bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reference‐Quality Free Energy Barriers in Catalysis from Machine Learning Thermodynamic Perturbation Theory
Authors: Rey Jérôme , Chizallet Céline , Rocca Dario , Bučko Tomáš , Badawi Michael 
Published: December 2023

AbstractFor the first time, we report calculations of the free energies of activation of cracking and isomerization reactions of alkenes that combine several different electronic structure methods with molecular dynamics simulations. We demonstrate that the use of a high level of theory (here Random Phase Approximation—RPA) is necessary to bridge the gap between experimental and computed values. These transformations, catalyzed by zeolites and proceeding via cationic intermediates and transition states, are building blocks of many chemical transformations for valorization of long chain paraffins originating, e.g., from plastic waste, vegetable oils, Fischer–Tropsch waxes or crude oils. Compared with the free energy barriers computed at the PBE+D2 production level of theory via constrained ab initio molecular dynamics, the barriers computed at the RPA level by the application of Machine Learning thermodynamic Perturbation Theory (MLPT) show a significant decrease for isomerization reaction and an increase of a similar magnitude for cracking, yielding an unprecedented agreement with the results obtained by experiments and kinetic modeling.
Discovery of Natural Potent HMG‐CoA Reductase Degraders for Lowering Cholesterol
Authors: Su Xiao‐Zheng , Zhang Lin‐Fei , Hu Kun , An Yang , Zhang Qiao‐Peng , Tang Jian‐Wei , Yan Bing‐Chao , Li Xing‐Ren , Cai Jie , Li Xiao‐Nian , Sun Han‐Dong , Jiang Shi‐You , Puno Pema‐Tenzin 
Published: December 2023

AbstractExploitation of key protected wild plant resources makes great sense, but their limited populations become the major barrier. A particular strategy for breaking this barrier was inspired by the exploration of a resource‐saving fungal endophyte Penicillium sp. DG23, which inhabits the key protected wild plant Schisandra macrocarpa. Chemical studies on the cultures of this strain afforded eight novel indole diterpenoids, schipenindolenes A−H (1–8), belonging to six diverse skeleton types. Importantly, semisyntheses suggested some key nonenzymatic reactions constructing these molecules and provided targeted compounds, in particular schipenindolene A (Spid A, 1) with low natural abundance. Remarkably, Spid A was the most potent HMG‐CoA reductase (HMGCR) degrader among the indole diterpenoid family. It degraded statin‐induced accumulation of HMGCR protein, decreased cholesterol levels and acted synergistically with statin to further lower cholesterol. Mechanistically, transcriptomic and proteomic profiling suggested that Spid A potentially activated the endoplasmic reticulum‐associated degradation (ERAD) pathway to enhance the degradation of HMGCR, while simultaneously inhibiting the statin‐activated expression of many key enzymes in the cholesterol and fatty acid synthesis pathways, thereby strengthening the efficacy of statins and potentially reducing the side effects of statins. Collectively, this study suggests the potential of Spid A for treating cardiovascular disease.
Catalytic Enantioselective [4+2] Cycloadditions of Salicylaldehyde Acetals with Enol Ethers
Authors: Hu Xiaojun , Zhu Zhengbo , Li Zhongzheng , Adili Alafate , Odagi Minami , Abboud Khalil A. , Seidel Daniel 
Published: December 2023

AbstractA readily accessible conjugate‐base‐stabilized carboxylic acid (CBSCA) catalyst facilitates highly enantioselective [4+2] cycloaddition reactions of salicylaldehyde‐derived acetals and cyclic enol ethers, resulting in the formation of polycyclic chromanes with oxygenation in the 2‐ and 4‐positions. Stereochemically more complex products can be obtained from racemic enol ethers. Spirocyclic products are also accessible.
A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface
Authors: Tu Xiaojin , Zhu Xiaorong , Bo Shuowen , Zhang Xiaoran , Miao Ruping , Wen Guobin , Chen Chen , Li Jing , Zhou Yangyang , Liu Qinghua , Chen Dawei , Shao Huaiyu , Yan Dafeng , Li Yafei , Jia Jianfeng , Wang Shuangyin 
Published: December 2023

AbstractElectrocatalytic C−N coupling process is indeed a sustainable alternative for direct urea synthesis and co‐upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C−N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C−N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li+<Na+<Cs+<K+. In the presence of K+, a world‐record performance was achieved with a urea yield rate of 212.8±10.6 mmol h−1 g−1 on a single‐atom Co supported TiO2 catalyst at −0.80 V versus reversible hydrogen electrode. Theoretical calculations and operando synchrotron‐radiation Fourier transform infrared measurements revealed that the energy barriers of C−N coupling were significantly decreased via K+ mediated intermediate assembly. By applying this strategy to various catalysts, we demonstrate that intermediate assembly at the electrode/electrolyte interface is a universal approach to boost sustainable urea synthesis.
Crystal Growth Regulation of Ruddlesden–Popper Perovskites via Self‐Assembly of Semiconductor Spacers for Efficient Solar Cells
Authors: Chen Mingqian , Dong Xiyue , Xin Yufei , Gao Yuping , Fu Qiang , Wang Rui , Xu Zhiyuan , Chen Yu , Liu Yongsheng 
Published: December 2023

AbstractThe crystal growth and orientation of two‐dimensional (2D) perovskite films significantly impact solar cell performance. Here, we incorporated robust quadrupole‐quadrupole interactions to govern the crystal growth of 2D Ruddlesden–Popper (RP) perovskites. This was achieved through the development of two unique semiconductor spacers, namely PTMA and 5FPTMA, with different dipole moments. The ((5FPTMA)0.1(PTMA)0.9)2MAn−1PbnI3n+1 (nominal n=5, 5F/PTMA−Pb) film shows a preferred vertical orientation, reduced grain boundaries, and released residual strain compared to (PTMA)2MAn−1PbnI3n+1 (nominal n=5, PTMA−Pb), resulting in a decreased exciton binding energy and reduced electron‐phonon coupling coefficients. In contrast to PTMA−Pb device with an efficiency of 15.66 %, the 5F/PTMA−Pb device achieved a champion efficiency of 18.56 %, making it among the best efficiency for 2D RP perovskite solar cells employing an MA‐based semiconductor spacer. This work offers significant insights into comprehending the crystal growth process of 2D RP perovskite films through the utilization of quadrupole‐quadrupole interactions between semiconductor spacers.
Coronary anatomy in neotropical carnivores: A comparative analysis
Authors: Viotto‐Souza Wilson , Santos André Luiz Quagliatto , Abidu‐Figueiredo Marcelo , Kasper Carlos Benhur , de Carvalho Amarílis Díaz , de Souza‐Junior Paulo 
Published: December 2023

AbstractThis study aims to investigate the anatomy of coronary arteries and their primary branches in neotropical carnivores, given the functional significance of coronary circulation and the limited existing descriptions in this order. For this purpose, coronary arteries were dissected, and their branches were counted in 74 hearts from 20 species belonging to five families: Canidae, Mustelidae, Procyonidae, Mephitidae, and Felidae. In all specimens of the suborder Caniformia, the subsinuosal interventricular branch originated at the end of the circumflex branch of the left coronary artery (LCA). In contrast, in all hearts of Felidae specimens, the subsinuosal branch was derived from the right coronary artery. Among the 50 neotropical specimens of the suborder Caniformia, 13.1 ± 5.2 ventricular branches originated from the LCA and only 4.6 ± 1.4 from the right (p < 0.0001), characterizing a consistent left dominance. However, in the 24 specimens of the Felidae family, 10.5 ± 4.0 ventricular branches were found originating from the LCA and 10.4 ± 3.4 from the right, with no difference between the means (p = 0.82), defining a balanced pattern. It is suggested that the type of coronary circulation may correlate with the phylogeny of carnivorans.
Synthesis of Phenothiazine Embedded Heteroporphyrins
Authors: Tripathi Neha , Sinha Avisikta , Ravikanth Mangalampalli 
Published: December 2023

AbstractA series of phenothiazine embedded heteroporphyrins containing one phenothiazine unit, two pyrrole rings and one heterocycle such as furan, thiophene, selenophene and tellurophene connected via four meso carbons were synthesized. The macrocycles were synthesized by condensing the phenothiazine based tripyrrane with corresponding 2,5‐bis(hydroxymethyl)heterocycle under BF3 ⋅ OEt2 catalyzed conditions and compared the structural, spectral, and electrochemical properties with the reported phenothiazinophyrins. The studies showed that the phenothiazine embedded heteroporphyrins were nonaromatic and electronic properties were significantly altered by replacing the pyrrole ring from phenothiazinophyrin with different heterocycles. The X‐ray structure of phenothiazine embedded thiaporphyrin revealed that the macrocycle was distorted with an inverted thiophene ring. Both mono‐protonated and diprotonated derivatives of macrocycles were generated by the controlled addition of trifluoroacetic acid to the macrocycles. The macrocyclic protons experienced upfield/downfield shifts in protonated derivatives compared to their corresponding neutral phenothiazine embedded heteroporphyrins. However, the heterocyclic ring in both mono‐ and diprotonated derivatives retained its inverted conformation. The macrocycles in their neutral and protonated form exhibit nonaromatic absorption features. The studies indicated the electron rich nature of macrocycles and DFT/TD‐DFT studies were carried out to justify the experimental observations.
From pixels to insights: Machine learning and deep learning for bioimage analysis
Authors: Jan Mahta , Spangaro Allie , Lenartowicz Michelle , Mattiazzi Usaj Mojca 
Published: December 2023

AbstractBioimage analysis plays a critical role in extracting information from biological images, enabling deeper insights into cellular structures and processes. The integration of machine learning and deep learning techniques has revolutionized the field, enabling the automated, reproducible, and accurate analysis of biological images. Here, we provide an overview of the history and principles of machine learning and deep learning in the context of bioimage analysis. We discuss the essential steps of the bioimage analysis workflow, emphasizing how machine learning and deep learning have improved preprocessing, segmentation, feature extraction, object tracking, and classification. We provide examples that showcase the application of machine learning and deep learning in bioimage analysis. We examine user‐friendly software and tools that enable biologists to leverage these techniques without extensive computational expertise. This review is a resource for researchers seeking to incorporate machine learning and deep learning in their bioimage analysis workflows and enhance their research in this rapidly evolving field.
Transcription factor support for the dual embryological origin of the sternocleidomastoid and trapezius muscles
Authors: Dawson Timothy , Iwanaga Joe , Zou Binghao , Anbalagan Muralidharan , Dumont Aaron S. , Loukas Marios , Rowan Brian G. , Tubbs R. Shane 
Published: December 2023

AbstractThe embryological origin of the trapezius and sternocleidomastoid muscles has been debated for over a century. To shed light on this issue, the present anatomical study was performed. Five fresh frozen human cadavers, three males and two females, were used for this study. Samples from each specimen's trapezius and sternocleidomastoid were fixed in 10% formalin and placed in paraffin blocks. As Paired like homeodomain 2 (Pitx2) and T‐box factor 1(Tbx1) have been implicated in the region and muscle type regulation, we performed Tbx1 and Pitx2 Immunohistochemistry (IHC) on these muscle tissue samples to identify the origin of the trapezius and sternocleidomastoid muscles. We have used the latest version of QuPath, v0.4.3, software to quantify the Tbx and Pitx2 staining. For the sternocleidomastoid muscle, for evaluated samples, the average amount of positively stained Tbx1 and Pitx2 was 25% (range 16%–30%) and 18% (range 12%–23%), respectively. For the trapezius muscles, for evaluated samples, the average amount of positively stained Tbx1 and Pitx2 parts of the samples was 17% (range 15%–20%) and 15% (14%–17%), respectively. Our anatomical findings suggest dual origins of both the trapezius and sternocleidomastoid muscles. Additionally, as neither Pitx2 nor Tbx1 made up all the staining observed for each muscle, other contributions to these structures are likely. Future studies with larger samples are now necessary to confirm these findings.
Recent Progress in the Application of Transition‐Metal Containing MFI topologies for NH3‐SCR‐DeNOx and NH3 oxidation
Authors: Jabłońska Magdalena , Potter Matthew E. , Beale Andrew M. 
Published: December 2023

AbstractTransition metal‐containing MFI‐based catalysts are widely investigated in the selective catalytic reduction of NOx with ammonia (NH3‐SCR‐DeNOx), and the selective catalytic oxidation of ammonia (NH3‐SCO) into nitrogen and water vapor. While MFI‐based catalysts are less intensively studied than smaller pore zeolites (i. e., chabazite, CHA) they are still used commercially for these processes and are of great interest for future study in particular to better understand structure‐activity relationships. Hierarchically porous MFI catalysts (containing both micropores and mesopores) often show enhanced catalytic properties compared to conventional (microporous) materials in both NH3‐SCR‐DeNOx and NH3‐SCO. Thus, a critical overview of the current understanding of the salient physico‐chemical properties that influence the performance of these catalysts is examined. Furthermore, strategies for the development of ZSM‐5 based catalysts with enhanced catalytic lifetime, supported by the investigations of reaction mechanisms are reviewed and discussed.
Effectiveness of m‐health technology‐enabled physical activity program on physical activity adoption and adherence in people with hypertension in India: A randomized controlled trial protocol
Authors: Thakar Vidhi , Kamalakannan Sureshkumar , Prakash V. 
Published: December 2023

AbstractBackgroundExercise and medication have similar benefits in reducing blood pressure (BP); however, hypertension management initiatives primarily focus on medicines. This is due to scarce research on the effectiveness of implementation strategies for optimal exercise adoption and adherence. Smartphones were found to be effective in delivering hypertension care and increase exercise adherence. Despite this, only a small number of research projects in India have used smartphones as a strategy for managing hypertension.MethodsWe hypothesized that smartphone application‐based care would lead to higher exercise adherence among adults (30–79 years) with hypertension compared to those who receive usual care. It will be a multicentric, randomized controlled, parallel‐design, superiority clinical trial. The outcome assessor and data analyst will be blinded to group allocation. Participants in the intervention group will receive mobile application‐based care for 6 weeks. Participants in the usual care group will receive a standard intervention. Both groups will receive the same number of follow‐ups.ResultsThe primary outcome is the difference in the proportion of people adherent to the recommended level of physical activity evaluated using an exercise adherence rating scale in the intervention group and the control group. Exercise adoption will be measured as the percentage of eligible participants in each study setting willing to initiate the exercise program. The secondary outcome includes differences in systolic and diastolic BP and self‐management (evaluated using the Hypertension Self‐Care Profile). The trial outcome will be accompanied by a process evaluation.ConclusionsThis research will inform about the comparative effectiveness of conventional and m‐health interventions for exercise adoption and adherence in people with hypertension in resource‐constrained settings.
Practical experiences in the use of a combination of calcined clay and limestone as clinker substitute in cement
Authors: Martirena Fernando 
Published: December 2023

AbstractThe acceleration of the impact of climate change prompts the cement industry for swift and effective solutions to reduce a large part of the carbon dioxide associated with cement manufacture. The use of Supplementary Cementitious Materials, SCM, such as fly ash and slag have enabled so far, the possibility of partially replacing clinker, the most energy intensive and main responsible component in cement for carbon emissions. However, reserves of both SCM are declining and their price is increasing, and replacing more than 30% clinker with these SCM can compromise early strength. In recent years a global team of scientists from Switzerland, Cuba and India have proven the possibility of dropping clinker content in cement down to 50% or even less through the combined use of calcined kaolinitic clays and limestone, both cheap and abundant materials, to produce a new cement called “LC3”. The resulting cement matches the properties of a CEM I (EN‐197) at all ages, and carbon emission reduction is reportedly around 25‐40%, depending on the cement to compare with. This paper presents the accumulated experience in the investigation of the new cementitious system and the introduction at the industrial level. Issues like the choice of the right clay, calcination technology, product formulation, standardization and economic feasibility will be discussed. The information in this paper is intended to encourage industrial partners to invest in the new technology.
Der Einfluss von Zusatzmitteln auf das Recycling von calciumsulfat‐basierten Bindemitteln Teil II (Ausgangsstoff technischer Gips)
Authors: Zeitoun Edrees Abu , Pritzel Christian , Trettin Reinhard , Killian Manuela S. 
Published: December 2023

KurzfassungRecycling von Gips ist ein Vorgang, der immer mehr in den Fokus der Wissenschaft rückt. Bisher liegt der Fokus jedoch im Wesentlichen auf der Entfernung von Fasern und anderen Verunreinigungen, wie z.B. Papier aus dem Recyclingmaterial. In diesem Beitrag soll untersucht werden inwiefern häufig verwendete Additive die Eigenschaften des Recyclingmaterials beeinflussen. Nachdem an einzelnen Kristallen bereits gezeigt wurde, dass einige Additive im Recyclingmaterial verbleiben, soll nun anhand von technischen Gipsproben gezeigt werden, wie diese Additive die technischen Eigenschaften des aus dem Recyclingmaterial hergestellten Gipses verändern. Es konnte gezeigt werden, dass die Additive einen wesentlichen Einfluss auf das neue Material haben, aber auch durch das Recycling ohne Additive werden das neue Rohmaterial und der abgebundenen Gips wesentlich beeinflusst. Insbesondere die Oberfläche des aus dem Recyclinggips hergestellten Halbhydrats verändert sich deutlich, wodurch der Wasseranspruch und verschiedene technische Eigenschaften verändert werden.
Gipsgebundene Bauplatten aus feinem Rezyklat‐Porenbeton‐Brechsand
Authors: Aycil Hakan , Eichhorn Simon , Ruff Ariane , Ufermann‐Wallmeier Daniel 
Published: December 2023

KurzfassungDer beschlossene Ausstieg aus der Kohleverstromung führt in Deutschland zu einer Verknappung von technischem Gips. Um den Gipsbedarf dennoch decken zu können, müssen Alternativen geschaffen werden. Das vorliegende Forschungsvorhaben verfolgt daher das Ziel, sulfatisch gebundene Mörtel unter Verwendung von Porenbetonrezyklaten (PBR) zur Herstellung von Bauprodukten in Anlehnung an gängige Gipsbaustoffe zu entwickeln und zu erproben. Gipsgehalte sollen durch Porenbeton, einem vermehrt im Bauschutt anfallenden Material, das üblicherweise aussortiert und beseitigt wird, substituiert werden.Die bisherigen Untersuchungsergebnisse belegen die grundlegende Machbarkeit des Ansatzes. Die Eigenschaften der untersuchten Mörtel lassen erwarten, dass selbst bei einer Substitution von bis zu 50 Ma.‐% des Gipsgehalts durch PBR die Herstellung von Gipsprodukten möglich ist.
Shotcrete 3D Printing ‐ Interaction of nozzle geometry, homogeneity and hardened concrete properties
Authors: Freund Niklas , David Martin , Böhler David , Mai Inka , Ullmann Stefan , Dröder Klaus , Lowke Dirk 
Published: December 2023

AbstractShotcrete 3D Printing (SC3DP) applies concrete layer by layer using a wet‐spray process. The resulting hardened concrete properties of the applied SC3DP layers (e.g. height, width or mechanical strength) are largely dependent on the selected material and process parameters. In this context, the nozzle geometry is an important influencing parameter. During printing, the velocity of the shotcrete jet is significantly influenced by the nozzle outlet diameter. Therefore, in the present study, the effect of the nozzle outlet diameter (15 ‐ 30 mm) is investigated with regard to the resulting layer homogeneity, i.e. local density and aggregate distribution in the cross‐section, and hardened concrete properties, i.e. flexural strength. By analysing the manufactured specimens, an uneven distribution of the aggregate is observed horizontally across the cross‐section of the layers. An accumulation of aggregate is present in the core of the layer resulting in a cement paste‐rich region in the edge areas. This leads to increased local densities in the core of the specimen. The application of the concrete with small nozzle outlet diameters results in the highest local densities and the highest flexural strength.
Today's and future slags ‐ Potentials and Challenges
Authors: Ehrenberg Andreas 
Published: December 2023

AbstractThe steel industry produces the most widely used metal on earth. The main challenge of the industry for the next decade is the steel production transformation process. The CO2 intensive blast furnace/basic oxygen furnace (BOF) route will be substituted by a combination of a Direct Reduced Iron plant (based on natural gas, at later stage on “green” hydrogen) with an Electric Arc Furnace (EAF) or a Submerged Arc Furnace (SAF), heated with renewable energy. Thus, the well‐known latent hydraulic granulated blast furnace slag (GBS) being successfully used in cement and concrete for more than 140 years will vanish step by step. GBS is used as a supplementary cementitious material (SCM) not only, but in particular, due to its clinker reduction and from there its CO2 reduction potential for the cement and concrete production. Whereas the DRI process itself does not generate any slag, EAF and SAF will do. These slags will be very different. Moreover, the new EAF slags will be also different compared to today's scrap based EAF slag. However, specific slag/metal ratios, resulting slag volumes, chemical and mineralogical compositions and physical properties of the new slags are yet unknown. Thus, also their cementitious and environmental properties are still unknown. Different running projects aim mainly to create slags being similar to GBS. The main objective is to provide the cement and concrete industry furthermore with a (latent) hydraulic SCM.