jablonkagroup/rise_ai_scientists huggingface dataset:
Authors: Ezra A. Baghdady | J. Will Medlin | Daniel K. Schwartz
Source: Catalysis Science & Technology (article, 2025-01-01)
Field: Chemistry — Organic Chemistry

Tuning formate surface coverage with cosolvents for liquid-phase catalytic transfer hydrogenation Changes in solvent composition are used to control the adsorption of formate on metal catalysts and thus the rate of formate-driven transfer hydrogenation. Catalysis ; Formate ; Phase (matter) ; Transfer hydrogenation ; Chemistry ; Liquid phase ; Photochemistry ; Chemical engineering ; Combinatorial chemistry ; Organic chemistry ; Ruthenium ; Thermodynamics Nanomaterials for catalytic reactions ; Catalysis and Hydrodesulfurization Studies ; Catalysis for Biomass Conversion
Authors: Emanuele Giuliani | Maria Sbacchi | Serena Agostini | Giacomo Filippini | Beatrice Bartolomei | Pierangelo Gobbo | Maurizio Prato
Source: Angewandte Chemie International Edition (article, 2025-08-08)
Field: Materials Science — Materials Chemistry

Molecular Insights into the Formation and Functionalization of Carbon Nanodots: From Precursor Intermediates to Surface Chemistry Quantification Understanding the mechanistic pathways underlying carbon nanodot (CND) formation is essential for the rational design of synthesis strategies and the development of well-defined nanomaterials. In this work, we combine chromatographic isolation, spectroscopic characterization, and synthetic validation to identify key molecular intermediates in the early stages of CND formation from arginine (Arg) and ethylenediamine (EDA) under hydrothermal conditions. Using reverse-phase high-performance liquid chromatography, <sup>1</sup>H/<sup>13</sup>C nuclear magnetic resonance (NMR) spectroscopy, and mass spectrometry, we isolate and structurally confirm multiple reaction intermediates, including species arising from Arg cyclization and EDA-derived condensation products. Each proposed intermediate was validated via direct synthesis and comparative analysis. Fully formed CNDs were then isolated and extensively characterized through several techniques. Multi-detection gel permeation chromatography enabled the determination of absolute number average molecular weight (M<sub>n</sub> = 4,400 ± 458 g mol<sup>-1</sup>), dispersity (Đ = 1.34), and hydrodynamic diameter (2.8 ± 0.2 nm). Quantification of amine functionalities using Kaiser test and <sup>19</sup>F NMR, upon condensation with a fluorinated aldehyde probe, established the presence of 6-7 amines per particle. Together, this systematic approach not only elucidates the mechanistic origin of CND formation but also establishes a robust framework for molecular-level CND design and functionalization. Surface modification ; Chemistry ; Dispersity ; Ethylenediamine ; Gel permeation chromatography ; Mass spectrometry ; Nanodot ; Combinatorial chemistry ; Organic chemistry ; Chromatography ; Physical chemistry Carbon and Quantum Dots Applications ; Analytical chemistry methods development ; Electrochemical sensors and biosensors
Authors: Mallory E. Thomas | Alistair J. Lees
Source: Sustainable Chemistry (review, 2025-06-14)
Field: Chemistry — Spectroscopy

A Review of the Molecular Aggregation of Small-Molecule Anion Sensors for Environmental Contaminates in Aqueous Media A primary challenge in the further development of anion sensors in real water samples of environmental concern is the need for highly water-soluble compounds that are able to detect low concentrations of analytes. Small-molecule sensors can mitigate solubility constraints and highly aromatic or conjugated systems may provide a new way to recognize target analytes with high sensitivity and/or selectivity. Organic aggregates that have the ability to form large frameworks can exhibit aggregated-induced emissions to detect target analytes, and their coagulation can provide enhanced detection via colorimetric or fluorescent measurements. This review aims to draw attention to the emerging area of small-molecule organic chemosensors that utilize aggregation to detect environmentally detrimental anions in an aqueous solution. A number of mechanisms of interaction for anion recognition are recognized and discussed here, including electrostatic interactions, covalent bond formation, hydrophobic interactions, and even complexation. Aqueous medium ; Molecule ; Aqueous solution ; Ion ; Chemistry ; Chemical engineering ; Materials science ; Nanotechnology ; Chemical physics ; Organic chemistry ; Engineering Molecular Sensors and Ion Detection ; Luminescence and Fluorescent Materials ; Advanced biosensing and bioanalysis techniques
Authors: Nesrine Mohamed Bhiri | Herman Duim | Eduard Madirov | Justine S. Nyarige | Bryce S. Richards | Andrey Turshatov
Source: Journal of Materials Chemistry C (article, 2025-01-01)
Field: Materials Science — Materials Chemistry

Optimizing the short-wavelength infrared photoluminescence quantum yield and brightness of Er<sup>3+</sup>, Yb<sup>3+</sup> co-doped yttrium orthophosphate phosphors for tracer-based sorting Development of efficient inorganic luminescent tracers is essential for various applications, including plastic sorting. Yttrium ; Phosphor ; Materials science ; Photoluminescence ; Doping ; Quantum yield ; Infrared ; Lanthanide ; TRACER ; Luminescence ; Brightness ; Sorting ; Ion ; Wavelength ; Analytical Chemistry (journal) ; Optoelectronics ; Optics ; Fluorescence ; Metallurgy ; Chemistry ; Environmental chemistry ; Organic chemistry ; Computer science Luminescence Properties of Advanced Materials ; Advanced Chemical Sensor Technologies ; Luminescence and Fluorescent Materials
Authors: Masahiro Yamaguchi | Kentaro Yonesato | Kaito Shioya | Chifeng Li | Kei Murata | Kazuyuki Ishii | Kazuya Yamaguchi | Kosuke Suzuki
Source: Chemical Science (article, 2025-01-01)
Field: Materials Science — Materials Chemistry

Engineering cofacial porphyrin dimers using lacunary polyoxotungstates Cofacial porphyrin dimers have garnered extensive attention for their unique photophysical and catalytic properties, which strongly depend on structural configurations. However, precisely controlling key parameters, such as lateral and rotational displacements, interfacial distance, and stability, remains challenging. Herein, we present a novel strategy for engineering porphyrin dimer structures and properties using multivacant lacunary polyoxometalates (POMs), [SiW<sub>10</sub>O<sub>36</sub>]<sup>8-</sup> or [SiW<sub>9</sub>O<sub>34</sub>]<sup>10-</sup>, as linkers. By adjusting the types and coordination modes of lacunary POMs, three distinct hybrids were obtained <i>via</i> the self-assembly of two 5,10,15,20-tetra(4-pyridyl)porphyrin molecules and four lacunary POM units, each exhibiting modulated stacking geometries, interfacial distances and interactions, and photophysical properties. These hybrids demonstrated efficient visible-light-responsive photosensitized reactions to generate singlet oxygen from ground-state triplet oxygen (<sup>3</sup>O<sub>2</sub>), leading to the photooxidation of various organic substrates. Notably, hybrid II, constructed using [SiW<sub>10</sub>O<sub>36</sub>]<sup>8-</sup>, exhibited the strongest π-π interactions, distinct optical properties, and enhanced resistance to -induced degradation. These findings highlight the potential of POMs as versatile tools for the precise control of porphyrin dimer architectures and the development of materials with tailored photophysical and catalytic functions. Lacunary function ; Porphyrin ; Chemistry ; Photochemistry ; Mathematics ; Pure mathematics Polyoxometalates: Synthesis and Applications ; Porphyrin and Phthalocyanine Chemistry ; Metal-Organic Frameworks: Synthesis and Applications
Authors: Weiyuan Xu | Zheng Cai | Fabio Carniato | Yi Lü | Xinjian Ye | Xinhui Xiao | Jiao Xu | Gengshen Mo | Yinghui Ding | Yong Jian | Xinzhong Ruan | Zhihan Yan | Fangfu Ye | Carlos Platas‐Iglesias | Mauro Botta | Lixiong Dai
Source: Communications Chemistry (article, 2025-07-26)
Field: Materials Science — Materials Chemistry

Design of Mn(1,4-DO2A) derivatives as stable and inert contrast agents for magnetic resonance imaging Manganese(II) is considered a valuable alternative to gadolinium(III) in developing contrast agents (CAs) for magnetic resonance imaging (MRI). However, due to the labile nature of common Mn(II) complexes, designing ligands that enable stable and inert complexation is essential before clinical application. Mn(1,4-Et4DO2A) bearing four ethyl groups, is found to have a log K<sub>MnL</sub> as high as 17.86, together with a pMn of 7.52 at pH 7.4. Kinetically, Mn(1,4-Et4DO2A) is approximately 20 times more inert than Mn(1,4-DO2A) in the presence of a 25-fold excess of Zn(II) at pH 6.0 and 37 °C, with the incorporation of a benzoic group to one pendant arm extending the half-life time (t<sub>1/2</sub>) to around 22 hours. Its r<sub>1</sub> is measured as 2.34 and 2.20 mM<sup>-1</sup> s<sup>-1</sup> at 310 K and 1.5 and 3.0 T, respectively, representing an approximate 50% increase compared to Mn(1,4-DO2A). Mn(1,4-Et4DO2A) shows hepatic preference in mice, and its efficacy in diagnosing orthotopic hepatocellular carcinoma (HCC) is also confirmed. Contrast (vision) ; Magnetic resonance imaging ; Inert ; Nuclear magnetic resonance ; Materials science ; Chemistry ; Medicine ; Radiology ; Physics ; Organic chemistry ; Optics Lanthanide and Transition Metal Complexes ; Medical Imaging Techniques and Applications ; Advanced MRI Techniques and Applications
Authors: Sourav Datta | Nargis Khatun | Pravat Ghorai | Narayan Ch. Jana | Seikh Mafiz Alam | Masoom Raza Siddiqui | Saikh Mohammad Wabaidur | Basudeb Dutta | Priyabrata Banerjee | A. K. M. Maidul Islam | Mohammad Hedayetullah Mir
Source: ChemistrySelect (article, 2025-03-01)
Field: Materials Science — Electronic, Optical and Magnetic Materials

Synthesis and Characterization of a V‐Shaped Heteroleptic Hg(II) Complex with Enhanced Conductivity Abstract In this article, we report the synthesis of the first example of V‐shaped unique structure of complex {[Hg(nvp) 2 (NCS)(Cl)][Hg(nvp) 2 (NCS) 2 ]} ( 1 ; 4‐nvp = 4‐(1‐naphthylvinyl)pyridine and SCN − = thiocyanate) containing two heteroleptic monometallic Hg(II) based units. The complex 1 undergoes a variety of conventional and unconventional supramolecular interactions, such as hydrogen bonding, chalcogen⋯π, halogen⋯π, π⋯π and chalcogen⋯halogen interactions to generate higher dimensional architecture. These supramolecular assemblies, along with the presence of d 10 metal ion Hg(II) promote large charge transportation and make the material to behave as a semiconductor as well as Schottky diode. The complex shows high conductivity (1.73 × 10 −3 S/m), maintaining a 1.54 ideality factor. This allows quick response times with low noise, enhancing signal clarity and efficiency in electronic devices, making it ideal for high‐speed photodetectors. The semiconducting behavior is also realized by density functional theory (DFT) computed band gap study. Characterization (materials science) ; Conductivity ; Materials science ; Chemistry ; Nanotechnology ; Physical chemistry Magnetism in coordination complexes ; Organic and Molecular Conductors Research ; Metal complexes synthesis and properties
Authors: Jessica Zhong | Maxime Boudjelel | Jonathan D. Evans | Ian Vanswearingen | Christian A. Malapit
Source: ChemRxiv (preprint, 2025-01-16)
Field: Chemistry — Organic Chemistry

The radical-radical cross-coupling of alkyl carboxylic acids and organoborons Carbon–carbon bond-forming reactions are fundamental in organic chemistry, constructing molecular backbones. Despite over a century of research on radicals from carboxylic acids and boronic acids, efficient cross-coupling between these species has not been achieved. Here, we revisit radical-radical cross-coupling to enable the first direct coupling of carboxylic and boronic acids to form alkyl-alkyl C–C bonds using abundant precursors. This breakthrough is enabled by integrating redox-matched alternating polarity electrolysis with controlled activation of redox-active species, ensuring high reactivity, selectivity, and broad scope. This radical-radical cross-coupling strategy opens new directions in C–C bond-forming transformations in organic synthesis. Alkyl ; Coupling (piping) ; Chemistry ; Organic chemistry ; Materials science ; Composite material Radical Photochemical Reactions
Authors: Chen‐Yan Cai | Chao Hu | Katherine E. Colbaugh | Rohan R. Merchant | Shuming Chen | Tian Qin
Source: Angewandte Chemie International Edition (article, 2025-11-17)
Field: Chemistry — Organic Chemistry

Direct Access to Acylboranes via Formal Condensation of Carboxylic Acids with Ligated Boranes The unique synthetic potential of acylboron species has long attracted attention from the synthetic chemistry community, but their broader application has been limited by challenges associated with their preparation. In this work, we report a mechanistically distinct radical-based C(acyl)-B cross-coupling strategy that enables a "formal condensation" between readily available carboxylic acids and easily accessible ligated boranes. The success of this transformation relies on the distinctive use of a phosphonite ligand, which achieves an optimal balance between the stability and reactivity of the borane moiety. This method demonstrates a broad substrate scope with high practical utility, and its strategic value has been further highlighted through diverse downstream derivatizations of the resulting acylborane compounds. Boranes ; Scope (computer science) ; Reactivity (psychology) ; Borane ; Amine gas treating ; Substrate (aquarium) ; Condensation Organoboron and organosilicon chemistry ; Radical Photochemical Reactions ; Catalytic C–H Functionalization Methods
Authors: Maialen Alonso | Giovanni Lonardi | Enrique M. Arpa | Baptiste Roure | Alessandro Ruffoni | Daniele Leonori
Source: Nature Communications (article, 2025-08-13)
Field: Chemistry — Organic Chemistry

Photochemical permutation of meta-substituted phenols Phenols and their derivatives are highly relevant motifs in pharmaceuticals, natural products, and other functional materials. Conventional strategies for phenol synthesis rely on classical aromatic functionalization, which is often dictated by electronic and steric factors. Herein, we report an alternative approach for phenol synthesis where irradiation in the presence of Lewis or Brønsted acids enables the selective migration of alkyl and aryl groups from meta to either the ortho or para positions. This method exploits the intrinsic photochemical properties of phenolic arenium ions and their rearrangement via 4π electrocyclization and following "1,2-methylene shift". By leveraging selective photoexcitation of these species, we can achieve precise control over the directionality of the permutation process. Specifically, short-wavelength irradiation (λ = 310 nm) promotes meta→para migration, while longer-wavelength irradiation (λ = 390 nm) meta→ortho. This approach offers a late-stage method to use readily available phenols as templates for the preparation of other isomers without de novo synthesis. The applicability of the method has been demonstrated on the isomerization of poly-substituted derivatives including some bioactive species. Chemistry ; Phenol ; Phenols ; Aryl ; Photochemistry ; Isomerization ; Combinatorial chemistry ; Surface modification ; Alkyl ; Organic chemistry ; Catalysis Radical Photochemical Reactions ; Synthesis of Indole Derivatives ; Catalytic C–H Functionalization Methods
Authors: Mostafa M. Amer | Timothy J. Donohoe
Source: Chemical Communications (review, 2025-01-01)
Field: Chemistry — Organic Chemistry

Recent advances in the use of pentamethylphenyl (Ph*) ketones in organic synthesis Pentamethylphenyl (Ph*) ketones have gained prominence as versatile and valuable motifs in organic synthesis. The presence of the two <i>ortho</i>-methyl groups forces the aromatic ring to adopt a twisted conformation relative to the carbonyl group and gives Ph* ketones a distinctive and unconventional reactivity profile, differentiating them from traditional aromatic ketones. The main goal of this feature article is to demonstrate how the properties of Ph* ketones facilitate innovative chemical transformations. A range of applications are explored, concentrating not only on hydrogen borrowing catalysis, but also including acceptorless dehydrogenation, dynamic kinetic resolution and reduction chemistry, thereby showcasing the exceptional potential that these compounds exhibit. Furthermore, a detailed review of strategies for cleaving the Ph* group into a variety of functional derivatives is presented, highlighting their broad synthetic utility. Organic synthesis ; Chemistry ; Combinatorial chemistry ; Organic chemistry ; Nanotechnology ; Materials science ; Catalysis Synthesis of heterocyclic compounds ; Synthesis and Reactions of Organic Compounds ; Asymmetric Synthesis and Catalysis
Authors: Pradeep Kumar Yadav | Ganesh Jabotra | Sudhanshu Sharma
Source: Hydrogen (article, 2025-07-16)
Field: Materials Science — Materials Chemistry

Effect of Partial Noble Metal (M = Pd, Rh, Ru, Pt) Substitution in La1−xSrxCo1−yMyO3 Perovskite-Derived Catalysts for Dry Reforming of Methane This study examines the surface chemistry of platinum, palladium, rhodium, and ruthenium-substituted lanthanum strontium cobaltate perovskite catalysts in the context of the dry reforming of methane (DRM). The catalysts were synthesized by the solution combustion method and characterized by using a series of techniques. To explore the effect of noble metal ion substitution on the DRM, surface reaction was probed by CH4/CO2 TPSR using mass spectroscopy. It was recognized that La1−xSrxCo1−yPdyO3 show the best activities for the reaction in terms of the temperature but became deactivated over time. CH4/CO2 temperature-programmed surface reactions (TPSRs) were set up to unravel the details of the surface phenomena responsible for the deactivation of the DRM activity on the LSPdCO. The CH4/CO2 TPSR analysis conclusively demonstrated the importance of lattice oxygen in the removal of carbon, which is responsible for the stability of the catalysts on the synthesized perovskites upon noble metal ion substitution. Catalysis ; Noble metal ; Methane ; Perovskite (structure) ; Carbon dioxide reforming ; Substitution (logic) ; Rhodium ; Materials science ; Chemistry ; Inorganic chemistry ; Syngas ; Crystallography ; Organic chemistry Catalytic Processes in Materials Science ; Catalysts for Methane Reforming ; Catalysis and Oxidation Reactions
Authors: Yuping Chen | Guo‐Qing Bian | Zhikun Wu | Qing Tang
Source: Chemical Science (article, 2025-01-01)
Field: Materials Science — Materials Chemistry

Revealing the exchange kinetics of thiol-capped Au<sub>25</sub> nanoclusters with alkynyl ligands Ligand exchange is an important strategy to functionalize metal nanoclusters (NCs) for enhanced properties. Thiolates and alkynyls have been widely used for NC protection; however, the possibility for alkynyl-for-thiolate exchange as well as the kinetics for the ligand exchange process have remained largely unexplored. Herein, we have reported for the first time a kinetic investigation into the alkynyl-for-thiolate exchange through the reaction of thiolated Au<sub>25</sub>(SR)<sub>18</sub> with the incoming alkynyl ligands. Interestingly, our simulations revealed the electronic and steric effects of alkynyl ligands and the precursor cluster's charge state collectively govern the exchange efficiency and regioselectivity. Notably, the alkynyl-for-thiolate exchange is highly facile when reacting with the nucleophilic lithium or gold(i)-alkynyl complex (Au(C[triple bond, length as m-dash]CR) or Li(C[triple bond, length as m-dash]CR)), but fails when using HC[triple bond, length as m-dash]CR as the exchange ligand. The Au(C[triple bond, length as m-dash]CPh) complex exhibits charge-state-dependent exchange at the S<sub>1</sub> or S<sub>2</sub> position, whereas the sterically bulky Au(C[triple bond, length as m-dash]C <sup><i>t</i></sup> Bu) complex decelerates the exchange kinetics and universally targets the S<sub>1</sub> position as the exchange product. By contrast, the lithium-alkynyl complex (Li(C[triple bond, length as m-dash]CPh) or Li(C[triple bond, length as m-dash]C <sup><i>t</i></sup> Bu)) preferentially leads to the exchange isomer, driven by the ionic Li-C bonding that enhances the C[triple bond, length as m-dash]C π*-electron density and alkynyl nucleophilicity. Our predictions are further validated by the ligand exchange experiments between phenyl ethanethiol (PET) protected [Au<sub>25</sub>(PET)<sub>18</sub>]<sup>-</sup> and Au(C[triple bond, length as m-dash]C <sup><i>t</i></sup> Bu). The electrospray ionization mass spectra (ESI-MS) unambiguously confirm the successful substitution of 4, 5 and 6 PET ligands by the -C[triple bond, length as m-dash]C <sup><i>t</i></sup> Bu ligand, and the absorption spectrum drastically changes upon alkynyl exchange. This work establishes an important atomic-level understanding of the alkynyl-for-thiolate exchange mechanism, offering a convenient strategy for realizing alkynyl and thiolate co-protected gold clusters under mild conditions. Nanoclusters ; Steric effects ; Ligand (biochemistry) ; Kinetics ; Ion exchange ; Ionic bonding ; Electrospray ionization Nanocluster Synthesis and Applications ; Nanomaterials for catalytic reactions ; Gold and Silver Nanoparticles Synthesis and Applications
Authors: Jędrzej P. Perdek | Rafał A. Grzelczak | Bartosz Szyszko
Source: ChemPlusChem (review, 2025-01-27)
Field: Chemistry — Organic Chemistry

Open Rotaxane Surgery: What Molecular Editing Can Offer to Supramolecular Chemistry? The skeletal editing approach represents a paradigm shift in organic synthesis by directly targeting the molecular skeleton instead of relying on often long and complicated series of organic transformations. Recent advancements in nitrogen atom deletion reactions have enabled unprecedented late-stage, precise modifications of bioactive compounds and complex natural products, influencing a seemingly distant field such as supramolecular chemistry. In a recent contribution, the Leigh group demonstrated the extrusion of a nitrogen atom from an axle of a [2]rotaxane, extending the applicability of molecular editing to complex, mechanically interlocked architectures. This highlight seeks to examine the significance of the skeletal editing method in supramolecular chemistry, address its challenges, and offer an outlook on future directions in this emerging field. Supramolecular chemistry ; Rotaxane ; Nitrogen atom ; Chemistry ; Nanotechnology ; Molecular machine ; Combinatorial chemistry ; Molecule ; Materials science ; Group (periodic table) ; Organic chemistry Supramolecular Chemistry and Complexes ; Advanced biosensing and bioanalysis techniques ; Porphyrin and Phthalocyanine Chemistry