bluuebunny/crossref_metadata_2025_split huggingface dataset:
Allylic C(sp3)−C(sp3) Bond Formation Through Pd‐Catalyzed C(sp3)−H Activation of Alkenes and 1,4‐Dienes
Authors: Muzart Jacques 
Published: May 2022

AbstractThis review highlights the allylic C−H alkylation of alkenes (AAH) with nucleophiles under Pd0 or PdII catalysis and achiral or chiral conditions. The η3‐allylpalladium intermediates of these reactions are formed from the cleavage of an allylic hydrogen which becomes a leaving group, like the acetate moiety of allyl acetates during the classical Tsuji‐Trost procedure. Most of these cross‐dehydrogenative‐couplings require quinones as key components; they may play the role of ligand, proton trap and oxidant. Efficient asymmetric allylic C−H alkylations (AAAH’s) have been performed. The diversity of the procedures, their limitation and application in synthesis are underlined as well as the proposed mechanisms with, in some cases, personal comments. The data are grouped according to the reaction conditions.magnified image
Plant‐Mediated Green Synthesis of Magnetic Spinel Ferrite Nanoparticles: A Sustainable Trend in Nanotechnology
Authors: Wani Tasaduk Ahmad , Suresh Gopalakrishnan 
Published: May 2022

AbstractNanotechnology is very important in developing sustainable technologies for the future. Increased demand for metal and metal oxide nanoparticles has led to their large‐scale production using conventional chemical methods with various toxic solvents. These techniques produce poisonous and harsh products that present a biological risk to the environment and have terrible effects on the life of microbes, plants, vertebrates, and invertebrates at different trophic levels. Thus eco‐friendly “green” synthesis methods have become necessary to synthesize nanoparticles using biological entities, such as plants and microorganisms. When compared to other methods, “green” synthesis is safer for human health and the environment. Plants, the main factory for the green synthesis of nanoparticles, have been used extensively for this purpose. This review, focuses on eco‐friendly synthesis to design spinel ferrite nanoparticles, particularly, using extracts from plant products that act not only as precursors but also as reductants and stabilizers during the synthesis process. The outstanding features of these nanoparticles allows for their promising applications in catalysis, lithium‐ion batteries, information storage, magnetic cores, ferrofluids, microwave, and medicine. This important review also highlights noteworthy recent developments related to the green synthesis of plant‐mediated magnetic spinel nanoparticles and their fundamental applications.
Discovery of High‐Performing Metal–Organic Frameworks for On‐Board Methane Storage and Delivery via LNG–ANG Coupling: High‐Throughput Screening, Machine Learning, and Experimental Validation
Authors: Kim Seo‐Yul , Han Seungyun , Lee Seulchan , Kang Jo Hong , Yoon Sunghyun , Park Wanje , Shin Min Woo , Kim Jinyoung , Chung Yongchul G. , Bae Youn‐Sang 
Published: May 2022

AbstractLiquefied natural gas (LNG) gasification coupled with adsorbed natural gas (ANG) charging (LNG–ANG coupling) is an emerging strategy for efficient delivery of natural gas. However, the potential of LNG–ANG to attain the advanced research projects agency‐energy (ARPA‐E) target for onboard methane storage has not been fully investigated. In this work, large‐scale computational screening is performed for 5446 metal–organic frameworks (MOFs), and over 193 MOFs whose methane working capacities exceed the target (315 cm3(STP) cm−3) are identified. Furthermore, structure–performance relationships are realized under the LNG–ANG condition using a machine learning method. Additional molecular dynamics simulations are conducted to investigate the effects of the structural changes during temperature and pressure swings, further narrowing down the materials, and two synthetic targets are identified. The synthesized DUT‐23(Cu) and DUT‐23(Co) show higher working capacities (≈373 cm3(STP) cm−3) than that of any other porous material under ANG or LNG–ANG conditions, and excellent stability during cyclic LNG–ANG operation.
Sustainable Electric Vehicle Batteries for a Sustainable World: Perspectives on Battery Cathodes, Environment, Supply Chain, Manufacturing, Life Cycle, and Policy
Authors: Yang Zhijie , Huang Haibo , Lin Feng 
Published: May 2022

AbstractLi‐ion batteries (LIBs) can reduce carbon emissions by powering electric vehicles (EVs) and promoting renewable energy development with grid‐scale energy storage. However, LIB production and electricity generation still heavily rely on fossil fuels at present, resulting in major environmental concerns. Are LIBs as environmentally friendly and sustainable as expected at the current stage? In the past 5 years, a skyrocketing growth of the EV market has been witnessed. LIBs have garnered huge attention from academia, industry, government, non‐governmental organizations, investors, and the general public. Tremendous volumes of LIBs are already implemented in EVs today, with a continuing, exponential growth expected for the years to come. When LIBs reach their end‐of‐life in the next decades, what technologies can be in place to enable second‐life or recycling of batteries? Herein, life cycle assessment studies are examined to evaluate the environmental impact of LIBs, and EVs are compared with internal combustion engine vehicles regarding environmental sustainability. To provide a holistic view of the LIB development, this Perspective provides insights into materials development, manufacturing, recycling, legislation and policy, and beyond. Last but not least, the future development of LIBs and charging infrastructures in light of emerging technologies are envisioned.
Ultrahigh Electron Thermal Conductivity in T‐Graphene, Biphenylene, and Net‐Graphene
Authors: Tong Zhen , Pecchia Alessandro , Yam ChiYung , Dumitrică Traian , Frauenheim Thomas 
Published: May 2022

AbstractAlthough isolated nonhexagonal carbon rings in graphene are associated with strain relaxation and curvature, dense and ordered arrangements of four‐, five‐, and eight‐membered rings with strained carbon–carbon bonds can tile 2D planar layers. Using the Boltzmann transport equation formalism in combination with density functional theory calculations, how the presence of nonhexagonal rings impacts the thermal conductivity of three 2D carbon allotropes: T‐graphene (four and eight rings), biphenylene (four, six, and eight rings), and net‐graphene (four, six, and eight rings), is investigated. The phonon thermal conductivity (κph), which captures three‐phonon, four‐phonon, and phonon–electron interactions, is significantly lowered with respect to pristine graphene. In compensation, the electron thermal conductivity (κe), which captures electron–phonon interactions, is enhanced to record high values, such that the room‐temperature total thermal conductivity κtotal = κph + κe approaches the values of pristine graphene. 2D carbon allotropes could be of interest for applications requiring thermal energy transfer by a combination of diffusion of electrons and phonon vibrations.
Optimal therapy design with tumor microenvironment normalization
Authors: Wang Chenyu , Degnan‐Morgenstern Samuel , Martin John D. , Stuber Matthew D. 
Published: May 2022

AbstractTumor microenvironment (TME) normalization improves efficacy by increasing anticancer nanocarrier delivery by restoring transvascular pressure gradients that induce convection. However, transport depends on TME biophysics, normalization dose, and nanocarrier size. With increased understanding, we could use computation to personalize normalization amount and nanocarrier size. Here, we use deterministic global dynamic optimization with novel bounding routines to validate mechanistic models against in vivo data. We find that normalization with dexamethasone increases the maximum transvascular convection rate of nanocarriers by 48‐fold, the tumor volume fraction with convection by 61%, and the total amount of convection by 360%. Nonetheless, 22% of the tumor still lacks convection. These findings underscore both the effectiveness and limits of normalization. Using artificial neural network surrogate modeling, we demonstrate the feasibility of rapidly determining the dexamethasone dose and nanocarrier size to maximize accumulation. Thus, this digital testbed quantifies transport and performs therapy design.
Enantioselective Synthesis of Chiral 3‐Alkynyl‐3‐Hydroxyindolin‐ 2‐Ones by Zn/bis(Sulfonamide)‐Diamine Catalyzed Asymmetric Addition of Alkynes to Isatins
Authors: Qu Hongmin , Chen Yu , Ceng Xiangling , Tang Pei , Wang Huijing , Chen Fener 
Published: May 2022

AbstractThe catalytic enantioselective alkynylation of isatins, catalyzed by a Zn(OCOCF3)2/chiral bis(sulfonamide)‐diamine (BSDA) catalyst under mild condition, has been developed. The desired chiral 3‐alkynyl‐3‐hydroxy‐2‐oxindoles were obtained in moderate to excellent yields (up to 96%) and good to excellent enantioselectivites (up to 97% ee). The reaction is broad in scope with respect to aryl‐substituted terminal alkynes and substituted isatins.
Pickering Emulsion Catalysis: Interfacial Chemistry, Catalyst Design, Challenges, and Perspectives
Authors: Ni Lin , Yu Chang , Wei Qianbing , Liu Dongming , Qiu Jieshan 
Published: May 2022

AbstractPickering emulsions are particle‐stabilized surfactant‐free dispersions composed of two immiscible liquid phases, and emerge as attractive catalysis platform to surpass traditional technique barrier in some cases. In this review, we have comprehensively summarized the development and the catalysis applications of Pickering emulsions since the pioneering work in 2010. The explicit mechanism for Pickering emulsions will be initially discussed and clarified. Then, summarization is given to the design strategy of amphiphilic emulsion catalysts in two categories of intrinsic and extrinsic amphiphilicity. The progress of the unconventional catalytic reactions in Pickering emulsion is further described, especially for the polarity/solubility difference‐driven phase segregation, “smart” emulsion reaction system, continuous flow catalysis, and Pickering interfacial biocatalysis. Challenges and future trends for the development of Pickering emulsion catalysis are finally outlined.
Stereocontrolled Synthesis of Fluorinated Isochromans via Iodine(I)/Iodine(III) Catalysis
Authors: Häfliger Joel , Sokolova Olga O. , Lenz Madina , Daniliuc Constantin G. , Gilmour Ryan 
Published: May 2022

AbstractThe success of saturated, fluorinated heterocycles in contemporary drug discovery provides a stimulus for creative endeavor in main group catalysis. Motivated by the ubiquity of isochromans across the bioactive small molecule spectrum, the prominence of the anomeric effect in regulating conformation, and the metabolic lability of the benzylic position, iodine(I)/iodine(III) catalysis has been leveraged for the stereocontrolled generation of selectively fluorinated analogs. To augment the current arsenal of fluorocyclization reactions involving carboxylic acid derivatives, the reaction of readily accessible 2‐vinyl benzaldehydes is disclosed (up to >95 : 05 d.r. and 97 : 03 e.r.). Key stereoelectronic interactions manifest themselves in the X‐ray crystal structures of the products, thereby validating the [CH2‐CHF] fragment as a stereoelectronic mimic of the [O‐CH(OR)] acetal motif.
Advances in characterization of triacylglycerols: Expansion of materials used in Joint JOCS/AOCS Official Method Ch 3a‐19
Authors: Mochizuki Mamiko , Watanabe Yomi , Taha Ameer Y. , Masuyama Araki 
Published: May 2022

AbstractJoint JOCS/AOCS Official Method Ch 3a‐19 was an improvement over triacylglycerol characterization methods based on hydrolysis with pancreatic lipase. In this study we developed three further improvements and applied them to the analysis of the fatty acid distribution in triacylglycerols from trout. First, the liquid–liquid extraction of lipid by chloroform and methanol from fish meat was replaced with a single extraction step using pre‐packed columns. This allowed the extraction time to be reduced from 30 min/sample to 5 min/sample with ca. 10% higher yield using half the volume of the extraction solvent, chloroform. Both extraction methods gave similar FA composition of the extracted oil. Furthermore, an alternative CALB lipase and an alternative normal‐phase solid phase extraction column were shown to reliably duplicate the results obtained with the Official Method Ch 3a‐19. In addition, the SPE columns could be used at least 5 times without loss of separation and without carryover.
Water, saltwater, and concrete leachate solution effects on durability of ambient‐temperature cure carbon‐epoxy composites
Authors: Karbhari Vistasp M. , Hassanpour Behnaz 
Published: May 2022

AbstractWet layup carbon epoxy composites are extensively used for rehabilitation of civil infrastructure. This study focuses on foundation building for understanding durability of such materials through long‐term (up to 5 years) hygrothermal aging in water, saltwater, and concrete leachate, solutions. Moisture uptake is described using a two‐stage model incorporating diffusion and relaxation/deterioration parameters with the concrete leachate solution showing further transitions and the highest value of the relaxation/deteriorative coefficient. Glass transition temperatures decreased with an increase in moisture content reaching an initial minimum followed by fluctuations and small increases with an increase in the time of exposure. Immersion in concrete leachate results in the largest decrease. Tan δ height shows an initial decrease followed by an increase and then a continued decrease indicative of an initial plasticization and post‐cure followed by deterioration at the resin and fiber–matrix levels. Although short‐term response in mechanical properties shows differences with immersion in water having the least effect, solution type had very little difference on residual mechanical characteristics at the end of the 60‐month period of immersion. The results emphasize the need for further understanding of competing effects in ambient‐cured composites and of the need for longer term testing for determination of design factors.
Parameter learning for the nonlinear system described by Hammerstein model with output disturbance
Authors: Li Feng , Zhu Xinjian , He Naibao , Gu Ya 
Published: May 2022

AbstractA novel parameter learning scheme using multi‐signal processing is developed that aims at estimating parameters of the Hammerstein nonlinear model with output disturbance in this paper. The Hammerstein nonlinear model consists of a static nonlinear block and a dynamic linear block, and the multi‐signals are devised to estimate separately the nonlinear block parameters and the linear block parameters; the parameter estimation procedure is greatly simplified. Firstly, in view of the input–output data of separable signals, the linear block parameters are computed through correlation analysis method, thereby the influence of output noise is effectively handled. In addition, model error probability density function technology is employed to estimate the nonlinear block parameters with the help of measurable input–output data of random signals, which not only controls the space state distribution of model error but also makes error distribution tends to normal distribution. The simulation results demonstrate that the developed approach obtains high learning accuracy and small modeling error,  which verifies the effectiveness of the developed approach.
Robust three‐parameter fractional‐order proportional integral derivative controller synthesis for permanent magnet synchronous motor speed servo system
Authors: Chen Pengchong , Zheng Weijia , Luo Ying , Peng Yibing , Chen Yangquan 
Published: May 2022

AbstractThis paper proposes a three‐parameter fractional‐order PID (TPFOPID) controller synthesis for the PMSM speed servo system. This TPFOPID contains complete proportional/integral/differential elements but with only three parameters to tune. A systematic design scheme of this TPFOPID to satisfy a flat phase constraint and two specifications, that is, gain crossover frequency ( ) and phase margin ( ), is presented for the PMSM speed servo system. Furthermore, the entire achievable region of and can be collected following the scheme. With this region, one can choose feasible combination specifications of and before the controller design. To show the effectiveness of the TPFOPID controller, the achievable region of specifications is compared with the fractional‐order PI (FOPI) also with three parameters. Simulation illustration and experimental verifications using the TPFOPID for the PMSM speed servo system are presented and compared with those using FOPI controller, IOPI controller, and IOPID controller to demonstrate the advantages of the designed TPFOPID controller, and also compared with FOPID based on differential evolution (DE) algorithm to present comparable control performance.
Controller tuning with Bayesian optimization and its acceleration: Concept and experimental validation
Authors: Fujimoto Yusuke , Sato Hiroki , Nagahara Masaaki 
Published: May 2022

AbstractThis work discusses a data‐driven approach to controller parameter tuning based on Bayesian optimization. In particular, we propose to design the prior mean function based on a model of the plant. By encoding the information on the model, the optimization needs a much fewer iterations than standard approaches. The effectiveness of the proposed method is demonstrated with a practical experiment.
HIVEP3 cooperates with ferroptosis gene signatures to confer adverse prognosis in acute myeloid leukemia
Authors: Zhang Xiaoning , Zhang Xiaoyu , Liu Kuo , Li Wenwen , Wang Jiazheng , Liu Peng , Ma Wanshan 
Published: May 2022

AbstractBackgroundThe human immunodeficiency virus type I enhancer binding protein (HIVEP) family, which contains zinc finger and acid‐rich (ZAS) domains, has been demonstrated to be implicated in vital biological processes, such as cell survival, tumor necrosis factor (TNF) signaling, and tumor formation. However, its expression patterns, prognostic relevance, and functional implications in acute myeloid leukemia (AML) remain elusive.MethodsWe inspected HIVEP mRNA expression levels in datasets from The Cancer Genome Atlas (TCGA) and GSE24006. Survival analyses were orchestrated using the web‐based bioinformatics platforms and R studio in two AML cohorts. Prognostic value and capacity were assessed by Cox regression analyses. Association of HIVEP3 expression levels with clinical characteristics were analyzed with R and UALCAN. Subsequentially, functional enrichment analyses were operated to interpret HIVEP3 co‐expressed gene clusters. A prognostic gene signature was created by the least absolute shrinkage and selection operator (LASSO) regression algorithm. Moreover, bone marrow aspirate smears of AML patients were stained for HIVEP3 by immunohistochemistry (IHC). HIVEP3 expression was examined by qRT‐PCR in leukemia cell lines treated with ferroptosis compounds in vitro.ResultsAugmented transcriptional levels of HIVEP2 and 3 were noted in AML patients (p<0.001). HIVEP3 not only could confer adverse prognosis independently in AML patients, but also was associated with AML subtypes, age, cytogenetic risk, and disease‐related molecules. Co‐expressed gene clusters of HIVEP3 were enriched in functional pathways related to AML leukemogenesis, such as ribosome, metabolism, and calcium signaling. Combined with multiple tumorigenesis signaling pathways, we proposed an integrated LASSO model with HIVEP3 and ferroptosis regulators AIFM2 and LPCAT3, to predict the outcome for AML patients. Furthernore, altered HIVEP3 expression at the mRNA or protein level was confirmed in sorted leukemia cells and blast cells in bone marrow tissues. In vitro experiments authenticated the involvement of HIVEP3 in ferroptosis signaling pathways.ConclusionsOur findings suggest that HIVEP3 is a de novo independent prognostic indicator, and the crosstalk between HIVEP3 and ferroptosis signaling pathways may inspire a specific perspective on the oncological network of AML.
Volumetric reduction of brain metastases after stereotactic radiotherapy: Prognostic factors and effect on local control
Authors: Kanayama Naoyuki , Ikawa Toshiki , Ohira Shingo , Hirata Takero , Morimoto Masahiro , Ogawa Kazuhiko , Teshima Teruki , Konishi Koji 
Published: May 2022

AbstractBackground and PurposeFew reports include volumetric measurements as endpoints after stereotactic radiotherapy (SRT) despite the importance of such measurements. This study aimed to (1) investigate the impact of the volumetric response (specifically, an over 65% and over 90% volume reduction in brain metastases) at 6 months post‐SRT on local control and (2) identify the predictive factors for a volumetric response of over 65% and over 90%.Materials and MethodsThis study included 250 unresected brain metastases (>0.3 cc) treated with SRT. Doses were stratified according to the biological effective dose (BED). The BED was calculated using four models: linear‐quadratic (LQ): α/β = 10; LQ: α/β = 20; LQ cubic: α/β = 12; and LQ linear: α/β = 10. The median prescription dose was 30 Gy/3 fractions (BED20, 45). The median follow‐up time after SRT was 18.6 months (range, 6.4–81.8 months).ResultsIn the multivariate analysis, over 65% volume reduction and over 90% volume reduction were prognostic factors for local control (hazard ratio: 2.370, p = 0.011 and hazard ratio: 3.161, p = 0.014, respectively). A dose of 80% of the gross tumor volume (GTV) D80 > BED20 58 was a predictive factor for over 65% and over 90% volume reductions (odds ratio: 1.975, p = 0.023; odds ratio: 3.204, p < 0.001, respectively).ConclusionRobust volume reduction of brain metastases at 6 months post‐SRT can predict local control. GTV D80 in the LQ model: α/β = 20 may be warranted for good volume reduction.
Clown doctors and forensic paediatricians enhance the patient experience at the Royal Children's Hospital in Melbourne
Authors: Brys Trusha , Symons David , Dean Joanne , Smith Jennifer Anne Sutherland 
Published: May 2022

AbstractWe evaluated medical clown intervention in suspected child abuse and neglect assessments. A mixed method methodology (Likert scales and free text responses) was used to measure the impact of clown doctors at 49 forensic consultations. Of 35 responding children, 43 per cent reported neutral or negative feelings on arrival whereas 97 per cent reported either positive feelings or sadness at leaving the clown doctor. Children’s memories of the consultation were of interacting with clown doctors, not their physical examinations. Of 45 responding caregivers, 95 per cent deemed the clown doctor developed a positive connection with the child, 96 per cent felt their child enjoyed their visit and 93 per cent felt the clown doctor improved their own experience. Both caregivers (94%) and paediatricians (92%) valued an opportunity to talk privately while children engaged with clown doctors. All 45 responding caregivers felt their child would be willing to return to hospital in the future. In all 49 cases, paediatricians reported that clown doctors increased children’s willingness to cooperate with the medical assessment. Forensic paediatricians (92%) reported that clown doctors actively supported the medical evaluation process while 100 per cent reported no harm from the intervention. We concluded that clown doctors positively impact the patient, carer and paediatricians experience during children’s forensic medical assessments.
BIAN‐Aluminium‐Catalysed Imine Hydrogenation
Authors: Pölker Jennifer , Schaarschmidt Dieter , Bernauer Josef , Villa Matteo , Jacobi von Wangelin Axel 
Published: May 2022

AbstractHydrogenations have been dominated by transition metal catalysis, while the use of more abundant and inexpensive main group metal catalysts has remained a great challenge. Here, a bimetallic Li/Al dihydride was successfully applied to catalytic hydrogenations of imines. The catalyst [(DippBIAN)Al(μ‐H)2Li(OEt2)2] was easily prepared from the 2e‐reduced BIAN derivative and LiAlH4.