bluuebunny/crossref_metadata_2025 huggingface dataset:
Generation of all-fiber third-order orbital angular momentum modes based on femtosecond laser processing of long-period grating
Authors: Wu Hang , Chen Liao , Shu Xue-Wen , Zhang Xin-Liang ,   Wuhan National Laboratory for Optoelectronics and School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan 430074, China
Published: December 2022

The generation of orbital angular momentum (OAM) modes is very important, for they have a variety of applications such as in optical tweezers, quantum optics, and optical communication systems. Particularly, how can high-order OAM modes be generated efficiently in fibers with the advantage of low cost and compatible with fiber system? The Traditional method for first order to third order OAM is based on long period fiber grating (LPFG) fabricated by carbon dioxide laser. However, high power and large focused spot of carbon dioxide laser are unfavorable for stable and repeatable generation of higher-order OAM, which needs the LPFG with small grating pitch. In order to solve this problem, a third-order OAM mode converter based on femtosecond microfabrication is proposed and fabricated for the first time. With the advantage of 4.4 μm focused spot size near the core, lower power and lower heat absorption efficiency, this method can be more stable and promising. Therefore, we first carry out the mode filed analysis and simulate the intensity and phase profiles of the superposed mode field in LP odd-even mode on different scales and phases patterns to obtain OAM mode. Second, we use the coupled-mode theory to analyze and simulate the transmission spectrum of LPFG, which guides the setting of the grating parameters such as the grating pitch, the depth of modulation and the length of the grating. By experimental verification, an asymmetric modulated long-period fiber grating with a pitch setting to 194 μm is fabricated on a six-mode fiber. The fundamental mode can be converted into the third-order angular linear polarization mode LP31 mode with 98% mode conversion efficiency near 1550 nm, and further converted into the OAM±3 modes by superposition of the odd and even LP31 mode with ±π/2 phase difference. At the same time, this fiber grating can also generate LP12 mode with 90% mode conversion efficiency near 1325 nm. Then we can take the same approach to transform LP12 mode into OAM modes with angular first-order as well as radial second-order. The experimental result is consistent with the simulation result. Thus, this scheme provides an idea for generating the high-order OAM modes in all-fiber systems by using only one grating with high repeatability.
Differential axonal trafficking of Neuropeptide Y-, LAMP1-, and RAB7-tagged organelles in vivo
Authors: Nassal Joris P , Murphy Fiona H , Toonen Ruud F , Verhage Matthijs
Published: December 2022

Different organelles traveling through neurons exhibit distinct properties in vitro, but this has not been investigated in the intact mammalian brain. We established simultaneous dual color two-photon microscopy to visualize the trafficking of Neuropeptide Y (NPY)-, LAMP1-, and RAB7-tagged organelles in thalamocortical axons imaged in mouse cortex in vivo. This revealed that LAMP1- and RAB7-tagged organelles move significantly faster than NPY-tagged organelles in both anterograde and retrograde direction. NPY traveled more selectively in anterograde direction than LAMP1 and RAB7. By using a synapse marker and a calcium sensor, we further investigated the transport dynamics of NPY-tagged organelles. We found that these organelles slow down and pause at synapses. In contrast to previous in vitro studies, a significant increase of transport speed was observed after spontaneous activity and elevated calcium levels in vivo as well as electrically stimulated activity in acute brain slices. Together, we show a remarkable diversity in speeds and properties of three axonal organelle marker in vivo that differ from properties previously observed in vitro.
Transcriptome-wide identification of WRKY transcription factors and their expression profiles under different stress in Cynanchum thesioides
Authors: Chang Xiaoyao , Yang Zhongren , Zhang Xiaoyan , Zhang Fenglan , Huang Xiumei , Han Xu
Published: December 2022

Cynanchum thesioides (Freyn) K. Schum. is an important economic and medicinal plant widely distributed in northern China. WRKY transcription factors (TFs) play important roles in plant growth, development and regulating responses. However, there is no report on the WRKY genes in Cynanchum thesioides. A total of 19 WRKY transcriptome sequences with complete ORFs were identified as WRKY transcriptome sequences by searching for WRKYs in RNA sequencing data. Then, the WRKY genes were classified by phylogenetic and conserved motif analysis of the WRKY family in Cynanchum thesioides and Arabidopsis thaliana. qRT–PCR was used to determine the expression patterns of 19 CtWRKY genes in different tissues and seedlings of Cynanchum thesioides under plant hormone (ABA and ETH) and abiotic stresses (cold and salt). The results showed that 19 CtWRKY genes could be divided into groups I-III according to their structure and phylogenetic characteristics, and group II could be divided into five subgroups. The prediction of CtWRKY gene protein interactions indicates that CtWRKY is involved in many biological processes. In addition, the CtWRKY gene was differentially expressed in different tissues and positively responded to abiotic stress and phytohormone treatment, among which CtWRKY9, CtWRKY18, and CtWRKY19 were significantly induced under various stresses. This study is the first to identify the WRKY gene family in Cynanchum thesioides, and the systematic analysis lays a foundation for further identification of the function of WRKY genes in Cynanchum thesioides.
The effects of a set amount of regular maternal exercise during pregnancy on gut microbiota are diet-dependent in mice and do not cause significant diversity changes
Authors: Duan Xia , Xu Jingjing , Yang Ping , Liang Xinyuan , Zeng Zichun , Luo Huijuan , Tang Xiaomei , Wu Xin , Xiao Xiaomin
Published: December 2022

Background

Diet and exercise can affect the gut microbiota (GM); however, the effects of the same amount of exercise on gut microbiota changes in people on a low-fat diet (LFD) and high-fat diet (HFD) during pregnancy are unknown. Do different nutritional conditions respond equally to exercise intervention? This study aimed to investigate the effects of regular maternal exercise during pregnancy on the GM in mice fed different diets during pregnancy.

Methods

Six-week-old nulliparous female KunMing mice were fed either a HFD or LFD before and during pregnancy. Each group of mice were then randomly divided into two groups upon confirmation of pregnancy: sedentary (HFD or LFD; n = 4 and 5, respectively) and exercised (HFDex or LFDex, n = 5 and 6, respectively). Mice were sacrificed on day 19 of gestation and their colon contents were collected. We then performed 16S rDNA gene sequencing of the V3 and V4 regions of the GM.

Results

The pregnancy success rate was 60% for LFDex and 100% for HFDex. Both Chao1 and Simpson indices were not significantly different for either LFD vs. LFDex or HFD vs. HFDex. Desulfobacterota, Desulfovibrionia Desulfovibrionales, Desulfovibrionaceae, Desulfovibrio, Coriobacteriia, Coriobacteriales, and Eggerthellaceae were markedly decreased after exercise intervention in LFDex vs. LFD, whereas Actinobacteria, Bifidobacteriales, Bifidobacteriaceae, Bifidobacterium, and Bifidobacterium pseudolongum were significantly increased in LFDex vs. LFD. Furthermore, decreased Peptostreptococcales-Tissierellales and Peptostreptococcaceae and increased Bacteroides dorei were identified in the HFDex vs. HFD group. p_Desulfobacterota, c_Desulfovibrionia, o_Desulfovibrionales, f_Desulfovibrionaceae and g_Desulfovibrio were markedly decreased in the LFDex group vs. HFDex group.

Conclusions

Our data suggested that quantitative maternal exercise during pregnancy resulted in alterations in GM composition, but did not significantly change the diversity of the GM. These findings may have important implications when considering an individual’s overall diet when recommending exercise during pregnancy.
Exploration on Teaching Method of Art Design Basic Course
Authors: Mingli Shui
Published: December 2022

Exploration on teaching method of art design basic course is the main focus of this paper. Due to its special professional nature, the art design major needs to form a real "double-qualified" art design teacher team integrating production and education. Hence, the efficient guiding will be essential. The existing digital media art design professional assessment is often based on the theoretical knowledge assessment, which cannot well demonstrate the importance of professional practice. Then, this paper gives the novel suggestions.
Discussion on the Coordinated Development of University Ideological and Political Education and Party-Building Work
Authors: Xicheng Ma
Published: December 2022

Discussion on the coordinated development of university ideological and political education and party building work is studied in this paper. As engineers of the human soul, in the face of historical tasks in the new era, college teachers, especially professional course teachers, must advance with the times, improve moral education awareness, improve moral education ability, and strengthen teachers' ethics. In the new era, choosing a core forward-looking educational concept that keeps pace with the times has practical significance for shaping the correct ideological values of the college students. Then, we consider the combination with the party building to construct the efficient education.
Evaluation of Lilium Cultivars for Vegetative and Propagation Traits under Temperate Conditions of Kashmir
Authors: Masoodi Nasir Hamid
Published: December 2022

Morphological characterization of 15 genotypes viz. Navona, Malesco, Litouwen, Black Out, Revenna, Pink Palace, Tiber, Conca-D, Nello, Yellow Diamond, Tresor, Rialto, Courier, Cobra, Pavia genotypes was carried out during year 2018 at Division Of Floriculture and Landscape Architecture SKUAST- K Shalimar with an objective  to assess the response to traits of growth and propagation ratio. On the basis of data maximum plant height of 90.70 cm resulted with cultivar black out and minimum 50.60cm with cultivar Navona. Number of leaves per plant followed the same trend with maximum 99.87 noticed in cultivar Black out and minimum 62.20 in cultivar Navano. Leaf area per plant ranged from 166.30 cm2 in cultivar Tiber to 443.50 cm2 in Pink Palace. The leaf area index varied between 1.20 and 1.96 in Tiber and Pink Palace cultivars, respectively. Weight of bulb cluster plant-1 (gm) ranged from 30.81 (gm) in Navona to 72.97 (gm) in Black Out. Variability for weight of subsidiary bulbs per plant varied from 32.65 g in Navona to 80.45 g in Black Out respectively.  Highest values for weight of main bulb plant-1 (73.65 gm) resulted with cultivar Black out and minimum 31.52(gm) in Navona. Weight of subsidiary bulbs plant -1 (gm) followed the same trend recoding maximum 7.30 (gm) with cultivar Black out and minimum 2.70 (gm) for cultivar Navano.  Size of main bulb (cm) ranged between 4.63(cm) in cultivar Navano to 6.33(cm) in cultivar blackout.
Creating an Effective Conference Presentation: A Reflective Practice on Challenges in Creating an Effective Conference Presentation
Authors: Downing Matthew ,   Upper Darby School District
Published: December 2022

The purpose of this reflective practice was to examine my conference presentations to K-12 teachers and administrators in order to increase their effectiveness. I have often felt frustrated by my conference presentations not accomplishing their intended objective for the attendees. I possessed a general understanding of the suspected reasons; however, I wanted to identify specifics so that I could implement change through a conference presenting protocol (Appendix A). This reflection occurred through a series of three conference presentations. This allowed me to iterate through each conference presentation, focus on specific areas, and arrive at beneficial insights. Ultimately, this reflective practice demonstrated the need to keep the audience central, narrow the focus, and provide guided assistance with the design thinking process. The lessons learned will assist in creating more effective conference presentations, which can also be applied to additional contexts, such as leading professional development for K-12 teachers.
A Preliminary Pilot Study Of The College Exodus Health Professions Program In San Bernardino County, CA
Authors:   Department of Psychology, California Baptist University, Park John C.
Published: December 2022

The College Exodus Health Professions (CEHP) program is a multidisciplinary health professions (HP) enrichment pipeline program for African American (AA) students in San Bernardino County, California. The main components of the program are the following: academic enrichment and hands-on exploration into the HP, such as nursing, medicine, dentistry, pharmacy, allied health, and public health. Participants include 48 predominantly AA students from 7th to 12th grades. Results of the pilot study show promising improvements in the awareness and knowledge of the HP after the participation in the program as well as increased academic motivation, social support, and academic and career goals. Policy implications and further developments are discussed.
Pulmonary disorder induced by cross-linked polyacrylic acid
Authors: Higashi Yasuyuki , Morimoto Yasuo , Nishida Chinatsu , Tomonaga Taisuke , Izumi Hiroto , Wang Ke-Yong , Higashi Hidenori , Ono Ryohei , Sumiya Kazuki , Sakurai Kazuo , Yamasaki Kei , Yatera Kazuhiro
Published: December 2022

Objectives

Organic polymers are materials widely used in our daily lives, such as daily necessities, foods, and medicines. There have been reports recently that cross-linked polyacrylic acid (CL-PAA) can possibly cause serious lung disease. We investigated whether intratracheal instillation of CL-PAA causes pulmonary disorder in rats.

Methods

Male F344 rats were administered low (0.2 mg/rat) and high (1.0 mg/rat) doses of CL-PAA intratracheally and were dissected 3 days, 1 week, 1 month, 3 months, and 6 months after exposure to examine inflammatory and fibrotic responses in the lungs. Only the high-dose specimens were subjected to ultrasonic dispersion treatment of the administered material.

Results

There was a dose-dependent increase in the total cell count, neutrophil count, neutrophil percentage, lactate dehydrogenase (LDH), surfactant protein D (SP-D), cytokine-induced neutrophil chemoattractant (CINC)-1 and CINC-2 values in bronchoalveolar lavage fluid (BALF) from 3 days to at least 3 months after intratracheal administration of CL-PAA. Heme oxygenase-1 (HO-1) in lung tissue was also persistently elevated from 3 days to 6 months after exposure. Alkaline phosphatase (ALP) in BALF was elevated at 3 days and 1 month after exposure only in the high-dose group. Histopathological findings in lung tissue showed inflammatory and fibrotic changes from 3 days after administration, and we observed obvious inflammatory changes for up to 3 months and fibrotic changes for up to 6 months.

Conclusion

Intratracheal administration of CL-PAA induced persistent neutrophilic inflammation and fibrosis in the rats' lungs, suggesting that CL-PAA may have inflammogenic and fibrogenic effects.
Fluorinated Liquid Crystals
Authors: Kirsch Peer , Bremer Matthias
Published: December 2022

The element fluorine is essential for the operation of modern liquid crystal displays (LCDs). It is “visible” to billions of people who mostly are unaware of its presence—in the same room, their pockets, and very often close to their faces. Fluorine makes liquid crystals polar, so they can be switched in an electric field. It imparts conformational rigidity, chemical stability, low polarizability, and viscosity—all crucial factors for the smooth operation of the state‐of‐the‐art LCDs.

This chapter presents the syntheses and structure–property relationships of a wide variety of fluorinated materials. Their uses range from standard LCDs to yet unrealized technologies such as Blue Phase displays and future applications of the newly discovered ferroelectric nematic phases. The design of new compounds is often based on rational arguments and a detailed analysis of the physical properties expected for a given structural feature. This is then realized by employing sophisticated synthetic methods unheard of in standard materials chemistry. Even after four decades of research, there is still room for fascination, progress, and surprises.
Electrochemical Fluorination
Authors: Fuchigami Toshio , Inagi Shinsuke
Published: December 2022

Recent studies on electrochemical fluorination of organic molecules and macromolecules are summarized in this chapter. At first, electrochemical perfluorination is briefly explained, and then selective fluorination and fluorodesulfurization including recent advances in electrochemical fluorination systems such as solvent free, use of recyclable mediators, and bipolar electrolysis are mainly described. Furthermore, electrochemical fluorination using alkali metal fluoride salts and radioactive [
18
F]fluorination are also described.
Synthesis and Manipulation of Colloid and Interface Structure and Properties by Exposure to Perfluorocarbon Gases
Authors: Krafft Marie Pierre
Published: December 2022

This chapter exposes the notion of physical reactivity of chemically inert nonfunctional compounds and the decisive role it can play in the synthesis of colloids and interfaces and in controlling their properties. Thus, introduction of perfluorocarbon vapor in the atmosphere above an aqueous dispersion of phospholipids promotes the adsorption of the latter to the air/water interface. When contacted with a monolayer of dipalmitoylphosphatidylcholine, perfluorocarbons fluidize this monolayer, inhibiting the formation of the ordered semicrystalline phase upon compression. Perfluorohexane can help desorb serum albumin from a phospholipid film, allowing the phospholipid to respread upon expansion. The perfluorocarbon also effectively counteracts lung surfactant deactivation by serum proteins. Exposure to perfluorohexane gas of a monolayer of phospholipids spread on aqueous solutions of C
2
F
5
‐labeled molecules prompts their selective adsorption into the interfacial film. When the phospholipid forms liquid‐condensed monolayers, the C
2
F
5
‐labeled species remain partially trapped in the monolayer after the perfluorohexane is removed. Perfluorocarbons can also impact the behavior of nanoparticles. Thus, nanodiamond clusters are efficiently disaggregated, which promotes their adsorption to the air/water interface, thereby enabling the formation of perfluorocarbon‐stabilized, nanodiamond‐shelled microbubbles. Prospective applications include lung surfactant substitutes that resist deactivation by serum proteins for treating lung conditions, novel drug‐loaded medical microbubbles, and nanodiamond‐based microbubbles for multimodal diagnostic and delivery purposes.
Modern Fluorine‐Containing Agrochemicals
Authors: Pazenok Sergii , Bernier David , Donnard Morgan , Hanquet Gilles , Panossian Armen , Leroux Frédéric R.
Published: December 2022

Today, modern fluorine‐containing agrochemicals are of the utmost importance to control weeds, insect pests, and many plant diseases and, ultimately, to ensure sustainable yields, thereby securing the food supply for a growing world population. Over the past two decades, new fluorine‐containing pesticides have gained a significant market share, reflecting the enormous global economic success of modern crop protection. But despite the commercialization of many highly potent pesticides, new regulatory requirements and the need for new modes of action and resistance‐breaking products are still driving efforts to identify and introduce new compounds with even better efficacy and safety profiles.

This chapter describes the structures, chemotypes, modes of action, and syntheses of some of the newest organofluorine agrochemicals (fungicides, herbicides, and insecticides) recently commercialized or under development. The main objective of this review is to describe the evolutionary approaches of the latest generation of “small molecule” fluorinated pesticides as well as the associated synthetic challenges.

This chapter also describes new and “old” fluorine‐containing building blocks and focuses on their synthetic accessions for subsequent incorporation into large‐scale production of agrochemical active ingredients.

Since the majority of modern agrochemicals are protected by patents, the analysis of chemical processes in this review is primarily based on the original patent literature. Commercial production of crop protection compounds requires robust, environmentally friendly, safe, and ultimately economically viable processes. Numerous process patents impressively demonstrate how producers have met these criteria, solved synthesis problems, and ultimately developed pathways to economically viable agrochemical manufacturing. Finally, this review also aims to demonstrate the impact of fluorination on the environmental fate and possible metabolism pathways of certain fluorinated pesticides, with or without the release of polyfluoroalkyl carboxylic acids.
Revisiting the Nature of Chemical Bonding in Chalcogenides to Explain and Design their Properties
Authors: Wuttig Matthias , Schön Carl‐Friedrich , Lötfering Jakob , Golub Pavlo , Gatti Carlo , Raty Jean‐Yves
Published: December 2022

Quantum chemical bonding descriptors have recently been utilized to design materials with tailored properties. Their usage to facilitate a quantitative description of bonding in chalcogenides as well as the transition between different bonding mechanisms is reviewed. More importantly, these descriptors can also be employed as property predictors for several important material characteristics, including optical and transport properties. Hence, these quantum chemical bonding descriptors can be utilized to tailor material properties of chalcogenides relevant for thermoelectrics, photovoltaics, and phase‐change memories. Relating material properties to bonding mechanisms also shows that there is a class of materials, which are characterized by unconventional properties such as a pronounced anharmonicity, a large chemical bond polarizability, and strong optical absorption. This unusual property portfolio is attributed to a novel bonding mechanism, fundamentally different from ionic, metallic, and covalent bonding, which is called “metavalent.” In the concluding section, a number of promising research directions are sketched, which explore the nature of the property changes upon changing bonding mechanism and extend the concept of quantum chemical property predictors to more complex compounds.
Electron‐Phonon Coupling Suppression by Enhanced Lattice Rigidity in 2D Perovskite Single Crystals for High‐Performance X‐Ray Detection
Authors: Zhang Bobo , Zheng Tao , You Jiaxue , Ma Chuang , Liu Yucheng , Zhang Lu , Xi Jun , Dong Guohua , Liu Ming , Liu Shengzhong (Frank)
Published: December 2022

2D Dion−Jacobson (DJ) perovskite single crystals (PSCs) usually demonstrate better X‐ray detection performance than Ruddlesden‐Popper (RP) PSCs. However, the mechanism of the improved performance is still elusive. Here, by the aid of strong interactions between dimethylbiguanide (DGA) and PbI2, a novel DJ‐perovskitoid (DGA)PbI4 is designed. From the comparison of (DGA)PbI4 to other 2D PSCs, it is discovered that the tiniest lattice distortion and increased hydrogen bonds in the atom‐scaled analysis strengthen lattice rigidity and weaken electron‐phonon coupling to suppress disordered scattering of carriers, resulting in significantly improved carrier transport and stability. Therefore, high carrier mobility (78.1 cm2 V−1 s−1) and a pronounced sensitivity of 4869.0 µC Gyair−1cm−2 are achieved using (DGA)PbI4, which are the best in 2D Pb‐based PSC devices to date. Finally, the (DGA)PbI4 devices exhibit good spatial resolution in X‐ray imaging and excellent long‐term stability to work as a promising candidate for medical diagnostics and nondestructive determination.
Improvement of the Photoelectrochemical Stability of Cu2O Photocathode by PhCCCu Grafting
Authors: Zhang Wen , Bai Yadi , Tian Meng , Liu Ya‐Ge , Hou Jiawei , Li Chengbo , Jiang Hai‐Ying , Tang Junwang
Published: December 2022

As one of the most efficient photocathodes, Cu2O has attracted substantial attention because of its theoretically high solar‐to‐hydrogen (STH) efficiency. However, its applications in photoelectrochemical (PEC) fields are severely restricted by the poor stability derived from serious photocorrosion. In this work, high‐quality phenylethynyl copper (PhCCCu) are successfully self‐assembled on the surface of Cu2O photocathode by a novel photothermal method to improve its photostability. With the protection of the PhCCCu layer, 85% of the initial photocurrent density can be remained, while only 28% of initial photocurrent density is left on bare Cu2O photocathode prepared on a copper foam (CF) substrate. The significantly improved photostability of Cu2O photocathode by the PhCCCu protective layer is attributed to its strong hydrophobicity, which can efficiently inhibit the corrosion of Cu2O by the aqueous electrolyte solution due to its special crystal structure. Based on the obtained PhCCCu/Cu2O photocathode, a two‐photoelectrode cell with excellent stability (>5 h) has also been successfully constructed for water splitting without the need of an electric bias.
A Multimodal Study on the Unique Sensing Behavior of a Guest@Metal‐Organic Framework Material for the Detection of Volatile Acetone
Authors: Möslein Annika F. , Gutiérrez Mario , Titov Kirill , Donà Lorenzo , Civalleri Bartolomeo , Frogley Mark D. , Cinque Gianfelice , Rudić Svemir , Tan Jin‐Chong
Published: December 2022

Owing to their unique functionalities and tailorable properties that are unattainable in conventional materials, metal‐organic frameworks (MOFs) have emerged as candidate materials for next‐generation chemical sensors and optoelectronics. For instance, the ZnQ@OX‐1 composite material, comprising a light‐emitting guest encapsulated in the pores of the OX‐1 framework, affords excellent sensing performance: a visible color change upon exposure to volatile acetone. In this work, a multimodal study on the exceptional vapochromism of this composite material using high‐resolution spectroscopy techniques based on inelastic neutron scattering and synchrotron radiation is presented, supported by density functional theory calculations. While FTIR spectroscopy in the far‐IR and mid‐IR regions reveals the underlying interactions between ZnQ, OX‐1, and acetone, the limit of detection at 50 ppm is determined through in situ gas dosing experiments using fluorescence spectroscopy. In addition, in situ gas dosing on the single crystal level is achieved with near‐field infrared nanospectroscopy.
Thru‐Hole Epitaxy: A Highway for Controllable and Transferable Epitaxial Growth
Authors: Jang Dongsoo , Ahn Chulwoo , Lee Youngjun , Lee Seungjun , Lee Hyunkyu , Kim Donghoi , Kim Yongsun , Park Ji‐Yong , Kwon Young‐Kyun , Choi Jaewu , Kim Chinkyo
Published: December 2022

Controllable growth and facile transferability of a crystalline film with desired characteristics, acquired by tuning composition and crystallographic orientation, become highly demanded for advanced flexible devices. Here the desired crystallographic orientations and facile transferability of a crystalline film can be achieved by “thru‐hole epitaxy” in a straightforward and undemanding manner with no limitation on the layer number and polarity of a 2D space layer and the surface characteristics. The crystallographic alignment can be established by the connectedness of the grown material to the substrate through a small net cross‐sectional area of thru‐holes, which also allows the straightforward detachment of the grown material. Thru‐hole epitaxy can be adopted for the realization of advanced flexible devices on large scale with desired crystallographic orientation and facile transferability.
Formation of Monolayer Charge Density Waves and Anomalous Edge Doping in Na Doped Bulk VSe2
Authors: Chazarin Ulysse , Lezoualc'h Mahé , Chou Jyh‐Ping , Pai Woei Wu , Karn Abhishek , Sankar Raman , Chacon Cyril C. , Girard Yann , Repain Vincent , Bellec Amandine , Rousset Sylvie , Smogunov Alexander , Dappe Yannick J. , Lagoute Jérôme
Published: December 2022

Alkali atom doping is an efficient way to induce charge transfer and Fermi level tuning in layered materials through intercalation. However, there is a general lack of microscopic understanding of the effect of doping inhomogeneity in geometric and electronic aspects. Here, we report surface doping of a bulk VSe2 crystal by sodium. Na atoms form intercalated subsurface islands that modify the electronic phase of the top layer of VSe2. In addition to n‐doping, the charge density wave of the intercalated VSe2 surface layer changes from the (4 × 4) bulk phase to the () known in monolayer phase of VSe2. Surprisingly, an electronic state at the edges of Na‐intercalated area shift anomalously upward in energy as detected by scanning tunneling spectroscopy. This is explained by a local gating effect resulting from local dipoles at the edges. The study illustrates a clear example of intercalation effect that should be general in alkali‐intercalated bulk layered materials.
Hybrid Image Graphene Polaritons with Extremely Confined Mode and Field Enhancement in the Terahertz Regime
Authors: Huang Chia‐Chien
Published: December 2022

Guiding terahertz waves below the diffraction limit of light typically excite graphene plasmons (GPs). However, the mode confinements of conventional GPs using graphene–dielectric interfaces are limited. To further squeeze the optical mode sizes, a graphene–dielectric–metal (GDM) configuration supporting an image graphene plasmon (IGP) has been reported recently through the plasmon interactions in a graphene sheet and its mirror image inside a metal with out‐of‐phase charge oscillations. This study proposes a waveguide structure consisting of a cylindrical dielectric wire over a GDM to achieve an ultraconfined mode area by coupling a dielectric waveguide and an IGP mode. Furthermore, this work examines the dependence of waveguide dimensions and material properties on the mode characteristics of the proposed hybrid IGP (HIGP). This HIGP achieves plasmon wavelengths 20 times shorter and normalized propagation lengths twice longer than GPs, accompanying a mode size of 3 × 10−8A0, where A0 is the diffraction‐limited mode area. Moreover, the simple structure makes the HIGP easy to be verified experimentally. This work demonstrates that the HIGP delivering strong light–matter interactions at extremely compact dimensions can be exploited for building highly integrated, enhanced nonlinear, high‐resolution sensing and imaging THz devices.
Synthesis of Functionalized 3‐(1H‐Isochromen)‐chromones via Ag2O‐Catalyzed Cascade Cyclization Reaction of o‐Hydroxyarylenaminones with o‐Alkynylbenzaldehydes
Authors: Zhang Mingshuai , Liu Zhuoyuan , Chen Longkun , Liu Donghan , Sun Yulin , Chai Zhangmengjie , Chen Xue‐Bing , Yu Fuchao
Published: December 2022

A silver‐catalyzed protocol for the synthesis of 3‐(1H‐isochromen)‐chromones is described. The method involves an initial 6‐endo‐dig cyclization of o‐alkynylbenzaldehydes and domino C−H alkylation and chromone annulation of the o‐hydroxyarylenaminones, which enables the installation of 1H‐isochromen and chromone in a single structure. This synthetic strategy is advantageous for the excellent regioselectivity, step economy, concise one‐pot methodology, gram‐scale synthesis, as well as high bond‐forming efficiency.

magnified image
Facile and Efficient SynthesisofFluorene and Indenoarene Carboxylates from Biaryldiazoacetates via BlueLight‐promoted Intramolecular CarbeneC−H Insertion
Authors: Zeng Tong‐Tong , Zhang Hao‐Yuan , Xie Zhen‐Biao , Dong Ying‐Ying , Gong Shan‐Shan , Sun Qi
Published: December 2022

Inspired by the recent discovery that aryldiazoacetates could be excited with visible light to generate carbenes in a mild and catalyst‐free manner, we tested the possibility to induce the cyclization of fluorenes from biaryldiazoacetate precursors simply by visible light irradiation at ambient temperature. The experimental results showed that 455 nm blue light is most effective on the synthesis of a diversity of fluorenes and indenoarenes in excellent yields. Analysis of UV absorbance and electronic transition properties of biaryldiazoacetates revealed that their absorbance peaks in the blue light region are due to the n–π* transition of diazo group. Their small ϵ420 nm values well explains the fact that only when exposed to intense blue light could biaryldiazoaetates be excited to generate carbenes. Theoretical calculations and kinetic isotopic effect (KIE) study illustrated that the fluorene cyclization proceeds via the intramolecular carbene C−H insertion pathway rather than the cyclopropanation pathway. In addition, a furan ring‐opening mechanism for the unexpected formation of an indene‐based unsaturated aldehyde was also proposed based on the calculated potential energy surfaces of three plausible reaction pathways.
Cytochrome P450 Catalyzes Benzene Ring Formation in the Biosynthesis of Trialkyl‐Substituted Aromatic Polyketides
Authors: Yang Yu Meng , Zhao Er Juan , Wei Wanqing , Xu Zi Fei , Shi Jing , Wu Xuan , Zhang Bo , Igarashi Yasuhiro , Jiao Rui Hua , Liang Yong , Tan Ren Xiang , Ge Hui Ming
Published: December 2022

Lorneic acid and related natural products are characterized by a trialkyl‐substituted benzene ring. The formation of the aromatic core in the middle of the polyketide chain is unusual. We characterized a cytochrome P450 enzyme that can catalyze the hallmark benzene ring formation from an acyclic polyene substrate through genetic and biochemical analysis. Using this P450 as a beacon for genome mining, we obtained 12 homologous type I polyketide synthase (PKS) gene clusters, among which two gene clusters are activated and able to produce trialkyl‐substituted aromatic polyketides. Quantum chemical calculations were performed to elucidate the plausible mechanism for P450‐catalyzed benzene ring formation. Our work expands our knowledge of the catalytic diversity of cytochrome P450.
An Engineered OmpG Nanopore with Displayed Peptide Motifs for Single‐Molecule Multiplex Protein Detection
Authors: Foster Joshua C. , Pham Bach , Pham Ryan , Kim Minji , Moore Matthew D. , Chen Min
Published: December 2022

Molecular detection via nanopore, achieved by monitoring changes in ionic current arising from analyte interaction with the sensor pore, is a promising technology for multiplex sensing development. Outer Membrane Protein G (OmpG), a monomeric porin possessing seven functionalizable loops, has been reported as an effective sensing platform for selective protein detection. Using flow cytometry to screen unfavorable constructs, we identified two OmpG nanopores with unique peptide motifs displayed in either loop 3 or 6, which also exhibited distinct analyte signals in single‐channel current recordings. We exploited these motif‐displaying loops concurrently to facilitate single‐molecule multiplex protein detection in a mixture. We additionally report a strategy to increase sensor sensitivity via avidity motif display. These sensing schemes may be expanded to more sophisticated designs utilizing additional loops to increase multiplicity and sensitivity.
DNA‐Encoded Libraries: Towards Harnessing their Full Power with Darwinian Evolution
Authors: Dockerill Millicent , Winssinger Nicolas
Published: December 2022

DNA‐encoded library (DEL) technologies are transforming the drug discovery process, enabling the identification of ligands at unprecedented speed and scale. DEL makes use of libraries that are orders of magnitude larger than traditional high‐throughput screens. While a DNA tag alludes to a genotype–phenotype connection that is exploitable for molecular evolution, most of the work in the field is performed with libraries where the tag serves as an amplifiable barcode but does not allow “translation” into the synthetic product it is linked to. In this Review, we cover technologies that enable the “translation” of the genetic tag into synthetic molecules, both biochemically and chemically, and explore how it can be used to harness Darwinian evolutionary pressure.
Giant Water Uptake Enabled Ultrahigh Proton Conductivity of Graphdiyne Oxide
Authors: Li Weiqi , Xu Cong , Xiong Tianyi , Jiang Yanan , Ma Wenjie , Yu Ping , Mao Lanqun
Published: December 2022

Proton conductors have attracted great attention in various fields, especially in energy production. Here, we find that graphdiyne oxide (GDYO), derived from graphdiyne (GDY), features the highest proton conductivity of 0.54 S cm−1 (100 % RH, 348 K) among the oxidized carbon allotropes reported so far. The sp‐ and sp2‐co‐hybridized carbon skeleton of GDY enables GDYO with the giant water uptake, which is 2.4 times larger than that of graphene oxide (GO), resulting in ultrahigh proton conductivity by increasing the proton concentration and proton conduction pathways. This ultrahigh proton conductivity of GDYO is further proved in a methanol fuel cell by using GDYO membrane as proton exchange membrane. The GDYO membrane enables the cell with higher open circuit voltage, larger power density and lower methanol permeability, compared with commercial Nafion 117. Moreover, the GDYO membrane bears high ion exchange capacity, good acidic stability and low swelling ratio.
Stabilizing Cobalt‐free Li‐rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two‐phase Ru Doping
Authors: Fan Yameng , Olsson Emilia , Liang Gemeng , Wang Zhijie , D'Angelo Anita M. , Johannessen Bernt , Thomsen Lars , Cowie Bruce , Li Jingxi , Zhang Fangli , Zhao Yunlong , Pang Wei Kong , Cai Qiong , Guo Zaiping
Published: December 2022

The application of Li‐rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt‐free Li1.2Ni0.2Mn0.6O2 and demonstrates the positive impact of two‐phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2Ni0.2Mn0.6O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post‐mortem synchrotron analyses. The two‐phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2−) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity‐retention rate during long‐term cycling. The understanding of the structure‐function relationship of Li1.2Ni0.2Mn0.6O2 sheds light on the selective doping strategy and rational materials design for better‐performance Li‐rich layered oxides.
Synthesis of N‐Glycosides by Silver‐Assisted Gold Catalysis
Authors: Chakraborty Saptashwa , Mishra Bijoyananda , Kumar Das Pratim , Pasari Sandip , Hotha Srinivas
Published: December 2022

The synthesis of N‐glycosides from stable glycosyl donors in a catalytic fashion is still challenging, though they exist ubiquitously in DNA, RNA, glycoproteins, and other biological molecules. Herein, silver‐assisted gold‐catalyzed activation of alkynyl glycosyl carbonate donors is shown to be a versatile approach for the synthesis of purine and pyrimidine nucleosides, asparagine glycosides and quinolin‐2‐one N‐glycosides. Thus synthesized nucleosides were subjected to the oxidation–reduction sequence for the conversion of Ribf‐ into Araf‐ nucleosides, giving access to nucleosides that are otherwise difficult to synthesize. Furthermore, the protocol is demonstrated to be suitable for the synthesis of 2’‐modified nucleosides in a facile manner. Direct attachment of an asparagine‐containing dipeptide to the glucopyranose and subsequent extrapolation to afford the dipeptide disaccharide unit of chloroviruses is yet another facet of this endeavor.
Up/Down Tuning of Poly(ionic liquid)s in Aqueous Two‐Phase Systems
Authors: Tang Yuntao , Zhang Yige , Chen Xi , Xie Xiaowen , Zhou Ning , Dai Zhifeng , Xiong Yubing
Published: December 2022

Thermally induced reversible up/down migration of poly(ionic liquid)s (PILs) in aqueous two‐phase systems (ATPSs) was achieved for the first time in this study. Novel ATPSs were fabricated using azobenzene (Azo)‐ and benzyl (Bn)‐modified PILs, and their upper and lower phases could be easily tuned using the grafting degree (GD) of the Azo and Bn groups. Bn‐PIL with higher GDBn could go up into the upper phase and Azo‐PIL come down to the lower phase when the temperature increased (>65 °C); this behavior was reversed at lower temperatures. Moreover, a reversible two‐phase/single‐phase transition was realized under UV irradiation. Experimental and simulation results revealed that the difference in the hydration capacity between Bn‐PIL and Azo‐PIL accounted for their unique phase‐separation behavior. A versatile platform for fabricating ATPSs with tunable stimuli‐responsive behavior can be realized based on our findings, which can broaden their applications in the fields of smart separation systems and functional material development.
Synthesis of Fibrous Phosphorus Micropillar Arrays with Pyro‐Phototronic Effects
Authors: Zhang Shuai , Ma Shufang , Cao Ben , Zhuang Qiandong , Xu Yang , Wang Jiahui , Zhang Xishuo , Nan Xiaoye , Hao Xiaodong , Xu Bingshe
Published: December 2022

The bottom‐up preparation of two‐dimensional material micro‐nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.[1] However, to date, there are no bottom‐up micro‐nano structure preparation methods for crystalline phosphorus allotropes.[1c, 2] Herein, we present the bottom‐up preparation of fibrous phosphorus micropillar (FP‐MP) arrays via a low‐pressure gas‐phase transport (LP‐CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self‐powered photodetectors (PD) of FP‐MP arrays with pyro‐phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom‐up preparation of other crystalline allotropes of phosphorus.
Synthesis of water‐soluble protoporphyrin IX polymers and their photodynamic application
Authors: Shi Jiahao , Lu Zhengnan , Pan Yan , Sheng Yang , Sun Yixin , Deng Linhong , Bradley Mark , Zhou Le , Zhang Rong
Published: December 2022

Protoporphyrin IX (PpIX) is a photosensitizer used in photodynamic therapy, however, its poor aqueous solubility always presents challenges and limits its application. To solve these problems water‐soluble derivatives of PpIX were synthesized by esterification with polyethylene glycol, and polymerization of the PpIX diol with hexamethylene diisocyanate to form a water‐soluble polyurethane. The polyurethane PpIX derivatives were characterized and showed high levels of singlet oxygen generation. The photodynamic antibacterial activity of the PpIX derivatives were explored on Escherichia coli, Staphylococcus aureus and methicillin‐resistant Staphylococcus aureus indicated that 100% antibacterial killing was achieved with a concentration of 40 μM upon 405 nm irradiation for 5 min. The polyurethane showed high biocompatibility in the dark with a variety of cell lines, but when exposed to 405 nm light (for 5 min) cytotoxic singlet oxygen was generated, resulting in cell death. Importantly, this was also possible with 635 nm illumination. In summary this novel protoporphyrin polyurethane overcomes the issues of solubility, and offers enhanced killing (singlet oxygen) generation with the potential to be used in photodynamic therapy for both antibacterial and anticancer treatment.
Incorporating free‐flowing rivers into global biodiversity targets: Prioritization and targeted interventions to maintain ecological integrity
Authors: Petersen Chantel R. , van Deventer Heidi , Smith‐Adao Lindie B. , Nel Jeanne L.
Published: December 2022

Free‐flowing rivers (FFRs) are important surrogates for freshwater biodiversity as there are increasingly fewer rivers that reflect intact habitat and species diversity from source to sea. The status and changes in the ecological condition or protection of FFRs is not explicitly reported on in global biodiversity targets. Indices are proposed for reporting such changes to the Sustainable Development Goals (SDGs) 6 and 15, Aichi Target 11, and the post‐2020 global biodiversity framework.

FFRs were identified at a countrywide scale in South Africa for protection, planning, monitoring, and assessing changes in their ecological condition and protection status. They were selected and prioritized using criteria co‐produced with national, provincial, and local river managers and policy makers. Given the high competition for water resources and the unlikely possibility for strictly protecting all FFRs, a subset of FFRs, termed ‘flagship FFRs’, was identified.

Methods for reporting changes in the protection levels of prioritized FFRs at a countrywide scale were developed, which included indices of FFRs related to global targets: the loss of the extent of FFRs in a natural and largely natural ecological condition for SDG 6; changes in the connectivity of FFRs included in the post‐2020 global biodiversity framework targets; and changes in protection levels of FFRs for Aichi Target 11 and SDG 15.1.2.

Flagship FFRs attracted targeted management initiatives and thus maintained their connectivity and ecological condition. This was not true when all FFRs were considered; in the broader set of FFRs, longitudinal fragmentation increased and ecological condition declined from 2011 to 2018.

Considering the increasing pressures rivers are likely to experience from human and climate change impacts, particularly in semi‐arid to temperate environments, urgent prioritization and monitoring of FFRs is called for so that a targeted set of protection and management strategies can be applied.
The topography of diet: Orientation patch count predicts diet in turtles
Authors: Shipps Brenlee K. , Peecook Brandon R. , Angielczyk Kenneth D.
Published: December 2022

Use of quantitative morphological methods in biology has increased with the availability of 3D digital data. Rotated orientation patch count (OPCr) leverages such data to quantify the complexity of an animal's feeding surface, and has previously been used to analyze how tooth complexity signals diet in squamates, crocodilians, and mammals. These studies show a strong correlation between dental complexity and diet. However, dietary prediction using this technique has not been tested on the feeding structures of edentulous (toothless) taxa. This study is the first to test the applicability of OPCr to the triturating surface morphology of a beaked clade. Fifty‐five turtle specimens, 42 of which preserved both the skull and rhamphotheca, were categorized into dietary categories based on the food sources comprising 90% or 60% of their diets. Photogrammetric models of each specimen were read into molaR, producing OPCr results. Comparison of bone and rhamphotheca OPCr values shows no significant difference in complexity, implying that bone can suffice for predicting diet from morphology when keratin is absent. Carnivorous taxa have significantly lower OPCr values than herbivorous or omnivorous taxa, showing that feeding surface complexity in edentulous animals varies with diet similarly to tooth complexity in toothed taxa. Comparison of bone OPCr values by family shows that Testudinidae (tortoises) are more complex than Cheloniidae (sea turtles) and Chelydridae (snapping turtles), but that Cheloniidae and Chelydridae are not significantly different from each other. We therefore find that OPCr can be used to differentiate between carnivores and other dietary categories in edentulous taxa.