bluuebunny/crossref_metadata_2025 huggingface dataset:
Assessment of Medical Industry Compensation to US Physicians by Gender
Authors: Sullivan Brittany G. , Al-Khouja Fares , Herre Margaret , Manasa Morgan , Kreger Alexander , Escobar Jessica , Dinicu Andreea , Naaseh Ariana , Dehkordi-Vakil Farideh , Stamos Michael , Pigazzi Alessio , Jafari Mehraneh D.
Published: September 2022

Importance

It has been well established that female physicians earn less than their male counterparts in all specialties and ranks despite controlling for confounding variables.

Objective

To investigate payments made from highest-grossing medical industry companies to female and male physicians and to assess compensation and engagement disparities based on gender.

Design, Setting, and Participants

This retrospective, population-based cross-sectional study used data from the Open Payments database for the 5 female and 5 male physicians who received the most financial compensation from each of the 15 highest-grossing medical supply companies in the US from January 2013 to January 2019.

Main Outcomes and Measures

The primary outcome was total general payments received by female and male physicians from medical industry over time and across industries. The secondary outcome was trends in industry payment to female and male physicians from 2013 to 2019.

Results

Among the 1050 payments sampled, 1017 (96.9%) of the 5 highest earners were men and 33 (3.1%) were women. Female physicians were paid a mean (SD) of $41 320 ($88 695), and male physicians were paid a mean (SD) of $1 226 377 ($3 377 957) (P < .001). On multivariate analysis, male gender was significantly associated with higher payment after adjusting for rank, h-index, and specialty (mean [SD], $1 025 413 [$162 578]; P < .001). From 2013 to 2019, the payment gap between female and male physicians increased from $54 343 to $166 778 (P < .001).

Conclusions and Relevance

This study found that male physicians received significantly higher payments from the highest-grossing medical industry companies compared with female physicians. This disparity persisted across all medical specialties and academic ranks. The health care industry gender payment gap continued to increase from 2013 to 2019, with a wider compensation gap in 2019.
Treatment Utilization and Outcomes for Locally Advanced Rectal Cancer in Older Patients
Authors: Nassoiy Sean , Christopher Wade , Marcus Rebecca , Keller Jennifer , Weiss Jessica , Chang Shu-Ching , Foshag Leland , Essner Richard , Fischer Trevan , Goldfarb Melanie
Published: September 2022

Importance

The number of older patients (80 years and older) diagnosed with locally advanced rectal cancer (LARC) is expected to increase. Although current guidelines recommend neoadjuvant chemoradiation therapy (NACRT) followed by resection, little is known about management and outcomes in this older population.

Objective

To assess the trends in management of older patients diagnosed with LARC who had a surgical resection.

Design, Setting, and Participants

Patients 80 years and older who had a surgical resection for LARC were identified in the 2004-2016 National Cancer Database. Patients were grouped based on therapy sequence: (1) surgery followed by adjuvant therapy (AT), ie, chemotherapy or radiation; (2) surgery alone; or (3) NACRT followed by surgical resection. Data were analyzed in May 2021.

Exposures

NACRT followed by surgery, and surgery with or without AT.

Main Outcomes and Measures

Overall survival (OS) was assessed using Kaplan-Meier analyses with inverse probability of treatment weighting (IPTW) and Cox proportional hazards regression were performed to examine the association of NACRT with the risk of death.

Results

Of 3868 patients with LARC who underwent surgical resection, 2042 (52.8%) were male, and the mean (SD) age was 83.4 (3.0) years. A total of 2273 (58.8%) received NACRT followed by surgical resection. Factors independently associated with NACRT were more recent diagnosis, age 80 to 85 years (vs 86 years and older), fewer comorbidities, larger tumors, and node-positive disease. The Kaplan-Meier analyses with IPTW showed that 3-year and 5-year OS for NACRT (3-year: 68.9%; 95% CI, 67.0-70.8; 5-year: 51.1%; 95% CI, 49.0-53.4) vs surgery with AT (3-year: 64.4%; 95% CI, 59.0-70.2; 5-year: 43.0%; 95% CI, 37.4-49.5) vs surgery alone (3-year: 55.8%; 95% CI, 52.0-60.0; 5-year: 34.7%; 95% CI, 30.8-39.0) was significantly different (P < .001). After adjusting for confounders, patients who received NACRT were more likely to undergo an R0 resection (adjusted odds ratio, 2.16; 95% CI, 1.62-2.88), which independently improved OS (P < .001). Moreover, receipt of NACRT was independently associated with a 25% decreased risk of death (adjusted hazard ratio, 0.75; 95% CI, 0.69-0.82) compared with alternative treatment sequences.

Conclusions and Relevance

Approximately 40% of older patients with LARC did not receive the current standard of care. In this cohort, NACRT was associated with a higher likelihood of an R0 resection and improved OS. Clinicians should advocate for receipt of NACRT in older patients with LARC.
Rhodium‐Catalyzed C(sp
3
)H Functionalization
Authors: Chatani Naoto
Published: September 2022

Enormous progress has been made in the functionalization of CH bonds in the last two decades as testified by the great number of publications that have appeared in the literature. Herein, a comprehensive overview on the rhodium‐catalyzed functionalization of C(sp
3
)H bonds including activated C(sp
3
)H bonds, including a CH bond adjacent to a nitrogen atom or benzylic CH bond until spring 2021 is presented.
Rhodium‐Catalyzed CH Halogenation
Authors: Dhiman Ankit K. , Sharma Upendra
Published: September 2022

Organic molecules with halogens provide opportunity for a wide range of synthetic manipulations and are also used in organometallic reagent synthesis. Conventional methods to synthesize organohalide compounds involve harsh reaction conditions and require multistep synthesis. In this context, transition metal‐catalyzed CH activation strategy is considered to be efficient and environmentally friendly. This strategy also helps to selectively halogenate certain sp
2
and sp
3
CH bonds of organic molecules that can be difficult to access by traditional methods. Although transition metal‐based catalysts such as copper, palladium, ruthenium, and gold have been applied continuously for important halogenation reactions, rhodium is standing apart due to its reactivity combined with high selectivity. In this article, CX bond formation via rhodium‐catalyzed CH activation is summarized, with emphasis on the mechanistic aspects including DFT studies.
Rhodium(III)‐Catalyzed Oxidative CH and NH/OH Annulation
Authors: Tanaka Ken
Published: September 2022

Nitrogen and oxygen‐containing heterocycles are important core structures in pharmaceutical, agrochemicals, and functional organic materials. The rhodium(III)‐catalyzed oxidative CH and NH/OH annulation reactions of aromatic substrates with alkynes, alkenes, carbene precursors, and so on enable the synthesis of these important heterocycles. Since these reactions generate a rhodium(I) species after the oxidative annulation, an external or internal oxidant is required to regenerate catalytically active rhodium(III) species. A wide variety of directing groups can be used and these directing groups are incorporated into the annulation products. Although rhodium is very expensive, the use of rhodium complexes as catalysts is advantageous compared to other transition‐metal complexes due to high functional group tolerance and operational simplicity.
Copper‐Catalyzed CH Functionalization Involving Radicals
Authors: Xu Jun , Shen Jiabin , Zhang Pengfei , Liu Xiaogang
Published: September 2022

Copper salts have been regarded as powerful catalysts for radical CH functionalization in organic synthesis. This article summarizes recent advances in copper‐catalyzed CH functionalization via radical pathways, with particular emphasis on CC, CN, CO, CSi, CP, CS, and C–halogen bond formation. These CH functionalization methodologies aim toward a broad readership that includes chemists in academia and those active in the industrial community.
Contribution to the Understanding of the Dielectric Breakdown Mechanism of ZTA Ceramics
Authors: Zhang Tao , Ai Jundi , Du Jishi
Published: September 2022

Herein, the breakdown mechanism of alumina‐based ceramics (Al2O3–ZrO2) is studied. The specimens are characterized for their density, phase structure, micromorphology, breakdown process, and breakdown channel by micro computed tomography, high‐speed cameras, etc. The study reveals that the dielectric breakdown stability of the samples shows a decreasing trend and the dielectric loss shows an upward trend with the increase of ZrO2 content. The tetragonal phase zirconia is beneficial to enhance the dielectric breakdown strength of the sample, which is related to the martensitic transformation to prevent crack propagation. Before the ceramic breakdown, the insulating oil first breaks down, causing electric sparks. Once the ceramic breakdown occurs, the charges are rearranged, and a large amount of heat energy is generated instantly to melt the substance around the breakdown channel and erupt to the surface to form pits under the action of high internal stress.
Sensitive Label‐Free Immunoassay by Colorimetric Plasmonic Biosensors Using Silver Nanodome Arrays
Authors: Toma Mana , Itakura Yuji , Namihara Shinnosuke , Kajikawa Kotaro
Published: September 2022

The sensitive direct detection of biomolecules is demonstrated by a colorimetric plasmonic biosensor utilizing the surface colors of plasmonic metasurfaces named Ag nanodome arrays. The Ag nanodome arrays consist of polystyrene bead monolayers coated with Ag thin films whose surface colors are optimized by changing the size of the polystyrene beads. The bulk refractive index sensitivity of colorimetric detection evaluated using the hue angle is 590° RIU−1 (RIU: refractive index unit). For selected geometry, the refractive index resolution (5.0 × 10−5 RIU) obtained by colorimetric detection surpasses that of spectroscopic detection evaluated via the dip wavelength in the reflection spectrum. The numerical simulations predict an enhanced sensing performance when the hue angle of the surface colors of the Ag nanodome arrays changes from 300° to 200°, corresponding to changes in the dip wavelength from 570 to 600 nm in the reflection spectra. Furthermore, the detection sensitivity of the biomolecules is characterized using a direct IgG immunoassay format. The detection limit of the IgG concentration is as low as 134 pM using simple colorimetric detection. The feasibility of sensitive label‐free immunoassays using a colorimetric plasmonic biosensor is expected to accelerate the development of highly sensitive and reliable smartphone‐based plasmonic biosensors.
Heteroanionic Lead‐Free Double‐Perovskite Halides for Bandgap Engineering
Authors: Ahn Chang Won , Jo Jae Hun , Choi Jin San , Hwang Young Hun , Kim Ill Won , Kim Tae Heon
Published: September 2022

Anion‐substituted lead‐free double perovskite halides through mechanochemical synthesis is realized. According to molar concentration (x), some of the Br atoms in Cs2AgBiBr6 are replaced by halogen Cl atoms, which allows us to achieve heteroanionic Cs2AgBiBr6−xClx. X‐ray diffraction (XRD) analyses show that the as‐synthesized Cs2AgBiBr6−xClx compounds undergo structural transitions with a shift of diffraction peaks attributed to changes in their lattice parameters. The chemical compositions and the optical properties of the anion‐mixed Cs2AgBiBr6−xClx compounds using energy‐dispersive X‐ray spectroscopy (EDS), UV–visible optical absorption, and photoluminescence spectroscopy are examined. It is found that the electronic bandgap in the heteroanionic Cs2AgBiBr6−xClx increases progressively with increasing Cl content and the emitted colors are blueshifted from orange to yellow color with increasing Cl content in Cs2AgBi(Br,Cl)6 powders. The results can be used to fabricate lead‐free optoelectronic devices with high performance via bandgap engineering.
Metal–Nitrogen–Carbon Single‐Atom Aerogels as Self‐Supporting Electrodes for Dechlorination of 1,2‐Dichloroethane
Authors: Gan Guoqiang , Zhang Xiaoqing , Bu Shuyu , Gao Qili , Kong Xin , Lei Yechen , Zhu Anquan , Liu Kai , Luan Chuhao , Zhang Tian , Li Yang , Lee Chun‐Sing , Zhang Wenjun
Published: September 2022

Single‐atom catalysts (SACs) have received widespread interest for their high atomic efficiency, enriched active sites, excellent catalytic performance, and low cost. However, the agglomeration of single metal atoms and the use of inactive additives for affixing powdery SACs on planar electrodes may reduce the density of active sites, diminish the charge transport to active sites, and thus suppress their performance. Herein, a series of metal–nitrogen–carbon single‐atom aerogels (M‐SAAs, M: Cu, Ni, Au, Ru) are synthesized via a universal strategy, in which the merits of metal organic frameworks and carbon aerogels are perfectly combined to prevent the agglomeration of single metal atoms and overcome the problem of poor electrical conductivity. The as‐prepared M‐SAAs can be directly employed as self‐supporting electrodes for the electrochemical dechlorination of 1,2‐dichloroethane, and outstanding activity and stability are observed. Significantly, the Cu‐SAA with abundant Cu−N4 sites shows an extraordinarily high ethylene production rate of 446 µmol h−1, with a selectivity of 99% and Faradaic efficiency of 64%. Moreover, theoretical calculations are performed to demonstrate the selectivity and activity of different metal active sites. This study provides a new strategy to exploit highly effective SACs and offers an intensive insight into the mechanism of electrochemical dechlorination reactions.
Facially Coordinated, Tris‐bidentate Purin‐8‐ylidene Ir(III) Complexes for Blue Electrophosphorescence and Hyperluminescence
Authors: Qin Yanyan , Yang Xilin , Jin Jibiao , Li Deli , Zhou Xiuwen , Zheng Zhong , Sun Yingjie , Wong Wai‐Yeung , Chi Yun , Su Shi‐Jian
Published: September 2022

Homoleptic fac‐substituted Ir(III) carbene complexes exhibit higher emission energy (in purple region) in comparison to their mer‐counterparts, prohibiting them to be employed in fabrication of blue emissive organic light‐emitting diode (OLED) devices. Now, the design of two distinctive CF3‐functionalized purin‐8‐ylidene Ir(III) complexes, namely, m‐ and f‐CF3 and m‐ and f‐PhCF3, from new carbene motifs, 9‐(3‐(tert‐butyl)phenyl)‐7‐isopropyl‐2‐(trifluoromethyl)‐7,9‐dihydro‐8H‐purin‐8‐ylidene (A4) and 9‐(3‐(tert‐butyl)phenyl)‐7‐methyl‐6‐phenyl‐2‐(trifluoromethyl)‐7,9‐dihydro‐8H‐purin‐8‐ylidene (B7), having notably stabilized lowest unoccupied molecular orbital energy levels is reported. Hence, the corresponding f‐isomers f‐CF3 and f‐PhCF3 exhibit electroluminescence with peak max. at 478 and 495 nm, max. external quantum efficiencies (EQEs) of 10.4% and 12.8%, respectively. By using f‐CF3 as assistant dopant to convey its energy to terminal emitter t‐DABNA and from f‐PhCF3 donor to 2TCzBN acceptor, two hyper‐OLED devices are successfully fabricated, giving high max. EQE of 23.8%, full‐width at half‐maximum (FWHM) of 30 nm, and CIEx,y coordinate of (0.13, 0.14) for the acceptor t‐DABNA, and max. EQE of 24.0%, FWHM of 28 nm, and CIEx,y of (0.11, 0.36) for the acceptor 2TCzBN, confirming the advantages of these purin‐8‐ylidene Ir(III) complexes.
Electro‐Microfluidic Assembly Platform for Manipulating Colloidal Structures inside Water‐in‐Oil Emulsion Droplets
Authors: Shen Shitao , Qin Xiaofeng , Feng Haoqiang , Xie Shuting , Yi Zichuan , Jin Mingliang , Zhou Guofu , Akinoglu Eser Metin , Mulvaney Paul , Shui Lingling
Published: September 2022

Colloidal assembly is a key strategy in nature and artificial device. Hereby, an electromicrofluidic assembly platform (eMAP) is proposed and validated to achieve 3D colloidal assembly and manipulation within water droplets. The water‐in‐oil emulsion droplets autoposition in the eMAP driven by dielectrophoresis, where the (di)electrowetting effect induces droplet deformation, facilitating quadratic growth of the electric field in water droplet to achieve “far‐field” dielectrophoretic colloidal assembly. Reconfigurable 3D colloidal configurations are observed and dynamically programmed via applied electric fields, colloidal properties, and droplet size. Binary and ternary colloidal assemblies in one droplet allow designable chemical and physical anisotropies for functional materials and devices. Integration of eMAP in high throughput enables mass production of functional microcapsules, and programmable optoelectronic units for display devices. This eMAP is a valuable reference for expanding fundamental and practical exploration of colloidal systems.
Multicomponent Copper‐Zinc Alloy Layer Enabling Ultra‐Stable Zinc Metal Anode of Aqueous Zn‐ion Battery
Authors: Li Boyu , Yang Ke , Ma Jiabin , Shi Peiran , Chen Likun , Chen Changmiao , Hong Xin , Cheng Xing , Tang Man‐Chung , He Yan‐Bing , Kang Feiyu
Published: September 2022

Constructing stable surface modification layer is an effective strategy to suppress dendrite growth and side reactions of Zinc (Zn) metal anode in aqueous Zn‐ion battery. Herein, a multicomponent Cu−Zn alloy interlayer with superior Zn affinity, high toughness and effective inhibition effect on lattice distortion is constructed on Zn foil (Cu−Zn@Zn) to fabricate ultra‐stable Zn metal anode. Owning to the advantages of high binding energy of Cu−Zn alloy layer with Zn atoms and less contact area between metallic Zn and electrolyte, the as‐prepared Cu−Zn@Zn electrode not only restricts the aggregation of Zn atoms, but also suppresses the pernicious hydrogen evolution and corrosion, leading to homogeneous Zn deposition and outstanding electrochemical performances. Accordingly, the symmetric battery with Cu−Zn@Zn electrode exhibits an ultra‐long cycle life of 5496 h at 1 mA cm−2 for 1 mAh cm−2, and the Cu−Zn@Zn//V2O5 pouch cell demonstrates excellent cycling stability with a capacity retention of 88 % after 600 cycles.
Total Synthesis of (+)‐Cinereain and (−)‐Janoxepin through a Fragment Coupling/Retro‐Claisen Rearrangement Cascade
Authors: Ronzon Quentin , Zhang Wei , Charote Thomas , Casaretto Nicolas , Frison Gilles , Nay Bastien
Published: September 2022

Total syntheses of (+)‐cinereain and (−)‐janoxepin, two fungal cyclotripeptides featuring a complex heterocyclic core and interesting phytotoxic and antimalarial activities, have been achieved in a convergent manner. A key step in this synthesis is a one‐pot cascade initiated by the cyclocondensation of two fragments—a hindered 2‐vinylcyclopropane‐1‐acyl fluoride and an electron‐deficient cyclic amidine—to release a reactive spiro[2‐vinylcyclopropane‐1,5′‐pyrimidine‐4′,6′‐dione]. This intermediate underwent a spontaneous retro‐Claisen rearrangement that was rationalized by DFT calculations. The cascade directly afforded a 2,5‐dihydrooxepin‐fused heterotricyclic product, and the challenging oxepin ring was finally forged by the palladium‐catalyzed β‐hydride elimination of an allylic fluoride intermediate.
Steric, Electronic and Conformational Synergistic Effects in the Gold(I)‐catalyzed α‐C−H Bond Functionalization of Tertiary Amines**
Authors: León Rayo David F. , Mansour Ali , Wu Wenbin , Bhawal Benjamin N. , Gagosz Fabien
Published: September 2022

Direct C−H bond functionalization is a useful strategy for the straightforward formation of C−C and C−Heteroatom bonds. In the present work, a unique approach for the challenging electrophilic Au‐catalyzed α‐C−H bond functionalization of tertiary amines is presented. Electronic, steric and conformational synergistic effects exerted by the use of a malonate unit in the substrate were key to the success of this transformation. This new reactivity was applied to the synthesis of tetrahydro‐γ‐carboline products which, under oxidative conditions, could be converted into valuable structural motifs found in bioactive alkaloid natural products.
FRET Monitoring of a Nonribosomal Peptide Synthetase Elongation Module Reveals Carrier Protein Shuttling between Catalytic Domains
Authors: Rüschenbaum Jennifer , Steinchen Wieland , Mayerthaler Florian , Feldberg Anna‐Lena , Mootz Henning D.
Published: September 2022

Nonribosomal peptide synthetases (NRPSs) employ multiple domains, specifically arranged in modules, for the assembly‐line biosynthesis of a plethora of bioactive peptides. It is poorly understood how catalysis is correlated with the domain interplay and associated conformational changes. We developed FRET sensors of an elongation module to study in solution the intramodular interactions of the peptidyl carrier protein (PCP) with adenylation (A) and condensation (C) domains. Backed by HDX‐MS analysis, we discovered dynamic mixtures of conformations that undergo distinct population changes in favor of the PCP‐A and PCP‐C interactions upon completion of the adenylation and thiolation reactions, respectively. To probe this model we blocked PCP binding to the C domain by photocaging and triggered peptide bond formation with light. Changing intramodular domain affinities of the PCP appear to result in conformational shifts according to the logic of the templated assembly process.
Copper‐Catalyzed Quadruple Borylation of Terminal Alkynes to Accesssp3‐Tetra‐Organometallic Reagents
Authors: Li Jia , Ge Shaozhong
Published: September 2022

Copper‐catalyzed regioselective quadruple borylation of terminal alkynes has been developed employing a copper catalyst generated from CuI and dcpe (1,2‐bis(dicyclohexylphosphino)ethane). A wide range of terminal alkynes undergo this multi‐borylation reaction to afford the corresponding 1,1,2,2‐tetraborylalkanes in high yields. Mechanistic studies reveal that this quadruple borylation reaction proceeds through copper‐catalyzed sequential double 1,2‐diborylation of alkynes and 1,2‐diborylalkene intermediates. This protocol represents the most straightforward and atom‐economic approach to preparesp3‐tetra‐organometallic reagents from readily accessible alkynes with commercially available copper catalysts.
Dynamic Bonds: Adaptable Timescales for Responsive Materials
Authors: Wanasinghe Shiwanka V. , Dodo Obed J. , Konkolewicz Dominik
Published: September 2022

Dynamic bonds introduce unique properties such as self‐healing, recyclability, shape memory, and malleability to polymers. Significant efforts have been made to synthesize a variety of dynamic linkers, creating a diverse library of materials. In addition to the development of new dynamic chemistries, fine‐tuning of dynamic bonds has emerged as a technique to modulate dynamic properties. This Review highlights approaches for controlling the timescales of dynamic bonds in polymers. Particularly, eight dynamic bonds are considered, including urea/urethanes, boronic esters, Thiol–Michael exchange, Diels–Alder adducts, transesterification, imine bonds, coordination bonds, and hydrogen bonding. This Review emphasizes how structural modifications and external factors have been used as tools to tune the dynamic character of materials. Finally, this Review proposes strategies for tailoring the timescales of dynamic bonds in polymer materials through both kinetic effects and modulating bond thermodynamics.
Palladium‐Catalyzed Stereoselective Cleavage of C−P Bond: Enantioselective Construction of Atropisomers Containing a P‐Stereogenic Center
Authors: Pang Liangzhi , Sun Qilin , Huang Zhan , Li Gen , Liu Jiaojiao , Guo Jiaxu , Yao Chuanzhi , Yu Jie , Li Qiankun
Published: September 2022

The transition‐metal‐catalyzed C−P bond cleavage has emerged as a powerful tool for the formation of both C−C and C−P bond. However, the transition‐metal‐catalyzed stereoselective cleavage of C−P bond is still undeveloped. Herein, we report a palladium‐catalyzed stereoselective cleavage of C−P bond for the construction of P‐stereogenic phosphines and stereogenic axis. This protocol enables the quick synthesis of atropisomers bearing a P‐stereogenic center in high yields, diastereo‐ and enantioselectivities of up to 98 % ee, >25 : 1 dr. The product is able to serve as chiral catalyst in phosphine catalyzed [3+2] cycloaddition of allenoates to imines, showing the great potential of the present methodology.
Evaluating the feasibility of using lignin–alginate beads with starch additive for entrapping and releasing Rhizobium spp.
Authors: Adjuik Toby A. , Nokes Sue E. , Montross Michael D.
Published: September 2022

Cell immobilization in polymers have proven successful in protecting the nitrogen‐fixing bacteria Rhizobium. This study evaluated the feasibility of using lignin to develop lignin–alginate beads with a starch additive to immobilize and release Rhizobial cells. A lignin–alginate hydrogel was synthesized and cultured at different concentrations with 1 ml inoculum of Rhizobium meliloti and Rhizobium leguminosarum to determine the hydrogel's compatibility with the Rhizobium spp. The Rhizobium cells (3 ml inoculum) were then entrapped into the lignin–alginate beads (ratio of 2 g lignin to 1 g alginate) with starch additive and their entrapment efficiency, cell release and surface morphology investigated. The results suggest concentration of the lignin–alginate hydrogel had no effect on the survival of Rhizobium cells with time. Dried lignin–alginate beads increased the survival of Rhizobium cells from 61% to 73% while dried lignin–alginate beads with starch additive increased the survival of Rhizobium cells from 61% to 84% compared to only alginate beads. Light microscopy suggests alginate beads lost their sphericity without lignin and starch additive while fixed SEM images highlighted Rhizobium cells attached to starch granules. Overall, the results indicate the potential applicability of lignin as a component for the manufacture of carrier materials for entrapping Rhizobial cells.
Effect of halloysite nanotubes on deformation mechanism and work of fracture of thermoplastic elastomer toughened polypropylene
Authors: Kakeh Behnam , Fasihi Mohammad , Ghasemi Faramarz Ashenai , Rajaee Pouya
Published: September 2022

In this research, the impact of two different types of ethylene and propylene‐based thermoplastic polyolefin elastomers (TPOs) as well as halloysite nanotubes (HNTs) on the fracture and mechanical characteristics of polypropylene (PP)/TPOs/HNTs blend nanocomposites were studied. The fracture toughness and deformation process were examined employing the essential work of fracture (EWF) methodology and microstructural observation. The validity of the method for all compounds was demonstrated through self‐similarity diagrams of load–displacement and Hill's analysis. TPOs and HNTs had a synergistic impact on the activation of distinct toughness micro‐mechanisms, resulting in the toughness of ternary systems being higher than that of binary blends. The results revealed that the dominant fracture process of the specimen is the cavities, and/or pull out of dispersed TPOs. Also, according to the results, it can be understood that the incorporation of HNTs in increased the EWF and consequently decreased the non‐EWF. The maximum EWF on blend composites increased by 170% compared to neat PP.
Ionic Liquid‐Incorporated Metal‐Organic Framework with High Magnesium Ion Conductivity for Quasi‐Solid‐State Magnesium Batteries
Authors: Wei Zhixuan , Maile Ruben , Riegger Luise M. , Rohnke Marcus , Müller‐Buschbaum Klaus , Janek Jürgen
Published: September 2022

Magnesium batteries are promising candidates for post‐lithium energy storage systems due to their low cost, high volumetric energy density, and low risk of dendrite formation. This study reports a new magnesium ion conducting ionogel electrolyte based on a Metal‐Organic Framework (MOF) structure (UiO‐66) impregnated with an ionic liquid, magnesium bis[(trifluoromethyl)sulfonyl]imide in 1‐ethyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]imide. Comparably high conductivity of 5.7×10−5 S cm−1 can be achieved at room temperature. By employing the prepared MOF‐ionogel electrolyte, a reversible quasi‐solid‐state magnesium battery (QSSMB) is reported. Surface analysis unveils the possible origin of the large overpotential of magnesium plating and stripping. The findings suggest that MOF‐based materials are a promising class of ionogel electrolyte templates for QSSMBs. The results on the magnesium anode will be useful to define optimization strategies for magnesium metal anodes in SSMBs.
Recent trends using natural polymeric nanofibers as supports for enzyme immobilization and catalysis
Authors: Khan Rumysa S. , Rather Anjum H. , Wani Taha U. , Rather Sami‐ullah , Amna Touseef , Hassan M. Shamshi , Sheikh Faheem A.
Published: September 2022

All the disciplines of science, especially biotechnology, have given continuous attention to the area of enzyme immobilization. However, the structural support made by material science intervention determines the performance of immobilized enzymes. Studies have proven that nanostructured supports can maintain better catalytic performance and improve immobilization efficiency. The recent trends in the application of nanofibers using natural polymers for enzyme immobilization have been addressed in this review article. A comprehensive survey about the immobilization strategies and their characteristics are highlighted. The natural polymers, e.g., chitin, chitosan, silk fibroin, gelatin, cellulose, and their blends with other synthetic polymers capable of immobilizing enzymes in their 1D nanofibrous form, are discussed. The multiple applications of enzymes immobilized on nanofibers in biocatalysis, biosensors, biofuels, antifouling, regenerative medicine, biomolecule degradation, etc.; some of these are discussed in this review article.
Semaglutide (GLP‐1 receptor agonist) stimulates browning on subcutaneous fat adipocytes and mitigates inflammation and endoplasmic reticulum stress in visceral fat adipocytes of obese mice
Authors: Martins Fabiane F. , Marinho Thatiany S. , Cardoso Luiz E. M. , Barbosa‐da‐Silva Sandra , Souza‐Mello Vanessa , Aguila Marcia B. , Mandarim‐de‐Lacerda Carlos A.
Published: September 2022

Semaglutide (GLP‐1 agonist) was approved for treating obesity. Although the effects on weight loss and metabolism are known, the responses of adipocytes to semaglutide are yet limited. C57BL/6 male mice (n = 20/group) were fed a control diet (C) or a high‐fat (HF) diet for 16 weeks and then separated into four groups (n = 10/group) for an additional four weeks: C, C diet and semaglutide, HF, and HF diet and semaglutide. Epididymal white adipose tissue (eWAT) and subcutaneous white adipose tissue (sWAT) fat pads were studied with biochemistry, immunohistochemistry/fluorescence, stereology, and reverse transcription‐quantitative polymerase chain reaction. In obese mice, semaglutide reduced the fat pad masses (eWAT, −55%; sWAT, −40%), plasmatic cytokines, and proinflammatory gene expressions: tumor necrosis factor‐alpha (−60%); interleukin (IL)‐6 (−55%); IL‐1 beta (−40%); monocyte chemoattractant protein‐1 (−90%); and leptin(−80%). Semaglutide also lessened endoplasmic reticulum (ER) stress genes of activating transcription factor‐4 (−85%), CCAAT enhancer‐binding protein homologous protein (−55%), and growth arrest and DNA damage‐inducible gene 45 (−45%). The obese mice's adipocyte hypertrophy and macrophage infiltration were equally reduced by semaglutide. Semaglutide enhanced multiloculation and uncoupled protein 1 (UCP1) labeling in obese mice: peroxisome proliferator‐activated receptor‐alpha (+560%) and gamma (+150%), fibronectin type III domain‐containing protein 5 (+215%), peroxisome proliferator‐activated receptor‐alpha coactivator (+110%), nuclear respiratory factor 1 (+260%), and mitochondrial transcription factor A (+120%). Semaglutide also increased thermogenetic gene expressions for the browning phenotype maintenance: beta‐3 adrenergic receptor (+520%), PR domain containing 16 (+90%), and Ucp1 (+110%). In conclusion, semaglutide showed significant beneficial effects beyond weight loss, directly on fat pads and adipocytes of obese mice, remarkably anti‐inflammatory, and reduced adipocyte size and ER stress. Besides, semaglutide activated adipocyte browning, improving UCP1, mitochondrial biogenesis, and thermogenic marker expressions help weight loss.
Apoptotic susceptibility of pancreatic alpha cells to environmentally relevant dose levels of bisphenol‐A versus dibutyl phthalate is mediated by HSP60/caspase‐3 expression in male albino rats
Authors: Morsi Ahmed A. , Mersal Ezat A. , Alsabih Ahmed O. , Abdelmoneim Ahmed M. , Sakr Eman M. , Alakabawy Shaimaa , Elfawal Riham G. , Naji Mohammed , Aljanfawe Hatem J. , Alshateb Farah H. , Shawky Tamer M.
Published: September 2022

Unfortunately, humanity is exposed to mixed plasticizers such as bisphenol‐A (BPA) and dibutyl phthalate (DBP) that are leached from the daily used plastic products. Previous studies have demonstrated their potential in pancreatic beta cell injury and diabetes induction. The study hypothesized that both compounds would affect the pancreatic alpha cells in albino rats when administered at environmentally relevant doses. Heat shock protein 60 (HSP60) and caspase‐3 protein expression was also investigated as potential mechanisms. Thirty‐six male Wistar albino rats were separated into four equal groups: control, BPA alone, DBP alone, and BPA + DBP combined groups. BPA and DBP were given in drinking water for 45 days in a dose of 4.5 and 0.8 µg/L, respectively. Fasting blood glucose, serum insulin, pancreatic tissue levels of malondialdehyde, and superoxide dismutase were measured. Pancreatic sections were subjected to hematoxylin & eosin (H & E) staining, glucagon, HSP60, and caspase‐3 immunohistochemistry. Although all three experimental groups showed diffuse islet cell HSP60 immunoreactivity, rats exposed to BPA alone showed α‐cell‐only apoptosis, indicated by H & E changes and caspase‐3 immunoreactivity, associated with reduced glucagon immunoreaction. However, rats exposed to DBP alone showed no changes in either α or β‐cells. Both combined‐exposed animals displayed α and β apoptotic changes associated with islet atrophy and reduced glucagon expression. In conclusion, the study suggested HSP60/caspase‐3 interaction, caspase‐3 activation, and initiation of apoptosis in α‐cell only for BPA‐alone exposure group, meanwhile DBP alone did not progress to apoptosis. Interestingly, both α/β cell effect was observed in the mixed group implying synergetic/additive action of both chemicals when combined.
The miRNA‐144‐5p/IRS1/AKT axis regulates the migration, proliferation, and mineralization of osteoblasts: A mechanism of bone repair in diabetic osteoporosis
Authors: Miao Maomao , Zhang Yang , Wang Xuping , Lei Shanshan , Huang Xiaowen , Qin Luping , Shou Dan
Published: September 2022

Diabetic osteoporosis (DOP) is a disorder of bone metabolism induced by multiple mechanisms. Previous studies have revealed that microRNAs (miRNAs) play crucial roles in bone metabolism. MiRNA‐144‐5p has been proven to participate in the regulation of osteoblast activities; however, its specific mechanism in DOP has not been elucidated. This study investigated whether high glucose (HG) inhibited osteoblasts by regulating miRNA‐144‐5p. Our results showed that HG inhibited bone formation not only in vivo but also in vitro. We observed that HG severely hindered the migration, proliferation and mineralization of osteoblasts, while miRNA‐144‐5p was upregulated by way of the cell counting kit‐8 assay, wound healing assay, alkaline phosphatase (ALP) activity assay and alizarin red staining. Double luciferase reporter experiments showed that miRNA‐144‐5p directly targeted insulin receptor substrate 1 (IRS1). The IRS1/AKT signaling pathway is closely related to osteoblasts' migration, proliferation, and mineralization. Silencing miRNA‐144‐5p promoted the mRNA, and protein expression of IRS1, thereby letting the expression of total AKT down, and then preventing phosphorylation of AKT into the nucleus to regulate migration, proliferation, and mineralization genes of osteoblasts. In conclusion, this study indicated that HG regulated the migration, proliferation, and mineralization of osteoblasts via the miRNA‐144‐5p/IRS1/AKT axis, which suggested a possible mechanism for DOP pathology.
Epidemiology of biopsy‐proven glomerular diseases in Chinese children: A scoping review
Authors: Li Yetong , Yang Yue , Zhuo Li , Wu Dan , Li Wenge , Liu Xiaorong
Published: September 2022

Background

Glomerular disease is the leading cause of chronic kidney disease globally. No scoping review reports have focused on China's spectrum of glomerular diseases in children. This study aimed to systematically identify and describe retrospective studies on pediatric glomerular disease based on available data on sex, age, study period, and region.

Methods

Six databases were systematically searched for relevant studies from initiation to December 2021 in PubMed, Embase, Web of Science, Global Health Library, Wangfang Database, and CNKI.

Results

Thirty‐four studies were identified in the scoping review, including 40,430 patients with biopsy‐proven diagnoses. The proportion of boys was significantly higher than that of girls. In this study, 28,280 (70%) cases were primary glomerular disease, 10,547 (26.1%) cases were diagnosed as secondary glomerular disease, and 1146 (2.8%) cases were hereditary glomerular disease. Minimal change disease is the most common glomerular disease among children in China, followed by mesangial proliferative glomerulonephritis, IgA nephropathy, and purpura nephritis. We observed increments in glomerular diseases in periods 2 (2001–2010) and 3 (2011–2021). The proportion of major glomerular diseases varies significantly in the different regions of China.

Conclusion

The spectrum of pediatric glomerular diseases varied across sex, age groups, study periods, and regions, and has changed considerably over the past 30 years.
Systematic review of monotherapy with biologicals for children and adults with IgE‐mediated food allergy
Authors: Silva Debra de , Singh Chris , Arasi Stefania , Muraro Antonella , Zuberbier Torsten , Ebisawa Motohiro , Alvaro Lozano Montserrat , Roberts Graham
Published: September 2022

Background

Biological therapies relieve symptoms in allergic inflammatory diseases so we systematically reviewed the evidence about whether biological monotherapy could benefit people with IgE‐mediated food allergy.

Methods

We searched six bibliographic databases from 1946 to 30 September 2021 for randomised and non‐randomised controlled trials about biological monotherapy in people with IgE‐mediated food allergy confirmed by oral food challenge. We used the Grading of Recommendations, Assessment, Development and Evaluation approach to narratively summarise findings from three trials with 118 participants. The studies were too heterogeneous and sparse to conduct meta‐analysis.

Results

We included one randomised trial about etokimab, one about omalizumab and one about the discontinued TNX‐901. All were in people with peanut allergy in the USA, mostly aged 13+ years. There was a trend towards improved tolerance of peanut during treatment, with few side effects. However, we have very low certainty about the evidence due to the small number of trials and participants. No included trial reported on quality of life or cost‐effectiveness.

Conclusions

There is not yet enough certainty to support offering etokimab or omalizumab widely for food allergy. Clinicians may consider the merits for individuals, but large randomised trials with standardised measures are needed to confirm the safety, efficacy and most suitable candidates, doses and durations of treatment before more universal use.
Pharmacokinetics, Bioavailability, and Swallowing Safety With Riluzole Oral Film
Authors: Wymer James , Apple Stephen , Harrison Antoinette , Hill Bryan Alan
Published: September 2022

Dysphagia is highly prevalent in patients with amyotrophic lateral sclerosis (ALS). Riluzole is a US Food and Drug Administration‐approved treatment for ALS. Riluzole oral film (ROF; Exservan™) contains riluzole in a polymer‐based film matrix. The ROF is administered by placing on the tongue, where it dissolves and the drug is ingested with the saliva. Two clinical trials assessed the safety and tolerability of the ROF. Bioavailability and pharmacokinetics (PK) were evaluated in an open‐label, randomized, single‐dose, replicate crossover study of 50 mg of ROF and riluzole 50‐mg tablets in 32 healthy volunteers. The second study was a videofluoroscopic swallowing examination conducted with nine patients with ALS before and after receiving a single dose of 50 mg of ROF. The primary outcome was change on penetration‐aspiration scale (PAS) scores from pre‐ to post‐dose. Overall, the PK parameters for ROF and riluzole tablets were comparable between treatments and administrations when administered under fasting conditions. Administration of ROF with food resulted in a 15% reduction in area under the curve and a 45% reduction in maximum serum concentration. A total of 44 treatment‐emergent adverse events (AEs) were reported in the study; all were mild in severity. No serious AEs were observed and no subjects discontinued due to AEs. In the swallowing study, very little numerical or categorical change was observed following the dose of ROF. No evidence of deterioration of swallowing function was observed post‐dose. The ROF was bioequivalent to riluzole tablets, was well tolerated, and had no detrimental effect on swallowing.
Hybrid Functional and Plane Waves based Ab Initio Molecular Dynamics Study of the Aqueous Fe2+/Fe3+ Redox Reaction**
Authors: Mandal Sagarmoy , Kar Ritama , Meyer Bernd , Nair Nisanth N.
Published: September 2022

Kohn‐Sham density functional theory and plane wave basis set based ab initio molecular dynamics (AIMD) simulation is a powerful tool for studying complex reactions in solutions, such as electron transfer (ET) reactions involving Fe2+/Fe3+ ions in water. In most cases, such simulations are performed using density functionals at the level of Generalized Gradient Approximation (GGA). The challenge in modelling ET reactions is the poor quality of GGA functionals in predicting properties of such open‐shell systems due to the inevitable self‐interaction error (SIE). While hybrid functionals can minimize SIE, standard plane‐wave based AIMD at that level of theory is typically 150 times slower than GGA for systems containing ∼100 atoms. Among several approaches reported to speed‐up AIMD simulations with hybrid functionals, the noise‐stabilized MD (NSMD) procedure, together with the use of localized orbitals to compute the required exchange integrals, is an attractive option. In this work, we demonstrate the application of the NSMD approach for studying the Fe2+/Fe3+ redox reaction in water. It is shown here that long AIMD trajectories at the level of hybrid density functionals can be obtained using this approach. Redox properties of the aqueous Fe2+/Fe3+ system computed from these simulations are compared with the available experimental data for validation.
Relativistic Density Functional NMR Tensors Analyzed with Spin‐free Localized Molecular Orbitals
Authors: Fernández‐Alarcón Alberto , Autschbach Jochen
Published: September 2022

The implementation of fast relativistic methods based on density functional theory, in conjunction with localized molecular orbital (LMO) based analysis, allows straightforward interpretations of NMR parameters in terms of contributions from core shells, lone pairs, and bonds, for compounds containing elements from across the periodic table. We present a conceptual review of a frequently used LMO analysis of NMR parameters calculated in the presence of spin‐orbit interactions and other relativistic effects. An accompanying example focuses on the 15N shielding in a heavy metal complex.
Chlorofullerene C60Cl6 Enables Efficient and Stable Tin‐Based Perovskite Solar Cells
Authors: Chen Jingfu , Tian Chengbo , Sun Chao , Yang Panpan , Feng Wenjing , Zheng Lingfang , Yang Liu , Hou Enlong , Luo Jiefeng , Xie Liqiang , Wei Zhanhua
Published: September 2022

Tin‐based perovskite solar cells (TPSCs) have received great attention due to their eco‐friendly properties and high theoretical efficiencies. However, the fast crystallization feature of tin‐based perovskites leads to poor film quality and limits the corresponding device performance. Herein, a chlorofullerene, C60Cl6, with six chlorine attached to the C60 cage, is applied to modulate the crystallization process and passivate grain boundary defects of the perovskite film. The chemical interactions between C60Cl6 and perovskite components retard the transforming process of precursors to perovskite crystals and obtain a high‐quality tin‐based perovskite film. It is also revealed that the C60Cl6 located at the surfaces and grain boundaries can not only passivate the defects but also offer a role in suturing grain boundaries to suppress the detrimental effects of water and oxygen on perovskite films, especially the oxidation of Sn2+ to Sn4+. As a result, the C60Cl6‐based device yields a remarkably improved device efficiency from 10.03% to 13.30% with enhanced stability. This work provides a new strategy to regulate the film quality and stability of TPSCs using functional fullerene materials.
A coreless axial flux‐switching generator for micro‐wind turbine application
Authors: Dehshiri Mohsen , Ketabi Abbas
Published: September 2022

The efficiency, power density, and torque of axial flux generators are higher than those of radial flux generators. In this paper, a new axial flux switching generator with a coreless stator is designed for micro wind turbine applications. Generator parts are designed based on nominal values, and their dimensions are determined. Cogging torque is an undesired torque ripple intrinsic in the design of a permanent magnet generator, which should be minimized due to its effects: vibration and noise. In addition, since aerodynamic power is low during start‐up at low wind speeds, the cogging torque must be as low as possible to achieve a low cut‐in speed. The design, optimization, and fabrication of a new coreless axial flux‐switching generator for micro‐wind turbine application are investigated and compared with the conventional one. The prototype machine is an axial‐field flux‐switching permanent magnet generator with a two‐rotor‐one‐stators configuration. The stator of the proposed generator is made up of coils and magnets and has no iron core. First, the generator's design to reduce cogging torque is investigated using nominal values, and the dimensions of the various parts of the generator are calculated according to these values. Then the designed generator was simulated three‐dimensionally using the FEM. Finally, a prototype of the desired generator is built. Comparing the results obtained from the finite element method and laboratory testing shows that these results are broadly consistent.