jablonkagroup/rise_ai_scientists huggingface dataset:
Authors: Brian G. Diamond | Lillian I. Payne Torres | Christopher H. Hendon
Source: Communications Chemistry (article, 2023-04-12)
Field: Chemistry — Inorganic Chemistry

Ligand field tuning of d-orbital energies in metal-organic framework clusters Linker functionalization is a common route used to affect the electronic and catalytic properties of metal-organic frameworks. By either pre- or post-synthetically installing linkages with differing linker moieties the band gap, workfunction, and exciton lifetimes have been shown to be affected. One overlooked aspect of linker functionalization, however, has been the impact on the metal d-orbital energies to which they are bound. The ligand field differences should result in substantial changes in d-splitting. In this study we use density functional theory (DFT) to study the energetics of d-orbital energy tuning as a function of linker chemistry. We offer a general descriptor, linker pK<sub>a</sub>, as a tool to predict resultant band energies in metal-organic frameworks (MOFs). Our calculations reveal that simple functionalizations can affect the band energies, of primarily metal d lineage, by up to 2 eV and illustrate the significance of this band modularity using four archetypal MOFs: UiO-66, MIL-125, ZIF-8, and MOF-5. Together, we show that linker functionalization dramatically affects d-energies in MOF clusters and highlight that linker functionalization is a useful route for fine-tuning band edges centered on the metals, rather than linkers themselves. Ligand field theory ; Field (mathematics) ; Ligand (biochemistry) ; Metal ; Physics ; Chemistry ; Receptor ; Quantum mechanics ; Mathematics ; Organic chemistry ; Ion Metal-Organic Frameworks: Synthesis and Applications ; Advanced Condensed Matter Physics ; Inorganic Fluorides and Related Compounds
Authors: Srivatsa Chakravarthi | Nicholas Yama | Alex Abulnaga | Ding Huang | Christian Pederson | Karine Hestroffer | Fariba Hatami | Nathalie P. de Leon | Kai‐Mei C. Fu
Source: Nano Letters (article, 2023-04-25)
Field: Materials Science — Materials Chemistry

Hybrid Integration of GaP Photonic Crystal Cavities with Silicon-Vacancy Centers in Diamond by Stamp-Transfer Optically addressable solid-state defects are emerging as some of the most promising qubit platforms for quantum networks. Maximizing photon-defect interaction by nanophotonic cavity coupling is key to network efficiency. We demonstrate fabrication of gallium phosphide 1-D photonic crystal waveguide cavities on a silicon oxide carrier and subsequent integration with implanted silicon-vacancy (SiV) centers in diamond using a stamp-transfer technique. The stamping process avoids diamond etching and allows fine-tuning of the cavities prior to integration. After transfer to diamond, we measure cavity quality factors (<i>Q</i>) of up to 8900 and perform resonant excitation of single SiV centers coupled to these cavities. For a cavity with a <i>Q</i> of 4100, we observe a 3-fold lifetime reduction on-resonance, corresponding to a maximum potential cooperativity of <i>C</i> = 2. These results indicate promise for high photon-defect interaction in a platform which avoids fabrication of the quantum defect host crystal. Diamond ; Optoelectronics ; Materials science ; Vacancy defect ; Silicon ; Gallium phosphide ; Photonic crystal ; Fabrication ; Photon ; Photonics ; Etching (microfabrication) ; Nanotechnology ; Optics ; Physics ; Condensed matter physics Diamond and Carbon-based Materials Research ; Advanced Fiber Laser Technologies ; Photonic and Optical Devices
Authors: Kan Hatakeyama‐Sato | Naoki Yamane | Yasuhiko Igarashi | Yuta Nabae | Teruaki Hayakawa
Source: Science and Technology of Advanced Materials Methods (article, 2023-09-20)
Field: Materials Science — Materials Chemistry

Prompt engineering of GPT-4 for chemical research: what can/cannot be done? This paper evaluates the capabilities and limitations of the Generative Pre-trained Transformer 4 (GPT-4) in chemical research. Although GPT-4 exhibits remarkable proficiencies, it is evident that the quality of input data significantly affects its performance. We explore GPT-4’s potential in chemical tasks, such as foundational chemistry knowledge, cheminformatics, data analysis, problem prediction, and proposal abilities. While the language model partially outperformed traditional methods, such as black-box optimization, it fell short against specialized algorithms, highlighting the need for their combined use. The paper shares the prompts given to GPT-4 and its responses, providing a resource for prompt engineering within the community, and concludes with a discussion on the future of chemical research using large language models. Cheminformatics ; Computer science ; Transformer ; Generative grammar ; Data science ; Machine learning ; Artificial intelligence ; Bioinformatics ; Engineering ; Biology Machine Learning in Materials Science ; Computational Drug Discovery Methods
Authors: Vignesh Palani | Alison E. Wendlandt
Source: Journal of the American Chemical Society (article, 2023-08-30)
Field: Chemistry — Organic Chemistry

Strain-Inducing Positional Alkene Isomerization Small, strained ring systems are important pharmacophores in medicinal chemistry and versatile intermediates in organic synthesis. However, the kinetic and thermodynamic instability of many strained organic molecules renders them challenging to prepare. Here, we report a strain-inducing positional alkene isomerization reaction that provides mild and selective access to cyclobutene building blocks from readily obtained cyclobutylidene precursors. This endergonic isomerization relies on the sequential and synergistic action of a decatungstate polyanion photocatalyst and cobaloxime co-catalyst to store potential energy in the form of ring strain. The versatility of the cyclobutene products is demonstrated through diverse subsequent strain-releasing transformations. Mechanistic studies reveal a steric basis for strain-selective product formation. Isomerization ; Chemistry ; Cyclobutene ; Alkene ; Ring strain ; Strain (injury) ; Steric effects ; Photochemistry ; Catalysis ; Ring (chemistry) ; Stereochemistry ; Organic chemistry Click Chemistry and Applications ; Synthetic Organic Chemistry Methods ; Cyclopropane Reaction Mechanisms
Authors: Alessandro Messori | Anna Gagliardi | Cristiana Cesari | Francesco Calcagno | Tommaso Tabanelli | Fabrizio Cavani | Rita Mazzoni
Source: Catalysis Today (article, 2023-01-20)
Field: Chemistry — Inorganic Chemistry

Advances in the homogeneous catalyzed alcohols homologation: The mild side of the Guerbet reaction. A mini-review The Guerbet reaction would be an optimal solution for bio-ethanol refinery by homologation and it substantially requires the development of active and highly selective catalysts. Although heterogeneous catalysis remains more desirable, homogeneous Guerbet catalytic systems are nowadays acknowledged as challenging proposals for high selectivity and conversion under mild reaction conditions. Several molecular bi-functional catalysts, based on ruthenium, iridium and manganese complexes bearing different ligands such as phosphine, bidentate bisphosphine (P-P) and phosphamine (P-N), pincer (N-N-N), (P-N-P) and cyclopentadienone, are active in the co-presence of a base, which is essential in all the cases for the condensation reaction. This mini-review is aimed to describe the state of the art, with incremental steps forward to understand the role of the catalytic systems and the reaction conditions on conversion and selectivity. While showing different efficiency, mutable behavior by minimal change in the ligand scaffold, variation in water tolerance and only one example of recyclability, metal catalysts are found to be similar in terms of proposed mechanisms. The influence of additives and capability to maintain activity in fermentation broth and bio-ethanol from wine value chain to second generation bio-fuel are also discussed. Although not yet completely rationalized, experimental and theoretical mechanistic investigations pave the way for the design of more stable and efficient catalysts toward improved applicability. Catalysis ; Chemistry ; Phosphine ; Selectivity ; Combinatorial chemistry ; Homogeneous catalysis ; Heterogeneous catalysis ; Pincer ligand ; Organic chemistry ; Ruthenium ; Ligand (biochemistry) ; Pincer movement Asymmetric Hydrogenation and Catalysis ; Chemical Synthesis and Reactions ; Chemical Synthesis and Analysis
Authors: Zheng Zhou | Marina A. Petrukhina
Source: Coordination Chemistry Reviews (article, 2023-04-13)
Field: Chemistry — Organic Chemistry

Planar, curved and twisted molecular nanographenes: Reduction-induced alkali metal coordination Chemistry ; Graphene ; Fullerene ; Alkali metal ; Intercalation (chemistry) ; Carbon fibers ; Nanotechnology ; Planar ; Carbon nanotube ; Inorganic chemistry ; Organic chemistry ; Materials science Synthesis and Properties of Aromatic Compounds ; Graphene research and applications ; Fullerene Chemistry and Applications
Authors: Yonela Ngungeni | Jumoke A. Aboyewa | Koena Leah Moabelo | Nicole Remaliah Samantha Sibuyi | Samantha Meyer | Martin O. Onani | Mervin Meyer | Abram M. Madiehe
Source: ACS Omega (article, 2023-07-11)
Field: Materials Science — Materials Chemistry

Anticancer, Antioxidant, and Catalytic Activities of Green Synthesized Gold Nanoparticles Using Avocado Seed Aqueous Extract Disposal of agricultural waste has a negative impact on the environment and human health and may contribute to the greenhouse effect. The field of nanotechnology could provide alternative solutions to upcycle agricultural wastes in a safer manner into high-end value products. Organic waste from plants contain biomaterials that could serve as reducing and capping agents in the synthesis of nanomaterials with enhanced activities for use in biomedical and environmental applications. <i>Persea americana</i> (avocado) is a fruit with a high nutritional value; however, despite its rich phytochemical profile, its seed is often discarded as waste. Therefore, this study aimed to upcycle avocado seeds through the synthesis of gold nanoparticles (AuNPs) and evaluate their anticancer, antioxidant, and catalytic activities. The biosynthesis of avocado seed extract (AvoSE)-mediated AuNPs (AvoSE-AuNPs) was achieved following the optimization of various reaction parameters, including pH, temperature, extract, and gold salt concentrations. The AvoSE-AuNPs were poly-dispersed and anisotropic, with average core and hydrodynamic sizes of 14 ± 3.7 and 101.39 ± 1.4 nm, respectively. The AvoSE-AuNPs showed excellent antioxidant potential in terms of ferric reducing antioxidant power (343.88 ± 0.001 μmolAAE/L), 2,2-diphenyl-1-picrylhydrazyl (128.80 ± 0.0159 μmolTE/L), and oxygen radical absorbance capacity (1822.02 ± 12.6338 μmolTE/L); significantly reduced the viability of Caco-2 and PC-3 cells in a dose-dependent manner; and efficiently reduced 4-nitrophenol (4-NP) to 4-aminophenol. This study demonstrated how avocado seeds, an agricultural waste, can be used as sources of new bioactive materials for the synthesis of AuNPs, which have excellent antioxidant, anticancer, and catalytic activities, showing AvoSE-AuNPs' versatility in various applications. In addition, the AvoSE-AuNPs exhibited good stability and recyclability during the catalytic activity, which is significant because some of the primary issues with the use of metallic NPs as catalysts are around the cost-effectiveness, recovery, and reusability of the catalyst. Antioxidant ; Chemistry ; Phytochemical ; Colloidal gold ; Catalysis ; Ferric ; Absorbance ; Food science ; Oxygen radical absorbance capacity ; Nuclear chemistry ; Nanoparticle ; Horticulture ; Antioxidant capacity ; Organic chemistry ; Nanotechnology ; Biochemistry ; Materials science ; Biology ; Chromatography Nanoparticles: synthesis and applications ; Phytochemicals and Antioxidant Activities ; Botanical Research and Applications
Authors: Valeria Allizond | Giuliana Banche | Matteo Salvoni | Mery Malandrino | Claudio Cecone | Annamaria Cuffini | Pierangiola Bracco
Source: Polymers (article, 2023-03-16)
Field: Materials Science — Biomaterials

Facile One-Step Electrospinning Process to Prepare AgNPs-Loaded PLA and PLA/PEO Mats with Antibacterial Activity Nanofibers can play an important role in developing new kinds of medical applications. Poly(lactic acid) (PLA) and PLA/poly(ethylene oxide) (PEO) antibacterial mats containing silver nanoparticles (AgNPs) were prepared by a simple one-step electrospinning method that allows AgNPs to be synthesized simultaneously with the preparation of the electrospinning solution. The electrospun nanofibers were characterized by scanning electron microscopy, transmission electron microscopy and thermogravimetry, while silver release over time was monitored by inductively coupled plasma/optical emission spectroscopy. The antibacterial activity was tested against <i>Staphylococcus epidermidis</i> and <i>Escherichia coli</i> by colony forming unit (CFU) count on agar after 15, 24 and 48 h of incubation. AgNPs were found to be mainly concentrated in the PLA nanofiber core, and the mats showed steady but slow Ag release in the short term; in contrast, AgNPs were uniformly distributed in the PLA/PEO nanofibers, which released up to 20% of their initial silver content in 12 h. A significant (<i>p</i> < 0.05) antimicrobial effect towards both tested bacteria, highlighted by a reduction in the CFU/mL counts, was observed for the nanofibers of PLA and PLA/PEO embedded with AgNPs, with a stronger effect exerted by the latter, confirming the more efficient silver release from these samples. The prepared electrospun mats may have good potential for use in the biomedical field, particularly in wound dressing applications, where a targeted delivery of the antimicrobial agent is highly desirable to avoid infections. Electrospinning ; Nanofiber ; Silver nanoparticle ; Antibacterial activity ; Materials science ; Polylactic acid ; Nuclear chemistry ; Antibacterial agent ; Scanning electron microscope ; Chemical engineering ; Nanotechnology ; Nanoparticle ; Chemistry ; Bacteria ; Polymer ; Composite material Electrospun Nanofibers in Biomedical Applications ; biodegradable polymer synthesis and properties ; Graphene and Nanomaterials Applications
Authors: Xiangbing Zeng | Benjamin Glettner | Ute Baumeister | Bin Chen | Goran Ungar | Feng Liu | Carsten Tschierske
Source: Nature Chemistry (article, 2023-03-23)
Field: Materials Science — Materials Chemistry

A columnar liquid quasicrystal with a honeycomb structure that consists of triangular, square and trapezoidal cells Chemistry ; Square (algebra) ; Quasicrystal ; Honeycomb ; Crystallography ; Hexagonal crystal system ; Honeycomb structure ; Nanotechnology ; Composite material ; Geometry Quasicrystal Structures and Properties ; Liquid Crystal Research Advancements ; Phase-change materials and chalcogenides
Authors: Jai Kumar | Rana R. Neiber | Zaheer Abbas | Razium Ali Soomro | Amal BaQais | Mohammed A. Amin | Zeinhom M. El‐Bahy
Source: Micromachines (article, 2023-02-19)
Field: Materials Science — Electronic, Optical and Magnetic Materials

Hierarchical NiMn-LDH Hollow Spheres as a Promising Pseudocapacitive Electrode for Supercapacitor Application Layered double hydroxides (LDH) are regarded as attractive pseudocapacitive materials due to their impressive capacitive qualities that may be adjustable to their morphological features. However, the layered structure of LDH renders them susceptible to structural aggregation, which inhibits effective electrolyte transport and limits their practical applicability after limited exposure to active areas. Herein, we propose a simple template-free strategy to synthesize hierarchical hollow sphere NiMn-LDH material with high surface area and exposed active as anode material for supercapacitor application. The template-free approach enables the natural nucleation of Ni-Mn ions resulting in thin sheets that self-assemble into a hollow sphere, offering expended interlayer spaces and abundant redox-active active sites. The optimal NiMn-LDH-12 achieved a specific capacitance of 1010.4 F g<sup>-1</sup> at a current density of 0.2 A g<sup>-1</sup> with capacitance retention of 70% at 5 A g<sup>-1</sup> after 5000 cycles with lower charge transfer impedance. When configured into an asymmetric supercapacitors (ASC) device as NiMn-LDH//AC, the material realized a specific capacitance of 192.4 F g<sup>-1</sup> at a current density of 0.2 A g<sup>-1</sup> with a good energy density of 47.9 Wh kg<sup>-1</sup> and a power density of 196.8 W kg<sup>-1</sup>. The proposed morphological-tuning route is promising for designing template-free NiMn-LDHs spheres with practical pseudocapacitive characteristics. Supercapacitor ; Materials science ; Electrode ; SPHERES ; Nanotechnology ; Chemical engineering ; Electrochemistry ; Chemistry ; Engineering ; Aerospace engineering Supercapacitor Materials and Fabrication ; Catalytic Processes in Materials Science ; Aerogels and thermal insulation
Authors: Orestis Kontogiannis | Dimitriοs Selianitis | Nefeli Lаgopati | Νatassa Pippa | Stergios Pispas | Maria Gazouli
Source: Pharmaceutics (review, 2023-02-02)
Field: Materials Science — Biomaterials

Surfactant and Block Copolymer Nanostructures: From Design and Development to Nanomedicine Preclinical Studies The medical application of nanotechnology in the field of drug delivery has so far exhibited many efforts in treating simple to extremely complicated and life-threatening human conditions, with multiple products already existing in the market. A plethora of innovative drug delivery carriers, using polymers, surfactants and the combination of the above, have been developed and tested pre-clinically, offering great advantages in terms of targeted drug delivery, low toxicity and immune system activation, cellular biomimicry and enhanced pharmacokinetic properties. Furthermore, such artificial systems can be tailor-made with respect to each therapeutic protocol and disease type falling under the scope of personalized medicine. The simultaneous delivery of multiple therapeutic entities of different nature, such as genes and drugs, can be achieved, while novel technologies can offer systems with multiple modalities often combining therapy with diagnosis. In this review, we present prominent, innovative and state-of-the-art scientific efforts on the applications of surfactant-based, polymer-based, and mixed surfactant-polymer nanoparticle drug formulations intended for use in the medical field and in drug delivery. The materials used, formulation steps, nature, properties, physicochemical characteristics, characterization techniques and pharmacokinetic behavior of those systems, are presented extensively in the length of this work. The material presented is focused on research projects that are currently in the developmental, pre-clinical stage. Nanomedicine ; Drug delivery ; Nanotechnology ; Niosome ; Computer science ; Scope (computer science) ; Personalized medicine ; Materials science ; Nanoparticle ; Chemistry ; Bioinformatics Nanoparticle-Based Drug Delivery ; Advanced Polymer Synthesis and Characterization ; RNA Interference and Gene Delivery
Authors: B. Rivas‐Murias | Martín Testa‐Anta | Alexander Skorikov | Miguel Comesaña‐Hermo | Sara Bals | Verónica Salgueiriño
Source: Nano Letters (article, 2023-02-27)
Field: Materials Science — Materials Chemistry

Interfaceless Exchange Bias in CoFe<sub>2</sub>O<sub>4</sub> Nanocrystals Oxidized cobalt ferrite nanocrystals with a modified distribution of the magnetic cations in their spinel structure give place to an unusual exchange-coupled system with a double reversal of the magnetization, exchange bias, and increased coercivity, but without the presence of a clear physical interface that delimits two well-differentiated magnetic phases. More specifically, the partial oxidation of cobalt cations and the formation of Fe vacancies at the surface region entail the formation of a cobalt-rich mixed ferrite spinel, which is strongly pinned by the ferrimagnetic background from the cobalt ferrite lattice. This particular configuration of exchange-biased magnetic behavior, involving two different magnetic phases but without the occurrence of a crystallographically coherent interface, revolutionizes the established concept of exchange bias phenomenology. Ferrimagnetism ; Spinel ; Exchange bias ; Cobalt ; Coercivity ; Nanocrystal ; Materials science ; Magnetization ; Condensed matter physics ; Ferrite (magnet) ; Chemical physics ; Crystallography ; Chemistry ; Nanotechnology ; Magnetic anisotropy ; Metallurgy ; Magnetic field ; Physics Magnetic Properties and Synthesis of Ferrites ; Magnetic properties of thin films ; Iron oxide chemistry and applications
Authors: Simone Di Cataldo | Lilia Boeri
Source: Physical review. B./Physical review. B (article, 2023-02-02)
Field: Materials Science — Materials Chemistry

Metal borohydrides as ambient-pressure high-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mi>T</mml:mi><mml:mi>c</mml:mi></mml:msub></mml:math>superconductors The extreme pressures required to stabilize the recently discovered superhydrides represent a major obstacle to their practical application. In this Letter, we propose and substantiate a route to attain high-temperature superconductivity in hydrides at ambient pressure, by doping commercial metal borohydrides. Using first-principles calculations based on density functional theory and Migdal-Eliashberg theory, we demonstrate that in $\mathrm{Ca}{({\mathrm{BH}}_{4})}_{2}$ a moderate hole doping of 0.03 holes per formula unit, obtained through a partial replacement of Ca with monovalent K, is sufficient to achieve ${T}_{\text{c}}$'s as high as 110 K. The high ${T}_{\text{c}}$ arises because of the strong electron-phonon coupling between the B-H $\ensuremath{\sigma}$ molecular orbitals and bond-stretching phonons. Using a random sampling of large supercells to estimate the local effects of doping, we show that the required doping can be achieved without significant disruption of the electronic structure and at moderate energetic cost. Given the wide commercial availability of metal borohydrides, the ideas presented here can find prompt experimental confirmation. If successful, the synthesis of high-${T}_{\text{c}}$ doped borohydrides will represent a formidable advancement towards the technological exploitation of conventional superconductors. Doping ; Density functional theory ; Superconductivity ; High pressure ; Materials science ; Metal ; Atomic orbital ; Physics ; Condensed matter physics ; Thermodynamics ; Electron ; Quantum mechanics Hydrogen Storage and Materials ; Superconductivity in MgB2 and Alloys ; Rare-earth and actinide compounds