jablonkagroup/rise_ai_scientists huggingface dataset:
Authors: Ramagonolla Kranthikumar | Yoshito Kishi
Source: Organic Letters (article, 2024-08-19)
Field: Chemistry — Organic Chemistry

Application of Ni/Zr-Mediated Ketone Coupling for the Scalable Synthesis of Homohalichondrin B A practical and improved synthetic route for the scalable synthesis of homohalichondrin B has been developed. Formation of the highly stereoselective [6,6]-spiroskeleton system through a convergent Ni/Zr-mediated ketone coupling, followed by acid-promoted spiroketalization, simplified the route considerably. Higher coupling efficiency was achieved by fine-tuning the Ni<sup>I</sup>/Ni<sup>II</sup> (1:50) catalyst loadings with an equimolar (1:1) mixture of coupling partners. Chemistry ; Coupling (piping) ; Ketone ; Scalability ; Stereoselectivity ; Catalysis ; Combinatorial chemistry ; Organic chemistry ; Metallurgy ; Materials science ; Computer science ; Database Synthetic Organic Chemistry Methods ; Microbial Natural Products and Biosynthesis ; Marine Sponges and Natural Products
Authors: Ning Li | Shanshan Xiao | Xiaoxiong Jin | Ziyuan Song
Source: Chinese Journal of Chemistry (article, 2024-02-06)
Field: Materials Science — Biomaterials

Reduced Macrophage Uptake of Nanoparticles through Surface Modification of Polypeptides with Valine Residues<sup>†</sup> Comprehensive Summary The structural and surface properties of nanomedicines play an important role in determining their biological fate. Surface chemistry of nanomedicines is one of the key parameters, where researchers used various strategies such as PEGylation to avoid the undesired clearance of nanoparticles (NPs) for enhanced targeting effect. Nevertheless, the fine‐tuning of surface chemistry through polymer functionalization remains largely unexplored. In this concise report, we find that the incorporation of only 10 mol% valine residues into the surface‐anchored poly( L ‐glutamic acid) significantly lowered the macrophage uptake of NPs. The introduction of other hydrophobic amino acid residues, however, increased the NPs internalization instead. The chirality and the side‐chain structure of valine played an important role in the unexpected uptake behavior. We believe this work highlights the impact of slight changes of the surface‐anchored polymer structure on the behavior of NPs, drawing people's attention to the careful design of surface chemistry to optimize the nanomedicine design. Chemistry ; Nanomedicine ; Internalization ; Surface modification ; Nanoparticle ; Valine ; Chirality (physics) ; PEGylation ; Polymer ; Nanotechnology ; Biophysics ; Amino acid ; Combinatorial chemistry ; Organic chemistry ; Biochemistry ; Cell Nanoparticle-Based Drug Delivery ; Polymer Surface Interaction Studies ; Dendrimers and Hyperbranched Polymers
Authors: Emma J. Jordan | Ethan Calder | Bethan L. Greene | Holly V. Adcock | Louise Male | Paul Davies | Andrew R. Jupp
Source: ChemRxiv (preprint, 2024-07-08)
Field: Chemistry — Inorganic Chemistry

Tuning the Electronic Properties of Azophosphines as Ligands and their Application in Base-Free Transfer Hydrogenation Catalysis The design and tuning of new ligands is crucial for unlocking new reactivity at transition metal centres. Azophosphines have recently emerged as a new class of 1,3-P,N ligands in ruthenium piano-stool complexes. This work shows that the azophosphine synthesis can tolerate N-aryl substituents with strongly electron-donating and electron-withdrawing para-R groups, and that the nature of this R group can affect the spectroscopic and structural properties of the azophosphines, as measured by NMR spectroscopy, UV-Vis spectroscopy, single crystal X-ray diffraction and DFT studies. Azophosphines are shown to be relatively weak phosphine donors, as shown by analysis of the 1JP–Se coupling constants of the corresponding azophosphine selenides, but the donor properties can be fine-tuned within this area of chemical space. Monodentate and bidentate Ru-azophosphine complexes were prepared, and their first use as catalysts was probed. The Ru-azophosphine complexes were found to promote the transfer hydrogenation of acetophenone to 1-phenylethanol without the requirement of a harsh base additive, and the bidentate complex was more active than the monodentate analogue. Catalysis ; Base (topology) ; Transfer hydrogenation ; Transfer (computing) ; Chemistry ; Combinatorial chemistry ; Organic chemistry ; Computer science ; Parallel computing ; Mathematics ; Ruthenium Asymmetric Hydrogenation and Catalysis ; Chemical Synthesis and Reactions ; Organophosphorus compounds synthesis
Authors: Isis Janilkarn-Urena | Andy K.-S. Tse | Jieye Lin | Bliss Tafolla-Aguirre | Alina Idrissova | Mindy Zhang | Samantha G. Skinner | Nader Mostowfi | Jinah Kim | Nikhila Kalapatapu | Xinmin Chang | Christina Efthymiou | Christopher Kwesi O. Williams | Shino Magaki | Harry V. Vinters | Tamir Gonen | S. Kaleem Ahmed | Hovhannes J. Gukasyan | Daryl L. Davies | Paul M. Seidler
Source: PNAS Nexus (article, 2024-12-23)
Field: Materials Science — Materials Chemistry

Improving the solubility of pseudo-hydrophobic chemicals through co-crystal formulation Natural products are ligands and in vitro inhibitors of Alzheimer's disease (AD) tau. Dihydromyricetin (DHM) bears chemical similarity to known natural product tau inhibitors. Despite having signature polyphenolic character, DHM is ostensibly hydrophobic owing to intermolecular hydrogen bonds that shield hydrophilic phenols. Our research shows DHM becomes ionized at near-neutral pH, allowing the formulation of salts with transformed solubility. The MicroED co-crystal structure with trolamine reveals DHM salts as metastable co-crystalline solids with unlocked hydrogen bonding and a thermodynamic bent to solubilize in water. All co-crystal formulations show better inhibitory activity against AD tau than the nonsalt form, with efficacies correlating to enhanced solubilities. In vitro and in vivo pharmacokinetic measures demonstrate that DHM co-crystals display enhanced absorption and distribution with altered rates of elimination, suggesting that co-crystal formulations could be strategically used to fine-tune delivery properties. These results underscore the role of structural chemistry in guiding the selection of solubilizing agents for chemical formulation. We propose DHM co-crystals are appropriate formulations for research as dietary supplements to promote healthy aging by combating protein misfolding, although central nervous system (CNS) delivery remains a major limitation. DHM may be a suitable backbone for medicinal chemistry and possible development of pharmaceuticals with enhanced CNS exposure. Solubility ; Chemical engineering ; Chemistry ; Materials science ; Organic chemistry ; Engineering Crystallization and Solubility Studies ; Crystallography and molecular interactions ; Polymer Synthesis and Characterization
Authors: Keren Iudanov | Noy B. Nechmad | Albert Poater | N. Gabriel Lemcoff
Source: Angewandte Chemie (article, 2024-09-21)
Field: Chemistry — Organic Chemistry

Selective Cross‐Metathesis Versus Ring‐Closing Metathesis of Terpenes, Taking the Path Less Travelled Abstract A diiodo ruthenium olefin metathesis pre‐catalyst was employed to achieve remarkably selective cross‐metathesis reactions of prenylated 1,6‐dienes, effectively overcoming the entropically favored intramolecular ring‐closing metathesis. This reaction was investigated using Density Functional Theory (DFT) computations and fine‐tuned through the application of a Design of Experiments (DoE) approach. The potential of this innovative process was demonstrated through the unprecedented functionalization of various terpene natural products via cross‐metathesis, resulting in the synthesis of new derivatives in a single step. Ring-closing metathesis ; Closing (real estate) ; Metathesis ; Path (computing) ; Salt metathesis reaction ; Chemistry ; Organic chemistry ; Computer science ; Political science ; Operating system Synthetic Organic Chemistry Methods
Authors: Kui He | Yuan‐Fu Ding | Zhipeng Zhao | Ben Liu | Wenyan Nie | Xiaoxi Luo | Hua‐Zhong Yu | Jinbin Liu | Ruibing Wang
Source: Advanced Functional Materials (article, 2024-02-01)
Field: Materials Science — Materials Chemistry

Cucurbit[7]uril‐Mediated Organ‐Specific Delivery of Ultrasmall NIR‐II Luminescent Gold Nanocarriers for Therapy of Acute Kidney Injury (Adv. Funct. Mater. 6/2024) Kidney-Specific Delivery In article number 2309949, Jinbin Liu, Ruibing Wang, and co-workers develop a series of ultrasmall NIR-II emitting gold nanocarriers, allowing for fine-tuning liver or kidney-specific delivery via altering the surface chemistry using cucurbit[7]uril and Cys-Arg-Gly-Asp peptide. Accordingly, the selected ultrasmall nanocarriers could facilitate kidney-targeted delivery in acute kidney injury mice, which significantly boosts drug accumulation at the site of injured kidneys, thereby achieving improved therapeutic results. Materials science ; Nanocarriers ; Nanotechnology ; Luminescence ; Acute kidney injury ; Drug delivery ; Medicine ; Optoelectronics ; Internal medicine Nanocluster Synthesis and Applications ; Luminescence and Fluorescent Materials ; Nanoplatforms for cancer theranostics
Authors: Nirob K. Saha | William S. Salvia | Dominik Konkolewicz | C. Scott Hartley
Source: ChemRxiv (preprint, 2024-03-07)
Field: Chemistry — Organic Chemistry

Transient polymers through carbodiimide-driven assembly Biochemical systems make use of out-of-equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular polymers driven by chemical fuel reactions have been reported. Conversely, polymers based on transient covalent bonds have received little attention, even though they have the potential to complement supramolecular systems by generating transient structures based on stronger bonds and by offering a straightforward tuning of reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with the carbodiimide EDC. Transient covalent polymers with molecular weights exceeding 15,000 are generated which then decompose over the course of days. Disassembly kinetics can be controlled using simple substituent effects in the monomer design. The impact of solvent polarity, carbodiimide concentration, and monomer concentration on polymer properties and lifetimes has been investigated. The results reveal substantial control over polymer assembly and disassembly kinetics, highlighting the potential for fine-tuned kinetic control in nonequilibrium polymerization systems. Carbodiimide ; Transient (computer programming) ; Polymer ; Materials science ; Computer science ; Polymer chemistry ; Composite material Advanced Polymer Synthesis and Characterization
Authors: Pablo Serna-Gallén
Source: Crystals (article, 2024-08-27)
Field: Materials Science — Materials Chemistry

Fantastic Photons and Where to Excite Them: Revolutionizing Upconversion with KY3F10-Based Compounds This review delves into the forefront of upconversion luminescence (UCL) research, focusing on KY3F10-based compounds, particularly their cubic α-phase. These materials are renowned for their exceptional luminescent properties and structural stability, making them prime candidates for advanced photonic applications. The synthesis methods and structural characteristics of the existing works in the literature are meticulously analyzed alongside the transformative effects of various doping strategies on UCL efficiency. Incorporating rare earth (RE) sensitizer ions such as Yb3+, along with activator ions like Er3+, Ho3+, Nd3+, or Tm3+, researchers have achieved remarkable enhancements in emission intensity and spectral control. Recent and past breakthroughs in understanding the local structure and phase transitions of single-, double-, and triple-RE3+-doped KY3F10 nanocrystals are highlighted, revealing their pivotal role in fine-tuning luminescent properties. Furthermore, the review underscores the untapped potential of lesser-known crystal structures, such as the metastable δ-phase of KY3F10, which offers promising avenues for future exploration. By presenting a comprehensive analysis and proposing innovative research directions, this review aims to inspire continued advancements in the field of upconversion materials, unlocking new potentials in photonic technologies. Photon upconversion ; Photon ; Nanotechnology ; Computer science ; Materials science ; Optoelectronics ; Physics ; Optics ; Laser Luminescence Properties of Advanced Materials ; Radiation Detection and Scintillator Technologies ; Atomic and Subatomic Physics Research
Authors: Rudi Fasan | John G. Bennett | Andrew Bortz
Source: ChemRxiv (preprint, 2024-07-05)
Field: Chemistry — Organic Chemistry

Chemoenzymatic Skeletal Editing: P450-Controlled Site-Selective Ring Expansion of Natural Product Scaffolds at Aliphatic C—H Sites Methods for introducing subtle modifications at the level of single atoms/bonds (‘skeletal editing’) are highly desirable in organic and medicinal chemistry, owing to their potential for fine-tuning the structure and biological activity of organic molecules. While contemporary methods for skeletal editing of organic molecules largely rely on modification of pre-existing functional groups, opportunities for executing these transformations at ubiquitous yet unreactive aliphatic C(sp3)—H sites are currently unavailable. Here, we report a chemoenzymatic strategy for enabling skeletal editing via ring expansion with high site-selectivity at the level of one or more aliphatic C—H sites in complex molecules. By combining cytochrome P450-catalyzed C—H oxidation with chemical oxidation and subsequent Baeyer-Villiger rearrangement or ketone homologation, a panel of structurally and functionally diverse natural products were edited by inserting a lactone or carbonylmethylene moiety into aliphatic regions of their carbocyclic skeletons. Using engineered P450 catalysts with divergent regioselectivity, a set of different ring-expanded products could be readily obtained from a single parent molecule, highlighting the potential of this approach for skeletal edit scanning and/or library generation. By enabling the targeting of aliphatic C—H sites with tunable site-selectivity, this strategy provides a powerful tool to rapidly access skeletally edited derivatives of natural products and other bioactive molecules that would be hard to attain by purely chemical means. We envision this approach can also enable the device of non-traditional retrosynthetic disconnections for the synthesis of complex molecules. Regioselectivity ; Moiety ; Chemistry ; Ring (chemistry) ; Molecule ; Ketone ; Natural product ; Combinatorial chemistry ; Small molecule ; Catalysis ; Retrosynthetic analysis ; Chemical space ; Drug discovery ; Stereochemistry ; Organic chemistry ; Total synthesis Catalytic C–H Functionalization Methods ; Synthesis and Catalytic Reactions ; Innovative Microfluidic and Catalytic Techniques Innovation
Authors: Mingzhao Li | Xiaoyi Jing | Jiehui Xia | Tian Qi | Qiang Zhang | Bingnan Wang | Anjun Qin | Ben Zhong Tang
Source: Angewandte Chemie (article, 2024-08-06)
Field: Materials Science — Materials Chemistry

Water‐Involved Carbon‐Nitrogen Triple‐Bond Monomer Based Polymerization toward Processable Functional Polyamides under Ambient Conditions Abstract Polyamide plays a pivotal role in engineering thermoplastics. Constrained by the harsh conditions and arduous procedures for its industrial synthesis, developing facile synthesis of polyamides is still challengeable and holds profound significance. Herein, we successfully utilized water as one of the monomers to synthesize functional polyamides under ambient conditions. A powerful multicomponent polymerization of water, isocyanides, and chlorooximes was established in phosphate‐buffered saline. Soluble and thermally stable polyamides with high weight‐average molecular weights (up to 53 900) were obtained in excellent yields (up to 95 %). The polymerization exhibits unique polymerization‐induced emission characteristics, successfully converting non‐emissive monomers into unconventional emissive polymers. Notably, the resultant polyamides could undergo effective post‐modification via the hydroxyl‐yne click reaction. By incorporating various functional groups into the polyamide, its emission color could be fine‐tuned from blue to green and to red. Remarkably, the refractive index ( n ) of the polyamide at 589 nm could be increased from 1.6173 to 1.7227 and the Δ n could be unprecedentedly as high as 0.1054 for non‐heavy atom‐containing polymers after post‐modification, and its micron‐thick films exhibited excellent transparency in the visible region. Thus, this work not only establishes a powerful polymerization toward novel polyamides but also opens up an avenue for their versatile functionalization. Polyamide ; Polymerization ; Monomer ; Interfacial polymerization ; Polymer ; Polymer chemistry ; Surface modification ; Materials science ; Chemistry ; Chemical engineering ; Organic chemistry Luminescence and Fluorescent Materials ; Synthesis and properties of polymers ; Silicone and Siloxane Chemistry
Authors: Florian Dorchies | Alessandra Serva | Astrid Sidos | Laurent J. Michot | Michaël Deschamps | Mathieu Salanne | Alexis Grimaud
Source: ChemRxiv (preprint, 2024-06-03)
Field: Chemistry — Electrochemistry

Correlating substrates reactivity at electrified interfaces with electrolyte structure in synthetically relevant organic solvent/water mixtures Optimizing electrosynthetic reactions requires fine tuning of a vast chemical space, including charge transfer at electrocatalyst/electrode surfaces, engineering of mass transport limitations and complex interactions of reactants and products with their environment. Hybrid electrolytes, in which supporting salt ions and substrates are dissolved in a binary mixture of organic solvent and water, represent a new piece to this complex puzzle, as they offer a unique opportunity to harvest water as the oxygen or proton source in electrosynthesis. In this work, we demonstrate that modulating water-organic solvent interactions drastically impacts the solvation properties of hybrid electrolytes. Combining various spectroscopies with synchrotron small-angle X-ray scattering (SAXS) and classical molecular dynamics (MD) simulations, we show that the size and composition of aqueous domains forming in hybrid electrolytes can be controlled. We demonstrate that water is more reactive for the hydrogen evolution reaction (HER) in aqueous domains than when strongly interacting with solvent molecules, which originates from a change in reaction kinetics rather than from a thermodynamic effect. We examplify novel opportunities arising from this new knowledge for optimizing electrosynthetic reactions in hybrid electrolytes. For reactions proceeding first via the activation of water, fine tuning of aqueous domains impact the kinetics and potentially the selectivity of the reaction. Instead, for organic substrates reacting prior to water, aqueous domains have no impact on reaction kinetics, while selectivity may be affected. We believe that such fine comprehension of solvation properties of hybrid electrolytes can be transposed to numerous electrosynthetic reactions. Electrolyte ; Reactivity (psychology) ; Organic solvent ; Solvent ; Chemistry ; Chemical engineering ; Inorganic chemistry ; Materials science ; Organic chemistry ; Physical chemistry ; Electrode ; Engineering Electrochemical Analysis and Applications ; Advanced Chemical Sensor Technologies ; Analytical Chemistry and Sensors
Authors: Florian Dorchies | Alessandra Serva | Astrid Sidos | Laurent J. Michot | Michaël Deschamps | Mathieu Salanne | Alexis Grimaud
Source: ChemRxiv (preprint, 2024-04-22)
Field: Chemistry — Electrochemistry

Correlating substrates reactivity at electrified interfaces with electrolyte structure in synthetically relevant organic solvent/water mixtures Optimizing electrosynthetic reactions requires fine tuning of a vast chemical space, including charge transfer at electrocatalyst/electrode surfaces, engineering of mass transport limitations and complex interactions of reactants and products with their environment. Hybrid electrolytes, in which supporting salt ions and subtrates are dissolved in a binary mixture of organic solvent and water, represent a new piece to this complex puzzle, as they offer a unique opportunity to harvest water as the oxygen or proton source in electrosynthesis. In this work, we demonstrate that modulating water-organic solvent interactions drastically impacts the solvation properties of hybrid electrolytes. Combining various spectroscopies with synchrotron small-angle X-ray scattering (SAXS) and classical molecular dynamics (MD) simulations, we show that the size and composition of aqueous domains forming in hybrid electrolytes can be controlled. We demonstrate that water is more reactive for the hydrogen evolution reaction (HER) in aqueous domains than when strongly interacting with solvent molecules, which originates from a change in reaction kinetics rather than from a thermodynamic effect. We examplify novel opportunities arising from this new knowledge for optimizing electrosynthetic reactions in hybrid electrolytes. For reactions proceeding first via the activation of water, fine tuning of aqueous domains impact the kinetics and potentially the selectivity of the reaction. Instead, for organic substrates reacting prior to water, aqueous domains have no impact on reaction kinetics, while selectivity may be affected. We believe that such fine comprehension of solvation properties of hybrid electrolytes can be transposed to numerous electrosynthetic reactions. Electrolyte ; Reactivity (psychology) ; Organic solvent ; Solvent ; Chemistry ; Materials science ; Chemical engineering ; Organic chemistry ; Physical chemistry ; Electrode ; Engineering Electrochemical Analysis and Applications ; Advanced Chemical Sensor Technologies ; Analytical Chemistry and Sensors
Authors: Karan Gehlot | Anil Chandra Kothari | Sangeeta Tiwari | Rajaram Bal | Sandeep Tiwari
Source: Journal of Nanoparticle Research (article, 2024-05-27)
Field: Materials Science — Materials Chemistry

Catalytic properties of TiO2 nanofibers in CO2 conversion: a comparative analysis of polymer matrices Materials science ; Catalysis ; Nanofiber ; Polymer ; Chemical engineering ; Nanotechnology ; Polymer science ; Composite material ; Organic chemistry Catalytic Processes in Materials Science ; Carbon dioxide utilization in catalysis ; CO2 Reduction Techniques and Catalysts
Authors: Xiaodan Shi | Peipei Ai | Yu Zhang | Jiangtao Zhao | Wei Huang
Source: Molecular Catalysis (article, 2024-12-03)
Field: Materials Science — Materials Chemistry

Tuning the interaction between Cu and surface -OH in Cu/Ti3C2 MXene derived catalyst for enhanced semi-hydrogenation of dimethyl oxalate Catalysis ; Oxalate ; Copper ; Chemistry ; Materials science ; Chemical engineering ; Inorganic chemistry ; Metallurgy ; Organic chemistry MXene and MAX Phase Materials ; Nanomaterials for catalytic reactions ; Aluminum Alloys Composites Properties