bluuebunny/crossref_metadata_2025_split huggingface dataset:
Divergent Coupling of 2‐Aryl‐1,3‐Indandiones with Alkenes Enabled by Iodine Catalyst
Authors: Shi Yue , Wang Di , Sun Ruzhong , Chen Xin , Xu Xuefeng , Xie Haiquan , Zhang Xu 
Published: February 2023

AbstractHerein, we report an iodine‐catalyzed protocol for cross‐coupling of 2‐aryl‐1,3‐indandiones with alkenes. Divergent reactivity was achieved in the transformation by varying additives and solvents, thus allowing selective access to tertiary alkylated ketones and alkenes. The present approach features commercially available starting materials, broad substrate scope, general functional‐group (including halogen, ester, nitrile, thioether) tolerance. Furthermore, we proposed plausible pathways to rationalize the divergent selectivity through preliminary mechanism study.magnified image
Ex Vivo Liver Machine Perfusion Reduces the Length of Hospital Stay in Recipients of Allografts from Elderly Donors: A Systematic Review
Authors: Boerger Leonard , Hillebrandt Karl H. , Czigany Zoltan , Lurje Georg , Gassner Joseph M.G.V. , Patel Madhukar S. , Pratschke Johann , Sauer Igor M. , Raschzok Nathanael , Moosburner Simon 
Published: February 2023

AbstractLiver transplantation is the only curative treatment option for end‐stage liver disease. As the population ages worldwide, utilization of grafts from elderly donors has the potential to expand the donor pool. Unfortunately, these allografts are associated with increased rates of primary non‐function and early allograft dysfunction. Ex vivo machine perfusion (MP) may be a promising technique to overcome these challenges. A systematic review of PubMed, Web of Science, and ClinicalTrials.gov is presented for trials comparing MP to static cold storage for elderly human allografts (≥70 years) (PROSPERO ID352930). Six clinical trials (n = 1189 patients) are included. Hypothermic oxygenated perfusion (HOPE) is used in five trials and normothermic MP (NMP) in one trial. There is limited evidence that machine perfusion has the potential to mitigate the risks associated with older livers and shorten the length of hospital stay after transplantation. There is no evidence to support superiority of one perfusion type or differences in patient and graft survival. Risk of bias is high, and level of evidence is limited regarding MP of allografts form elderly donors. Nevertheless, MP is associated with length of hospital stay. Further research is warranted to analyze MP for allografts of older age.
National winter oilseeds review for potential in the US Mid‐South: Pennycress, Canola, and Camelina
Authors: Keadle Stefanie B. , Sykes Virginia R. , Sams Carl E. , Yin Xinhua , Larson James A. , Grant Jerome F. 
Published: February 2023

AbstractWinter oilseeds are cool season Brassica crops currently being grown in the upper Midwest and North‐West of the United States. They have the potential to function as dual crops when grown in rotation with corn, soybean, and small grains. They provide many of the benefits of typical cover crops over winter, with the added benefit of extra revenue to growers who sell the seeds for uses such as biofuel, industrial products, human consumption, or animal feed. This review gathers current agronomic and industrial use information about canola (Brassica napus L.), camelina [Camelina sativa (L.) Crantz], and pennycress (Thlaspi arvense L.). Currently, most research involving these crops is specific to the Midwest. This review also poses questions regarding how these crops could be adapted to grow in the Mid‐South, with further research being necessary in several areas before promoting adoption in the region.
A Compartmentalized Nanoreactor Formed by Interfacial Hydrogelation for Cascade Enzyme Catalytic Therapy
Authors: He Xingyue , Wu Qing , Hou Chen , Hu Min , Wang Qigang , Wang Xia 
Published: February 2023

AbstractSome cellular enzymatic pathways are located within a single organelle, while most others involve enzymes that are located within multiple compartmentalized cellular organelles to realize the efficient multi‐step enzymatic process. Herein, bioinspired by enzyme‐mediated biosynthesis and biochemical defense, a compartmented nanoreactor (Burr‐NCs@GlSOD) was constructed through a self‐confined catalysis strategy with burr defect‐engineered molybdenum disulfide/Prussian blue analogues (MoS2/PBA) and an interfacial diffusion‐controlled hydrogel network. The specific catalytic mechanism of the laccase‐like superactivity induced hydrogelation and cascade enzyme catalytic therapy were explored. The confined hydrogelation strategy introduces a versatile means for nanointerface functionalization and provides insight into biological construction of simulated enzymes with comparable activity and also the specificity to natural enzymes.
Heterostructures with Built‐in Electric Fields for Long‐lasting Chemodynamic Therapy
Authors: Zhang Huilin , Chen Yang , Hua Wei , Gu Wenjun , Zhuang Hongjun , Li Huiyan , Jiang Xingwu , Mao Ying , Liu Yanyan , Jin Dayong , Bu Wenbo 
Published: February 2023

AbstractSustained signal activation by hydroxyl radicals (⋅OH) has great significance, especially for tumor treatment, but remains challenging. Here, a built‐in electric field (BIEF)‐driven strategy was proposed for sustainable generation of ⋅OH, thereby achieving long‐lasting chemodynamic therapy (LCDT). As a proof of concept, a novel Janus‐like Fe@Fe3O4−Cu2O heterogeneous catalyst was designed and synthesized, in which the BIEF induced the transfer of electrons in the Fe core to the surface, reducing ≡Cu2+ to ≡Cu+, thus achieving continuous Fenton‐like reactions and ⋅OH release for over 18 h, which is approximately 12 times longer than that of Fe3O4−Cu2O and 72 times longer than that of Cu2O nanoparticles. In vitro and in vivo antitumor results indicated that sustained ⋅OH levels led to persistent extracellular regulated protein kinases (ERK) signal activation and irreparable oxidative damage to tumor cells, which promoted irreversible tumor apoptosis. Importantly, this strategy provides ideas for developing long‐acting nanoplatforms for various applications.
Post‐synthetic Chemical Fixation of Fe2+ in MOF to Prepare Fe2N‐Embedded N‐Doped Graphene Nanoribbons for Superior Oxygen Reduction Reaction
Authors: Xu Wenli , Yang Limeng , Li Liangjun , Shao Junwei , Liu Tao , Xing Tao , Wang Muzhou , Li Zhi , Wu Mingbo 
Published: February 2023

AbstractThe construction of efficient non‐precious metal electrocatalysts for oxygen reduction reaction (ORR) with controlled structures and active sites is of fundamental importance for the wide utilization of hydrogen fuel cells. Herein, we report a controllable chemical fixation strategy that enables the simultaneous optimization in both of local and external structure of the Fe−N−C catalyst. The post‐synthetic single‐atomic chemical fixation of Fe2+ ions in coordinated‐free bi‐pyridine sites combined with the carbonation afford a Fe2N‐embedded N‐doped graphene nanoribbon (Fe2N/NGNR) with dispersing Fe2N nanoparticles embedded in NGNR. When used as ORR electrocatalyst, Fe2N/NGNR exhibits a half‐wave potential of 0.87 V and 0.79 V vs. RHE in alkaline and acid medium, respectively, comparable to commercial Pt/C (20 wt%) catalysts. The prominent ORR activity of Fe2N/NGNR is verified an H2‐O2 fuel cell which displayed a peak power density of 307.7 mW/cm2 when using the Fe2N/NGNR as the catalyst in the cathode electrode.
An integrative analytical approach designed for feasible tranexamic acid assay using o‐phthalaldehyde as a fluorogenic probe: applications to tablets, ampoules, and urine
Authors: El Hamd Mohamed A. , Alshehri Sultan , Abu‐hassan Ahmed A. 
Published: February 2023

AbstractAntifibrinolytic tranexamic acid (TRX) suppresses plasminogen activation to plasmin in a competitive way. TRX is approved for the management of heavy menstrual periods, hereditary angioedema, hemophilia, postpartum hemorrhage, surgery, tooth extraction, and severe blood loss after acute trauma. Here, the practical use of an isoindole derivative was established for a novel, easy‐to‐use, and affordable TRX assay. In the presence of a molecule containing a sulfhydryl group (2‐mercaptoethanol) 0.02% v/v, the primary amine moiety in TRX allows its combination with o‐phthalaldehyde to produce a luminous product. Excitation (338.8 nm) and emission (433.9 nm) wavelengths were used to monitor the isoindole fluorophore yield, and each operational variable was carefully examined and adjusted. The calibration graph was constructed with fluorescence intensity versus TRX concentration, excellent linearity was observed at concentrations between 40 and 950 ng/ml, and limit of detection and limit of quantitation were 41.3 and 13.6 ng/ml, respectively. The International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use guidelines were used to validate the method. The developed method for TRX assay in various dosage forms and urine was successfully implemented and was shown to be an effective, simple, and quick replacement for the TRX assay in clinical trials and quality control.
Cryotherapy for partial gland ablation of prostate cancer: Oncologic and safety outcomes
Authors: Aker Mamdouh N. , Brisbane Wayne G. , Kwan Lorna , Gonzalez Samantha , Priester Alan M. , Kinnaird Adam , Delfin Merdie K. , Felker Ely , Sisk Anthony E. , Kuppermann David , Marks Leonard S. 
Published: February 2023

AbstractBackgroundPartial gland ablation (PGA) is a new option for treatment of prostate cancer (PCa). Cryotherapy, an early method of PGA, has had favorable evaluations, but few studies have employed a strict protocol using biopsy endpoints in men with clinically significant prostate cancer (csPCa).Methods143 men with unilateral csPCa were enrolled in a prospective, observational trial of outpatient PGA‐cryotherapy. Treatment was a 2‐cycle freeze of the affected prostate part. Participants were evaluated with MRI‐guided biopsy (MRGB) at baseline and at 6 months and 18 months after treatment. Absence of csPCa upon MRGB was the primary endpoint; quality‐of‐life at baseline and at 6 months after treatment was assessed by EPIC‐CP questionnaires in the domains of urinary and sexual function.ResultsOf the 143 participants, 136 (95%) completed MRGB at 6 months after treatment. In 103/136 (76%), the biopsy revealed no csPCa. Of the 103, 71 subsequently had an 18‐month comprehensive biopsy; of the 71 with 18‐month biopsies, 46 (65%) were found to have no csPCa. MRI lesions became undetectable in 96/130 (74%); declines in median serum PSA levels (6.9 to 2.5 ng/mL), PSA density (0.15 to 0.07), and prostate volume (42 to 34cc) were observed (all p < 0.01). Neither lesion disappearance on MRI nor PSA decline correlated with biopsy outcome. Urinary function was affected only slightly and sexual function moderately.ConclusionIn the near to intermediate term, partial gland ablation with cryotherapy was found to be a safe and moderately effective treatment of intermediate‐risk prostate cancer. Eradication of cancer was better determined by MRI‐guided biopsy than by MRI or PSA.
Necrolytic acral erythema associated with hypothyroidism in hepatitis C virus seronegative patient
Authors: Baroudi Ihsan , Alakhras Ola , Alkasem Alaa , Douri Thaer 
Published: February 2023

AbstractNecrolytic acral erythema (NAE) is a rare cutaneous sign of hepatitis C virus (HCV), which generally presents as circumscribed keratotic plaques on the extremities. Many studies reported NAE in the absence of HCV. This case presents a female diagnosed with NAE and hypothyroidism in the absence of HCV infection.
Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh3 Complexes
Authors: Tóth Imre , Tukacs József M. , Mika László T. 
Published: February 2023

Abstractγ‐Valerolactone as a renewable, polar aprotic solvent was evaluated in the selective hydrogenation of carbon‐carbon double bond of chalcones from both catalytic and mechanistic aspects. By using triphenylphosphine‐modified cationic rhodium catalyst systems reasonably high activities (TOFinitial∼1200 h−1) were achieved in the selective hydrogenation of (E)‐chalcone (CHL), as a common model substrate for α,β‐unsaturated ketones, to dihydrochalcone (DHC). Various derivatives of CHL, which were substituted on the styryl phenyl groups also showed exclusive selectivity for the hydrogenation of the C=C double bond. The optimal PPh3/Rh ratio was between 2.5 to 3, but higher ratios were advantageously also tolerated, which is beneficial for the process chemistry. The solvent GVL proved to stable enough under the reaction conditions for waste‐free recycling. Kinetic studies and NMR spectra from the analogous deuteration of chalcone by using the cationic Rh‐PPh3 system clearly show the olefin insertion as the rate‐determining step with definite irreversibility. By investigating the substituent effect on the phenyl ring of the styryl moiety of chalcone, a quasi‐linear correlation was found between the electronic parameters of the para‐substituents and the activity with electron donor groups being favorable for the reaction rate. In summary, an environmentally friendly and feasible method is presented for the production of valuable DHC intermediates in view of their pharmaceutical importance.
Thiophosphinoyl‐Tethered Ylide‐Substituted Heavier Carbenes: Synthesis, Structures and Stabilities
Authors: Jörges Mike , Gauld Richard M. , Steinert Henning , Kelling Leif , Swamy V. S. V. S. N. , Kroll Alexander , Mallick Bert , Gessner Viktoria H. 
Published: February 2023

AbstractThe synthesis and structure analysis of a series of mono and diylide‐substituted tetrylenes of type YEX and Y2E (E=Ge, Sn, Pb; X=Cl or Br) using a thiophosphinoyl‐tethered metallated ylide (Y=Ph2P(S)−C−P(pip)Ph2 with pip=piperidyl) is reported, amongst the first ylide‐substituted plumbylenes. The tetrylenes feature distinct trends in the spectroscopic and structural properties of the ylide ligand with increasing atomic number of the tetrel element. For instance, an increasingly high‐field shifted signal for the thiophosphinoyl group is observed in the 31P{1H} NMR spectrum as a consequence of the increasing polarity of the element‐carbon bond, which likewise results in a shortening of the ylidic C−P bond in the solid‐state structure. The diylidyltetrylenes are unstable towards transylidation forming the mono(ylide)tetrylenes when treated with the tetrel dihalides according to the stability trend: Y2Pb<Y2Sn<Y2Ge<YPbBr<YSnCl<YGeCl. Starting from the monoylide‐substituted chlorotertrylenes the first unsymmetrical diylidyltetrylenes of type YEY’ can be accessed, whose solid‐state structures revealed that not the C−E but the S−E bond to the thiophosphinoyl group is most affected by the second ylide substituent.
Mechanistic Insights into Enhanced Hydrogen Evolution of CrOx/Rh Nanoparticles for Photocatalytic Water Splitting
Authors: Higashi Tomohiro , Seki Kazuhiko , Sasaki Yutaka , Pihosh Yuriy , Nandal Vikas , Nakabayashi Mamiko , Shibata Naoya , Domen Kazunari 
Published: February 2023

AbstractThe hydrogen evolution reaction (HER) of Rh nanoparticles (RhNP) coated with an ultrathin layer of Cr‐oxides (CrOx) was investigated as a model electrode for the Cr2O3/Rh‐metal core‐shell‐type cocatalyst system for photocatalytic water splitting. The CrOx layer was electrodeposited over RhNP on a transparent conductive fluorine‐doped tin oxide (FTO) substrate. The CrOx layer on RhNP facilitates the electron transfer process at the CrOx/RhNP interface, leading to the increased current density for the HER. Impedance spectroscopic analysis revealed that the CrOx layer transferred protons via the hopping mechanism to the RhNP surface for HER. In addition, CrOx restricted electron transfer from the FTO to the electrolyte and/or RhNP and suppressed the backward reaction by limiting oxygen migration. This study clarifies the crucial role of the ultrathin CrOx layer on nanoparticulate cocatalysts and provides a cocatalyst design strategy for realizing efficient photocatalytic water splitting.
Biopolymer‐Based Nanocomposites for Removal of Cr(VI) from Aqueous Systems: A Review
Authors: More Ramdev , Shukla Shatakshi , Garg Shashank , Singh Shalini , Shah Maulin P. 
Published: February 2023

AbstractHexavalent chromium Cr(VI) has emerged as a contaminant of prime concern for the environmentalists because of its improper disposal by tannery, dye, and electroplating industries. Adsorption is the most exploited method for its removal from industrial wastewater because of its high removal efficiency even at low Cr(VI) concentration, minimal sludge, and ease of regeneration. In recent years, several adsorbents of biological origin such as plants, algae, fungi, and bacteria have been explored for Cr(VI) remediation. This review comprehends the recent studies involving usage of biopolymer‐based nano‐composites with respect to its adsorption mechanisms, adsorption capacities, isotherms, and kinetics. The conventional abiotic and biotic techniques for removal of Cr(VI) are also discussed with a comparative insight of their adsorption capacity and removal efficiency. Nano‐biocomposites integrate the functional properties of both nanoparticles and biopolymers, which make them efficient biosorbents. Nano‐biocomposites offer a large surface area, reduced particle loss, minimal particle agglomeration on the surface, and high stability. Common kinetic models among the nano‐biocomposites, and various equilibrium models are also analyzed to understand the mode of adsorption and associated factors. These materials are mostly found to follow monolayer adsorption with ion exchange, electrostatic interaction, and surface complexation as major players in the process.
Optimized U‐Net convolutional neural network based breast cancer prediction for accuracy increment in big data
Authors: Kirola Madhu , Memoria Minakshi , Dumka Ankur 
Published: February 2023

SummaryBig data is data collected with huge dimensions and continuous exponential growth over time. In recent years, big data in health care has been commonly used to predict diseases. Breast cancer is one of the most common diseases and the secondary cause of death among women. Early diagnosis of breast cancer can prevent the risk of death. Few types of research have been done on breast cancer prediction on big data. However, the traditional prediction models have less efficient in terms of accuracy and error rate. The Optimized U‐Net Convolutional neural network (OU‐NetCNN) model is proposed in this paper to overcome these challenges. Hadoop is the storage system generated to store the datasets samples for big data. The data samples from two datasets, namely BreakHis and Kaggle (Breast Histopathology Images), are preserved in this storage system. The BreakHis data are considered for further processes like pre‐processing, segmentation, feature extraction, feature selection, and classification from the stored data samples. The noise is removed from the histopathological breast images in pre‐processing using the adaptive fast peer‐group filtering (AFPGF) approach. Then the morphological operations such as erosion and dilation are used to eradicate unwanted portions and the quality of the image is enhanced using the improved balance contrast enhancement method (IBCE). Next, edges of breast images are detected using an adaptive artificial ecosystem optimization (AAEO) algorithm‐based edge detection approach in the segmentation process. The features are extracted using the Spatial Gray Level Dependence Matrix (SGLDM) and the optimal features are selected by the modified selfish herd optimization (MSHO) algorithm. Finally, the selected features are fed into the proposed OU‐NetCNN model to classify the histopathology images as benign and malignant images. This hybridization minimizes the error rate, computational complexity and over fitting issues. The simulation analysis is performed in the PYTHON tool. Two datasets, namely BreakHis and Kaggle (Breast Histopathology Images), are considered. Some of the measures such as precision, sensitivity, accuracy and F‐measure are considered to evaluate the performance of the proposed model and compared with existing approaches.
Hydrophobization of a TIP60 Protein Nanocage for the Encapsulation of Hydrophobic Compounds
Authors: Yamashita Maika , Kawakami Norifumi , Miyamoto Kenji 
Published: February 2023

AbstractEncapsulation of hydrophobic molecules in protein‐based nanocages is a promising approach for dispersing these molecules in water. Here, we report a chemical modification approach to produce a protein nanocage with a hydrophobic interior surface based on our previously developed nanocage, TIP60. The large pores of TIP60 act as tunnels for small molecules, allowing modification of the interior surface by hydrophobic compounds without nanocage disassembly. We used four different hydrophobic compounds for modification. The largest modification group tested, pyrene, resulted in a modified TIP60 that could encapsulate aromatic photosensitizer zinc phthalocyanine (ZnPC) more efficiently than the other modification compounds. The encapsulated ZnPC generated singlet oxygen upon light activation in the aqueous phase, whereas ZnPC alone formed inert aggregates under the same experimental conditions. Given that chemical modification allows a wider diversity of modifications than mutagenesis, this approach could be used to develop more suitable nanocages for encapsulating hydrophobic molecules of interest.
Photo‐Modulating CO2Uptake of Hypercross‐linked Polymers Upcycled from Polystyrene Waste
Authors: Liu Aotian , Mollart Catherine , Trewin Abbie , Fan Xianfeng , Lau Cher Hon 
Published: February 2023

AbstractIncorporating photo‐switches into skeletal structures of microporous materials or as guest molecules yield photo‐responsive materials for low‐energy CO2capture but at the expense of lower CO2uptake. Here, we overcome this limitation by exploitingtrans–cisphotoisomerization of azobenzene loaded into the micropores of hypercross‐linked polymers (HCPs) derived from waste polystyrene. Azobenzene in HCP pores reduced CO2uptake by 19 %, reaching 37.7 cm3 g−1, but this loss in CO2uptake was not only recovered bytrans–cisphotoisomerization of azobenzene, but also increased by 22 %, reaching 56.9 cm3 g−1, when compared to as‐prepared HCPs. Computational simulations show that this increase in CO2uptake is due to photo‐controlled increments in 10–20 Å micropore volume, i. e., adsorption sites and a photo‐reversible positive dipole moment. Irradiating these HCPs with visual‐range light reverted CO2uptake to 33 cm3 g−1. This shows that it is feasible to recycle waste polystyrene into advanced materials for low‐energy carbon capture.