bluuebunny/crossref_metadata_2025 huggingface dataset:
Triaxial Cyclic Loading Fracture of Rock-Encased-Backfill Structure by Xray and Acoustic Emission
Authors: Yu Xin , Song Weidong , Tan Yuye , Kemeny John , Qi Shengwen , Zheng Bowen
Published: November 2022

The strain softening behavior of the rock-encased-backfill (RB) structure decides the stability of the underground backfilling stope during cyclic excavation and blasting. To investigate the cyclic failure behavior of the RB specimen, a series of triaxial cyclic loading experiments were conducted in different volume fractions of rock, confining pressures, and cyclic loading rates. Results show the strain hysteresis curve increases from sparse to dense with the increase of the confining pressure, showing a significant strain-softening characteristic. The elastic strain energy increases linearly and the dissipation energy increases exponentially with the number of cycles. The percentage of shear microcracks during each circle increased quadratically, which was very similar to the trend of dissipation energy. When VF=0.73 and the loading and unloading rate was 400 N/s, the percentage of shear microcracks in RB specimens was higher than that in other cases, especially higher under 9 MPa. This finding indicates that RB specimens are more prone to meso damage and elastic-plastic transformation under a specific condition, and the importance to conduct more studies on the coupling mechanism of the bi-geological-materials structure.

Introduction

Backfill is one kind of artificial and green material reserved in the underground, which is made with waste tailings after mining excavation. Its mechanical properties are similar to soil and cement, which is far away from that rock mass nearby. After the backfill is consolidated, the field stress will be redistributed in the rock-encased-backfill structure (RB).
Le dossier photographique de la société Maurice Dufrène et Cie (1912-1921), 22, rue Bayard, Paris
Authors: Cerman Jérémie
Published: November 2022

Débutant sa carrière à l’époque de l’Art nouveau avant de devenir l’un des décorateurs prépondérants de l’Art déco, Maurice Dufrène exerce son activité de 1912 à 1921 dans le cadre d’une société, la Maurice Dufrène & Cie, installée dans un hôtel particulier du 22, rue Bayard à Paris, dont il dessine la façade et où il aménage ses showrooms. Bien que cette étape de sa carrière soit particulièrement féconde, l’histoire de cette entreprise a passablement été oubliée. Le contenu d’un dossier constitué en 1918 par le Casier archéologique et artistique de la Ville de Paris constitue l’une des rares sources visuelles à ce sujet. L’étude de ces documents, croisés à d’autres sources éparses, permet de faire revivre l’activité de Dufrène à cette époque.
The state of the art of macroprogramming in IoT: An update
Authors: Júnior Iwens G. S. , Santana Thalia S. de , Bulcão-Neto Renato de F. , Porter Barry F.
Published: November 2022

Macroprogramming's primary goal is to increase developers' productivity by providing high-level specifications of applications' behaviour at the system level. Macroprogramming may be a viable solution for developing complex IoT applications, such as those manipulating high data volume and heterogeneity. This paper updates a recent work identifying and analysing primary research on macroprogramming in IoT through a systematic literature mapping (SLM). We extended the search strategy scope by conducting an automatic search over five new databases and also performed the snowballing technique. As a result, besides the 38 studies group found in previous SLM, nine new papers were classified as relevant and rigorously analysed, totalising forty-seven studies. In comparison to previous work, results still point out the recurrence of abstractions in the network infrastructure, highlighting the use of frameworks in one-third of the applications and contributing with an overview of macroprogramming by researchers in different knowledge areas.
What makes an Internet troll? On the relationships between temperament (BIS/BAS), Dark Triad, and Internet trolling
Authors: Molenda Zuzanna Aleksandra , Marchlewska Marta , Rogoza Marta , Michalski Piotr , Górska Paulina , Szczepańska Dagmara , Cislak Aleksandra
Published: November 2022

Internet trolling is a provocative or offensive online behavior linked to engaging in anonymous activities that evoke negative feelings in other people. We analyzed the relationships between Internet trolling, Dark Triad traits (i.e., psychopathy, narcissism, and Machiavellianism), and the Behavioral Inhibition System (BIS)/Behavioral Approach System (BAS) in two studies. Study 1 involved a national quota sample representative of Polish young adults (N = 1,048, aged 18–25), and Study 2 involved a national quota sample of adult Poles (N = 432, aged 18–84). In both studies, we hypothesized and found that Internet trolling is predicted by low BIS and high BAS and that these relationships are mediated by high levels of psychopathy. These findings suggest that the basic temperamental dispositions may predispose individuals to irritate others on the Internet for one’s own enjoyment due to high (vs. low) levels of psychopathy. We discuss the role of temperamental and personality traits in shaping offensive online behavior.
CULTURAL AND ARCHITECTURAL HERITAGE AMONG THE PROJECT OF CONSERVATION, ENHANCEMENT AND LOCAL COMMUNITIES’ IDENTITY
Authors:   Politecnico di Milano, dept A.B.C Milano, Lombardini Nora
Published: November 2022

The safeguarding of cultural heritage and, specifically, architectural heritage, as an expression of cultural identity, meansthe defense, asthe Faro Convention argues, of human rights and is part of the concept of democracy. Therefore, there is a need for a collective participation in its protection and enhancement which concerns not only the governing bodies but also the communities that identify themselves in cultural heritage (Faro Convention, 2005). Governments have, in fact, the duty to interface with communities guaranteeing them the care of everything that can help to create "understanding, identity, cohesion and creativity". It is evident that the extreme difficulty of implementing this process is answered by adopting all the most suitable tools for safeguarding the cultural good itself (Treccani, Item: Identità). The idea of protection is linked to the awareness that cultural heritage, and the architectural one, belongs to every people and this assertion assumes that it is not really the people, but the government is the guarantor of the people who take in care the protection of the goods which is awarded with universal value.
CULTURAL HERITAGE MANAGEMENT: PROJECT DELIVERY SYSTEM OF CONSERVATION PROJECTS
Authors:   I, Kambek Erkan , Tanyeli Gülsüm
Published: November 2022

In general, cultural heritage projects are accepted as construction work. For this reason, traditional project management and delivery systems applied for construction projects are also applied for conservation projects. However, conservation projects are more of an activity of conserving and improving the existing structure than constructing, due to the existence of the structure subject to the project. This conservation activity, which should be done scientifically, also necessitates developing a management approach apart from that of an ordinary building, due to the values embodied in the cultural heritage. Understanding and defining these values are the cornerstones of conservation projects. So, what are the ways of planning a project delivery system that will respect the values defined for the cultural heritage? Seeking for possible answers to this question could support producing a higher quality process and result for cultural heritage conservation projects.Currently, it has been seen that the most common applied project delivery system for cultural heritage conservation is the traditional project delivery system. However, it is obvious that the issues arising from the characteristics of the conservation projects can not be solved by continuing within the traditional delivery systems. The aim of this paper is to show the necessity to develop a delivery system specific to conservation projects due to the basic characteristics of conservation projects. It is believed that a proposal for the project delivery system for conservation projects including features of conservation project facts will contribute to conduct and achieve conservation works with better quality.
THE CURRENT DISCOURSES IN PRESERVATION AND PRESENTATION OF ARCHAELOGICAL HERITAGE
Authors:   Dokuz Eylül University İzmir, Zeren Mine Tanac
Published: November 2022

Archaeological studies are considered as a principal source of knowledge of prehistoric, ancient, and extinct cultures. The unearthed evidence as architectural artefacts are very important resources of the history and cultural and architectural heritage values. Archaeological areas are cultural heritage sites, which have ruins that can be easily damaged by destructive and corrosive effects. Therefore it is hard to protect this cultural heritage sites from effects stemming from nature and human. In archaeological sites, both preservation and exhibition of the findings are very important items that are taken into consideration in today’s preservation manner. This Paper aims to put forward the main principles of the applications on Archaeological Sites in terms of preservation and exhibition. And mainly will concern on; Main Intervention principles related on site planning; Methods for raising the attraction of the archaeological sites, methods for making sites visible from outside. Planning principles of walking routes of the site, the entry points and related items. Main Intervention principles related on archaeological findings; Conservation methods of the archaeological remains, Archaeological Restoration methods of archaeological findings both for preservation and exhibition criteria. Design criteria of protection roofs. Design criteria of walking platforms
ARCHITECTURE OF THE IMARETS OF SHUSHA
Authors:   Azerbaijan University of Architecture and Construction, Amenzade Rayiha
Published: November 2022

Reconstruction, restoration and preservation of the historical cities of Azerbaijan is one of the urgent problems of modern architecture. Among them, one of the most interesting cities is Shusha, which was declared the cultural capital of the Turkic world in 2023. In the presented article, for your attention are some notes about imarets (palaces), the genetic roots of which date back to folk housing. Historically, palaces - villas and palace complexes were built in medieval Azerbaijan. The construction of palaces was carried out in cities, no fewer of them were in the suburbs, their choice was due to the urban situation, the landscape of the area, the presence of a river, a lake.
PRESERVATION AND RESTORATION OF THE ARCHITECTURAL HERITAGE IN VIEW OF THE STRUCTURAL ENGINEERING PERSPECTIVE
Authors:   Azerbaijan University of Architecture and Construction, Gasimzade Azer ,   Ondokuz Mayis University,   Ondokuz Mayis University, Nematli Emin , Serra Danis
Published: November 2022

Evaluation of the current building situation, which is one of the priority stages of the preservation and restoration - repair and strengthening (P&R-R&S) of historic buildings, so as not to damage the originality of the structure, using the non-destructive Operational Modal Analyzes-OMA method is on target. That is also the fundamental method for calibrating (estimating the current state of the structural, material, soil interaction, etc.) the finite element model of the structure. On the other hand, applying materials with high strength and as light as possible in these studies is efficient, such as Carbon Fiber Reinforced Polymers- CFRP. Another importance of using this material is that it is more resistant to corrosion and has a long service life. These properties have caused CFRP to have a vast and fundamental place in structures P&R-R&S. In the presented work, with the aforementioned methods, the project of repairing and strengthening the old tobacco factory and transforming it into a modern shopping center is shown, which was implemented in 2011. Afterward, the application limits of these studies to the historical buildings in the East Zangezur and Karabakh regions, which were liberated from the occupation, are explained on the historical building examples in the mentioned region.
Endoscopic ultrasound-directed transgastric endoscopic retrograde cholangiopancreatography for patients with Roux-en-Y gastric bypass anatomy: technical overview
Authors: Honda Hirokazu , Mosko Jeffrey D. , Kobayashi Ryosuke , Fecso Andras , Kim Bong Sik , Scott Schoeman , May Gary R.
Published: November 2022

Endoscopic retrograde cholangiopancreatography (ERCP) in patients with Roux-en-Y gastric bypass anatomy is a well-documented challenge. Traditionally, this problem has been overcome with adjunctive techniques, such as device-assisted ERCP, including double-balloon or single-balloon enteroscopy and laparoscopy-assisted transgastric ERCP. Endoscopic ultrasound-directed transgastric ERCP (EDGE) is a novel technique that enables access to the ampulla using a duodenoscope without surgical intervention and has shown high clinical and technical success rates in recent studies. However, this approach is technically demanding, necessitating a thorough understanding of the gastrointestinal anatomy as well as high operator experience. In this review, we provide a technical overview of EDGE in parallel with our personal experience at our center and propose a simple algorithm to select patients for its appropriate application. In conjunction, the outcomes of EDGE compared with those of device-assisted and laparoscopy-assisted transgastric ERCP will be discussed.
A motor neuron disease-associated mutation produces non-glycosylated Seipin that induces ER stress and apoptosis by inactivating SERCA2b
Authors: Saito Shunsuke , Ishikawa Tokiro , Ninagawa Satoshi , Okada Tetsuya , Mori Kazutoshi
Published: November 2022

A causal relationship between endoplasmic reticulum (ER) stress and the development of neurodegenerative diseases remains controversial. Here, we focused on Seipinopathy, a dominant motor neuron disease, based on the finding that its causal gene product, Seipin, is a protein that spans the ER membrane twice. Gain-of-function mutations of Seipin produce non-glycosylated Seipin (ngSeipin), which was previously shown to induce ER stress and apoptosis at both cell and mouse levels albeit with no clarified mechanism. We found that aggregation-prone ngSeipin dominantly inactivated SERCA2b, the major calcium pump in the ER, and decreased the calcium concentration in the ER, leading to ER stress and apoptosis in human colorectal carcinoma-derived cells (HCT116). This inactivation required oligomerization of ngSeipin and direct interaction of the C-terminus of ngSeipin with SERCA2b, and was observed in Seipin-deficient neuroblastoma (SH-SY5Y) cells expressing ngSeipin at an endogenous protein level. Our results thus provide a new direction to the controversy noted above.
Brasil chegou a vez das Anas, Terezas e Dalvas: Reflexões sobre racismo junto às idosas do Programa Renascer - HUGG
Authors: Velasco Loureiro Camila , Rubano de Oliveira Carolina , Gonçalves dos Santos Silva Erick José , Lima de Oliveira Graziele , Teixeira da Paz Mariana , Silva de Oliveira Marta Claudia , Da Silva Santos Thaís , Bezerra de Souza Vanessa
Published: November 2022

O presente trabalho visa relatar as atividades realizadas pelo projeto de extensão “Luz, Câmera, Ação: a presença das relações de gênero e racismo no cinema” no Programa Renascer no Hospital Universitário Gaffrée e Guinle. O programa tem o caráter multidisciplinar e envolveu estudantes de teatro, medicina, enfermagem, direito, nutrição, e serviço social. As atividades realizadas pelo projeto “Luz, Câmera, Ação no Programa Renascer” buscaram levar debates sobre gênero e racismo para idosas através de filmes. Esses debates tiveram o intuito de conduzir temas muito discutidos no meio acadêmico para além dos muros da universidade, gerando uma troca mútua de aprendizado.
A method for patient‐specific DVH verification using a high‐sampling‐rate log file in an Elekta linac
Authors: Nishiyama Shiro , Takemura Akihiro
Published: November 2022

We have proposed a method for patient‐specific dose–volume histogram (DVH) verification using a 40‐ms high‐sampling‐rate log file (HLF) available in an Elekta linac. Ten prostate volumetric‐modulated arc therapy plans were randomly selected, and systematic leaf position errors of ±0.2, ±0.4, or ±0.8 mm were added to the 10 plans, thereby producing a total of 70 plans. An RTP file was created by interpolating each leaf position in the HLF to obtain values at each control point, which is subsequently exported to a treatment planning system. The isocenter dose calculated by the HLF‐based plan to a phantom (Delta4 Phantom+) was compared to that measured by the diode in the phantom in order to evaluate the accuracy of the HLF‐based dose calculation. The D95 of the planning target volume (PTV) was also compared between the HLF‐based plans and the original plans with the systematic leaf position errors, the latter being referred to as theory‐based plans. Sensitivities of the DVH parameters in the target, the rectum, and the bladder were also calculated with the varied systematic leaf position errors. The relative differences in the isocenter doses between the HLF‐based calculations and the measurements among the 70 plans were 0.21% ± 0.67% (SD). The maximum relative differences in PTV D95 between the HLF‐based and the theory‐based plans among the 70 cases were 0.11%. The patient‐specific DVH verification method detected a change in the target DVH parameters of less than 1% when the systematic leaf position error was ±0.2 mm. It is therefore suggested that the proposed DVH verification method may simplify patient‐specific dose quality assurance procedures without compromising accuracy and sensitivity.
Nanostructured‐Based Optical Readouts Interfaced with Machine Learning for Identification of Extracellular Vesicles
Authors: del Real Mata Carolina , Jeanne Olivia , Jalali Mahsa , Lu Yao , Mahshid Sara
Published: November 2022

Extracellular vesicles (EVs) are shed from cancer cells into body fluids, enclosing molecular information about the underlying disease with the potential for being the target cancer biomarker in emerging diagnosis approaches such as liquid biopsy. Still, the study of EVs presents major challenges due to their heterogeneity, complexity, and scarcity. Recently, liquid biopsy platforms have allowed the study of tumor‐derived materials, holding great promise for early‐stage diagnosis and monitoring of cancer when interfaced with novel adaptations of optical readouts and advanced machine learning analysis. Here, recent advances in labeled and label‐free optical techniques such as fluorescence, plasmonic, and chromogenic‐based systems interfaced with nanostructured sensors like nanoparticles, nanoholes, and nanowires, and diverse machine learning analyses are reviewed. The adaptability of the different optical methods discussed is compared and insights are provided into prospective avenues for the translation of the technological approaches for cancer diagnosis. It is discussed that the inherent augmented properties of nanostructures enhance the sensitivity of the detection of EVs. It is concluded by reviewing recent integrations of nanostructured‐based optical readouts with diverse machine learning models as novel analysis ventures that can potentially increase the capability of the methods to the point of translation into diagnostic applications.
Template Directed Synthesis of Boron Carbon Nitride Nanotubes (BCN‐NTs) and Their Evaluation for Energy Storage Properties
Authors: Karbhal Indrapal , Chaturvedi Vikash , Yadav Poonam , Patrike Apurva , Shelke Manjusha V.
Published: November 2022

A unique approach has been applied for the synthesis of 1D boron carbon nitride nanotubes (BCN‐NTs) using MnO2 nanowires as templates. BCN‐NTs have been evaluated in Na‐ion batteries, Li‐ion batteries, and supercapacitors as electrode material and exhibited excellent and stable electrochemical performance. BCN‐NTs as an anode for Na‐ion battery has been shown to be highly stable up to 3000 cycles with capacity retention of 95 mAh g−1, at a high current density of 1 A g−1. In the case of the Li‐ion battery, these BCN‐NTs show a specific capacity of 563 mAh g−1 at a current density of 50 mA g−1. Finally, when used as an electrode for a supercapacitor, BCN‐NTs display a specific capacity of 221 F g−1 at a current density of 3 A g−1 and 168 F g−1 even at a very high current density of 30 A g−1 exemplifying the excellent rate performance. The multifunctionality and stable performance of BCN‐NTs among various electrochemical energy storage systems highlight the robustness of the material and make it an excellent candidate for scalable production and commercialization.
Ultrathin Solid Polymer Electrolyte Design for High‐Performance Li Metal Batteries: A Perspective of Synthetic Chemistry
Authors: Wang Qian , Wang Shi , Lu Tiantian , Guan Lixiang , Hou Lifeng , Du Huayun , Wei Huan , Liu Xiaoda , Wei Yinghui , Zhou Henghui
Published: November 2022

Li metal batteries (LMBs) have attracted widespread attention in recent years because of their high energy densities. But traditional LMBs using liquid electrolyte have potential safety hazards, such as: leakage and flammability. Replacing liquid electrolyte with solid polymer electrolyte (SPE) can not only significantly improve the safety, but also improve the energy density of LMBs. However, till now, there is only limited success in improving the various physical and chemical properties of SPE, especially in thickness, posing great obstacles to further promoting its fundamental and applied studies. In this review, the authors mainly focus on evaluating the merits of ultrathin SPE and summarizing its existing challenges as well as fundamental requirements for designing and manufacturing advanced ultrathin SPE in the future. Meanwhile, the authors outline existing cases related to this field as much as possible and summarize them from the perspective of synthetic chemistry, hoping to provide a comprehensive understanding and serve as a strategic guidance for designing and fabricating high‐performance ultrathin SPE. Challenges and opportunities regarding this burgeoning field are also critically evaluated at the end of this review.
Reaction‐controlled microgel‐lipase co‐stabilized compartmentalized emulsion for recyclable biodiesel production
Authors: Guan Xin , Wan Zhili , Ngai To
Published: November 2022

Pickering emulsions have been widely used for biphasic catalysis in the past decade. However, it remains a great challenge to achieve simple product collection and enzyme recovery. Poly(N‐isopropylacrylamide) (PNIPAM)‐based microgels can endow Pickering emulsions with stimuli‐responsiveness, while most microgel‐stabilized emulsions are oil‐in‐water (O/W) type and not ideal for interfacial catalysis. Besides, altering temperature or pH value for demulsification is time‐ and energy‐consuming and may cause irreversible deactivation of enzymes. In this work, inverse water‐in‐oil (W/O) Pickering emulsions were formed using hexanoic acid‐swollen microgels as the sole emulsifiers. When lipase was added in the water phase, stable oil‐in‐water‐in‐oil (O/W/O) Pickering double emulsions could be formed through one‐step emulsification, owing to the synergistic effect of the hydrophobic microgels and hydrophilic lipase at the interface. Compared with other biphasic systems, such double emulsion systems represent a desirable platform for highly efficient biodiesel production because of the ultra‐high interfacial areas and fast mass transport between two phases. More importantly, the switchable transition between hydrophobicity/hydrophilicity of microgels is controlled by the catalytic reaction. Therefore, double emulsions demulsify spontaneously when substrates are used up without the need for energy input or loss of enzymatic activity, enabling the facile collection of products and demonstrating the excellent recyclability of the biphasic catalysis system.
Revealing the effect of synergistic interaction between ZnO and ZnCr2O4 on the syngas aromatization
Authors: Ma Zixuan , Tan Minghui , Cao Fenghai , Yang Yuhao , Gong Nana , Wu Yingquan , Zhang Junfeng , Yang Guohui , Tan Yisheng
Published: November 2022

Zn‐Cr‐based catalysts are widely used as oxide catalysts for syngas aromatization, and it is difficult to study the synergistic effect of ZnO and Zn‐Cr spinel due to the complex system of non‐stoichiometric Zn‐Cr spinels. In order to reveal the synergistic effect, we physically mixed ZnO and ZnCr2O4 with definite structure to avoid ambiguous structure of non‐stoichiometric Zn‐Cr spinels. The results showed that the introduced ZnO affected the oxygen vacancies generation and promoted the activation of CO and H2, leading to an increase of oxygenates compared to the sole ZnCr2O4. Due to the synergy of ZnO and ZnCr2O4, the xZZC catalysts could produce more adsorbed species than the ZnCr2O4 catalyst, while the ZnCr2O4/ZSM‐5 catalyst was more difficult to convert formate species. The ZnO in xZZC/ZSM‐5 decreased the formate adsorption strength, which favored the continued conversion of formate and further realized the enhanced pulling effect on CO conversion.
Design and Manipulation of a Minimalistic Hydrocarbon Nanocar on Au(111)
Authors: Barragán Ana , Nicolás‐García Tomás , Lauwaet Koen , Sánchez‐Grande Ana , Urgel José I. , Björk Jonas , Pérez Emilio M. , Écija David
Published: November 2022

Nanocars are carbon‐based single‐molecules with a precise design that facilitates their atomic‐scale control on a surface. The rational design of these molecules is important in atomic and molecular‐scale manipulation to advance the development of molecular machines, as well as for a better understanding of self‐assembly, diffusion and desorption processes. Here, we introduce the molecular design and construction of a collection of minimalistic nanocars. They feature an anthracene chassis and four benzene derivatives as wheels. After sublimation and adsorption on an Au(111) surface, we show controlled and fast manipulation of the nanocars along the surface using the tip of a scanning tunneling microscope (STM). The mechanism behind the successful displacement is the induced dipole created over the nanocar by the STM tip. We utilized carbon monoxide functionalized tips both to avoid decomposition and accidentally picking the nanocars up during the manipulation. This strategy allowed thousands of maneuvers to successfully win the Nanocar Race II championship.
Reversible Isomerization Between Silacyclopropyl Cation and Cyclic (Alkyl)(Amino)Silylene
Authors: Nougué Raphaël , Takahashi Shintaro , Baceiredo Antoine , Saffon‐Merceron Nathalie , Branchadell Vicenç , Kato Tsuyoshi
Published: November 2022

A phosphine‐stabilized silacyclopropyl cation2has been synthesized and fully characterized. Of particular interest,2reversibly isomerizes into the corresponding seven‐membered cyclic (alkyl)(amino)silylene3at room temperature via a formal migratory ethylene insertion into the Si−P bond. Although silylene3has not been spectroscopically detected, its transient formation has been evidenced by the isolation of the corresponding disilene dimer5as well as by trapping reactions.
Numerical simulation and modeling of viscous fluid residence time distribution in the melt spinning pack
Authors: Zhu Yiwei , Li Xin , Wu Pengfei , Gan Lihua , Hao Haoran , Ma Xin , Cai Ziqi
Published: November 2022

Melt spinning is an important method in fiber production. The hydrodynamic performance of fluid in the melt spinning process's core device, spinning pack, can directly affect the quality of fiber products. To guarantee the uniform distribution of flow in the spinning pack, the residence time distribution (RTD) characteristics of high viscosity fluid in the spinning pack were investigated experimentally and numerically in this work. Peak and trailing of RTD curves indicate the existence of short circuit and dead zone in the spinning pack. Results show that the porous media and gland can reduce the dead zone, and baffles could reduce the short circuit. Based on the experiment and numerical simulation results, a one‐dimensional axial diffusion model was established to describe the RTD characteristics of viscous fluid in the spinning pack. This work can be valuable references for the understanding and optimization of the spinning pack in melt spinning process.
Serum cholesterol and the risk of developing hormonally driven cancers: A narrative review
Authors: Murdock Dana J. , Sanchez Robert J. , Mohammadi Kusha A. , Fazio Sergio , Geba Gregory P.
Published: November 2022

Although cholesterol has been hypothesized to promote cancer development through several potential pathways, its role in the risk of developing hormonally driven cancer is controversial. This literature review summarizes evidence from the highest quality studies to examine the consistency and strength of the relationship between serum cholesterol parameters and incidence of hormonally driven cancer. Articles were identified using EMBASE. Longitudinal observational studies published between January 2000 and December 2020 were considered for inclusion. The endpoint of interest was incident prostate, ovary, breast, endometrium, and uterine cancers. In total, 2732 reports were identified and screened; 41 studies were included in the review. No associations were found for ovarian cancer. Most endometrial cancer studies were null. The majority (76.9%) of studies reported no association between cholesterol and prostate cancer. Data on breast cancer were conflicting, associations limited, and effect sizes modest. Our results do not provide evidence for a clear association between cholesterol and different types of incident, hormonally driven reproductive cancers. Future studies should investigate the impact of lipid‐lowering therapy.
Data are data: Do we need a randomized trial of transcatheter aortic valve replacement for bicuspid valves?
Authors: Ueyama Hiroki , Block Peter C.
Published: November 2022

Key Points

No randomized trials have been done for TAVR in bicuspid aortic valve (BAV) and probably will never be done.

TAVR for BAV has a similar risk profile to tricuspid aortic valve patients except for a higher risk of permanent pacemaker implantation at 30 and 180 days after the index procedure.

Further real‐world data are needed to refine patient selection, procedural technique, and lifetime planning of intervention.
“Does gender equality also apply to chronic total occlusion management?”
Authors: Di Mario Carlo , Di Muro Francesca Maria
Published: November 2022

Key Points

Women are less frequently referred to CTO recanalizations according to their ambiguous presentation

Gender has a great impact on technical procedural success and also on procedural complication rate

It is important to adopt tricks to avoid the most common complications in women such as cardiac tamponade, access problems, and contrast nephropathy
A new method for detecting proanthocyanidin content in wheat reveals the relationship between R‐1 gene to grain color deepness
Authors: Himi Eiko , Matsuura Takakazu , Miura Hideho , Yoshihara Naoya , Maekawa Masahiko
Published: November 2022

Background and Objectives

Grain color of wheat is one of the important quality parameters that affect the flour color and its product such as bread and noodles. R‐1 gene, a regulator of grain color, is located on chromosomes 3A, 3B, and 3D, and at least one dominant allele is responsible for the red color of the grain. It has been thought that the number of dominant R‐1 allele relates to the deepness of the red color of grain; however, methods to quantify grain pigments have not been established yet. The aim of this work was to establish a method for quantifying pigments using 4‐dimethylaminocinnamaldehyde (DMACA), which reacts with precursors of which constitute major pigments of wheat grain.

Findings

Wheat proanthocyanidins were detectable in immature seeds by the DMACA method but became undetectable as the grains matured. Comparison between lines with the same flowering time and genetic background revealed that the amount of pigment was determined by the number of dominant R‐1 alleles.

Conclusions

We established the DMACA method for quantifying wheat seed pigments and used that to clarify the relationship between the number of R‐1 alleles and pigment content.

Significance and Novelty

Since the method developed in this study is not affected by other pigments such as chlorophyll, it can be universally applied to other plants and tissues in addition to wheat grains.
Revisiting the Reaction of IPr with Tritylium: An Alternative Mechanistic Pathway**
Authors: Song Hayoung , Lee Eunsung
Published: November 2022

Despite a recent proposal on the mechanism of a single‐electron transfer (SET) process between tritylium and 2,6‐bis(diisopropylphenyl)imidazol‐2‐ylidene (IPr) based on evidence of transient IPr radical cation intermediate ([IPr]⋅+) formation, such oxidation is still contentious because of the high oxidation potential of N‐heterocyclic carbenes. Our experimental analysis indicates that the appearance of deep purple color, previously considered to be from transient [IPr]⋅+, originates from a zwitterionic intermediate (3 a), not a radical cation. Here, we propose an alternative mechanism for the reaction involving tritylium and IPr. This mechanism is noteworthy for explaining how [NHC−H]+ can be generated without the formation of transient [NHC]⋅+, which has been frequently proposed as an intermediate for the reaction between NHC and oxidants. These results also show that a transient strong single‐electron donor (3 a) could be generated by the alternative mechanism for oxidants using NHCs, which is a more feasible explanation for the reactivity of NHCs with oxidants.
Construction of TiO2/SrTiO3Heterojunction Derived from Monolayer Ti3C2MXene for Efficient Photocatalytic Overall Water Splitting
Authors: Zhuo Zhenzhen , Wang Xue , Shen Cheng , Cai Mengdie , Jiang Yong , Xue Zhaoming , Fu Zhiyuan , Wang Qi , Wei Yuxue , Sun Song
Published: November 2022

Construction of heterojunction at the atomic scale to ensure efficient charge separation for improvement of photocatalytic water splitting is challenging. Herein, a facile hydrothermal method has been applied for the in situ fabrication of TiO2/SrTiO3heterojunction, using the monolayer Ti3C2MXene as the template and reactant. It is found that the sample with the hydrothermal reaction time of 60 min exhibits the highest H2evolution rate with the sacrificial reagent, due to the efficient charge separation of TiO2/SrTiO3heterojunction as Ti3C2derivative. In addition, the sample shows the best overall water splitting performance at a hydrothermal reaction time of 120 min, where TiO2is nearly converted to SrTiO3, due to the fast kinetic process and low structural defects of SrTiO3. This work not only provides a simple strategy for the fabrication of heterojunction photocatalysts but also demonstrates the difference in optimization of half‐reaction and overall water splitting reaction.
Disentangling the Effect of Pressure and Mixing on a Mechanochemical Bromination Reaction by Solid‐State NMR Spectroscopy**
Authors: Bartalucci Ettore , Schumacher Christian , Hendrickx Leeroy , Puccetti Francesco , d'Anciães Almeida Silva Igor , Dervişoğlu Rıza , Puttreddy Rakesh , Bolm Carsten , Wiegand Thomas
Published: November 2022

Mechanical forces, including compressive stresses, have a significant impact on chemical reactions. Besides the preparative opportunities, mechanochemical conditions benefit from the absence of any organic solvent, the possibility of a significant synthetic acceleration and unique reaction pathways. Together with an accurate characterization of ball‐milling products, the development of a deeper mechanistic understanding of the occurring transformations at a molecular level is critical for fully grasping the potential of organic mechanosynthesis. We herein studied a bromination of a cyclic sulfoximine in a mixer mill and used solid‐state nuclear magnetic resonance (NMR) spectroscopy for structural characterization of the reaction products. Magic‐angle spinning (MAS) was applied for elucidating the product mixtures taken from the milling jar without introducing any further post‐processing on the sample. Ex situ13C‐detected NMR spectra of ball‐milling products showed the formation of a crystalline solid phase with the regioselective bromination of theS‐aryl group of the heterocycle in position 4. Completion is reached in less than 30 minutes as deduced from the NMR spectra. The bromination can also be achieved by magnetic stirring, but then, a longer reaction time is required. Mixing the solid educts in the NMR rotor allows to get in situ insights into the reaction and enables the detection of a reaction intermediate. The pressure alone induced in the rotor by MAS is not sufficient to lead to full conversion and the reaction occurs on slower time scales than in the ball mill, which is crucial for analysing mixtures taken from the milling jar by solid‐state NMR. Our data suggest that on top of centrifugal forces, an efficient mixing of the starting materials is required for reaching a complete reaction.
C−C Coupling through Nitrogen Deletion: Application to Library Synthesis
Authors: Holovach Serhii , Melnykov Kostiantyn P. , Poroshyn Illia , Iminov Rustam T. , Dudenko Dmytro , Kondratov Ivan , Levin Mark , Grygorenko Oleksandr O.
Published: November 2022

A protocol for parallel C(sp3)−C(sp3) coupling of (hetero)aromatic aldehydes and (hetero)arylmethyl amines based on a reductive amination – “nitrogen deletion” reaction sequence has been developed. After preliminary validation experiments, an illustrative compound library of 25 members was prepared with 76 % synthetic efficiency. The estimated chemical space accessible by the proposed approach covers almost 600 000 representatives that are scarcely represented in current compound databases.
Intermolecular n→π* Interactions Based on a Tailored Multicarbonyl‐Containing Macrocycle
Authors: Zhu Jun , Wang Xu‐Dong , Ao Yu‐Fei , Wang Qi‐Qiang , Wang De‐Xian
Published: November 2022

Towards unexplored intermolecular n→π* interactions, presented herein are the synthesis, structure, self‐assembly and function of a multicarbonyl‐containing macrocycle calix[2]arene[2]barbiturate 1. X‐ray single crystal diffraction reveals the presence of Cl⋅⋅⋅C=O interactions in CH2Cl2⊂1 host‐guest complex and multiple intermolecular C=O⋅⋅⋅C=O interactions between molecules 1 in crystalline state. The intermolecular C=O⋅⋅⋅C=O interactions as attractive driving force led to unprecedented self‐assembly of nanotube with diameter around 1.4 nm and inner surface engineered by aromatic rings. SEM and TEM images of the self‐assembly of 1 demonstrated temperature‐dependent morphologies which allows the observation of spheres at 25 °C and rods at 0 °C, respectively. XRD analysis indicated consistent hexagonal patterns in the self‐assembly and single crystal lattice, indicating the nanotubes driven by C=O⋅⋅⋅C=O interactions constitute the basic structural architectures of both aggregates. The nanoscopic tubes (pores) formed in the rodlike single crystal engendering the separation of moving dyes were preliminarily investigated by a single‐crystal chromatography and crystal‐packed column chromatography.
Molecular insights into triple‐negative breast cancer metastasis: Epithelial– mesenchymal transition
Authors: Nierengarten Mary Beth
Published: November 2022

This news section offers Cancer readers timely information on events, public policy analysis, topical issues, and personalities. In this issue, researchers examine the molecular drivers behind triple‐negative breast cancer to effectively target its heterogenous molecular makeup and help curb the incidence of metastasis. In addition, identifying which patients with glioblastoma may benefit from drugs that inhibit epidermal growth factor receptor may improve treatment efficacy, and a new assay for detecting early‐stage hepatocellular carcinoma shows great potential for improving current surveillance methods.
Incorporation of Conjugated Diynes in Perovskites and their Post‐Synthetic Modification
Authors: Román‐Román Priscila I. , Ortiz‐Cervantes Carmen , Vasquez‐Matias Jessica I. , Vazquez‐Chavez Josué , Hernández‐Rodríguez Marcos , Solis‐Ibarra Diego
Published: November 2022

Two‐dimensional (2D) organic–inorganic hybrid perovskites have rapidly become an attractive alternative to three‐dimensional (3D) perovskites as solar cell absorbers, owing to their improved stability, versatility, and ease of processing. Despite their advantages, the insulating nature of the organic cations makes these materials have lower absorbing and conducting properties, resulting in lower device efficiencies. A way to circumvent these issues is the integration of functional molecules that help mitigate these limitations. In this study, six new perovskites composed of three distinct diynes are synthesized, all of which can be thermally polymerized to form conjugated polymers within the perovskite layers. The incorporation of conjugated polymers results in drastic changes in these materials’ optoelectronic properties and their overall stability. Furthermore, depending on the nature of the diyne and the inorganic layers, the materials show varying polymerization yields, optical bandgaps, and charge carrier densities. These results afford significant insight into the chemical nature of the polymerized species and thus highlight the versatility of this approach to post‐synthetically generate conducting polymers within the layers of 2D perovskites, paving the way toward their use in optoelectronic devices.
Photo‐Activity of Silacyclopropenes and their Application in Metal‐Free Curing of Silicones
Authors: Nobis Matthias , Futter Jonas , Moxter Maximilian , Inoue Shigeyoshi , Rieger Bernhard
Published: November 2022

Silicone elastomers are usually produced via addition or condensation curing by means of platinum‐ or tin‐based catalysis. The employed catalysts remain in the final rubber and cannot be recovered, thus creating various economic and environmental challenges. Herein, a light‐mediated curing method using multifunctional silacyclopropenes as crosslinker structures was introduced to create an effective alternative to the conventional industrial crosslinking. To evaluate the potential of the photoreaction a model study with small monofunctional silirenes was conducted. These investigations confirmed the required coupling reactivity upon irradiation and revealed an undesired rearrangement formation. Further optimization showed the reaction selectivity to be strongly influenced by the substitution of the three‐membered ring system and the reaction temperature. The synthesis of multifunctional silirenes was described based on the most suitable model compound to create active crosslinker scaffolds for their application in silicone curing. This photo‐controlled process produces catalyst and additive free elastomers from liquid silicones, including hydride‐, hydroxy‐, or vinyl terminated polydimethylsiloxanes.
Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters
Authors: Shakouri Shirin , Abouzari‐Lotf Ebrahim , Chen Jie , Diemant Thomas , Klyatskaya Svetlana , Pammer Frank Dieter , Mizuno Asato , Fichtner Maximilian , Ruben Mario
Published: November 2022

Porphyrin derivatives represent an emerging class of redox‐active materials for sustainable electrochemical energy storage. However, their structure–performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A2B2‐type porphyrin 5,15‐bis(ethynyl)‐10,20‐diphenylporphyrin and its first‐row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource‐friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage.
Enabling Aqueous Processing of Ni‐Rich Layered Oxide Cathode Materials by Addition of Lithium Sulfate
Authors: Heidbüchel Marcel , Schultz Thorsten , Placke Tobias , Winter Martin , Koch Norbert , Schmuch Richard , Gomez‐Martin Aurora
Published: November 2022

Aqueous processing of Ni‐rich layered oxide cathode materials is a promising approach to simultaneously decrease electrode manufacturing costs, while bringing environmental benefits by substituting the state‐of‐the‐art (often toxic and costly) organic processing solvents. However, an aqueous environment remains challenging due to the high reactivity of Ni‐rich layered oxides towards moisture, leading to lithium leaching and Al current collector corrosion because of the resulting high pH value of the aqueous electrode paste. Herein, a facile method was developed to enable aqueous processing of LiNi0.8Co0.1Mn0.1O2 (NCM811) by the addition of lithium sulfate (Li2SO4) during electrode paste dispersion. The aqueously processed electrodes retained 80 % of their initial capacity after 400 cycles in NCM811||graphite full cells, while electrodes processed without the addition of Li2SO4 reached 80 % of their capacity after only 200 cycles. Furthermore, with regard to electrochemical performance, aqueously processed electrodes using carbon‐coated Al current collector outperformed reference electrodes based on state‐of‐the‐art production processes involving N‐methyl‐2‐pyrrolidone as processing solvent and fluorinated binders. The positive impact on cycle life by the addition of Li2SO4 stemmed from a formed sulfate coating as well as different surface species, protecting the NCM811 surface against degradation. Results reported herein open a new avenue for the processing of Ni‐rich NCM electrodes using more sustainable aqueous routes.