bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers
Authors: Keyes Anthony , Dau Huong , Matyjaszewski Krzysztof , Harth Eva 
Published: December 2021

AbstractPractical synthesis of polyolefin–polyvinyl block copolymers remains a challenge for transition‐metal catalyzed polymerizations. Common approaches functionalize polyolefins for post‐radical polymerization via insertion methods, yet sacrifice the livingness of the olefin polymerization. This work identifies an orthogonal radical/spin coupling technique which affords tandem living insertion and controlled radical polymerization. The broad tolerance of this coupling technique has been demonstrated for diverse radical/spin traps such as 2,2,5‐trimethyl‐4‐phenyl‐3‐azahexane‐3‐nitroxide (TIPNO), 1‐oxyl‐(2,2,6,6‐tetramethylpiperidine) ‐4‐yl‐α‐bromoisobutyrate (TEMPO‐Br), and N‐tert‐butyl‐α‐phenylnitrone (PBN). Subsequent controlled radical polymerization is demonstrated with nitroxide‐mediated polymerization (NMP) and atom transfer radical polymerization (ATRP), yielding polyolefin–polyvinyl di‐ and triblock copolymers (Đ<1.3) with acrylic, vinylic and styrenic segments. These findings highlight radical trapping as an approach to expand the scope of polyolefin‐functionalization techniques to access polyolefin macroinitiators.
Semiconducting Polymer Nano‐regulators with Cascading Activation for Photodynamic Cancer Immunotherapy
Authors: He Shasha , Liu Jing , Zhang Chi , Wang Jun , Pu Kanyi 
Published: December 2021

AbstractCombination photoimmunotherapy holds promise for tumor suppression; however, smart phototherapeutic agents that only activate their immune pharmaceutical action in tumors have been rarely developed. Herein, we report a semiconducting polymer (SP) nano‐regulator (SPNT) with cascading activation for combinational photodynamic cancer immunotherapy. SPNT comprises an immunoregulator (M‐Trp: 1‐methyltryptophan) conjugating to the side chain of the SP backbone via an apoptotic biomarker‐cleavable linker. Under near‐infrared photoirradiation, SPNT produces singlet oxygen to induce immunogenic apoptosis. Concurrently, an apoptotic biomarker is upregulated, which triggers the specific cleavage of M‐Trp for indoleamine 2,3‐dioxygenase (IDO) activity inhibition, regulatory T cells reduction and cytotoxic T lymphocytes infiltration. SPNT‐mediated combination photodynamic immunotherapy thus reprograms the tumor immune microenvironment, resulting in efficient suppression of tumors, and inhibition of lung metastasis.
Two‐Dimensional Polycyclic Photovoltaic Molecule with Low Trap Density for High‐Performance Photocatalytic Hydrogen Evolution
Authors: Zhang Zhenzhen , Si Wenqin , Wu Baohua , Wang Wei , Li Yawen , Ma Wei , Lin Yuze 
Published: December 2021

AbstractTypical organic semiconductors show a high trap density of states (1016–1018 cm−3), providing a large number of centers for charge‐carrier recombination, thus hindering the development of photocatalytic hydrogen evolution. Here, we design and synthesize a two‐dimensional polycyclic photovoltaic material, named as TPP, to reduce the trap density to as low as 2.3×1015 cm−3, which is 1–3 orders of magnitude lower than those of typical organic semiconductors. Moreover, TPP exhibits a broad and strong absorption, ordered molecular packing with a large crystalline coherence length and enhanced electron mobility. Then, the bulk heterojunction nanoparticles (BHJ‐NPs) based on a blend of polymer donor (PM6) and TPP exhibit an average hydrogen evolution rate (HER) of 64.31 mmol h−1 g−1under AM1.5G sunlight (100 mW cm−2), and 72.75 mmol h−1 g−1under 330–1100 nm illumination (198 mW cm−2) higher than that of the control NPs based on typical PM6 : Y6 (62.67 mmol h−1 g−1).
Research progress on the correlation between properties of nanoparticles and their dispersion states in polymer matrix
Authors: Sui Yang , Cui Yi , Meng Xiaoyu , Zhou Qiong 
Published: December 2021

AbstractWhen fabricating polymer nanocomposites (PNCs), it is difficult for nanoparticles to disperse stably in polymer matrix since their high‐surface energy can cause them to attract each other. In this paper, we review the effects of nanoparticle size, surface chemical properties, and thermodynamic parameters on the dispersion state of nanoparticles (including inorganic and organic particles) in PNCs and describe some key measures to promote the nanoparticles dispersion. The ideal nanoparticles dispersion in polymer melt is available when the particle size is smaller than the rotation radius of polymer chains and the particle surface is highly compatible or has interactions with the matrix. In polymer solution, establishing proper thermodynamic parameters is necessary to ensure the balance interactions among particles, solvents, and polymers, leading to the successful preparation of PNCs with ideal structure. These results could supply theoretical suggestions for the design of PNCs. Moreover, the equilibrium dispersion may be unavailable without reasonable kinetic parameters, even if the dispersion process is thermodynamically favorable. Therefore, more studies are required on both thermodynamics and kinetics of the dispersion process.
Modification of poly(butylene succinate) with biodegradable glycolic acid: Significantly improved hydrolysis rate retaining high toughness property
Authors: Ding Yue , Wang Jingxi , Luo Congcong , Yao Bing , Dong Liming , Du Xihua , Ji Junhui 
Published: December 2021

AbstractMarine microplastic pollution damages the marine biodiversity and endangers human health. Poly(butylene succinate) (PBS) is considered a biodegradable polyester; however, PBS has a slow degradation rate in seawater. In this research, glycolic acid (GA) segments were introduced in PBS main unit via melt polycondensation. The number‐average weight of PBSGA copolymer ranged from 3.1 to 4.1 × 104 g mol−1 with GA contents of 0%–40%. PBSGA possessed excellent mechanical properties and thermal stability. The tensile strength was 6 ~ 40 MPa, the elongation at break was more than 220% and the thermal decomposition temperature was high than 380°C. It was also found that the weight loss of PBSGA copolymer showed a tendency of alkaline > lipase > acidic > neutral > salt. In alkaline solution, the PBSGA copolymer completely decomposed after 21 days. In acidic and neutral solution, the increase of GA content improved the degradation rate of copolymer. In phosphate buffered solution, lipase accelerated the rate of ester bonds hydrolysis; however, salt had the opposite effect in NaCl solution. Thus, by introducing easily hydrolyzable GA groups, seawater degradable materials can be obtained to overcome the unfavorable factors of seawater environment.
Transcriptomic analysis provides insights into the immune responses and nutrition in Ostrinia furnacalis larvae parasitized by Macrocentrus cingulum
Authors: Chen Kangkang , Song Jiahui , Song Qisheng , Dou Xiaoyi , Wang Yin , Wei Youheng , Chen Jiaqian , Wang Libao , Alradi Mohamed F. , Liu Xu , Han Zhaoyang , Feng Congjing 
Published: December 2021

AbstractMacrocentrus cingulum is a principal endoparasite of Ostrinia furnacalis larvae. M. cingulum larvae repress host immune responses for survival and ingest host nutrients for development until emerging. However, most investigations focused on the mechanisms of how wasps repress the host immunity, the triggered immune responses and nutrient status altered by wasps in host are neglected. In this study, we found that parasitized O. furnacalis larvae activated fast recognition responses and produced some effectors such as lysozyme and antimicrobial peptides, along with more consumption of trehalose, glucose, and even lipid to defend against the invading M. cingulum. However, the expression of peroxidase 6 and superoxide dismutase 2 (SOD 2) was upregulated, and the messenger RNA (mRNA) levels of cellular immunity‐related genes such as thioester‐containing protein 2 (TEP 2) and hemocytin were also reduced, suggesting that some immune responses were selectively shut down by wasp parasitization. Taken together, all the results indicated that parasitized O. furnacalis larvae selectively activate the immune recognition response, and upregulate effector genes, but suppress ROS reaction and cellular immunity, and invest more energy to fuel certain immune responses to defend against the wasp invading. This study provides useful information for further identifying key components of the nutrition and innate immune repertoire which may shape host‐parasitoid coevolutionary dynamics.
Linked biaromatic compounds as cardioprotective agents
Authors: Mokrov Grigory V. 
Published: December 2021

AbstractCardiovascular diseases (CVDs) are widespread in the modern world, and their number is constantly growing. For a long time, CVDs have been the leading cause of morbidity and mortality worldwide. Drugs for the treatment of CVD have been developed almost since the beginning of the 20th century, and a large number of effective cardioprotective agents of various classes have been created. Nevertheless, the need for the design and development of new safe drugs for the treatment of CVD remains. Literature data indicate that a huge number of cardioprotective agents of various generations and mechanisms correspond to a single generalized pharmacophore model containing two aromatic nuclei linked by a linear linker. In this regard, we put forward a concept for the design of a new generation of cardioprotective agents with a multitarget mechanism of action within the indicated pharmacophore model. This review is devoted to a generalization of the currently known compounds with cardioprotective properties and corresponding to the pharmacophore model of biaromatic compounds linked by a linear linker. Particular attention is paid to the history of the creation of these drugs, approaches to their design, and analysis of the structure–action relationship within each class.
A randomized trial comparing cadaveric dissection and examination of prosections as applied surgical anatomy teaching pedagogies
Authors: Koh Zong Jie , Yeow Marcus , Srinivasan Dinesh Kumar , Ng Yee Kong , Ponnamperuma Gominda G. , Chong Choon Seng 
Published: December 2021

AbstractAnatomy is an important component in the vertical integration of basic science and clinical practice. Two common pedagogies are cadaveric dissection and examination of prosected specimens. Comparative studies mostly evaluate their immediate effectiveness. A randomized controlled trial design was employed to compare both the immediate and long‐term effectiveness of dissection and prosection. Eighty third‐year medical students undergoing their surgical rotation from the Yong Loo Lin School of Medicine were randomized into two groups: dissection and prosection. Each participated in a one‐day hands‐on course following a similar outline that demonstrated surgical anatomy in the context of its clinical relevance. A pre‐course test was conducted to establish baseline knowledge. A post‐course test was conducted immediately after and at a one‐year interval to evaluate learner outcome and knowledge retention. A post‐course survey was conducted to assess participant perception. Thirty‐nine and thirty‐eight participants for the dissection and prosection groups, respectively, were included for analysis. There was no significant difference between mean pre‐course test scores between the dissection and prosection groups [12.6 (3.47) vs. 12.7 (3.16), P > 0.05]. Both the mean immediate [27.9 (4.30) vs. 24.9 (4.25), P < 0.05] and 1 year [23.9 (4.15) vs. 19.9 (4.05), P < 0.05] post‐course test scores were significantly higher in the dissection group. However, when adjusted for course duration [dissection group took longer than prosection group (mean 411 vs. 265 min)], these findings were negated. There is no conclusive evidence of either pedagogy being superior in teaching surgical anatomy. Based on learner surveys, dissection provides a greater learner experience.
Direct electrodeposition of various metal nanocrystals on silicon oxide dielectric layer and insights into electrochemical behavior
Authors: Shin Samuel J. , An Sohee , Lee Sul , Lee Jae Gyeong , Chung Taek Dong 
Published: December 2021

AbstractElectrochemistry of thermally grown silicon oxide can address many interesting features and it was further embellished by the development of defective 200 nm thermal oxide grown on highly n‐doped silicon (n+‐Si/SiO2). However, there are still space to uncover underlying conduction mechanism and applications, specifically for defective 200 nm n+‐Si/SiO2 electrode. These could be addressed by direct electrodeposition, so various kinds of metal nanocrystals, Fe, Cr, Ir, Ru, Co, Pd, Cu, Ni, and Ag, were electrodeposited on it. Their shapes were characterized by SEM and electrodeposited amounts were quantified by ICP‐MS. Furthermore, voltammetry was conducted to provide insights into the direct electrodeposition mechanism of either H atom mediated electrochemistry or electron transfer through percolation paths. This work can further provide intuition toward the development of metal‐supported catalysts.
Is there a role for endovascular stent implantation in the management of postoperative right ventricular outflow tract obstruction in the era of transcatheter valve implantation?
Authors: Kang Sok‐Leng , Ramroop Ronand , Manojlovich Larissa , Runeckles Kyle , Fan Steve , Chaturvedi Rajiv R. , Lee Kyong‐Jin , Benson Lee N. 
Published: December 2021

AbstractBackgroundThe optimal management pathway for the dysfunctional right ventricular outflow tract (RVOT) is uncertain. We evaluated the long‐term outcomes and clinical impact of stent implantation for obstructed RVOTs in an era of rapidly progressing transcatheter pulmonary valve technology.MethodsRetrospective review of 151 children with a biventricular repair who underwent stenting of obstructed RVOT between 1991 and 2017.ResultsRVOT stenting resulted in significant changes in peak right ventricle (RV)‐to‐pulmonary artery (PA) gradient (39.4 ± 17.1–14.9 ± 8.3; p < 0.001) and RV‐to‐aortic pressure ratio (0.78 ± 0.22–0.49 ± 0.13; p < 0.001). Subsequent percutaneous reinterventions in 51 children to palliate recurrent stenosis were similarly effective. Ninety‐nine (66%) children reached the primary outcome of subsequent pulmonary valve replacement (PVR). Freedom from PVR from the time of stent implantation was 91%, 51%, and 23% at 1, 5, and 10 years, respectively. Small balloon diameters for stent deployment were associated with shorter freedom from PVR. When additional children without stent palliation (with RV‐to‐PA conduits) were added to the stent cohort (total 506 children), the multistate analysis showed the longest freedom from PVR in those with stent palliation and subsequent catheter reintervention. Pulmonary regurgitation was well‐tolerated clinically. Indexed RV dimensions and function estimated by echocardiography remained stable at last follow up or before primary outcome.ConclusionProlongation of conduit longevity with stent implant remains an important strategy to allow for somatic growth to optimize the risk‐benefit profile for subsequent surgical or transcatheter pulmonary valve replacement performed at an older age.
Bandgap Engineering for Photocatalytic Polymerization of 3, 4‐Ethylenedioxythiophene (EDOT) over Cs3BixSb(2‐x)Br9 Inverse Opals
Authors: Zhao Siwei , Jin Shaohua , Liu Huanmin , Su Youxin , Liu Wei , Li Shengfu , She Chongchong , Li Haonan , Chen Kun 
Published: December 2021

AbstractA series of all‐inorganic lead‐free halide perovskite inverse opals were prepared and furtherly used as the photocatalysts to promote the polymerization of 3, 4‐ethylenedioxythiophene (EDOT) under the irradiation of visible light. All the samples exhibited the nice replica of the artificial template and high crystallinity. The bandgap of the catalysts was adjusted by screening the ratios of bromide to iodide and antinomy to bismuth, respectively. Among all the samples, Cs3Bi0.5Sb1.5Br9 inverse opal showed the best catalytic performance and the excellent stability in terms of the morphology and the crystalline phase after four cycles of photocatalytic polymerization. Since EDOT is commercially available, the present observation suggested a convenient protocol of preparing the composited materials or optoelectronic devices based on the lead‐free halide perovskites and the conductive poly(3, 4‐ethylenedioxythiophene).
Removal of Cu Ions in Wastewater through a Combined Foam Separation‐Cell Adsorption Approach
Authors: Hou Hongya , Li SiYu , Meng ZhiChao , Li Zhiqiang , Darwesh Osama M. , Zheng Huijie 
Published: December 2021

AbstractThe removal of heavy metal pollutants from industrial wastewater is important to ensure the safety of the environment and humans. In this study, rhamnolipids from Pseudomonas aeruginosa were used to treat synthetic wastewater containing Cu ions (100 mg L−1) by foam separation. A high removal efficiency of 99.52 % was achieved when the somatic cells of inactivated P. aeruginosa were used as biosorbents. The analysis of the adsorption kinetics showed that dynamic biosorption followed the Langmuir isotherm model and that the bacterial cells had a strong adsorption effect on Cu ions. The novel technology based on the combination of foam separation and biosorption serves as an effective approach for the removal of Cu ions from industrial wastewater.
A Solid Support‐Based Synthetic Strategy for the Site‐Selective Functionalization of Peptides with Organometallic Half‐Sandwich Moieties
Authors: Truong Dianna , Lam Nelson Y. S. , Kamalov Meder , Riisom Mie , Jamieson Stephen M. F. , Harris Paul W. R. , Brimble Margaret A. , Metzler‐Nolte Nils , Hartinger Christian G. 
Published: December 2021

AbstractThe number of donor atoms available on peptides that can competitively coordinate to metal centers renders the site‐selective generation of advanced metal‐peptide conjugates in high purity a challenging venture. Herein, we present a transmetalation‐based synthetic approach on solid support in which an imidazolium pro‐ligand can be used to selectively anchor a range of transition metal half‐sandwich complexes onto peptides in the presence of multiple coordinative motifs. Amenable to solid support, a range of N‐terminus and/or lysine conjugated metal‐peptide conjugates were obtained in high purity after cleavage from the resin. The metalated peptides were evaluated for their anticancer properties against human cancer cell lines. While no cytotoxic activity was observed, this platform has the potential to i) provide a pathway to site‐selective peptide labelling, ii) be explored as a biorthogonal handle and/or iii) generate a new strategy for ligand design in transition metal catalysts.
Borane Adducts of Aromatic Phosphorus Heterocycles: Synthesis, Crystallographic Characterization and Reactivity of a Phosphinine‐B(C6F5)3 Lewis Pair
Authors: Lin Jinxiong , Wossidlo. Friedrich , Coles Nathan T. , Weber Manuela , Steinhauer Simon , Böttcher Tobias , Müller Christian 
Published: December 2021

AbstractA phosphinine‐borane adduct of a Me3Si‐functionalized phosphinine and the Lewis acid B(C6F5)3 has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α‐position of the phosphorus heterocycle. In contrast, the reaction of B2H6 with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine–borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct (6‐B(C6F5)3) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro‐1‐phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1‐R‐phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me3Si−C≡CH and styrene to cleanly form unprecedented derivatives of 1‐R‐phosphabarrelenium salts.
Copper‐Catalyzed Enantioselective Reductive Aldol Reaction of α,β‐Unsaturated Carboxylic Acids to Alkyl Aryl Ketones: Silanes as Activator and Transient Protecting Group
Authors: Suzuki Hirotsugu , Yoneoka Kenji , Kondo Sora , Matsuda Takanori 
Published: December 2021

AbstractThe first enantioselective reductive aldol reaction of unprotected α,β‐unsaturated carboxylic acids was developed by employing a copper/bisphosphine catalyst. The reaction features in situ protection and activation of an α,β‐unsaturated carboxylic acid by a hydrosilane. The copper enolate formed in situ reacts with an alkyl aryl ketone to afford the β‐hydroxy carboxylic acid with excellent enantioselectivity (up to 99 % ee). The corresponding gram‐scale reaction with a low catalyst loading and the derivatization of the β‐hydroxy carboxylic acids highlight the practicality of this transformation.
Evaluating the Safety, Tolerability, and Disposition of Trazpiroben, a D2/D3 Receptor Antagonist: Phase I Single‐ and Multiple‐Ascending Dose Studies in Healthy Japanese Participants
Authors: Yamaguchi Takayoshi , Kudou Kentarou , Okamoto Hiroyuki , Chen Chunlin , Whiting Roger , Sekino Hisakuni 
Published: December 2021

AbstractTrazpiroben (TAK‐906) is a peripherally selective dopamine D2/D3 receptor antagonist being developed to treat chronic gastroparesis. This phase I, randomized, double‐blind, placebo‐controlled, single‐ and multiple‐ascending dose, parallel‐group study evaluated the safety, tolerability, pharmacokinetics, and pharmacodynamics of trazpiroben in healthy Japanese men. Findings were compared with those from a prior US trial in healthy individuals. Overall, 24 participants were enrolled into 3 cohorts (each n = 8). Per cohort, 6 participants received trazpiroben (cohort 1, 50 mg; 2, 100 mg; 3, 10 mg) once on day 1 and twice daily on days 3 through 7, and two received placebo. Trazpiroben was well tolerated, with no clinically meaningful adverse events observed. Following single‐ and multiple‐dose administration, trazpiroben was rapidly absorbed and eliminated (mean elimination half‐life, 1.89‐6.45 hours; median time to maximum serum concentration [steady state], 1.00‐1.25 hours). Serum prolactin increased with trazpiroben treatment (mean maximum serum concentration 93.32 ng/mL [10 mg] vs. 10.83 ng/mL [placebo]), illustrating receptor target engagement. Results reflected those from healthy US participants, indicating a lack of differences between these ethnic populations in trazpiroben disposition and safety profile. Trazpiroben may represent a promising therapy for chronic gastroparesis across different populations, with further evaluation ongoing in a phase IIb study (NCT03544229).