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Lung cancer poses a serious threat to people's lives and health due to its high incidence rate and high mortality rate, making it necessary to effectively conduct early screening. As an important biomarker for lung cancer, the detection of n-propanol gas suffers from a low response value and a high detection limit. In this paper, flower-like Ho-doped ZnO was fabricated by the coprecipitation method for n-propanol detection at subppm concentrations. The gas sensor based on the 3% Ho-doped ZnO showed selectivity to n-propanol gas. Its response value to 100 ppm n-propanol was 341 at 140 °C, and its limit of detection (LOD) was about 25.6 ppb, which is lower than that of n-propanol in the breath of a healthy person (150 ppb). The calculation results show that the adsorption of n-propanol on a Ho-doped ZnO surface releases more energy than isopropanol, ethanol, formaldehyde, acetone, and ammonia. The enhanced gas-sensing properties of the Ho-doped ZnO material can be attributed to the fact that the Ho-doping distorts the crystal lattice of the ZnO, increases the specific surface area, and generates a large amount of oxygen defects. In addition, the doped Ho partially forms a Ho2O3/ZnO heterojunction in the material and improves the gas-sensing properties. The 3% Ho-doped ZnO material is expected to be a promising candidate for the trace detection of n-propanol gas.
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The pursuit of highly efficient electrocatalysts for the alkaline hydrogen evolution reaction (HER) is of paramount importance for water splitting. However, it is still a formidable task in Mo2C-based materials because of the agglomeration and strong Mo-H binding of Mo2C units. Herein, a novel CeOCl-CeO2/Mo2C heterostructure nesting within a three-dimensional porous nitrogen-doped carbon matrix has been designed and used for catalyzing HER via simultaneous morphology and heterointerface engineering. As expected, the optimal CeOCl-CeO2(0.2)/Mo2C@3DNC exhibits impressive HER activity, with a low overpotential of 156 mV at a current density of 10 mA cm-2 coupled with a slight Tafel slope of 62.20 mV dec-1. Introducing a Ce promoter, that is CeOCl and CeO2, would endow the interface with an internal electric field and electron redistribution between CeOCl-CeO2 and Mo2C induced by the heterogeneous work function difference. Moreover, experimental investigation and density functional calculations confirm that the CeOCl-CeO2/Mo2C heterointerface can downshift the d-band center of the active Mo center, weakening the strength of the Mo-H coupling. This proposed concept, engineering Ce-based promoters into active entities involved in the heterostructure to modulate intermediate adsorption, offers a great opportunity for the design of superior electrocatalysts for energy conversion.
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Triethylamine is a common volatile organic compound (VOC) that plays an important role in areas such as organic solvents, chemical industries, dyestuffs, and leather treatments. However, exposure to triethylamine atmosphere can pose a serious threat to human health. In this study, gas-sensing semiconductor materials of LaFeO3 nano materials with different Mo-doping ratios were synthesized by the sol-gel method. The crystal structures, micro morphologies, and surface states of the prepared samples were characterized by XRD, SEM, and XPS, respectively. The gas-sensing tests showed that the Mo doping enhanced the gas-sensing performance of LaFeO3. Especially, the 4% Mo-doped LaFeO3 exhibited the highest response towards triethylamine (TEA) gas, a value approximately 11 times greater than that of pure LaFeO3. Meantime, the 4% Mo-doped LaFeO3 sensor showed a remarkably robust linear correlation between the response and the concentration (R2 = 0.99736). In addition, the selectivity, stability, response/recovery time, and moisture-proof properties were evaluated. Finally, the gas-sensing mechanism is discussed. This study provides an idea for exploring a new type of efficient and low-cost metal-doped LaFeO3 sensor to monitor the concentration of triethylamine gas for the purpose of safeguarding human health and safety.
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Herein, a patterned rod-like CoP@NiCoP core-shell heterostructure is designed to consist of CoP nanowires cross-linked with NiCoP nanosheets in tight strings. The interfacial interaction within the heterojunction between the two components generates a built-in electric field that adjusts the interfacial charge state and create more active sites, accelerating the charge transfer and improving supercapacitor and electrocatalytic performance. The unique core-shell structure suppresses the volume expansion during charging and discharging, achieving excellent stability. As a result, CoP@NiCoP exhibits a high specific capacitance of 2.9 F cm-2 at a current density of 3 mA cm-2 and a high ion diffusion rate (Dion is 2.95 × 10-14 cm2 s-1 ) during charging/discharging. The assembled asymmetric supercapacitor CoP@NiCoP//AC exhibits a high energy density of 42.2 Wh kg-1 at a power density of 126.5 W kg-1 and excellent stability with a capacitance retention rate of 83.8% after 10 000 cycles. Furthermore, the modulated effect induced by the interfacial interaction also endows the self-supported electrode with excellent electrocatalytic HER performance with an overpotential of 71 mV at 10 mA cm-2 . This research may provide a new perspective on the generation of built-in electric field through the rational design of heterogeneous structures for improving the electrochemical and electrocatalytical performance.
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It is a challenging task to utilize efficient electrocatalytic metal hydroxide-based materials for the oxygen evolution reaction (OER) in order to produce clean hydrogen energy through water splitting, primarily due to the restricted availability of active sites and the undesirably high adsorption energies of oxygenated species. To address these challenges simultaneously, we intentionally engineer a hollow star-shaped Ag/CoMo-LDH heterostructure as a highly efficient electrocatalytic system. This design incorporates a considerable number of heterointerfaces between evenly dispersed Ag nanoparticles and CoMo-LDH nanosheets. The heterojunction materials have been prepared using self-assembly, in situ transformation, and spontaneous redox processes. The nanosheet-integrated hollow architecture can prevent active entities from agglomeration and facilitate mass transportation, enabling the constant exposure of active sites. Specifically, the powerful electronic interaction within the heterojunction can successfully regulate the Co3+/Co2+ ratio and the d-band center, resulting in rational optimization of the adsorption and desorption of the intermediates on the site. Benefiting from its well-defined multifunctional structures, the Ag0.4/CoMo-LDH with optimal Ag loading exhibits impressive OER activity, the overpotential being 290 mV to reach a 10 mA cm-2 current density. The present study sheds some new insights into the electron structure modulation of hollow heterostructures toward rationally designing electrocatalytic materials for the OER.
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Accomplishing a green hydrogen economy in reality through water spitting ultimately relies upon earth-abundant efficient electrocatalysts that can simultaneously accelerate the oxygen and hydrogen evolution reactions (OER and HER). The perspective of electronic structure modulation via interface engineering is of great significance to optimize electrocatalytic output but remains a tremendous challenge. Herein, an efficient tactic has been explored to prepare nanosheet-assembly tumbleweed-like CoFeCe-containing precursors with time-/energy-saving and easy-operating features. Subsequently, the final metal phosphide materials containing multiple interfaces, denoted CoP/FeP/CeOx, have been synthesized via the phosphorization process. Through the optimization of the Co/Fe ratio and the content of the rare-earth Ce element, the electrocatalytic activity has been regulated. As a result, bifunctional Co3Fe/Ce0.025 reaches the top of the volcano for both OER and HER simultaneously, with the smallest overpotentials of 285 mV (OER) and 178 mV (HER) at 10 mA cm-2 current density in an alkaline environment. Multicomponent heterostructure interface engineering would lead to more exposed active sites, feasible charge transport, and strong interfacial electronic interaction. More importantly, the appropriate Co/Fe ratio and Ce content can synergistically tailor the d-band center with a downshift to enhance the per-site intrinsic activity. This work would provide valuable insights to regulate the electronic structure of superior electrocatalysts toward water splitting by constructing rare-earth compounds containing multiple heterointerfaces.
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Mononuclear rare-earth metal alkyl complexes supported by tetradentate dianionic bis(amino-oxazoline) ligands have been synthesized, and their reactivity toward small molecules and catalytic performance on ring-opening polymerization have been studied. Treatment of Ln(CH2SiMe3)3(THF)2 (Ln = Sc, Y; THF = tetrahydrofuran) with the bis(amino-oxazoline) proligand H2L afforded the corresponding rare-earth metal monoalkyl complexes L-Ln(CH2SiMe3)(THF)x (Ln = Sc, x = 0 (1); Ln = Y, x = 1 (2)). The isopropyl-substituted Sc alkyl complex L'-Sc(CH2SiMe3) (3) and the analogue Y silylamide complex L-Y[N(SiHMe2)2] (4) have been prepared by a similar method. Complexes 1 and 2 were stable in solution at room temperature but transformed gradually at elevated temperature to give a nucleophilic addition product for Sc (5) and an oxazoline ring-opened dimeric complex for Y (6). Reactions of 1 with elemental sulfur and selenium each led to insertion of one chalcogen into the Sc-C bond, and the corresponding six-coordinate mononuclear chalcogenolate complexes L-Sc(ECH2SiMe3)(THF) (E = S (7), Se (8)) were isolated. Treatment of 1 with an equimolar amount of aniline yielded the Sc anilide complex L-Sc(NHC6H5) (9), whereas the reaction of 1 with [NHEt3][BPh4] afforded the Sc ion-pair [L-Sc][BPh4] (10), which upon recrystallization led to formation of a THF-solvated product [L-Sc(THF)][BPh4] (11). Single-crystal X-ray diffraction analyses of complexes 1-3, 7-9, and 11 revealed the flexible coordination capability of the tetradentate bis(amino-oxazoline) ligand of upholding a mononuclear metal center via a torsion of the diaminobiphenyl axis. Complexes 1-4 were active catalysts for initiating the ring-opening polymerization of rac-lactide with good activity (TOF up to 3204 h-1) and heteroselectivity (Pr = 0.65-0.71). This study highlights the applicability of the well-defined tetradentate bis(amino-oxazoline) ligands for mononuclear rare-earth metal complexation and shed light on the new potential of rare-earth metal catalysts bearing this type of easily derivatizable polydentate ligand.
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Herein, through a morphology-inherited annealing treatment of a hollow Fe-doped MOF-5 octahedron as the self-sacrificing template, we report the synthesis of concave ZnFe2O4 hollow octahedral nanocages as sensing materials, which exhibited high performance, including unprecedented excellent sensitivity, good selectivity, and cyclic stability at ultralow working temperature (120 °C).
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Mercury(II) ions have emerged as a widespread environmental hazard in recent decades. Despite different kinds of detection methods reported to sense Hg(2+) , it still remains a challenging task to develop new sensing molecules to replenish the fluorescence-based apparatus for Hg(2+) detection. This communication demonstrates a novel fluorescent sensor using UiO-66-NH2 and a T-rich FAM-labeled ssDNA as a hybrid system to detect Hg(2+) sensitively and selectively. To the best of our knowledge, it has rarely been reported that a MOF is utilized as the biosensing platform for Hg(2+) assay.
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Técnicas Biossensoriais/métodos , DNA de Cadeia Simples/química , DNA/química , Íons/química , Mercúrio/análise , Mercúrio/química , Limite de DetecçãoRESUMO
A new anionic framework {[Me2NH2]0.125[In0.125(H2L)0.25]â xDMF}n (1) with one-dimensional (1D) channels along the c axis of about 13.06×13.06â Å(2), was solvothermally synthesized and well characterized. Post-synthetic cation exchange of 1 with Eu(3+), Tb(3+), Dy(3+), Sm(3+) afforded lanthanide(III)-loaded materials, Ln(3+)@1, with different luminescent behavior, indicating that compound 1 could be used as a potential luminescent probe toward different lanthanide(III) ions. Additionally, compound 1 exhibits selective adsorption ability toward cationic dyes. Moreover, the RhB@1 realized the probing of different organic solvent molecules by tuning the energy transfer efficiency between two different emissions, especially for sensing DMF. This work highlights the practical application of luminescent guest@MOFs as sensors, and it paves the way toward other one/multi-color luminescent host-guest systems by rational selection of MOF hosts and guest chromophores with suitable emissive colors and energy levels.
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High-/medium-entropy materials have been explored as promising electrocatalysts for water splitting due to their unique physical and chemical properties. Unfortunately, state-of-the-art materials face the dilemma of explaining the enhancement mechanism, which is now limited to theoretical models or an unclear cocktail effect. Herein, a medium-entropy NiCoFeMnP with an advanced hierarchical particle-nanosheet-tumbleweed nanostructure has been synthesized via simple precursor preparation and subsequent phosphorization. Evaluated as the electrocatalyst for oxygen evolution reaction (OER), the medium-entropy NiCoFeMnP displays a lower overpotential of 272 mV at a current density of 10 mA cm-2, and more favorable kinetics than the binary NiFeP, ternary NiCoFeP, quaternary NiCoFeCuP and NiCoFeCrP counterparts, and other reported high-/medium-entropy electrocatalysts. Careful experimental analyses reveal that the incorporation of Mn can significantly regulate the electronic structure of Ni, Co, and Fe sites. More importantly, the Mn introduction and entropy stabilization effect in the reconstructed metal (oxy)hydroxide simultaneously promote the lattice oxygen mechanism, improving the activity. This work sheds new light on the design of high-/medium-entropy materials from an in-depth understanding of the underlying mechanism for improving energy conversion efficiency.
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Nano bowl-like Co-Co6Mo6C2 coated by N,P co-doped carbon (Co-Co6Mo6C2@NPC) is reported as an electrocatalyst for Zn-air batteries. Co-Co6Mo6C2@NPC only needs an overpotential of 210 mV at 10 mA cm-2 for the OER, and the half-wave potential for the ORR is 0.81 V. In addition, the Co-Co6Mo6C2@NPC based battery shows a large open-circuit voltage of 1.335 V and a maximum power density of 160.5 mW cm-2, as well as good stability. The improved catalytic performance can be ascribed to the co-existence of Co6Mo6C2 and Co species to improve the intrinsic catalytic activity, and the bowl-like nanostructure to facilitate the mass transfer.
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In recent years, nitrosamines have been discovered in some types of drug products that becomes a current regulatory hotspot, and have attracted a lot attention from both regulatory authorities and industry. This manuscript provided an industry perspective on the nitrosamines research. A liquid chromatography coupled with tandem mass spectrometryï¼LC-MS/MSï¼method was developed and applied for the quantification of N-nitrosodimethylamine (NDMA) in metformin hydrochloride sustained-release tablets (MET). The key factors resulting in the NDMA formation in MET were identified through forced degradation and drug-excipient studies, which included high temperature, dimethylamine, strong alkali and oxidation conditions, peroxide and alkaline components contained in the formulation as well as the nitrite and nitrate impurities that might be presented in certain excipients. Further, API particle size and water content of the drug product would also affect the growth rate of NDMA. Therefore, the following mitigation strategies to reduce the risk of nitrosamines in the finished drug product are proposed in this manuscript: 1) avoid the use of excipients containing nitrite, nitrate and peroxide impurities; 2) avoid high temperature and strong alkaline environment in the production and storage condition; 3) maintain an appropriate water content level in the formulation. Based on the above principles, it was recommended to add antioxidant or incorporate excipient such as Na2CO3 to modify the formulation pH to weak basic environment in the formulation of MET, which can could effectively prevent formation of NDMA in the stability process.
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Metformina , Nitrosaminas , Dimetilnitrosamina/química , Derivados da Hipromelose , Excipientes/análise , Cromatografia Líquida , Nitritos , Preparações de Ação Retardada , Nitratos , Espectrometria de Massas em Tandem , Nitrosaminas/química , Comprimidos , Peróxidos , ÁguaRESUMO
Oseltamivir phosphate is widely used to treat and prevent influenza, and is available in the form of capsules, powder for oral suspension, pediatric solutions, and granules. Because of the amino group, oseltamivir is easy to react with the excipients of the formulation to generate drug-excipient interaction impurities. In this research, two degradation products in a commercial oseltamivir phosphate powder for oral suspension due to interaction between API and citrate were investigated. They were characterized to be 3-((-6-acetamido-3-(ethoxycarbonyl)-5-(pentan-3-yloxy)cyclohex-3-en-1-yl)carbamoyl)-3-hydroxypentanedioic acid and 2-(2-((-6-acetamido-3-(ethoxycarbonyl)-5-(pentan-3-yloxy)cyclohex-3-en-1-yl)amino)-2-oxoethyl)-2-hydroxysuccinic acid by MS and NMR, respectively. Furthermore, the formation mechanisms of these impurities were verified, and the method of analysis of covariance was used to assess the rate of impurities' degradation. HIGHLIGHTS: Two excipient interaction degradation products in commercial oseltamivir phosphate powder for oral suspension were studied and elucidated in detail via LC-MS/MS and NMR. The incompatibility risk of pH conditioners such as citrate and citric acid with formulations that contain an amino group was disclosed in this article. Analysis of covariance was demonstrated to assess the impact of various formulations and preparation techniques on the rate of impurity degradation.
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Excipientes , Oseltamivir , Humanos , Criança , Oseltamivir/química , Excipientes/química , Pós , Cromatografia Líquida , Espectrometria de Massas em Tandem , Contaminação de Medicamentos , Fosfatos , CitratosRESUMO
The oxygen evolution reaction (OER) is kinetically sluggish due to the limitation of the four-electron transfer pathway, so it is imperative to explore advanced catalysts with a superior structure and catalytic output under facile synthetic conditions. In the present work, an easily accessible strategy was proposed to implement the plant-polyphenol-involved coordination assembly on Co(OH)2 nanosheets. A TA-Fe (TA = tannic acid) coordination assembly growing on Co(OH)2 resulted in the heterostructure of Co(OH)2@TA-Fe as an electrocatalyst for OER. It could significantly decrease the overpotential to 297 mV at a current density of 10 mA cm-2. The heterostructure Co(OH)2@TA-Fe also possessed favorable reaction kinetics with a low Tafel slope of 64.8 mV dec-1 and facilitated a charge-transfer ability. The enhanced electrocatalytic performance was further unraveled to be related to the confined growth of the coordination assembly on Co(OH)2 to expose more active sites, the modulated surface properties and their synergistic effect. This study demonstrated a simple and feasible strategy to utilize inexpensive biomass-derived substances as novel modifiers to enhance the performance of energy-conversion electrocatalysis.
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Electrochemical N2 reduction reaction (NRR) emerges as a highly attractive alternative to the Haber-Bosch process for producing ammonia (NH3) under ambient circumstances. Currently, this technology still faces tremendous challenges due to the low ammonia production rate and low Faradaic efficiency, urgently prompting researchers to explore highly efficient electrocatalysts. Inspired by the Fe-Mo cofactor in nitrogenase, we report Mo-doped hematite (Fe2O3) porous nanospheres containing Fe-O-Mo subunits for enhanced activity and selectivity in the electrochemical reduction from N2 to NH3. Mo-doping induces the morphology change from a solid sphere to a porous sphere and enriches lattice defects, creating more active sites. It also regulates the electronic structures of Fe2O3 to accelerate charge transfer and enhance the intrinsic activity. As a consequence, Mo-doped Fe2O3 achieves effective N2 fixation with a high ammonia production rate of 21.3 ± 1.1 µg h-1 mgcat.-1 as well as a prominent Faradaic efficiency (FE) of 11.2 ± 0.6%, superior to the undoped Fe2O3 and other iron oxide catalysts. Density functional theory (DFT) calculations further unravel that the Mo-doping in Fe2O3 (110) narrows the band gap, promotes the N2 activation on the Mo site with an elongated N≡N bond length of 1.132 Å in the end-on configuration, and optimizes an associative distal pathway with a decreased energy barrier. Our results may pave the way toward enhancing the electrocatalytic NRR performance of iron-based materials by atomic-scale heteroatom doping.
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The addition of an extra metal source induces the transformation from crystalline α-Ni(OH)2 to an amorphous NiCoFeCrMo-based high-entropy hydroxide (HEH) and maximizes the high-valence Ni3+ content in HEH. For OER electrocatalysis, the quinary HEH possesses an overpotential of 292 mV at 10 mA cm-2, a Tafel slope of 54.31 mV dec-1 and the boosted intrinsic activity, surpassing other subsystems.
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The modulation of the electronic structure is the effective access to achieve highly active electrocatalysts for the hydrogen evolution reaction (HER). Transition-metal phosphide-based heterostructures are very promising in enhancing HER performance but the facile fabrication and an in-depth study of the catalytic mechanisms still remain a challenge. In this work, the catalytically inactive n-type CeOx is successfully combined with p-type CoP to form the CoP/CeOx heterojunction. The crystalline-amorphous CoP/CeOx heterojunction is fabricated by the phosphorization of predesigned Co(OH)2/CeOx via the as-developed reduction-hydrolysis strategy. The p-n CoP/CeOx heterojunction with a strong built-in potential of 1.38 V enables the regulation of the electronic structure of active CoP within the space-charge region to enhance its intrinsic activity and facilitate the electron transfer. The functional CeOx entity and the negatively charged CoP can promote the water dissociation and optimize H adsorption, synergistically boosting the electrocatalytic HER output. As expected, the heterostructured CoP/CeOx-20:1 with the optimal ratio of Co/Ce shows significantly improved HER activity and favorable kinetics (overpotential of 118 mV at a current density of 10 mA cm-2 and Tafel slope of 77.26 mV dec-1). The present study may provide new insight into the integration of crystalline and amorphous entities into the p-n heterojunction as a highly efficient electrocatalyst for energy storage and conversion.
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Metal-organic frameworks are often used as a chemotherapeutic drug carrier due to their diverse metal sites and good acid degradation ability. Herein Co-doped Zn-MOF-5 nanoparticles with a high Co doping rate of 60% were synthesized for chemo-chemodynamic synergistic therapy of tumor. Co ions can mediate chemodynamic therapy through Fenton-like reaction and regulate the tumor microenvironment by consuming the reduced glutathione. The CoZn-MOF-5 shows high drug loading capacity with doxorubicin loading rate of 72.8%. The CoZn-MOF-5@PEG@DOX nanodrugs has a strong killing effect on 4T1 cancer cells, suggesting the chemo-chemodynamic synergistic effect on tumor therapy.
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Nanopartículas , Neoplasias , Linhagem Celular Tumoral , Cobalto/farmacologia , Doxorrubicina/metabolismo , Doxorrubicina/farmacologia , Doxorrubicina/uso terapêutico , Humanos , Neoplasias/patologia , Microambiente Tumoral , Zinco/farmacologiaRESUMO
Two unknown solution degradants were found during the dissolution testing in 0.1-M HCl for olmesartan medoxomil (OLM) tablets. The structure of the degradants was identified and characterized by liquid chromatography-ultraviolet (LC-UV), liquid chromatography with tandem mass spectrometry (LC-MS/MS), and nuclear magnetic resonance (NMR) and demonstrated to be cyclization of tetrazole and benzene in the olmesartan (OL) and OLM structures. A series of studies including stress studies, simulation studies, and mechanism-based studies were performed to reveal the potential mechanisms that lead to the formation of the unknown degradants. The study results demonstrated that the degradation was catalyzed with radicals that originated from the metal ions leached from the inner surface of high-performance liquid chromatography (HPLC) glass vials with dissolved oxygen under acidic condition. Prerinsing the glass vials with acidic solution dissolved with EDTA can effectively avoid the generation of such oxidative impurities. The present work provides new insights into the understanding of degradation pathways of OLM, which might support the development of OLM tablets.