Straightforward Methodologies Research Articles

Optimal formulation and performance evaluation of functional ultra-high performance concrete with barium ferrite

The employment of a core catcher is instrumental in enhancing the safety of nuclear power facilities in the event of severe accidents, with sacrificial materials serving as fundamental constituents. Currently, cement-based sacrificial materials are prevalently utilized due to their straightforward construction methodologies and economical production costs. These materials are designed to withstand significant impact loads arising from the descent of core melt during severe accidents. To augment the impact resilience of sacrificial materials, a novel functional ultra-high performance concrete (FUHPC) incorporating barium ferrite has been developed. Using the Modified Andreasen and Andersen particle packing model to determine the initial mixture of FUHPC, and the impact of barium ferrite on the mechanical and thermal properties of FUHPC was systematically evaluated. Furthermore, the influence of barium ferrite on the FUHPC's microstructure was examined with mercury intrusion porosity and scanning electron microscopy techniques. The findings indicate: (1) Optimal barium ferrite incorporation led to a decrease in the porosity and the threshold pore diameter of FUHPC; (2) The flexural and compressive strengths, as well as the elastic modulus of FUHPC, were found to increase within the ranges of 4.41%–17.50 %, 2.88%–22.91 %, and 5.80%–15.06 %, respectively, as a result of suitable barium ferrite additions; (3) At a barium ferrite concentration of 2 vol%, the chloride migration coefficient of FUHPC was reduced by 21.43 %; (4) The presence of barium ferrite enhanced the impact performance of FUHPC, with a 21.38 % increase in impact resistance noted at a barium ferrite content of 2 vol%; (5) In high-temperature scenarios, the formation of channels from melted polypropylene fibers served to mitigate the spalling of FUHPC; (6) Upon considering the effects of barium ferrite on both room temperature and elevated temperature performance, as well as on microstructural characteristics, the optimal barium ferrite content was determined to be 2 vol%.

Copper-Catalyzed Remote Regio- and Enantioselective Yne-Allylic Substitution of Coumarins.

Chiral coumarins and their derivatives are prominent bioactive structural units present in a wide range of natural products and pharmaceutical candidates. Therefore, the development of straightforward and efficient methodologies for the synthesis of readily functionalized chiral coumarins is of significant interest. Herein we report an enantioselective copper-catalyzed yne-allylic substitution of coumarins, resulting in a highly regioselective synthesis of diverse new classes of chiral coumarin derivatives with high efficiency and excellent functional group tolerance. Subsequent versatile transformations further demonstrate the substantial synthetic potential of this strategy in the field of biochemical research.

Abstract A023: Stratification of bladder cancer patients with the use of flow cytometry is increasing the diagnostic potential of molecular classifiers

Abstract Recent research suggests the potential categorization of bladder cancer (BLCa) patients into molecular subtypes to aid in the selection of appropriate treatment strategies, be it conventional, targeted, or a combination thereof. However, the practical implementation of molecular classifiers has faced obstacles due to the intricate nature of gene regulation, tumor heterogeneity, and challenges related to tumor sampling caused by substantial stromal infiltration and tumor multifocality. Hence, there is a pressing need for more straightforward marker-based methodologies to assist in genomic and transcriptomic subtyping efforts. Our study addressed this gap by establishing and validating a panel of antibodies for application in flow cytometry (FCM) to enhance the stratification of BLCa patients. We curated a set of 17 FCM markers capable of delineating four cell clusters (epithelial, immune, endothelial, and stromal) and defining tumor classification (basal and luminal), immune infiltration, and hot-target expression on BLCa tissue samples. This FCM panel was deployed on ex vivo tissue samples treated with chemotherapy and targeted therapy agents. Initially tested on a cohort of 10 BLCa tissue samples, our validation of the FCM panel revealed correlations between marker expression and clinical-pathological features, such as the presence of metastasis and heightened immune and stromal infiltration. Notably, samples exhibiting lower claudin-4 levels displayed increased immune infiltration, while those with metastases at diagnosis showcased elevated basal marker expression. The translational potential of the FCM panel was demonstrated in ex vivo experiments where tissue slices from six patients were subjected to chemotherapy and targeted therapy agents, leading to observable shifts in marker expression post-treatment, particularly pronounced with chemotherapy. Noteworthy effects included reductions in epithelial cells expressing FGFR3 and EGFR following targeted therapy with erdafitinib or lapatinib, alongside alterations in the basal/luminal cell ratio indicated by increased CD44, CD90, and CD239 marker expressions. Our findings underscore the value of FCM in categorizing BLCa patients based on specific marker expression, supplementing conventional histological analyses to enhance cancer diagnosis, guide personalized therapeutic approaches, and monitor treatment efficacy. Citation Format: Martina Radic, Federico La Manna, Martina Minoli, Panagiotis Chouvardas, George N. Thalmann, Roland Seiler-Blarer, Marianna Kruithof-de Julio, Bernhard Kiss. Stratification of bladder cancer patients with the use of flow cytometry is increasing the diagnostic potential of molecular classifiers [abstract]. In: Proceedings of the AACR Special Conference on Bladder Cancer: Transforming the Field; 2024 May 17-20; Charlotte, NC. Philadelphia (PA): AACR; Clin Cancer Res 2024;30(10_Suppl):Abstract nr A023.

Synthesis and Study of Steering of Azido-tetrazole Behavior in Tetrazolo[1,5-c]pyrimidin-5-amine-Based Energetic Materials.

Tetrazoles and their derivatives are essential for compound synthesis due to their versatility, effectiveness, stability in air, and cost-efficiency. This has stimulated interest in developing techniques for their production. In this work, four compounds, tetrazolo[1,5-c]pyrimidin-5-amine (1), N-(4-azidopyrimidin-2-yl)nitramide (2), tetrazolo[1,5-c]pyrimidin-5(6H)-one (3), and tetrazolo[1,5-a]pyrimidin-5-amine (4), were obtained from commercially available reagents and straightforward synthetic methodologies. These new compounds were characterized by infrared (IR), 13C, and 1H NMR spectroscopy, differential scanning calorimetry (DSC), and single-crystal X-ray diffraction. The solvent, temperature, and electron-donating group (EDG) factors that were responsible for the steering of azido-tetrazole equilibrium in all compounds were also studied. In addition, the detonation performance of the target compounds was calculated by using heats of formation (HOFs) and crystal densities. Hirshfeld surface analysis was used to examine the intermolecular interactions of the four synthesized compounds. The results show that the excellent properties of 1-4 are triggered by ionic bonds, hydrogen bonds, and π-π stacking interactions, indicating that these compounds have the potential to be used in the development of high-performance energetic materials. Additionally, DFT analysis is in support of experimental results, which proved the effect of different factors that can influence the azido-tetrazole equilibrium in the synthesized pyrimidine derivatives in the solution.

Visible-Light-Induced Alkoxypyridylation of Alkenes Using N-Alkoxypyridinium Salts as Bifunctional Reagents.

Considering the ubiquitous presence of pyridine moieties in pharmaceutical compounds, it holds immense value to develop practical and straightforward methodologies for accessing heterocyclic aromatic hydrocarbons. In recent years, N-alkoxypyridinium salts have emerged as convenient radical precursors, enabling the generation of the corresponding alkoxy radicals and pyridine through single-electron transfer. Herein, we present the first report on visible-light-mediated intermolecular alkoxypyridylation of alkenes employing N-alkoxylpyridinium salts as bifunctional reagents with an exceptionally low catalyst loading (0.5 mol %).

Photovoltaic cooling techniques’ effect on the average monthly performance

Nowadays, mitigating climate-altering emissions resulting from air conditioning and mechanical ventilation of indoor spaces is of utmost importance. Encourage the adoption of renewable energy sources for power generation is a critical approach in this regard. Among the available technologies, photovoltaic technology stands as the most mature option. However, it does have limitations, such as reduced efficiency and performance degradation at elevated temperatures. To enhance the efficiency of photovoltaic systems, various solutions have been proposed over time, with significant research focusing on the exploration of new materials. One of the most promising solutions involves panel cooling through the utilization of external fluids, either in a forced or natural manner. Furthermore, the extracted heat from this cooling process can be effectively reused in other industrial processes, adding to its appeal. Nonetheless, despite its potential, the application of panel cooling technology is relatively recent, and assessing its suitability in specific scenarios at an early stage can be challenging. Currently, there is a lack of clear and straightforward methodologies to evaluate the performance gains achievable through the implementation of panel cooling. The primary objective of this research is to present an innovative methodology that can effectively assess panel cooling efficiency on an average daily-monthly basis. Specifically, we propose corrective parameters that modify the widely used Siegel method, which determines the monthly average daily efficiency of uncooled panels. Throughout the study, it has become evident that the input values derived from the UNI standard do not fully represent the real-world conditions. This finding may indicate the necessity for regulatory updates to accurately account for the practical operational environment.

Characterization of Synthetic Peptides by Mass Spectrometry.

In the quality control of synthetic peptides, mass spectroscopy (MS) serves as an optimal method for evaluating authenticity and integrity. Typically, the sequence of a synthetic peptide is already established, thereby directing the focus of analysis towards validating its identity and purity. This chapter outlines straightforward methodologies for conducting MS analyses specifically tailored for synthetic peptides.

Mapping The Terrain: A Study of Contour Analysis

Contour analysis is a pivotal process for architects and landscape designers, integral in seamlessly integrating designs with the natural terrain. By scrutinizing the geographical features of a site, designers gain invaluable insights that inform decisions in overall site planning. This research delves into the art of interpreting contours, offering a nuanced understanding of spatial navigation, sensory experiences, and aesthetics within architectural spaces through straightforward methodologies. Understanding the subtle undulations of the land enables architects to harmonize structures with the existing landscape, fostering a sense of unity. The contours serve as a blueprint for creating designs that not only blend seamlessly but also enhance the overall user experience. This investigation focuses on distilling complex topographical information into practical insights, providing designers with accessible tools to navigate the intricate relationship between built environments and natural surroundings. By unraveling the language of contours, architects and designers can unlock the potential for creating spaces that not only aesthetically please but also prioritize functionality and coherence with the environment. Key Words: Contour, fist, water flow, landscape.

Sp-ICP-MS and HR–CS–GFAAS as useful available techniques for the size characterization and speciation of ionic and nanoparticular zinc in cosmetic and pharmaceutical samples

The use of zinc oxide nanoparticles (ZnO NPs) in cosmetic and pharmaceutical industry has been increased in recent years due to their good properties as solar radiation filters and antibacterial agent. According to the literature, the potential toxicity of these NPs could be size-dependent and the amount of solubilized metal. This work investigates new reliable and straightforward methodologies that enables the determination of ZnO NPs, discriminating them from ionic zinc in cosmetic samples. Two different techniques of analysis have been applied in this study: high-resolution continuum source graphite furnace atomic absorption spectrometry (HR–CS–GFAAS), and “single particle” inductively coupled plasma mass spectrometry (sp-ICP-MS). Triton X-100 has been used as a surfactant for the formation of homogeneous and stable slurries which allowed the determination of the concentration and sizes of ZnO NPs and Zn2+ in baby creams, eyeshadows, and lotions. A central composite design (CCD) was performed for the two techniques to optimize the concentration of Triton X-100 and sonication time. For validation purpose, the results of Zn2+ and ZnO NPs contents achieved by HR–CS–GFAAS were compared with the total Zn content obtained by acid digestion of the samples. A size comparison of the ZnO NPs was also carried out with the data obtained through the two methodologies and validated with transmission electron microscopy (TEM). In the case of TEM analysis, two different media were tried to study possible agglomerates and interactions between the particles and the matrix.

Synthesis of Metabolites and Metabolite-like Compounds Using Biocatalytic Systems.

Methodologies for the synthesis and purification of metabolites, which have been developed following their discovery, analysis, and structural identification, have been involved in numerous life science milestones. The renewed focus on the small molecule domain of biological cells has also created an increasing awareness of the rising gap between the metabolites identified and the metabolites which have been prepared as pure compounds. The design and engineering of resource-efficient and straightforward synthetic methodologies for the production of the diverse and numerous metabolites and metabolite-like compounds have attracted much interest. The variety of metabolic pathways in biological cells provides a wonderful blueprint for designing simplified and resource-efficient synthetic routes to desired metabolites. Therefore, biocatalytic systems have become key enabling tools for the synthesis of an increasing number of metabolites, which can then be utilized as standards, enzyme substrates, inhibitors, or other products, or for the discovery of novel biological functions.

Recent progress in metal assisted multicomponent reactions in organic synthesis.

To prepare complicated organic molecules, straightforward, sustainable, and clean methodologies are urgently required. Thus, researchers are attempting to develop imaginative approaches. Metal-catalyzed multicomponent reactions (MCRs) offer optimal molecular diversity, high atomic efficiency, and energy savings in a single reaction step. These versatile protocols are often used to synthesize numerous natural compounds, heterocyclic molecules, and medications. Thus far, the majority of metal-catalyzed MCRs under investigation are based on metal catalysts such as copper and palladium; however, current research is focused on developing novel, environmentally friendly catalytic systems. In this regard, this study demonstrates the effectiveness of metal catalysts in MCRs. The aim of this study is to provide an overview of metal catalysts for safe application in MCRs.

Methodology for determination of critical crack depth in a class-I component

In this study, a methodology for the determination of critical crack depth in a class-I component using the failure assessment diagram has been proposed and implemented through the finite element method. Overviewing the literature in the field of fracture mechanics, the need for the development of such methodology was felt, as such straightforward methodologies are difficult to find in contemporary literature. As a case study, the proposed methodology was then successfully applied to a pressurized water reactor’s pressure vessel closure head (class-I component). Subsequently, the critical crack depth was determined through a failure assessment diagram under pressurized thermals shock induced during the small break loss of coolant accidental and Rancho-Seco transient accidental conditions of the reactor.

Proposal of 14- Step Total Synthesis Route of Dihydrolucilactaene, a Potent Antimalarial Compound

Malarial disease has been under heated discussion. The Osada group has extracted and purified pot antimalarial compounds, including dihydrolucilactaene and its derivatives. In this work, a 14-step total synthetic route of Dihydrolucilactaene, the compound with the highest pharmaceutical value among its derivatives, is designed and presented after considering and combining four partially feasible but hindered approaches. The complex molecule is first split into lactam-containing and long unsaturated fragments. The long unsaturated carbon chain can be effectively synthesized by two subsequent aldol condensations and the enabling Wittig reaction. Dicarbonyl synthesis and a basemediated intramolecular nucleophilic attack can synthesize the lactam fragment. The final connection between two fragments are conducted through an enolate attack of electrophilic nitrile followed by hydrolysis. Three protection groups, named trimethyl silyl, acetal, and N-Boc, facilitate the synthesis in the last step. This research successfully developed a 14-step efficient total synthetic route of dihydrolucilactaene with commercially available building blocks and catalysts. The proposed total synthesis route consists of developed and straightforward synthetic methodologies and therefore is expected to be efficient and have a high overall yield.

Synthesis, Reactivity, and Anticancer Activity Evaluation of 4‐Amino‐3‐Mercapto‐6‐Methyl‐1,2,4‐Triazin‐5(4H)‐One Derivatives

Abstract1,2,4‐Triazine and its derivatives occupy a fundamental position in the field of medicinal chemistry because of their diverse biological applications, such as anticancer. To search for promising anticancer agents, a new series of 4‐amino‐3‐mercapto‐6‐methyl‐1,2,4‐triazin‐5(4H)‐one derivatives was prepared. Straightforward synthetic methodologies were employed, such as condensation, cyclization, hydrazinolysis, alkylation, and condensation‐addition reactions. All of the new compounds were characterized by a combination of spectral data and elemental analysis. The molecular structures of several compounds on a single crystal X‐ray provided confirmation. The anticancer activity was evaluated against three cancer cell lines, which are hepatocellular carcinoma (HEPG‐2), colorectal carcinoma (HCT‐116) and mammary gland breast cancer (MCF‐7). The results revealed that a representative number of compounds have potent cytotoxicity against HEPG‐2, HCT‐116 and MCF‐7 cell lines with IC50 values ranging from 6.71 to 31.25 μg/mL.

Template‐ and Surfactant‐Free Room Temperature Synthesis of Pt/C and Pt−Rh/C Nanowires/Nanoparticles for Ethanol Electro‐Oxidation

AbstractThe synthesis of Pt−Rh alloy nanowires (NWs) using straightforward methodologies remains a challenge. Here, carbon‐supported Pt and Pt−Rh nanowire catalysts were synthesised by chemical reduction at room temperature, without using surfactants or templates. The method of synthesis used yielded Pt/C NWs and a mixture of nanowires with some nanoparticles for the Pt−Rh/C catalysts (characterised using XRD, TEM, EDX, XPS, and XAS). The nanoparticles form due to differences in the surface energy and atomic radius between Pt and Rh. The binary NWs are found to be more active towards ethanol oxidation than the commercial Pt/C reference catalyst. Additionally, the Pt−Rh/C NW catalyst displays a specific activity 2.5‐fold higher than the Pt/C NWs and Pt/C reference catalysts after 15 min of chronoamperometric tests (at 0.5 V vs RHE). Thus, the synthesised carbon‐supported Pt NWs and Pt−Rh nanowires‐nanoparticles are promising alternatives for direct ethanol fuel cell anodes.

Pyridine-Based Small-Molecule Fluorescent Probes as Optical Sensors for Benzene and Gasoline Adulteration

Here we present simple fluorophores based on the pyridine core, obtained with straightforward synthetic methodologies. These compounds present in solution absorption maxima in the UV region and fluorescence emission of between 300 and 450 nm, depending on the solvent and chemical structure of the fluorophore. The nature of the solvent was shown to play a fundamental role in their excite-state deactivation, which allowed successful exploration of these compounds as optical sensors for benzene and fuel adulteration in gasoline. In ethanolic solution, upon the addition of benzene, in general the fluorophores presented fluorescence quenching, where a linear correlation between the emission intensity and the amount of benzene (quencher) was observed. In addition, the application of an optical sensor for the detection of fuel adulteration in commercial standard and premium gasoline was successfully presented and discussed. Theoretical calculations were also applied to better understand the solvent–fluorophore interactions.

Decoration of A-Ring of a Lupane-Type Triterpenoid with Different Oxygen and Nitrogen Heterocycles.

Betulinic acid (BA) was used as starting building block to create a library of novel BA-derived compounds containing O- and N-heterocycles. Firstly, BA was converted into methyl betulonate (BoOMe), which was used as intermediate in the developed methodologies. 1,2-Oxazine-fused BoOMe compounds were obtained in 12–25% global yields through a Michael addition of nitromethane to methyl (E)-2-benzylidenebetulonate derivatives, followed by nitro group reduction and intramolecular cyclization. Remarkably, the triterpene acts as a diastereoselective inducer in the conjugate addition of nitromethane, originating only one diastereomer out of four possible ones. Furthermore, other oxygen and nitrogen-containing heterocycles were installed at the A-ring of BoOMe, affording 2-amino-3-cyano-4H-pyran-fused BoOMe, diarylpyridine-fused BoOMe and 1,2,3-triazole–BoOMe compounds, using simple and straightforward synthetic methodologies. Finally, BA was revealed to be a versatile starting material, allowing the creation of a molecular diversification of compounds containing a triterpenic scaffold and O- and N-heterocycles.

Room Temperature, Ambient Pressure Synthesis of Urea By Electrolysis and Its Accurate and Consistent Measurement

There is rapidly growing interest in the electrochemical reduction of both nitrite and carbon dioxide to mitigate environmental concerns and produce fuels and commodity chemicals (1). Urea is an important target in this area since it is the most widely used nitrogen fertilizer, and can also be used as a fuel and source of hydrogen. It can be produced simultaneously by electrochemical coreduction of NO2 - and CO2 (2-7). Various TiO2 based catalysts such as Cu-doped TiO2 (7) and FeTiO3 (4) have been reported to be effective for co-reduction of CO2 and NO2 -. Metallophthalocyanine catalysts have also been found to be effective in a gas-diffusion electrode configuration under ambient conditions (3).The primary objective of this research is to develop fast and straightforward methodologies that can be routinely used to comprehensively evaluate and compare commercial and new catalysts for co-electrolysis of CO2 and NO2 - in an anion exchange membrane multi-cathode electrolysis cell under ambient conditions. The second objective is using this methodology to synthesize urea and develop reliable and consistent urea measurement methods using various techniques including spectrophotometric, 1H-NMR, mass spectrometry, and enzyme-based methods. It was found that NO2 - and the electrolyte can cause interference during urea measurement. In this research, commercial catalysts such as iron (II) phthalocyanine were used for co-electrolysis of CO2 and NO2 -. Acknowledgements This project is funded in part by the Government of Canada. / Ce projet est financé en partie par le gouvernement du Canada, and by Memorial University References C. Tang, Y. Zheng, M. Jaroniec and S. Z. Qiao, Angew. Chem. Int. Ed., 60, 19572 (2021).M. Shibata, K. Yoshida and N. Furuya, J. Electrochem. Soc., 145, 2348 (1998).M. Shibata and N. Furuya, Electrochim. Acta, 48, 3953 (2003).P. Siva, P. Prabu, M. Selvam, S. Karthik and V. Rajendran, Ionics, 23, 1871 (2017).Y. G. Feng, H. Yang, Y. Zhang, X. Q. Huang, L. G. Li, T. Cheng and Q. Shao, Nano Lett., 20, 8282 (2020).N. N. Meng, Y. M. Huang, Y. Liu, Y. F. Yu and B. Zhang, Cell Reports Physical Science, 2 (2021).N. Cao, Y. L. Quan, A. X. Guan, C. Yang, Y. L. Ji, L. J. Zhang and G. F. Zheng, J. Colloid Interface Sci., 577, 109 (2020).

Excited-State Intramolecular Proton Transfer in 2-(2'-Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies.

The development of fluorescence materials with switched on/off emission has attracted great attention owing to the potential application of these materials in chemical sensing. In this work, the photophysical properties of a series of original 2-(2′-hydroxyphenyl)pyrimidines were thoroughly studied. The compounds were prepared by following well-established and straightforward methodologies and showed very little or null photoluminescence both in solution and in the solid state. This absence of emission can be explained by a fast proton transfer from the OH group to the nitrogen atoms of the pyrimidine ring to yield an excited tautomer that deactivates through a nonradiative pathway. The key role of the OH group in the emission quenching was demonstrated by the preparation of 2′-unsubstituted derivatives, all of which exhibited violet or blue luminescence. Single crystals of some compounds suitable for an X-ray diffraction analysis could be obtained, which permitted us to investigate inter- and intramolecular interactions and molecular packing structures. The protonation of the pyrimidine ring by an addition of trifluoroacetic acid inhibited the excited-state intramolecular proton transfer (ESIPT) process, causing a reversible switch on fluorescence response detectable by the naked eye. This acidochromic behavior allows 2-(2′-hydroxyphenyl)pyrimidines to be used as solid-state acid–base vapor sensors and anticounterfeiting agents. Extensive density functional theory and its time-dependent counterpart calculations at the M06-2X/6-31+G** level of theory were performed to rationalize all the experimental results and understand the impact of protonation on the different optical transitions.

DEMSA Protocol: Deterioration Effect Modelling for Structural Assessment of RC Buildings

The effects of deterioration strongly impact the expected future service life and the structural performances of existing reinforced concrete structures. Currently, straightforward methodologies are required to include such effects in the assessment and renovation of the RC buildings’ heritage. A simplified protocol enabling the detection, evaluation, and modelling of corrosion effects is presented in this paper. The protocol provides the guidance for the design and management of the on-site diagnostic campaign, aimed at identifying a possible corrosion risk scenario. Then, equivalent damage parameters describing corrosion effects in the structural models can be calibrated. Structural performances over time can be assessed to predict the structural residual life, maintenance management criteria and timing, and major indications on the feasibility of the retrofit intervention, or the unavoidable need of demolition. The application of the proposed protocol to some case studies emphasises the effectiveness of the procedure for detecting possible activated corrosion processes and for supporting engineers in their decision-making process and choice of renovation strategy.