bluuebunny/crossref_metadata_2025 huggingface dataset:
Boosting the Sonodynamic Cancer Therapy Performance of 2D Layered Double Hydroxide Nanosheet‐Based Sonosensitizers Via Crystalline‐to‐Amorphous Phase Transformation
Authors: Hu Tingting , Shen Weicheng , Meng Fanqi , Yang Shuqing , Yu Shilong , Li Hai , Zhang Qinghua , Gu Lin , Tan Chaoliang , Liang Ruizheng
Published: February 2023

Sonodynamic therapy (SDT) has been a promising therapeutic modality for cancer because of its superior advantages compared with other therapeutic strategies. However, the current sonosensitizers used for SDT normally exhibit low activity for ultrasound (US)‐induced reactive oxygen species (ROS) generation. Herein, the crystalline‐to‐amorphous phase transformation is reported as a simple but powerful strategy to engineer ultrathin 2D CoW‐LDH and NiW‐LDH nanosheets as highly efficient sonosensitizers for SDT. The phase transformation of CoW‐LDH and NiW‐LDH nanosheets from polycrystalline to amorphous ones is achieved through a simple acid etching treatment. Importantly, compared with the polycrystalline one, the amorphous CoW‐LDH (a‐CoW‐LDH) nanosheets possess higher ROS generation activity under US irradiation, which is ≈17 times of the commercial TiO2 sonosensitizer. The results suggest that the enhanced performance of ultrathin a‐CoW‐LDH nanosheets for US‐induced ROS generation may be attributed to the phase transformation‐induced defect generation and electronic structure changes. After polyethylene glycol modification, the a‐CoW‐LDH nanosheets can serve as a high‐efficiency sonosensitizer for SDT to achieve cell death in vitro and tumor eradication in vivo under US irradiation.
Scalable Synthesis of 2D Mo2C and Thickness‐Dependent Hydrogen Evolution on Its Basal Plane and Edges
Authors: Wu Jiabin , Su Jianwei , Wu Tao , Huang Liang , Li Qun , Luo Yongxin , Jin Hongrun , Zhou Jun , Zhai Tianyou , Wang Dingsheng , Gogotsi Yury , Li Yadong
Published: February 2023

2D transition metal carbides (2D TMCs and MXenes) are promising candidates for applications of energy storage and catalysis. However, producing high‐quality, large 2D flakes of Mo2C MXene has been challenging. Here, a new salt‐assisted templating approach is reported that enables the direct synthesis of 2D Mo2C with low defect concentrations. KCl acts as a template to form an intermediate 2D product, facilitating Mo2C formation without coarsening upon melting. The thickness of the flakes produced can range from monolayer (0.36 nm) to 10 layers (4.55 nm), and the electrocatalytical hydrogen evolution reaction (HER) activity of 2D Mo2C is inversely proportional to its thickness. The monolayer Mo2C shows remarkable HER performance with a current density of ≈6800 mA cm−2 at 470 mV versus reversible hydrogen electrode and an ultrahigh turnover frequency of ≈17 500 s−1. This salt‐assisted synthesis approach can also produce WC and V8C7 nanosheets, expanding the family of 2D carbides. The new pathway eliminates the need for layered ceramic precursors, making it a versatile approach to direct synthesis of MXene‐like 2D carbides.
The transition from Elasto‐Hydrodynamic to Mixed Regimes in Lubricated Friction of Soft Solid Surfaces
Authors: Dong Hao , Moyle Nichole , Wu Haibin , Khripin Constantine Yuri , Hui Chung‐Yuen , Jagota Anand
Published: February 2023

Lubricated contacts in soft materials are common in various engineering and natural settings, such as tires, haptic applications, contact lenses, and the fabrication of soft electronic devices. Two major regimes are elasto‐hydrodynamic lubrication (EHL), in which solid surfaces are fully separated by a fluid film, and mixed lubrication (ML), in which there is partial solid‐to‐solid contact. The transition between these regimes governs the minimum sliding friction achievable and is thus very important. Generally, the transition from EHL to ML regimes is believed to occur when the thickness of the lubricant layer is comparable with the amplitude of surface roughness. Here, it is reported that in lubricated sliding experiments on smooth, soft, poly(dimethylsiloxane) substrates, the transition can occur when the thickness of the liquid layer is much larger than the height of the asperities. Direct visualization of the “contact” region shows that the transition corresponds to the formation of wave‐like surface wrinkles at the leading contact edge and associated instabilities at the trailing contact edge, which are believed to trigger the transition to the mixed regime. These results change the understanding of what governs the important EHL–ML transition in the lubricated sliding of soft solids.
Unveiling the Intrinsic Structure and Intragrain Defects of Organic–Inorganic Hybrid Perovskites by Ultralow Dose Transmission Electron Microscopy
Authors: Yang Chen‐Quan , Zhi Rui , Rothmann Mathias Uller , Xu Yue‐Yu , Li Li‐Qi , Hu Zhi‐Yi , Pang Shuping , Cheng Yi‐Bing , Van Tendeloo Gustaaf , Li Wei
Published: February 2023

Transmission electron microscopy (TEM) is a powerful tool for unveiling the structural, compositional, and electronic properties of organic–inorganic hybrid perovskites (OIHPs) at the atomic to micrometer length scales. However, the structural and compositional instability of OIHPs under electron beam radiation results in misunderstandings of the microscopic structure–property–performance relationship in OIHP devices. Here, ultralow dose TEM is utilized to identify the mechanism of the electron‐beam‐induced changes in OHIPs and clarify the cumulative electron dose thresholds (critical dose) of different commercially interesting state‐of‐the‐art OIHPs, including methylammonium lead iodide (MAPbI3), formamidinium lead iodide (FAPbI3), FA0.83Cs0.17PbI3, FA0.15Cs0.85PbI3, and MAPb0.5Sn0.5I3. The critical dose is related to the composition of the OIHPs, with FA0.15Cs0.85PbI3 having the highest critical dose of ≈84 e Å−2 and FA0.83Cs0.17PbI3 having the lowest critical dose of ≈4.2 e Å−2. The electron beam irradiation results in the formation of a superstructure with ordered I and FA vacancies along <110>c, as identified from the three major crystal axes in cubic FAPbI3, <100>c, <110>c, and <111>c. The intragrain planar defects in FAPbI3 are stable, while an obvious modification is observed in FA0.83Cs0.17PbI3 under continuous electron beam exposure. This information can serve as a guide for ensuring a reliable understanding of the microstructure of OIHP optoelectronic devices by TEM.
Coexistence of Merons with Skyrmions in the Centrosymmetric Van Der Waals Ferromagnet Fe5–xGeTe2
Authors: Casas Brian W. , Li Yue , Moon Alex , Xin Yan , McKeever Conor , Macy Juan , Petford‐Long Amanda K. , Phatak Charudatta M. , Santos Elton J. G. , Choi Eun Sang , Balicas Luis
Published: February 2023

Fe5–xGeTe2 is a centrosymmetric, layered van der Waals (vdW) ferromagnet that displays Curie temperatures Tc (270–330 K) that are within the useful range for spintronic applications. However, little is known about the interplay between its topological spin textures (e.g., merons, skyrmions) with technologically relevant transport properties such as the topological Hall effect (THE) or topological thermal transport. Here, via high‐resolution Lorentz transmission electron microscopy, it is shown that merons and anti‐meron pairs coexist with Néel skyrmions in Fe5–xGeTe2 over a wide range of temperatures and probe their effects on thermal and electrical transport. A THE is detected, even at room T, that senses merons at higher T's, as well as their coexistence with skyrmions as T is lowered, indicating an on‐demand thermally driven formation of either type of spin texture. Remarkably, an unconventional THE is also observed in absence of Lorentz force, and it is attributed to the interaction between charge carriers and magnetic field‐induced chiral spin textures. These results expose Fe5–xGeTe2 as a promising candidate for the development of applications in skyrmionics/meronics due to the interplay between distinct but coexisting topological magnetic textures and unconventional transport of charge/heat carriers.
Advances in Designing 3D‐Printed Systems for CO2 Reduction
Authors: Padinjareveetil Akshay Kumar K. , Pumera Martin
Published: February 2023

The increasing level of atmospheric carbon dioxide (CO2), and the resultant global warming is a matter of growing concern among scientists, environmentalists, and climate experts across the globe over the past several decades. Numerous attempts are being undertaken today that seek solutions to mitigate this global crisis. This includes designing functional catalysts, devices and reactors to convert greenhouse gasses such as CO2 into useful products like low‐carbon fuels and chemicals, thereby reducing the amount of CO2 considerably in the atmosphere. Advancements in emerging technologies like 3D‐printing can effectively aid in the fabrication of electrodes and devices to tackle the rising CO2 concerns. Low cost, rapid prototyping ability, and printing simple and complex structure are few of the significant merits of this technology. Thus, in this perspective article, discussions on fabricating 3D‐printed (electro)catalysts, customized devices, reactors, etc., via multiple strategies are put forward with emphasis on the electrochemical reduction of CO2. Also, a detailed discussion on the post‐printing treatments, catalyst modifications, and other CO2 mitigation strategies is provided as well. Although studies in this direction are scarcely reported, observations made hitherto show promising possibilities of broadening this field for large scale CO2 reduction reaction applications, and similar catalytic applications in the near future.
Influence of a Tailored Oxide Interface on the Quality Factor of Microelectromechanical Resonators
Authors: Lynes David D. , Chandrahalim Hengky
Published: February 2023

Piezoelectric microelectromechanical systems (MEMS) are used as sensors, actuators, energy harvesters, accelerometers, and communication modules. Aluminum nitride (AlN) is an especially attractive piezoelectric material because its fabrication process allows it to be integrated into semiconductor circuitry to deliver a fully integrated solution. Microelectromechanical resonators with AlN sandwiched between n‐type silicon (Si) and top metal electrode with and without a silicon oxide layer are designed and fabricated. The effect of the oxide film is up to a fourfold increase in quality factor (Q) that is consistent from very high frequency (VHF) to super high frequency (SHF). This effect is demonstrated using thin plate bulk acoustic wave modes from 70–80 MHz using the second contour mode and first width extensional mode and from 9.5–10.5 GHz using high overtone thickness modes. To explore potential applications of AlN‐transduced Q‐enhanced MEMS devices in harsh environments, measurements from −200 °C to +200 °C are performed. The Q enhancement is persistent across a wide temperature range for both VHF and SHF resonators with the added oxide layer. Furthermore, AlN‐on‐Si resonators that have a comparable temperature coefficient of frequency to silicon carbide‐based resonators in commercial applications are demonstrated.
Polarization Conversion of Light Diffracted from InP Nanowire Photonic Crystal Arrays
Authors: Tu Chia‐Wei , Kaveh Masoud , Fränzl Martin , Gao Qian , Tan Hark Hoe , Jagadish Chennupati , Schmitzer Heidrun , Wagner Hans Peter
Published: February 2023

This work investigates the polarization state of light diffracted from uncoated and gold‐coated InP nanowire photonic crystal arrays grown by selective area epitaxy. Experimental data and finite‐difference time‐domain simulations show that both the intensity and the ellipticity of the polarization state of the diffracted light beam can be controlled by the nanowire dimensions and gold coating, while the diffracted angle remains unchanged with respect to variations of these parameters. A nominally 10 nm‐thick gold film deposited around the nanowires enhances the diffraction intensity by plasmonic effects. These results demonstrate that the controlled conversion of incident linearly polarized light to circularly polarized or rotated linearly polarized diffracted light can find applications in photonic integrated circuits. The high sensitivity of the polarization state with respect to alterations of the nanowire dimension opens new prospects in the areas of semiconductor metrology and microchip inspection as well as for submicron particle detection.
Metabolic Modulation of Intracellular Ammonia via Intravesical Instillation of Nanoporter‐Encased Hydrogel Eradicates Bladder Carcinoma
Authors: Jing Weiqiang , Chen Chen , Wang Ganyu , Han Maosen , Chen Shouzhen , Jiang Xin , Shi Chongdeng , Sun Peng , Yang Zhenmei , Shi Benkang , Jiang Xinyi
Published: February 2023

Tumor protein 53 (TP53) mutation in bladder carcinoma (BC), upregulates the transcription of carbamoyl phosphate synthetase 1 (CPS1), to reduce intracellular ammonia toxicity. To leverage ammonia combating BC, here, an intravesically perfusable nanoporter‐encased hydrogel system is reported. A biomimetic fusogenic liposomalized nanoporter (FLNP) that is decorated with urea transporter‐B (UT‐B) is first synthesized with protonated chitosan oligosaccharide for bladder tumor‐targeted co‐delivery of urease and small interfering RNA targeting CPS1 (siCPS1). Mussel‐inspired hydrogel featured with dual functions of bio‐adhesion and injectability is then fabricated as the reservoir for intravesical immobilization of FLNP. It is found that FLNP‐mediated UT‐B immobilization dramatically induces urea transportation into tumor cells, and co‐delivery of urease and siCPS1 significantly boosts ammonia accumulation in tumor inducing cell apoptosis. Treatment with hybrid system exhibits superior anti‐tumor effect in orthotopic bladder tumor mouse model and patient‐derived xenograft model, respectively. Combined with high‐protein diet, the production of urinary urea increases, leading to an augmented intracellular deposition of ammonia in BC cells, and ultimately an enhanced tumor inhibition. Together, the work establishes that cascade modulation of ammonia in tumor cells could induce tumor apoptosis and may be a practical strategy for eradication of TP53‐mutated bladder cancer.
Leaf‐Inspired Patterned Organohydrogel Surface for Ultrawide Time‐Range Open Biosensing
Authors: Gao Hongxiao , Wan Xizi , Yang Yuemeng , Lu Jingwei , Zhu Qinglin , Xu Li‐Ping , Wang Shutao
Published: February 2023

Droplet arrays show great significance in biosensing and biodetection because of low sample consumption and easy operation. However, inevitable water evaporation in open environment severely limits their applications in time‐consuming reactions. Herein, inspired by the unique water retention features of leaves, it is demonstrated that an open droplet array on patterned organohydrogel surface with water evaporating replenishment (POWER) for ultrawide time‐range biosensing, which integrated hydrophilic hydrogel domains and hydrophobic organogel background. The hydrogel domains on the surface can supply water to the pinned droplets through capillary channels formed in the nether organohydrogel bulk. The organogel background can inhibit water evaporation like the wax coating of leaves. Such a unique bioinspired design enables ultrawide time‐range biosensing in open environment from a few minutes to more than five hours involving a variety of analytes such as ions, small molecules, and macromolecules. The POWER provides a feasible and open biosensing platform for ultrawide time‐range reactions.
Intermolecular Metallic Single‐Site Complexes Dispersed on Mo2TiC2Tx/MoS2 Heterostructure Induce Boosted Solar‐Driven Water Splitting
Authors: Tran Phan Khanh Linh , Tran Duy Thanh , Austeria P Muthu , Kim Do Hwan , Kim Nam Hoon , Lee Joong Hee
Published: February 2023

Successful development of an electrocatalyst capable to promote the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) elements of water electrolysis is desirable for green hydrogen gas production. Herein, this work designs intermolecular metallic single‐site complexes of iron phthalocyanine (FePc) and vanadium oxide phthalocyanine (VOPc) dually immobilized on 3D hierarchical MoS2‐coated MXene Mo2TiC2Tx (MX/MoS2) heterostructures as a high‐performance bifunctional electrocatalyst. The well‐organized structure with an unusual coordination environment and electronic localization impressively enhances water adsorption and activation to remarkably accelerate HER and OER kinetics. Therefore, the hybrid material requires overpotentials as small as 17.4 and 300 mV to drive 10 mA cm−2 for the HER and 50 mA cm−2 for the OER in 1.0 m KOH media, respectively. The electrolyzer of MX/MoS2‐FePcVOPc(+,−) exhibits low cell voltage of only 1.45 V to reach a current response of 10 mA cm−2 in 7.0 m KOH at 75 °C along with excellent current retention stability of 99%/94% after long‐term operations of 30 h at 10/50 mA cm−2. Moreover, a solar‐to‐hydrogen conversion efficacy of 19.96% is achieved in a solar energy‐powered water electrolysis system, highlighting the great potential of the developed MX/MoS2‐FePcVOPc electrocatalyst toward water electrolysis.
Diastereoselective Alkylation of Activated Nitrogen Heterocycles with Alkenyl Boronate Complexes
Authors: McGettigan James E. , Ready Joseph M.
Published: February 2023

Alkenyl boronate complexes react with acylated quinolines and isoquinolines via 1,2‐metalate rearrangement to give alkylated, dearomatized heterocycles in good yields, diastereoselectivities, and regioselectivities. This multi‐component coupling is highly modular and can be used to access a wide scope of heterocyclic scaffolds. Chiral boronic esters made through this methodology possess high synthetic potential and can be transformed into various functional groups in one step without racemization.
Effector Regulated Catalytic Cyclization of Alkynoic Acids Using Pt2L4 Cages
Authors: Bobylev Eduard O. , Ruijter Julian , Poole David A. , Mathew Simon , de Bruin Bas , Reek Joost N. H.
Published: February 2023

Metabolic pathways are highly regulated by effector molecules that influences the rate of enzymatic reactions. Inspired by the catalytic regulation found in living cells, we report a Pt2L4 cage of which the activity can be controlled by effectors that bind inside the cage. The cage shows catalytic activity in the lactonization of alkynoic acids, with the reaction rates dependent on the effector guest bound in the cage. Some effector guests enhance the rate of the lactonization by up to 19‐fold, whereas one decreases it by 5‐fold. When mixtures of specific substrates are used, both starting materials and products act as guests for the Pt2L4 cage, enhancing its catalytic activity for one substrate while reducing its activity for the other. The reported regulatory behavior obtained by the addition of effector molecules paves the way to the development of more complex, metabolic‐like catalyst systems.
The jet emitting disk‐standard accretion disk model applied to the active galactic nuclei ultra violet–X‐ray correlation
Authors: Barnier S. , Petrucci P.‐O. , Ferreira J. , Marcel G.
Published: February 2023

The non‐linear correlation between the UV and X‐ray emission observed in active galactic nuclei remains a puzzling question that challenges accretion models. While the UV emission originates from the cold disk, the X‐ray emission is emitted by a hot corona whose physical characteristics and geometry are still highly debated. The jet emitting disk‐standard accretion disk (JED‐SAD) is a spectral model stemming from self‐similar accretion‐ejection solutions. It is composed of an inner highly magnetized and hot accretion flow launching jets, the JED, and an outer SAD. The model has been successfully applied to X‐ray binaries outbursts. The AGN UV–X‐ray correlation represents another essential test for the JED‐SAD model. We use multiple AGN samples to explore the parameter space and identify the regions able to reproduce the observations. In this first paper, we show that the JED‐SAD model is able to reproduce the UV–X‐ray correlation.
Prognostische Ermittlung der Lebenszyklusrendite mit BIM
Authors: Mösl Martin , Tautschnig Arnold
Published: February 2023

Der Werterhalt von Immobilien wird zunehmend durch die Einbeziehung von Nachhaltigkeitsaspekten in der Planung sichergestellt. Dadurch ist bereits in der Phase der Projektentwicklung die lebenszyklusbezogene Betrachtung der künftigen Ertragssituation einer Immobilie erforderlich. Durch Gegenüberstellung der Erlöse zu den Lebenszykluskosten lässt sich die von den Autoren so bezeichnete Lebenszyklusrendite (LZR) als prognostischer Parameter zur Beurteilung der Rentabilität einer Investition ermitteln. In diesem Beitrag werden zur Ermittlung der LZR die zu einem frühen Zeitpunkt vorhandenen Projektinformationen in ein digitales Bauwerksmodell eingebunden. Durch Building Information Modeling (BIM) kann in einer frühen Projektphase die Unschärfe der Kostenermittlung durch Verknüpfung des digitalen Planungsstands mit relevanten Gebäudeinformationen verringert werden. Auf Basis eines digitalen Bauwerksmodells gelingt so eine nachvollziehbare und auf Planungsvarianten anpassbare Ermittlung der LZR. Die Aufgliederung aller für den Lebenszyklus relevanten Erlöse bzw. Einnahmen und Kosten bzw. Ausgaben ist dazu erforderlich. Änderungen und Ergänzungen am Bauwerksmodell erfordern eine laufende und durch das digitale Modell rasch mögliche Anpassung der Berechnungen an den jeweiligen Planungsstand. Eine laufende Kontrolle der zu Projektbeginn definierten Ausgangsparameter ist dadurch möglich.
Simultaneous extraction of chlorophylls, proteins, and carbohydrates from isolated Chlorella thermophila using a triphasic separation technique: A biorefinery approach
Authors: Sarkar Sambit , Bhowmick Tridib Kumar , Gayen Kalyan
Published: February 2023

The separation of multiple products from microalgae using a biorefinery approach is essential for the economic sustainability of microalgae‐based products. In the current study, a technique for the simultaneous extraction of such products was investigated for the complete valorization of microalgae biomass. Three principal metabolites – chlorophylls, carbohydrates and proteins – were simultaneously fractionated from the biomass of isolated Chlorella thermophila using a modified version of the triphasic separation (TPS) process. Optimized process parameters were determined as: (i) ammonium sulfate as the salt; (ii) 40% (w/v) as the salt concentration; (iii) 1:1 as the salt/alcohol ratio; (iv) 0.25% (w/w) as biomass loading; (v) 6 min of homogenization time, and (vi) 10 000 rpm as homogenization speed. These optimized process parameters resulted in the simultaneous recovery of 71%, 40%, and 22% yields for proteins, carbohydrates, and chlorophylls, respectively. Ultrastructure analysis revealed that intracellular metabolites could be extracted without complete cell disruption. Finally, a comparative analysis between triphasic separation with and without homogenization demonstrated the economic feasibility of the optimized extraction process.
Multiple myeloma with plasmacytoma of the clivus bone presenting with multiple cranial nerve III, IV, and VI palsy: A diagnostic dilemma
Authors: Shah Chiranjiwi Prasad , Chamlagain Rajan , Shah Sangam , Paudel Subodh , Sah Sanjit Kumar , Koirala Bipin , Pandit Kamal , Sitaula Sanjeeta , Shrestha Anjan
Published: February 2023

Central nervous system (CNS) manifestation with cranial nerve palsy in multiple myeloma (MM) is a rare manifestation. Plasmacytoma originates from the bones of the skull base in 3% patients with MM but rarely develops from the soft tissues of the nasal cavity and paranasal sinuses. Here, we present a case of 68‐year‐old male patient with multiple myeloma, clivus bone plasmacytoma, and cavernous sinus syndrome.
SnS−SnO2Heterostructures Anchored on GO as a High‐Performance Anode for Sodium Ion Battery
Authors: Li Qian , Yu Fuyuan , Cui Yaru , Wang Juan , Zhao Yan , Peng Jianhong
Published: February 2023

SnO2is a theoretically excellent transformed anode material with high theoretical capacity for SIBs. However, SnO2faces serious volume effect and high resistance, which greatly damages its electrochemical performance. Given that, the SnS−SnO2heterostructures is constructed with special internal electric field, which is beneficial to promote the transfer ability of sodium ions. Besides, the graphene oxide (GO) modification is carried out to isolate the intrinsic materials from direct contact with electrolyte, and alleviate volume expansion of the anode, ultimately promote the electrochemical performance. Furthermore, the structure and the conductivity characteristics of SnS, SnO2, SnS−SnO2and SnS−SnO2@ GO are simulated respectively by first principles and are compared with the correspondence experiment results to verify the accuracy of established models. Owing to the special p‐n junction in SnS−SnO2@GO heterostructures, the resistance of SnS−SnO2@GO can be reduced to 36.23 Ω, much lower than that of SnO2(Rct=341.9 Ω). Notably, the combination of GO has effectively alleviated the volume expansion of SnS−SnO2@GO electrodes, and present excellent capacity higher than 384.7 mAh g−1after 100 cycles. Thus, the efficient synthesis of SnS−SnO2@GO heterostructure electrodes with excellent performance for sodium storage is expected to provide valuable direction for SIBs anode materials.
Synthesis of Polysubstituted Naphthofurans and Indenofurans Based on a Regiodivergent Intramolecular Carbometalation Strategy with 2‐(2’‐Alkynylaryl)‐3‐iodofurans
Authors: Kondoh Azusa , Aita Kohei , Terada Masahiro
Published: February 2023

Efficient methods for the synthesis of two types of furan‐fused tricyclic compounds were developed based on a regiodivergent intramolecular carbometalation strategy using 2‐(2’‐alkynylaryl)‐3‐iodofurans as a common substrate. The iodine‐magnesium exchange/copper‐mediated 6‐endo‐anti intramolecular carbometalation sequence followed by nucleophilic substitution or palladium‐catalyzed cross‐coupling provided 2,3,4,5‐tetrasubstituted naphtho[1,2‐b]furans. On the other hand, the formal intramolecular 5‐exo‐anti carbopalladation/cross‐coupling sequence afforded 2,3‐disubstituted 4‐alkylidene‐4H‐indeno[1,2‐b]furans. The present methods provide new access to a wide range of well‐organized polysubstituted naphtho[1,2‐b]furans and indeno[1,2‐b]furans in a positional selective manner that are otherwise difficult to access.
Evaluating the performance of designed terpolymers for polymer flooding
Authors: Scott Alison J. , Bhicajee Priyadarshini , Kistamah Rowan , Romero‐Zerón Laura , Penlidis Alexander
Published: February 2023

In this work, polymeric materials designed for enhanced oil recovery (EOR) were evaluated for their intended application. Properties including viscosity, flow through porous media (resistance factor and residual resistance factor), and heavy oil displacement (incremental oil recovery) were assessed for designed terpolymers of 2‐acrylamido‐2‐methylpropane sulphonic acid (AMPS), acrylamide (AAm), and acrylic acid (AAc). The same properties were evaluated for two commercially available reference materials (e.g., partially hydrolyzed polyacrylamides or HPAM) with similar characteristics, which allowed for direct comparison between the newly designed terpolymers and materials that are currently on the market for the polymer flooding application. The incremental oil recovery directly associated with polymer flooding, which includes both the polymer flooding and post‐polymer waterflooding stages (excluding the initial waterflooding injection (or secondary) oil recovery), demonstrates that the designed terpolymers provided a higher incremental recovery (42% and 58%) than the reference materials (33% and 46%). Therefore, the terpolymers provided a higher contribution to incremental (or enhanced) oil recovery than the typical HPAM. Additionally, both designed terpolymers showed better injectivity in unconsolidated porous media and are less likely to cause plugging than the commercially available reference materials. Therefore, using a targeted design approach ultimately led to polymeric materials with excellent performance for EOR polymer flooding applications.
Pseudoknots in RNA Structure Prediction
Authors: Hollar Andrew , Bursey Hunter , Jabbari Hosna
Published: February 2023

RNA molecules play active roles in the cell and are important for numerous applications in biotechnology and medicine. The function of an RNA molecule stems from its structure. RNA structure determination is time consuming, challenging, and expensive using experimental methods. Thus, much research has been directed at RNA structure prediction through computational means. Many of these methods focus primarily on the secondary structure of the molecule, ignoring the possibility of pseudoknotted structures. However, pseudoknots are known to play functional roles in many RNA molecules or in their method of interaction with other molecules. Improving the accuracy and efficiency of computational methods that predict pseudoknots is an ongoing challenge for single RNA molecules, RNA‐RNA interactions, and RNA‐protein interactions. To improve the accuracy of prediction, many methods focus on specific applications while restricting the length and the class of the pseudoknotted structures they can identify. In recent years, computational methods for structure prediction have begun to catch up with the impressive developments seen in biotechnology. Here, we provide a non‐comprehensive overview of available pseudoknot prediction methods and their best‐use cases. © 2023 Wiley Periodicals LLC.
Platelet Phenotyping by Full Spectrum Flow Cytometry
Authors: Spurgeon Benjamin E. J. , Frelinger Andrew L.
Published: February 2023

Platelets play key roles in hemostasis, immunity, and inflammation, and tests of platelet phenotype and function are useful in studies of disease biology and pathology. Full spectrum flow cytometry offers distinct advantages over standard tests and enables the sensitive and simultaneous detection of many biomarkers. A typical assay provides a wealth of information on platelet biology and allows the assessment of in vivo activation and in vitro reactivity, as well as the discovery of novel phenotypes. Here, we describe the analysis of platelets by full spectrum flow cytometry and discuss a range of controls and methods for interpreting results. © 2023 Wiley Periodicals LLC.

Basic Protocol: Platelet phenotyping by full spectrum flow cytometry

Support Protocol 1: Spectral unmixing

Support Protocol 2: Data preprocessing
Can early caucus improve a community mediation model? Counteracting stressors prior to joint session
Authors: Tanz Jill S. , McClintock Martha K. , Kyritsi Rae
Published: February 2023

This investigation tests whether adding an early caucus (EC) before joint session is beneficial or detrimental to the mediation process. Parties and mediators were asked open‐ended questions about the use of EC to evaluate its benefits and costs. Party and mediator responses were overwhelmingly positive. In addition, there was no evidence of potential costs of EC, increasing mediator bias or impinging on time for joint session. Most responses showed that EC helped foster a sense of control, set a calm tone, and build rapport, counteracting the typical stressors in a joint session that can hamper settlement. EC also improved the process for the mediator, providing crucial information on what to expect in joint session, time to plan for emotional joint sessions, and an early opportunity to build rapport prior to the joint session. When surveyed 5 years later, mediators had sustained their positive views about EC. To supplement these findings in a wider range of cases, the parties' evaluations of the entire mediation session were also studied, comparing previous cases without an EC, to cases with EC and other types of Prior Meetings (IPVA Screens and both EC and IPVA Screens). Prior Meetings did not degrade perception of the mediation. In fact, Prior Meetings increased parties' perceptions that mediators understood and respected them and tended to increase perceptions that the mediator clearly explained what would happen and gave everyone a chance to talk about what was important. The EC experience can be generalized to other types of meetings with the mediator prior to joint session. This empirical study has implications for the current discussions about use of pre‐mediation sessions and concerns about declining use of joint session.
A Bifunctional Fluorine‐Free Electrolyte Additive for Realizing Dendrite‐Free Lithium Anodes
Authors: Zhou Hanxiao , Li Tianhui , Liu Wenjing , Guo Zhihao , Su Zihao , Gao Jingjing , Qu Meizhen , Peng Gongchang
Published: February 2023

Owing to the strong energy advantage of lithium anodes, the development of lithium‐metal batteries has become an inevitable trend. However, plagued by the instability of solid‐electrolyte interphase (SEI) films, lithium metal anodes face challenges such as lithium dendrite formation and volume expansion. Studies have proven that modulating the composition and structure of SEI films by using electrolyte additives is a convenient and valid method. Currently, it is widely accepted that fluoride is an effective additive but, based on the high cost of fluoride production and environmental concerns, the development of fluoride‐free additives is of great significance. In this work, the bifunctional additive N,O‐bis(trimethylsilyl)acetamide (BSA) is proposed, which can build up a SEI layer that is rich in SiOx and Li3N on the surface of the lithium anode to control the deposition behavior of lithium and clean the electrolyte of HF to protect the electrode. The experimental results indicate that BSA suppresses the generation of lithium dendrites and controls the volume expansion of lithium anodes. Moreover, compared with the commonly used carbonate electrolytes, the battery containing BSA has the best overall performance. Methodologically, the results can be extended to other additives containing Si−O functional groups to replace the same type of fluorine‐containing additives.
Emerging roles of planar cell polarity proteins in glutamatergic synapse formation, maintenance and function in health and disease
Authors: Freitas Andiara E. , Gorodetski Lilach , Lim Wei Ling , Zou Yimin
Published: February 2023

The local signaling mechanism which directly assembles and maintains glutamatergic synapses has not been well understood. Glutamatergic synapses are made of presynaptic and postsynaptic compartments with distinct sets of proteins. The planar cell polarity (PCP) pathway is highly conserved and responsible for establishing and maintaining the cell and tissue polarity along the tissue plane. The six core PCP proteins form antagonizing complexes within the cells and asymmetric intercellular complexes across neighboring cells which regulate cell‐cell interactions during planar polarity signaling. Accumulating evidence suggests that the PCP proteins play essential roles in glutamatergic synapse assembly, maintenance and function in the brain. This review summarizes the key evidence that PCP proteins may be responsible for the formation and stability of the vast majority of the glutamatergic synapses in hippocampus and medial prefrontal cortex, the progress in understanding the mechanisms of how PCP proteins assemble and maintain glutamatergic synapses and initial insights on how disruption of the function of the PCP proteins can lead to neurodegenerative, neurodevelopmental and neuropsychiatric disorders. The PCP proteins may be the missing pieces of a long‐standing puzzle and filling this gap of knowledge may provide the basis for understanding many unsolved questions in synapse biology.
Synthesis and Structural Analysis of Organic Cyclic Polyselenides Obtained from the Reaction of a Bissilylcarbenoid with Selenium
Authors: Sugamata Koh , Asakawa Teppei , Minoura Mao
Published: February 2023

The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane, obtained from the reaction of a bissilylcarbenoid (RSi2CBrLi; RSi=SiMePh2) with elemental selenium, is reported. The molecular structures of these cyclic polyselenides were determined using single‐crystal X‐ray diffraction analysis. The selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane with triphenylphosphine afforded the corresponding tetraselenolane in quantitative yield. Further deselenation of the tetraselenolane with excess triphenylphosphine did not furnish the expected selenoketone but the diselenirane, as confirmed by spectroscopic analysis.
Transition‐Metal‐Free Radical Borylation Reactions
Authors: Shang Zhi‐Hao , Pan Jun , Wang Zeyu , Zhang Ze‐Xin , Wu Jingjing
Published: February 2023

Organoboron compounds are versatile synthons in synthetic chemistry, materials science, and medicinal chemistry. The preparation of them often requires either reactive organometallic reagents or transition metals. In recent years, transition‐metal‐free borylation methodologies using radical chemistry for C−B bond formation have attracted much attention and developed rapidly, which circumvents the use of preformed organometallic reagents. Various successful approaches from different radical precursors (such as carboxylic acids, amines and alcohols, which are abundant in nature) through either thermochemical, photochemical or electrochemical pathways have been developed. Therefore, in this review, we hope to provide an overview of recent advances in the discovery, development, and mechanistic study of transition‐metal‐free radical borylation processes.
Reactivity Tuning of Metal‐Free Artificial Photoenzymes through Binding Site Specific Bioconjugation
Authors: Kuckhoff Thomas , Brewster Richard C. , Ferguson Calum T. J. , Jarvis Amanda G.
Published: February 2023

The design and development of artificial metal‐free photoenzymes aims to combine the selectivity of enzymatic reactions with the benefits of modern synthetic photocatalysts. Removing the need for rare earth metals and allowing for milder reaction conditions, leading to a more sustainable catalytic system. Here, we present the design of a novel artificial photoenzyme by integrating an organophotocatalytic moiety based on a donor‐acceptor design into a steroid carrier protein (SCP‐2L). SCP‐2L possesses a hydrophobic tunnel facilitating substrate binding in aqueous media. The photocatalyst was site‐selectively bound to three SCP‐2L variants, possessing a non‐native cysteine residue strategically placed around the hydrophobic tunnel of the protein. The three modified photoenzymes were shown to be selective for the oxidation of organic sulfides giving up to 192 turnovers.
Syntheses and Preliminary Biological Evaluations of the Dibromopyrrole‐Containing Marine Natural Products Agesasine A, Agesasine B, Longamide E and Various Congeners
Authors: Chen Chengzhi , Yuan Tingting , Lan Ping , White Lorenzo V. , Chen Jing , Banwell Martin G.
Published: February 2023

Total syntheses of the title marine natural products have been achieved and so confirming the structures originally assigned to them. Upon subjecting agesasine A and its corresponding ethyl ester to Mitsunobu conditions, a 1,5‐cyclodehydration reaction takes place to give 2‐oxazolines. In contrast, on subjecting agesasine B to the same Mitsunobu conditions, a simple dehydration reaction occurs to give the corresponding acrylate. A total synthesis of longamide E was achieved by engaging a 1,2‐disubstituted pyrrole in a lactam‐forming reaction and this was followed by a two‐fold and fully regio‐controlled bromination reaction. A distinctly different and possibly biomimetic route was used to synthesize, via the open‐chain natural product nakamurine B, longamide B and its methyl ester. Preliminary biological evaluations of the title alkaloids and various analogues against a small human cancer cell line panel reveals cytotoxic properties that vary significantly with structure.
Synthetic Studies Concerned with the Proposed Structure of Ribisin F, a Compound with Nerve Growth Factor Potentiating Activity Isolated from the Medicinal Fungus Phellinus ribis
Authors: Zhang Yuqi , Lan Ping , Banwell Martin G.
Published: February 2023

The synthesis of the enantiomer of the structure assigned to the title natural product has been achieved from abundant quinic acid. However, the NMR spectral data acquired on the synthetic material do not match those reported for ribisin F (which are of rather modest quality). In an effort to establish the true structure of ribisin F, an epimer of the assigned structure was also prepared from quinic acid. A comparison of the spectral data obtained on this epimer with those reported for the natural product proved a better match and based on optical rotation data the possible true structure of this distinctive, dihydroxylated and benzofuran‐containing compound is tentatively proposed.
An electrochemical sensor based on molecularly imprinted polydopamine coated on reduced graphene oxide for selective detection of ornidazole
Authors: Güney Sevgi
Published: February 2023

The electrochemical sensing of ornidazole (OR) was achieved with a highly selective sensor fabricated by a combination of an electrochemically reduced graphene oxide (ERGO) and molecularly imprinted polydopamine (PDA). The sensor (OR‐imp@PDA/ERGO/GCE) was synthesized by electrochemical polymerization of dopamine (DA) on ERGO modified glassy carbon electrode (GCE). The analytical response of the sensor changed linearly with OR concentration varying from 1.5 × 10−9 M to 1.0 × 10−8 M and 1.0 × 10−8 M to 2.0 × 10−7 M, and the detection limit was defined as 1.1 × 10−9 M. The proposed sensor ensured the highly sensitive detection of OR concentration because of the advantages of ERGO and molecularly imprinted PDA.
The evidence base of US Food and Drug Administration approvals of novel cancer therapies from 2000 to 2020
Authors: Gloy Viktoria , Schmitt Andreas M. , Düblin Pascal , Hirt Julian , Axfors Cathrin , Kuk Hanna , Pereira Tiago V. , Locher Clara , Caquelin Laura , Walter‐Claudi Martin , Lythgoe Mark P. , Herbrand Amanda , Kasenda Benjamin , Hemkens Lars G.
Published: February 2023

Concerns have been raised that regulatory programs to accelerate approval of cancer drugs in cancer may increase uncertainty about benefits and harms for survival and quality of life (QoL). We analyzed all pivotal clinical trials and all non‐pivotal randomized controlled trials (RCTs) for all cancer drugs approved for the first time by the FDA between 2000 and 2020. We report regulatory and trial characteristics. Effects on overall survival (OS), progression‐free survival and tumor response were summarized in meta‐analyses. Effects on QoL were qualitatively summarized. Between 2000 and 2020, the FDA approved 145 novel cancer drugs for 156 indications based on 190 clinical trials. Half of indications (49%) were approved without RCT evidence; 82% had a single clinical trial only. OS was primary endpoint in 14% of trials and QoL data were available from 25%. The median OS benefit was 2.55 months (IQR, 1.33‐4.28) with a mean hazard ratio for OS of 0.75 (95%CI, 0.72‐0.79, I2 = 42). Improvement for QoL was reported for 7 (4%) of 156 indications. Over time, priority review was used increasingly and the mean number of trials per indication decreased from 1.45 to 1.12. More trials reported results on QoL (19% in 2000‐2005; 41% in 2016‐2020). For 21 years, novel cancer drugs have typically been approved based on one single, often uncontrolled, clinical trial, measuring surrogate endpoints. This leaves cancer patients without solid evidence that novel drugs improve their survival or QoL and there is no indication towards improvement.
Effects of rapeseed residue organic fertilizer on cadmium toxicity in soil and its uptake and transfer by rice plants (Oryza sativa L.)
Authors: Yang Wentao , Jing Haonan , Yang Liyu , Li Xuexian , Chen Manzhi , Xu Mengqi , Chen Yonglin , Wu Pan , Liu Hongyan , Wang Ping
Published: February 2023

Cadmium (Cd) contamination of rice fields is a global agro‐environmental issue. Rapeseed (canola) residue organic fertilizer (RROF) as a potential strategy to minimize Cd accumulation in rice planted in acidic soil. The results showed that application of 7.5–30.0 g kg−1 RROF increased the soil pH value by 0.01–0.55 units, increased soil organic matter (OM) by 7.8–25.0%, increased soil microbial biomass carbon (MBC) and nitrogen (MBN) by 0.0–89.7% and 0.0–47.5%, respectively, and increased soil dehydrogenase (DH), acid phosphatase (ACP), and urease (UA) activities by 14.3–344.0%, 0.0–127.1%, and 3.5–14.3%, respectively. The application of RROF treatments reduced the soil acid‐extractable Cd (ACI–Cd) content by 8.1–36.4% and increased the reducible Cd (RED–Cd) and oxidizable Cd (OXI–Cd) by 1.3–36.4% and 16.2–47.9%, respectively. The path analysis demonstrated that soil OM, ACP activity, Mn, and Ca ions had a significant negative indirect effect on the decrease in soil ACI‐Cd (rOM = −0.628, rACP = −0.582, rMn = −0.627, rCa = −0.341), while Zn ions showed a strong direct effect (bZn = 0.567) and indirect positive effect (rZn = 0.580). In rice plants, the contents of Cd, Fe, K, Mg, P, and Zn in rice tissues increased, and the Cd content in rice grains decreased by 3.1–31.3% under RROF application. The results of the correlation analysis found that K and Zn in rice husks and Mg in grains were significantly and negatively correlated with the husk–grain translocation factor of Cd (r = −0.88** for Zn, r = −0.81** for K, and r = −0.59* for Mg). In addition, a significant negative correlation of root–straw translocation factors of Cd with Ca and Fe ions in the roots was observed (r = −0.63* and r = −0.60* for Ca at the filling and maturity stages of rice, r = −0.61* for Fe at the tillering stage of rice). RDA showed that the distribution fraction of soil Cd controlled the accumulation of Cd in various parts of rice, with soil ACI–Cd content explaining 22.4% of the total eigen values at a significant level, followed by 14.1% for OXI–Cd. This means that ACI–Cd was the primary factor that controlled Cd accumulation in rice grain, followed by OXI–Cd.
High‐Speed Graphene–Silicon–Graphene Waveguide PDs with High Photo‐to‐Dark‐Current Ratio and Large Linear Dynamic Range
Authors: Guo Jingshu , Liu Chaoyue , Yu Laiwen , Xiang Hengtai , Xiang Yuluan , Dai Daoxin
Published: February 2023

2D materials (2DMs) meet the demand of broadband and low‐cost photodetection on silicon for many applications. Currently, it is still very challenging to realize excellent silicon‐2DM photodetectors (PDs). Here, graphene–silicon–graphene waveguide PDs operating at the wavelength bands of 1.55 and 2 µm, showing the potential for large‐scale integration, are demonstrated. For the fabricated PDs, the measured responsivities are ≈0.15 and ≈0.015 mA W−1 for the wavelengths of 1.55 and 1.96 µm, respectively. In particular, the PDs exhibit a high bandwidth of ≈30 GHz, an ultra‐low dark current of tens of pico‐amperes, a high normalized photo‐to‐dark‐current ratio of 1.63 × 106 W−1, as well as a high linear dynamic range of 3 µW to 1.86 mW (and beyond) at 1.55 µm. According to the measurement results for the wavelength bands of 1.55/2.0 µm and the theoretical modeling for the silicon–graphene heterostructure, it is revealed that internal photoemission and photo‐assisted thermionic field emission dominantly contribute to the photoresponse in the graphene–silicon Schottky junctions under moderately high bias voltage, which helps the future work to further improve the performance.