jablonkagroup/rise_ai_scientists huggingface dataset:
Authors: Oscar F. Odio | Giuseppina Tommasini | Francisco J. Terán | Jesús G. Ovejero | J. Rubín | María Moros | Susel Del Sol‐Fernández
Source: Nanoscale Horizons (article, 2025-01-01)
Field: Materials Science — Materials Chemistry

Unraveling the Mn<sup>2+</sup> substitution effect on the anisotropy control and magnetic hyperthermia of Mn<sub><i>x</i></sub>Fe<sub>3−<i>x</i></sub>O<sub>4</sub> nanoparticles Composition is a key parameter to effectively tune the magnetic anisotropy of magnetic nanoparticles, which in turn can modulate their structural-magnetic properties and final applications. The Mn<sup>2+</sup> content of manganese ferrite nanoparticles (Mn<sub><i>x</i></sub>Fe<sub>3-<i>x</i></sub>O<sub>4</sub>) deeply impacts their structure, anisotropy, magnetism, and their heating capacity. However, a direct correlation between Mn<sup>2+</sup> content, magnetic properties and heating efficiency is not yet clear. Herein, we report the synthesis of a wide range of Mn<sub><i>x</i></sub>Fe<sub>3-<i>x</i></sub>O<sub>4</sub> with <i>x</i> = 0.14 to 1.40, with similar polyhedral morphologies and sizes (13 to 15 nm). By varying the Mn<sup>2+</sup> content (in the range of <i>x</i> = 0.0 up to 0.70), we successfully tuned the effective anisotropy while maintaining saturation magnetization nearly constant. Highest Mn<sup>2+</sup> levels (<i>x</i> = 1.40) lead to structural changes and strain defects reflected in their poor saturation magnetization. Mn<sup>2+</sup> substitution is not uniform, instead promotes a compositional gradient across the MNPs, with the surface layers having a higher concentration of Mn<sup>2+</sup> than the core. The Mn<sup>2+</sup>-rich surface likely exhibits superparamagnetic (SPM) relaxation, while the core remains predominantly ferrimagnetic (FiM). Water transference results in cation leaching, promoting vacancies and changes in the local ferrite structure but with a minor impact on the magnetic properties compared with initial MNPs. We obtained the optimal Mn<sup>2+</sup> content that maximizes anisotropy toward improved specific loss power (SLP) values. The Néel relaxation mechanism is warranted regarding variable composition when sizes and shapes are maintained. Our detailed analysis provides a better understanding of the effect of Mn<sup>2+</sup> substitution on the heating efficiency through anisotropy modulation and straightforward guidance on optimizing MNP design for magnetic hyperthermia. Substitution (logic) ; Anisotropy ; Magnetic anisotropy ; Nanoparticle ; Materials science ; Condensed matter physics ; Nuclear magnetic resonance ; Physics ; Crystallography ; Chemistry ; Nanotechnology ; Magnetization ; Magnetic field ; Computer science ; Optics ; Quantum mechanics Magnetic Properties and Synthesis of Ferrites ; Characterization and Applications of Magnetic Nanoparticles ; Iron oxide chemistry and applications
Authors: Feng Zhang | Lingyan Liu | Yifeng Yin | Weixing Chang | Jing Li
Source: Chemistry - A European Journal (article, 2025-04-16)
Field: Chemistry — Organic Chemistry

Practical Electrochemical Hydroxynitration and Chloronitration Bifunctionalization of Alkenes with NaNO<sub>2</sub> We herein developed a novel method for generating nitryl free radicals using sodium nitrite for the first time under electrocatalytic conditions. A series of vicinal hydroxynitro or chloronitro compounds was generated in good yields. This methodology features a simple reaction setup, mild reaction conditions, and cheap electrodes and shows excellent functional group tolerance and broad substrate scope, enabling efficient gram-scale reactions with good to excellent yields. Besides, the electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) results provided deeper insights into the reaction mechanism. Further extensions of the method have also confirmed the practicality of the strategy developed. Electrochemistry ; Chemistry ; Electrode ; Physical chemistry Chemical Synthesis and Reactions ; Radical Photochemical Reactions ; Synthesis and Catalytic Reactions
Authors: Satyajit Patra | S.C. Dhiman | Subi J. George
Source: Angewandte Chemie International Edition (article, 2025-04-07)
Field: Materials Science — Biomaterials

Redox‐Controlled, Sequential Self‐Sorting of Supramolecular Assemblies in Model Protocells Self-sorting of cellular components is essential for maintaining order and function in living systems, enabling complex processes to operate seamlessly. Emulating such self-sorting in synthetic self-assembly, however, has conventionally relied on structural or chirality mismatches of monomers yielding self-sorted systems under thermodynamic conditions. In contrast, reaction-coupled, kinetically controlled self-assembly, ubiquitous in biological systems, is critical for achieving spatiotemporal characteristics. Extending this principle to temporally self-sorted synthetic assemblies is key to developing multi-component biomimetic systems. Herein, we present a strategy towards this direction, to achieve sequential self-sorting of supramolecular assemblies through differences in the chemical-reactivity of monomers, coupled to redox-reactions. This approach exploits the distinct redox potentials of monomers to achieve precise temporal-control over self-sorting, while inherent structural mismatches among monomers ensure the kinetic stability of self-sorted state. Reduction reactions transiently disrupt their assemblies into dormant inactive monomeric states, while subsequent kinetically controlled reassembly occurs via reversible oxidation reactions. Finally, utilizing this sequential self-sorting, we aim to mimic multicomponent cellular self-organization by demonstrating the kinetically controlled growth of self-sorted structures in the presence of model protocells, using lipid vesicles as compartments. Although spatial-distribution remains non-selective, the dormant monomeric states facilitate monomer encapsulation and the unprecedented stepwise-formation of self-sorted assemblies within model protocells. Protocell ; Supramolecular chemistry ; Self-assembly ; Monomer ; Redox ; Biological system ; Nanotechnology ; Chemistry ; Vesicle ; Biophysics ; Materials science ; Molecule ; Membrane ; Biology ; Polymer Supramolecular Self-Assembly in Materials ; Photoreceptor and optogenetics research ; Polydiacetylene-based materials and applications
Authors: Moushakhi Ghosh | Kumar Gaurav | Prakash Panwaria | Rishukumar Panday | Srinu Tothadi | Shabana Khan
Source: Chemical Science (article, 2025-01-01)
Field: Chemistry — Organic Chemistry

Driving diverse bond functionalisation with <i>N</i> -heterocyclic silylene-coinage metal–aryl complexes Anchoring homolytic and heterolytic bond functionalisation at low-coordinate coinage metal centres is important due to their potential use as active catalysts in organic transformations. In the realm of carbene-stabilised coinage metal chemistry, heteroatom functionalised coinage metal precursors synthesised from such bond activations have long been explored. Interestingly, <i>N</i>-heterocyclic silylene, being an equally potent neutral donor ligand, has not been used for the same. Of note, carbene-stabilised heteroatom functionalised coinage metal precursors are vastly developed with copper centres only, while silver has been underexplored. This work reports the isolation of a variety of [PhC{N( <sup><i>t</i></sup> Bu)}<sub>2</sub>SiN(SiMe<sub>3</sub>)<sub>2</sub>] (1) coordinated aryl-copper(i) and aryl-silver(i) complexes (2-8). We have also examined the reactivity pattern of organo-copper with differently substituted silylenes (9-11). These complexes were then utilised to cleave various homolytic and heterolytic bonds to access silylene-coordinated heteroatom functionalised coinage metal complexes (12-24). We have shown the reaction of reactive aryl-coinage metal precursors towards homolytic bonds, having B-B and Se-Se bonds, which led to the formation of an NHSi-supported dimeric μ-boryl bound Cu(i) complex (12) and a new class of unprecedented NHSi-supported coinage metal-selenogenolates (14-16). These aryl-coinage metal precursors also smoothly afforded several elusive NHSi-copper and silver amides (17-22) <i>via</i> N-H bond cleavage. A heterolytic cleavage of the P-Si bond resulted in the formation of NHSi stabilised copper and silver phosphide complexes (23 and 24), among which the latter is the first precedent of the dimeric Ag-phosphide complex. Lastly, we have utilised NHSi → copper-aryl complexes as aryl transfer reagents in C-C coupling reactions, which led to the formation of products in excellent yields with a high TON. The analogous silver complex was employed in the three-component α-aminonitrile synthesis efficiently. Our report establishes NHSi coordinated aryl copper and silver complexes as a perfect and robust platform for accessing a diverse array of reactive coinage metal precursors that were hitherto unknown. Aryl ; Silylene ; Metal ; Chemistry ; Bond ; Combinatorial chemistry ; Medicinal chemistry ; Organic chemistry ; Business ; Silicon Catalytic Cross-Coupling Reactions ; Coordination Chemistry and Organometallics ; Organoboron and organosilicon chemistry
Authors: Bonan Zhao | Jinjia Wei | Rüdiger Berger | Lin Jian | Kaloian Koynov | Heyang Zhang | Matthias Barz
Source: Macromolecular Bioscience (article, 2025-04-22)
Field: Materials Science — Biomaterials

Polypept(o)ide‐Based Core–Shell Bottlebrush Polymers: A Versatile Platform for Drug Encapsulation Cylindrical bottlebrush polymers (CBPs) enable the precise adjustment of nanoparticle properties such as size, shape, and functionality exclusively by polymer synthesis. In addition, block copolymer side chains enable direct access to core-shell structure. In this study, the synthesis of polypept(o)ides-based core-shell CBPs is presented through a "grafting-from" strategy. While, poly-lysine (pLys) serves as the backbone, poly(γ-benzyl-l-glutamic acid)-block-polysarcosine (pGlu(OBn)-b-pSar) copolymers form the side chains. This approach enables the synthesis of core-shell nanoparticles, referred as core-shell brushes (CSBs), with hydrodynamic radius (R<sub>h</sub>) from 17 to 70 nm, and molecular weights (1320-4000 kg mol<sup>-1</sup>) with dispersity indices ≈1.3 as determined by size-exclusion chromatography. Dasatinib is chosen as a drug molecule model to explore the potential of such synthetical CSBs as a platform for drug encapsulation by π-π-interactions. An overall loading efficiency of 10% is achieved, which also displayed sustained release within 72 h, cellular uptake into human glioblastoma (U-87 MG) cells, and drug-related therapeutic efficacy. While drug release can be further optimized by covalent drug attachment, these results establish a strong foundation for the use of CSBs in nanomedicine. Copolymer ; Dispersity ; Nanoparticle ; Polymer ; Chemistry ; Drug delivery ; Nanomedicine ; Polymer chemistry ; Covalent bond ; Side chain ; Nanotechnology ; Materials science ; Chemical engineering ; Organic chemistry Nanoparticle-Based Drug Delivery ; Advanced Polymer Synthesis and Characterization ; RNA Interference and Gene Delivery
Authors: Muhammad Khalid | Fatima Tayyab | Muhammad Adeel | Nayab Tahir | Ataualpa Albert Carmo Braga | Khalid Abdullah Alrashidi
Source: Scientific Reports (article, 2025-04-28)
Field: Materials Science — Electronic, Optical and Magnetic Materials

Exploration of selenophene analogue and different acceptor influence on photovoltaic properties of pyrrole-4,6(5-H)-dione based chromophores via quantum chemical investigations Non-fullerene organic compounds are considered efficient photovoltaic materials in the development of solar cells. Therefore, considering the importance of non-fullerene organic compounds, a series of non-fullerene organic chromophores (SPF1-SPF6) was designed via molecular engineering at terminal acceptors of reference compound (SPFR). Further, owing to the interesting features of selenium than sulphur towards charge transfer, thiophene was replaced with selenophene in designed derivatives and analyzed using quantum chemical approach. Through benchmark study, CAM-B3LYP/6-311G(d, p) functional was selected for the current study. Several parameters, such as frontier molecular orbitals, density of states, binding energy, transition density matrix, optical properties, reorganization energies of electron and hole, open circuit voltage, and charge transfer analyses were assessed to comprehend the photovoltaic properties of designed compounds. A energy gap: 4.433-4.764 eV with absorption spectra as 465.1-512.7 nm in chloroform and 445.4-494.0 nm in the gas phase and greater charge transference rate was studied in selenophene derivatives. The lower E<sub>b</sub> and the behavior of holes and electrons implied a higher rate of exciton separation and considerable transfer of charges towards LUMO from the HOMO. The results of DOS and TDM analysis further corroborated these findings. Furthermore, the V<sub>oc</sub>, in relation to the HOMO<sub>PTB7</sub>-LUMO<sub>Acceptor</sub>, depicted that the proposed molecules have good V<sub>oc</sub> values. Furthermore, a comparative study with spiro-OMeTAD, a standard hole transport material (HTM) demonstrated a good correlation, indicating that the proposed compounds have the potential to function as efficient HTMs. Therefore, it can be deduced that the use of molecular engineering with various acceptor molecules has the potential to enhance the effectiveness of photovoltaic materials. Chromophore ; Pyrrole ; Quantum chemical ; Acceptor ; Photovoltaic system ; Quantum ; Chemistry ; Materials science ; Computer science ; Combinatorial chemistry ; Photochemistry ; Molecule ; Organic chemistry ; Physics ; Quantum mechanics ; Engineering ; Electrical engineering Nonlinear Optical Materials Research ; Photochemistry and Electron Transfer Studies ; Organic Electronics and Photovoltaics
Authors: Yao Ma | Dongxu Li | Xin Chen | Xinqiang Hua | Chengshan Yuan | Jianguo Wang | Zitong Liu | Hao‐Li Zhang | Xiangfeng Shao
Source: Chemical Science (article, 2025-01-01)
Field: Materials Science — Materials Chemistry

Valence state engineering in multi-heteroatom-doped PAHs: a strategy for tunable photophysical properties and phototheranostic potentials Precise modulation of the electronic structures in heteroatom-doped polycyclic aromatic hydrocarbons (hetero-PAHs) is essential for advancing organic optoelectronic materials. Herein, we report a facile synthetic strategy for hetero-PAHs co-doped with N, O, and S/Se, achieved <i>via</i> acid-catalyzed Pictet-Spengler reactions and thermally induced <i>ipso</i>-substitution. Systematic π-extension results in a large redshift in optical absorption/emission and enhances fluorescence quantum yield (<i>Φ</i> <sub>F</sub>) from 4.0% to 30.5%. Furthermore, a post-synthetic valence state engineering approach enables precise tuning of photophysical properties: (i) oxidation of thiophene units to thiophene <i>S</i>,<i>S</i>-dioxides increases <i>Φ</i> <sub>F</sub> to 42.3% and enhances singlet oxygen generation, and (ii) pyridinium-functionalized hetero-PAHs exhibit strong near-infrared absorption, leading to high photothermal conversion efficiency (up to 61%) at the molecular level. Notably, Se-doped derivatives outperform their S-doped counterparts, underscoring the heavy-atom effect in triplet-state modulation. This work provides a versatile platform for tailoring hetero-PAH electronic structures <i>via</i> valence state manipulation, offering potential applications for organic electronics and phototheranostics. Heteroatom ; Valence (chemistry) ; Photochemistry ; Thiophene ; Doping ; Molecular engineering ; Materials science ; Organic electronics ; Quantum yield ; Chemistry ; Fluorescence ; Nanotechnology ; Optoelectronics ; Organic chemistry Luminescence and Fluorescent Materials ; Covalent Organic Framework Applications ; Metal-Organic Frameworks: Synthesis and Applications
Authors: Saeid Mehvari | Gražyna Simha Martynková | Gabriela Kratošová | Jana Kupková | S. González | Yolanda Sánchez‐Vicente | Khalid Lafdi
Source: Polymer Composites (article, 2025-06-04)
Field: Materials Science — Materials Chemistry

Electrical Behavior of Green‐Synthesized Nano Silver Particles Embedded in Polyurethane: Numerical and Experimental Studies ABSTRACT This study explores the electrical properties of a nanocomposite composed of green‐synthesized silver nanoparticles (AgNPs) embedded in a polyurethane (PU) matrix, employing both experimental and numerical methods. The AgNPs were synthesized using an eco‐friendly approach, utilizing non‐toxic phytochemicals derived from Urtica dioica (stinging nettle) as reducing and stabilizing agents. These nanoparticles were then integrated into PU matrices, and their dispersion, structural integrity, and electrical characteristics were thoroughly analyzed. To predict the composite's electrical behavior, finite element method (FEM) simulations were performed using Digimat software, based on a representative volume element (RVE) model. The results revealed that electrical conductivity increases with higher concentrations of AgNPs and applied pressure, reaching a maximum conductivity of 1.4 S/m at 43.3 wt.% AgNPs filler under 20 kPa pressure. Additionally, the study demonstrated that introducing a washing step prior to combining AgNPs with PU reduces the concentration of phyto‐stabilizers, enhancing nanoparticle dispersion, composite quality, and overall electrical conductivity. This research highlights the potential of green‐synthesized nanocomposites for advanced electrical applications. Materials science ; Composite material ; Polyurethane ; Nano- ; Silver Nano Nanoparticles: synthesis and applications ; Polymer Nanocomposite Synthesis and Irradiation ; Conducting polymers and applications
Authors: Susital Mal | Chris H. J. Franco | B. Anantha Kumar | Alexander M. Kirillov | Subrata Das
Source: CrystEngComm (article, 2025-01-01)
Field: Chemistry — Physical and Theoretical Chemistry

Exploring uracil derivatives: synthesis, crystal structure insights, and antibacterial activity Four uracil derivatives were synthesized and analyzed to reveal how molecular modifications influence crystal packing, stability, and antibacterial properties. Uracil ; Crystal structure ; Antibacterial activity ; Chemistry ; Combinatorial chemistry ; Stereochemistry ; Crystallography ; Biochemistry ; Biology ; Bacteria ; DNA ; Genetics Crystallography and molecular interactions ; Enzyme Structure and Function ; Protein Structure and Dynamics
Authors: Sarah Spreckelmeyer | Sophie R. Thomas | Franziska Schuderer | Catarina I. G. Pinto | Ana Luiza de Andrade Querino | Fritz Böhm | Mihyun Park | Christopher Geppert | C. Gorges | Filipa Mendes | Angela Casini
Source: Journal of Medicinal Chemistry (article, 2025-08-13)
Field: Chemistry — Organic Chemistry

N-Heterocyclic Carbenes as Ligands to <sup>198</sup> Au(I)-Radiolabeled Compounds: A New Platform for Radiopharmaceutical Design The radionuclide <sup>198</sup>Au, with a half-life of 2.7 days, emits γ radiation ideal for diagnostic purposes and generates β<sup>-</sup> particles suitable for effective cancer radiotherapy, making it a perfect nuclide for "theranostics". However, the application of coordination compounds of Au(I)/Au(III) in medicine is limited by their instability in vivo. Here, we explore N-heterocyclic carbene (NHC) organometallic chemistry to stabilize <sup>198</sup>Au(I) in radiopharmaceuticals. Thus, Au(I) NHC compounds featuring different scaffolds were selected for <sup>198</sup>Au radiolabeling. Eventually, two compounds featuring imidazole (<b>AuNHC-1</b>) and theophylline (<b>AuTMX</b><sub><b>2</b></sub>) scaffolds were successfully radiolabeled (radiochemical purity = 92.9% and 40.2%, respectively). Instead, two peptidic Au(I) benzimidazolylidene derivatives, capable of blood-brain barrier translocation in vitro, were subjected to ligand exchange reactions under the applied radiolabeling conditions. The obtained proof-of-concept results showed that NHCs are suitable ligands to achieve isotope exchange in Au(I) complexes. Overall, our work reveals the still untapped potential of organometallic chemistry in radiopharmaceutical design. Chemistry ; Combinatorial chemistry ; Stereochemistry ; Radiochemistry N-Heterocyclic Carbenes in Organic and Inorganic Chemistry ; Asymmetric Hydrogenation and Catalysis ; Catalytic Cross-Coupling Reactions
Authors: Kazuhiro Okamoto | Simon L. Homölle | Tristan von Münchow | Sven Erik Peters | Sven Trienes | João C. A. Oliveira | Lutz Ackermann
Source: Angewandte Chemie International Edition (article, 2025-09-04)
Field: Chemistry — Organic Chemistry

Nickelaelectro‐Catalyzed C─H Activation to <i>β</i>‐Arylated Pyrroles <i>via</i> Multiple Dehydrogenation Nickel electrocatalysis has emerged as a powerful strategy for sustainable C─H activation, offering an environmentally benign alternative to traditional methods based on stoichiometric oxidants. We, herein, report a nickela-electrocatalyzed approach for the expedient synthesis of β-arylated pyrroles via a unique multiple dehydrogenative C─H activation approach. Hence, direct C─C bond formation between pyrroles and arenes was enabled, obviating the need for prefunctionalized substrates. The reaction proceeded under electrochemical conditions in a user-friendly undivided cell, utilizing electricity as a traceless oxidant. Mechanistic studies, including cyclic voltammetry, provided support for a nickel(II/III/IV) regime, wherein anodic oxidation facilitates the dehydrogenation and C─H activation paired with the valuable hydrogen evolution reaction (HER). Our findings highlight the potential of electrocatalysis to unlock distinct reaction manifolds and provides a sustainable platform for accessing complex heteroaryl frameworks. Dehydrogenation ; Electrocatalyst ; Chemistry ; Catalysis ; Cyclic voltammetry ; Combinatorial chemistry ; Electrochemistry ; Nickel ; Hydrogenase ; Anode ; Stoichiometry ; Organic chemistry ; Electrode ; Physical chemistry Radical Photochemical Reactions ; Catalytic C–H Functionalization Methods ; Sulfur-Based Synthesis Techniques
Authors: Chao Yang | W MA | Jie Zhang | Wenbo Wei | Zhuoran Kuang | Hongping Zhou | Qi‐Long Zhu
Source: Advanced Functional Materials (article, 2025-11-22)
Field: Materials Science — Materials Chemistry

Conformation‐Induced Dipole Polarization Engineering in Hierarchical Vinylene‐Linked Covalent Organic Frameworks for Enhanced Photocatalytic H <sub>2</sub> O <sub>2</sub> Production Abstract Hierarchical vinylene‐linked covalent organic frameworks (COFs) are gaining recognition as highly promising materials for various applications, owing to their exceptional stability, efficient electronic transfer capability and intrinsic hierarchical porosity. However, designing and constructing hierarchical vinylene‐linked COFs with adaptable electronic structures remains a nascent and challenging field. Herein, two hierarchical vinylene‐linked COFs ( SM‐PT and AM‐PT ) with symmetrical and asymmetrical conformations, respectively, were successfully constructed from two innovative pyrimidine‐based monomers through an asymmetric conformation strategy. Specially, the conformation modulation allows directional control over the local electronic structures of thes COFs. As a result, AM‐PT with an asymmetric conformation demonstrates improved dipole polarization, greatly facilitating the exciton dissociation and charge transfer, which leads to remarkable efficiency in the photocatalytic H 2 O 2 production, exceedingly outperforming its symmetric counterpart SM‐PT . Consequently, AM‐PT achieved remarkable photocatalytic H 2 O 2 production rates of 5936 µmol g −1 h−1 in pure water and 11427 µmol g −1 h −1 with benzyl alcohol as a hole sacrificial agent. Remarkably, AM‐PT achieves high H 2 O 2 concentrations and robust photocatalytic degradation activity toward environmental pollutants in a continuous‐flow system, underscoring its considerable promise for future industrial applications. Photocatalysis ; Dipole ; Covalent bond ; Electronic structure ; Exciton ; Monomer Covalent Organic Framework Applications ; Advanced Photocatalysis Techniques ; Solar-Powered Water Purification Methods