bluuebunny/crossref_metadata_2025_split 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

ImportanceIt has been well established that female physicians earn less than their male counterparts in all specialties and ranks despite controlling for confounding variables.ObjectiveTo 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 ParticipantsThis 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 MeasuresThe 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.ResultsAmong 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 &amp;lt; .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 &amp;lt; .001). From 2013 to 2019, the payment gap between female and male physicians increased from $54 343 to $166 778 (P &amp;lt; .001).Conclusions and RelevanceThis 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

ImportanceThe 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.ObjectiveTo assess the trends in management of older patients diagnosed with LARC who had a surgical resection.Design, Setting, and ParticipantsPatients 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.ExposuresNACRT followed by surgery, and surgery with or without AT.Main Outcomes and MeasuresOverall 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.ResultsOf 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 &amp;lt; .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 &amp;lt; .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 RelevanceApproximately 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

Abstract

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

Abstract

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

Abstract
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

Abstract
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.
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

AbstractSingle‐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

AbstractHomoleptic 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

AbstractColloidal 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

AbstractConstructing 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

AbstractTotal 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

AbstractDirect 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

AbstractNonribosomal 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

AbstractCopper‐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

AbstractDynamic 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

AbstractThe 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

AbstractCell 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

AbstractIn 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.