Chemical Phenomena Research Articles

Crucial role of the internalisation of the distinction between dependent and independent variables for clearer chemistry understanding

Abstract Mathematics constitutes a fundamental key for the description and understanding of many phenomena. The chemistry discourse incorporates mathematics in various ways and instances. At educational level, interchanges occur in two directions: mathematics provides support for clearer understanding of chemical phenomena, and the level at which students use the relevant mathematics is an indication of the clarity of their conceptual understanding in chemistry. The present work focuses on an issue for which mathematics tightly links to the conceptual understanding of physical terms – the issue of independent and dependent variables. The definition is in principle well known. On the other hand, the distinction between the two types of variables and their roles is not always clearly underlined at explanation level, and is often not sufficiently internalised by students. This results in a variety of misunderstandings and errors. Careful analysis of students’ works enables the identification of errors that can be tracked down to unclear distinction between the dependent and independent variables in a given context; such errors appear in several areas of chemistry, at both undergraduate and postgraduate levels. The present work considers and analyses a number of representative examples, highlighting the impact of their unclear distinction and the ensuing importance of devoting specific attention to it. Selected addressing approaches from direct experience are included and their outcomes discussed.

Abstract 484: Enhancing therapeutic responses in NSCLC using iron-oxide nanoparticles combined with pharmacological ascorbate

Abstract High dose Vitamin C (pharmacological ascorbate; P-AscH‒ > 20 mM plasma levels) given intravenously (I.V.), has made a remarkable re-emergence as an adjuvant to combined modality approaches in cancer therapy. P-AscH‒ can be readily oxidized in the presence of redox active metals (i.e., P-AscH‒ serves as an iron reducing agent), which can result in increased fluxes of H2O2. This chemical phenomenon allows for the tumor-selective enhancement of chemo-radiation in NSCLC. We hypothesized that enhancing labile Fe2+ in cancer cells using iron-oxide nanoparticles (ferumoxytol, FMX) can increase the effectiveness of P-AscH‒ in enhancing cancer cell sensitivity to chemo-radiation in NSCLC by increasing H2O2 production. To test this hypothesis, we performed clonogenic cell survival assays in-vitro. To test the role of H2O2 in the combined effect of P-AscH‒ and FMX, we developed lentiviral-based doxycycline-inducible overexpression models for catalase, and to determine the changes in Fe, we used fluorescent probes that specifically detect changes in labile Fe2+. Results from these experiments showed FMX enhanced clonogenic cell killing in NSCLC. Furthermore, catalase overexpression inhibited this effect, suggesting that enhanced H2O2 production plays a central role in the additive effect of P-AscH- and FMX. Finally, staining the cells with the fluorescent iron probes showed that FMX enhanced labile Fe2+ in cells treated with P-AscH‒. These studies continue to support the hypothesis that H2O2 plays a significant role in P-AscH‒ toxicity in cancer cells that can be exacerbated using iron oxide nanoparticles. Future studies will test these findings in-vivo using preclinical xenograft models. (supported by P01 CA217797, P30 CA086862, T32 CA078586, and P01 CA244091). Citation Format: Mekhla Singhania, Miachael S. Petronek, Casey F. Pulliam, Kranti A. Mapuskar, Amira Zaher, Douglas R. Spitz. Enhancing therapeutic responses in NSCLC using iron-oxide nanoparticles combined with pharmacological ascorbate [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 484.

Discovering invariant spatial features in electron energy loss spectroscopy images on the mesoscopic and atomic levels

Over the last two decades, Electron Energy Loss Spectroscopy (EELS) imaging with a scanning transmission electron microscope has emerged as a technique of choice for visualizing complex chemical, electronic, plasmonic, and phononic phenomena in complex materials and structures. The availability of the EELS data necessitates the development of methods to analyze multidimensional data sets with complex spatial and energy structures. Traditionally, the analysis of these data sets has been based on analysis of individual spectra, one at a time, whereas the spatial structure and correlations between individual spatial pixels containing the relevant information of the physics of underpinning processes have generally been ignored and analyzed only via the visualization as 2D maps. Here, we develop a machine learning-based approach and workflows for the analysis of spatial structures in 3D EELS data sets using a combination of dimensionality reduction and multichannel rotationally invariant variational autoencoders. This approach is illustrated for the analysis of both the plasmonic phenomena in a system of nanowires and in the core excitations in functional oxides using low loss and core-loss EELS, respectively. The code developed in this manuscript is open sourced and freely available and provided as a Jupyter notebook for the interested reader.

Finite Element Modeling of Cells Adhering to a Substrate: An Overview

In tissue formation and regeneration processes, cells often move collectively, maintaining connections through intercellular adhesions. However, the specific roles of cell–substrate and cell-to-cell mechanical interactions in the regulation of collective cell migration are not yet fully understood. Finite element modeling (FEM) may be a way to assess more deeply the biological, mechanical, and chemical phenomena behind cell adhesion. FEM is a powerful tool widely used to simulate phenomena described by systems of partial differential equations. For example, FEM provides information on the stress/strain state of a cell adhering to a substrate, as well as on its mechanobiological behavior. This review paper, after briefly describing basic principles of cell adhesion, surveys the most important studies that have utilized FEM to investigate the structural response of a cell adhering to a substrate and how the forces acting on the cell–substrate adhesive structures affect the global cell mechanical behavior.

Chemical reaction effect across the moving flat plate with heat generation and MHD flow of Maxwell fluid with viscous dissipation

In this paper, the investigation centered on examining a Maxwell fluid’s convective double diffusive flow carefully considers factors such as chemical reactions, radiation, and the presence of a permeable moving flat plate. Additionally, the study encompassed the effects of heat generation and magnetohydrodynamics (MHD). The governing equations, initially expressed as partial differential equations, were converted into ordinary differential equations using a similarity transformation technique to facilitate the analysis. The computational power of MATLAB’s BVP4C software was harnessed to solve this resultant system of ODEs efficiently. The outcomes of this investigation were presented in the form of graphical representations that vividly depicted the behavior of the flow field, energy conservation, and concentration profiles under various parameter combinations. The research findings were thoughtfully summarized in a table, offering a comprehensive overview of temperature, velocity, and mass profiles across various parameters. These parameters included the Deborah number, chemical reaction rate, Eckert number, Lewis number, Prandtl number, porosity parameter, and MHD parameter. A notable discovery emerging from this study was the inverse relationship observed between nondimensional concentration contours and the magnitude of the chemical reaction rate. Simultaneously, it was observed that higher values of the Maxwell fluid led to a rise in the thickness of the temperature boundary layer. These findings offer valuable insights into the intricate interplay of physical and chemical phenomena in convective flows involving complex fluid properties and boundary conditions. The temperature outline diminishes as the heat generation rate increases, while the concentration profile declines with an elevation in the chemical reaction rate.

Modeling Framework for Cost Optimization of Process-Scale Desalination Systems with Mineral Scaling and Precipitation.

Cost-optimization models are powerful tools for evaluating emerging water treatment processes. However, to date, optimization models do not incorporate detailed chemical reaction phenomena, limiting the assessment of pretreatment and mineral scaling. Moreover, novel approaches for high-salinity and high-recovery desalination are typically proposed without direct quantification of pretreatment needs or mineral scaling. This work addresses a critical gap in the literature by presenting a modeling framework that includes complex water chemistry predictions with process-scale optimization. We use this approach to conduct a technoeconomic assessment on a conceptual high-recovery treatment train that includes chemical pretreatment (i.e., soda ash softening and recarbonation) and membrane-based desalination (i.e., standard and high-pressure reverse osmosis). We demonstrate how to develop and integrate accurate multidimensional surrogate models for predicting precipitation, pH, and mineral scaling tendencies. Our findings show that cost-optimal results balance the costs of pretreatment with reverse osmosis system design. Optimizing across a range of water recoveries (i.e., 50-90%) reveals multiple cost-optimal schemas that vary the chemical dosing in pretreatment and the design and operation of reverse osmosis. Our results reveal that pretreatment costs can be more than double the cost of the primary desalination process at high recoveries due to the extensive pretreatment required to control scaling. This work emphasizes the importance of and provides a framework for including chemistry and mineral scaling predictions in the evaluation of emerging technologies in high-recovery desalination.

Maximising the consistency of the presentation of the molecular level with its quantum mechanical description: challenges and opportunities

Abstract Reasoning in terms of molecules has since long become fully embedded in any chemistry discourse. On the other hand, students’ familiarization with the molecular level in pre-university instruction is not always satisfactory, and their ability to view chemical phenomena in terms of what molecules do may not reach the extent and quality that would be needed to ensure effective conceptual understanding. Students may remain uncertain about the interpretation of the molecular features of a number of phenomena even through undergraduate instruction. Removing uncertainties and promoting comfortable familiarization is increasingly becoming an imperative for chemistry education, in view of the novel central role that the molecular level is acquiring not only for the customary interpretation of phenomena, but for the high variety of applications that have been blooming in recent years. Consequently, learners’ familiarization with the world of molecules needs to become more informative and complete. It is equally important that the information that they acquire about molecules be consistent with the modern descriptions, which are based on quantum mechanics. This requires accurate search for optimal balances between the need to simplify the terms of the descriptions in order to make them accessible to leaners according to the different levels of chemistry learning, and the simultaneous need to maintain adequate conceptual rigour. The present work outlines approaches which have proved viable and effective, and which rely on accurate use of language and visualization as the major explanation resources.

Thenovel numerical solutions for conformable fractional Kuramoto-Sivashinsky equations by using Cq-HATM and CHPETM

The present study used the novel conformable fractional methods to examine the nonlinear Kuramoto-Sivashinsky equations of the conformable fractional derivative. The Kuramoto-Sivashinsky equation is a mathematical model employed to elucidate a diverse range of chemical and physical phenomena, encompassing chemical reaction-diffusion processes, plasma instabilities, viscous flow issues, flame front propagation, and magnetized plasmas. The present inquiry provides an examination of convergence and error for the future scheme. The conformable q-homotopy analysis transform method (Cq-HATM) provides h-curves that illustrate the convergence range of the series solution achieved. In order to validate the effectiveness and suitability of the Cq-HATM, we examine separate instances. In this study, we introduce an application that demonstrates the potential benefits and effectiveness of the proposed approach. Furthermore, an error analysis is performed in order to verify the accuracy of the scheme. Numerical simulations are conducted to validate the precision of the forthcoming approach. The findings obtained from the numerical and graphical analyses are presented in this study. The method provided in this study showcases a notable degree of computational precision and ease in examining and resolving intricate phenomena related to conformable fractional nonlinear partial differential equations within the domains of science and technology.

Unveiling the Crucial Role of Chemical Enhancement in the SERS Analysis of Amphetamine-Metal Interactions on Gold and Silver Surfaces: Importance of Selective Amplification of the Narrow Interval of Vibrational Modes.

The use of addictive substances, including drugs, poses significant health risks and contributes to various social problems, such as increased crime rates associated with substance-induced aggressive behavior. To address these challenges, possession of addictive substances is legally prohibited. However, detecting and analyzing these substances remain a complex task for law enforcement, primarily due to the presence of adulterants or limited sample quantities. In response to the evolving illicit market, continuous development and adaptation of analytical techniques are essential. One approach is the utilization of surface-enhanced Raman scattering (SERS) spectroscopy, which involves adsorbing the analyte onto nanostructured plasmonic surfaces. This study explores the potential of SERS in detecting amphetamine-based addictive stimulants with a specific focus on the properties of enhancing surfaces chosen. Comparative investigations were performed using silver and gold surfaces, with gold colloidal systems demonstrating a favorable performance. Moreover, to provide a comprehensive interpretation of the measured spectra, extensive density functional theory (DFT) calculations were conducted, allowing for a deeper understanding of the observed spectral features and molecular interactions with the metal surfaces. This review presents insights into the role of chemical enhancement in SERS analysis of amphetamine-metal interactions, shedding light on the selective amplification of vibrational modes. These findings, supported by DFT calculations, have implications in the fields of spectroscopy, physical chemistry, and drug analysis, providing valuable contributions to forensic applications and a deeper understanding of chemical enhancement phenomena. We present the impact of the secondary resonances of Stokes-scattered photons. This illustrates the significance of recognizing the constraints of the frequently employed "E4" approximation, even in measurements involving multiple molecules rather than single molecules.

Green Synthesis of Dy2Sn2O7 Nanostructures Employing Gum of Ferula Assa Feotida for Formation of N3-substituted Quinazoline-2,4(1H,3H)- diones

Introduction: Dy2Sn2O7 nanoparticles (Dy2Sn2O7 NPs) were generated in the attendance of rheum gum, papaver somniferum gum, ferula assa feotida gum, barberry juice from Dy(NO3)3·5H2O and SnCl4·5H2O. Methods: The study of the structure of the specimens verified the generation of nanocatalysts in the scope of 20±5 nm. Synthesized catalysts with a variety of natural compounds were investigated by employing various methods. The characteristics of Dy2Sn2O7 were determined by SEM, TEM, EDX, and XRD. Due to the persistent colloidal stability, high mechanical, thermal sustainability, and high ionic internal character, the system can be deemed as an efficient catalyst by deploying the guest-host approaches. Results: Using industrial waste as raw materials and turning it into valuable products is an important phenomenon in green chemistry. Carbon dioxide is among these substances. This substance is less reactive and it is difficult to use them in a reaction. Conclusion: We announce the employment of CO2, isocyanides, and o-halo anilines in a multicomponent reaction for the production of quinazolines in the participation of Dy2Sn2O7 as a nanocatalyst.

Self-assembled ultrathick MoS2 conductive hydrogel membrane via ionic gelation for superior capacitive energy storage

Conductive hydrogel membranes with nanofluids channels represent one of the most promising capacitive electrodes due to their rapid kinetics of ion transport. The construction of these unique structures always requires new self-assembly behaviors with different building blocks, intriguing phenomena of colloidal chemistry. In this work, by delicately balancing the electrostatic repulsions between 2D inorganic nanosheets and the electrostatic adsorption with cations, we develop a general strategy to fabricate stable free-standing 1T molybdenum disulphide (MoS2) hydrogel membranes with abundant fluidic channels. Given the interpenetrating ionic transport network, the MoS2 hydrogel membranes exhibit a high-level capacitive performance 1.34 F/cm2 at an ultrahigh mass loading of 11.2 mg/cm2. Furthermore, the interlayer spacing of MoS2 in the hydrogel membranes can be controlled with ångström-scale precision using different cations, which can promote further fundamental studies and potential applications of the transition-metal dichalcogenides hydrogel membranes.

Aging Mechanisms of Lithium-ion Batteries

<p>Modern society is making numerous efforts to reduce reliance on carbon-based energy systems. A notable solution in this transition is the adoption of lithium-ion batteries (LIBs) as potent energy sources, owing to their high energy and power densities. Driven by growing environmental challenges, the application scope of LIBs has expanded from their initial prevalence in portable electronic devices to include electric vehicles (EVs) and energy storage systems (ESSs). Accordingly, LIBs must exhibit long-lasting cyclability and high energy storage capacities to facilitate prolonged device usage, thereby offering a potential alternative to conventional sources like fossil fuels. Enhancing the durability of LIBs hinges on a comprehensive understanding of the reasons behind their performance decline. Therefore, comprehending the degradation mechanism, which includes detrimental chemical and mechanical phenomena in the components of LIBs, is an essential step in resolving cycle life issues. The LIB systems presently being commercialized and developed predominantly employ graphite anode and layered oxide cathode materials. A significant portion of the degradation process in LIB systems takes place during the electrochemical reactions involving these electrodes. In this review, we explore and organize the aging mechanisms of LIBs, especially those with graphite anodes and layered oxide cathodes.</p>

Bridging of Cove Regions: A Strategy for Realizing Persistently Chiral Double Heterohelicenes with Attractive Luminescent Properties

AbstractThe racemization of chiral organic compounds is a common chemical phenomenon. However, it often poses configurational‐stability issues to the application of this class of compounds. Achieving chiral organic compounds without the risk of racemization is fascinating, but it is challenging due to a lack of strategies. Here, we reveal the cove‐regions bridging strategy for achieving persistently chiral multi‐helicenes (incapable of racemization), based on the synthesized proof‐of‐concept double hetero[4]helicenes featuring macrocycle structures with a small 3D cavity. Additionally, we demonstrate that the strategy is also effective in tuning the electronic structures of multi‐helicenes, resulting in a conversion from luminescence silence into thermally activated delayed fluorescence (TADF) for the present system. Furthermore, red circularly polarized TADF based on small double [4]helicene systems is achieved for the first time using this strategy. The disclosed cove‐regions bridging strategy provides an opportunity to modulate the electronic structures and luminescent properties of multi‐helicenes without concern for racemization, thus significantly enhancing the structural and property diversity of multi‐helicenes for various applications.

Bridging of Cove Regions: A Strategy for Realizing Persistently Chiral Double Heterohelicenes with Attractive Luminescent Properties.

The racemization of chiral organic compounds is a common chemical phenomenon. However, it often poses configurational-stability issues to the application of this class of compounds. Achieving chiral organic compounds without the risk of racemization is fascinating, but it is challenging due to a lack of strategies. Here, we reveal the cove-regions bridging strategy for achieving persistently chiral multi-helicenes (incapable of racemization), based on the synthesized proof-of-concept double hetero[4]helicenes featuring macrocycle structures with a small 3D cavity. Additionally, we demonstrate that the strategy is also effective in tuning the electronic structures of multi-helicenes, resulting in a conversion from luminescence silence into thermally activated delayed fluorescence (TADF) for the present system. Furthermore, red circularly polarized TADF based on small double [4]helicene systems is achieved for the first time using this strategy. The disclosed cove-regions bridging strategy provides an opportunity to modulate the electronic structures and luminescent properties of multi-helicenes without concern for racemization, thus significantly enhancing the structural and property diversity of multi-helicenes for various applications.

Численное моделирование водородопроницаемости с концентрационной зависимостью коэффициента диффузии

The paper presents a nonlinear mathematical model of alloys hydrogen permeability for membrane technologies of high-purity hydrogen production. Diffusion processes in the material bulk are taken into account as well as physical and chemical phenomena at the surface: adsorption, desorption and relatively fast dissolution. The iterative computational algorithm and software in Scilab have been developed to model the hydrogen permeability with dynamic boundary conditions and concentration-dependent diffusion coefficient.

Numerical modeling of Joule heated ceramic melter

Computational fluid dynamics and heat transfer models of waste glass melters are being developed to support the vitrification campaign at the Waste Treatment and Immobilization Plant (WTP) as part of the United States nuclear waste stewardship and environmental protection programs. The WTP mission aims to achieve the stable and durable processing of vitrified waste in the safest, most efficient, and economical manner possible. Hanford’s tank waste is far more complex and varied than the waste treated by other vitrification facilities and both startup and long-term operational challenges are likely to be even greater than prior experience has shown. There are thousands of different waste compositions, which makes processing the waste a complex and challenging task. Models of test melters, pilot-scale, and full-scale melters have been developed to provide understanding and insight into the various physical and chemical phenomena occurring during vitrification. The results of these modeling activities will be used to support the WTP operations to process legacy nuclear waste into a stable form for disposal.

An innovative methodology for monitoring the sacrificial layer removal process in MEMS structures

The sacrificial layer is a key component for the fabrication of a released structure in the MEMS sensors and actuators. Wet etching is a practical microfabrication process that minimizes costs compared to dry etching. Since the sacrificial layer exists between the structural layer and the substrate, characterization of the etching process is unavailable to observe and evaluate directly. This research, for the first time, presents a methodology for monitoring sacrificial layer removal. It takes advantage of using a transparent substrate (during process development) to observe the removal process from the backside. This method can be used as a separate test during surface micromachining to monitor and optimize the release process of the MEMS device. To evaluate the efficiency of the method, the copper sacrificial layer was selected. The removal process was investigated for typical structures used in MEMS sensors and actuators including the etch-holes, the cantilever beams, comb fingers, and the pads. The experimental test showed the removal of the sacrificial layer, the non-uniformity of the etching, and all the veritable chemical reactions and phenomena under the structural layer. In addition, the etch-rate were obtained in the order of 0.35–5.5 μm min−1 for various structural features. The procedure developed in this research is an approach to the process monitoring of the sacrificial layer removal. Therefore, it can be used to organize the quality control in the released structures of MEMS and optimization in batch processing. This method can be adopted for non-metallic sacrificial layers and dry etching as well.

Pnictogen bond-driven control of the molecular interaction between organophosphorus and acetylcholinesterase enzyme.

This study addresses a comprehensive assessment of the interaction between chemical warfare agents (CWA) and acetylcholinesterase (AChE) systems, focus on the intriguing pnictogen-bond interaction (PnB). Utilizing the crystallographic data from the Protein Data Bank pertaining to the AChE-CWA complex involving Sarin (GB), Cyclosarin (GF), 2-[fluoro(methyl)phosphoryl]oxy-1,1-dimethylcyclopentane (GP) and venomous agent X (VX) agents, the CWA is systematically displaced by increments of 0.1 Å along the PO bond axis, extending its distance by 4 Å from the original position. The AIM analysis was carried out and consistently revealed the presence of a significant interaction along the PO bond. Investigating the intrinsic nature of the PnB, the NBO and the EDA analysis unearthed the contribution of orbital factors to the overall energy of the system. Strikingly, this observation challenges the conventional σ-hole explanation commonly associated with such interactions. This finding adds a layer of complexity to understanding of PnB, encouraging further exploration into the underlying mechanisms governing these intriguing chemical phenomena.

Low-energy spin-polarized electrons: their role in surface physics

Low-energy (∼100eV) electrons have been employed for more than half a century to investigate physical, chemical and electronic phenomena in condensed matter and surface physics. A particular role may be attributed to a purely quantum-mechanical property of the electron–its spin or intrinsic angular momentum. Since the 1970s the electron spin has been indispensable in determining the role of spin-dependent interactions, such as exchange interaction and spin-orbit coupling and their consequences. Most recently, the aspect of topology and its role in condensed matter systems has given a new drive to the investigation of the electron spin and spin textures in such materials. New results on time-dependent ultrafast phenomena may become available by the availability of new intense lasers and laser-driven sources.

A work in progress: William Bateson's vibratory theory of repetition of parts.

In 1891 Cambridge biologist William Bateson (1861-1926) announced his idea that the symmetrical segmentation in living organisms resulted from energy peaks of some vibratory force acting on tissues during morphogenesis. He also demonstrated topographically how folding a radially symmetric organism could produce another with bilateral symmetry. Bateson attended many lectures at the Cambridge Philosophical Society and viewed mechanical models prepared by eminent physicists that illustrated how vibrations affected materials. In his subsequent research, Bateson utilized analogies and metaphors based upon his observations of nature to build a thought model on the effects of vibrations on living tissue, because he realized that the chemistry and biology of his day lacked technologies to perform actual experiments on the subject. He concluded the production of organic segmentation was both a chemical and mechanical phenomenon. By the time of his death Bateson had incorporated new ideas about embryonic organizer regions to suggest a center from which a rhythmic force emanated and then produced the observed repetitive segmentation as a common feature in living organisms.