jablonkagroup/rise_ai_scientists huggingface dataset:
Authors: Carles Bofill-Bonet | Maria Gil-Vives | Margalida Artigues | Marta Hernández | Salvador Borrós | Cristina Fornaguera
Source: Journal of Molecular Liquids (article, 2023-09-04)
Field: Materials Science — Biomaterials

Fine-tuning formulation and biological interaction of doxorubicin-loaded polymeric nanoparticles via electrolyte concentration modulation Nanoparticle ; Chemistry ; Electrolyte ; Aqueous solution ; Emulsion ; Doxorubicin ; Aqueous two-phase system ; Dissolution ; Chemical engineering ; Solubility ; Poloxamer ; Chromatography ; Materials science ; Nanotechnology ; Organic chemistry ; Electrode ; Polymer Nanoparticle-Based Drug Delivery ; Electrohydrodynamics and Fluid Dynamics ; Electrostatics and Colloid Interactions
Authors: Victoria Richards
Source: Communications Chemistry (article, 2023-07-04)
Field: Chemistry — Physical and Theoretical Chemistry

Enhanced enantioselectivity in halogen-bonding catalysis Chiral halogen-bonding catalysts have emerged as a new approach towards asymmetric catalysis, but enantioselectivities have thus far remained low. Now, fine-tuning the substrate–catalyst halogen–halogen interactions is shown to significantly enhance enantioselectivity for a model anion-binding-catalyzed dearomatization reaction. Catalysis ; Halogen ; Halogen bond ; Substrate (aquarium) ; Chemistry ; Enantioselective synthesis ; Combinatorial chemistry ; Polymer chemistry ; Organic chemistry Crystallography and molecular interactions ; Molecular spectroscopy and chirality ; Asymmetric Synthesis and Catalysis
Authors: Nazanin Moeini | Hamidreza Teimoury | Mehrdad Salimi | Naeimeh Bahri‐Laleh | Mohammad Joshaghani | Josep Duran | Albert Poater | Sergio Posada‐Pérez
Source: Polymer (article, 2023-12-29)
Field: Materials Science — Polymers and Plastics

Influence of the reaction conditions on the Ziegler-Natta catalyzed ethylene polymerization: Kinetics and properties of the resulting polymers This work conducts an investigation into how the polymerization conditions affect the kinetics of ethylene homopolymerization and the properties of the final polyethylene using a commercially available Ziegler-Natta catalyst with the formula TiCl4/MgCl2. By employing a mathematical model, we estimated the apparent propagation (kp), activation (ka), and deactivation (kd) rate constants under different reaction conditions, including cocatalyst and catalyst concentration, hydrogen/ethylene ratio, and polymerization temperature. Additionally, we examined the properties of the resulting polyethylene products, such as particle size, molecular weight (Mw), melting temperature, and % crystallinity. We found that the trend of polymer particle size was similar to that of the propagation rate constant under the employed polymerization conditions. Our results indicated that parameters enhancing the polymerization rate also increased kp and reduced crystallinity. The quantitative rate constants and polymer characteristics reported in this study provide valuable insights for industrial polyethylene manufacturers, allowing them to fine-tune plant operation conditions and achieve precise control over polymer particle properties. Furthermore, Density Functional Theory (DFT) calculations provided additional insights into the polymerization process, particularly regarding the role of hydrogen as a chain transfer agent and the fundamental significance of MgCl2, emphasizing the need for a minimal-dimensional model to evaluate this role. Polyethylene ; Polymerization ; Crystallinity ; Polymer ; Materials science ; Polymer chemistry ; Natta ; Reaction rate constant ; Ethylene ; Chemical engineering ; Catalysis ; Coordination polymerization ; Ziegler–Natta catalyst ; Kinetics ; Solution polymerization ; Chemistry ; Organic chemistry ; Composite material Polymer crystallization and properties ; biodegradable polymer synthesis and properties ; Microplastics and Plastic Pollution
Authors: Xinyu Li | Zhaoxin Liu | Can Li | Rong Gao | Yanpeng Qi | Yi Ren
Source: The Journal of Organic Chemistry (article, 2023-09-11)
Field: Chemistry — Inorganic Chemistry

Synthesis and Photophysical Properties of Carbazole-Functionalized Diazaphosphepines via Sequent P–N Chemistry Chemical structure tunability of organic π-conjugated molecules (OCMs) is highly appealing for fine-tuning the optoelectronic properties. Herein, we report a new series of carbazole-functionalized diazaphosphepines (DPP-CBZs) via one-pot phosphorus-nitrogen (P-N) chemistry. The one-pot synthesis harnessed the mild and selective P-N chemistry that successively installed carbazole moieties and seven-membered heterocycles at one P-center. Single-crystal structure studies revealed the tweezer-like structures for <b>1PO</b>, <b>2PO</b>, and <b>3PO</b> that maintained the intramolecular donor-acceptor interactions between [d]-aryl moieties and carbazole. DPP-CBZs exhibited a more twisted central-diazaphosphepine ring compared with the reference molecules (<b>1-3MO</b> without carbazole group). DPP-CBZs with strong electron-accepting [d]-Ars generally showed lower photoluminescence quantum yields (PLQYs) than those of the reference molecules, which is probably due to the intramolecular charge transfer (ICT) from electron-donating carbazole to electron-withdrawing [d]-Ars. Upon the oxidation of the P-centers, PLQYs of DPP-CBZs increased. Furthermore, photophysical studies and theoretical studies suggested that the carbazole group had a strong impact on the structures of DPP-CBZs. As a proof of concept, we showed that grinding the mixture of <b>1PO</b> as the electron-donating tweezer and benzene-1,2,4,5-tetracarbonitrile (<b>BzCN</b>) as the electron acceptor induced the formation of the CT complex. Carbazole ; Intramolecular force ; Chemistry ; Molecule ; Aryl ; Photoluminescence ; Photochemistry ; Electron acceptor ; Acceptor ; Stereochemistry ; Materials science ; Organic chemistry ; Alkyl Synthesis and characterization of novel inorganic/organometallic compounds ; Organoboron and organosilicon chemistry ; Organometallic Complex Synthesis and Catalysis
Authors: Ronghui Huang | Minyan Wang | Hong Deng | Jingkai Xu | Hong Yan | Yue Zhao | Zhuangzhi Shi
Source: Science Advances (article, 2023-01-13)
Field: Chemistry — Organic Chemistry

Stereospecific nickel-catalyzed [4+2] heteroannulation of alkynes with aminophosphanes Enantioenriched phosphorus compounds play crucial roles in many fields ranging from catalyst to materials science to drug development. Despite advances in the construction of phosphacycles, incorporation of a P-chirogenic center into heterocycles remains challenging. Here, we report an effective method for the preparation of phosphacycles through nickel-catalyzed [4+2] heteroannulation of internal alkynes with aminophosphanes derived from <i>o</i>-haloanilines. Notably, chiral 2-λ5-phosphaquinolines can be prepared from P-stereogenic substrates via NH/PH tautomeric equilibrium without loss of stereochemical integrity. The strategy is found to exhibit a broad scope in terms of both reaction components, enabling modular construction of libraries of 2-λ5-phosphaquinolines with different steric and electronic properties for fine-tuning photophysical properties, where some of these compounds showed distinct fluorescence with high quantum yields. A series of mechanistic studies further shed light on the pathway of the heteroannulation and reasons for stereospecificity. Stereocenter ; Stereospecificity ; Steric effects ; Catalysis ; Combinatorial chemistry ; Tautomer ; Chemistry ; Nickel ; Stereochemistry ; Organic chemistry ; Enantioselective synthesis Catalytic C–H Functionalization Methods ; Organoboron and organosilicon chemistry ; Sulfur-Based Synthesis Techniques
Authors: Guonan Ji | Xuetao Zheng | Xiangdie Hou | Xiao Sun | Shijie Wang | Xiaohong Li | Jianjun Cheng | Ziyuan Song
Source: Chinese Chemical Letters (article, 2023-07-31)
Field: Chemistry — Organic Chemistry

Modulation of polymerization rate of N-carboxyanhydrides in a biphasic system Polymerization ; Chemistry ; Aqueous solution ; Polymer chemistry ; Kinetics ; Ionic polymerization ; Amine gas treating ; Radical polymerization ; Polymer ; Organic chemistry Advanced Polymer Synthesis and Characterization ; Dendrimers and Hyperbranched Polymers ; Luminescence and Fluorescent Materials
Authors: Enrico Di Russo | Alessandro Tonon | Arianna Mischianti | Francesco Sgarbossa | E. Coleman | Farzan Gity | Luca Panarella | Brendan Sheehan | В. А. Лебедев | D. De Salvador | Ray Duffy | E. Napolitani
Source: ACS Applied Electronic Materials (article, 2023-05-05)
Field: Materials Science — Materials Chemistry

Synthesis of Large-Area Crystalline MoS<sub>2</sub> by Sputter Deposition and Pulsed Laser Annealing The wafer-scale synthesis of layered transitional metal dichalcogenides presenting good crystal quality and homogeneous coverage is a challenge for the development of next-generation electronic devices. This work explores a fairly unconventional growth method based on a two-step process consisting in sputter deposition of stochiometric MoS2 on Si/SiO2 substrates followed by nanosecond UV (248 nm) pulsed laser annealing. Large-scale 2H-MoS2 multi-layer films were successfully synthetized in a N2-rich atmosphere thanks to a fine-tuning of the laser annealing parameters by varying the number of laser pulses and their energy density. The identification of the optimal process led to the success in achieving a (002)-oriented nanocrystalline MoS2 film without performing post-sulfurization. It is noteworthy that the spatial and temporal confinement of laser annealing keeps the Si/SiO2 substrate temperature well below the back-end-of-line temperature limit of Si CMOS technology (770 K). The synthesis method described here can speed up the integration of large-area 2D materials with Si-based devices, paving the way for many important applications. Materials science ; Annealing (glass) ; Optoelectronics ; Laser ; Wafer ; Nanocrystalline material ; Sputtering ; Pulsed laser deposition ; Nanosecond ; CMOS ; Nanotechnology ; Thin film ; Optics ; Metallurgy 2D Materials and Applications ; Gas Sensing Nanomaterials and Sensors ; MXene and MAX Phase Materials
Authors: Sandra Schüttner | Maximilian Krappel | Martha Koziol | Lucas Marquart | Ingo Schneider | Thomas Sottmann | Holger Frey
Source: Macromolecules (article, 2023-08-17)
Field: Chemistry — Organic Chemistry

Anionic Ring-Opening Copolymerization of Farnesyl Glycidyl Ether: Fast Access to Terpenoid-Derived Amphiphilic Polyether Architectures Motivated by increasing attention to biobased and potentially sustainable polymers from renewable sources, this work describes the synthesis and anionic ring-opening polymerization (AROP) of the terpenoid-derived farnesyl glycidyl ether (FarGE) as a hydrophobic epoxide building block for the synthesis of biobased, amphiphilic polyethers that represent novel, nonionic surfactants. In combination with ethylene oxide (EO), the synthetic strategies employed provide access to both amphiphilic diblock (mPEG114-b-PFarGEm) and statistical copolymers (PEGn-co-PFarGEm), featuring facile tunability of their amphiphilic and surfactant properties. The versatile application of FarGE for different polyether architectures is demonstrated by the well-controlled molecular weights in the range of 5040–11170 g mol–1 and narrow molecular weight distributions (Đ = 1.04–1.11), both for block and statistical architectures. Owing to the unexpected, nearly ideally random microstructure of the statistical EO/FarGE copolyethers, determined by in situ kinetics (rEO = 1.18 and rFarGE = 0.85), the branched alkenyl side chain impedes the crystallization of polyethylene glycol (PEG) with increasing FarGE incorporation, allowing for fine-tuning of polymer properties. Observing a low glass transition temperature (Tg) of around −70 °C for the PFarGE homopolymer, the thermal analysis also unveils farnesyl side-chain control of the Tg even at low FarGE content (7.6 mol %). Detailed investigations of aqueous polymer solutions reveal self-assembly of the amphiphilic copolymers into micelles and aggregates, characterized by very low critical micelle concentrations (CMC, 10–53 mg L–1), as well as larger clusters (RH,micelle = 17–35 nm and RH,cluster = 59–107 nm). The results demonstrate the enormous potential of terpenes and terpenoids for partially biobased surfactant alternatives. Amphiphile ; Copolymer ; Micelle ; Polymer chemistry ; Polymerization ; Polymer ; Materials science ; Critical micelle concentration ; Chemistry ; Chemical engineering ; Organic chemistry ; Aqueous solution Advanced Polymer Synthesis and Characterization ; biodegradable polymer synthesis and properties ; Polymer composites and self-healing
Authors: Zhikai Zhang | Boyang Zhang | Xue Han | Hongyi Chen | Cece Xue | Min Peng | Guijun Ma | Yi Ren
Source: Chemical Science (article, 2023-01-01)
Field: Materials Science — Polymers and Plastics

Stille type P–C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution Recently, exploring new type polymerization protocols has been a major driving force in advancing organic polymers into highly functional materials. Herein we report a new polycondensation protocol to implant the phosphorus (P) atom in the main backbone of crosslinked polythiophenes. The polycondensation harnesses a Stille phosphorus-carbon (P-C) coupling reaction between phosphorus halides and aryl stannanes that has not been reported previously. Mechanistic studies uncovered that the P-electrophile makes the reactivity of a catalytic Pd-center highly sensitive towards the chemical structures of aryl stannanes, which is distinct from the typical Stille carbon-carbon coupling reaction. The efficient P-C polycondensation afforded a series of P-crosslinked polythiophenes (PC-PTs). Leveraging on the direct P-crosslinking polymerization, solid-state <sup>31</sup>P NMR studies revealed highly uniform crosslinking environments. Efficient post-polymerization P-chemistry was also applied to the PC-PTs, which readily yielded the polymers with various P-environments. As a proof of concept, new PC-PTs were applied as the photocatalysts for H<sub>2</sub> evolution under visible light irradiation. PC-PTs with an ionic P(Me)-center exhibit a H<sub>2</sub> evolution rate up to 2050 μmol h<sup>-1</sup> g<sup>-1</sup>, which is much higher than those of PC-PTs with a P(O)-center (900 μmol h<sup>-1</sup> g<sup>-1</sup>) and P(iii)-center (155 μmol h<sup>-1</sup> g<sup>-1</sup>). For the first time, the studies reveal that regulating P-center environments can be an effective strategy for fine tuning the photocatalytic H<sub>2</sub> evolution performance of organic polymers. Stille reaction ; Condensation polymer ; Photocatalysis ; Coupling (piping) ; Black phosphorus ; Polymer chemistry ; Phosphorus ; Chemistry ; Photochemistry ; Materials science ; Organic chemistry ; Polymer ; Catalysis ; Optoelectronics ; Composite material Conducting polymers and applications ; Sulfur-Based Synthesis Techniques ; Radical Photochemical Reactions
Authors: Ruben Falkenburg | Maximilian J. Notheis | Gregor Schnakenburg | Larissa K. S. von Krbek
Source: Organic & Biomolecular Chemistry (article, 2023-01-01)
Field: Materials Science — Materials Chemistry

Twelve-membered ring photoswitches with excellent<i>Z</i>→<i>E</i>conversion under ambient light Incorporation of azobenzenes into macrocycles is an intriguing approach for fine tuning the photophysical properties of these photoswitches and tailoring them to specific applications. A versatile synthesis of macrocyclic azobenzenes has been developed that allows for facile modification of these photoswitches. One example shows high chemical stability, long half-life of its <i>Z</i>-isomers, quantitative <i>Z</i> → <i>E</i> conversion under white light, and excellent separation of excitation bands to address either the <i>E</i> or <i>Z</i>-state selectively. The near quantitative <i>Z</i> → <i>E</i> conversion under white light is a unique feature with an important impact on applications, in which the configuration under ambient light needs to be close to 100%. Photoswitch ; White light ; Ring (chemistry) ; Materials science ; Chemistry ; Photochemistry ; Nanotechnology ; Optoelectronics ; Organic chemistry Photochromic and Fluorescence Chemistry ; Photoreceptor and optogenetics research ; Luminescence and Fluorescent Materials
Authors: Suchitra D. Panigrahi | Collin M. Mayhan | Ajaz A. Dar | Steven P. Kelley | Alexander I. Greenwood | Daniel J. Hassett | Carol A. Deakyne | Harshita Kumari
Source: Crystal Growth & Design (article, 2023-01-17)
Field: Chemistry — Organic Chemistry

Supramolecule-Driven Host–Guest Co-Crystallization of Cyclic Polyphenols with Anti-Fibrotic Pharmaceutical Drug Host–guest complexes are of interest as supramolecular drugs in pharmaceutical sciences because the activity of antibacterial agents can be enhanced upon complexation with various cyclic oligomers or metal ions, with some complexes possessing higher healing properties than the parent drugs. Herein, to develop a microbiologically potent supramolecular drug, we investigated the complexation of macrocyclic hosts (resorcinarenes and β-cyclodextrin) with pirfenidone (PFD), an FDA-approved antifibrotic drug containing an antibacterial pyridone core. Electronic structure calculations gave insights into the interactions in the host–PFD complexes. Further, complex formation and clinical activities were investigated using spectroscopic techniques and in vitro measurements of antibacterial activity against Gram-positive and Gram-negative bacteria. An unprecedented interplay between the antibacterial activity of the polyphenolic resorcinarene hosts and their ability to interact chemically with PFD was found to improve the overall antibacterial activity of PFD. These results could revolutionize the use of synthetically modifiable resorcinarene and their analogues for fine-tuning the clinical behavior of drugs. Resorcinarene ; Chemistry ; Antibacterial activity ; Supramolecular chemistry ; Combinatorial chemistry ; Drug ; Stereochemistry ; Organic chemistry ; Molecule ; Bacteria ; Pharmacology Supramolecular Chemistry and Complexes ; Molecular Sensors and Ion Detection ; Luminescence and Fluorescent Materials
Authors: Niklas B. Arndt | Thorsten Adolphs | Heinrich F. Arlinghaus | Bastian Heidrich | Bart Jan Ravoo
Source: Langmuir (article, 2023-04-03)
Field: Materials Science — Surfaces, Coatings and Films

Arylazopyrazole-Modified Thiolactone Acrylate Copolymer Brushes for Tuneable and Photoresponsive Wettability of Glass Surfaces Photoswitches have long been employed in coatings for surfaces and substrates to harness light as a versatile stimulus to induce responsive behavior. We previously demonstrated the viability of arylazopyrazole (AAP) as a photoswitch in self-assembled monolayers (SAMs) on silicon and glass surfaces for photoresponsive wetting applications. We now aim to transfer the excellent photophysical properties of AAPs to polymer brush coatings. Compared to SAMs, polymer brushes offer enhanced stability and an increase of the thickness and density of the functional organic layer. In this work, we present thiolactone acrylate copolymer brushes which can be post-modified with AAP amines as well as hydrophobic acrylates, making use of the unique chemistry of the thiolactones. This strategy enables photoresponsive wetting with a tuneable range of contact angle change on glass substrates. We show the successful synthesis of thiolactone hydroxyethyl acrylate copolymer brushes by means of surface-initiated atom-transfer radical polymerization with the option to either prepare homogeneous brushes or to prepare micrometer-sized brush patterns by microcontact printing. The polymer brushes were analyzed by atomic force microscopy, time-of-flight secondary ion spectrometry, and X-ray photoelectron spectroscopy. Photoresponsive behavior imparted to the brushes by means of post-modification with AAP is monitored by UV/vis spectroscopy, and wetting behavior of homogeneous brushes is measured by static and dynamic contact angle measurements. The brushes show an average change in static contact angle of around 13° between <i>E</i> and <i>Z</i> isomer of the AAP photoswitch for at least five cycles, while the range of contact angle change can be fine-tuned between 53.5°/66.5° (<i>E</i>/<i>Z</i>) and 81.5°/94.8° (<i>E</i>/<i>Z</i>) by post-modification with hydrophobic acrylates. Contact angle ; Materials science ; Atom-transfer radical-polymerization ; Polymer brush ; Wetting ; Acrylate ; Photoswitch ; Trichlorosilane ; Polymer ; Copolymer ; Polymer chemistry ; Chemical engineering ; Monolayer ; Methacrylate ; X-ray photoelectron spectroscopy ; Polymerization ; Nanotechnology ; Photochemistry ; Silicon ; Chemistry ; Composite material Polymer Surface Interaction Studies ; Electrowetting and Microfluidic Technologies ; Surface Modification and Superhydrophobicity
Authors: Srinivasa Budagumpi | Brinda Kadur Narayana | Rangappa S. Keri | D. H. Nagaraju | Monica Vijayakumar | Periasamy Viswanathamurthi
Source: Applied Organometallic Chemistry (article, 2023-09-04)
Field: Chemistry — Organic Chemistry

Recent advances in catalytic and electrocatalytic applications of half‐sandwich nickel(0/II) <i>N</i>–heterocyclic carbene complexes Diverse structural and catalytic features of half‐sandwich nickel N –heterocyclic carbene (NHC) complexes provide an encouraging platform not only to address the drawbacks of other group X (palladium and platinum) metal NHC catalysts but also to bring about their superior performance. The chemistry of nickel NHC complexes has gained substantial interest from the organometallic community owing to their remarkable stability to air and moisture, easier preparation protocols, and availability of wide scope for structural fine tuning in order to achieve targeted applications. The recent progress in the field of half‐sandwich nickel(0/II) NHC complexes is covered in this review article with a special emphasis on the different synthetic strategies employed, structural characterization including spectral and X‐ray diffraction techniques, and surface morphology of the films of complexes. Both, homogeneous and electrocatalytic applications of half‐sandwich nickel NHC complexes are discussed with respect to their potential in various C–C and C–S bond constructions, targeted C–H bond activations, reductions using silylating agents, electrocatalytic glucose sensing, and electrocatalytic hydrogen evolution reactions. Donor functionalized complexes displayed improved catalytic potential in several C–C and C–S coupling reactions over non–functionalized counterparts. Overall, this assessment, from a comprehensive standpoint, affords evidence that is advantageous in the design of novel NHC ligands to access targeted half‐sandwich nickel(0/II) NHC complexes encompassing potential homogeneous catalytic and electrocatalytic applications. Nickel ; Carbene ; Catalysis ; Chemistry ; Palladium ; Platinum ; Combinatorial chemistry ; Homogeneous catalysis ; Organometallic chemistry ; Homogeneous ; Nanotechnology ; Polymer chemistry ; Organic chemistry ; Materials science Sulfur-Based Synthesis Techniques ; N-Heterocyclic Carbenes in Organic and Inorganic Chemistry ; Catalytic C–H Functionalization Methods
Authors: Muhammad Ahmad | Tehseen Nawaz | Iftikhar Hussain | Qudrat Ullah | Xi Chen | Rajat Walia | Shafqat Ali | Saikh Mohammad Wabaidur | Waqas Ul Arifeen | Kaili Zhang
Source: Journal of Energy Storage (article, 2023-07-21)
Field: Materials Science — Electronic, Optical and Magnetic Materials

Experimental and theoretical insights of binder-free magnesium nickel cobalt selenide star-like nanostructure as electrode Supercapacitor ; Materials science ; Electrode ; Electrochemistry ; Nanostructure ; Nanotechnology ; Electrolyte ; Selenide ; Energy storage ; Ternary operation ; Power density ; Nanoporous ; Cobalt ; Chemical engineering ; Metallurgy ; Chemistry ; Computer science ; Power (physics) Supercapacitor Materials and Fabrication ; Advancements in Battery Materials ; MXene and MAX Phase Materials