bluuebunny/crossref_metadata_2025_split huggingface dataset:
Iridium‐Catalyzed Chemo‐, Diastereo‐, and Enantioselective Allyl‐Allyl Coupling: Accessing All Four Stereoisomers of (E)‐1‐Boryl‐Substituted 1,5‐Dienes by Chirality Pairing
Authors: Jung Yongsuk , Yoo Seok Yeol , Jin Yonghoon , You Jaehyun , Han Seungcheol , Yu Jeongwoo , Park Yoonsu , Cho Seung Hwan 
Published: January 2023

AbstractHere, we report a highly chemo‐, diastereo‐, and enantioselective allyl‐allyl coupling between branched allyl alcohols and α‐silyl‐substituted allylboronate esters, catalyzed by a chiral iridium complex. The α‐silyl‐substituted allylboronate esters can be chemoselectively coupled with allyl electrophiles, affording a diverse set of enantioenriched (E)‐1‐boryl‐substituted 1,5‐dienes in good yields, with excellent stereoselectivity. By permuting the chiral iridium catalysts and the substrates, we efficiently and selectively obtained all four stereoisomers bearing two consecutive chiral centers. Mechanistic studies via density functional theory calculations revealed the origins of the diastereo‐ and chemoselectivities, indicating the pivotal roles of the steric interaction, the β‐silicon effect, and a rapid desilylation process. Additional synthetic modifications for preparing a variety of enantioenriched compounds containing contiguous chiral centers are also included.
Peroxodicarbonate as a Green Oxidizer for the Selective Degradation of Kraft Lignin into Vanillin
Authors: Zirbes Michael , Graßl Tobias , Neuber Rieke , Waldvogel Siegfried R. 
Published: January 2023

AbstractLignin, the world's largest resource of renewable aromatics, with annually roughly 50 million tons of accruing technical lignin, mainly Kraft lignin, is highly underdeveloped regarding the production of monoaromatics. We demonstrate the oxidative depolymerization of Kraft lignin at 180 °C to produce vanillin 1 in yields up to 6.2 wt % and 92 % referred to the maximum yield gained from the quantification reaction utilizing nitrobenzene. Using peroxodicarbonate (C2O62−) as “green” oxidizer for the degradation, toxic and/or harmful reagents are prevented. Also, the formed waste can serve as makeup chemical in the pulping process. Na2C2O6 is synthesized in an ex‐cell electrolysis of aqueous Na2CO3 at BDD anodes, achieving a yield of Na2C2O6 with 41 %. At least, the oxidation and degradation of Kraft lignin is analysis via UV/Vis and NMR spectroscopy.
Copolymer Mediated Engineering of Halide Perovskites and Associated Devices: Current State and Future
Authors: Mathur Avi , Khamgaonkar Saikiran , Maheshwari Vivek 
Published: January 2023

AbstractThe field of halide perovskites has advanced significantly within a decade, as engineering strategies are addressing many of the challenges and as a result improved environmental stability and electro‐optical properties have been achieved. The use of the copolymer additive strategy has received significant attention in recent years as a variety of polymers with significant differences in properties such as water affinity, polarity, elastic modulus, ion conductivity and basis for interaction with perovskite can be selected and combined with halide perovskite. As a result, there has been a rapid increase in publications reporting the effectiveness of the inexpensive and readily available copolymer additives in altering the physicochemical, mechanical, and electro‐optical properties of the halide perovskites‐based high‐performance devices. This article is an effort to provide insight into the current state of copolymer‐mediated engineering of halide perovskites with a perspective on the reported improvements in the properties and performance of the perovskite‐based devices. Critical analysis is done on the potential of the copolymer–perovskite materials toward realizing commercial applications.
Fractional‐order PID and internal model control‐based dual‐loop load frequency control using teaching–learning optimization
Authors: Veerendar Tejavath , Kumar Deepak , Sreeram Victor 
Published: January 2023

AbstractA load frequency controller is essential to counter load disturbances and minimize unscheduled power flow between interlinked areas of a power system. Hence, this paper proposes a fractional‐order proportional‐integral derivative (FOPID)‐based dual‐loop control approach for load frequency control of multi‐area nonreheated thermal power systems (NRTPS) using teaching–learning optimization (TLO). A stability equation‐based predictive model is used with internal model control in the internal loop of the proposed approach, whereas the external loop contains TLO‐based FOPID controller. The proposed method is tested on two‐area and three‐area NRTPSs under various operating conditions. It is validated from the simulation results that the proposed approach improves the system response substantially compared to the well‐known existing techniques. The robustness of the proposed method is also demonstrated by performing sensitivity analysis with parametric uncertainties, random load disturbances, generation rate constraints, and governor dead zone.
It is not the time to abandon intraoperative frozen section in endometrioid adenocarcinoma: A large‐scale, multi‐center, and retrospective study
Authors: Yang Xiaohang , Yin Jingjing , Fu Yu , Shen Yuanming , Zhang Chuyao , Yao Shuzhong , Xu Congjian , Xia Min , Lou Ge , Liu Jihong , Lin Bei , Wang Jianliu , Zhao Weidong , Zhang Jieqing , Cheng Wenjun , Guo Hongyan , Guo Ruixia , Xue Fengxia , Wang Xipeng , Han Lili , Li Xiaomao , Zhang Ping , Zhao Jianguo , Li Wenting , Dou Yingyu , Wang Zizhuo , Liu Jingbo , Li Kezhen , Chen Gang , Sun Chaoyang , Wang Beibei , Yang Xingsheng 
Published: January 2023

AbstractIntroductionStage IB (deep myometrial invasion) high‐grade endometrioid adenocarcinoma (EA), regardless of LVSI status, is classified into high‐intermediate risk groups, requiring surgical lymph node staging. Intraoperative frozen section (IFS) is commonly used, but its adequacy and reliability vary between reports. Hence, we determined the utility of IFS in identification of high‐risk factors, including deep myometrial invasion and high‐grade.MethodWe retrospectively analyzed 9,985 cases operated with hysterectomy and diagnosed with FIGO stage I/II EA in postoperative paraffin section (PS) results at 30 Chinese hospitals from 2000 to 2019. We determined diagnostic performance of IFS and investigated whether the addition of IFS to preoperative biopsy and imaging could improve identification of high‐risk factors.ResultsIFS and postoperative PS presented the highest concordance in assessing deep myometrial invasion (Kappa: 0.834), followed by intraoperative gross examination (IGE Kappa: 0.643), MRI (Kappa: 0.395), and CT (Kappa: 0.207). IFS and postoperative PS presented the highest concordance for high‐grade EA (Kappa: 0.585) compared to diagnostic curettage (D&C 0.226) and hysteroscope (Hys 0.180). Sensitivity and specificity for detecting deep myometrial invasion were 86.21 and 97.20% for IFS versus 51.72 and 88.81% for MRI, 68.97 and 94.41% for IGE. These figures for detecting high‐grade EA were 58.21 and 96.50% for IFS versus 16.42 and 98.83% for D&C, 13.43 and 98.64% for Hys. Parallel strategies, including MRI‐IFS (Kappa: 0.626), D&C‐IFS (Kappa: 0.595), and Hys‐IFS (Kappa: 0.578) improved the diagnostic efficiencies of individual preoperative examinations. Based on the high sensitivity of IFS, parallel strategies improved the sensitivities of preoperative examinations to 89.66% (MRI), 64.18% (D&C), 62.69% (Hys), respectively, and these differences were statistically significant (p = 0.000).ConclusionIFS presented reasonable agreement rates predicting postoperative PS results, including deep myometrial invasion and high‐grade. IFS helps identify high‐intermediate risk patients in preoperative biopsy and MRI and guides intraoperative lymphadenectomy decisions in EA.
Tailored BiVO4/In2O3 nanostructures with boosted charge separation ability toward unassisted water splitting
Authors: Lee Mi Gyoung , Yang Jin Wook , Park Ik Jae , Lee Tae Hyung , Park Hoonkee , Cheon Woo Seok , Lee Sol A. , Lee Hyungsoo , Ji Su Geun , Suh Jun Min , Moon Jooho , Kim Jin Young , Jang Ho Won 
Published: January 2023

AbstractThe development of new heterostructures with high photoactivity is a breakthrough for the limitation of solar‐driven water splitting. Here, we first introduce indium oxide (In2O3) nanorods (NRs) as a novel electron transport layer for bismuth vanadate (BiVO4) with a short charge diffusion length. In2O3 NRs reinforce the electron transport and hole blocking of BiVO4, surpassing the state‐of‐the‐art photoelectrochemical performances of BiVO4‐based photoanodes. Also, a tannin–nickel–iron complex (TANF) is used as an oxygen evolution catalyst to speed up the reaction kinetics. The final TANF/BiVO4/In2O3 NR photoanode generates photocurrent densities of 7.1 mA cm−2 in sulfite oxidation and 4.2 mA cm−2 in water oxidation at 1.23 V versus the reversible hydrogen electrode. Furthermore, the “artificial leaf,” which is a tandem cell with a perovskite/silicon solar cell, shows a solar‐to‐hydrogen conversion efficiency of 6.2% for unbiased solar water splitting. We reveal significant advances in the photoactivity of TANF/BiVO4/In2O3 NRs from the tailored nanostructure and band structure for charge dynamics.
A Simple Four‐Step Synthesis of the Potato Alkaloid Demissidine from the Common Sapogenin Tigogenin
Authors: Baj Aneta , Kaewnok Nirawit , Rivas‐Loaiza Juan A. , Szymańska Magdalena , Witkowski Stanisław , Wojtkielewicz Agnieszka , Morzycki Jacek W. 
Published: January 2023

AbstractA simple synthesis method of solanidane alkaloids from common steroidal sapogenins was developed. Previously described multi‐step transformations of tigogenin to demissidine (8–12 steps) were shortened to four steps only. The key‐step of the present synthesis was the epimerization at C25 of the lactam intermediate. Different approaches to this reaction, i. e., a classical one via enolate, and a chemoselective umpolung transformation, were thoroughly investigated. The epimerization step is unnecessary if the starting sapogenin has the same configuration at C25 as the target alkaloid because the configuration at C25 (either R or S) remains intact throughout the synthesis. Thus, the related solanidane alkaloids, 12β‐hydroxy‐25‐epi‐demissidine and 5‐epi‐demissidine, were synthesized in the three‐step procedure with retention of configuration at this stereogenic center from rockogenin (25R‐5α‐sapogenin) or sarsasapogenin (25S‐5β‐sapogenin), respectively.
In Situ X‐ray Diffraction Studies on the Reduction of V2O5 and WO3 by Using Hydrogen
Authors: Keilholz Simon , Paul Roman , Dorsch Leonhard Yuuta , Kohlmann Holger 
Published: January 2023

AbstractThe reduction of metal oxides with hydrogen is widely used for the production of fine chemicals and metals both on the laboratory and industry scale. In situ methods can help to elucidate reaction pathways and to gain control over such synthesis reactions. In this study, the reduction of WO3 and V2O5 with hydrogen was investigated by in situ X‐ray powder diffraction with regard to intermediates and the influence of heating rates and hydrogen flow rates. Mixtures of V4O9, V6O13 and VO2 in two modifications were identified as intermediates on the way to phase‐pure V2O3. None of the intermediates occurs in a single phase and therefore cannot be prepared this way. In contrast, the intermediates of the WO3 reduction, H0.23WO3 and W10O29, appear consecutively and can be isolated. For both reactions, the heating and flow rates have little influence on the formation of intermediates.
Belongingness on the go: Examining road warrior consultants’ experiences of belongingness with their firms
Authors: Bhatt Mamta , Vakkayil Jacob 
Published: January 2023

AbstractWe examine how “road warrior consultants,” who spend a majority of workweek at the client location, describe their experiences of belongingness with their companies. Based on observations and semi‐structured interviews with consultants, we identified three facets of consultants' experiences that were significant for organizational belongingness, namely: (1) connection with colleagues which refers to their interactions with others at their firm; (2) differentiation at the client firm which signifies experiences of differences and being an outsider at the client firm; (3) centrality of oneself at the consulting firm or experiences of handling significant roles in their firm. Our findings contribute to the literatures on consulting and belongingness, and also have broader implications for understanding belongingness dynamics in client‐service professions.
Design of recustomize finite impulse response filter using truncation based scalable rounding approximate multiplier and error reduced carry prediction approximate adder for image processing application
Authors: Senthilkumar S. , Samuthira Pandi V. , Sripriya T. , Pragadish N. 
Published: January 2023

SummaryRecustomize finite impulse response (RFIR) filter is designed to achieve lesser power consume, cost, area, and higher speed of system operation. This is used to remove the noises from the image and signal. Previously, several filters were designed for removing noises, but that filters consume more area, power, cost, and delay and did not provide accurate results and the error rate was increased. To overcome these issues, this work is proposed. In this work, the Recustomize finite impulse response (RFIR) filter is designed using truncation‐based scalable rounding approximate multiplier (TOSAM) and error reduced carry prediction approximate adder (ERCPAA) for image processing application. Here, TOSAM‐ERCPAA is used to speed up the filter design with less area and less power consumption. The proposed ERCPAA adder is divided into three blocks, such as carry prediction logic, approximate full adder cells array, constant truncation along error lessening logic, which can reduce the power and area. The proposed RFIR‐ TOSAM‐ERCPAA filter is designed and executed in Verilog programming language and the simulation is done in Xilinx ISE 14.5 design tools.
Inter‐Alkali‐Metal Dative Bond in the MMN3−(M=Alkali Metal) Cluster
Authors: Kanti Guha Ankur 
Published: January 2023

AbstractAlkali metals are generally Lewis acids. On the contrary, Lewis basic character of alkali metals forming donor – acceptor complexes is a very rare phenomenon. In this contribution, I have theoretically designed an anionic cluster MMN3−(M=alkali metals) on the basis of experimentally known reagent, alkali salt of azide ion MN3, which shows unprecedented M:−→M donor‐acceptor interaction. To the best of author's knowledge, the characterization of such donor‐acceptor interaction among alkali metals is unprecedented. Formation of the 2c–2e donor‐acceptor bonds have been confirmed by quantum theory of atoms in molecules and electron localization function analyses. The calculated bond dissociation energies are significant suggesting their possible spectroscopic identification.
Discriminative accuracy of the A/T/N scheme to identify cognitive impairment due to Alzheimer's disease
Authors: Pascoal Tharick A. , Leuzy Antoine , Therriault Joseph , Chamoun Mira , Lussier Firoza , Tissot Cecile , Strandberg Olof , Palmqvist Sebastian , Stomrud Erik , Ferreira Pamela C. L. , Ferrari‐Souza João Pedro , Smith Ruben , Benedet Andrea Lessa , Gauthier Serge , Hansson Oskar , Rosa‐Neto Pedro 
Published: January 2023

AbstractIntroductionThe optimal combination of amyloid‐β/tau/neurodegeneration (A/T/N) biomarker profiles for the diagnosis of Alzheimer's disease (AD) dementia is unclear.MethodsWe examined the discriminative accuracy of A/T/N combinations assessed with neuroimaging biomarkers for the differentiation of AD from cognitively unimpaired (CU) elderly and non‐AD neurodegenerative diseases in the TRIAD, BioFINDER‐1 and BioFINDER‐2 cohorts (total n = 832) using area under the receiver operating characteristic curves (AUC).ResultsFor the diagnosis of AD dementia (vs. CU elderly), T biomarkers performed as well as the complete A/T/N system (AUC range: 0.90–0.99). A and T biomarkers in isolation performed as well as the complete A/T/N system in differentiating AD dementia from non‐AD neurodegenerative diseases (AUC range; A biomarker: 0.84–1; T biomarker: 0.83–1).DiscussionIn diagnostic settings, the use of A or T neuroimaging biomarkers alone can reduce patient burden and medical costs compared with using their combination, without significantly compromising accuracy.
Differences in red blood cell mass profiles impact intravascular volume and outcome risk in chronic heart failure
Authors: Miller Wayne L. , Grill Diane E. , Mullan Brian P. 
Published: January 2023

AbstractAimsTo identify different red blood cell mass (RBCM) profiles, separate from haemoglobin concentrations, and their impact on blood volume expansion and clinical outcomes in chronic heart failure.Methods and resultsRBCM was measured at hospital discharge using standardized nuclear medicine indicator‐dilution methodology in patients following diuretic treatment for clinical congestion. Individual RBCM phenotypes were prospectively identified and analysed for heart failure‐related mortality or first rehospitalization over 1 year.Of 132 patients, 42 (32%) demonstrated normal RBCM, 36 (27%) RBCM deficit (true anaemia), and 54 (41%) RBCM excess (erythrocythemia). Dilutional ‘anaemia’ defined by haemoglobin <12 g/dL with normal or an excess in RBCM with plasma volume expansion was identified in 37 (28%) patients. There were 61 composite outcome events, which included 38 deaths (29% of cohort) occurring over the 1 year follow‐up period [14/36 (39%) in RBCM deficit, 12/42 (29%) in normal RBCM, and 12/54 (22%) in RBCM excess subgroups]. By Kaplan–Meier and multivariate analyses, RBCM excess was independently associated with the best event‐free survival while RBCM deficit (true anaemia) the poorest outcomes; both compared with normal RBCM (P < 0.001). Dilutional ‘anaemia’ demonstrated a lower risk compared with true anaemia (P = 0.03).ConclusionsMarkedly different RBCM profiles are identifiable among comparably compensated heart failure patients, and this variability carries significant implications for post‐hospital outcomes. Novel to this analysis and in contrast to RBCM deficit is the independent association of RBCM excess with better event‐free survival compared with normal RBCM. The distinction of RBCM profiles to guide risk stratification and individualized patient management strategies warrants further study.
Decrease of air pollution during lockdown in Tuscany (Italy): An effect on sperm DNA fragmentation?
Authors: Calamai Costanza , Ammar Oumaima , Marchiani Sara , Degl'Innocenti Selene , Fino Marisa , Righi Lorenzo , Dabizzi Sara , Maggi Mario , Baldi Elisabetta , Vignozzi Linda , Muratori Monica 
Published: January 2023

AbstractIn March 2020, the Italian government imposed a national lockdown which was almost completely removed in June 2020. Due to the abrupt stop of human activities, emissions of air pollutants decreased. Air pollution is an environmental risk factor for noncommunicable disease and mortality. Emerging evidence also suggests a role in male infertility. In this study, we compared sperm DNA fragmentation (sDF) levels and conventional semen parameters between subjects undergoing sDF determination and routine semen analysis in a single Italian centre, during about 6 months before (N = 119) and after lockdown (N = 105). After lockdown, we found an improvement of sperm progressive motility (48.00[38.50–58.00]% vs. 42.00[33.00–53.00]%) and sDF levels (as total: 24.79[18.33–33.97]% vs. 35.02[25.04–45.73]%, p < .001; brighter: 14.02[10.69–17.93]% vs 18.54[13.58–25.82]%, p < .001 and dimmer sDF: 9.24[5.64–15.78]% vs. 12.24[8.08–19.10]%, p < .01), mirrored by a decrease of leukocyte semen concentration (p < .01). The improvement of sperm motility and DNA quality was maintained after adjusting for leukocyte concentration and several conditions known to affect sperm motility and/or sDF levels. With a significant decrease in air pollution observed in Tuscany during and after lockdown, associated improvement in sperm motility and DNA quality in patients referred to the infertility clinic is suggestive of the potential role of air pollution in male infertility.
A high‐order stabilized solver for the volume averaged Navier‐Stokes equations
Authors: Geitani Toni El , Golshan Shahab , Blais Bruno 
Published: January 2023

AbstractThe volume‐averaged Navier‐Stokes equations are used to study fluid flow in the presence of fixed or moving solids such as packed or fluidized beds. We develop a high‐order finite element solver using both forms A and B of these equations. We introduce tailored stabilization techniques to prevent oscillations in regions of sharp gradients, to relax the Ladyzhenskaya–Babuska–Brezzi inf‐sup condition, and to enhance the local mass conservation and the robustness of the formulation. We calculate the void fraction using the particle centroid method. Using different drag models, we calculate the drag force exerted by the solids on the fluid. We implement the method of manufactured solution to verify our solver. We demonstrate that the model preserves the order of convergence of the underlying finite element discretization. Finally, we simulate gas flow through a randomly packed bed and study the pressure drop and mass conservation properties to validate our model.
Stability effect of multidimensional velocity components in numerical flux SLAU
Authors: Furusawa Yoshikatsu , Kitamura Keiichi 
Published: January 2023

AbstractIn computational fluid dynamics of compressible fluid flow, the simple low‐dissipation advection upstream (SLAU) scheme formulated with multidimensional velocity components (normal and parallel to a cell interface) is a widely employed all‐speed scheme. As a variant of SLAU, the mSLAU scheme, which adopts only a velocity component normal to the cell interface instead of multidimensional velocity components, is used for rotorcraft calculations. However, although mSLAU has been claimed to be empirically stable, it has been pointed out that using only the cell‐interface‐normal velocity component instead of the multidimensional velocity components causes numerical instability. Therefore, to clarify the roles of the multidimensional velocity components for computational stability, we solved some benchmark problems associated with using SLAU or mSLAU. We discovered that the multidimensional velocity components contributed to stability against poor‐quality grids by isotropically producing enough amount of numerical dissipation, especially in low‐subsonic and supersonic flows. Although mSLAU could practically treat moderate Mach number flows (approximately 0.1 < M < 1.0) when coupled with the minmod limiter, using only the cell‐interface‐normal velocity component can deteriorate convergence of calculations and lead to susceptibility in the grid geometry.