bluuebunny/crossref_metadata_2025 huggingface dataset:
Comparison of Calculations of the Financial Impact of Fellowship Training by Data Source
Authors: Freed Gary L. , Wickham Kyle
Published: July 2023

Background

Previous comparisons of potential lifetime earnings between general pediatricians and pediatric subspecialties have demonstrated that many subspecialties have lower potential lifetime earnings than general pediatrics. However, those studies selectively used specific data sources for different portions of analyses.

Objective

To assess the presence and magnitude of differences in earning forecasts using different authoritative data sources.

Methods

This quality improvement study analyzed compensation data for 14 pediatric subspecialties and general pediatrics from the Association of Administrators in Academic Pediatrics (AAAP), Association of American Medical Colleges (AAMC), and Medical Group Management Association (MGMA) for the 2021 to 2022 academic year.

Main Outcomes and Measures

The potential lifetime compensation was calculated using the net present value (NPV), which accounts both for compensation throughout training (residency and fellowship) and compensation after graduation. The potential lifetime compensation for the subspecialties and general pediatrics was compared separately for each data source.

Results

This study included data from 3 sources about 14 subspecialties and general pediatrics. Depending on the data source, the magnitude of the difference in lifetime earnings between subspecialties and general pediatrics varied greatly. For all sources, there was a greater difference in lifetime earnings between higher- and lower-paid subspecialties compared with each other relative to general pediatrics. For the AAAP, the subspecialty with the greatest lifetime NPV is neonatal medicine, and the subspecialty with the least lifetime NPV is endocrinology, with a difference of $2 787 539. For the AAMC, cardiology has the greatest lifetime NPV and endocrinology the least, with a difference of $3 557 492. For the MGMA, neonatal medicine has the greatest lifetime NPV and adolescent medicine the least, with a difference of $4 210 477. Additionally, there is a notable difference in lifetime earnings in private vs academic practice.

Conclusions and Relevance

These findings suggest that the difference in lifetime compensation between many pediatric subspecialties and general pediatrics is not as large as previously reported. Also, greater differences exist when comparing private practice vs academic medicine and between higher- and lower-paid subspecialties.
Phosphorylation by CIPK23 regulates the high‐affinity Mn transporter NRAMP1 in Arabidopsis
Authors: Kosuth Thibault , Leskova Alexandra , Ródenas Reyes , Vert Gregory , Curie Catherine , Castaings Loren
Published: July 2023

Manganese (Mn) is essential for plants but is toxic when taken up in excess. To maintain Mn homeostasis, the root Mn transporter natural resistance associated macrophage protein 1 (NRAMP1) cycles from the plasma membrane to endosomes upon phosphorylation. To identify the kinase involved, a split‐luciferase screening was carried out between NRAMP1 and kinases of the CIPK family and identified CIPK23 as a partner of NRAMP1. The interaction was confirmed by split‐mCitrine bimolecular fluorescence complementation and co‐immunoprecipitation assays. In vitro phosphorylation assays pinpointed two CIPK23 target residues in NRAMP1, among which serine 20, important for endocytosis. Interestingly, Mn‐induced internalization of NRAMP1 was unaffected by cipk23 mutation suggesting a potential redundancy between CIPK23 and other kinase(s). How CIPK23 could regulate NRAMP1 in response to Mn availability is discussed.
Sepals
Authors: Roeder Adrienne HK
Published: July 2023

Sepals are the outermost organs of a flower. They are sterile and generally green leaf‐like organs that surround and protect the developing reproductive structures inside the bud before the flower blooms. The sepals are the first organs initiated from the floral meristem and quickly grow to cover the floral meristem and initiating organ primordia. The sepals and petals in the flower interact with the environment by both attracting pollinators as well as defending against predators and abiotic factors such as the weather. Sepal organ identity is specified by the A function in the ABC model.
Arabidopsis
sepals are a model system for investigating morphogenesis (development of organ size and shape) and patterning (differentiation of specialised cell types such as giant cells). Current and future research on the development of sepals is leading to a better understanding of floral organ formation as well as underlying principles of cell division and growth.

Key Concepts

Sepals are the outermost floral organs, which are typically green leaf‐like organs that enclose and protect the developing flower bud before blooming.

Sepals are thought to have evolved from leaves.

Sepal organ identity is specified by A and E function in the ABC model of floral organ identity, and A function is specified by AP1/CAL/FUL clade MADS domain transcription factors, AP2 domain family transcription factors and microRNAs.

The sepal is a commonly studied in
Arabidopsis
to discover fundamental principles of morphogenesis, such as how plant organs grow to reach the right size and shape.

Arabidopsis
sepals are the first floral organs to initiate on the flanks of the floral meristem where they quickly grow to cover and protect the developing reproductive organs, keep the bud closed until blooming and senesce and abscise after the fruit is fertilised.

A scattered pattern of giant cells forms in between smaller cells in the outer epidermis of
Arabidopsis
sepals.

The
Arabidopsis thaliana
MERISTEM LAYER1 (ATML1) transcription factor concentration fluctuates in epidermal cells of the developing sepal; if ATML1 reaches a high concentration during G2 phase of the cell cycle, the cell becomes giant.

Giant cells become enlarged through endoreplication (also known as endoreduplication), during which a cell replicates its DNA and grows without division, becoming highly enlarged and polyploid.

Sepal size and shape are highly reproducible; synchronous timing of both the initiation of sepal primordia and their maturation and cessation of growth are required for all four sepals in the
Arabidopsis
flower to maintain the same size to enclose the flower bud.

The growth and division of sepal cells are highly variable, and gene expression is stochastic; however, sepals maintain robust size and shape through spatiotemporal averaging of growth variability and suppression of gene expression noise by the Paf1C complex.
Mannose‐Decorated Co‐Polymer Facilitates Controlled Release of Butyrate to Accelerate Chronic Wound Healing
Authors: Lauterbach Abigail L. , Slezak Anna J. , Wang Ruyi , Cao Shijie , Raczy Michal M. , Watkins Elyse A. , Jimenez Carlos J. Medina , Hubbell Jeffrey A.
Published: July 2023

Butyrate is a key bacterial metabolite that plays an important and complex role in modulation of immunity and maintenance of epithelial barriers. Its translation to clinic is limited by poor bioavailability, pungent smell, and the need for high doses, and effective delivery strategies have yet to realize clinical potential. Here, a novel polymeric delivery platform for tunable and sustainable release of butyrate consisting of a methacrylamide backbone with butyryl ester or phenyl ester side chains as well as mannosyl side chains, which is also applicable to other therapeutically relevant metabolites is reported. This platform's utility in the treatment of non‐healing diabetic wounds is explored. This butyrate‐containing material modulated immune cell activation in vitro and induced striking changes in the milieu of soluble cytokine and chemokine signals present within the diabetic wound microenvironment in vivo. This novel therapy shows efficacy in the treatment of non‐healing wounds through the modulation of the soluble signals present within the wound, and importantly accommodates the critical temporal regulation associated with the wound healing process. Currently, the few therapies to address non‐healing wounds demonstrate limited efficacy. This novel platform is positioned to address this large unmet clinical need and improve the closure of otherwise non‐healing wounds.
Zwitterionic Granular Hydrogel for Cartilage Tissue Engineering
Authors: Asadikorayem Maryam , Surman František , Weber Patrick , Weber Daniel , Zenobi‐Wong Marcy
Published: July 2023

Zwitterionic hydrogels have high potential for cartilage tissue engineering due to their ultra‐hydrophilicity, nonimmunogenicity, and superior antifouling properties. However, their application in this field has been limited so far, due to the lack of injectable zwitterionic hydrogels that allow for encapsulation of cells in a biocompatible manner. Herein, a novel strategy is developed to engineer cartilage employing zwitterionic granular hydrogels that are injectable, self‐healing, in situ crosslinkable and allow for direct encapsulation of cells with biocompatibility. The granular hydrogel is produced by mechanical fragmentation of bulk photocrosslinked hydrogels made of zwitterionic carboxybetaine acrylamide (CBAA), or a mixture of CBAA and zwitterionic sulfobetaine methacrylate (SBMA). The produced microgels are enzymatically crosslinkable using horseradish peroxidase, to quickly stabilize the construct, resulting in a microporous hydrogel. Encapsulated human primary chondrocytes are highly viable and able to proliferate, migrate, and produce cartilaginous extracellular matrix (ECM) in the zwitterionic granular hydrogel. It is also shown that by increasing hydrogel porosity and incorporation of SBMA, cell proliferation and ECM secretion are further improved. This strategy is a simple and scalable method, which has high potential for expanding the versatility and application of zwitterionic hydrogels for diverse tissue engineering applications.
Luminescence Properties of the Hexagonal Boron Nitride Epilayer
Authors: Wang Gaokai , Cheng Yong , Chen Jingren , Meng Junhua , Zeng Libin , Yin Zhigang , Wu Jinliang , Zhang Xingwang
Published: July 2023

As an emerging 2D ultrawide bandgap semiconductor, hexagonal boron nitride (h‐BN) is gaining significant attention for its superior properties and wide applications. Although optical properties of h‐BN have been partially revealed by using h‐BN bulk single crystal, luminescence properties of the h‐BN few‐layer are rare due to its poor crystallinity. In this work, the h‐BN epilayers have been synthesized on sapphire substrates by the submicron‐spacing vapor deposition method. The crystalline quality of the h‐BN epilayer is improved with the increase of the growth temperature, and the full width at half‐maximum of the Raman peak is only ≈13 cm−1. The low temperature cathodoluminescence spectra of h‐BN epilayers exhibit two strong deep ultraviolet (DUV) luminescence peaks at 5.49 and 5.35 eV, as well as a weaker and broader defect‐related emission band at ≈4.0 eV. The DUV emission band is ascribed to the recombination of bound excitons and its phonon replica. Based on the theoretically predicted energy levels, the 4.0 eV emission band is tentatively attributed to the radiative transition from C impurities occupying the B sites to the B vacancies. Moreover, the h‐BN‐based DUV photodetectors exhibit an outstanding performance, making it a promising prospect for optoelectronic applications.
High Crystallinity 2D π–d Conjugated Conductive Metal–Organic Framework for Boosting Polysulfide Conversion in Lithium–Sulfur Batteries
Authors: Guo Tong , Ding Yichen , Xu Chang , Bai Wuxin , Pan Shencheng , Liu Mingliang , Bi Min , Sun Jingwen , Ouyang Xiaoping , Wang Xin , Fu Yongsheng , Zhu Junwu
Published: July 2023

The catalytic performance of metal–organic frameworks (MOFs) in Li‐S batteries is significantly hindered by unsuitable pore size, low conductivity, and large steric contact hindrance between the catalytic site and lithium polysulfide (LPSs). Herein, the smallest π‐conjugated hexaaminobenzene (HAB) as linker and Ni(II) ions as skeletal node are in situ assembled into high crystallinity Ni‐HAB 2D conductive MOFs with dense Ni‐N4 units via dsp2 hybridization on the surface of carbon nanotube (CNT), fabricating Ni‐HAB@CNT as separator modified layer in Li‐S batteries. As‐obtained unique π‐d conjugated Ni‐HAB nanostructure features ordered micropores with suitable pore size (≈8 Å) induced by HAB ligands, which can cooperate with dense Ni‐N4 chemisorption sites to effectively suppress the shuttle effect. Meanwhile, the conversion kinetics of LPSs is significantly accelerated owing to the small steric contact hindrance and increased delocalized electron density endued by the planar tetracoordinate structure. Consequently, the Li‐S battery with Ni‐HAB@CNT modified separator achieves an areal capacity of 6.29 mAh cm−2 at high sulfur loading of 6.5 mg cm−2 under electrolyte/sulfur ratio of 5 µL mg−1. Moreover, Li‐S single‐electrode pouch cells with modified separators deliver a high reversible capacity of 791 mAh g−1 after 50 cycles at 0.1 C with electrolyte/sulfur ratio of 6 µL mg−1.
Nanoscale Engineering of P‐Block Metal‐Based Catalysts Toward Industrial‐Scale Electrochemical Reduction of CO2
Authors: Li Pengfei , Yang Fangqi , Li Jing , Zhu Qiang , Xu Jian Wei , Loh Xian Jun , Huang Kuo‐Wei , Hu Wenping , Lu Jiong
Published: July 2023

The efficient conversion of CO2 to value‐added products represents one of the most attractive solutions to mitigate climate change and tackle the associated environmental issues. In particular, electrochemical CO2 reduction to fuels and chemicals has garnered tremendous interest over the last decades. Among all products from CO2 reduction, formic acid is considered one of the most economically vital CO2 reduction products. P‐block metals (especially Bi, Sn, In, and Pb) have been extensively investigated and recognized as the most efficient catalytic materials for the CO2 electroreduction to formate. Despite remarkable progress, the future implementation of this technology at the industrial‐scale hinges on the ability to solve remaining roadblocks. In this review, the current research status, challenges, and prospects of p‐block metal‐based catalysts primarily for CO2 electroreduction to formate are comprehensively reviewed. The rational design and nanostructure engineering of these p‐block metal catalysts for the optimization of their electrochemical performances are discussed in detail. Subsequently, the recent progress in the development of state‐of‐the‐art operando characterization techniques together with the design of advanced electrochemical cells to uncover the intrinsic catalysis mechanism is discussed. Lastly, a perspective on future directions including tackling critical challenges to realize its early industrial implementation is presented.
Bifunktionelle carbanionische Synthese vollständig biobasierter Triblock‐Copolymere aus β‐Farnesen und LL‐Dilactid: Thermoplastische Elastomere
Authors: Meier‐Merziger Moritz , Imschweiler Jan , Hartmann Frank , Niebuur Bart‐Jan , Kraus Tobias , Gallei Markus , Frey Holger
Published: July 2023

Aktuelle ökologische Herausforderungen und die Endlichkeit fossiler Rohstoffe sind wichtige Kriterien, welche für die nächste Generation von Polymermaterialien eine zentrale Rolle spielen. In diesem Zusammenhang wird ein vollständig biobasiertes Material mit potenzieller Anwendung als thermoplastisches Elastomer (TPE) vorgestellt. Durch die Verwendung der Monomere β‐Farnesen und l‐Lactid können biobasierte Rohstoffe wie Zuckerrohr und Mais verwendet werden. Für die carbanionische Polymerisation wurde ein bifunktioneller Initiator eingesetzt, um eine effiziente Synthese von ABA‐artigen Blockstrukturen zu ermöglichen. Zusätzlich kam das potenziell nachhaltige Lösungsmittel MTBE (Methyl‐tert‐butylether) zum Einsatz, da es eine hervorragende Löslichkeit des bifunktionellen Initiators gewährleistet. Dies ermöglichte die Herstellung von telechelen Polyfarnesen‐Makroinitiatoren mit niedrigen Dispersitäten (Đ=1.07 bis 1.10). Diese wurden anschließend für die Lactidpolymerisation verwendet, um H‐förmige Triblockcopolymere zu erhalten. TEM und SAXS‐Messungen zeigten deutlich phasengetrennte Morphologien, und mittels Zugversuche konnten elastische Eigenschaften nachgewiesen werden. Die Triblockstrukturen weisen jeweils zwei Glasübergangstemperaturen bei −66 °C und 51 °C sowie gyroide oder zylindrische Morphologien auf, was bei Raumtemperatur zu weichelastischen Materialien führt.
Bifunctional Carbanionic Synthesis of Fully Bio‐Based Triblock Structures Derived from β‐Farnesene and ll‐Dilactide: Thermoplastic Elastomers
Authors: Meier‐Merziger Moritz , Imschweiler Jan , Hartmann Frank , Niebuur Bart‐Jan , Kraus Tobias , Gallei Markus , Frey Holger
Published: July 2023

Current environmental challenges and the shrinking fossil‐fuel feedstock are important criteria for the next generation of polymer materials. In this context, we present a fully bio‐based material, which shows promise as a thermoplastic elastomer (TPE). Due to the use of β‐farnesene and L‐lactide as monomers, bio‐based feedstocks, namely sugar cane and corn, can be used. A bifunctional initiator for the carbanionic polymerization was employed, to permit an efficient synthesis of ABA‐type block structures. In addition, the “green” solvent MTBE (methyl tert‐butyl ether) was used for the anionic polymerisation, enabling excellent solubility of the bifunctional anionic initiator. This afforded low dispersity (Đ=1.07 to 1.10) and telechelic polyfarnesene macroinitiators. These were employed for lactide polymerization to obtain H‐shaped triblock copolymers. TEM and SAXS revealed clearly phase‐separated morphologies, and tensile tests demonstrated elastic mechanical properties. The materials featured two glass transition temperatures, at ‐ 66 °C and 51 °C as well as gyroid or cylindrical morphologies, resulting in soft elastic materials at room temperature.
Nitrogen‐doped biochar as an efficient sensing material for the electrochemical detection of heavy metal ion Pb2+ and Cd2+
Authors: Yang Tianming , Xin Xin , Jiang Jin‐Chi , Yin Zhenhao , Meng Long‐Yue
Published: July 2023

The sensitive detection of heavy metal ions with high toxicity and mobility is extremely important for environmental monitoring. In this study, nitrogen‐doped biochar (N‐BC) was synthesized using waste mushroom bran as a raw material, and nitrogen atoms were successfully doped onto the surface of the biochar via a facile process using an activation‐carbonation strategy. The functional groups on the surface of the biochar were enriched via doping, and the roughness of the biochar surface was significantly improved. Experimental results showed that N‐BC was an efficient sensing material for electroanalysis; therefore, it was used to construct a novel electrochemical sensing platform. The electrochemical response of the biochar‐modified working electrodes was effectively improved for the detection of heavy metals. Under optimized deposition potential, enrichment time, and pH, the N‐BC‐based sensing platform could detect Pb2+ and Cd2+ separately as well as simultaneously, indicating its significant potential for electrochemical sensing.
Anatomy of the female reproductive tract organs of the brown anole (Anolis sagrei)
Authors: Kircher Bonnie K. , Stanley Edward L. , Behringer Richard R.
Published: July 2023

Female reproduction in squamate reptiles (lizards and snakes) is highly diverse and mode of reproduction, clutch size, and reproductive tract morphology all vary widely across this group of ~11,000 species. Recently, CRISPR genome editing techniques that require manipulation of the female reproductive anatomy have been developed in this group, making a more complete understanding of this anatomy essential. We describe the adult female reproductive anatomy of the model reptile the brown anole (Anolis sagrei). We show that the brown anole female reproductive tract has three distinct anterior‐to‐posterior regions, the infundibulum, the glandular uterus, and the nonglandular uterus. The infundibulum has a highly ciliated epithelial lip, a region where the epithelium is inverted so that cilia are present on the inside and outside of the tube. The glandular uterus has epithelial ducts that are patent with a lumen as well as acinar structures with a lumen. The nonglandular uterus has a heterogeneous morphology from anterior to posterior, with a highly folded, ciliated epithelium transitioning to a stratified squamous epithelium. This transition is accompanied by a loss of keratin‐8 expression and together, these changes are similar to the morphological and gene expression changes that occur in the mammalian cervix. We recommend that description of the nonglandular uterus include the regional sub‐specification of a “cervix” and “vagina” as this terminology change more accurately describes the morphology. Our data extend histological studies of reproductive organ morphology in reptiles and expand our understanding of the variation in reproductive system anatomy across squamates and vertebrates.
Lactococcus lactis NZ3900/pNZ8149‐IL‐4‐IL‐2 as an adjuvant to reduce vaccine dose in chicken coccidia live mixed vaccine
Authors: Zheng Longlong , Zhang Li , Tan Fan , Zhang Honghui , Wang Liming , Zheng Mingxue
Published: July 2023

Although live mixed coccidiosis vaccines are widely used for Eimeria control, the side effects (e.g., damaging the intestinal mucosa and decreasing their weight gain) are not negligible. This study aimed to filter out the lowest dose of coccidiosis mixed vaccine with Lactococcus lactis (L. lactis) NZ3900/pNZ8149‐IL‐4‐IL‐2 (RLIL4/2) coimmunization against Eimeria reduces the side effects for Eimeria vaccination. Chickens oral 1.0 ×, 0.9 ×, 0.8 ×, 0.6 ×, 0.4 × dose of live vaccine, and RLIL4/2 with 1.0 × 109 CFU/chicken, respectively. The blank control group, challenge‐only group and 1.0 × dose vaccine‐only group are used as references. The survival rate, weight gain, bloody stool, intestinal lesions scores, oocyst output oocysts per gramme (OPG), and anticoccidial index (ACI) were detected by challenging with virulent coccidiosis. All the results indicated that the weight gain during the immune period or bloody stool/intestinal lesions scores/OPG during the challenge period were oppositely correlated with vaccine doses. The survival rate, weight gain, and ACI were positively correlated with vaccine doses during the challenge period. The ACI of 0.6 × the dose group was 167.69, which was considered a moderate efficiency. The weight gain, ACI of 1.0 ×, 0.9 × and 0.8 × dose groups were higher or intestinal lesions were lower than 1.0 × dose vaccine‐only group (p < 0.05), respectively. In conclusion, the coimmunization of RLIL4/2 with Eimeria mixed vaccine could reduce 40% of the dose and the side effects (e.g., weight gain and intestinal lesions) from live mixed coccidiosis vaccine.
Photoredox and Copper Dual‐Catalyzed Cyclization of Alkyne‐tethered α‐Bromocarbonyls
Authors: Wang Zi‐Ying , Cai Xue‐Er , Zhang Can‐Can , Yang Wen‐Hui , Wang Ling‐Tao , Xu Qing , Liu Hongxin , Wei Wen‐Ting
Published: July 2023

The synergistic systems of photoredox and copper catalyst have already appeared as a novel formation of green synthetic chemistry, which open new avenues for chemical synthesis applications. We describe a novel strategy for the cyclization of alkyne‐tethered α‐bromocarbonyls initiated by the cleavage of C(sp3)−Br bond via the collaboration of photoredox and copper catalyst. The present protocol exhibits mildness using economical copper catalyst and visible‐light at room temperature. The gram‐scale and sunlight irradiation experiments proceeded smoothly to show the practicality of the methodology. It is notable that the newly generated oxygen in the product originates from H2O.
Stabilization of delayed fractional‐order T‐S fuzzy systems with input saturations and system uncertainties
Authors: Hao Yilin , Fang Zhiming , Liu Heng
Published: July 2023

By adopting the Takagi–Sugeno (T‐S) fuzzy theory, this paper focuses on the adaptive control of fractional‐order time‐delay systems involving unknown parameters and input saturations. T‐S fuzzy systems with “IF‐THEN” rules are employed to describe fractional‐order nonlinear systems. The influence of input saturation is handled by designing an auxiliary system. By using a norm conversion, the system's time‐delay term is converted into a non‐delayed form. Adaptive updating rules are devised to evaluate uncertainties of the system, and a new control approach is proposed. The devised controller can not only guarantee the boundedness of variables involved but also make state variables converge into a sufficiently small neighborhood of the origin, even in the presence of uncertainties, saturation functions, and system parameters. Finally, numerical studies are given to verify the correctness of the designed scheme.
Titin UN2A Acts as a Stable, Non‐Polymorphic Scaffold in its Binding to CARP
Authors: Stehle Juliane , Fleming Jennifer R. , Bauer Piera‐Maria , Mayans Olga , Drescher Malte
Published: July 2023

The N2A segment of titin functions as a pivotal hub for signal transduction and interacts with various proteins involved in structural support, chaperone activities, and transcriptional regulation. Notably, the “unique N2A” (UN2A) subdomain has been shown to interact with the stress‐regulated cardiac ankyrin repeat protein (CARP), which contributes to the regulation of sarcomeric stiffness. Previously, the UN2A domain's three‐dimensional structure was modelled based on its secondary structure content identified by NMR spectroscopy, considering the domain in isolation. In this study, we report experimental long‐range distance distributions by electron paramagnetic resonance (EPR) spectroscopy between the three helixes within the UN2A domain linked to the immunoglobulin domain I81 in the presence and absence of CARP. The data confirm the central three‐helix bundle fold of UN2A and show that this adopts a compact and stable conformation in absence of CARP. After binding to CARP, no significant conformational change was observed, suggesting that the UN2A domain retains its structure upon binding to CARP thereby, mediating the interaction approximately as a rigid‐body.
Could Drug Availability Be Improved through Shape Modification?
Authors: Prlić Kardum Jasna , Zokić Iva , Sokač Katarina
Published: July 2023

The possibility of spherical agglomeration was investigated for two active pharmaceutical ingredients from different classes of the Biopharmaceutics Classification System. The effects of different batch crystallization solvent systems on the granulometric properties and structures of dronedarone hydrochloride and ceritinib were investigated. Light and stereomicroscopy were used to determine the size and shape of the agglomerates, while X‐ray powder diffraction was applied to assess the changes in polymorphic form. Since the change in the solvent system had no effect on the crystal structure but did alter the size and shape of the crystals, dissolution experiments were carried out to determine drug release profiles.
Highly Scalable and Inherently Safer Preparation of Di, Tri and Tetra Nitrate Esters Using Continuous Flow Chemistry
Authors: Mittal Ankit Kumar , Pathak Pramod , Prakash Gaurav , Maiti Debabrata
Published: July 2023

Nitrate esters are important organic compounds having wide application in energetic materials, medicines and fuel additives. They are synthesized through nitration of aliphatic polyols. But the process safety challenges associated with nitration reaction makes the production process complicated and economically unviable. Herein, we have developed a continuous flow process wherein polyol and nitric acid are reacted in a microreactor to produce nitrate ester continuously. Our developed process is inherently safer and efficient. The process was optimized for industrially important nitrate esters containing two, three and four nitro groups. Substrates include glycol dinitrates: 1,2‐propylene glycol dinitrate (PGDN), ethylene glycol dinitrate (EGDN), diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN); trinitrates: trimethylolethane trinitrate (TMETN), 1,2,4‐butanetriol trinitrate (BTTN); and tetranitrates: erythritol tetranitrate (ETN). The optimized process for each molecule provided yield >90 % in a short residence time of 1 min corresponding to a space time yield of >18 g/h/mL of reactor volume.
Design and Synthesis of Co‐initiators via Base‐Catalysed Sequential Conjugate Addition: Application in Photoinduced Radical Polymerisation Reaction
Authors: Ahmad Asrar , Siddiqui Shakir Ali , Mittal Garvisha , Sukumar N. , Dubey Kshatresh Dutta , Kapat Ajoy
Published: July 2023

Applications of photochemistry are becoming very popular in modern‐day life due to its operational simplicity, environmentally friendly and economically sustainable nature in comparison to thermochemistry. In particular photoinduced radical polymerisation (PRP) reactions are finding more biological applications and especially in the areas of dental restoration processes, tissue engineering and artificial bone generation. A type‐II photoinitiator and co‐initiator‐promoted PRP turned out to be a cost‐effective protocol, and herein we report the design and synthesis of a new efficient co‐initiator for a PRP reaction via a barrierless sequential conjugate addition reaction. Experimental mechanistic observations have been further complemented by computational data. Time for newly synthesised 1,2‐benzenedithiol (DTH) based co‐initiator promoted polymerisation of urethane dimethacrylate (UDMA, 70 %) and triethylene glycol dimethacrylate (TEGDMA, 30 %) in presence of 450 nm LED (15 W) under the aerobic conditions is 38 seconds. Polymeric material has high glass transition temperature, improved mechanical strength (860 BHN) and longer in‐depth polymerisation (3 cm).
A Bifunctional Coordination‐Chain‐Based Hydrogen‐Bonded Framework for Quantitative Enantioselective Sensing
Authors: Han Zongsu , Wang Mengmeng , Wang Kunyu , Cheng Peng , Shi Wei
Published: July 2023

Enantioselective sensing is highly crucial and challenging due to the highly similar physical/chemical properties of enantiomers which may have different chemical impact on organism. Luminescent coordination compounds have attracted great attention as sensing materials based on their controllable chemical and electric structures that can be highly matched with the targeted species. To achieve high‐performance enantioselective sensing, the direct synthesis of chiral and luminescent bifunctional coordination compounds is a rational way but highly challenging due to the price and synthesis difficulty. Herein, an anionic coordination‐chain‐based hydrogen‐bonded framework was applied as a host to accommodate chiral and luminescent centers via a facile cation exchange reaction, affording a bifunctional framework that possesses enantioselective sensing properties for the mixture of enantiomers. This study paves a pathway for constructing multifunctional coordination chain‐based hydrogen‐bonded frameworks for rapidly enantioselective sensing function.
Single Molecular Persistent Room‐Temperature Phosphorescence and Circularly Polarized Luminescence from Binaphthol‐Decorated Optically Innocent Cyclotriphosphazenes
Authors: Jena Satyam , Thayyil Muhammed Munthasir Akkarakkaran , Pradhan Sambit , Kitahara Maho , Seika Suzuki , Imai Yoshitane , Thilagar Pakkirisamy
Published: July 2023

Circularly polarized luminescence (CPL) features of BINOL‐decorated cyclotriphosphazenes (CPs) are reported for the first time. The luminescence dissymmetry factor (glum) of these compounds in chloroform solutions and polymethyl methacrylate (PMMA) thin films with wt 1 % doping concentrations are found to be 1.0×10−3, and 2.9×10−3, respectively. However, no CPL signal is observed for the pristine solids. The enantiomers (CP‐(R)/CP‐(S)) show ultraviolet photoluminescence (~350–360 nm) in solution and the solid state. These compounds show ~10 times larger absolute photoluminescence quantum yield (PLQY) than the simple BINOLs in the solutions state. In the solid state, CP‐(R) shows larger PLQY than binaphthol‐(R); in contrast, the S enantiomer shows lower PLQY than binaphthol‐(S); this indicates that the isomer‐dependent solid‐state packing of these compounds plays a crucial role in controlling the PL. Thin films with more than 1 % doping concentration and pristine solids of these compounds do not show persistent room‐temperature phosphorescence (pRTP) due to concentration‐caused quenching. However, thin films with wt 1 % of these chiral emitters exhibit pRTP characteristics with a ~159‐343 ms lifetime under vacuum. Theoretical calculations reveal that the cyclophosphazene acts as an optically innocent dendritic core, and the optical features of these compounds are dictated by the pendent BINOL chromophore.
Nucleophile‐Triggered π‐Topological Transformation: A New Synthetic Approach to Near‐Infrared‐Emissive Rhodamines
Authors: Harada Mei , Kutsuna Misa , Kitamura Taichi , Usui Yusuke , Ujiki Masayoshi , Nakamura Yuka , Obata Tohru , Tanioka Masaru , Uchiyama Masanobu , Sawada Daisuke , Kamino Shinichiro
Published: July 2023

We describe a π‐topological transformation‐based synthetic method for the preparation of a new type of near‐infrared (NIR)‐emissive rhodamine dye called Polymethine‐embedded Rhodamine Fluorophore (PeR Fluor). In contrast to conventional NIR‐emissive dyes that require tedious synthetic steps and/or a high cost, linear fully π‐conjugated PeR Fluor can be regioselectively prepared in one step by mixing different nucleophiles with ABPXs, a family of rhodamines with a cross‐conjugated structure. PeR Fluor exhibits bright NIR fluorescence emission and high photostability owing to the cooperative π‐electron system of rhodamines and polymethine scaffolds. Large bathochromic shifts of the absorption and fluorescence emission maxima can be achieved by modifying the N‐substituted group to obtain NIR‐absorbing/emitting PeR Fluor. We also demonstrate the stimulus‐responsive functionality of PeR Fluor through the addition of chemicals (acid/base), which shows switchable NIR and visible fluorescence response. Our π‐topological transformation‐based synthetic method is a promising approach to produce new functionalized rhodamine dyes.
Inetetamab in combination with rapamycin and chemotherapy for trastuzumab‐treated metastatic human epidermal growth factor receptor 2‐positive breast cancer with abnormal activation of PI3K/Akt/mTOR pathway
Authors: Wang Aijuan , Li Chenghui , Jiang Qi'an , Jiang Shu
Published: July 2023

Background

Human epidermal growth factor receptor 2 (HER2) overexpression is an independent prognostic factor of poor prognosis and a predictor of efficacy of anti‐HER2 therapy. A limited number of patients can receive standard second‐line therapy (DS‐8201 or T‐DM1) for metastatic HER2‐positive in some parts of the world, including China, due to many factors, such as cost–benefit ratios.

Case

A 51‐year‐old premenopausal woman was diagnosed with HER2‐positive breast cancer. The pathological stage was ypT3N2M0 and stage IIIA. Trastuzumab targeted therapy combined with goserelin depot was started along with letrozole endocrine therapy. After eight courses of treatment, magnetic resonance imaging (MRI) examination revealed new multiple metastases in the liver, and progression disease (PD) was evaluated. Due to abnormal activation of the phosphatidylinositol 3‐kinase/protein kinase B/mammalian target of rapamycin (PI3K/AKT/mTOR) pathway in the patient, treatment was changed to the mammalian target of rapamycin (mTOR) inhibitor combined with the anti‐HER‐2 agents inetetamab and paclitaxel, while partial response (PR) was evaluated after 6 cycles of treatment. As the patient was hormone receptor (HR) positive, treatment was changed to the inetetamab + rapamycin + exemestane regimen. The lesion continued to shrink and PR was evaluated for 8 cycles. The original regimen was continued, PR was evaluated after 12 courses of treatment. The abdominal MRI performed showed an increase in the volume of intrahepatic multiple metastatic tumor lesion. Efficacy was used to assess for PD and the progression‐free survival (PFS) was 317 days.

Conclusion

A phosphatidylinositol‐4, 5‐bisphosphate 3‐kinase catalytic subunit alpha (PIK3CA) mutation in trastuzumab‐treated metastatic HER2‐positive breast cancer female had a long PFS by treating with the mammalian target of rapamycin inhibitor in combination with the anti‐HER‐2 agent inetetamab.
Stability of the tangent bundle through conifold transitions
Authors: Collins Tristan , Picard Sebastien , Yau Shing‐Tung
Published: July 2023

Let X be a compact, Kähler, Calabi‐Yau threefold and suppose , for , is a conifold transition obtained by contracting finitely many disjoint curves in X and then smoothing the resulting ordinary double point singularities. We show that, for sufficiently small, the tangent bundle admits a Hermitian‐Yang‐Mills metric with respect to the conformally balanced metrics constructed by Fu‐Li‐Yau. Furthermore, we describe the behavior of near the vanishing cycles of as .
Extending the Chemistry of Layered Solids and Nanosheets: Chemistry and Structure of MAX Phases, MAB Phases and MXenes
Authors: Kubitza Niels , Büchner Carina , Sinclair Jordan , Snyder Rose M. , Birkel Christina S.
Published: July 2023

MAX phases are layered solids with unique properties combining characteristics of ceramics and metals. MXenes are their two‐dimensional siblings that can be synthesized as van der Waals‐stacked and multi‐/single‐layer nanosheets, which possess chemical and physical properties that make them interesting for a plethora of applications. Both families of materials are highly versatile in terms of their chemical composition and theoretical studies suggest that many more members are stable and can be synthesized. This is very intriguing because new combinations of elements, and potentially new structures, can lead to further (tunable) properties. In this review, we focus on the synthesis science (including non‐conventional approaches) and structure of members less investigated, namely compounds with more exotic M‐, A‐, and X‐elements, for example nitrides and (carbo)nitrides, and the related family of MAB phases.
A new indica rice germplasm with Arabidopsis‐like life cycle and high‐efficiency genetic transformation as a model system for functional genomics research
Authors: Xiang Zhipan , Zhang Lin , Chen Yi , Zhang Mingze , Yao Yuxian , Long Yingxia , Chen Qiuhong , Mao Dandan , Chen Liangbi
Published: July 2023

Functional genomics research on indica rice is often hindered by its long growth cycle and recalcitrance to genetic transformation. Therefore, there is an urgent need for Arabidopsis‐like indica rice varieties that have a high efficiency in genetic transformation in order to facilitate functional genomics research. Here, we report the development of a new indica variety, named 6‐23, which has a significantly short growth cycle and can be used as an indica model system. 6‐23 is a recombinant inbred line created by crossing Chaling common wild rice with indica rice Guanglu'ai‐4. The heading date of 6‐23 is 45–55 days, which is about 30 days shorter than the model japonica rice Nipponbare (Nip). Additionally, 6‐23 has more primary branches and grains per panicle compared to Nip. We further optimized the Agrobacterium‐mediated genetic transformation system of 6‐23, achieving a transformation efficiency of over 80%, equivalent to that of japonica rice. The callus regeneration efficiency of 6‐23 exceeded 95%, which was superior to Nip. The highest genome editing efficiency mediated by CRISPR (clustered regularly interspaced short palindromic repeats) was ∼71% under the 6‐23 background, and the genome‐edited plants were suitable for phenotypic analysis. Moreover, the construction of transgenic and genome‐edited plants using 6‐23 does not affect the heading date. Taken together, 6‐23 can be used as an indica model system for functional genomics research.
All‐Organic Battery Based on Deep Eutectic Solvent and Redox‐Active Polymers**
Authors: Uhl Matthias , Sadeeda  , Penert Philipp , Schuster Philipp A. , Schick Benjamin W. , Muench Simon , Farkas Attila , Schubert Ulrich S. , Esser Birgit , Kuehne Alexander J. C. , Jacob Timo
Published: July 2023

Sustainable battery concepts are of great importance for the energy storage demands of the future. Organic batteries based on redox‐active polymers are one class of promising storage systems to meet these demands, in particular when combined with environmentally friendly and safe electrolytes. Deep Eutectic Solvents (DESs) represent a class of electrolytes that can be produced from sustainable sources and exhibit in most cases no or only a small environmental impact. Because of their non‐flammability, DESs are safe, while providing an electrochemical stability window almost comparable to established battery electrolytes and much broader than typical aqueous electrolytes. Here, we report the first all‐organic battery cell based on a DES electrolyte, which in this case is composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N‐methylacetamide (NMA) alongside the electrode active materials poly(2,2,6,6‐tetramethylpiperidin‐1‐yl‐oxyl methacrylate) (PTMA) and crosslinked poly(vinylbenzylviologen) (X‐PVBV2+). The resulting cell shows two voltage plateaus at 1.07 V and 1.58 V and achieves Coulombic efficiencies of 98 %. Surprisingly, the X‐PVBV/X‐PVBV+ redox couple turned out to be much more stable in NaTFSI : NMA 1 : 6 than the X‐PVBV+/X‐PVBV2+ couple, leading to asymmetric capacity fading during cycling tests.
Design theory of broadband high‐efficiency continuous Class EF power amplifier based on new continuous factor
Authors: Chang Rong , Luo Yonglun , Hong Guoping
Published: July 2023

This paper presents the design theory for continuous Class EF power amplifier (PA). This theory facilitates the implementation of broadband designs for high‐efficient Class EF PA. First, combining with the switching operating conditions and harmonic tuning technique, the drain waveform expressions of Class EF PA is derived. The corresponding third harmonic component can get its impedance in form of pure reactance, which simplifies the matching process while maintaining the efficiency. Second, a new continuous factor (CF) dedicated to the continuous Class EF PA can be obtained, with applying waveform mapping concept. The new CF expands the impedance point of Class EF PA into the impedance space. This greatly enhance the flexibility of broadband design. With this new theory, the design of broadband Class EF PA becomes very simple. As a verification, a Class EF PA operating at 2.4–3.8 GHz has been designed using CREE GaN HEMT CGH40010F. The PA can achieve the gain of 9.1–11.2 dB, the output power of 39.1–41.2 dBm, the PAE of 66.3%–74.1%, and the DE of 69.5%–76.2%. Both simulated and measured data show very good consistency and prove the rationality and validity of the proposed theory.
State of charge estimation for the vanadium redox flow battery based on the Sage–Husa adaptive extended Kalman filter
Authors: Zixuan Luo , Dawei Qu , Luyan Fan , Shuo Yang
Published: July 2023

Focusing on improving the accuracy of vanadium redox flow battery (VRFB) state of charge (SOC) estimation, this paper will combine the extended Kalman filter (EKF) estimator with the Sage–Husa adaptive method, referred to as the SAEKF estimator. Firstly, a second‐order Equivalent Circuit Model (ECM) is established to provide the correct parameterization and degrees of freedom. Next, under a hybrid pulse power characterization (HPPC) text, the parameter estimator in MATLAB/Simulink is utilized to identify the ECM parameters by using nonlinear least squares method with Trust‐Region‐Reflective (TRR) iterative algorithm. Then, during the HPPC test, the estimators implemented on the ARM‐Cortex STM32F103 estimate the VRFB SOC under both the 0°C and 5°C conditions. Finally, the mean absolute error (MAE) of the IEKF estimator are 4.66% at the 0°C and 0.895% at the 5°C. In the meantime, the MAE of the SAEKF estimator are 4.15% at the 0°C and 0.703% at the 5°C. The evaluation factors of the 0°C and 5°C experiments in the SAEKF estimator are smaller than those of the IEKF and EKF estimators, indicating that the SAEKF estimator outperforms the IEKF estimator in VRFB SOC estimation.
Differential gene expression in response to fungal pathogen exposure in the aquatic invertebrate, Daphnia dentifera
Authors: Terrill Sondag Emily E. , Stewart Merrill Tara E. , Drnevich Jenny , Holmes Jessica R. , Fischer Eva K. , Cáceres Carla E. , Strickland Lynette R.
Published: July 2023

While vertebrate immune systems are appreciated for their complexity and adaptability, invertebrate immunity is often considered to be less complex. However, immune responses in many invertebrates likely involve sophisticated processes. Interactions between the crustacean host Daphnia dentifera and its fungal pathogen Metschnikowia bicuspidata provide an excellent model for exploring the mechanisms underlying crustacean immunity. To explore the genomic basis of immunity in Daphnia, we used RNA‐sequencing technology to quantify differential gene expression between individuals of a single host genotype exposed or unexposed to M. bicuspidata over 24 h. Transcriptomic analyses showed that the number of differentially expressed genes between the control (unexposed) and experimental (exposed) groups increased over time. Gene ontology enrichment analysis revealed that differentially expressed genes were enriched for immune‐related molecules and processes, such as cuticle development, prostaglandin, and defense response processes. Our findings provide a suite of immunologically relevant genes and suggest the presence of a rapidly upregulated immune response involving the cuticle in Daphnia. Studies involving gene expression responses to pathogen exposure shine a light on the processes occurring during the course of infection. By leveraging knowledge on the genetic basis for immunity, immune mechanisms can be more thoroughly understood to refine our understanding of disease spread within invertebrate populations.
Liposoluble vitamin B1 microcapsules: Preparation, characterization, stabilization, and bioaccessibility
Authors: Tian Juan , Peng Guilin , Qu Xiaodi , Yao Yunping , Li Changmo
Published: July 2023

Thiamine (VB1) is an essential water‐soluble vitamin that is necessary in our daily diet. However, its instability when exposed to external factors poses a limitation on its application in the food industry. To address this issue and increase its application in fat‐rich food systems, this study developed liposoluble VB1 microcapsules via freeze‐drying, utilizing β‐cyclodextrin as a wall material and polyglycerol fatty acid ester as an emulsifying agent. The VB1 microcapsules were characterized in terms of their particle size distribution, morphology, solubility, and stability in soybean oil, as well as their in vitro bioaccessibility. The results showed that the average particle size of VB1 microcapsules was 83.73 μm with a nonuniform, somewhat wrinkled spherical structure. The solubility of the VB1 microcapsules in soybean oil was increased to 142.86 mg kg–1. The retention rates of VB1 in soybean oil was found to be above 95% after 48 h of UV irradiation and 96.44% after heating for 7 days at 60°C. The presence of VB1 microcapsules did not significant impact on the oxidation stability of soybean oil. The bioaccessibility of VB1 in soybean oil was 82.81%. This work provides a useful and novel direction for the application of VB1 in high‐fat diets.

Practical applications: VB1 is one of the B‐group vitamins that assists in maintaining normal glucose metabolism. However, it is readily inactivated when exposed to UV radiation, certain pH conditions, and other factors. In this work, the VB1 microcapsules prepared by freeze‐drying exhibited high liposolubility, stability, and bioaccessibility, rendering them suitable for applications in oil‐based systems. This work not only provides a new delivery system to facilitate VB1 supplementation in humans, but also helps to elucidate its application prospect of VB1 in fat‐rich foods, such as edible oil, butter, margarine, rich‐fat dressings, and so on, thus improves the application value of VB1.