Ethyl Group Research Articles

Alkyl zinc complexes derived from formylfluorenimide ligands: synthesis, characterization and catalysis for hydroboration of aldehydes and ketones.

Five new alkyl zinc complexes supported by different formylfluorenimide ligands were prepared and characterized. Complex 1 was obtained by the reaction of 9-[N(CH3)2-Cy-NCH]Fl (Cy = 2-cyclohexyl) (Fl = fluorenyl) (L1) with diethylzinc (ZnEt2) in tetrahydrofuran. Reacting 9-[2-pyridyl-CH-NCH]Fl (L2) with ZnEt2 in tetrahydrofuran yielded complex 2. Under analogous conditions, complexes 3 and 4 were obtained through the reaction of 9-[2-pyridyl-CH(CH3)-NCH]Fl (L3) and 9-[8-quinoline-CH-NCH]Fl (L4) with ZnEt2 in tetrahydrofuran, respectively. The above ligands formed a tridentate four-coordinate structure with the introduction of a THF molecule along with the elimination of one ethyl group during its coordination with zinc. Notably, the formylfluorenimide ligand 9-[2-phenoxy-Ph-NCH]Fl (Ph = phenyl) (L5) bearing a phenoxy group exhibited unique reactivity compared to the other ligands and formed a bidentate three-coordinated structure when reacting with ZnEt2 in THF. All complexes were characterized via1H NMR, 13C NMR spectroscopy, and elemental analysis, with structural determination confirmed through single-crystal X-ray diffraction. Furthermore, the catalytic properties of these complexes were investigated. All these complexes exhibited excellent catalytic activities for the hydroboration of benzaldehyde, among which complex 5 demonstrated excellent catalytic performance (up to 99% yield) with a versatile substrate scope and high tolerance to functional groups (27 substrates) at a low catalyst loading (0.8 mol%) under mild reaction conditions.

Multi-stimuli actuation of a photoresponsive azobenzene based molecular switch.

There has been considerable interest in building switching functions into self-assembled monolayers with switching actuated by external stimuli such as light, electrical current, heat, pressure or chemical changes. In this study, dual switching functionality has been built into azobenzene based molecular monolayers. Switching behaviour has been compared for unsubstituted azobenzene monolayer adsorbates and two other monolayers whose ortho position on the terminal phenyl group is substituted by ethyl and isopropyl chains, respectively. The dual molecular switching functionality with light or protonation actuation is compared. EGaIn contacts to the monolayers have been used to record the J-V curves and characterize the on/off switching. This is complemented with further characterization by transition voltage spectroscopy (TVS), ultraviolet photoelectron spectroscopy (UPS), water contact angle determination, atomic force microscopy (AFM) and theoretical computations. It is concluded that side chains (the ethyl and isopropyl groups) are able to decouple neighbouring azobenzene adsorbates which promotes the photo-efficiency of isomerisation and switching. In addition, acid treatment is also applied to these three molecular layers to try to achieve dual stimuli actuation. The absorption wavelength of the azobenzene moiety red shifts by ∼100 nm for all the three protonated molecules. In the case of the unsubstituted azobenzene, its triggering wavelength is totally reversed once it is protonated. A logic truth table has been constructed for the SAM device, which shows that the simple azobenzene molecular layers exhibit the behaviour of an 'AND' logic gate which uses blue light and acid as two inputs.

Imperfections Immobilization and Regeneration in Perovskite with Redox-Active Supramolecular Assembly for Stable Solar Cells.

Imperfections in metal halide perovskites, such as those induced by light exposure or thermal stress, compromise device performance and stability. A key challenge is immobilizing volatile iodine produced by iodide oxidation and regenerating impurities like elemental lead and iodine. Here, we address this by integrating a redox-active supramolecular assembly of nickel octaethylporphyrin into perovskite film, functioning as both an immobilizer and redox shuttle. Decorated ethyl groups in porphyrin distorts the π ring, increasing the axial ligand adsorption capacity of central metal ion, while reducing intermolecular interactions and promoting iodine adsorption achieving a maximum uptake of 3.83 mg mg-1 to iodine. Adsorbed iodine transfers more electrons to Ni ions, leading to a weakened interaction within I-I bond and facilitating the production of iodide ions. Such a situation further enables selective oxidation of metallic lead defects to Pb2+. Porphyrin supramolecule facilitates hole transport across perovskite grain boundaries, leading to a champion device efficiency of 25.37% for a 0.10 cm2 active area, outperforms the value of control device being 23.96%. Modified devices without encapsulation exhibit significantly enhanced stability, maintaining over 90% of its initial performance after 1,000 hours of continuous 1-sun illumination at maximum power point at 65 oC.

Convergent Synthesis, Kinetics, and Computational Studies of Indole(Phenyl)Triazole Bi-Heterocycles Modified With Propanamides as Elastase Inhibitors.

Biological screening combined with the synthesis of heterocyclic compounds with numerous functions is the most effective approach available for pharmacological assessment of potential future medications. In the under taken research that is presented here, 4-(1H-indol-3-yl)butanoic acid was sequentially converted into 4-(1H-indol-3-yl)butanoate, 4-(1H-indol-3-yl)butanohydrazide, and 5-[3-(1H-indol-3-yl)propyl]-1,2,4-triazole-2-thiol as a nucleophile. By treating aryl amines with 3-bromopropanoyl chloride in a series of parallel reactions, different electrophiles were created, leading to the formation of N-(aryl)-3-bromopropanamides. After that, several electrophiles were used in the nucleophilic substitution process of 5 to produce the final bi-heterocyclic derivative. The structural confirmation of all the synthesized compounds was done by IR, 1H-NMR, 13C-NMR, and CHN analysis data. The enzyme inhibitory effects of these bi-heterocyclic propanamides were evaluated against elastase, and all these molecules were identified as potent inhibitors relative to the standard oleanolic acid with IC50 value 13.453±0.015µM used. The kinetics mechanism was ascribed by evaluating the Lineweaver-Burk plots, which revealed that compound 9d inhibited elastase competitively to form an enzyme-inhibitor complex. The inhibition constant Ki calculated from Dixon plots for this compound was 0.51µM. Compound 9d's activity (IC50=0.142±0.014µM) significantly increased when a slightly bulky ethyl group was replaced for the solitary methyl group in 9c at the para-position. However, compound 9e's activity was significantly lower (IC50=38.338±0.993µM) when a more polar ethoxy group was replaced at the same para-position. This was likely because of electronic considerations. These molecules also exhibited mild cytotoxicity toward red blood cell membranes, when analyzing through hemolysis. So, these molecules might be deliberated as nontoxic medicinal scaffolds for dealing with the elastase-related ailments such as lung diseases, cyclic neutropenia, pruritic skin disease, and liver infection.

水性レドックスフロー電池用アントラキノン系陽極液の機能化

Redox flow batteries (RFBs) are developed as grid-scale load-leveling technologies for renewable energy. Commercial RFBs use vanadium ions as active materials. However, their low energy density and high cost hinder wide deployment in electrical grids. To address these issues, 2,2′-(anthraquinone-2,6-diyldioxy)dipropionic acid (1Me) was reported as an aqueous anolyte to achieve two-electron redox capability, long cycle life, and high solubility.1 In this work, we improve the cycle stability by introducing a sterically bulkier substituent into the side chain of the anthraflavic acid derivative: 2,2′-(anthraquinone-2,6-diyldioxy)dibutyric acid (1Et; Figure 1). 1Et was synthesized by introducing methyl 2-bromobutyrate into anthraflavic acid, followed by saponification and subsequent neutralization with hydrochloric acid. Both 1Me and 1Et exhibit a redox potential of −0.68 V (vs. Ag/AgCl) in 1 mol L−1 KCl and 0.01 mol L−1 KOH aqueous solutions, indicating little influence of the substituent modification to a redox potential. Interestingly, 1Et shows higher solubility (1.73 mol L−1) than 1Me (1.54 mol L−1) despite an elongated hydrophobic alkyl side chain moiety. An ethyl group possesses a higher degree of freedom for rotation and vibration than a methyl group, resulting in larger dissolution entropy and hence higher solubility. Charge/discharge measurements using an H-type cell reveal that 1Et shows a higher capacity retention (0.029%/cycle) than that of 1Me (0.047%/cycle) (Figure 2) owing to a bulkier substituent preventing from nucleophilic attack on the side chain of anthraquinone. Levich analyses show comparable diffusion coefficients for 1Et (4.55×10−6 cm2 s−1) and 1Me (3.26×10− 6 cm2 s−1). These results demonstrate that introducing a bulkier substituent is an effective strategy to improve solubility in water and cycle stability without degrading other physical properties (e.g., redox potential and diffusivity).Reference[1] R. G. Godon, M. J. Aziz, et al., ACS Energy Lett. 2023, 8, 600. Figure 1

Universal Neural Network Potential Driven Molecular Dynamics Study of CO2 and O2 Evolution at the Ethylene-Carbonate/Charged-Electrode Interface

Lithium-ion batteries are currently used in large power sources such as automobiles, for which durability and safety are required. However, LIB suffers from degradation such as CO2 generation from electrolyte decomposition and O2 emission from cathode materials. These side reactions and gas generation can cause serious problems leading to ignition and explosion. It is important to understand how reactions occur at the interface during charging to generate CO2 and O2.This reaction at the cathode/electrolyte interface has been studied by various experimental and computational methods. In particular, density functional theory (DFT) simulation studies are effective in clarifying the decomposition process of the electrolyte at the atomic level. However, DFT calculations for liquid electrolytes are computationally demanding, since the number of molecules are prone to be large when considering molecule-molecule interaction1. To solve, we apply universal neural network potential (UNNP) molecular dynamics (MD) simulations to the reaction at the electrolyte solution / solid electrode interface.In this study, we focused on LixCoO2 (0≤x≤1) and LixNiO2 (0≤x≤1) as cathode materials, and ethylene carbonate (EC) as the electrolyte solvent. The model consists of Li180(1-x)Ni180O360 (Li180(1-x)Co180O360) slab and 100 EC molecules. After the structural relaxation calculations, MD calculations were performed for a 500 ps in a canonical (NVT) ensemble with a time step of 1 fs. Temperatures were 373 K and 473 K, which are below the boiling point of EC.In LiCoO2, no decomposition of the electrode or electrolyte was observed. On the other hand, CO2 was generated in the MD calculation for LiNiO2. The generation process (3 steps) is shown below.(1) Hydrogen dissociation/desorption from EC molecules.(2) Combination of the ethylene group carbon of the EC molecule, from which hydrogen dissociation has occurred, with the oxygen on the cathode surface.(3) Ring-opening between the ethylene group carbon of the EC molecule and oxygen, resulting in CO2 generation.The O2 generation phenomenon was observed to occur in the following three steps as shown in Figure 1.(1) Ni moves to the Li layer to form NiO4 tetrahedron. (Figure 1 (a) → (b))(2) Oxygen dimer is formed by the bonding of NiO4 tetrahedron and NiO5 polyhedron derived from NiO6 octahedron. (Figure 1 (c))(3) Oxygen dimer is released. (Figure 1 (d))Technical details will be presented, in particular on CO2 evolution, at the poster session.

Development of LAT1-Selective Nuclear Medicine Therapeutics Using Astatine-211.

We investigated nuclear medicine therapeutics targeting the L-type amino acid transporter 1 (LAT1). We previously reported that a nuclear medicine therapeutic drug using astatine 211 (211At), an alpha-emitting nuclide that can be produced in an accelerator and targets LAT1 as a molecular target, is effective. The seed compound was 3-[211At] Astato-α-methyl-L-tyrosine (211At-AAMT-OH-L). We used a unique labeling method. By changing the OH group of phenol to a methyl group, retention was successfully increased. It was also found that the amount of the L-isomer taken up by the D-isomer and L-isomer was clearly higher, and the L-isomer was superior as a therapeutic drug. Compounds in which the methyl group was replaced with an ethyl or propyl group were also examined, but their retention did not increase significantly. In fact, we observed increased non-specific accumulation and dynamics, suggesting that labeling may be off. In addition, 211At-AAMT-O-Me-L, which has a simple structure, was clearly superior in terms of uptake speed for several candidate compounds. As a result, we were able to develop a compound that can be easily labeled, has high specific radioactivity, is stable, and has a strong therapeutic effect.

Investigation on the development of Novel PAM structure as high-performance clay inhibitor in HT/HP conditions by using functional groups

Polyacrylamide (PAM) molecular structures are not stable at higher temperatures, limiting their effectiveness in water-based drilling fluid (WBDF) applications. This study focuses on identifying functional groups that can enhance the thermal stability of PAM structure. It presents a comprehensive and comparative analysis of the swelling inhibition capacity of both low and high molecular weight (MW) PAM-based polymers at high temperature and high pressure (HT/HP). The mechanism by which modified PAM interacts with and adsorbs to the clay (Na-MMT) surface is examined, along with an analysis of the surface properties of the clay minerals. Therefore, molecular dynamic (MD) simulation results revealed that the Novel PAM polymers with high MW containing ethyl and benzyl groups demonstrate greater stability and more controlled deformation behavior compared to conventional PAM at HT conditions. Surface modification and hydrophobic effects were observed in the interactions between polymers and Na-MMT. Low MW PAM-based polymers showed larger fluctuations in d-spacing, indicating various or more disruptive interactions. In contrast, the insertion of high MW PAM-based polymer resulted in significantly narrower and lower d-spacing fluctuation ranges. The Novel PAM exhibited superior performance, providing lower d-spacing fluctuations compared to both low MW PAM-based polymers and standard PAM. Across a temperature range from 300 to 600°K, the Novel PAM consistently improved polymer adsorption on the Na-MMT surface compared to standard PAM. Indicating that the modifications effectively reduce the interaction between Na-MMT particles and water molecules while enhancing the interaction between the polymer and Na-MMT, potentially leading to more stable structures in HT/HP environments. The enhanced stability suggests that Novel PAM is more suitable for WBDF applications, as it is less prone to structural changes and can maintain its integrity under harsh conditions. The modifications provide the polymer with better resilience, potentially leading to improved performance in practical applications.

Comprehensive Study on Cell Components in High‐Voltage Pouch Cells with Lithium Perchlorate: Decomposition, Transesterification, Chlorination, Deposition, and Self‐Discharge

AbstractBattery development has traditionally focused on high energy and long lifetime cells, but there is now a shift towards their sustainability and safety. One example of this trend is the search for fluorine‐free conductive salts. The overwhelming majority of lithium‐ion conductive salts contain fluorine, which is critical regarding their environmental impact, sustainability, and toxicology. In this study, we perform a comprehensive investigation of the performance and aging mechanisms of cell components with LiClO4 as conductive salt in high‐voltage NMC622‖Graphite pouch cells. The cells containing LiClO4 show poorer electrochemical performance compared to their LiPF6 equivalents. However, to the best of our knowledge, a mechanistic understanding of the effect of LiClO4 on the aging of electrode and electrolyte components for high‐voltage cells is largely missing. Developing such an understanding will pave the way toward designing alternative salts to LiPF6, ultimately leading to fluorine‐free and more sustainable battery cells. Our results show, that the chlorination of ethyl methyl carbonate at both methyl and ethyl groups and the formation of large (Liw)AlxOyClz composite deposits on the cathode surface result from perchlorate degradation at the cathode. This leads to increased cell resistance, reduced capacity retention, and accelerated degradation of the LiClO4‐containing electrolytes.

Computational Study of Carbon Dioxide Capture by Tertiary Amines.

The reaction mechanisms and corresponding structure-activity relationships of tertiary amines with respect to CO2 capture have been investigated using density functional theory (DFT) calculations. The reaction mechanism for CO2 capture via base-catalyzed hydration to form bicarbonate is proposed to proceed in a single step involving proton transfer and the formation of a carbon-oxygen bond. Based on the height of the reaction barriers, we suggest that amines containing side chains with the ethyl group, along with a single hydroxyl group, and cyclic structures, are especially active for CO2 capture. The activation barrier is shown to be a descriptor for predicting the experimental CO2 loading values. To enhance the prediction accuracy for CO2 loading, we employ the sure-independence screening and sparsifying operator (SISSO) method, which can scan a large pool of mathematical terms stemming from combining DFT-derived descriptors to select the superior ones. Thus, we can predict the CO2 loading with acceptable accuracy from the obtained mathematical expression. Since the computational workload of applying this expression is negligible, this facilitates high-throughput screening and accelerates the design of tertiary amines for CO2 capture.

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks.

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both -F and -iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet-mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high-performance BLMs using porous materials for enantioselective separation.

Highly Enantioselective Transportation Across Liquid Membranes Mediated by Porous Covalent Organic Frameworks

Chiral liquid membrane separation is crucial in pharmaceuticals and chemical synthesis for its simplicity and stability, yet designing membrane carriers that enable efficient enantioseparation remains a challenge. Here, we demonstrated for the first time that chiral porous materials can act as mobile carriers of bulk liquid membranes (BLMs) to enhance enantioselective transport and separation. We design and prepare three 2D chiral covalent organic frameworks (CCOFs) by imine condensations of a chiral dialdehyde with triamines containing ethyl, fluorine and/or isopropyl groups. These isostructural CCOFs feature ABC stacking, excellent water, acid and base tolerance, and chiral amine groups in 1D porous channels, promoting efficient enantioselective transportation of amino acid enantiomers. Among them, the CCOF with both ‐F and ‐iPr groups showing superior transport performance. Exfoliating the CCOF into chiral nanosheets creates flexible layers with accessible active sites, enabling nanosheet‐mediated liquid membranes to separate chiral drug enantiomers, a feat unattainable with the pristine CCOF. This work establishes CCOFs as a promising platform for chiral BLM separations and will guide the design of high‐performance BLMs using porous materials for enantioselective separation.

The reaction mechanism of p-hydroxystyryl-substituted BODIPY with ABTS•+ and Fe3+ in solutions and in liposomes

The reaction mechanism of p-hydroxystyryl-substituted BODIPY (BOH) with two oxidative cations, namely ABTS•+ and Fe3+, was investigated in a water–ethanol mixed solution and in liposome suspensions, respectively, using different spectroscopic methods. In solution, the oxidation of BOH (with orange fluorescence) by the two cations occurred at the ethylene group (CC) locating between the dipyrrole and phenol groups and resulted in conjugation-truncated products exhibiting characteristic green fluorescence emission. In heterogeneous small unilamellar vesicles (SUV), water soluble ABTS•+ was evidenced to oxidize BOH embedded in the lipid bilayers of SUV, while Fe3+ did not. The lack of reaction between Fe3+ and BOH was attributed to the complexation between Fe3+ and the phenolic hydroxyl group of BOH on the surface of the SUV. The reaction kinetics results indicated that, in homogeneous solution, the oxidation rate of Fe3+ was three orders of magnitude slower than that of ABTS•+ for BOH. The location and orientation of BOH within the SUV were discussed based on the reaction phenomena. BOH could be as a good antioxidant fluorescent prober for ABTS•+ detection with a detection limit of 1.5 * 10−7 M and a linear rang of 0–4.93 μM. What’s more, the amphiphilic BOH dispersed in the round GUV (BOH + GUV) could show the bright red fluorescence. This research suggests the significant potential of BOH as an antioxidant fluorescent probe for in situ bioimaging.

Crystal structure, Hirshfeld surface analysis, DFT and molecular docking studies of ethyl 5-amino-2-bromoisonicotinate

In the title compound, C8H9BrN2O2, the C—O—C—C torsion angle between isonicotine and the ethyl group is 180.0 (2)°. Intramolecular N—H...O and C—H...O interactions consolidate the molecular structure. In the crystal, N—H...N interaction form S(5) zigzag chains along [010]. The most significant contributions to the Hirshfeld surface arise from H...H (33.2%), Br...H/H...Br (20.9%), O...H/H...O (11.2%), C...H/H...C (11.1%) and N...H/H...N (10%) contacts. The topology of the three-dimensional energy frameworks was generated using the B3LYP/6–31 G(d,p) model to calculate the total interaction energy. The net interaction energies for the title compound are E ele = 59.2 kJ mol−1, E pol = 15.5 kJ mol−1, E dis = 140.3 kJ mol−1 and E rep = 107.2 kJ mol−1 with a total interaction energy E tot of 128.8 kJ mol−1. The molecular structure was optimized by density functional theory (DFT) at the B3LYP/6–311+G(d,p) level and the theoretical and experimentally obtained parameters were compared. The frontier molecular orbitals HOMO and LUMO were generated, giving an energy gap ΔE of 4.0931 eV. The MEP was generated to identify active sites in the molecule and molecular docking studies carried out with the title compound (ligand) and the covid-19 main protease PDB ID: 6LU7, revealing a moderate binding affinity of −5.4 kcal mol−1.

Structural mechanisms of potent lysophosphatidic acid receptor 1 activation by nonlipid basic agonists.

Lysophosphatidic acid receptor 1 (LPA1) is one of the G protein-coupled receptors activated by the lipid mediator, lysophosphatidic acid (LPA). LPA1 is associated with a variety of diseases, and LPA1 agonists have potential therapeutic value for treating obesity and depression. Although potent nonlipid LPA1 agonists have recently been identified, the mechanisms of nonlipid molecule-mediated LPA1 activation remain unclear. Here, we report a cryo-electron microscopy structure of the human LPA1-Gi complex bound to a nonlipid basic agonist, CpY, which has 30-fold higher agonistic activity as compared with LPA. Structural comparisons of LPA1 with other lipid GPCRs revealed that the negative charge in the characteristic binding pocket of LPA1 allows the selective recognition of CpY, which lacks a polar head. In addition, our structure show that the ethyl group of CpY directly pushes W2716.48 to fix the active conformation. Endogenous LPA lacks these chemical features, which thus represent the crucial elements of nonlipid agonists that potently activate LPA1. This study provides detailed mechanistic insights into the ligand recognition and activation of LPA1 by nonlipid agonists, expanding the scope for drug development targeting the LPA receptors.

Systematic study on the hydrogen abstraction reactions from oxygenated compounds by H and HO2

AbstractTo extend the rule‐based approach for hydrogen abstraction reactions from oxygenated compounds, a systematic investigation was performed to examine the reactivity of gas‐phase hydrogen abstraction reactions from alkyl groups (methyl and ethyl groups) bound to oxygen atoms in five types of oxygenated compounds (alcohols, ethers, formate esters, acetate esters, and carbonate esters) by H atoms and HO2 radicals comprehensively considering rotational conformers. Quantum chemical calculations were conducted at the CBS‐QB3 level for stationary points. Rate constants were determined employing conventional transition state theory (TST). For hydrogen abstraction reactions by H, the rotational conformer distribution partition function was employed to approximate partition functions, owing to the similarity in vibrational energy‐level structures among conformers. In hydrogen abstraction reactions by HO2, the vibrational structures of transition‐state (TS) conformers varied significantly due to the hydrogen bonding, leading to an inappropriate evaluation of rate constants when using the lowest‐energy conformer as a representative. Therefore, the rate constants were calculated by the multi‐structural TST. It was revealed that the differences in functional groups containing O atoms mainly affect the bond dissociation energies of the C–H bonds and the activation energies of hydrogen abstraction reactions only when the C atoms are adjacent to the O atoms. Additionally, it was found that hydrogen bonds formed in the TSs show minor effect on rate parameters for the overall rate constants, apart from the reduction of the pre‐exponential factors for the H‐abstraction reactions from the methylene position of ethyl groups. The comparison with the rate constants from previous studies showed reasonable results, indicating that the rate constants in this study, which thoroughly consider rotational conformers, can be the current best estimates.

Formation of Radical-like NH Ligand from NH3 at Ambient Conditions Mediated by Dialkyl Rare-Earth Complexes.

Although intensive work on ammonia activation has been carried out in recent decades, generating nitrogen-centered radicals from NH3 under ambient conditions remains quite challenging. In the presented research, the conversion of NH3 to radical-like NH ligand has been achieved by the reactions of a series of dialkyl rare-earth (RE) complexes (1-RE, RE = Tb, Dy, Y, Ho, Er, Yb, and Lu) supported by β-diketiminate ligands with NH3 in n-hexane at room temperature, resulting in the formations of the radical-like μ3-NH ligands containing trinuclear RE complexes (2-RE). The radical-like feature of the μ3-NH ligand was revealed by electron paramagnetic resonance and magnetic measurements, radical trapping experiments, and computational spin density analysis. In addition, H2 was detected to form during the reaction of 1-RE with NH3, indicating that the radical-like μ3-NH ligand was likely to be generated via N-H bond homolysis. Moreover, the solvents and coordination pattern of β-diketiminate ligands are crucial for the formation of the radical-like μ3-NH ligand from NH3. When toluene instead of n-hexane was used in the reaction of 1-RE with NH3, an array of octaamido tetranuclear RE complexes (3-RE) was obtained. The reaction of the dialkyl yttrium complex (4-Y) bearing a modified β-diketiminate ligand, in which the two mesityl substituents are replaced by a 2,6-diisopropylphenyl group and a 2-(dimethylamino)ethyl group, with NH3 in both n-hexane and toluene only yielded a tetranuclear yttrium complex carrying the dianionic closed-shell μ3-NH ligands (5-Y).

Biotoxicity Evaluation of Biodegradable Polymeric Particles: Exploring the Possible Adverse Impacts on Biological Systems

ABSTRACTThis study aimed to investigate the impact of plastic particles on cell viability and tissue toxicity. The cells were subjected to incubation with plastic particles immobilized in agar gels, resulting in minimal cell death and cytotoxicity. Furthermore, direct exposure of various cell types to suspended plastic particles showed negligible effects on cell viability, with no observed lysis or growth inhibition. Staining techniques revealed minimal plastic particle‐induced cell death, with the majority of cells remaining viable. However, histological evaluations of mouse tissues demonstrated that the nondegradable low‐density poly(ethylene) (LDPE) groups exhibited severe irritation, characterized by an excessive presence of macrophages, neutrophils, fibrosis, fat infiltration, and increased blood vessel formation in subcutaneous tissue. In contrast, biodegradable neat poly(butylene succinate) (KRICT‐PBS) and cellulose nanocrystals/PBS nanocomposite (CNC‐PBS) groups induced minimal toxicity. Interestingly, the intravenous injection of KRICT‐PBS and CNC‐PBS degradate solutions in mice exhibited mild toxicity, suggesting no significant damage to normal kidney and liver function.

(1H-Benzo-diazol-2-ylmeth-yl)di-ethyl-amine.

In the crystal of the title compound, C12H17N3, the mol-ecules are linked by N-H⋯N hydrogen bonds, generating a C(4) chain extending along the c-axis direction. One of the ethyl groups is disordered over two sets of sites with a refined occupancy ratio of 0.582 (15):0.418 (15).

Icosapent ethyl by baseline small dense low-density lipoprotein cholesterol: an analysis of REDUCE-IT

Abstract Background Small dense low-density lipoprotein cholesterol (sdLDL-C) is associated with cardiovascular (CV) risk. Purpose We assessed if baseline sdLDL-C modified the effect of icosapent ethyl among patients in REDUCE-IT. Methods REDUCE-IT randomized patients to icosapent ethyl vs placebo. In this post hoc analysis, patients ≥45 years with CV disease or ≥50 years with diabetes and CV risk factors were included. Patients were required to have triglycerides of 135-499 mg/dL and low-density lipoprotein cholesterol (LDL-C) of 41-100 mg/dL. Exclusion criteria included severe heart failure, acute severe liver disease, or hemoglobin A1c >10%. Patients were stratified by baseline calculated sdLDL-C. A threshold of 46 mg/dL was chosen because sdLDL-C greater than this cutoff has predicted CV risk despite well-controlled LDL-C. The primary outcome included a composite of CV death, nonfatal myocardial infarction (MI), nonfatal stroke, coronary revascularization, or unstable angina. The key secondary composite outcome included CV death, nonfatal MI, or nonfatal stroke. Outcomes were assessed with Cox proportional hazard models and interaction analyses were conducted to assess heterogeneity in treatment effect by baseline sdLDL-C. Results REDUCE-IT included 8179 patients, with 8157 (99.7%) patients having sdLDL-C data. Among these patients, 7698 (94.4%) had sdLDL-C <46 mg/dL and 459 (5.6%) had sdLDL-C ≥46 mg/dL. Median sdLDL-C was 34.2 mg/dL (interquartile range [IQR]: 30.3, 38.4 mg/dL) in the lower sdLDL-C group and 48.4 mg/dL (IQR: 47.1, 50.6 mg/dL) in the higher sdLDL-C group (Table). The placebo group had a greater event rate in the higher sdLDL-C group compared to the lower sdLDL-C group (72.0 vs 56.4 events per 1000 p-y), though event rates in the icosapent ethyl group were similar by sdLDL-C group (44.1 vs 43.3 events per 1000 p-y, respectively). Icosapent ethyl reduced the rate of the primary outcome compared with placebo (17.2% vs 22.0%; hazard ratio [HR]: 0.75 [95% CI: 0.68, 0.83]; P<0.0001). The number needed to treat [NNT] to avoid one primary endpoint event was 21. In the lower sdLDL-C group, icosapent ethyl decreased rates of the primary outcome (43.3 events per 1000 patient-years [p-y]) compared with the placebo group (56.4 events per 1000 p-y) (17.3% vs 21.7%; HR: 0.77 [95% CI: 0.69, 0.85]; NNT: 22). Similarly, in the higher sdLDL-C group, icosapent ethyl decreased the rate of the primary outcome (44.1 events per 1000 p-y) compared with the placebo group (72.0 events per 1000 p-y) (16.6% vs 26.4%; HR: 0.58 [95% CI: 0.38, 0.88]; NNT: 10). There was no significant interaction between treatment benefit and baseline sdLDL-C for the primary (Pinteraction = 0.22) and key secondary outcome (Pinteraction = 0.82). Findings were overall similar for the other secondary outcomes (Figure). Conclusion Icosapent ethyl reduced CV outcomes in patients with high CV risk and elevated triglycerides irrespective of low or high sdLDL-C.