas in one complex bulky tBu groups only provide space for one additional THF molecule.
Reactivity of Silylene with Gallium‐ and Boron Trihalide at Reductive Conditions Resulting in Unforeseen Products
Authors: Nazish Mohd , Harinath Adimulam , Lüert Daniel , Köhler Christian , Herbst‐Irmer Regine , Stalke Dietmar , Roesky Herbert W.
Published: February 2023

Herein, we report a one‐pot reaction of gallium and boron halides with potassium graphite in the presence of benzamidinate stabilized silylene LSi‐R, (L=PhC(NtBu)2). The reaction of LSiCl with an equivalent amount of GaI3 in the presence of KC8 leads to the direct substitution of one chloride group by gallium diiodide simultaneously additional coordination of silylene resulted in L(Cl)Si→GaI2‐Si(L)→GaI3 (1). In compound 1, the structure comprises two differently coordinated gallium atoms where one gallium presents between two silylenes and the other gallium is only coordinated by one silylene. In this Lewis acid‐base reaction the oxidation states of the starting materials remain unchanged. The same is valid in the silylene boron adduct formation of L(tBu)Si‐BPhCl2 (2) and L(tBu)Si‐BBr3 (3). This new route provides access to galliumhalosilanes challenging to synthesize by any other method.
Antibodies Directed Against GalNAc‐ and GlcNAc‐O‐Tyrosine Posttranslational Modifications – a New Tool for Glycoproteomic Detection
Authors: Behren Sandra , Schorlemer Manuel , Schmidt Gudula , Aktories Klaus , Westerlind Ulrika
Published: February 2023

In the last decade, it was discovered that protein mucin‐type O‐glycosylation and O‐GlcNAcylation modify Tyr residues besides the well explored Thr and Ser amino acids. Several glycoproteomic studies have identified α‐GalNAc‐O‐Tyr modifications, and studies propose that β‐GlcNAc‐O‐Tyr also exists as a new group of posttranslational modifications (PTMs). Specific bacterial toxins have further been identified to modify host GTPases with α‐GlcNAc‐O‐Tyr to promote bacterial virulence. Despite being identified on numerous proteins, the biological roles, biosynthesis and expression of GalNAc‐ and GlcNAc‐O‐Tyr modifications are poorly understood. A major obstacle is the lack of tools to specifically detect and identify proteins containing these modifications. With this in mind, we prepared vaccine constructs and raised antibodies to enable selective detection of proteins carrying these new PTMs. The obtained polyclonal antibody sera were evaluated using ELISA and glycopeptide microarrays and were found to be highly selective for GlcNAc‐ and GalNAc‐O‐Tyr glycopeptides over the corresponding Ser‐ and Thr‐modifications. For microarray analysis, synthetic GlcNAc‐ and GalNAc‐O‐Tyr Fmoc‐amino acids were prepared and applied in Fmoc‐SPPS to obtain an extensive O‐glycopeptide library. After affinity purification, the antibodies were applied in western blot analysis and showed specific detection of α‐GlcNAc‐O‐Tyr modified RhoA GTPase.
Light‐Triggered Reversible Swelling of Polymeric Spheres via Surfactant‐Free RAFT Emulsion Polymerization‐Induced Self‐Assembly**
Authors: Deng Zichao , Zhang Chengyun , Sun Yalan , Wang Rui , Chen Tianhao , Liu Zhefeng , Chen Aihua
Published: February 2023

Responsive photonic crystals (RPCs) assembled by monodisperse colloidal particles have attracted enormous interest recently due to their tremendous applications in smart devices. Their structural colors can be determined by particle sizes. However, the lack of a reliable way to tune the sizes in situ limits their development. Herein, we present an efficient route to solve this problem through the fabrication of spherical polymeric particles with light‐triggered reversible swelling behavior via surfactant‐free reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization‐induced self‐assembly (PISA). Amphiphilic macro‐RAFT agents containing azobenzene groups were synthesized and subsequently employed to mediate the polymerization of methyl methacrylate. Uniform submicron spheres were obtained by modulating solid contents and other parameters. Benefiting from the photoisomerization of azobenzene moieties, the particle sizes expanded and contracted upon alternative ultraviolet/visible‐light irradiation accordingly. This strategy will be a supplement to the emulsion PISA and especially give aid to the progress of the RPC materials.
Recent Advances in Growth, Properties and Applications of 2D Inorganic Molecular Crystals†
Authors: Li Menghan , Guo Yang , Li Lin , Geng Dechao , Hu Wenping
Published: February 2023

Comprehensive Summary

Since the concept of 2D inorganic molecular crystals (2DIMCs) was introduced, intensive attentions have been gradually devoted to this field. Herein, the very recent advances in growth, properties, and applications of 2D inorganic molecular crystals are comprehensively reviewed. Firstly, the newly emerged 2DIMCs are classified into three categories. Then the two typical production methods are present, thus leading to discrepancy in size, distribution, morphology and structures of 2DIMCs. Moreover, the unique physicochemical properties of 2DIMCs are demonstrated on the basis of the as‐obtained 2DIMCs, the various applications are exhibited, demonstrating significant potential in related fields. Finally, the perspective and prospects are outlooked to offer insights in further development of 2DIMCs.
Discovery of Antitrypanosomal Indolylacetamides by a Deconstruction–Optimization Strategy Applied to Paullones
Authors: Lindhof Jens C. , Ihnatenko Irina , Müller Marco J. , Orban Oliver C. F. , Ortíz Cecilia , Benítez Diego , Dibello Estefanía , Seidl Leonardo L. , Comini Marcelo A. , Kunick Conrad
Published: February 2023

The parasitic kinetoplastid diseases Leishmaniasis, Chagas disease and Human African Trypanosomiasis constitute serious threats for populations throughout the (sub‐)tropics. Most available drugs to treat these diseases possess inadequate properties and candidates to fill the drug pipeline are urgently needed. Paullone‐N5‐acetamides inhibit trypanothione synthetase (TryS), an essential kinetoplastid enzyme, and exhibit antiparasitic activity in the low micromolar range, but lack the desired selectivity against mammalian cells (selectivity index (SI):<10). With the aim to identify the paullones’ moieties responsible for TryS inhibition and bioactivity, we applied molecular simplification and ring disconnection approaches. The new indolylacetamides lost activity against the expected molecular target (TryS) compared to the reference paullone MOL2008 (Leishmania infantum TryS IC50 : 150 nM; Trypanosoma brucei bloodstream form EC50: 4.3 μM and SI: 2.4). However, several of them retained potency (T. b. brucei EC50: 2.4–12.0 μM) and improved selectivity (SI: 5 to >25).