bluuebunny/crossref_metadata_2025 huggingface dataset:
Tunable, Homoepitaxial Hyperbolic Metamaterials Enabled by High Mobility CdO
Authors: Cleri Angela J. , Nolen J. Ryan , Wirth Konstantin G. , He Mingze , Runnerstrom Evan L. , Kelley Kyle P. , Nordlander Joshua , Taubner Thomas , Folland Thomas G. , Maria Jon‐Paul , Caldwell Joshua D.
Published: November 2022

Propagating light exhibits hyperbolicity in strongly anisotropic materials where the principal components of the dielectric tensor are opposite in sign. While hyperbolicity occurs naturally in anisotropic polar dielectrics, wherein optical phonons along orthogonal crystal axes are nondegenerate, such optical anisotropy can also be engineered in hyperbolic metamaterials (HMMs): thin film superlattices of alternating dielectric and metallic layers. Contrasted with the severely limited tunability of natural hyperbolic materials, the hyperbolic behavior of HMMs can be tailored significantly both through superlattice design and material selection. However, so far HMMs have suffered from high optical losses, hindering their performance. In this report, broadly tunable (λ = 2–5 µm) Type I and II hyperbolic modes with low losses (quality (Q)‐factors up to 19.7) are observed through attenuated total reflectance measurements of monolithic, homoepitaxial superlattices of high‐ and low‐doped cadmium oxide (CdO). Further, the low losses offered by CdO enable the first demonstration of real‐space imaging of hyperbolic plasmon polaritons in nanoresonators by scattering‐type scanning near‐field optical microscopy—previously only possible for hyperbolic phonon polariton materials. Tunable, low‐loss CdO HMMs promise designability for applications such as on‐chip photonics, super‐resolution imaging (hyperlensing), enhanced emission, novel emitter designs, and possibly quantum nanophotonic and time variant metasurfaces.
Synthesis of Ethyl 3‐(1‐Acetyl‐3‐phenyl‐4,5‐dihydro‐1H‐pyrazol‐4‐yl)‐2,2‐difluoropropanoate from N‐Allyl‐N′‐benzylideneacetohydrazide and Ethyl 2‐Bromo‐2,2‐difluoroacetate
Authors: Liu Yi , Zhu Wenjing , Yu Xiao , Liu Hongyan , Zhang Zenghui , Zhang Mei , Zhao Jinbo , Wang Yacong , Xia Chengcai
Published: November 2022

A route for cyclization reaction of N‐allyl‐N′‐benzylideneacetohydrazide and ethyl 2‐bromo‐2,2‐difluoroacetate to synthesize 3‐(1‐acetyl‐3‐phenyl‐4,5‐dihydro‐1H‐pyrazol‐4‐yl)‐2,2‐difluoropropanoate has been developed. This methodology features mild reaction conditions and good functional group tolerance, providing a direct approach for the preparation of dihydropyrazoles.

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Oncogenic RAS Networks Suppression: Reversibly Ionic Oligonucleotide‐Based Nanoparticles Caged microRNA‐143 Inhibit KRAS‐Mutated Colon Cancer Growth in Tumor‐Bearing Mice
Authors: Miyamoto Noriko , Kawasaki Riku , Sakuragi Mina , Yamana Keita , Isozaki Hinata , Kawamura Shogo , Akiba Isamu , Kitade Yukio
Published: November 2022

Oncogenic RAS has been a particular focus of attention as a pharmacological target over the last four decades. Tumor‐suppressor microRNA‐143 (miR‐143) silences oncogenic KRAS networks, but it requires a nucleic acid delivery vehicle for clinical application. DNA‐ or RNA‐based nucleic acid structures (NASs) are attractive as vehicles that can form unique sequence‐based structures. However, for the biological application of NASs, it is still challenging to create a nanostructure that is stable under physiological conditions by reducing intramolecular repulsion due to negative charges. Here, a novel NAS (named RIONmiR‐143: reversibly ionic oligonucleotide‐based nanoparticles caged miR‐143) is created by self‐assembly involving hybridization and electrostatic interaction via chemically modified oppositely charged ion oligonucleotides. RIONmiR‐143 are nanoparticles of about 70 nm in diameter with improved nuclease resistance under physiological conditions. Moreover, RIONmiR‐143 inhibit the expression of proteins in KRAS networks and cell growth in a dose‐dependent manner in KRAS‐mutated DLD‐1 cells. The anti‐tumor activity of RIONmiR‐143 is demonstrated in a DLD‐1 cell‐bearing mouse model, with a fourfold decrease in tumor volume compared with NakedmiR‐143. This report presents RIONmiR‐143 as a new option for oncogenic KRAS‐targeting medicine, which can be used as a potent nucleic acid delivery platform.
Internally Structured Conductive Composite for Reliable Stretchable Electronics
Authors: Park Jeonghwan , Myung Jin Suk , Cho Duho , Kim Taesu , Lee Su Yeon , Kim Yunseok , Choi Youngmin , Jung Sungmook
Published: November 2022

Designing reliable stretchable electronic devices is challenging as the stress caused by stretching deformation hinders material performances. Furthermore, electrode resistance considerably increases upon stretching, thereby distorting electrical signals and causing errors. Herein, a hydrophilic solution process for fabricating a stretchable conductive composite is reported. This process forms an internal structure that improves conductivity by concentrating conductive fillers to create a conductive path. It also minimizes changes in the electrical properties during stretching, which maximizes the elastic durability. The rate of change in resistance and decrease in conductivity of the composite are significantly low, and performance remains consistent and reliable. The conductive composite paste can be applied to direct writing, simplifying patterning processes.
Solvent Engineering of Ionic Liquids for Stable and Efficient Perovskite Solar Cells
Authors: Wang Fei , Zhou Xianfang , Liang Xiao , Duan Dawei , Ge Chuang-Ye , Lin Haoran , Zhu Quanyao , Li Liang , Hu Hanlin
Published: November 2022

Solution‐processed perovskite solar cells (PSCs) are widely and dramatically developed with certificated record efficiency up to 25.7%, which have been regarded as the most promising candidates for next‐generation photovoltaic devices. However, the current decent devices are dominantly fabricated based on traditional toxic organic solvents such as N,N‐dimethylformamide and dimethyl sulfoxide, which inevitably leads to environmental damage and potential safety accidents. As green and nontoxic molten salts at room temperature, ionic liquids (ILs) as promising alternatives for traditional toxic organic solvents have attracted intensive research interest worldwide in the field of perovskite photovoltaics with encouraging development.  Herein, especially concentrating on ILs solvent engineering rather than additive or post‐treatment, discussion and summarization upon the recent progress on perovskite photovoltaics including both 3D and 2D‐based PSCs is systematically carried out. An in‐depth understanding regarding the interactions between IL molecules and perovskite precursor materials is thoroughly explored and summarized. Moreover, the detailed influence of ILs as solvent(s) on the aspects of perovskite material crystallization regulation, surface defect passivation, and performance improvement of resultant device is comprehensively overviewed and discussed. Finally, prospects of the application of ILs in the PSCs through solvent engineering are provided for further developments.
Multivariate analyses reveal key traits in the identification of nitrogen‐use‐efficient cultivars of common beans
Authors: Zeffa Douglas Mariani , Moda‐Cirino Vania , dos Santos Neto José , Scapim Carlos Alberto , Simões Azeredo Gonçalves Leandro
Published: November 2022

Common bean (Phaseolus vulgaris L.) cultivars with higher nitrogen‐use efficiency (NUsE) are considered to be the main strategy to reduce the dependence on nitrogen (N) fertilizers. In this sense, the objective of this study was to identify key traits and common bean cultivars with higher NUsE using multivariate statistical approaches. Forty carioca common bean cultivars were analyzed in four environments under absence‐ (0 kg N ha−1) and presence N (40 kg N ha−1) applied as top‐dressing. A total of 15 NUsE‐related traits were evaluated. Multivariate analyses of variance identified the presence of a three‐way interaction of genotype, N level, and environment, showing that the differential behavior of cultivars depended on the N level and environment evaluated. Strong multicollinearity was observed among the total set of traits studied; however, after removal criteria used, a collection of eight traits remained for subsequent analyses. The path analysis indicated that the dry matter biomass could be used for the indirect determination of NUsE in contrasting N conditions. The cultivars IAC‐Alvorada, IPR Sabiá, and IPR Saracura performed the best from those selected in both N conditions by factor analysis. The cultivars that stood out positively in this study can be used as parents in breeding programs aimed at developing cultivar with higher NUsE and less dependence on N fertilizers.
Soil mineral nitrogen content and grain yield with enhanced efficiency fertilizers in maize
Authors: Torralbo Fernando , Boardman Dara , Houx James H. , Fritschi Felix B.
Published: November 2022

Urea is the most common N fertilizer worldwide, but N from urea breakdown can be easily lost through ammonia (NH3) volatilization, ammonium (NH4+) nitrification, nitrate (NO3−) denitrification or NO3−–leaching processes. Enhanced efficiency fertilizers (EEFs) are formulated to minimize N losses and maximize plant N uptake and crop yields. The capacity of urea EEFs (urea with urease inhibitor, nitrification inhibitor, both urease and nitrification inhibitors, and polymer‐coated) to maintain N in the soil profile throughout the growing season was determined by the analysis of [NH4+–N] and [NO3−–N] in three top‐soil depth increments at three dates in three seasons of no‐till maize (Zea mays L.). Surface‐applied EEFs, untreated urea, and injected urea ammonium nitrate (UAN) were compared at an application rate of 168 kg N ha−1. Within and across years, soil [NO3−–N] and [NH4+–N] typically decreased with depth and time since urea application. Among the EEFs, only a polymer‐coated urea produced greater [NO3−–N] and [NH4+–N] at several sampling dates and depths, and greater grain yields than untreated urea across the 3 yr. Nonetheless, the polymer‐coated urea resulted in significantly greater fertilizer use efficiency (FUE) than untreated urea in only 1 of 3 yr. Several EEFs increased grain yields compared to untreated urea each year, but FUE generally was similar to that with untreated urea. Environmental conditions influenced the effectiveness of EEFs in improving soil mineral N availability and increasing grain yield.
Agribusiness diversification and technological innovation efficiency: A U‐shaped relationship
Authors: Su Zhiwen , Zhang Mingyu , Sun Jianjun , Wu Wenbing
Published: November 2022

In recent years, agribusiness firms have increasingly diversified their product portfolio and expanded into new business areas through internal growth or acquisition, which can lead to the reallocation of innovation resources. This study examines the impact of agribusiness diversification (AD) on technological innovation efficiency (TIE) in China. Based on an 8‐year longitudinal dataset of 101 Chinese listed agribusiness firms from 2012 to 2019, this study applies the Tobit regression technique to reveal the underlying mechanism between AD and TIE. The empirical results show that: (1) the AD‐TIE relationship follows a U‐shaped pattern, that is, at low levels of AD, the AD‐TIE relationship is negative; at high levels of AD, the AD‐TIE relationship is positive. (2) government subsidies (GS) negatively moderate the U‐shaped relationship between AD and TIE, such that GS flattens the U‐shaped curve. Our findings have important implications for agribusiness managers and public policymakers. [EconLit citations: H25, L25, Q16].
Oxidative coupling of methane over strontium‐doped neodymium oxide: Parametric evaluations
Authors: Alahmadi Faisal , Bavykina Anastasiya , Poloneeva Daria , Ramirez Adrian , Schucker Robert , Gascon Jorge
Published: November 2022

Since its discovery in 1982, oxidative coupling of methane (OCM) has been considered one of the most promising approaches for the on‐purpose synthesis of ethylene. The development of more selective catalysts is essential to improve process economics. In this work, undoped neodymium oxide as well as neodymium oxide doped with high (20%) and low (2.5%) levels of strontium were tested in a high‐throughput fashion covering a wide range of operating conditions. The catalysts were shown to be able to achieve greater than 18% C2+ yield. Space velocity was shown to play a significant role in C2+ selectivity. For a methane to oxygen feed ratio of 3.5, selectivity increased with increasing space velocity, reaching a maximum of 62% at a methane conversion of 30% at an optimal space velocity of ~250,000 ml/h/g. The difference in activity between the three samples was linked to the contribution of different oxygen centers.
Kontinuierliche Elektrochemische Synthese von Gold‐Nanopartikeln in Nanoliter‐Reaktoren
Authors: Saucedo‐Espinosa Mario Alberto , Breitfeld Maximilian , Dittrich Petra Stephanie
Published: November 2022

Gold‐Nanopartikel (AuNP) werden in zahlreichen Gebieten wie Optik, Biosensorik und Katalyse eingesetzt. In der vorliegenden Studie wird gezeigt, dass AuNP in kleinen Nanoliter‐Reaktoren elektrochemisch ohne Einsatz von Stabilisatoren hergestellt werden können. Dazu werden zuerst Wassertropfen, die den Gold(III)‐Präkursor enthalten, in einem mikrofluidischen System erzeugt und dann kontinuierlich durch ein Elektrodenpaar geleitet. Das in diesem Bereich angelegte elektrische Feld führt zur Bildung von AuNP. Dabei verhindern interne Ströme innerhalb der Tröpfchen, die während des Durchfließens durch die Mikrokanäle entstehen, die Aggregation der Nanopartikel nach der Nukleation. Auf dieser Weise können AuNP in einem Größenbereich von 30 bis 100 nm hergestellt werden, ohne dass weitere Additive notwendig sind. Die durchschnittliche Teilchengröße wird durch die Konzentration des Präkursors und der Flussgeschwindigkeit der Tröpfchen beeinflusst. Die Ladungsmenge, die durch die Stärke des elektrischen Feldes bestimmt wird, hat dagegen nur einen geringen Einfluss auf die resultierende Partikelgröße. Das Verfahren ermöglicht nicht nur eine gezielte Steuerung der resultierenden Partikelgröße, sondern könnte in Zukunft auch für die Herstellung anderer Metall‐Nanopartikel eingesetzt werden.
Electron‐Deficient Polycyclic Molecules via Ring Fusion for n‐Type Organic Electrochemical Transistors
Authors: Duan Jiayao , Zhu Genming , Lan Liuyuan , Chen Junxin , Zhu Xiuyuan , Chen Chaoyue , Yu Yaping , Liao Hailiang , Li Zhengke , McCulloch Iain , Yue Wan
Published: November 2022

The primary challenge for n‐type small‐molecule organic electrochemical transistors (OECTs) is to improve their electron mobilities and thus the key figure of merit μC*. Nevertheless, few reports in OECTs have specially proposed to address this issue. Herein, we report a 10‐ring‐fused polycyclic π‐system consisting of the core of naphthalene bis‐isatin dimer and the terminal moieties of rhodanine, which features intramolecular noncovalent interactions, high π‐delocalization and strong electron‐deficient characteristics. We find that this extended π‐conjugated system using the ring fusion strategy displays improved electron mobilities up to 0.043 cm2 V−1 s−1 compared to our previously reported small molecule gNR, and thereby leads to a remarkable μC* of 10.3 F cm−1 V−1 s−1 in n‐type OECTs, which is the highest value reported to date for small‐molecule OECTs. This work highlights the importance of π‐conjugation extension in polycyclic‐fused molecules for enhancing the performance of n‐type small‐molecule OECTs.
Interparticle Charge‐Transport‐Enhanced Electrochemiluminescence of Quantum‐Dot Aerogels
Authors: Gao Xuwen , Jiang Guocan , Gao Cunyuan , Prudnikau Anatol , Hübner René , Zhan Jinhua , Zou Guizheng , Eychmüller Alexander , Cai Bin
Published: November 2022

Electrochemiluminescence (ECL) represents a widely explored technique to generate light, in which the emission intensity relies critically on the charge‐transfer reactions between electrogenerated radicals. Two types of charge‐transfer mechanisms have been postulated for ECL generation, but the manipulation and effective probing of these routes remain a fundamental challenge. Here, we demonstrate the design of quantum dot (QD) aerogels as novel ECL luminophores via a versatile water‐induced gelation strategy. The strong electronic coupling between adjacent QDs enables efficient charge transport within the aerogel network, leading to the generation of highly efficient ECL based on the selectively improved interparticle charge‐transfer route. This mechanism is further verified by designing CdSe‐CdTe mixed QD aerogels, where the two mechanistic routes are clearly decoupled for ECL generation. We anticipate our work will advance the fundamental understanding of ECL and prove useful for designing next‐generation QD‐based devices.
Charge‐Transfer Complex Doped Photothermal Hydrogels for Discriminating Circularly Polarized Near‐Infrared Light
Authors: Wang Zhuoer , Hao Aiyou , Xing Pengyao
Published: November 2022

Hydrogels behave as potential candidates to investigate circularly polarized light (CP)‐matter interaction, which however suffer from small sensitivity towards circular polarization. Here we report a general protocol to build hydrogels from π‐conjugated amino acids with coassembled charge‐transfer (CT) complexes, covering a wide scope of donors and acceptors, which were incorporated into stable hydrogel matrices. CT complexes formed block coassemblies with gelators, induced the emergence of macroscopic chiral helices, where efficient chirality transfer occurs to realize tunable Cotton effects from visible light to NIR‐I region depending on the structures of CT pairs. The hybrid hydrogels showed tunable photothermal performances with excellent heating‐cooling cycling durability. Circularly polarized NIR light selectively triggered gel‐solution phase transition at different timescales. Left‐ and right‐CP illumination generates up to 2.5 folds difference in gel collapse time that allows for direct discrimination by naked eyes.
Minimum Information Standards in Chemistry: A Call for Better Research Data Management Practices
Authors: Herres‐Pawlis Sonja , Bach Felix , Bruno Ian J. , Chalk Stuart J. , Jung Nicole , Liermann Johannes C. , McEwen Leah R. , Neumann Steffen , Steinbeck Christoph , Razum Matthias , Koepler Oliver
Published: November 2022

Research data management (RDM) is needed to assist experimental advances and data collection in the chemical sciences. Many funders require RDM because experiments are often paid for by taxpayers and the resulting data should be deposited sustainably for posterity. However, paper notebooks are still common in laboratories and research data is often stored in proprietary and/or dead‐end file formats without experimental context. Data must mature beyond a mere supplement to a research paper. Electronic lab notebooks (ELN) and laboratory information management systems (LIMS) allow researchers to manage data better and they simplify research and publication. Thus, an agreement is needed on minimum information standards for data handling to support structured approaches to data reporting. As digitalization becomes part of curricular teaching, future generations of digital native chemists will embrace RDM and ELN as an organic part of their research.
Tunable Strategy for the Asymmetric Synthesis of Sulfoglycolipids from Mycobacterium tuberculosis To Elucidate the Structure and Immunomodulatory Property Relationships
Authors: Mondal Soumik , Tseng Chieh‐Jen , Tan Janet Jia‐Yin , Lin Ding‐Yuan , Lin Hsien‐Ya , Weng Jui–Hsia , Lin Chun‐Hung , Mong Kwok‐Kong Tony
Published: November 2022

We developed a versatile asymmetric strategy to synthesize different classes of sulfoglycolipids (SGLs) from Mycobacterium tuberculosis. The strategy features the use of asymmetrically protected trehaloses, which were acquired from the glycosylation of TMS α‐glucosyl acceptors with benzylidene‐protected thioglucosyl donors. The positions of the protecting groups at the donors and acceptors can be fine‐tuned to obtain different protecting‐group patterns, which is crucial for regioselective acylation and sulfation. In addition, a chemoenzymatic strategy was established to prepare the polymethylated fatty acid building blocks. The strategy employs inexpensive lipase as a desymmetrization agent in the preparation of the starting substrate and readily available chiral oxazolidinone as a chirality‐controlling agent in the construction of the polymethylated fatty acids. A subsequent investigation on the immunomodulatory properties of each class of SGLs showed how the structures of SGLs impact the host innate immunity response.
Chiral Frustrated Lewis Pair@Metal‐Organic Framework as a New Platform for Heterogeneous Asymmetric Hydrogenation
Authors: Zhang Yin , Chen Songbo , Al‐Enizi Abdullah M. , Nafady Ayman , Tang Zhiyong , Ma Shengqian
Published: November 2022

Asymmetric hydrogenation, a seminal strategy for the synthesis of chiral molecules, remains largely unmet in terms of activation by non‐metal sites of heterogeneous catalysts. Herein, as demonstrated by combined computational and experimental studies, we present a general strategy for integrating rationally designed molecular chiral frustrated Lewis pair (CFLP) with porous metal–organic framework (MOF) to construct the catalyst CFLP@MOF that can efficiently promote the asymmetric hydrogenation in a heterogeneous manner, which for the first time extends the concept of chiral frustrated Lewis pair from homogeneous system to heterogeneous catalysis. Significantly, the developed CFLP@MOF, inherits the merits of both homogeneous and heterogeneous catalysts, with high activity/enantio‐selectivity and excellent recyclability/regenerability. Our work not only advances CFLP@MOF as a new platform for heterogeneous asymmetric hydrogenation, but also opens a new avenue for the design and preparation of advanced catalysts for asymmetric catalysis.
Platinum‐Iron(II) Oxide Sites Directly Responsible for Preferential Carbon Monoxide Oxidation at Ambient Temperature: An Operando X‐ray Absorption Spectroscopy Study**
Authors: Sadykov Ilia I. , Sushkevich Vitaly L. , Krumeich Frank , Nuguid Rob Jeremiah G. , van Bokhoven Jeroen A. , Nachtegaal Maarten , Safonova Olga V.
Published: November 2022

Operando X‐ray absorption spectroscopy identified that the concentration of Fe2+ species in the working state‐of‐the‐art Pt−FeOx catalysts quantitatively correlates to their preferential carbon monoxide oxidation steady‐state reaction rate at ambient temperature. Deactivation of such catalysts with time on stream originates from irreversible oxidation of active Fe2+ sites. The active Fe2+ species are presumably Fe+2O−2 clusters in contact with platinum nanoparticles; they coexist with spectator trivalent oxidic iron (Fe3+) and metallic iron (Fe0) partially alloyed with platinum. The concentration of active sites and, therefore, the catalyst activity strongly depends on the pretreatment conditions. Fe2+ is the resting state of the active sites in the preferential carbon monoxide oxidation cycle.
Synthesis and Studies of Di(p‐Benzi)Decaphyrin and Di(9,10‐Anthracenyl)Decaphyrin
Authors: Yadav Bharti , Rawat Nisha , Ravikanth Mangalampalli
Published: November 2022

Two novel macrocycles, di(p‐benzi)decaphyrin and di(9,10‐anthracenyl)decaphyrin have been synthesized by condensing appropriate p‐phenylene based pentapyrrane or 9,10‐anthracenyl based pentapyrrane with pentafluorobenzaldehyde under acid catalyzed conditions. The pentapyrrane precursors were synthesized over sequence of steps starting with commercially available 1,4‐dibromobenzene and 9,10‐dibromoanthracene. The decaphyrin macrocycles were freely soluble in common organic solvents and characterized and studied by HR‐MS, 1D and 2D NMR, absorption, cyclic voltammetry and computational techniques. The 1H NMR spectra of both decaphyrins were almost similar with very few resonances, indicating their symmetrical nature in solution and the position of chemical shifts of various protons supports nonaromatic nature of decaphyrins. The DFT optimized structures revealed that both decaphyrins showed a doubly twisted figure of eight conformation and the p‐phenylene rings in di(p‐benzi)decaphyrin and anthracenyl rings in di(9,10‐anthracenyl)decaphyrin did not participate in π‐delocalization with rest of the respective decaphyrin macrocycle. Both decaphyrins showed sharp intense band in the region of 400–500 nm and a broad band in the region of 600–900 nm. The absorption bands of di(p‐benzi)decaphyrin were significantly red shifted compared to di(9,10‐anthracenyl)decaphyrin. The protonated derivatives of decaphyrins generated by addition of TFA to the toluene solution of decaphyrins showed distinct changes in colour and absorption spectral bands. The redox studies indicated that both decaphyrins are electron rich and undergo easier oxidations. The electrochemical and computational studies revealed that HOMO‐LUMO energy gap was less in di(p‐benzi)decaphyrin compared to di(9,10‐anthracenyl)decaphyrin supporting the bathochromic shifts of absorption bands in di(p‐benzi)decaphyrin. TD‐DFT studies were in agreement with the experimental observations.
Influence of Proline Chirality on Neighbouring Azaproline Residue Stereodynamic Nitrogen Preorganization
Authors: Lal Jhajan , Prajapati Gurudayal , Meena Rachana , Kant Ruchir , Sankar Ampapathi Ravi , Reddy Damodara N.
Published: November 2022

We report herein the first systematic crystal structural investigation of azaproline incorporated in homo‐ and heterochiral diprolyl peptides. The X‐ray crystallography data of peptides 1–5 illustrates that stereodynamic nitrogen in azaproline adopted the stereochemistry of neighbouring proline residue without depending on its position in the peptide sequence. Natural bond orbital analysis of crystal structures indicates OazPro−C′Pro of peptides 4 and 5 participating in n→π* interaction with stabilization energy about 1.21–1.33 kcal/mol. Density functional theory calculations suggested that the endo‐proline ring puckering favoured over exo‐conformation by 6.72–7.64 kcal/mol. NBO and DFT data reveals that the n→π* interactions and proline ring puckering stabilize azaproline chirality with the neighbouring proline stereochemistry. The CD, solvent titration, variable‐temperature and 2D NMR experimental results further supported the crystal structures conformation.
Robust linear quadratic regulator applied to an inverted pendulum
Authors: Escalante Felix M. , Jutinico Andres L. , Terra Marco H. , Siqueira Adriano A. G.
Published: November 2022

The natural instability of an inverted pendulum and its dynamics richness, in terms of nonlinearity, provide a nice apparatus to reproduce behaviors of analogous systems. In this way, it is useful to perform benchmark tests for new control approaches developed. In this paper, we address the main inverted pendulum problems: pendulum stabilization, tracking, and catching swing‐up control. We show how robust recursive, control and filtering, techniques improve the system performance. They are developed to solve stochastic problems based on deterministic approaches, in order to decrease the worst influence of uncertainties. Experimental results of the proposed robust approach provide robust stability and performance despite parametric uncertainties, disturbances, and noise effects.
Neuroimaging for differential diagnosis of transient neurological attacks
Authors: Wang Ying , Zha Hao
Published: November 2022

Background

Rapid yet comprehensive neuroimaging protocols are required for patients with suspected acute stroke. However, stroke mimics can account for approximately one in five clinically diagnosed acute ischemic strokes and the rate of thrombolyzed mimics can be as high as 17%. Therefore, to accurately determine the diagnosis and differentiate mimics from true transient ischemic attacks, acute ischemic stroke is a challenge to every clinician.

Discussion

Medical history and neurological examination, noncontract head computed tomography, and routine magnetic resonance imaging play important roles in the assessment and management of patients with transient neurological attacks in the emergency department. This review attempts to summarize how neuroimaging can be utilized to help differentiate the most common mimics from transient ischemic attack and acute ischemic stroke.

Conclusion

Although imaging can help direct critical triage decisions for intravenous thrombolysis or endovascular therapy, more detailed medical history and neurological examination are crucial for making a prompt and accurate diagnosis for transient neurological attack patients.
Role of Natural Products in Developing Novel Anticancer Agents: A Perspective
Authors: Shaik Baji Baba , Katari Naresh Kumar , Jonnalagadda Sreekantha Babu
Published: November 2022

Cancer is a heterogeneous disease and is one of the significant health issues, especially in public health systems around the world. Natural products and their structural derivatives with outstanding chemical diversity have been investigated for potential anti‐cancer agents. Many natural products revealing potential anti‐cancer properties such as cytotoxicity, proliferation inhibition, induced apoptosis, retard metastasis, suppressing angiogenesis, and improved chemotherapy have been isolated from various plants and herbs. Several promising lead molecules have been identified recently; a few are in the clinical trial stage. This short communication summarises the role of natural products and their analogs in anti‐cancer drug developments, especially plant, marine and microbial‐based anti‐cancer agents.
Lignans and Phenylethanoid Glycosides from the Aerial Parts of Pogostemon cablin
Authors: Chen Jiaying , Han Linhang , Li Guangxia , Sun Liqin , Qian Fei , Chen Kaixian , Zhang Liuqiang , Li Yiming
Published: November 2022

Two new lignans (1–2) and a new octaketide (12), together with twenty‐nine known compounds (3–11, 13–32) were isolated and identified from the aerial part of Pogostemon cablin. Their chemical structures were revealed mainly through NMR and MS data. The absolute configuration of 1 and 2 was deduced by comparing its experimental CD with the calculated ECD spectra. The inhibitory activities of the isolated compounds on LPS‐stimulated nitric oxide (NO) production in RAW 264.7 cells were investigated. At a concentration of 25 μM, compounds 1 and 11 showed approximately equal NO inhibitory effects to that of aminoguanidine.
Diclofenac Sodium Solvent Extraction Based on Two‐Phase Flow Patterns
Authors: Ansarimehr Mahvash , Rahbar-Kelishami Ahmad , Shayesteh Hadi
Published: November 2022

Diclofenac (DF) solvent extraction using tetra‐n‐butyl ammonium bromide (TBAB) in Y‐type microfluidic junctions with liquid‐liquid two‐phase flow patterns was investigated. The hydrodynamics of parallel, slug, and droplet flows were examined. The results indicated that the extraction efficiency decreased with increasing velocity. At QO/QA greater than 2.5, the flow pattern was converted from slug into droplet flow, and due to the enlargement of the specific surface area, the extraction efficiency increased. Slug flow provided an equilibrium extraction efficiency of 99.2 %. The overall volumetric mass transfer coefficient at different lengths and widths was evaluated. The best mass transfer performance occurred in microchannels with a length of 9 cm and a width of 400 µm.
Phosphorescent Metal Halide Nanoclusters for Tunable Photodynamic Therapy
Authors: Medeiros Hyllana C. D. , Yang Chenchen , Herrera Christopher K. , Broadwater Deanna , Ensink Elliot , Bates Matthew , Lunt Richard R. , Lunt Sophia Y.
Published: November 2022

Photodynamic therapy (PDT) is currently limited by the inability of photosensitizers (PSs) to enter cancer cells and generate sufficient reactive oxygen species. Utilizing phosphorescent triplet states of novel PSs to generate singlet oxygen offers exciting possibilities for PDT. Here, we report phosphorescent octahedral molybdenum (Mo)‐based nanoclusters (NC) with tunable toxicity for PDT of cancer cells without use of rare or toxic elements. Upon irradiation with blue light, these molecules are excited to their singlet state and then undergo intersystem crossing to their triplet state. These NCs display surprising tunability between their cellular cytotoxicity and phototoxicity by modulating the apical halide ligand with a series of short chain fatty acids from trifluoroacetate to heptafluorobutyrate. The NCs are effective in PDT against breast, skin, pancreas, and colon cancer cells as well as their highly metastatic derivatives, demonstrating the robustness of these NCs in treating a wide variety of aggressive cancer cells. Furthermore, these NCs are internalized by cancer cells, remain in the lysosome, and can be modulated by the apical ligand to produce singlet oxygen. Thus, (Mo)‐based nanoclusters are an excellent platform for optimizing PSs. Our results highlight the profound impact of molecular nanocluster chemistry in PDT applications.
Recent Advances on High‐Capacity Sodium Manganese‐Based Oxide Cathodes for Sodium‐ion Batteries
Authors: Cao Yuge , Xiao Meijing , Sun Xuzhou , Dong Wujie , Huang Fuqiang
Published: November 2022

Sodium manganese‐based oxides (NMO) are attracting huge attention as safe and cost‐effective cathode materials for sodium‐ion batteries (SIBs). To date, one of the most important challenges of NMO‐based cathodes is the relatively low capacity. Therefore, it is of great significance to develop high‐capacity NMO‐based cathodes. Great efforts have been made to enhance the reversible capacity of NMO‐based cathodes, achieving considerable progress not only on electrochemical performance, but also the mechanism of massive sodium ion storage. In this paper, the structure and sodium storage mechanism for typical phases of NMO are reviewed, including P2, P3, O3, tunnel‐type, and spinel‐type NMO‐based cathodes. Strategies for high‐capacity NMO‐based cathodes, such as cationic substitution, anion redox activation, etc are introduced in detail. Last but not least, the future opportunities and challenges for high‐capacity NMO‐based cathode are prospected.
Qualification of a Single‐Use Disk Stack Separator for Cell Separation in Mammalian Cell‐Based Antibody Production
Authors: Ott Vivian , Müller Jan , Schirmer Cedric , Weiss Noémi , Göhmann Rüdiger , Biewald Andreas , Michel Andrej , Eibl Dieter , Eibl Regine
Published: November 2022

Single‐use technology is now an indispensable part of biopharmaceutical production processes. This not only applies to research and development, but also to commercial processes. The manufacturers of single‐use systems are working on improving them for use in intensified processes as well as on new developments. One of the bottlenecks was the availability of single‐use disk stack separators whose stainless steel variants are widely used in industry. In this study, the suitability of the new single‐use disk stack separator kytero 500 was investigated for the first time for cell separation in pilot‐scale Chinese hamster ovary cell‐based antibody production. The cells were completely separated over a wide range of separator settings with nearly no release of intracellular substances and no loss of the antibody.
Utility of high‐risk HPV RNA chromogenic in situ hybridization in cytology smears and liquid‐based preparations from metastatic head and neck squamous cell carcinoma
Authors: Velez Torres Jaylou M. , Alkathery Turky , Tjendra Youley , Zuo Yiqin , Kerr Darcy A. , Gomez‐Fernandez Carmen
Published: November 2022

Background

High‐risk human papillomavirus (HR‐HPV) status is critical for the diagnosis, prognosis, and treatment of patients with oropharyngeal squamous cell carcinoma (OPSCC). Patients often present with enlarged cervical nodes, and fine‐needle aspiration cytology (FNAC) is frequently the initial diagnostic procedure. Although p16 is the most widely used surrogate marker, problems with interpretation can limit its utility in FNAC. HR‐HPV RNA in situ hybridization (ISH) has emerged as a specific way to assess HPV status on cell block preparations of cervical nodes. The authors evaluated the utility of HR‐HPV ISH in conventional smears and liquid‐based cytology (LBC) preparations of metastatic head and neck squamous cell carcinoma (SCC).

Methods

Thirty‐one aspirates of proven, HPV‐related SCC (confirmed by p16 and/or HR‐HPV ISH in corresponding surgical specimens) were selected. Ten aspirates of HPV‐negative SCC were also retrieved. HR‐HPV ISH was performed on 27 smears and 14 LBC preparations. All results were scored as positive, equivocal, or negative.

Results

Eighty‐four percent of metastatic, HPV‐related SCCs were positive for HR‐HPV RNA ISH, with high number of signals (n = 19) and low number of signals (n = 7), whereas five HPV‐related SCCs were equivocal. All metastatic, HPV‐negative SCCs were negative for HR‐HPV ISH.

Conclusions

HR‐HPV ISH can be reliably performed on smears or LBC preparations, particularly when cell blocks are unavailable or paucicellular. Results were easy to interpret when high numbers of signals were present but were challenging in aspirates with low or rare number of signals. The current study suggests that HR‐HPV ISH could be used as the initial testing modality for determining HPV status in FNAC specimens of metastatic SCC.
A smartphone authentication system based on touch gesture dynamics
Authors: Jacob Susmi , Puthuvath Vinod , Akarsh Muralidharan , George Jackson , Joseph Jewel , Joy Jigil
Published: November 2022

Different authentication techniques that we use today, are prone to shoulder surfing attacks and mimicry attacks. Thus, keystroke dynamics combined with time and motion‐based typing patterns have been studied for years. In this paper, we introduce and evaluate a touch gesture‐based application to authenticate a user based on their typing behavior in distinct contexts such as lying, sitting, standing, walking, stationary, climbing up and down the stairs, by leveraging different features extracted from multiple built‐in smartphone sensors. We use various attributes including time‐based features such as dwell time and flight time and motion‐based features such as accelerometer, gyroscope, and magnetometer readings. The proposed authentication model distinguishes the legitimate smartphone owner from impostors using hand gestures, touch and keystroke dynamics. We experimented with different design alternatives such as a combination of motion sensor features, time‐based features extracted from multiple devices. In addition, we evaluated the performance using various supervised machine learning algorithms to show how to achieve high authentication accuracy and least equal error rate. A thorough evaluation shows that the system achieves authentication with 99.8% accuracy with a high AUC of 0.99 and EER of 0.11%.
Massively parallel computation of globally optimal shortest paths with curvature penalization
Authors: Mirebeau Jean‐Marie , Gayraud Lionel , Barrère Remi , Chen Da , Desquilbet François
Published: November 2022

We address the computation of paths globally minimizing an energy involving their curvature, with given endpoints and tangents at these endpoints, according to models known as the Reeds‐Shepp car (reversible and forward variants), the Euler‐Mumford elasticae, and the Dubins car. For that purpose, we numerically solve degenerate variants of the eikonal equation, on a three‐dimensional domain, in a massively parallel manner on a graphical processing unit. Due to the high anisotropy and nonlinearity of the addressed Partial Differential Equation, the discretization stencil is rather wide, has numerous elements, and is costly to generate, which leads to subtle compromises between computational cost, memory usage, and cache coherency. Accelerations by a factor 30 to 120 are obtained w.r.t a sequential implementation. The efficiency and the robustness of the method is illustrated in various contexts, ranging from motion planning to vessel segmentation and radar configuration.
How to Run the Pharmacogenomics Clinical Annotation Tool (PharmCAT)
Authors: Li Binglan , Sangkuhl Katrin , Keat Karl , Whaley Ryan M. , Woon Mark , Verma Shefali , Dudek Scott , Tuteja Sony , Verma Anurag , Whirl‐Carrillo Michelle , Ritchie Marylyn D. , Klein Teri E.
Published: November 2022

Pharmacogenomics (PGx) investigates the genetic influence on drug response and is an integral part of precision medicine. While PGx testing is becoming more common in clinical practice and may be reimbursed by Medicare/Medicaid and commercial insurance, interpreting PGx testing results for clinical decision support is still a challenge. The Pharmacogenomics Clinical Annotation Tool (PharmCAT) has been designed to tackle the need for transparent, automatic interpretations of patient genetic data. PharmCAT incorporates a patient's genotypes, annotates PGx information (allele, genotype, and phenotype), and generates a report with PGx guideline recommendations from the Clinical Pharmacogenetics Implementation Consortium (CPIC) and/or the Dutch Pharmacogenetics Working Group (DPWG). PharmCAT has introduced new features in the last 2 years, including a variant call format (VCF) Preprocessor, the inclusion of DPWG guidelines, and functionalities for PGx research. For example, researchers can use the VCF Preprocessor to prepare biobank‐scale data for PharmCAT. In addition, PharmCAT enables the assessment of novel partial and combination alleles that are composed of known PGx variants and can call CYP2D6 genotypes based on single and deletions in the input VCF file. This tutorial provides materials and detailed step‐by‐step instructions for how to use PharmCAT in a versatile way that can be tailored to users' individual needs.
Ecological and metabolomic responses of plants to deer exclosure in a suburban forest
Authors: Morrison Janet A. , Woldemariam Melkamu
Published: November 2022

Trees and shrubs in suburban forests can be subject to chronic herbivory from abundant white‐tailed deer, influencing survival, growth, secondary metabolites, and ecological success in the community. We investigated how deer affect the size, cover, and metabolomes of four species in the understory of a suburban forest in central New Jersey, USA: the woody shrubs Euonymus alatus and Lindera benzoin, the tree Nyssa sylvatica, and the semi‐woody shrub Rosa multiflora. For each species, we compared plants in 38 16 m2 plots with or without deer exclosure, measuring proportion cover and mean height after 6.5 years of fencing. We scored each species in all plots for deer browsing over 8 years and assessed selection by deer among the species. We did untargeted metabolomics by sampling leaves from three plants of each species in an equal number of fenced and unfenced plots, conducting chloroform–methanol extractions followed by LC–MS/MS, and conducting statistical analysis on MetaboAnalyst. The proportion of a species browsed ranged from 0.24 to 0.35. Nyssa sylvatica appeared most selected by and susceptible to deer; in unfenced plots, both its cover and mean height were significantly lower. Only cover or height was lower for E. alatus and L. benzoin in unfenced plots, while R. multiflora height was greater. The metabolomic analysis identified 2333 metabolites, which clustered by species but not fencing treatment. However, targeted analysis of the top metabolites grouped by fencing for all samples and for each species alone and was especially clear in N. sylvatica, which also grouped by fencing using all metabolites. The most significant metabolites that were upregulated in fenced plants include some involved in defense‐related metabolic pathways, e.g., monoterpenoid biosynthesis. In overbrowsed suburban forests, variation of deer impact on species' ecological success, potentially mediated by metabolome‐wide chemical responses to deer, may contribute to changes in community structure.
Feather characteristics of loral zone in an insectivorous passerine: The Iberian gray shrike Lanius meridionalis, in southern France
Authors: Labouyrie Frédéric
Published: November 2022

In the French Mediterranean plain, the northern extreme of its native range, the Iberian gray shrike, Lanius meridionalis, predominantly feeds on arthropods. Its type of loral plumage plays a key role in protecting its eyes while transporting large prey. The aims are to understand the role played by feathers in protecting the animal from various types of defensive prey. I combine an inspection of large insect prey types found on larders with a review of bird specimens found in museum collections to examine the morphometric characteristics of rictal feathers and culmen. In addition, precision photographs are used to observe the posture of the plumage in natura. I could identify four categories of protective feathers: clustered bristles, semi‐bristles, semi‐plumes distributed in the loral area, and semi‐plumes above the eyes. My results suggest that the Iberian gray shrike has a complex structure of loral feathers, specific to its foraging activity and prey types. The presence of these rictal bristles is probably a protection against the movements of larger prey items, which might damage loral zone of Lanius meridionalis.
Geologic, geomorphic, and edaphic underpinnings of dryland ecosystems: Colorado Plateau landscapes in a changing world
Authors: Duniway Michael C. , Benson Christopher , Nauman Travis W. , Knight Anna , Bradford John B. , Munson Seth M. , Witwicki Dana , Livensperger Carolyn , Van Scoyoc Matthew , Fisk Terry T. , Thoma David , Miller Mark E.
Published: November 2022

Drylands represent more than 41% of the global land surface and are at degradation risk due to land use and climate change. Developing strategies to mitigate degradation and restore drylands in the face of these threats requires an understanding of how drylands are shaped by not only soils and climate, but also geology and geomorphology. However, few studies have completed such a comprehensive analysis that relates spatial variation in plant communities to all aspects of the geologic–geomorphic–edaphic–plant–climate system. The focus of this study is the Colorado Plateau, a high‐elevation dryland in the southwestern United States, which is particularly sensitive to future change due to climate vulnerability and increasing land‐use pressure. Here, we examined 135 long‐term vegetation‐monitoring sites in three national parks and characterized connections between geology, geomorphology, soils, climate, and dryland plant communities. To first understand the geologic and geomorphic influences on soil formation and characteristics, we explore associations between soil pedons, bedrock geology, and geomorphology. Then, we characterize principal axes of variation in plant communities and ascertain controls and linkages between components of the edaphic–geomorphic system and plant community ordinations. Geologic and geomorphic substrate exerted controls on important properties of the soil profile, particularly depth, water‐holding capacity, rockiness, salinity, and fine sands. Ordination identified five distinct plant communities and three primary axes of variation, representing gradients of woody‐ to herbaceous‐dominated communities (Axis 1), saline scrublands to C3grasslands (Axis 2), and annual to perennial communities (Axis 3). Geology, geomorphology, and soil explained a large proportion of variation in Axis 1 (74%), while climate variables largely explained Axis 2 (68%), and Axis 3 was not well explained by the random forest models. The variables identified as most influential to each axis were, respectively: (1) soil depth; (2) aridity, lithology, and soil salinity; and (3) temperature and precipitation. We posit that Axis 3 represents a land degradation gradient due to historic grazing, likely exacerbated by dry conditions. Results provide a novel framework that links the geologic and geomorphic evolution of landscapes, with the distribution of soils and plant communities that can guide ecosystem management, exemplifying an approach applicable to drylands globally.