jablonkagroup/rise_ai_scientists huggingface dataset:
Authors: Paul A. Scattergood | Paul I. P. Elliott
Source: Inorganic Chemistry (article, 2024-09-05)
Field: Materials Science — Materials Chemistry

Prediction and Rationalization of Different Photochemical Behaviors of <i>mer</i>- and <i>fac</i>-Isomers of [Ru(pyridyltriazole)<sub>3</sub>]<sup>2+</sup> Facial and meridional isomerism of metal complexes is known to result in fundamental differences in photophysical properties. One may also envisage differences in their photochemical reactivity and therefore predict different outcomes of their light-triggered transformations. The <i>fac</i>- and <i>mer</i>-isomers of the complex [Ru(pytz)<sub>3</sub>]<sup>2+</sup> (<i>fac</i>-<b>1</b> & <i>mer</i>-<b>1</b>, pytz = 1-benzyl-4-(pyrid-2-yl)-1,2,3-triazole) were separated and isolated. <i>mer</i>-<b>1</b> undergoes a predicted pytz photodechelation process in acetonitrile to yield <i>trans</i>-[Ru(κ<sup>2</sup>-pytz)<sub>2</sub>(κ<sup>1</sup>-pytz)(NCMe)]<sup>2+</sup> (<b>2</b>) whereas unfavorable interligand steric interactions are predicted to, and indeed do prevent comparable photoreactivity for <i>fac</i>-<b>1</b>. Reversible photoisomerization of <i>fac</i>-<b>1</b> and <i>mer</i>-<b>1</b> is also observed, however. The differences in photochemical reactivity of the two isomers can be rationalized based on structural programming of the preferential accessibility of particular <sup>3</sup>MC excited states due to differences in their interligand steric interactions. Here we present an initial predictive thought experiment, subsequent experimental verification, and computational rationalization of the differences in photochemical reactivity of these two isomeric complexes. Chemistry ; Rationalization (economics) ; Reactivity (psychology) ; Zonal and meridional ; Metal ; Photochemistry ; Computational chemistry ; Stereochemistry ; Organic chemistry Photochromic and Fluorescence Chemistry ; Radical Photochemical Reactions ; Photochemistry and Electron Transfer Studies
Authors: Marcos Gadea | Aswin Asaithambi | Raúl Bernabeu‐Cabañero | Álex Farrando‐Pérez | Maria Ramos | J. C. Sancho-Garcı́a | Ilka Kriegel | María A. Díaz‐García | M. Reyes Calvo
Source: Advanced Functional Materials (article, 2024-05-27)
Field: Materials Science — Materials Chemistry

Enhancing Single‐Layer WSe<sub>2</sub> Light Emission in Perylene‐Doped Polymer Films through Efficient Energy Transfer Abstract The optical and mechanical properties of 2D semiconductors make them excellent candidates for the active components of plastic optoelectronic devices. Here, the integration of single‐layer WSe 2 (1L‐WSe 2 ) into a polystyrene (PS) film containing dispersed perylene orange (PDI‐O) molecules is investigated. The findings reveal a notable enhancement in the light emission of 1L‐WSe 2 , which occurs exclusively upon PDI‐O excitation and scales with the concentration of molecules in the PS film. Moreover, the increase in 1L‐WSe 2 photoluminescence coincides with a quenching of the PDI‐O light emission intensity and a decrease in its lifetime. These results point to efficient long‐range interactions, such as Förster energy transfer, between PDI‐O (acting as the donor) and 1L‐WSe 2 (acting as the acceptor), as the mechanism responsible for the enhanced light emission in the latter. These findings are of great interest for the development of flexible optoelectronic devices integrating active 2D materials; the polymeric matrix plays a dual role, serving as both physical support and host for organic dopants that can optimize the light emission properties of the active 2D material. Materials science ; Perylene ; Doping ; Energy transfer ; Polymer ; Layer (electronics) ; Optoelectronics ; Nanotechnology ; Optics ; Engineering physics ; Composite material ; Fluorescence 2D Materials and Applications ; Perovskite Materials and Applications ; MXene and MAX Phase Materials
Authors: Mario Mäkinen | Timo Weckman | Kari Laasonen
Source: Physical Chemistry Chemical Physics (article, 2024-01-01)
Field: Materials Science — Materials Chemistry

Modelling the growth reaction pathways of zincone ALD/MLD hybrid thin films: a DFT study ALD/MLD hybrid thin films can be fabricated by combining atomic layer deposition (ALD) and molecular layer deposition (MLD). Even though this deposition method has been extensively used experimentally, the computational work required to acquire the reaction paths during the thin film deposition process is still in dire demand. We investigated hybrid thin films consisting of diethyl zinc and either 4-aminophenol or hydroquinone using both gas-phase and surface reactions to gain extensive knowledge of the complex phenomena occurring during the process of hybrid thin film deposition. We used density functional theory (DFT) to obtain the activation energies of these kinetic-dependent deposition processes. Different processes of ethyl ligand removal as ethane were discovered, and we found that the hydroxyl group of 4-aminophenol was more reactive than the amino group in the migration of hydrogen to an ethyl ligand within a complicated branching reaction chain. Materials science ; Chemical engineering ; Chemistry ; Engineering ZnO doping and properties ; Semiconductor materials and devices ; Perovskite Materials and Applications
Authors: Maria L. Sushko
Source: MRS Bulletin (article, 2024-03-28)
Field: Materials Science — Biomaterials

Driving forces for particle-based crystallization: From experiments to theory and simulations Crystallization ; Particle (ecology) ; Biomineralization ; Monomer ; Materials science ; Chemical physics ; Crystal (programming language) ; Nanotechnology ; Crystal growth ; Nonlinear system ; Chemical engineering ; Computer science ; Chemistry ; Polymer ; Crystallography ; Physics ; Composite material ; Engineering ; Geology Calcium Carbonate Crystallization and Inhibition ; Minerals Flotation and Separation Techniques ; Paleontology and Stratigraphy of Fossils
Authors: Magdalena Bańkosz | Bożena Tyliszczak
Source: International Journal of Molecular Sciences (article, 2024-11-28)
Field: Materials Science — Materials Chemistry

Investigation of Silver- and Plant Extract-Infused Polymer Systems: Antioxidant Properties and Kinetic Release This study evaluated the impact of silver particles, suspended in <i>Arnica montana</i> flower extract, on the physicochemical characteristics and release dynamics of antioxidant compounds in PVP (polyvinylpyrrolidone)-based hydrogel systems. The hydrogels were synthesized via photopolymerization with fixed amounts of crosslinker (PEGDA) and photoinitiator, while the concentration of the silver-infused extract was systematically varied. Key properties, including the density, porosity, surface roughness, swelling capacity, and water vapor transmission rate (WVTR), were quantitatively analyzed. The results demonstrated that increasing the silver content reduced the hydrogel density from 0.6669 g/cm<sup>3</sup> to 0.2963 g/cm<sup>3</sup> and increased the porosity from 4% to 11.04%. The surface roughness parameters (Ra) rose from 8.42 µm to 16.33 µm, while the WVTR increased significantly from 65.169 g/m<sup>2</sup>·h to 93.772 g/m<sup>2</sup>·h. These structural changes directly influenced the release kinetics of antioxidant compounds, with kinetic modeling revealing silver-dependent variations in the evaluated release mechanisms. This innovative approach of integrating silver particles and plant-derived antioxidants into hydrogels highlights a novel pathway for tailoring material properties. The observed enhanced porosity and moisture regulation underscore the hydrogels' potential for biomedical applications, particularly in wound care, where controlled moisture and antioxidant delivery are critical. These findings provide new insights into how silver particles modulate hydrogel structures and functionalities. Antioxidant ; Kinetic energy ; Polymer ; Chemistry ; Chemical engineering ; Organic chemistry Nanoparticles: synthesis and applications ; Microplastics and Plastic Pollution ; Polymer Science and PVC
Authors: Jiyu Cui | Zhensong Qiu | Zhenglu Yang | Anye Jin | Xili Cui | Lifeng Yang | Huabin Xing
Source: Angewandte Chemie (article, 2024-04-06)
Field: Chemistry — Inorganic Chemistry

One‐Step Butadiene Purification in a Sulfonate‐Functionalized Metal–Organic Framework through Synergistic Separation Mechanism Abstract Porous materials that could recognize specific molecules from complex mixtures are of great potential in improving the current energy‐intensive multistep separation processes. However, due to the highly similar structures and properties of the mixtures, the design of desired porous materials remains challenging. Herein, a sulfonate‐functionalized metal–organic framework ZU‐609 with suitable pore size and pore chemistry is designed for 1,3‐butadiene (C 4 H 6 ) purification from complex C4 mixtures. The sulfonate anions decorated in the channel achieve selective recognition of C 4 H 6 from other C4 olefins with subtle polarity differences through C−H⋅⋅⋅O−S interactions, affording recorded C 4 H 6 / trans ‐2‐C 4 H 8 selectivity (4.4). Meanwhile, the shrunken mouth of the channel with a suitable pore size (4.6 Å) exhibits exclusion effect to the larger molecules cis ‐2‐C 4 H 8 , iso ‐C 4 H 8 , n ‐C 4 H 10 and iso ‐C 4 H 10 . Benefiting from the moderate C4 olefins binding affinity exhibited by sulfonate anions, the adsorbed C 4 H 6 could be easily regenerated near ambient conditions. Polymer‐grade 1,3‐butadiene (99.5 %) is firstly obtained from 7‐component C4 mixtures via one adsorption‐desorption cycle. The work demonstrates the great potential of synergistic recognition of size‐sieving and thermodynamically equilibrium in dealing with complex mixtures. Sulfonate ; Chemistry ; Adsorption ; Selectivity ; Molecule ; Metal ; Desorption ; Chemical engineering ; Inorganic chemistry ; Organic chemistry ; Catalysis ; Sodium Metal-Organic Frameworks: Synthesis and Applications ; Covalent Organic Framework Applications ; Gas Sensing Nanomaterials and Sensors
Authors: Wei Huang | Xingzhi Jiao | L. S. Hua | Qianjin Kang | Lili Zhang | Xiaoxia Luo | Linquan Bai
Source: Synthetic and Systems Biotechnology (article, 2024-11-08)
Field: Chemistry — Analytical Chemistry

Harnessing the microbial interactions from Apocynum venetum phyllosphere for natural product discovery Natural products (NPs) afforded by living-beings, especially by microscopic species, represent invaluable and indispensable reservoirs for drug leads in clinical practice. With the rapid advancement in sequencing technology and bioinformatics, the ever-increasing number of microbial biosynthetic gene clusters (BGCs) were decrypted, while a great deal of BGCs remain cryptic or inactive under standard laboratory culture conditions. Addressing this dilemma requires innovative tactics to awaken quiescence of BGCs by releasing the potential of microbial secondary metabolism for mining novel NPs. In this study, a universal strategy was proposed to induce the expression of silent BGCs by leveraging the dynamic interactions among coexisting microbial neighbors within a microbiota. This approach involves the deconstruction/reconstruction of binary interactions among the coexisting neighbors to create a pipeline for BGCs arousing. Coupled with the acquisition of 2760 microbial individuals from the <i>Apocynum venetum</i> (Luobuma, LBM) phyllosphere in a successive dilution procedure, 44 culturable isolates were screened using binary interaction, in which 12.6 % pairs demonstrated potent mutual interacting effects. Furthermore, after selecting the four most promising isolates, a full-scale metabolic inspection was conducted, in which 25.3 % of the interacting pairs showcased significant metabolomic variations with de-cryptic activities. Notably, with the aid of visualization of IMS technology, one of the physiologically functional entities, the bactericidal agent resistomycin, was elucidated from the core interacting pair between the co-culture of the <i>Streptomyces</i> sp. LBM_605 and the <i>Rhodococcus</i> sp. LBM_791. This study highlights the intrinsic interactions among coexisting microorganisms within a phyllosphere microbiota as novel avenues for exploring and harnessing NPs. Phyllosphere ; Natural product ; Natural (archaeology) ; Product (mathematics) ; Traditional medicine ; Biology ; Mathematics ; Medicine ; Bacteria Chromatography in Natural Products ; Microbial Natural Products and Biosynthesis ; Alkaloids: synthesis and pharmacology
Authors: V. S. Bondarenko | Ramin Hosseinnezhad | Andrei Voznyak
Source: Polymers (article, 2024-08-26)
Field: Materials Science — Polymers and Plastics

Role of Minor Phase Morphology on Mechanical and Shape-Memory Properties of Polylactide/Bio-Polyamide Nanocomposite In situ-generated nanofibrillar polymer-polymer composites are excellent candidates for the production of polymer materials, with high mechanical and SME properties. Their special feature is the high degree of dispersion of the in situ-generated nanofibers and the ability to form entangled nanofiber structures with high aspect ratios through an end-to-end coalescence process, which makes it possible to effectively reinforce the polymer matrix and, in many cases, increase its ductility. The substantial interfacial area, created by the in situ formed fiber/matrix morphology, significantly strengthens the interfacial interactions, which are crucial for shape fixation and shape recovery. Using the polylactide/bio-polyamide (PLA/PA) system as an example, it is shown that in situ PA fibrillation improves the mechanical and shape-memory properties of PLA. The modulus of elasticity increases by a factor of 1.4, the elongation at break increases by a factor of 30, and the shape-strain/fixity ratio and shape recovery increase from 80.2 to 97.4% and from 15.5 to 94.0%, respectively. The morphology of the minor PA phase is crucial. The best result is achieved when a physically entangled nanofibrous network is formed. Nanocomposite ; Materials science ; Polyimide ; Morphology (biology) ; Composite material ; Phase (matter) ; Chemistry ; Organic chemistry Polymer composites and self-healing ; biodegradable polymer synthesis and properties ; Silicone and Siloxane Chemistry
Authors: Rauno Sedrik | Olivier Bonjour | Nariê Rinke Dias de Souza | Alina Ismagilova | Iris Tamsalu | Veljo Kisand | Francesco Cherubini | Patric Jannasch | Lauri Vares
Source: ChemSusChem (article, 2024-08-24)
Field: Materials Science — Biomaterials

Aromatic Polymethacrylates from Lignin‐Based Feedstock: Synthesis, Thermal Properties, Life‐Cycle Assessment and Toxicity There is currently a great need for rigid, high-performance and processable bio-based polymers and plastics as alternatives to the fossil-based materials used today. Here, we report on the straightforward synthesis and polymerization of lignin-derived methacrylate monomers based on the methyl esters of 4-hydroxybenzoic, vanillic, and syringic acid, respectively. The corresponding homopolymethacrylates exhibit high glass transition temperatures (T<sub>g</sub>s) at 106, 128, and 197 °C, respectively. Rheological properties and thermal stability up to at least 277 °C indicate that these polymers are melt-processable. In addition, copolymers with methyl methacrylate are prepared to further vary and tune the polymer properties. An integrated ex-ante and prospective life-cycle assessment of key environmental impact parameters indicates similar or only slightly higher values compared to well-established fossil-based methyl methacrylate. Moreover, the toxicity towards human HeLa cell lines compares well with that of poly(methyl methacrylate). Hence, the potential availability of lignin-derived acids, combined with the straightforward and potentially upscalable monomer synthesis, make these rigid polymers appealing alternatives towards bio-based high-T<sub>g</sub> thermoplastic materials with low toxicity. Lignin ; Thermal stability ; Polymer ; Monomer ; Materials science ; Methyl methacrylate ; Polyhydroxyalkanoates ; Glass transition ; Methacrylate ; Syringic acid ; Polymerization ; Chemical engineering ; Organic chemistry ; Copolymer ; Polymer chemistry ; Chemistry biodegradable polymer synthesis and properties ; Lignin and Wood Chemistry ; Polymer composites and self-healing
Authors: Susana Ibáñez | Paula Salvà | Louise N. Dawe | Eduardo Peris
Source: Angewandte Chemie (article, 2024-01-08)
Field: Chemistry — Organic Chemistry

Guest‐Shuttling in a Nanosized Metallobox Abstract An iridium‐conjoined long and narrow metallorectangle was obtained by combining a quinoxalinophenanthrophenazine‐connected Janus‐di‐imidazolylidene ligand and pyrazine. The size and shape of this assembly together with the fused polyaromatic nature of its panels provides it with properties that are uncommon for other metallosupramolecular assemblies. For example, this nanosized ‘slit‐like’ metallobox is able show very large binding affinities with planar organic molecules in such a way, that the cavity is asymmetrically occupied by the guest molecule. This unsymmetrical conformation leads to the existence of a large amplitude motion of these guests, which slide between the two sides of the cavity of the host, thus constituting rare examples of molecular shuttles. Janus ; Planar ; Molecule ; Ligand (biochemistry) ; Affinities ; Chemistry ; Iridium ; Pyrazine ; Nanotechnology ; Chemical physics ; Crystallography ; Materials science ; Stereochemistry ; Computer science ; Organic chemistry ; Receptor Supramolecular Chemistry and Complexes ; Luminescence and Fluorescent Materials ; Porphyrin and Phthalocyanine Chemistry
Authors: Amin Hodaei | Vivek Subramanian
Source: Journal of Materials Chemistry A (article, 2024-01-01)
Field: Materials Science — Electronic, Optical and Magnetic Materials

Sub-mm<sup>3</sup> dimensional scaling of fully-integrated additively-fabricated microsupercapacitors for embedded energy storage applications Microsupercapacitors (MSCs) are attractive energy devices for applications in IoT, wireless sensors, and other microelectronic systems due to their small footprints. Microelectronics ; Materials science ; Energy storage ; Scaling ; Optoelectronics ; Nanotechnology ; Energy (signal processing) ; Physics ; Power (physics) Supercapacitor Materials and Fabrication ; Advanced Sensor and Energy Harvesting Materials ; MXene and MAX Phase Materials
Authors: Henric Steffenfauseweh | Dennis Rottschäfer | Yury V. Vishnevskiy | Beate Neumann | Hans‐Georg Stammler | Bas de Bruin | Rajendra S. Ghadwal
Source: Chemistry - A European Journal (article, 2024-08-14)
Field: Chemistry — Organic Chemistry

Non‐Kekulé <i>meta</i>‐Quinodimethane Singlet Diradicals Based on Classical N‐Heterocyclic Carbenes Diradicals based on a meta-quinodimethane (m-QDM) scaffold generally have a triplet ground state and are rather scarce. Herein, m-QDM-based non-Kekulé diradicals [3,3'-(NHC)<sub>2</sub>BP] (3-NHC) (NHC = SIPr = C{N(Dipp)CH<sub>2</sub>}<sub>2</sub>; IPr = C{N(Dipp)CH}<sub>2</sub>, Me-IPr = C{N(Dipp)CMe}<sub>2</sub>; Dipp = 2,6-iPr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>; BP = 1,1'-C<sub>6</sub>H<sub>4</sub>C<sub>6</sub>H<sub>4</sub>) featuring N-heterocyclic carbene (NHC) pendants are reported as crystalline solids. The EPR spectra of 3-NHC show both allowed (Δm<sub>s</sub> = 1) and forbidden (Δm<sub>s</sub> = 2; 'half-field') transitions characteristic for triplet diradicals. Variable temperature EPR studies however reveal a singlet ground state for 3-SIPr. Consistent with the EPR spectra, calculations predict a remarkably small singlet-triplet energy gap (ΔE<sub>ST</sub> ≤ 0.26 kcal/mol) for the 3-NHC compounds. The calculated singlet diradical character for the ground states of the 3-NHC compounds amounts to ~99 %. Diradical ; Singlet state ; Carbene ; Electron paramagnetic resonance ; Chemistry ; Ground state ; Triplet state ; Crystallography ; Stereochemistry ; Nuclear magnetic resonance ; Molecule ; Physics ; Excited state ; Atomic physics ; Organic chemistry ; Catalysis N-Heterocyclic Carbenes in Organic and Inorganic Chemistry ; Synthesis and characterization of novel inorganic/organometallic compounds ; Ammonia Synthesis and Nitrogen Reduction
Authors: Yeye Liu | Qian‐Cheng Luo | Peng‐Bo Jin | Yan‐Zhen Zheng
Source: Chinese Journal of Chemistry (article, 2024-10-07)
Field: Materials Science — Electronic, Optical and Magnetic Materials

Exploring the Magnetism of <scp>C<sub>5</sub></scp>/<scp>C<sub>2</sub>B<sub>3</sub></scp> Heteroleptic Organolanthanide Sandwiches Comprehensive Summary Two families of cyclopentadienyl (Cp)/carboranyl heteroleptic sandwiched organolanthanide complexes, namely [Ln{ η 5 : σ ‐Me 2 C(C 5 H 4 )(C 2 B 10 H 10 )} 2 ][Li(DME) 3 ] ( 1Ln , Ln = Tb, Dy, Ho, Er) and [2‐THF‐2'‐( μ 2 ‐Cl)Li(THF) 3 ‐2,2'‐Ln( nido ‐1,7‐C 2 B 9 H 11 )Cp*] ( 2Dy ), were synthesized. Family of 1Ln has been proposed based on the mixing‐ligands idea by linking Cp and nido ‐dicarborllide. However, the carborane cage of [Me 2 C(C 5 H 4 )(C 2 B 10 H 10 )] 2− deprotons and forms a mono‐C − anion rather than deboron to form dicarborllide dianion. Hence, the family of 1Ln features a dysprosocenium skeleton with extra two coordination of C − anions of carborllides. Such coordination geometry is more like a tetrahedron if abstracting the centroids of two coordinated Cp rings. In this cubic‐type geometry, no significant magnetic axiality is presented; only 1Dy and 1Tb show field‐induced slow magnetic relaxation behavior below 10 K. Inspired by 1Ln , the free pentamethylcyclopentadienyl (Cp* − ) and nido ‐dicarborllide ligands are used to sandwich central Dy 3+ ion, achieving heteroleptic complex 2Dy . The bending angle by linking the centroid of Cp* − , Dy 3+ and C 2 B 3 2− in 2Dy is increased to 132.8(1)°. As such, the effective energy barrier for magnetic reversal ( U eff ) and magnetic blocking temperature T B (ZFC) are both increased ( U eff = 616(10) K; T B = 6 K). The effort of further enhancing U eff and T B in such heteroleptic organolanthanide sandwiches should rely on keeping increasing the ligand axiality. Chemistry ; Magnetism ; Stereochemistry ; Crystallography ; Nanotechnology ; Condensed matter physics ; Physics Magnetism in coordination complexes ; Advanced NMR Techniques and Applications ; Lanthanide and Transition Metal Complexes