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Non-bonded force field parameters from MBIS partitioning of the molecular electron density improve binding affinity predictions of the T4-lysozyme double mutant ChemRxiv Pub Date : 2024-03-18 Esteban , Vöhringer-Martinez, Luis , Macaya, Duván , González
Binding affinity prediction using computer simulation has been increasingly incorporated in drug discovery projects. Its wide application, however, is limited by the prediction accuracy of the free energy calculations. The main error sources are force fields used to describe molecular interactions and incomplete sampling of the configurational space. To improve the quality of the force field, we developed
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Permutation Symmetry in Spin Adapted Many-Body Wave Functions ChemRxiv Pub Date : 2024-03-18 Giovanni, Li Manni, Maru, Song, Ali, Alavi
In the domain of exchange-coupled PNTM clusters, local emergent symmetries exist which can be exploited to greatly increase the sparsity of the CI eigensolutions of such systems. Sparsity of the CI secular problem is revealed by exploring the site permutation space within spin-adapted many-body bases, and highly compressed wave functions may arise by finding optimal site orderings. However, the factorial
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Purifying hydrogen from dilute hydrogen-natural gas mixtures using HT-PEM electrochemical hydrogen pumps ChemRxiv Pub Date : 2024-03-18 Karthik, Arunagiri, John M., Turssline, Christopher G., Arges
Reducing the cost of hydrogen transport is an important priority for proliferation of clean hydrogen to decarbonize various sectors of industry and heavy-duty vehicle transportation. Pipeline transport of gases is the lowest cost delivery method for gases over long distances, but there are only a few pipeline networks dedicated to hydrogen. It is possible to alleviate clean hydrogen transportation
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Hydroselenation of Simple Olefins: Elucidating the β-Selenium Radical Effect ChemRxiv Pub Date : 2024-03-18 Kirsten, Ruud, Hannah , Slocumb, Gabriel , Phun, Shaozhen , Nie, Cheyenne , Antonio, Filipp, Furche, Vy, Dong, Xiao-Hui, Yang
We report a light-promoted hydroselenation of alkenes with high anti-Markovnikov selectivity. Spectroscopic, kinetic, and computational mechanistic studies indicate that blue light activates an aryl diselenide to generate a seleno radical; this radical adds into an alkene to form a β-seleno carbon radical. Subsequent hydrogen atom transfer (HAT) generates the linear selenide with high selectivity in
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A semi-flexible tetrahydrazone macrocycle for binding of pyrophosphate and smaller anions ChemRxiv Pub Date : 2024-03-18 Hennie, Valkenier, Lau, Halgreen, Aaron, Torres-Huerta, Karolis, Norvaisa, Gaêl, De Leener, Nikolay, Tumanov, Johan, Wouters, Kristin, Bartik
Macrocyclization has proven to be a useful design strategy in the development of efficient anion receptors. In addition to ring size, the overall preorganization by structural rigidity is of key importance. To explore this in the context of developing an efficient pyrophosphate receptor, three macrocycles featuring a 26-membered interior ring size and similar H-bonding motifs have been synthesized
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Chirality Sensing in Coordination-driven Supramolecular Assemblies ChemRxiv Pub Date : 2024-03-18 ABHIK, PAUL, Subhadip , Roy
Chirality is a widespread structural characteristic found in nature and plays a vital role in the structure and functioning of almost all biological systems. Nevertheless, the translation of chirality into synthetic systems is highly intricate, yet captivating, as it not only applies fundamental understanding but also has the potential to tackle significant difficulties in biochemistry and medicine
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Tricycloquinazoline Based 2D Conjugated Metal-Organic Framework for Robust Sodium-Ion Batteries with Ion Co-Storage of Both Cations and Anions ChemRxiv Pub Date : 2024-03-18 Long, Chen, Dan, Chen, Linqi, Cheng, Weiben, Chen, Heng-Guo, Wang, Fengchao, Cui
There is growing interest in 2D conjugated metal-organic frameworks (2D c-MOFs) for batteries due to their reversible redox chemistry. Nevertheless, currently reported 2D c-MOFs based on n-type ligands are mostly focused on the storage of cations for batteries. Herein, we successfully synthesize the nitrogen-rich and electron-deficient p-type ligand-based Ni3(HATQ)2 assembled from 2, 3, 7, 8, 12,
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Machine Learning, Divergent Syntheses, and X-ray Analyses of Dithienobenzothiazole-based Semiconductors Controlled by S•••N and S•••S Interactions ChemRxiv Pub Date : 2024-03-18 Yasunori, Matsui, Haruki, Okamoto, Naoyuki, Nishida, Hiroyasu, Sato, Takuya, Ogaki, Toshio, Asada, Hiroyoshi, Naito, Hiroshi, Ikeda
Inspired by the previous machine-learning study that the number of hydrogen-bonding acceptor (NHBA) is important index for the hole mobility of organic semiconductors, we synthesized seven dithienobenzothiazole (DBT) derivatives 1a–g (NHBA = 5) by one-step functionalization from a common precursor. X-ray single-crystal structural analyses confirmed that the molecular arrangements of 1b (the diethyl
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DyFeO3 electrode material with ultra-wide voltage window for aqueous symmetric supercapacitors ChemRxiv Pub Date : 2024-03-18 Mohasin, Tarek, M.A., Basith, Ferdous, Yasmeen
Aqueous supercapacitors (SCs) encounter limitations in operational voltage and energy density due to the low decomposition voltage of water. Here, we fabricate aqueous symmetric supercapacitors (ASSCs) employing DyFeO3 as an electrode material. This hybrid SC in a 0.5 M Na2SO4 aqueous electrolyte exhibits a significantly high working voltage of 2.5 V, with an energy density of 41.81 W h kg-1 at a power
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Benchmarking ML in ADMET predictions: the practical impact of feature representations in ligand-based models ChemRxiv Pub Date : 2024-03-18 Gintautas, Kamuntavičius, Orestis, Bastas, Tanya, Paquet, Roy, Tal, Povilas, Norvaišas
This study, focusing on predicting Absorption, Distribution, Metabolism, Excretion, and Toxicology (ADMET) properties, addresses the key challenges of ML models trained using ligand-based representations. We propose a structured approach to data feature selection, taking a step beyond the conventional practice of combining different representations without systematic reasoning. Additionally, we enhance
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One-step Hydrothermal Synthesis of Sn-doped Sb2Se3 for Solar Hydrogen Production ChemRxiv Pub Date : 2024-03-18 David, Tilley, Zhenbin, Wang, Sanghyun, Bae, Miloš, Baljozović, Pardis, Adams, David, Yong, Erin, Service, Thomas, Moehl, Wenzhe, Niu
Antimony selenide (Sb2Se3) has recently been intensively investigated and has achieved significant advancement in photoelectrochemical (PEC) water splitting. In this work, a facile one-step hydrothermal method for the preparation of Sn-doped Sb2Se3 photocathodes with improved PEC performance was investigated. We present an in-depth study of the performance enhancement in Sn-doped Sb2Se3 photocathodes
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Engineering a Photoenzyme to Use Red Light ChemRxiv Pub Date : 2024-03-18 Todd, Hyster, Jose, Carceller, Bhumika, Jayee, Claire, Page, Daniel, Oblinsky, Nithin, Chintala, Gustavo, Mondragón-Solórzano, Jingzhe, Cao, Zayed, Alassad, Zheyu, Zhang, Nathaniel, White, Gregory, Scholes, Sijia, Dong
Photoenzymatic catalysis is an emerging platform for asymmetric synthesis. In most of these reactions, the protein templates a charge transfer complex between the cofactor and substrate, which absorbs in the blue region of the electromagnetic spectrum. Here, we report the engineering of a photoenzymatic ‘ene’-reductase to utilize red light (620 nm) for a radical cyclization reaction. Mechanistic studies
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Non-bonded force field parameters from MBIS partitioning of the molecular electron density improve thermophysical properties prediction of organic liquids ChemRxiv Pub Date : 2024-03-18 Esteban , Vöhringer-Martinez, Luis, Macaya, Jorge, Pulido
The accuracy of predicting thermophysical properties through molecular dynamics simulations is constrained by the precision of models used to describe molecular interactions. The Open Force Field initiative has established a computational structure to develop new models and introduced two non-polarizable force fields, Parsley and Sage. Sage version 2.0.0 focused on refining Lennard-Jones parameters
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Temporally controlled multistep division of DNA droplets for dynamic artificial cells ChemRxiv Pub Date : 2024-03-18 Masahiro, Takinoue, Tomoya, Maruyama, Jing, Gong
Bio-soft matter droplets formed via liquid-liquid phase separation (LLPS) of biopolymers have been found in living cells. Synthetic LLPS droplets have recently been employed in nanobiotechnology for artificial cell construction, molecular robotics, molecular computing, diagnosis, and therapeutics. Controlling the dynamics of bio-soft matter droplets is essential for developing such bio-inspired functional
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Localized nanopore fabrication in silicon nitride membranes by femtosecond laser exposure and subsequent controlled breakdown. ChemRxiv Pub Date : 2024-03-18 Shyamprasad N., Raja, Chrysovalantou V., Leva, Saumey, Jain, Kevin, Kistermann, Kasumi, Sakurai, Göran, Stemme, Anna, Herland, Joachim, Mayer, Frank, Niklaus
Controlled breakdown (CBD) has emerged as an effective method for fabricating solid-state nanopores in thin suspended dielectric membranes for various biomolecular sensing applications. On an unpatterned membrane, the site of nanopore formation by controlled breakdown is random. Nanopore formation on a specific site on the membrane has previously been realized using local thinning of the membrane by
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Water, Energy, and Cost: A Nexus Approach to Zero/Minimal Liquid Discharge Desalination Technologies ChemRxiv Pub Date : 2024-03-18 Jennifer B., Dunn, Margaret G., O'Connell, Neha, Rajendran, Menachem , Elimelech, Jack , Gilron
Desalination is increasingly essential to ensure water access as climate change and population growth stress fresh water supplies. Already in use in water-stressed regions around the world, desalination generates fresh water from salty sources, but forms a concentrated brine that requires disposal. There is a growing push for the adoption of zero/minimal liquid discharge (ZLD/MLD) technologies that
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Ratiometric Near Infrared Fluorescence Imaging of Dopamine with 1D and 2D nanomaterials ChemRxiv Pub Date : 2024-03-18 Bjoern F., Hill, Jennifer M., Mohr, Isabelle K., Sandvoss, Sebastian , Kruss, Juliana , Gretz, Phillip, Galonska, Lena , Schnitzler, Luise, Erpenbeck
Neurotransmitters are released by neuronal cells to exchange information. Resolving their spatiotemporal patterns is crucial to understand chemical neurotransmission. Here, we present a ratiometric sensor for the neurotransmitter dopamine that combines Egyptian Blue (CaCuSi4O10) nanosheets (EB-NS) and single-walled carbon nanotubes (SWCNTs). They both fluoresce in near infrared (NIR), which is beneficial
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Empowering Capacitive Devices: Harnessing Transfer Learning for Enhanced Data-Driven Optimization ChemRxiv Pub Date : 2024-03-18 Teslim, Olayiwola, Revati, Kumar, Jose, Romagnoli
Developing data-driven models has found successful applications in varying engineering problems. In capacitive devices like deionization and supercapacitors, there exists a potential to apply this data-driven machine learning (ML) model in optimizing it potential use in energy efficient separations or energy generation. However, these models are faced with limited datasets and even in large quantity
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Benchmarking Study of Deep Generative Models for Inverse Polymer Design ChemRxiv Pub Date : 2024-03-18 Tianle, Yue, Ying, Li, Lei, Tao, Vikas, Varshney
Molecular generative models based on deep learning have increasingly gained attention for their ability in de novo polymer design. However, there remains a knowledge gap in the thorough evaluation of these models. This benchmark study explores de novo polymer design using six popular deep generative models: Variational Autoencoder (VAE), Adversarial Autoencoder (AAE), Objective-Reinforced Generative
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Trapping Highly Reactive Photo-Induced Charge-Transfer Complex Between Amine and Imide by Light ChemRxiv Pub Date : 2024-03-18 Wenhuan, Huang, Xiaolong, Zhang, Hao, Su, Baicheng, Zhang, Airong, Feng, Jun, Jiang, Biao, Chen, Guoqing, Zhang
Complexation between two organic molecules can occur either for strong electron donor-acceptor pairs in the ground state known as charge-transfer complexes (CTCs), or for pairs of lesser strength in the excited state such as excimers and exciplexes. However, the characterization of chemically distinct CTCs in solution remains elusive. Here, we report a light-induced, solution-persistent 1:1 CTC between
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The Big Problem in Surface Catalysis Modelling ChemRxiv Pub Date : 2024-03-18 Chen-Chen, Er, Yee Wen, Teh, Xin Ying, Kong, Soungmin, Bae, Yu, Kumagai, Siang-Piao, Chai, Yee Sin, Ang
The existence of native point defects in crystalline solids are inevitable during synthesis. Such native defects will usually strongly impact the device performance of materials in catalysis applications. In recent years, the ability of first-principles approaches to accurately predict defect behavior has seen major progress. The underlying issue, as one would have guessed, is that these predictions
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The Development of the QM/MM Interface and Its Application for the on-the-fly QM/MM Nonadiabatic Dynamics in JADE Package: Theory, Implementation and Applications ChemRxiv Pub Date : 2024-03-18 Haiyi, Huang, Jiawei , Peng, Feng Long, Gu, Zhenggang, Lan, Chao, Xu
Understanding the nonadiabatic dynamics of complex systems is a challenging task in computational photochemistry. Herein, we present an efficient and user-friendly quantum mechanics/molecular mechanics (QM/MM) interface to run on-the-fly nonadiabatic dynamics. Currently, this interface consists of an independent set of codes designed for general-purpose use. Herein, we demonstrate the ability and feasibility
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Efficient and Selective Electrochemical CO2 to Formic Acid Conversion: A First-Principles Study of Single-Atom and Dual-Atom Catalysts on Tin Disulfide Monolayers ChemRxiv Pub Date : 2024-03-18 Guanming, Chen, Margherita, Buraschi, Rashid, Al-Heidous, Satyanarayana, Bonakala, Fedwa, El-Mellouhi, Clotilde S., Cucinotta
Electrochemical CO2 reduction reaction (CO2RR), is a sustainable approach to recycle CO2 and address climate issues, but needs selective catalysts that can operate at low electrode potentials. Single-atom catalysts (SACs) and dual-atom catalysts (DACs) have become increasingly popular, due to their versatility, unique properties and outstanding performances in electrocatalytic reactions. In this paper
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Multivariate data analysis of CHO cell line development data to identify cell line selection criteria ChemRxiv Pub Date : 2024-03-18 Alexei, Lapkin, Devi, Sietaram, Pavlos, Kotidis, Ruth, Rowland-Jones, Gary, Finka
This paper presents a multivariate data analysis (MVDA) of GS-CHO cell line development (CLD) data to uncover new insights for decision-making in CLD cell line selection. Developing a monoclonal antibody (mAb) using Chinese Hamster Ovary (CHO) cells entails a resource intensive CLD process to select an optimal, clonally derived CHO cell line with consistent mAb productivity, viability, and quality
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Sulfonate group improves the solubility and electrocatalytic performance of Ru-based bda- and pda-type water oxidation catalysts under neutral conditions ChemRxiv Pub Date : 2024-03-18 Yuezhi, Mao, Jake T., Kerkhof, Colton J., Breyer, Diane K., Smith, Douglas B., Grotjahn
Four ruthenium water oxidation catalysts that bear carboxylate and sulfonate groups in the active site have been synthesized and analyzed for their catalytic activity. The developed catalysts are modified from highly active species that traditionally have two carboxylate groups in the active site and are used to probe the effects of sulfonate substitution as well as the effects of other structural
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F-doped carbon/Co3O4 composite catalyst for alkaline oxygen evolution ChemRxiv Pub Date : 2024-03-18 Yunpu, Zhai, Mengjie, Gao, Zhaodi, Wang, Weiruo, Liu
Electrocatalytic water splitting is a sustainable way to produce hydrogen energy. However, the oxygen evolution reaction (OER) at the anode always has sluggish kinetics and low energy conversion efficiency, which is the major bottleneck for water splitting. In this paper, the electronic structure of the Co3O4/carbon composites was regulated by anion doping. The F-doped carbon substrate is compounded
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Metal–Ligand Redox in Layered Oxide Cathodes for Li-ion Batteries ChemRxiv Pub Date : 2024-03-18 Matthew J. W., Ogley, Ashok S., Menon, Gaurav, Pandey, Galo J., Páez Fajardo, Beth J., Johnston, Innes, McClelland, Veronika, Majherova, Steven , Huband, Debashis , Tripathy, Israel, Temprano, Stefano , Agrestini, Veronica , Celorrio, Gabriel E., Pérez, Clare P., Grey, Serena A., Cussen, Louis F. J., Piper, Samuel G., Booth
Understanding charge compensation in Li-ion battery cathodes is crucial for improving specific capacity and cycle life. This study clarifies some of the ambiguities and inaccuracies of the commonly used ionic-bonding model that requires separate transition metal (TM) and oxygen redox regimes, using an archetypal layered oxide cathode, LiNi0.8Mn0.1Co0.1O2. Contrary to the prevalent TM-centric ionic
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The role of organic cations in the electrochemical reduction of CO2 in aprotic solvents ChemRxiv Pub Date : 2024-03-18 Joaquin, Resasco, Joan, Brennecke, Jan , Rossmeisl, Louise, Canada, Jon-Marc, McGregor, Jay, Bender, Amanda, Petersen
The electrochemical reduction of CO2 is sensitive to the microenvironment surrounding catalytic active sites. Although the impact of changing electrolyte composition on CO2 reduction kinetics in aqueous electrolytes has been studied intensively, less is known about the influence of the electrochemical environment in non-aqueous solvents. Here, we present data demonstrating that organic alkyl ammonium
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Liquid-Liquid Transition and Ice Crystallization in a Machine-Learned Coarse grained Water Model ChemRxiv Pub Date : 2024-03-18 Valeria, Molinero, Debdas, Dhabal, Rajat, Kumar
Mounting experimental evidence supports the existence of a liquid-liquid transition (LLT) in high-pressure supercooled water. However, fast crystallization of supercooled water has impeded identification of the LLT line TLL(p) in experiments. While the most accurate all-atom (AA) water models display a LLT, their computational cost limits investigations of its interplay with ice formation. Coarse-grained
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Pretreatment Methods for Accelerated PFAS Degradation in Wastewater ChemRxiv Pub Date : 2024-03-18 Dandan, Rao, Jinyong, Liu
This study explored different pretreatment methods to enhance photochemical degradation of PFAS in still-bottom (SB) brine. The brine contained concentrated natural organic matter and inorganic salts, which severely inhibited PFAS destruction by prevailing technologies. Pretreatment methods evaluated included flocculation, Fenton oxidation, and Soxhlet extraction. Soxhlet extraction works by repeatedly
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Simultaneously Utilizing Excited Holes and Electrons for Piezoelectric-Enhanced Photoproduction of H2O2 from S-Scheme 2D S-doped VOx/g-C3N4 Nanostructures ChemRxiv Pub Date : 2024-03-18 Hoai Thanh, Vuong, Huynh Phuoc, Toan, Phan Pham Duc, Minh, Duc-Viet, Nguyen, Seung Hyun, Hur, Nguyen Hoai, Anh, Ly Pho, Phuong, Thuy Thi Dieu, Ung, Do Danh, Bich, Minh-Thuan, Pham
The simultaneous use of excited holes and electrons in photocatalytic research has become a strong driving force for rationalizing materials in design and development. As a promising strategy, step-scheme (S-scheme) photocatalysts have enormously ignited the photocatalytic community in recent decades. Introducing piezoelectric fields under light irradiations to generate valuable chemical products,
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Effect of Alkali Metal Cations and Trace Metal Impurities on Cathodic Corrosion of Gold Electrode Surfaces ChemRxiv Pub Date : 2024-03-18 Mohamed M., Elnagar, Ludwig A., Kibler, Timo, Jacob
Cathodic corrosion, a phenomenon critical for understanding the stability and performance of metal electrodes during several energy conversion reactions, is known to be influenced by various factors including the nature and concentration of alkali metal cations. However, a clear understanding of this behavior has not yet been developed. Through a comprehensive investigation of cathodic corrosion of
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Heterocycles as Supramolecular Handles for Crystal Engineering: A Case Study with 7-(diethylamino)coumarin Derivatives ChemRxiv Pub Date : 2024-03-18 Mauricio, Maldonado-Domínguez, Geraldyne, Castro, Margarita, Romero-Ávila, Norberto, Farfán, Rafael, Arcos-Ramos
In this study, we present the synthesis and detailed solid-state structural characterization of a Schiff-base-bridged derivative of 7-(diethyl)aminocoumarin (DAC) to carry out a comparative crystallographic analysis, within the broader context of a curated dataset of 50 DAC-containing molecules, retrieved from the literature, and their corresponding crystal packing. We uncover that the DAC moiety leverages
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Photochemical PFAS Degradation in Ion Exchange Resin Regeneration Brine: Effects of Water Matrix Components and Technical Solutions ChemRxiv Pub Date : 2024-03-18 Dandan, Rao, Jinyong, Liu
Ion-exchange (IX) is an effective method for PFAS removal from water and wastewater, but the treatment of concentrated PFAS from IX resin regeneration remains a major technical barrier. This study investigates the challenges and solutions associated with photochemical treatment of waste brines from resin regeneration. We first tested the defluorination of perfluorooctanoic acid (PFOA) by UV/sulfite/iodide
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Fine structural analysis of non-thermal degummed fibroin fibers reveals its superior mechanical capabilities ChemRxiv Pub Date : 2024-03-18 Dror, Eliaz, Israel, Kellersztein, Marco , Elvino Miali, Doron, Benyamin, Chiara, Daraio, Hanoch Daniel, Wagner, Uri, Raviv, Ulyana, Shimanovich, Ori, Brookstein
Bombyx mori silk fibroin fibers constitute a class of protein building blocks capable of func-tionalization and reprocessing into various material formats. The properties of these fibers are typically affected by the intense thermal treatments needed to remove the sericin gum coating layer. Additionally, their mechanical characteristics are often misinterpreted by assuming the asymmetrical cross-sectional
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Hydrophobic Sorption Properties of an Extended Series of Anionic Per- and Polyfluoroalkyl Substances Characterized by C18 Chromatographic Retention Measurement ChemRxiv Pub Date : 2024-03-18 Satoshi, Endo, Sadao, Matsuzawa
Partitioning from water to nonaqueous phases is an important process that controls the behavior of contaminants in the environment and biota. However, for ionic chemicals including many per- and polyfluoroalkyl substances (PFAS), environmentally relevant partition coefficients cannot be predicted using the octanol/water partition coefficient, which is commonly used as a hydrophobicity indicator for
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Synthesis of γ-butyrolactone hybrid imidazo[2,1-b][1,3]-thiazoles from limonene ChemRxiv Pub Date : 2024-03-18 Pushpinder, Kaur, Pralay , Das, Bikram, Singh
The substituted γ-butyrolactones are important structural motifs in several natural products and pharmaceuticals. In this paper γ-butyrolactone fused heterocyclic imidazo[2,1-b][1,3]-thiazole derivatives have been synthesized from thiazole amine (4) and different substituted α-bromo acetophenones in moderate yields. Electron rich substituents provided higher yields of the desired products. The screening
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Pd(COD)(DQ): A Stable, Versatile, and Monometallic Palladium(0) Source for Organometallic Synthesis and Catalysis ChemRxiv Pub Date : 2024-03-15 Keary, Engle, Wen-Ji, He, Wen-Zhuo, Qin, Shenghua, Yang, Senjie, Ma, Nana, Kim, Johnathan, Schultz, Maximilian, Palkowitz, Chi, He, Anqi, Ma, Michael, Schmidt, Steven, Wisniewski, Milan, Gembicky
Pd(COD)(DQ) (COD=1,5-cyclooctadiene, DQ=duroquinone) is a robust, air-stable, and well-defined 18-electron Pd(0)–olefin complex first synthesized by Sakai et al. in 1983. Herein, we describe an operationally convenient synthetic procedure to prepare this complex on decagram scale; we show that it undergoes facile ligand exchange with phosphines, N-heterocyclic carbenes, and other catalytically important
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Identifying Site-Specific Crosslinks Originating from a Genetically Incorporated, Photoreactive Amino Acid ChemRxiv Pub Date : 2024-03-15 Matthew, Bush, Lindsey, Ulmer, Daniele, Canzani, Christopher, Woods, Natalie, Stone, Maria, Janowska, Rachel, Klevit
In traditional crosslinking mass spectrometry, proteins are crosslinked using a highly selective, bifunctional chemical reagent, which limits crosslinks to residues that are accessible and reactive to the reagent. In this study, we employ an alternative approach using benzoylphenylalanine (BPA), a photoreactive amino acid, incorporated into a disordered region of the human protein HSPB5. BPA is incorporated
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Generic Conditions for Electromembrane Extraction of Acids with Low to Moderate Hydrophilicity in Human Plasma ChemRxiv Pub Date : 2024-03-15 Frederik André, Hansen, Chenchen, Song, Samira, Dowlatshah, Anne Oldeide, Hay, Grete, Hasvold, Somayeh, Gaznawi
The current paper reports the first set of generic conditions for electromembrane extraction of acidic substances from human plasma. Two systems were developed, based on eutectic solvents; A1 (“A” for acid) comprised dodecyl methyl sulfoxide and thymol in 1:2 ratio (w/w) as liquid membrane, while A2 used [6-methylcoumarin:thymol (1:2)]:2-nitrophenyl octyl ether in 2:1 ratio (w/w). A1 and A2 were applied
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Harnessing ultrasound-derived hydroxyl radicals for the selective oxidation of aldehyde functions ChemRxiv Pub Date : 2024-03-15 Ari F., Fischer, Zhangyue, Xie, Kaicheng, Qian, Renhong, Li, James, Kwan, François, Jérôme, Wen, Liu, Prince N., Amaniampong, Tej S., Choksi, Sabine, Valange, Teseer, Bahry
Ultrasonic irradiation holds potential for the selective oxidation of non-volatile organic substrates in the aqueous phase by harnessing hydroxyl radicals as chemical initiators. Here, a mechanistic description of hydroxyl radical-initiated glyoxal oxidation is constructed by gleaning insights from photolysis and radiation chemistry to explain the yields and kinetic trends for oxidation products. The
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C-Terminal Peptide Modification: Merging the Passerini Reaction with Chemo-Enzymatic Synthesis ChemRxiv Pub Date : 2024-03-15 Jordy M., Saya, Jay, Hanssens, Sam, van Dun, Tessa H.G., Lokate, Vincent R.A.M. , Reinartz, Leendert J. , van den Bos, Romano V.A., Orrù
Over the past few decades, peptide/protein synthesis and bio-conjugation has gained increasing interest in the research community owing to the high demand for strategies that provide modified protein adducts in a site-selective fashion. Herein, we report a novel approach that combines the Passerini multicomponent reaction and chemo-enzymatic peptide synthesis (CEPS) for the selective bio-conjugation
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Simultaneous near infrared photothermal therapy and temperature mapping by magnetic resonance in 3D cell aggregates loaded with Fe3Se4 nanoparticles ChemRxiv Pub Date : 2024-03-15 Joana F., Soeiro, Rute A., Pereira, Rui, Oliveira-Silva, Filipa L., Sousa, Vítor M., Gaspar, João F., Mano, Ángel, Millán, Claudia, Innocenti, Manuel, Mariani, Alessandro , Lascialfari, Nuno J. O., Silva
Control over temperature in space and time is of utmost importance in many contexts, including photothermal therapies, where a good temperature monitoring and control is expected to improve their clinical outcome. One of the most promising techniques involves the use of magnetic resonance imaging, exploring the temperature change of proton relaxometric properties or exploring the temperature change
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N-H Insertion of Anilines on N-Tosylhydrazones Induced by Visible Light Irradiation ChemRxiv Pub Date : 2024-03-15 Diana, Lamaa, Etienne, brachet, Clara, Faure, Salim, Benmaouche, Philippe, Belmont
Diazo compounds as well as their precursors represent an interesting category for organic synthesis. Particularly N-tosylhydrazones, have attracted attention for their easy accessibility and diverse reactivity, including carbene transfer reactions. We described a visible light induced N-H insertion reaction of anilines on in-situ generated diazo compounds. Optimal conditions using DBU in toluene yielded
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Biocatalytic nucleobase diversification of 4’-thionucleosides and de novo RNA synthesis using 5-ethynyl-4’-thiouridine ChemRxiv Pub Date : 2024-03-15 Gavin, Miller, Anke , Kurreck, Jens, Kurreck, Peter, Neubauer, Jonas, Motter, Viola, Röhrs, Sarah, Westarp, Yogesh, Sanghvi, Caecilie , Benckendorff
Nucleoside and nucleotide analogues have proven transformative in the treatment of viral infections and cancer. One branch of structural modification to deliver new nucleoside analogue classes explores replacement of canonical ribose oxygen with a sulfur atom. Whilst biological activity of such analogues has been shown in some cases, widespread exploration of this class of analogue is hitherto hampered
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Photosulfoxidation catalysis as the driving principle for the deazaoxaflavin photoredox catalyst formation ChemRxiv Pub Date : 2024-03-15 Petr, Kovaricek, Karolína, Křížová, Rimeh, Ismail, Anna, Geleverya, Valentino, Guerra
Catalysts are essential for sustainability because they decrease the energy and resource consumption in the production of high value-added products. The design of a novel catalyst is a challenging and expensive target, and a simplified methodology for catalyst development can trigger burgeoning progress in both academic and applied research. Here, we demonstrate a reaction network that autonomously
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Characterization of Indoor Atmospheric Nitrogenous Chemicals in Poultry Farms ChemRxiv Pub Date : 2024-03-15 Xinyang, Guo, Rowshon, Afroz, Shuang, Wu, Kimberly, Wong, Valerie, Carney, Martin, Zuidhof, Joey, Saharchuk, Hans, Osthoff, Ran, Zhao
Indoor air pollution is seen in poultry and many other animal husbandry industries. Small airborne nitrogenous chemicals (ANCs), such as ammonia and small amines, are common air pollutants in poultry farms. Elevated ANC concentration in poultry farms can significantly worsen the indoor air quality (IAQ) of the farm, which will affect animal productivity, animal welfare, and occupational health of producers
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Combined Machine Learning and Molecular Dynamics Reveal Two States of Hydration of a Single Functional Group of Cationic Polymeric Brushes ChemRxiv Pub Date : 2024-03-15 Siddhartha, Das, Raashiq, Ishraaq, Tanmay Sarkar, Akash
The state of hydration of a macromolecular system regulates a plethora of different properties of such a system. In this article, we develop a novel machine learning (ML) approach, based on the unsupervised clustering algorithm, for probing the hydration behavior of the {N(CH3)3}+ functional group of the PMETAC [Poly(2-(methacryloyloxy)ethyl trimethylammonium chloride] polyelectrolyte (PE) brush system
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NH3-SCR over Fe/SSZ-13 catalyst prepared by modification of natural chabazite ChemRxiv Pub Date : 2024-03-15 AMEEN, SHAHID, Nabeel, Ahmad, Nouman, Ahmad, Sher, Ahmad
Natural zeolites are typically found in abundance in various geological formations, including volcanic and sedimentary rocks. The properties of these natural chabazites such as crystallinity, surface area, and composition can be tailored to enhance their catalytic properties. In this work, the low-crystalline natural chabazite containing iron was transformed into a highly crystalline Fe/SSZ-13 catalyst
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Computational Investigations of the Detailed Mechanism of Reverse Intersystem Crossing in Inverted Singlet-Triplet Gap Molecules ChemRxiv Pub Date : 2024-03-15 Yoann, Olivier, Danillo, Valverde, Cher Tian, Ser, Gaetano, Ricci, Kjell, Jorner, Robert, Pollice, Alan, Aspuru-Guzik
Inverted singlet-triplet gap (INVEST) materials have promising photophysical properties for optoelectronic applications due to an inversion of their lowest singlet (S1) and triplet (T1) excited states. This results in an exothermic reverse intersystem crossing (rISC) process that potentially enhances triplet harvesting, compared to thermally activated delayed fluorescence (TADF) emitters with endothermic
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Charge compensation and structural adaptation to accommodate increased magnetic cation content in multiferroic Aurivillius phases ChemRxiv Pub Date : 2024-03-15 Lynette, Keeney, Jennifer, Halpin, Michael, Schmidt, Roger W., Whatmore
The five-layered (m = 5) Bi6Ti2.99Fe1.46Mn0.55O18 Aurivillius material is a rare example of a single-phase room temperature ferroelectric-ferromagnetic multiferroic that could ideally be suited to future energy-efficient memory devices. This study examines the effect of B-site substitution with the aim of increasing the proportion of magnetic ions within the structure and consequently increasing the
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pKalculator: A pKa predictor for C-H bonds ChemRxiv Pub Date : 2024-03-15 Jan, Jensen, Rasmus M., Borup, Nicolai, Ree
Determining the pKa values of various C-H sites in organic molecules offers valuable insights for synthetic chemists in predicting reaction sites. As molecular complexity increases, this task becomes more challenging. This paper introduces pKalculator, a quantum chemical (QM)-based workflow for automatic computations of C-H pKa values, which is used to generate a training dataset for a machine learning
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Heterogeneously Catalyzed Thioether Metathesis by a Supported Au–Pd Alloy Nanoparticle Design Based on Pd Ensemble Control ChemRxiv Pub Date : 2024-03-15 Takafumi, Yatabe, Takehiro, Matsuyama, Tomohiro, Yabe, Kazuya, Yamaguchi
C–S bond metathesis of thioethers has gained attention as a new approach to the late-stage diversification of already existing useful thioethers with intact molecular frameworks. However, direct or indirect thioether metathesis is scarcely reported, and heterogeneously catalyzed systems have not been explored. Here, we develop heterogeneously catalyzed direct thioether metathesis using a supported
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High-resolution 17O solid-state NMR as a unique probe for investigating oxalate binding modes in materials: The case study of calcium oxalate biominerals ChemRxiv Pub Date : 2024-03-15 Danielle, Laurencin, Ieva, Goldberga, Ivan, Hung, Vincent, Sarou-Kanian, Christel, Gervais, Zhehong, Gan, Jessica, Novák-Špačková, Thomas-Xavier, Métro, César, Leroy, Dorothée, Berthomieu, Arie, van der Lee, Christian, Bonhomme
Oxalate ligands are found in many classes of materials, including energy-storage materials and biominerals like hydrated calcium-oxalates. Determining their local environments at the atomic scale is thus paramount to establishing the structure and properties of numerous phases. Here, we show that high-resolution 17O solid-state NMR is a valuable asset for investigating the structure of crystalline
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Synthetic route design & assessment using vectors derived from similarity and complexity ChemRxiv Pub Date : 2024-03-15 Gareth, Howell, Samuel, Genheden
With the aim of improving the machine-interpretation of synthetic routes we describe a new theoretical approach to visualising and assessing synthetic pathways in the absence of empirical data such as yield, cost and waste. The representation of molecular structures as coordinates derived from molecular (fingerprint) similarity and complexity allows individual transformations to be viewed as vectors
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Using non-adiabatic excitation transfer for signal transmission between molecular logic gates ChemRxiv Pub Date : 2024-03-15 Arthur I., Martynov, Aleksandr S., Belov, Vladimir K., Nevolin
Molecular logic gates (MLG) are molecules which perform logic operations. Their integration into a computing system is a very difficult task which remains to be addressed. The problem lies in the field of signal exchange between the gates within the system. We propose using non-adiabatic excitation transfer between the gates to address this problem while absorption and fluorescence are left to communicate
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The pre-quantum atomic theory told by experiments ChemRxiv Pub Date : 2024-03-15 Massimiliano, Sipala
A survey was conducted among chemistry students and graduates of any level about atomic theory before quantum. The incorrect answers recorded show the students have many misconceptions about the origin of atomic theory and how the existence of atoms and molecules was first demonstrated. These results have suggested a clarification on the subject is needed. Here, the basic concepts of atomic theory
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Molecular set representation learning ChemRxiv Pub Date : 2024-03-15 Daniel, Probst, Maria, Boulougouri, Pierre, Vandergheynst
Computational representation of molecules can take many forms, including graphs, string-encodings of graphs, binary vectors, or learned embeddings in the form of real-valued vectors. These representations are then used in downstream classification and regression tasks using a wide range of machine-learning models. However, existing models come with limitations, such as the requirement for clearly defined
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Continuous flow synthesis of N,O-dimethyl-N'-nitroisourea monitored by inline FTIR: comparing machine learning and kinetic modeling for optimization ChemRxiv Pub Date : 2024-03-15 An, Su, Jiapeng, Guo, Guihua, Luo, Kejie, Chai, Weike, Su
The synthesis of N,O-Dimethyl-N'-nitroisourea, crucial intermediates in pesticide manufacturing, was explored through a substitution reaction between O-methyl-N-nitroisourea and methylamine within a novel continuous flow microreactor system, featuring FTIR inline analysis for real-time monitoring. This study embarked on a comparative analysis between two optimization approaches: the contemporary machine
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Efficient Exploration of Highly Conductive Pyrrolidinium-based Ionic Plastic Crystals Using Materials Informatics ChemRxiv Pub Date : 2024-03-15 Masahiro, Yoshizawa-Fujita, Takuto, Ootahara, Kan, Hatakeyama-Sato, Morgan L., Thomas, Yuko, Takeoka, Masahiro, Rikukawa
Ionic plastic crystals (IPCs), which are soft crystals with plasticity and ionic conductivity, are expected to be applied as solid electrolytes in battery applications. Further improvement of ionic conductivity is necessary for practical use as an electrolyte for energy storage devices. Materials Informatics (MI) is a method of incorporating information science in materials development. In this research