bluuebunny/crossref_metadata_2025_split huggingface dataset:
Pembrolizumab‐associated chronic rhinosinusitis: A new endotype and management considerations
Authors: Standiford Taylor C. , Patel Neil N. , Singh Amritpal , Gochman Grant , Jamie Wu Tara , Daud Adil I. , Goldberg Andrew N. 
Published: June 2023

KEY POINTS
Patients treated with pembrolizumab experience an increase in paranasal sinus inflammation
Use of topical triamcinolone in carboxymethylcellulose is a treatment option for such patients
Biology and function of pericytes in the vascular microcirculation
Authors: Wu Yue , Fu Jiaqi , Huang Yuxia , Duan Ruowang , Zhang Wentian , Wang Caihong , Wang Shang , Hu Xiaoyi , Zhao Hui , Wang Lan , Liu Jinming , Gao Guosheng , Yuan Ping 
Published: June 2023

AbstractPericytes are the main cellular components of tiny arteries and capillaries. Studies have found that pericytes can undergo morphological contraction or relaxation under stimulation by cytokines, thus affecting the contraction and relaxation of microvessels and playing an essential role in regulating vascular microcirculation. Moreover, due to the characteristics of stem cells, pericytes can differentiate into a variety of inflammatory cell phenotypes, which then affect the immune function. Additionally, pericytes can also participate in angiogenesis and wound healing by interacting with endothelial cells in vascular microcirculation disorders. Here we review the origin, biological phenotype and function of pericytes, and discuss the potential mechanisms of pericytes in vascular microcirculation disorders, especially in pulmonary hypertension, so as to provide a sound basis and direction for the prevention and treatment of vascular microcirculation diseases.
Single‐atom Iron Catalyst with Biomimetic Active Center to Accelerate Proton Spillover for Medical‐level Electrosynthesis of H2O2Disinfectant
Authors: Li Yan , Chen Junxiang , Ji Yaxin , Zhao Zilin , Cui Wenjun , Sang Xiahan , Cheng Yi , Yang Bin , Li Zhongjian , Zhang Qinghua , Lei Lecheng , Wen Zhenhai , Dai Liming , Hou Yang 
Published: June 2023

AbstractElectrosynthesis of H2O2has great potential for directly converting O2into disinfectant, yet it is still a big challenge to develop effective electrocatalysts for medical‐level H2O2production. Herein, we report the design and fabrication of electrocatalysts with biomimetic active centers, consisting of single atomic iron asymmetrically coordinated with both nitrogen and sulfur, dispersed on hierarchically porous carbon (FeSA‐NS/C). The newly‐developed FeSA‐NS/C catalyst exhibited a high catalytic activity and selectivity for oxygen reduction to produce H2O2at a high current of 100 mA cm−2with a record high H2O2selectivity of 90 %. An accumulated H2O2concentration of 5.8 wt.% is obtained for the electrocatalysis process, which is sufficient for medical disinfection. Combined theoretical calculations and experimental characterizations verified the rationally‐designed catalytic active center with the atomic Fe site stabilized by three‐coordinated nitrogen atoms and one‐sulfur atom (Fe‐N3S‐C). It was further found that the replacement of one N atom with S atom in the classical Fe‐N4‐C active center could induce an asymmetric charge distribution over N atoms surrounding the Fe reactive center to accelerate proton spillover for a rapid formation of the OOH* intermediate, thus speeding up the whole reaction kinetics of oxygen reduction for H2O2electrosynthesis.
Über Carbenintermediate in der AlI vermittelten Homologisierung von Isocyaniden
Authors: Zhang Cuijuan , Dankert Fabian , Jiang Ziang , Wang Baolu , Munz Dominik , Chu Jiaxiang 
Published: June 2023

AbstractIm Fischer–Tropsch (FT) Prozess werden C−C Bindungen zwischen C1 Bausteinen geknüpft. Die Knüpfung solcher C−C Bindungen ist von großem Interesse in vielen Katalysezyklen. In dieser Arbeit beschreiben wir die Reaktion zwischen dem neutralen AlI Komplex (MeNacNac)Al (1, MeNacNac=HC[(CMe)(NDipp)]2, Dipp=2,6‐diisopropylphenyl) und verschiedenen Isocyaniden, welche somit als Modelle für den FT‐Prozess dienen. Der Stufenmechanismus wurde mittels Tieftemperatur NMR Monitoring, Isotopenmarkierung sowie quantenchemischen Rechnungen untersucht. Drei verschiedene Produkte konnten nach der Reaktion von 1 mit dem sterisch anspruchsvollen 2,6‐bis(Benzhydryl)‐4‐Me‐Phenyl Isocyanid (BhpNC) isoliert werden und belegen transiente Carbenintermediate. Die Reaktion von 1 mit Adamantylisocyanid (AdNC) ergab ein Trimerisierungsprodukt, wobei ein Carbenintermediat in Form eines Mo0 Komplexes abgefangen werden konnte. Tri‐, Tetra‐, sowie Pentamerisierungsprodukte wurden mit den sterisch weniger anspruchsvollen Phenyl‐ und p‐Methoxyphenylisocyaniden (PhNC und PMPNC) unter Ausbildung von Quinolin‐ und Indolheterozyklen erhalten. Diese Arbeit belegt Carbenintermediate in der FT‐Chemie von AlI mit Isocyaniden.
Evidence for Carbene Intermediates in Isocyanide Homologation by Aluminium(I)
Authors: Zhang Cuijuan , Dankert Fabian , Jiang Ziang , Wang Baolu , Munz Dominik , Chu Jiaxiang 
Published: June 2023

AbstractThe C−C bond formation between C1 molecules plays an important role in chemistry as manifested by the Fischer–Tropsch (FT) process. Serving as models for the FT process, we report here the reactions between a neutral AlIcomplex (MeNacNac)Al (1,MeNacNac=HC[(CMe)(NDipp)]2, Dipp=2,6‐diisopropylphenyl) and various isocyanides. The step‐by‐step coupling mechanism was studied in detail by low‐temperature NMR monitoring, isotopic labeling, as well as quantum chemical calculations. Three different products were isolated in reaction of1with the sterically encumbered 2,6‐bis(benzhydryl)‐4‐Me‐phenyl isocyanide (BhpNC). These products substantiate carbene intermediates. The reaction between1and adamantyl isocyanide (AdNC) generated a trimerization product, and a corresponding carbene intermediate could be trapped in the form of a molybdenum(0) complex. Tri‐, tetra‐, and even pentamerization products were isolated with the sterically less congested phenyl andp‐methoxyphenyl isocyanides (PhNC and PMPNC) with concurrent construction of quinoline or indole heterocycles. Overall, this study provides evidence for carbene intermediates in FT‐type chemistry of aluminium(I) and isocyanides.
Synthesis of solid reactive organophosphorus‐nitrogen flame retardant and its application in epoxy resin
Authors: Chen Chaojiu , Wang Xinlong , Luo Tao , Zhen Honggang , Yang Xiuying , Yang Lin , Yan Zhengjuan 
Published: June 2023

AbstractA solid reactive organophosphorus‐nitrogen flame retardant 4N‐BDP was devised and synthesized in order to address the flaws of the widely used organophosphorus flame retardants BDP as well as the issue of flame retardant modification of epoxy resin (EP). A series of flame‐retardant EP composites were prepared by adding 4N‐BDP and BDP to EP in a specific proportion. The flame‐retardant properties of the two were compared, and the flame‐retardant mechanism of 4N‐BDP was deeply analyzed. The results of the UL‐94 test revealed that sample 4N‐BDP‐6 obtained the greatest V‐0 level, while BDP‐6 had no level, when the addition ratio of flame retardant was 8.03%. In the cone calorimeter test, the peak smoke production rate (pSPR) and total smoke production (TSP) of BDP‐6 were not significantly different from those of pure EP. In contrast, TSP and pSPR of 4N‐BDP‐6 decreased by 39.50% and 50.00% respectively compared with EP. Compared with BDP, 4N‐BDP shows better flame retardancy and smoke suppression performance, which can significantly improve the fire resistance of EP. The flame‐retardant mechanism of 4N‐BDP was resolved by scanning electron microscopy, XPS, and thermogravimetric analysis/infrared spectrometry. 4N‐BDP can increase the residual carbon rate of the composites, improve the residual carbon strength, play an excellent condensed phase flame retardant effect, and avoid further decomposition of the materials. In the gas phase, the decomposition of 4N‐BDP produces PO·, PO2· and NH3, which play a good quenching effect and dilution effect. The escape of NH3 will leave bubbles in the residual carbon, making the residual carbon more fluffy, further improving the ability of heat insulation and oxygen insulation, and enhancing the flame retardant effect of the condensed phase. In general, the flame‐retardant mechanism of 4N‐BDP is a synergistic combination of condensed phase and gas phase flame retardant mechanism. This work provides a new approach to improve the defects of organophosphorus flame retardant BDP commonly used in the market and enhance the fire resistance of EP.
Novel application of Zn‐containing Zeolitic Imidazolate Frameworks in promoting the vulcanization and mechanical properties of natural rubber composites
Authors: Tian Xing , Hu Jie , Sun Xin , Duan Yongxin , Jiang Min 
Published: June 2023

AbstractThree kinds of Zn‐containing Zeolitic Imidazolate Frameworks (Zn‐ZIFs, including ZIF‐8, ZIF‐11 and ZIF‐14) based on the zinc ions coordinating with different imidazolate ligands were added into the natural rubber (NR) using the DM and TMTD binary accelerators system, respectively. The influences of Zn‐ZIFs on the sulfur vulcanization behaviors and mechanical properties of NR matrix were evaluated. The results indicated that the addition of ZIF‐8 or ZIF‐14 could realize the fast vulcanization of NR at 130°C (the ordinary vulcanization temperature of NR is above 150°C), while ZIF‐11 did not show the obvious accelerating performance. Amongst the three Zn‐ZIFs, ZIF‐8 benefited NR matrix for the acquirement of the highest tensile strength and the largest crosslinking density. As an optimal additive, ZIF‐8 with 0.6 phr distinctly improved the physical‐mechanical, thermo‐oxidative aging resistance and dynamic mechanical properties of NR composites. It proved that Zn atom and its coordination porous network in Zn‐ZIFs played synergistic effects in accelerating vulcanization and enhancing mechanical properties of NR matrix besides its role of reinforcement filler. Then the above ZIF‐8/DM/TMTD vulcanization system was used to prepare the UHMWPE fibers/NR composites. The mechanical properties of the UHMWPE/NR composites were significantly improved in contrast to the pure NR matrix.
A Kuhnian revolution in molecular biology: Most genes in complex organisms express regulatory RNAs
Authors: Mattick John S. 
Published: June 2023

AbstractThomas Kuhn described the progress of science as comprising occasional paradigm shifts separated by interludes of ‘normal science’. The paradigm that has held sway since the inception of molecular biology is that genes (mainly) encode proteins. In parallel, theoreticians posited that mutation is random, inferred that most of the genome in complex organisms is non‐functional, and asserted that somatic information is not communicated to the germline. However, many anomalies appeared, particularly in plants and animals: the strange genetic phenomena of paramutation and transvection; introns; repetitive sequences; a complex epigenome; lack of scaling of (protein‐coding) genes and increase in ‘noncoding’ sequences with developmental complexity; genetic loci termed ‘enhancers’ that control spatiotemporal gene expression patterns during development; and a plethora of ‘intergenic’, overlapping, antisense and intronic transcripts. These observations suggest that the original conception of genetic information was deficient and that most genes in complex organisms specify regulatory RNAs, some of which convey intergenerational information. Also see the video abstract here: https://youtu.be/qxeGwahBANw
Influence of cell specific parameters in a dielectric spectroscopy conversion model used to monitor viable cell density in bioreactors
Authors: Schini Adèle , De Canditiis Bartolomeo , Sanchez Célia , Pierrelee Michaël , Voltz Karine‐Elise , Jourdainne Laurent 
Published: June 2023

AbstractIn the biopharmaceutical industry, the use of mammalian cells to produce therapeutic proteins is becoming increasingly widespread. Monitoring of these cultures via different analysis techniques is essential to ensure a good quality product while respecting good manufacturing practice (GMP) regulations. Process Analytical Technologies (PAT) tools provide real‐time measurements of the physiological state of the culture and enable process automation. Dielectric spectroscopy is a PAT that can be used to monitor the viable cell concentration (VCC) of living cells after processing raw permittivity data. Several modeling approaches exist and estimate biomass with different accuracy. The accuracy of the Cole–Cole and Maxwell Wagner's equations are studied here in the determination of the VCC and cell radius in Chinese hamster ovary (CHO) culture. A sensitivity analysis performed on the parameters entering the equations highlighted the importance of the cell specific parameters such as internal conductivity (σi) and membrane capacitance (Cm) in the accuracy of the estimation of VCC and cell radius. The most accurate optimization method found to improve the accuracy involves in‐process adjustments of Cm and σi in the model equations with samplings from the bioreactor. This combination of offline and in situ data improved the estimation precision of the VCC by 69% compared to a purely mechanistic model without offline adjustments.
Theoretical Investigation of the Mechanism of the Hock Rearrangement with InCl3 as Catalyst**
Authors: Fayet Agathe , Bourcier Sophie , Casaretto Nicolas , Nay Bastien , Frison Gilles 
Published: June 2023

AbstractThe Hock rearrangement is an acid catalyzed reaction involving organic hydroperoxides and resulting in an oxidative cleavage of adjacent C−C bonds. It has significant industrial applications, like the production of phenol (cumene process), but it remains scarcely used in organic synthesis. In addition, its detailed mechanism has never been studied. Thus, we report herein a theoretical study of the Hock rearrangement, using InCl3 as a Lewis acid catalyst. The aim of this work was to fully understand the mechanism of this fundamental reaction, and to rationalize the influence of the substrate electronic properties on the reaction outcome. Furthermore, the structure of the active indium(III) catalyst interacting with the peroxide substrate was investigated, revealing the co‐existence of several energetically close reaction pathways. The coordinated monomeric form of the Lewis acid emerges as the most active catalyst compared to dimeric species. However, we show that In2Cl6 species coordinated to the substrate are central in this catalytic cycle, primarily serving as a reservoir of active monomeric species.
Solid‐Contact Sensor Based on Molecularly Imprinted Polymers (MIPs) for Direct Potentiometric Assessment of 2,4,6‐Trichlorophenol as a Persistent Organic Pollutant
Authors: Shanaah Haneen H. , Ameen Zahraa , Jaafar Kawthar , Hefnawy A. , Abd‐Rabboh Hisham S. M. , Kamel Ayman H. 
Published: June 2023

Abstract2,4,6‐trichlorophenol (TCP) is regarded as a very harmful persistent organic pollutant. It is prohibited by the US EPA due to its stability, possible toxicity, and substantial carcinogenicity, which could result in long‐term harm to both the environment and living things. A novel solid‐contact electrode (SCE) is fabricated and characterized for potentiometric determination of 2,4,6‐trichlorophenol (2,4,6‐TCP). Molecularly imprinted trichlorophenol polymer (MIP) beads are used as a recognition receptor for potentiometric determination of this persistent organic pollutant. The MIPs are synthesized using 4‐vinyl pyridine (4‐VP) and N,N′‐Methylene bis(acrylamide) (N,N‐MBAA) as functional monomer and cross‐linking agent, respectively. They are embedded in a selective polyvinyl chloride (PVC) membrane on the top of multi‐walled carbon nanotubes (MWCNTs), which is used as an ion to electron transducer. The SCE exhibits a Nernstian response with a slope of −55.4±2.1 mV/decade (R2=0.999) over the concentration range of 8.0×10−6 to 1.0×10−4 M, a detection limit of 5.0×10−7 M (0.98 μg/mL), and a response time of <10 s. Using electrochemical impedance spectroscopy (EIS) and chronopotentiometry (CP), the suggested SCE′s interfacial capacitance is measured. The interfacial capacitance was increased using MWCNTs and reached 39.7 μF. Also, it prevented the undesirable thin water layer from forming between the conducting glassy carbon (GC) substrate and the sensing membrane. As a result, potential stability is improved, and membrane delamination is avoided. The suggested SCE had a wide range of applications for monitoring TCP in various environmental samples because of the high selectivity, sensitivity, and possible stability that were attained.
Plastic Waste Utilization via Chemical Recycling: Approaches, Limitations, and the Challenges Ahead
Authors: Biessey Philip , Vogel Julia , Seitz Mathias , Quicker Peter 
Published: June 2023

AbstractChemical recycling offers the opportunity to foster the transition towards a circular economy for plastics as a complementary strategy for mechanical recycling. For the implementation of chemical recycling technologies, there are still significant challenges ahead that – besides the definition of binding legal frameworks – need for intensified research: knowledge‐based methods for both the identification of suitable process technologies considering decentralized waste conditions and the design of conversion steps and downstream processing are strongly needed for process development and process evaluation.
Room‐Temperature High‐Performance Trace Level Acetone Sensor Based on Polypyrrole Nanotubes
Authors: Adhikari Monalisa , Das Sagnik , Chattopadhyay Dipankar , Saha Debdulal , Pal Mrinal 
Published: June 2023

AbstractRecently, precise detection of VOCs in particular acetone, ammonia alcohol has attracted huge attention for industrial safety, monitoring of environment and human health. In this article we have reported for a polypyrrole nanotube (PPNT)‐based chemiresistive sensor for the selective detection of trace acetone vapour at room temperature (25 °C). Polypyrrole (PPy) nanoparticles with different morphologies, viz. nanotubes, nanowire, and globular were synthesized using methyl orange (MO), cetyltrimethyl ammonium bromide (CTAB), and pure polypyrrole as the growth template. The as synthesized powders were exploited to fabricate Taguchi‐type thick‐film sensors. The synthesized powders and fabricated sensors were characterized by multiple sophisticated techniques, such as, XRD, FTIR, Raman spectroscopy, SEM, EDS, UV‐VIS spectroscopy, optical non‐contact profilometry, and current‐Voltage (I‐V) measurement. It is observed that the PPNT sensor shows the highest response to trace acetone vapour with a lower detection limit of 500 ppb at room temperature (25 °C) and quick response (∼5.4 sec) and recovery (∼73.94 sec) times. Achieved enhanced sensing behaviour can be attributed to formation of hydrogen bond between acetone and PPy. Combined with room temperature sensing, good stability, repeatability, produce sensor may find application in various sensing fields.
High Alkaline Electrochemical Hydrogen Evolution on a Pt/GaN Heterostructure
Authors: Liu Chaozhong , Niu Chunyao , Gao Bo , Jiang Pingli , Lin Qiyao , Wu Wenzhuo , Jia Yu , Wei Zhongming , Xu Qun 
Published: June 2023

AbstractThe construction of suitable metal/substrate interfaces that can synergistically optimize the water dissociation, hydrogen transfer and hydrogen adsorption processes has proved to be a promising approach to boost the alkaline electrochemical hydrogen evolution reaction (HER) but remains challenging. Herein, a Pt/GaN heterostructure electrocatalyst is constructed using the electrochemical deposition technique and used for alkaline electrochemical HER. The as‐synthesized Pt/GaN catalyst exhibits competitive HER performance, including low overpotentials of 24 and 441 mV to reach current densities of 10 and 1000 mA cm−2, respectively, and a superior mass activity (7.34 A mgPt−1 at the overpotential of 100 mV), which is 25.7 and 5.0 times higher than commercial Pt/C and as‐synthesized Pt/CP, respectively. First‐principle calculations suggest that the Pt/GaN heterostructure can greatly reduce the energy barrier for H2O dissociation, create a local acid‐like microenvironment through a H spillover process and optimize the value of ΔGH, leading to a remarkable acceleration of the alkaline HER kinetics. This discovery provides new insights for the development of alkaline HER catalysts.
Treatment of endoscopic ultrasound‐guided coil deployment for isolated gastric varices using 0.035‐inch hydrocoil: Experience of three cases
Authors: Nagashima Kazunori , Kashima Ken , Kunogi Yasuhito , Sakuma Fumi , Fukushi Koh , Yamamiya Akira , Abe Yoko , Tominaga Keiichi , Iijima Makoto , Goda Kenichi , Romero-Castro Rafael , Irisawa Atsushi 
Published: June 2023

AbstractEndoscopic ultrasound (EUS)‐guided coil deployment (EUS‐coiling) has been newly developed for treating isolated gastric varices (iGV). This report describes three cases of EUS‐coiling for iGV using a 0.035‐inch hydrocoil (Azur; Terumo Corp., Tokyo, Japan). When used for EUS‐coiling, this hydrocoil provides the following benefits: Its electrically detachable system allows pull back. It has smooth and dense deployment. Moreover, it has a strong blood‐flow blocking effect because of its long length and large diameter with internal swelling functions of the hydrogel. Technical success of coiling was achieved in all cases. After coiling, additional treatments such as cyanoacrylate and sclerosant injection were performed as deemed appropriate. All iGVs were obliterated successfully. No adverse event occurred during the procedure or during the mean follow‐up of six months. Our findings indicate that this 0.035‐inch hydrocoil can be used to treat iGV safely and effectively.
Maladaptive plastic responses of flowering time to geothermal heating
Authors: Ehrlén Johan , Valdés Alicia , Helmutsdóttir Vigdís F. , Marteinsdóttir Bryndís 
Published: June 2023

AbstractPhenotypic plasticity might increase fitness if the conditions under which it evolved remain unaltered, but becomes maladaptive if the environment no longer provides reliable cues for subsequent conditions. In seasonal environments, timing of reproduction can respond plastically to spring temperature, maximizing the benefits of a long season while minimizing the exposure to unfavorable cold temperatures. However, if the relationship between early spring temperatures and later conditions changes, the optimal response might change. In geothermally heated ecosystems, the plastic response of flowering time to springtime soil temperature that has evolved in unheated areas is likely to be non‐optimal, because soil temperatures are higher and decoupled from air temperatures in heated areas. We therefore expect natural selection to favor a lower plasticity and a delayed flowering in these areas. Using observational data along a natural geothermal warming gradient, we tested the hypothesis that selection on flowering time depends on soil temperature and favors later flowering on warmer soils in the perennial Cerastium fontanum. In both study years, plants growing in warmer soils began flowering earlier than plants growing in colder soils, suggesting that first flowering date (FFD) responds plastically to soil temperature. In one of the two study years, selection favored earlier flowering in colder soils but later flowering in warmer soils, suggesting that the current level of plastic advance of FFD on warmer soils may be maladaptive in some years. Our results illustrate the advantages of using natural experiments, such as geothermal ecosystems, to examine selection in environments that recently have undergone major changes. Such knowledge is essential to understand and predict both ecological and evolutionary responses to climate warming.