bluuebunny/crossref_metadata_2025 huggingface dataset:
Hybrid categorical expert system for use in content aggregation
Authors: Kiryanov Denis Aleksandrovich
Published: December 2021

The subject of this research is the development of the architecture of an expert system for distributed content aggregation system, the main purpose of which is the categorization of aggregated data. The author examines the advantages and disadvantages of expert systems, a toolset for the development of expert systems, classification of expert systems, as well as application of expert systems for categorization of data. Special attention is given to the description of the architecture of the proposed expert system, which consists of a spam filter, a component for determination of the main category for each type of the processed content, and components for the determination of subcategories, one of which is based on the domain rules, and the other uses the methods of machine learning methods and complements the first one. The conclusion is made that an expert system can be effectively applied for the solution of the problems of categorization of data in the content aggregation systems. The author establishes that hybrid solutions, which combine an approach based on the use of knowledge base and rules with the implementation of neural networks allow reducing the cost of the expert system. The novelty of this research lies in the proposed architecture of the system, which is easily extensible and adaptable to workloads by scaling existing modules or adding new ones.
INTEGRATION OF PRACTICE-ORIENTED AND THEORETICAL APPROACHES AS A NECESSARY CONDITION FOR THE TRAINING OF MODERN PERSONNEL IN VOCATIONAL AND PEDAGOGICAL EDUCATION
Authors:   South Ural State Humanitarian Pedagogical University, Pakhtusova N.A. , Podmareva A.V. , Samsonova I.G.
Published: December 2021

The article deals with the problem of improving the quality of training of teachers of vocational training by integrating practice-oriented and theoretical approaches for the implementation of the experimental project «Professionalism» as a priority direction in the development of secondary vocational education. It is noted that the professional activity of a teacher becomes more multitasking and requires the formation of professional skills while developing fl exibility of thinking, intelligence, and the ability to quickly respond to the demands of the labor market. The professional training of teachers provides for the integration of practice-oriented and theoretical approaches to form a competitive specialist. At the same time, the educational environment should diff er in the variability of approaches, educational technologies, didactic means and teaching methods. The article describes some forms of work with students that allow modeling the future professional activity of a teacher of vocational training and imply deepening and expanding the content of theoretical material and its refraction when performing practical tasks of a professional orientation. Noting the practice-oriented approach as an active form of organizing professional training of students, the authors consider the experience of working on the basis of the South Ural State Humanitarian Pedagogical University.
Ultrasound Guided Suprascapular Nerve Block versus Intra-articular Steroid Injection in the Treatment of Periarthritis Shoulder: A Randomised Clinical Trial
Authors: Jain Sakshi , Borah Diganta , Meena Dharam Singh , Ali Junis
Published: December 2021

Introduction: Suprascapular Nerve Block (SSNB) and Intra-articular (IA) steroid injection are used for management of Periarthritis (PA) of shoulder with variable results. Aim: To compare the efficacy of SSNB and IA steroid injection for management of PA shoulder. Materials and Methods: In this randomised clinical trial, 100 patients of PA shoulder from Physical Medicine and Rehabilitation (PMR) Outpatient Department (OPD) were enrolled over the period of 18 months and were divided in two equal groups using computerised block randomisation. Group A patients received IA methylprednisolone while Group B patients were subjected to Ultrasound (USG) guided SSNB. Assessment was done at baseline and at 1, 4 and 12 weeks after the intervention, using Numerical Pain Rating Scale (NPRS), active and passive Range Of Motion (ROM) of shoulder and Shoulder Pain And Disability Index (SPADI). Statistical significance was determined by Chi- square for qualitative variables and by unpaired t-test or paired t-test for quantitative variables. The p<0.05 was taken as a level of statistical significance. Results: Both groups had significant improvement (p<0.0005) in pain, ROM and functional index at all follow-ups. Comparison between the groups revealed a better outcome in Group A, in terms of NPRS, SPADI score, internal and external rotations at 1, 4 and 12 weeks (p<0.0005). Both the groups were comparable in terms of abduction, flexion and extension at first week (p<0.0005) with Group A showing better improvement at subsequent follow-up. Conclusion: Both SSNB and IA steroid injection can be used for treatment of PA shoulder but IA steroid injections gave better results as compared to SSNB. SSNB may be used as an adjunct to exercise therapy and as an alternative to IA steroid injection if required.
Estado antropométrico de pacientes pediátricos com doença inflamatória intestinal
Authors: Queiroz Aline Pereira , Conceição-Machado Maria Ester Pereira da , Jesus Gabriela dos Santos de , Silva Luciana Rodrigues
Published: December 2021

Introdução: a Doença Inflamatória Intestinal (DII) é decorrente de vários fatores que provocam alteração na homeostase do microbioma na resposta imune e no aumento da permeabilidade intestinal. O estado nutricional inadequado, principalmente em pacientes pediátricos com DII, representa prognóstico ruim e pode influenciar na resposta ao tratamento, à morbidade e à mortalidade. Objetivo: esse estudo teve objetivo de caracterizar o estado antropométrico de pacientes pediátricos atendidos em um ambulatório referência para DII. Metodologia: a amostra foi constituída por pacientes atendidos em primeira consulta no ambulatório, de junho de 2020 até fevereiro de 2021. Foram incluídos pacientes com diagnóstico clínico de Doença de Cronh e Colite Ulcerativa, de ambos sexos, com idade entre 2 a 19 anos. Resultados: dos pacientes com CU, 54,7% apresentaram adequado estado nutricional e 45,3% dos pacientes com DC. O percentual de déficit de massa muscular foi de 47,6% dos pacientes com CU e 52,4% dos pacientes com DC.A baixa estatura foi de 37,5% nos pacientes com CU e 62,5% com DC. Conclusão: a avaliação nutricional de crianças e adolescentes portadores de doenças inflamatórias intestinais deve fazer parte da rotina de atendimento, para que sejam promovidas práticas alimentares saudáveis que favoreçam o crescimento, recuperação ponderal e manutenção de massa muscular
Perfil das internações de crianças por malformações congênitas do aparelho circulatório no Brasil de 2010 a 2020
Authors: Sampaio Laís Fernanda Duarte , Barreto Nilo Manoel Pereira Vieira , Correia Helena França
Published: December 2021

Introdução: a malformação congênita do aparelho circulatório é definida como qualquer anormalidade na estrutura e/ou função do coração durante a fase do desenvolvimento embrionário, podendo interferir no fluxo sanguíneo. Suas manifestações ocorrem em qualquer fase do desenvolvimento. No Brasil, essa enfermidade representa a segunda principal causa de mortalidade em crianças menores de um ano, caracterizando-se um problema de saúde pública. Objetivo: descrever o perfil das internações de crianças por malformações congênitas do aparelho circulatório no Brasil, de 2010 a 2020. Metodologia: trata-se de um estudo ecológico, realizado por meio de dados secundários, no período de 2010 a 2020. Analisaram-se as variáveis número de internações, sexo, região, raça/cor, faixa etária, custos hospitalares, óbito e taxa de mortalidade. As informações coletadas foram armazenadas e analisadas no software Microsoft Excel Office, versão de 365. Resultados: entre 2010 e 2020, foram notificadas 118.792 internações por essa comorbidades de crianças por malformação congênita do aparelho circulatório, sendo 51% do sexo masculino, com predomínio da cor branca (36%), tendo a região Sudeste apresentado o maior percentual de internações (43,5%).  Observou-se maior ocorrência em crianças abaixo de um ano (62,7%), gerando um custo de 650 milhões de reais em serviços hospitalares. O maior percentual de internações ocorreu em 2019 (10,9%).  Houve 10.477 óbitos entre 2010 e 2020 (8,8%), sendo 85,8% na população abaixo de um ano e 37,7% na região Sudeste. A taxa de mortalidade de crianças por essa comorbidade foi de 8,82/100 mil habitantes. Conclusão: observou-se que as malformações congênitas do aparelho circulatório, no período analisado, apresentaram uma distribuição homogênea em relação ao sexo, sendo mais frequentes na raça/cor branca, na região Sudeste e na faixa etária menor que um ano, gerando altos custos em serviços hospitalares.
Quantitative assessment of intra‐ and inter‐modality deformable image registration of the heart, left ventricle, and thoracic aorta on longitudinal 4D‐CT and MR images
Authors: Omidi Alireza , Weiss Elisabeth , Wilson John S. , Rosu‐Bubulac Mihaela
Published: December 2021

Purpose

Magnetic resonance imaging (MRI)‐based investigations into radiotherapy (RT)‐induced cardiotoxicity require reliable registrations of magnetic resonance (MR) imaging to planning computed tomography (CT) for correlation to regional dose. In this study, the accuracy of intra‐ and inter‐modality deformable image registration (DIR) of longitudinal four‐dimensional CT (4D‐CT) and MR images were evaluated for heart, left ventricle (LV), and thoracic aorta (TA).

Methods and materials

Non‐cardiac‐gated 4D‐CT and T1 volumetric interpolated breath‐hold examination (T1‐VIBE) MRI datasets from five lung cancer patients were obtained at two breathing phases (inspiration/expiration) and two time points (before treatment and 5 weeks after initiating RT). Heart, LV, and TA were manually contoured. Each organ underwent three intramodal DIRs ((A) CT modality over time, (B) MR modality over time, and (C) MR contrast effect at the same time) and two intermodal DIRs ((D) CT/MR multimodality at same time and (E) CT/MR multimodality over time). Hausdorff distance (HD), mean distance to agreement (MDA), and Dice were evaluated and assessed for compliance with American Association of Physicists in Medicine (AAPM) Task Group (TG)‐132 recommendations.

Results

Mean values of HD, MDA, and Dice under all registration scenarios for each region of interest ranged between 8.7 and 16.8 mm, 1.0 and 2.6 mm, and 0.85 and 0.95, respectively, and were within the TG‐132 recommended range (MDA < 3 mm, Dice > 0.8). Intramodal DIR showed slightly better results compared to intermodal DIR. Heart and TA demonstrated higher registration accuracy compared to LV for all scenarios except for HD and Dice values in Group A. Significant differences for each metric and tissue of interest were noted between Groups B and D and between Groups B and E. MDA and Dice significantly differed between LV and heart in all registrations except for MDA in Group E.

Conclusions

DIR of the heart, LV, and TA between non‐cardiac‐gated longitudinal 4D‐CT and MRI across two modalities, breathing phases, and pre/post‐contrast is acceptably accurate per AAPM TG‐132 guidelines. This study paves the way for future evaluation of RT‐induced cardiotoxicity and its related factors using multimodality DIR.
A novel nonlinear optimization method for fitting a noisy Gaussian activation function
Authors: Li Jimei , Ding Feng , Hayat Tasawar
Published: December 2021

It is significant to fit a Gaussian function with the observation data for artificial intelligence or other engineering fields. Considering the influence of noises, this article proposes a nonlinear optimization method for fitting the Gaussian activation functions. By means of the gradient search and the Newton search, a direct gradient‐based iterative algorithm and a direct Newton iterative algorithm are presented for identifying the Gaussian functions. Considering the computational cost, the authors develop a multi‐innovation stochastic gradient algorithm for the noisy Gaussian functions. After introducing a forgetting factor, the parameter estimation accuracy can be further improved. The simulation results indicate that the proposed nonlinear optimization method and gradient‐based algorithms can fit the noisy Gaussian functions very well.
Enabling Anionic Redox Stability of P2‐Na5/6Li1/4Mn3/4O2 by Mg Substitution
Authors: Huang Yangyang , Zhu Yongcheng , Nie Anmin , Fu Haoyu , Hu Zhiwei , Sun Xueping , Haw Shu‐Chih , Chen Jin‐Ming , Chan Ting‐Shan , Yu Sijie , Sun Guang , Jiang Gang , Han Jiantao , Luo Wei , Huang Yunhui
Published: December 2021

Oxygen‐based anionic redox reactions have recently emerged as a lever to increase the capacity of Mn‐rich layered oxide cathodes in addition to the charge compensation based on cationic redox reactions for sodium‐ion batteries. Unfortunately, the irreversibility of anionic redox often aggravates irreversible structure change and poor cycling performance. Here, a stable anionic redox is achieved through substituting Na ions by Mg ions in P2‐type Na0.83Li0.25Mn0.75O2. Density functional theory (DFT) calculations reveal that Mg substitution effectively decreases the oxygen chemical potential, causing an improvement in lattice oxygen stability. Moreover, at a highly desodiated state, Mg ions that remain in the lattice and interact with O 2p orbitals can decrease the undercoordinated oxygen and the nonbonded, electron‐deficient O 2p states, facilitating the reversibility of oxygen redox. When cycled in the voltage range of 2.6–4.5 V where only anionic redox occurs for charge compensation, Na0.773Mg0.03Li0.25Mn0.75O2 presents a much better reversibility, giving a 4 times better cycle stability than that of Na0.83Li0.25Mn0.75O2. Experimentally, Na0.773Mg0.03Li0.25Mn0.75O2 exhibits a ≈1.1% volume expansion during sodium insertion/extraction, suggestive of a “zero‐strain” cathode. Overall, the work opens a new avenue for enhancing anionic reversibility of oxygen‐related Mn‐rich cathodes.
A New Durable Surface Nanoparticles‐Modified Perovskite Cathode for Protonic Ceramic Fuel Cells from Selective Cation Exsolution under Oxidizing Atmosphere
Authors: Liang Mingzhuang , Zhu Yijun , Song Yufei , Guan Daqin , Luo Zhixin , Yang Guangming , Jiang San Ping , Zhou Wei , Ran Ran , Shao Zongping
Published: December 2021

A high‐performance cathode of a protonic ceramic fuel cell (PCFC) should possess excellent oxygen reduction reactivity, high proton/oxygen‐ion/electron conductivity, and sufficient operational stability, thus requiring a delicate tuning of both the bulk and surface properties of the electrode material. Although surface modification of perovskites with nanoparticles from reducing‐atmosphere exsolution has been demonstrated effective at improving the electrochemical anodic oxidation, such nanoparticles would easily re‐incorporate into the perovskite lattice causing a big challenge for their application as a cathode. Here, a durable perovskite‐based nanocomposite cathode for PCFCs is reported, which is facilely prepared via the exsolution of nanoparticles in an oxidizing atmosphere. Through composition and cation nonstoichiometry manipulation, a precursor with the nominal composition of Ba0.95(Co0.4Fe0.4Zr0.1Y0.1)0.95Ni0.05O3−δ (BCFZYN‐095) is designed, synthesized, and investigated, which, upon calcination, gives rise to the formation of a perovskite‐based nanocomposite comprising a major perovskite phase and a minor NiO phase enriched on the perovskite surface. The major perovskite phase enabled by the proper cation nonstoichiometry manipulation promotes bulk proton conduction while the NiO nanoparticles facilitate the oxygen surface exchange process, leading to a superior cathodic performance with a maximum peak power density of 1040 mW cm−2 at 650 °C and excellent operational stability of 400 h at 550 °C.
Escalating Ferromagnetic Order via Se‐Vacancies Near Vanadium in WSe2 Monolayers
Authors: Yun Seok Joon , Cho Byeong Wook , Dinesh Thapa , Yang Dae Hee , Kim Yong In , Jin Jeong Won , Yang Sang‐Hyeok , Nguyen Tuan Dung , Kim Young‐Min , Kim Ki Kang , Duong Dinh Loc , Kim Seong‐Gon , Lee Young Hee
Published: December 2021

Magnetic order has been proposed to arise from a variety of defects, including vacancies, antisites, and grain boundaries, which are relevant in numerous electronics and spintronics applications. Nevertheless, its magnetism remains controversial due to the lack of structural analysis. The escalation of ferromagnetism in vanadium‐doped WSe2 monolayer is herein demonstrated by tailoring complex configurations of Se vacancies (SeVac) via post heat‐treatment. Structural analysis of atomic defects is systematically performed using transmission electron microscopy (TEM), enabled by the monolayer nature. Temperature‐dependent magnetoresistance hysteresis ensures enhanced magnetic order after high‐temperature heat‐treatment, consistent with magnetic domain analysis from magnetic force microscopy (MFM). The vanadium–Se vacancy pairing is a key to promoting ferromagnetism via spin‐flip by electron transfer, predicted from density‐functional‐theory (DFT) calculations. The approach toward nanodefect engineering paves a way to overcome weak magnetic order in diluted magnetic semiconductors (DMSs) for renovating semiconductor spintronics.
Acceleration of Bone Regeneration Induced by a Soft‐Callus Mimetic Material
Authors: Longoni Alessia , Utomo Lizette , Robinson Abbie , Levato Riccardo , Rosenberg Antoine J. W. P. , Gawlitta Debby
Published: December 2021

Clinical implementation of endochondral bone regeneration (EBR) would benefit from the engineering of devitalized cartilaginous constructs of allogeneic origins. Nevertheless, development of effective devitalization strategies that preserves extracellular matrix (ECM) is still challenging. The aim of this study is to investigate EBR induced by devitalized, soft callus‐mimetic spheroids. To challenge the translatability of this approach, the constructs are generated using an allogeneic cell source. Neo‐bone formation is evaluated in an immunocompetent rat model, subcutaneously and in a critical size femur defect. Living spheroids are used as controls. Also, the effect of spheroid maturation towards hypertrophy is evaluated. The devitalization procedure successfully induces cell death without affecting ECM composition or bioactivity. In vivo, a larger amount of neo‐bone formation is observed for the devitalized chondrogenic group both ectopically and orthotopically. In the femur defect, accelerated bone regeneration is observed in the devitalized chondrogenic group, where defect bridging is observed 4 weeks post‐implantation. The authors' results show, for the first time, a dramatic increase in the rate of bone formation induced by devitalized soft callus‐mimetics. These findings pave the way for the development of a new generation of allogeneic, “off‐the‐shelf” products for EBR, which are suitable for the treatment of every patient.
A Solar Water‐Heating Smart Window by Integration of the Water Flow System and the Electrochromic Window Based on Reversible Metal Electrodeposition
Authors: Wang Ling , Jiao Xiuling , Chen Dairong , Wang Ting
Published: December 2021

Various smart windows with dynamic modulation of the light transmittance have been developed rapidly in recent years. However, current design of the smart windows can only modulate the indoor solar irradiation instead of effectively utilize them. Here, a solar water‐heating (SWH) smart window is proposed by the integration of the traditional electrochromic window and the water flow system, which can not only provide dynamic daylight modulation but also harvest the solar energy and store them by heating water. In the SWH window, the reversible metal electrodeposition (RME) not only provides daylight modulation but also provides metal layer working as a flat‐plate solar collector for energy harvesting. Compared with traditional electrochromic windows, the SWH window with a water flow system can more effectively modulate the indoor temperature, owing to the significantly enhanced tunability of the thermal irradiation from the window. Compared with water‐flow windows, the RME provide a metallic layer for efficient light harvesting, up to 42% solar energy can be effectively harvested and stored as hot water. Such an SWH smart window is promising to reduce the heating, lighting, and air conditioning energy consumption, which may bring new insights in the design of the next‐generation green buildings.
Case‐fatality study of workers and residents with radiographic asbestos disease in Libby, Montana
Authors: Miller Albert , Black Charles B. , Loewen Gregory , Noonan Curtis W. , McNew Tracy , Whitehouse Alan C. , Frank Arthur L.
Published: December 2021

Background

Vermiculite ore from Libby, Montana contains on average 24% of a mixture of toxic and carcinogenic amphibole asbestiform fibers. These comprise primarily winchite (84%), with smaller quantities of richterite (11%) and tremolite (6%), which are together referred to as Libby amphibole (LA).

Methods

 A total of 1883 individuals who were occupationally and/or environmentally exposed to LA and were diagnosed with asbestos‐related pleuropulmonary disease (ARPPD) following participation in communitywide screening programs supported by the Agency for Toxic Substances and Disease Registry (ATSDR) and followed up at the Center for Asbestos Related Disease (CARD) between 2000 and 2010. There were 203 deaths of patients with sufficient records and radiographs. Best clinical and radiologic evidence was used to determine the cause of death, which was compared with death certificates.

Results

Asbestos‐related mortality was 55% (n = 112) in this series of 203 patients. Of the 203 deaths, 34 (17%) were from asbestos‐related malignancy, 75 (37%) were from parenchymal asbestosis, often with pleural fibrosis, and 3 (1.5%) were from respiratory failure secondary to pleural thickening.

Conclusions

Asbestos is the leading cause of mortality following both occupational and nonoccupational exposure to LA in those with asbestos‐related disease.
Public health risks from asbestos cement roofing
Authors: Kottek Michael , Yuen Man Lee
Published: December 2021

There is no identified risk‐free threshold exposure to asbestos. Based on epidemiology and toxicology, asbestos fiber dimensions have been implicated in causing asbestos‐related diseases. Phase‐contrast microscopy provides only a limited index of exposure to fiber dimensions implicated in mesothelioma induction. Installed asbestos‐containing materials (ACMs) create an ongoing risk of intense exposure during natural disasters and remodeling, along with low‐level exposure arising from the continual emission of airborne asbestos into the environment arising from weathering of installed ACM. Epidemiological studies have demonstrated a risk of disease associated with proximity to asbestos cement roofing (ACR), while ongoing environmental emissions of asbestos from installed ACR have also been demonstrated. Owing to the limitations of the available data, a precautionary approach is warranted; asbestos‐free roofing materials should be used in new construction and existing ACR should be removed at the earliest opportunity.
Halogen Bonding in Perovskite Solar Cells: A New Tool for Improving Solar Energy Conversion
Authors: Metrangolo Pierangelo , Canil Laura , Abate Antonio , Terraneo Giancarlo , Cavallo Gabriella
Published: December 2021

Hybrid organic–inorganic halide perovskites (HOIHPs) have recently emerged as a flourishing area of research. Their easy and low‐cost production and their unique optoelectronic properties make them promising materials for many applications. In particular, HOIHPs hold great potential for next‐generation solar cells. However, their practical implementation is still hindered by their poor stability in air and moisture, which is responsible for their short lifetime. Optimizing the chemical composition of materials and exploiting non‐covalent interactions for interfacial and defects engineering, as well as defect passivation, are efficient routes towards enhancing the overall efficiency and stability of perovskite solar cells (PSCs). Due to the rich halogen chemistry of HOIHPs, exploiting halogen bonding, in particular, may pave the way towards the development of highly stable PSCs. Improved crystallization and stability, reduction of the surface trap states, and the possibility of forming ordered structures have already been preliminarily demonstrated.
Highly Efficient Multiphoton Absorption of Zinc‐AIEgen Metal–Organic Frameworks
Authors: Liu Naifang , Chen Zhihui , Fan Wenxuan , Su Jie , Lin Tingting , Xiao Si , Meng Jianqiao , He Jun , Vittal Jagadese J. , Jiang Jianzhuang
Published: December 2021

A series of luminescent frameworks was synthesized from the selective combination of aggregation induced emission (AIE)‐linker tetra‐(4‐carboxylphenyl)ethylene (H4TCPE) and Zn2+. Complex 1 was formed by the close packing of Zn‐TCPE hinge, and isostructural complexes 2–5 were constructed by the linkage of Zn‐TCPE layer and pillar ligands. These complexes exhibit highly efficient multiphoton excited photoluminescence (MEPL) and concomitant third‐harmonic generation (THG). The multiphoton absorption (MPA) parameters of 1 are superior to other multiphoton emission materials including the perovskite nanocrystals. The incorporation of pillar linkers slows down the charge transfer between layers of Zn‐TCPE, and the aromatic core of pillar linkers has a great influence on the MPA performance of the corresponding frameworks.
Transformation of Covalent Organic Frameworks from N‐Acylhydrazone to Oxadiazole Linkages for Smooth Electron Transfer in Photocatalysis
Authors: Yang Shuailong , Lv Haowei , Zhong Hong , Yuan Daqiang , Wang Xinchen , Wang Ruihu
Published: December 2021

Covalent organic frameworks (COFs) are regarded as new platforms for solar‐to‐chemical energy conversion due to their tailor‐made functions and pre‐designable structures. Their intrinsic reversibility and the high polarization of organic linkages inevitably result in poor chemical stability and weak optoelectronic properties. Herein, one N‐acylhydrazone‐linked COF (H‐COF) was converted into a stable and π‐conjugated oxadiazole‐linked COF via post‐oxidative cyclization. Both chemical stability and π‐electron delocalization throughout the reticular framework are significantly improved, leading to a high hydrogen evolution rate of 2615 μmol g−1 h−1 upon visible light irradiation, which is over four times higher than that of H‐COF. This work provides a facile protocol for the fabrication of π‐conjugated COFs and the modulation of photophysical properties for photocatalytic application.
Symmetrically Tetra‐functionalized Pillar[6]arenes Prepared by Fragment Coupling
Authors: Zeng Hong , Liu Peiren , Xing Hao , Huang Feihe
Published: December 2021

Due to the highly symmetrical structures generated from one‐pot syntheses, the partial functionalization of macrocycles is usually beset with low yields and onerous purifications of the target multifunctional macrocycles. To improve this situation, taking pillar[6]arenes as an example, a two‐step fragment coupling method has been developed for synthesizing symmetrically tetra‐functionalized pillar[6]arenes, namely X‐pillar[6]arenes. This method is simple and versatile, which makes hetero‐fragment coupling and pre‐functionalization available. Nine new macrocycles and a pillar[6]arene‐based cage have been prepared. In addition, one of the newly synthesized macrocycles,COOEtEtXP[6], exhibits a strong cyan luminescence in the solid state under irradiation by 365 nm UV light. This emission originates from intramolecular through‐space conjugation. Meanwhile, formation of a supramolecular polymer by multiple non‐covalent intra/intermolecular interactions helps rigidify the structure and makeCOOEtEtXP[6]an efficient solid‐state emitter. It is believed that this fragment coupling can also be used to realize the multi‐functionalization of other macrocycles.
One‐Step Access to Heteroatom‐Functionalized Imidazol(in)ium Salts
Authors: Pasyukov Dmitry V. , Shevchenko Maxim A. , Shepelenko Konstantin E. , Khazipov Oleg V. , Burykina Julia V. , Gordeev Evgeniy G. , Minyaev Mikhail E. , Chernyshev Victor M. , Ananikov Valentine P.
Published: December 2021

Imidazolium salts have ubiquitous applications in energy research, catalysis, materials and medicinal sciences. Here, we report a new strategy for the synthesis of diverse heteroatom‐functionalized imidazolium and imidazolinium salts from easily available 1,4‐diaza‐1,3‐butadienes in one step. The strategy relies on a discovered family of unprecedented nucleophilic addition/cyclization reactions with trialkyl orthoformates and heteroatomic nucleophiles. To probe general areas of application, synthesized N‐heterocyclic carbene (NHC) precursors were feasible for direct metallation to give functionalized M/carbene complexes (M=Pd, Ni, Cu, Ag, Au), which were isolated in individual form. The utility of the chloromethyl function for the postmodification of the synthesized salts and Pd/carbene complexes was demonstrated. The obtained complexes and imidazolium salts demonstrated good activities in Pd‐ or Ni‐catalyzed model cross‐coupling and C−H activation reactions.
Diskrete gestapelte Dimere von aromatischen Oligoamid‐Helices
Authors: Bindl Daniel , Mandal Pradeep K. , Allmendinger Lars , Huc Ivan
Published: December 2021

Eine starke Bindung wurde zwischen den C‐terminalen Querschnitten von aromatischen Oligoamid‐Helices in wässriger Lösung beobachtet. Diese führt zur Bildung von diskreten Kopf‐an‐Kopf‐Dimeren, die im langsamen Austausch mit den entsprechenden Monomeren auf der NMR‐Zeitskala stehen. Die Art und Struktur der Dimere wurde durch 2D‐NOESY‐ und DOSY‐Spektroskopie, Massenspektrometrie und Röntgenkristallographie nachgewiesen. An der Bindungsschnittstelle beteiligt sind eine große hydrophobe aromatische Oberfläche und Wasserstoffbrückenbindungen. Die Dimerisierung setzt voraus, dass die Helices die gleiche Händigkeit aufweisen und eine C‐terminale Carboxyfunktion vorhanden ist. Der Protonierungszustand der Carboxygruppe spielt eine entscheidende Rolle und führt zu einer pH‐Abhängigkeit der Assoziation. Die Dimerisierung wird auch durch benachbarte Seitenketten beeinflusst und kann programmiert werden, um selektiv heteromere Aggregate zu bilden.
Selective Fluoromethyl Couplings of Alkynes via Nickel Catalysis
Authors: Li Huan , Wang Fang , Zhu Shengqing , Chu Lingling
Published: December 2021

We describe here a Ni‐catalyzed intermolecular carbo‐fluoromethylation of alkynes with aliphatic halides and fluoromethyl halides (BrCF2H and ICH2F) in the presence of zinc, enabling the facile and selective access to a diverse range of biologically valuable CF2H/CH2F‐incorporated alkenes with excellent regio‐ and stereoselectivity. Notably, merging intramolecular radical cyclization with fluoromethyl coupling enables the expedient constructions of CF2H/CH2F‐incorporated lactones and lactams with high efficiency and selectivity. Mechanistic studies disclose that this catalytic protocol proceeds via a radical addition to an alkyne followed by selective coupling with the fluoromethyl unit.
Assembling Metal Organic Layer Composites for High‐Performance Electrocatalytic CO2 Reduction to Formate
Authors: Liu Hang , Wang Hongguang , Song Qian , Küster Kathrin , Starke Ulrich , van Aken Peter A. , Klemm Elias
Published: December 2021

2D metal–organic‐framework (MOF) based composites have emerged as promising candidates for electrocatalysis due to their high structural flexibility and fully exposed active sites. Herein, a freestanding metal–organic layer (MOL) with a 2D kgd (kagome dual) lattice was constructed with abundant surface oxygenate groups serving as anchoring sites to immobilize diverse guests. Taking Bi as an example, tetragonal Bi2O3 nanowires can be uniformly grown on MOLs after solvothermal treatment, the structural evolution of which was followed by ex situ electron microscopy. The as‐prepared Bi2O3/MOL exhibits excellent CO2 electroreduction activity towards formate reaching a specific current of 2.3 A mgBi−1 and Faradaic efficiencies of over 85 % with a wide potential range from −0.87 to −1.17 V, far surpassing Bi2O3/UiO (a 3D Zr6‐oxo based MOF) and Bi2O3/AB (Acetylene Black). Such a post‐synthetic modification strategy can be flexibly extended to develop versatile MOL composites, highlighting the superiority of optimizing MOL‐based composites for electrocatalysis.
Acceleration of FeIII/FeII cycle enhanced by Pd/MOF‐808(Zr) composite in hydrogen promotion Fenton system for sulfamethazine elimination
Authors: Qiu Wen‐Jing , Gao Ming‐Wu , Chen Qi , Zheng Ao , Shi Yi‐Jia , Liu Xin , Li Juan‐Hong , Dai Guo‐Liang , Hu Yang , Lin Zi‐Xia
Published: December 2021

Under normal temperature and pressure, a novel improved Fenton system that was named MHACF‐MOF‐808(Zr) was constructed after the introduction of Pd/MOF‐808(Zr) and H2 to solve the inherent problem of the production of iron sludge in the classic Fenton system. Only trace amount of FeII was required during the whole reaction because FeIII could be rapidly reduced by the active hydrogen derived from the adsorption and activation of H2 on the surface of Pd/MOF‐808(Zr) composite. The concentration of FeII could be maintained more than 10 μM. The removal of target pollutant sulfamethazine in this system was mainly relied on the degradation of ·OH verified by both of the direct detection and indirect inhibition (using methanol). By using the calculation of Laplacian bond order, the degradation pathway of sulfamethazine followed by the cleavage of NS bond. This prediction was verified by the detection of intermediate products. Only 21% sulfamethazine could be degraded after 3‐h reaction in the classic Fenton reaction system, while it could be thoroughly degraded in 1.5 h in the MHACF‐MOF‐808(Zr) system. The influence of main parameters on the degradation effect of sulfamethazine, such as initial pH, the flow of H2, dosage of Pd/MOF‐808(Zr), concentration of sulfamethazine, ferrous, and hydrogen peroxide, were systematically studied. Based on the relative stability of Pd/MOF‐808(Zr) confirmed by the morphological characterization, sulfamethazine could be efficiently degraded in the MHACF‐MOF‐808(Zr) system.
B Cell Numbers Predict Humoral and Cellular Response Upon SARS–CoV‐2 Vaccination Among Patients Treated With Rituximab
Authors: Stefanski Ana‐Luisa , Rincon‐Arevalo Hector , Schrezenmeier Eva , Karberg Kirsten , Szelinski Franziska , Ritter Jacob , Jahrsdörfer Bernd , Schrezenmeier Hubert , Ludwig Carolin , Sattler Arne , Kotsch Katja , Chen Yidan , Claußnitzer Anne , Haibel Hildrun , Proft Fabian , Guerra Gabriela , Durek Pawel , Heinrich Frederik , Ferreira‐Gomes Marta , Burmester Gerd R. , Radbruch Andreas , Mashreghi Mir‐Farzin , Lino Andreia C. , Dörner Thomas
Published: December 2021

Objective

Patients with autoimmune inflammatory rheumatic diseases receiving rituximab (RTX) therapy are at higher risk of poor COVID‐19 outcomes and show substantially impaired humoral immune response to anti–SARS–CoV‐2 vaccine. However, the complex relationship between antigen‐specific B cells and T cells and the level of B cell repopulation necessary to achieve anti‐vaccine responses remain largely unknown.

Methods

Antibody responses to SARS–CoV‐2 vaccines and induction of antigen‐specific B and CD4/CD8 T cell subsets were studied in 19 patients with rheumatoid arthritis (RA) or antineutrophil cytoplasmic antibody–associated vasculitis receiving RTX, 12 patients with RA receiving other therapies, and 30 healthy controls after SARS–CoV‐2 vaccination with either messenger RNA or vector‐based vaccines.

Results

A minimum of 10 B cells per microliter (0.4% of lymphocytes) in the peripheral circulation appeared to be required for RTX‐treated patients to mount seroconversion to anti‐S1 IgG upon SARS–CoV‐2 vaccination. RTX‐treated patients who lacked IgG seroconversion showed reduced receptor‐binding domain–positive B cells (P = 0.0005), a lower frequency of Tfh‐like cells (P = 0.0481), as well as fewer activated CD4 (P = 0.0036) and CD8 T cells (P = 0.0308) compared to RTX‐treated patients who achieved IgG seroconversion. Functionally relevant B cell depletion resulted in impaired interferon‐γ secretion by spike‐specific CD4 T cells (P = 0.0112, r = 0.5342). In contrast, antigen‐specific CD8 T cells were reduced in both RA patients and RTX‐treated patients, independently of IgG formation.

Conclusion

In RTX‐treated patients, a minimum of 10 B cells per microliter in the peripheral circulation is a candidate biomarker for a high likelihood of an appropriate cellular and humoral response after SARS–CoV‐2 vaccination. Mechanistically, the data emphasize the crucial role of costimulatory B cell functions for the proper induction of CD4 responses propagating vaccine‐specific B cell and plasma cell differentiation.
A Two‐Photon Ratiometric Sensing Platform Based on Solid‐State Luminescent Benzocoumarin: Application to Prolonged Bioimaging of Hydrogen Peroxide
Authors: Rim Kim Hye , Sarkar Sourav , Han Ahn Kyo
Published: December 2021

Fluorescent probes provide essential tools for studying biological systems. For the prolonged imaging of cellular analytes, the fast clearance of small‐molecular probes and products is a matter of concern in the quantitative analysis. Activatable probes that produce insoluble products inside cells can be used for prolonged imaging, but those with ratiometric imaging capability are rare. We disclose a novel sensing platform that is capable of prolonged imaging, in addition to ratiometric signaling for reliable quantitative analysis. Specifically, 3‐(pyridin‐4‐yl)‐8‐(pyrrolidin‐1‐yl)‐2H‐benzo[g]chromen‐2‐one and its pyridinium salt as a product/probe couple constitute the ratiometric sensing platform. As the former dye produces highly emissive insoluble nanoaggregates inside cells, a fluorescent probe in the latter form enables prolonged imaging of the target analyte in cells as well as in tissue by two‐photon microscopy.
Determination of supermassive black hole spins in local active galactic nuclei
Authors: Piotrovich Mikhail Yu. , Buliga Stanislava D. , Natsvlishvili Tinatin M.
Published: December 2021

We estimated the radiative efficiency and spin value for a number of local active galactic nuclei (AGNs) with using three popular models connecting the radiative efficiency with such parameters of AGNs as mass of supermassive black hole (SMBH), angle between the line of sight and the axis of the accretion disk and bolometric luminosity. Analysis of the obtained data shows that the spin value decreases with cosmic time, which is in agreement with results of theoretical calculations for low‐redshift AGNs of other authors. Also, we found that the spin value increases with the increasing mass of SMBH and bolometric luminosity. This is the expected result that corresponds to theoretical calculations. Analysis of the distribution of the spin values shows a pronounced peak in the distribution in range. ∼40% of objects have spin and ∼50% of objects have spin . These results are in good agreement with our previous results and with the results of other authors.
Effective immobilization of lactate dehydrogenase onto mesoporous silica
Authors: Alagöz Dilek , Toprak Ali , Varan Nazlı Ece , Yildirim Deniz , Tükel S. Seyhan
Published: December 2021

This study presents that covalent immobilization technique has been utilized for the immobilization of l‐lactate dehydrogenase (l‐LDH) from porcine on mesoporous silica. To develop mesoporous silica as support material for use in l‐LDH immobilization, the particle surfaces were functionalized with 3‐aminopropyltrimethoxysilane and further conjugated with glutaraldehyde. The effect of some parameters such as glutaraldehyde concentration, immobilization pH, initial enzyme concentration, and immobilization time was investigated and the optimum conditions for these parameters were determined as 1% (w/v), pH 8.0, 1 mg/ml, and 120 min, respectively. The maximum working pH and temperature for the oxidation of lactate to pyruvate reaction were determined as 10.0 and 35°C for free and 9.0 and 40°C for immobilized l‐LDH, respectively. The kinetic parameters (Km and Vmax) of l‐LDH for the oxidation of lactate to pyruvate reaction were examined as 1.02 mM and 7.58 U/mg protein for free and 0.635 mM and 1.7 U/mg protein for immobilized l‐LDH, respectively. Moreover, the immobilized l‐LDH was 1.3‐fold more stable than free l‐LDH at 25°C according to calculated t1/2 values. The immobilized l‐LDH retained 80% of its initial activity in a batch reactor after 14 reuses.
Pulsed High‐Peak Power Microwaves at 9.4 GHz Do Not Affect Basic Endpoints in Caenorhabditis elegans
Authors: Sun Aihua , Li Zhihui , Zhao Xuelong , Zhou Hongmei , Gao Yan , Liu Qi , Zhou Sen , Zhang Chenggang , Dong Guofu , Wang Changzhen
Published: December 2021

Because of the extensive application of electromagnetic technology, its health impact on humans has attracted widespread attention. Due to the lack of a model organism with a stable response to electromagnetic waves, the research conclusions on the biological effects of electromagnetic waves have been vague. Therefore, the aim of this study was to investigate the effects of irradiation by pulsed 9.4 GHz high‐power microwaves with a peak power density of 2126 W/cm2 using Caenorhabditis elegans. The development, movement, egg production, ROS, and lifespan of C. elegans were detected at different times after irradiation with different repetitive frequencies of 10, 20, and 50 Hz for 30 min. The results indicated that no obvious changes in basic life indices were induced compared with the sham radiation group, but the survival rate of positive control was significantly decreased compared with other groups, which is of interest for microwave protection research based on C. elegans and provides data for updating safety standards with respect to pulsed high‐peak power microwave. © 2021 Bioelectromagnetics Society.
Small molecule epigenetic modulators for enhancing recombinant antibody production in CHO cell cultures
Authors: Kim Dongil , Yoon Chansik , Lee Gyun Min
Published: December 2021

Small molecule epigenetic modulators that modify epigenetic states in cells are useful tools for regulating gene expression by inducing chromatin remodeling. To identify small molecule epigenetic modulators that enhance recombinant protein expression in Chinese hamster ovary (CHO) cells, we examined eight histone deacetylase inhibitors (iHDACs) and six DNA methyltransferase inhibitors as chemical additives in recombinant CHO (rCHO) cell cultures. Among these, a benzamide‐based iHDAC, CI994, was the most effective in increasing monoclonal antibody (mAb) production. Despite suppressing cell growth, the addition of CI994 to mAb‐expressing GSR cell cultures at 10 μM resulted in a 2.3‐fold increase in maximum mAb concentration due to a 3.0‐fold increase in specific mAb productivity (qmAb). CI994 increased mAb messenger RNA levels and histone H3 acetylation in GSR cells, and chromatin immunoprecipitation‐quantitative polymerase chain reaction analysis revealed that CI994 significantly increased the histone H3 acetylation level at the cytomegalovirus promoter driving mAb gene expression, indicating that chromatin remodeling in the promoter region results in enhanced mAb gene transcription and qmAb. Similar beneficial effects of CI994 on mAb production were observed in mAb‐expressing CS13‐1.00 cells. Collectively, our findings indicate that CI994 increases mAb production in rCHO cell cultures by chromatin remodeling resulting from acetylation of histones in the mAb gene promoter.
Stimulated reversal of the strong adhesion of catechol onto a silica surface
Authors: Ilyas Muhammad , Mian Shabeer Ahmad , Rauf Abdur , Ahmed Ejaz , Rahman Gul , Sannyal Arindam , Jang Joonkyung
Published: December 2021

Marine mussels permanently adhere to various surfaces via catechol (1,2‐dihydroxybenzene) functional groups. Such biofouling causes adverse effects, including the corrosion and dragging of a marine vessel. By using the density functional theory, we show an electrical stimulus detach a catechol molecule that strongly adhered to a silica surface. A moderate electric field significantly decreases the binding energy of catechol adhered to a dry or wet silica surface.
Computational study of the pKa values of a modified G·C base pair in duplex DNA
Authors: Kim Hyeonjun , Pak Youngshang
Published: December 2021

During the demethylation of 5‐methyl cytosine residues in duplex DNAs, formyl or carboxyl cytosines are produced and these modified cytosines are preferentially recognized and excised by the thymine DNA glycosylase (TDG). It has been suggested that the TDG detects a soft spot created by weakening of the hydrogen bond of a G·C base pair (bp). Such bp destabilization is ascribed to the presence of electron‐withdrawing 5‐formyl or 5‐carboxyl group in the modified cytosine. Previously, this bp weakening was linked to reduced values of nucleoside molecules. However, the values of nucleosides can deviate from those of duplex DNAs. Thus, to improve agreement with experiments, the corresponding values for DNA environments are needed. In this computational study, we report two values of the N3‐ and the C5‐carboxyl sites in the 5‐carboxyl cytosine residue in a duplex DNA that enable more reasonable interpretations of previous experimental data.
The efficacy and safety of pyrotinib in treating HER2‐positive breast cancer patients with brain metastasis: A multicenter study
Authors: Gao Min , Fu Chao , Li Shanshan , Chen Fang , Yang Yongteng , Wang Chunjian , Qin Jie , Liu Shuaishuai , Zhang Ranran , Wang Changyuan , Zong Jinbao , Meng liping , Meng Xiangjiao
Published: December 2021

Purpose

To investigate the efficacy and safety of pyrotinib in treating patients with human epidermal growth factor receptor type 2 (HER2)‐positive breast cancers with brain metastasis.

Patients and Methods

This is a multicenter retrospective study, and the HER2‐positive breast cancer patients with brain metastasis were studied. The enrolled patients were given pyrotinib 400 mg orally once per day for 21 days as one cycle, and evaluated every two cycles. All relevant data were detected for final assessments including medical history, clinical examination, histopathology, immunohistochemistry, radiographic imaging, treatment outcome, and adverse events.

Results

Forty‐two female patients in total were enrolled in this study. The objective response rate (ORR) and disease control rate (DCR) of central nervous system (CNS), were found in 20 of 42 (47.6%) and in 39 of 42 (92.8%), respectively, while for extra‐CNS, the respective ORR and DCR were in 9 of 38 (23.6%) and in 36 of 38 (94.7%), respectively. The compounded ORR and DCR were seen in 17 of 42 (40.4%) and in 39 of 42 (92.8%), respectively. The improvement rate of craniocerebral symptoms after treatment was (19/19) 100% and the median duration was 15 months. The median effective time of brain metastases and other metastases was 43 and 50 days. The median follow‐up time was 22 months (interquartile range, 16.0–24.3 months). The median time for progression in brain metastasis was 16.6 months. The median time to progress for our group patients was 11.1 months. Sixteen patients (36%) with adverse reactions were recorded in the study.

Conclusion

Pyrotinib combined with chemotherapy/radiotherapy or alone showed significantly greater local control rates and progression free survival (PFS), with manageable toxicity for patients with HER2‐positive breast cancer with brain metastases, and further follow‐up will provide an overall survival (OS) data.