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1.
BMC Chem ; 18(1): 201, 2024 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-39420434

RESUMEN

Novel univariate and chemometrics-aided UV spectrophotometric methods were tailored to undergo the fundamentals of green and white analytical chemistry for the simultaneous estimation of a ternary mixture of olanzapine (OLA), fluoxetine HCL (FLU), and its toxic impurity 4-(Trifluoromethyl) phenol (FMP) without any prior separation. The dual-wavelength ratio spectrum univariate method was used to determine OLA and FLU in the presence of FMP in the range of (4-20) and (5-50) µg/ml, respectively. In compliance with the International Conference on Harmonization (ICH) standards, the technique was validated and established Remarkable accuracy (98-102%) and precision (< 2%) with limits of quantification (LOQs) of 0.432 and 2.002 µg/ml, respectively. Partial least squares (PLS) and artificial neural networks (ANNs) are chemometric methodologies that have advantages over the univariate method and use significant innovations employing Latin hypercube sampling (LHS), allowing the generation of a reliable validation set to guarantee the effectiveness and sustainability of these models. The concentration ranges used were (2-20), (2-20), and (5-50) µg/ml; for PLS, the LOQs were 0.602, 0.508, and 1.429 µg/ml, and the root mean square errors of prediction (RMSEPs) were 0.087, 0.048, and 0.159 for OLA, FMP, and FLU, respectively; and for ANNs, the LOQs were 0.551, 0.465, and 0.965 µg/ml, with RMSEPs of 0.056, 0.047, and 0.087 for OLA, FMP, and FLU, respectively. The developed methods yield a greener National Environmental Methods Index (NEMI) with an eco-scale assessment (ESA) score of 90 and a complementary Green Analytical Procedure Index (complex GAPI) in quadrants with an analytical greenness metric (AGREE) score of 0.8. The Red‒Green-Blue 12 algorithm (RGB 12) scored 88.9, outperforming on reported methods and demonstrating widespread practical and environmental approval. Statistical analysis revealed no noteworthy differences (P > 0.05) among the proposed and published techniques. Both pure powders and pharmaceutical capsules were analyzed via these methods.

2.
Chem Asian J ; : e202401129, 2024 Oct 29.
Artículo en Inglés | MEDLINE | ID: mdl-39469779

RESUMEN

A novel protocol for the visible-light-driven synthesis of ß-trifluoromethylated enamines has been developed, which operates without the use of transition metals or any photocatalysts, utilizing trifluoromethylthiosulfonium salts as the source of trifluoromethyl groups under mild conditions. According to this new protocol, more than 40 products have been prepared in moderate to good yields. In addition to eliminating the need for expensive or toxic transition metals and photocatalysts, this new methodology proves its potential scalability through air-stability, the use of safe and readily available reagents, a two-step one-pot procedure, and effective gram-scale reactions. This innovative approach not only demonstrates promise for green chemical synthesis but also offers a new pathway for the advancement of fluorine chemistry in sustainable organic synthesis.

3.
Curr Med Chem ; 2024 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-39411949

RESUMEN

INTRODUCTION: Prolyl-specific oligopeptidase (POP), one of the brain's highly expressed enzymes, is an important target for the therapy of central nervous system disorders, notably autism spectrum disorder, schizophrenia, Parkinson's, Alzheimer's disease, and dementia. METHOD: The current study was designed to investigate 2,4-bis(trifluoromethyl) benzaldehyde- based thiosemicarbazones as POP inhibitors to treat the above-mentioned disorders. A variety of techniques, such as nuclear magnetic resonance (NMR), mass spectrometry (MS), and Fourier-transform infrared spectroscopy (FTIR), were used for the structural confirmation of synthesized compounds. After in-vitro evaluation, all of these compounds were found to be prominent inhibitors of the POP enzyme (IC50= 10.14 - 41.73 µM). RESULT: Compound 3a emerged as the most active compound (IC50 10.14 ± 0.72 µM) of the series. The kinetic study of the most active 3a (Ki =13.66 0.0012 µM) indicated competitive inhibition of the aforementioned enzyme. CONCLUSION: Moreover, molecular docking depicted a noticeable role of thiosemicarbazide moiety in the binding of these molecules within the active site of the POP enzyme.

4.
Chemistry ; : e202403642, 2024 Oct 15.
Artículo en Inglés | MEDLINE | ID: mdl-39403856

RESUMEN

Considering the potential advantages of minimally sized corroles for diverse applications, this study reports a facile access to cyano-substituted derivatives via a rare CF3/CN conversion. Investigation of the fully characterized gallium, phosphorus, and cobalt complexes discloses multiple effects of the meso-nitrile groups attached to the macrocycle. This corrole appears to be the most electron poor derivative which comes into play in the redox potentials of the corresponding complexes. Compared to its precursor, both the absorption and emission are strongly red shifted and the fluorescence lifetime and quantum yield are much larger. The coordination chemistry is affected as well, by virtue of axial ligands being perpendicular rather than parallel relative to each other.

5.
J Inorg Biochem ; 262: 112752, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-39366100

RESUMEN

New silver(I) complexes of 5-(trifluoromethyl)uracil (5TFMU) and 6-(trifluoromethyl)uracil (6TFMU) isomers were synthesized, characterized, and evaluated as antibacterial and antiproliferative agents. Based on elemental and thermogravimetric analyses, the Ag-5TFMU and Ag-6TFMU species are formulated as AgC5H2F3N2O2 and Ag2C5HF3N2O2, respectively. Infrared and 13C solid-state nuclear magnetic resonance spectroscopies suggest coordination of the trifluoromethyluracil isomers to silver by both nitrogen and oxygen atoms. Confirmation of their structure and connectivity was achieved, in the absence of single crystals of suitable quality, by state-of-the-art structural powder diffraction methods. In Ag-5TFMU, the organic ligand is tridentate and two distinct metal coordination environments are found (linear AgN2 as well as C2v AgO4 geometries), whereas Ag-6TFMU contains a complex polymeric structure with tetradentate dianionic 6TFMU moieties and five distinct AgX2 (X = N, O) fragments, further stabilized by ancillary (longer) Ag…O contacts. These species presented modest activity over Gram-positive and Gram-negative bacterial strains, whereas Ag-6TFMU was active over a set of tumor cells, with the best activity over prostate (PC-3) and kidney cell lines and selectivity indices of 4.6 and 1.3, respectively. On the other hand, Ag-5TFMU was active over all considered tumor cells except MCF-7 (breast cancer). The best activity was found for PC-3 cells, but no selectivity was observed. The Ag-5TFMU and Ag-6TFMU species also reduced the proliferation of tongue squamous cell carcinoma cell lines SCC - 4 and SCC-15. Preliminary biophysical assays by circular dichroism suggest that the Ag-5TFMU complex interacts with DNA by intercalation, an effect not seen in Ag-6TFMU.

6.
Bioorg Chem ; 153: 107805, 2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-39255608

RESUMEN

A series of 3-(2-trifluoromethyl-3-aryl-4H-chromen-4-yl)-1H-indoles (5-1 to 5-29) were developed and characterized. Most of compounds were found to be potent for inhibiting the production of NO in LPS-induced RAW264.7 cells, of which 3-(3-(4-chlorophenyl)-6-methoxy-2-(trifluoromethyl)-4H-chromen-4-yl)-1H-indole (5-25) was the most optimal (IC50 = 4.82 ± 0.34 µΜ) and was capable of significantly suppressing the release of PGE2. The inhibitory effect of 5-25 on human recombinant COX-2 (IC50 = 51.7 ± 1.3 nM) was measured and molecular docking was performed, determining 5-25 as a COX-2 inhibitor. Additionally, the interaction between 5-25 and COX-2 was determined by the CETSA technique. Then, 5-25 inhibited the degradation of IκB, the phosphorylation and nuclear translocation of NF-κB p65, and the expression of COX-2 and iNOS. Moreover, it was verified that 5-25 exhibited efficacy in rodent models of inflammation and pain, encompassing the paw edema, cotton pellet-induced granuloma, acid-induced writhing, and adjuvant-induced arthritis models. Therefore, the mechanism of 5-25 may be to bind to COX-2 and exert anti-inflammatory and analgesic effects in vitro and in vivo by suppressing the NF-κB pathway. Encouragingly, in comparison with indomethacin, 5-25 exhibited a lower ulcerative potential in rats, as manifested by generating smaller areas and fewer ulcers, less inflammatory infiltration, a lower expression of MMP-9, and less apoptosis. In conclusion, 5-25 is a candidate drug with high activity and low ulcerogenic potential, and it deserves further research for the treatment of inflammation, pain, and other symptoms in which COX-2 plays a role in their pathogenesis.

7.
Int J Mol Sci ; 25(17)2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39273361

RESUMEN

A new complex of copper(II) with methyl-5-(trifluoromethyl)pyrazol-3-yl-ketazine (H2L) was synthesized with the composition [Cu2L2]∙C2H5OH (1). Recrystallization of the sample from DMSO yielded a single crystal of the composition [Cu2L2((CH3)2SO)] (2). The coordination compounds were studied by single-crystal X-ray diffraction analysis, IR spectroscopy, and static magnetic susceptibility method. The data obtained indicate that the polydentate ligand is coordinated by both acyclic nitrogen and heterocyclic nitrogen atoms. The cytotoxic activity of the ligand and complex 1 was investigated on human cell lines MCF7 (breast adenocarcinoma), Hep2 (laryngeal carcinoma), A549 (lung carcinoma), HepG2 (hepatocellular carcinoma), and MRC5 (non-tumor lung fibroblasts). The complex was shown to have a pronounced dose-dependent cytotoxicity towards these cell lines with LC50 values in the range of 0.18-4.03 µM.


Asunto(s)
Antineoplásicos , Complejos de Coordinación , Cobre , Hidrazonas , Humanos , Cobre/química , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Complejos de Coordinación/síntesis química , Hidrazonas/química , Hidrazonas/farmacología , Hidrazonas/síntesis química , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Línea Celular Tumoral , Pirazoles/química , Pirazoles/farmacología , Pirazoles/síntesis química , Cristalografía por Rayos X , Estructura Molecular , Ligandos , Células MCF-7 , Células Hep G2
8.
ACS Appl Mater Interfaces ; 16(33): 43602-43616, 2024 Aug 21.
Artículo en Inglés | MEDLINE | ID: mdl-39107098

RESUMEN

The development of advanced liquid electrolytes for high-voltage/high-energy rechargeable Li metal batteries is an important strategy to attain an effective protective surface film on both the Li metal anode and the high-voltage composite cathode. Herein, we report a study of two CF3-substituted ethylene carbonates as components of the electrolyte solutions for Li metal|NCM811 cells. We evaluated trifluoromethyl ethylene carbonate (CF3-EC) and trans-ditrifluoromethylethylene carbonate Di-(CF3)-EC as cosolvents and additives to the electrolyte solutions. Using CF3-substituted ethylene carbonates as additives to a fluoroethylene carbonate (FEC)-based electrolyte solution enables improved capacity retention of high-power Li metal|NCM811 cells. The composition of the products from the transformations of CF3-EC and Di-(CF3)-EC in Li|NCM811 cells was studied by FTIR, XPS, and 19F NMR spectroscopy. We concluded that fluorinated Li alkyl carbonates are the main reaction products formed from these cyclic carbonates during the cycling of Li|NCM 811 cells, and fragmentation of the ring with the formation of CO2, CO, or olefins is not characteristic of CF3-substituted ethylene carbonates. The NCM 811 cathodes and Li metal anodes were characterized by X-ray diffraction, SEM, XPS, and FTIR spectroscopy. The role of CF3-substituted ethylene carbonate additives in stabilizing high energy density secondary batteries based on Li metal anodes was discussed. A bright horizon for developing sustainable rechargeable batteries with the highest possible energy density is demonstrated.

9.
Mol Divers ; 2024 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-39117890

RESUMEN

Given the critical necessity for the development of more potent anti-cancer drugs, a series of novel compounds incorporating trifluoromethyl groups within the privileged 2-anilinoquinoline scaffold was designed, synthesized, and subjected to biological evaluation through a pharmacophore hybridization strategy. Upon evaluating the in vitro anti-cancer characteristics of the target compounds, it became clear that compound 8b, which contains a (4-(piperazin-1-yl)phenyl)amino substitution at the 2-position of the quinoline skeleton, displayed superior efficacy against four cancer cell lines by inducing apoptosis and cell cycle arrest. Following research conducted in a PC3 xenograft mouse model, it was found that compound 8b exhibited significant anti-cancer efficacy while demonstrating minimal toxicity. Additionally, the analysis of a 217-kinase panel pinpointed SGK1 as a potential target for this compound class with anti-cancer capabilities. This finding was further verified through molecular docking analysis and cellular thermal shift assays. To conclude, our results emphasize that compound 8b can be used as a lead compound for the development of anti-cancer drugs that target SGK1.

10.
Chemistry ; 30(50): e202401954, 2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-38958040

RESUMEN

Considering the broad use of the trifluoromethyl functional group (-CF3) in medicinal chemistry and taking into account the recent concerns on the negative environmental effects of CF3 containing compounds, we are searching for "greener" alternatives. Thus, different chemical groups (i. e. iodide, fluoride, cyclopropyl, isopropyl, cyclobutyl, 3-oxetyl, 2-oxetyl, methylsulfide, pentafluorosulfide, methylsulfonyl and sulfonamide) have been considered as potential bioequivalents of -CF3 aiming to use them in compounds with therapeutic interest instead of the polyfluoride functionality. Different structural (molecular surface and volume) and physicochemical (electronic and lipophilic) aspects of the bioequivalent functionalities proposed have been theoretically calculated and compared to those of -CF3. Additionally, the corresponding phenyl derivatives carrying these functionalities have been purchased or prepared and their experimental lipophilicity (i. e. LogP) measured using shake-flask experiments and UV-vis spectroscopy.

11.
Chemistry ; 30(54): e202401791, 2024 Sep 25.
Artículo en Inglés | MEDLINE | ID: mdl-38976449

RESUMEN

Copper(III) iodide and bromide complexes representing a unique combination of highly-coordinated metal and soft polarizable anions were synthesized and fully characterized, including X-ray crystallography. Ligand substitution in well-defined highly-coordinated copper complex PyCu(CF3)3 with pincer ligands was achieved to give formally octahedral copper(III) complexes.

12.
Chem Asian J ; 19(20): e202400698, 2024 Oct 16.
Artículo en Inglés | MEDLINE | ID: mdl-39039023

RESUMEN

A very simple and atom-economical method for the synthesis of vicinal trifluoromethyl thioethers via DBN-catalyzed hydrothiolation of α-(trifluoromethyl)styrenes with thiols was reported. The reaction proceeded smoothly under mild reaction conditions and provided the ß-CF3-thioethers in moderate to good yields in an anti-Markovnikov manner. Furthermore, this method features several remarkable advantages, such as the use of a catalytic amount of DBN, broad substrate scope, excellent functional group compatibility, and easy scalability.

13.
Angew Chem Int Ed Engl ; 63(44): e202409315, 2024 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-39072869

RESUMEN

In recent years, the electronic structures of organocuprates in general and the complex [Cu(CF3)4]- in particular have attracted significant interest. A possible key indicator in this context is the reactivity of these species. Nonetheless, this aspect has received only limited attention. Here, we systematically study the series of tetra-alkyl cuprates [MenCu(CF3)4-n]- and their unimolecular reactivity in the gas phase, which includes concerted formal reductive eliminations as well as radical losses. Through computational studies, we characterize the electronic structures of the complexes and show how these are connected to their reactivity. We find that all [MenCu(CF3)4-n]- ions feature inverted ligand fields and that the distinct reactivity patterns of the individual complexes arise from the interplay of different effects.

14.
Chemistry ; 30(52): e202401753, 2024 Sep 16.
Artículo en Inglés | MEDLINE | ID: mdl-38924636

RESUMEN

Gold(III) complexes containing trifluoromethyl ligands are efficient catalysts in the hydration of alkynes, operating at low catalyst loadings, without additives, using environmentally friendly solvents and at mild conditions (60 °C). Hydration of terminal and internal alkynes provides the corresponding ketones in quantitative yields without special precautions as dry solvents or inert atmospheres. Remarkably, hydration of asymmetric internal alkynes proceeds with moderate to notable regioselectivities, providing mixtures of the two possible isomers with ratios up to 90 : 10.

15.
Polymers (Basel) ; 16(11)2024 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-38891537

RESUMEN

With the increasing demand for innovative electronic products, LED transparent screens are gradually entering the public eye. Polyimide (PI) materials combine high temperature resistance and high transparency, which can be used to prepare flexible copper-clad laminate substrates. The physical and chemical properties of PI materials differ from copper, such as their thermal expansion coefficients (CTEs), surface energy, etc. These differences affect the formation and stability of the interface between copper and PI films, resulting in a short life for LED transparent screens. To enhance PI-copper interfacial adhesion, aminopropyl-terminated polydimethylsiloxane (PDMS) can be used to increase the adhesive ability. Two diamine monomers with a trifluoromethyl structure and a sulfone group structure were selected in this research. Bisphenol type A diether dianhydride is a dianhydride monomer. All three of the above monomers have non-coplanar structures and flexible structural units. The adhesion and optical properties can be improved between the interface of the synthesized PI films and copper foil. PI films containing PDMS 0, 1, 3, and 5 wt% were analyzed using UV spectroscopy. The transmittance of the PI-1/3%, PI-1/5%, PI-2/3%, and PI-2/5% films were all more than 80% at 450 nm. Meanwhile, the Td 5% and Td 10% heat loss and Tg temperatures decreased gradually with the increase in PDMS. The peel adhesion of PI-copper foil was measured using a 180° peel assay. The effect of PDMS addition on peel adhesion was analyzed. PIs-3% films had the greatest peeling intensities of 0.98 N/mm and 0.85 N/mm.

16.
Phytopathology ; 114(6): 1244-1252, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38916562

RESUMEN

Three novel trifluoromethylated compounds were designed and synthesized by reacting trifluoroacetimidoyl chloride derivatives with acetamidine hydrochloride or thiourea in the presence of potassium carbonate or sodium hydrogen carbonate as a base. In vitro and in vivo assays demonstrated the efficacy of the tested compounds in controlling root-knot nematode disease on pistachio rootstocks caused by Meloidogyne incognita. Bis-trifluoromethylated derivatives, namely N,N''-thiocarbonylbis(N'-(3,4-dimethylphenyl)-2,2,2-trifluoroacetimidamide) (compound A1), showed high efficacy as novel and promising nematicides, achieving up to 78.28% control at a concentration of 0.042 mg/liter. This effect is attributed to four methyl and two trifluoromethyl groups. In the pre-inoculation application of compound A1, all three concentrations (0.033, 0.037, and 0.042 mg/liter, and Velum) exhibited a higher level of control, with 83.79, 87.46, and 80.73% control, respectively. In the microplot trials, compound A1 effectively reduced population levels of M. incognita and enhanced plant growth at a concentration of 0.037 mg/liter. This suggests that compound A1 has the potential to inhibit hedgehog protein and could be utilized to prevent the progression of root-knot disease. Furthermore, the molecular docking results revealed that compounds A1 and A3 interact with specific amino acid residues (Gln60, Asp530, Glu70, Arg520, and Thr510) located in the active site of hedgehog protein. Based on the experimental findings of this study, compound A1 shows promise as a lead compound for future investigations.


Asunto(s)
Antinematodos , Simulación del Acoplamiento Molecular , Pistacia , Enfermedades de las Plantas , Raíces de Plantas , Tylenchoidea , Animales , Tylenchoidea/efectos de los fármacos , Antinematodos/farmacología , Enfermedades de las Plantas/parasitología , Enfermedades de las Plantas/prevención & control , Raíces de Plantas/parasitología , Pistacia/química
17.
Sci Rep ; 14(1): 13462, 2024 06 12.
Artículo en Inglés | MEDLINE | ID: mdl-38862591

RESUMEN

There have been 774,075,242 cases of COVID-19 and 7,012,986 deaths worldwide as of January 2024. In the early stages of the pandemic, there was an urgent need to reduce the severity of the disease and prevent the need for hospitalization to avoid stress on healthcare systems worldwide. The repurposing of drugs to prevent clinical deterioration of COVID-19 patients was trialed in many studies using many different drugs. Fluvoxamine (an SSRI and sigma-1 receptor agonist) was initially identified to potentially provide beneficial effects in COVID-19-infected patients, preventing clinical deterioration and the need for hospitalization. Fourteen clinical studies have been carried out to date, with seven of those being randomized placebo-controlled studies. This systematic review and meta-analysis covers the literature from the outbreak of SARS-CoV-2 in late 2019 until January 2024. Search terms related to fluvoxamine, such as its trade names and chemical names, along with words related to COVID-19, such as SARS-CoV-2 and coronavirus, were used in literature databases including PubMed, Google Scholar, Scopus, and the ClinicalTrials.gov database from NIH, to identify the trials used in the subsequent analysis. Clinical deterioration and death data were extracted from these studies where available and used in the meta-analysis. A total of 7153 patients were studied across 14 studies (both open-label and double-blind placebo-controlled). 681 out of 3553 (19.17%) in the standard care group and 255 out of 3600 (7.08%) in the fluvoxamine-treated group experienced clinical deterioration. The estimated average log odds ratio was 1.087 (95% CI 0.200 to 1.973), which differed significantly from zero (z = 2.402, p = 0.016). The seven placebo-controlled studies resulted in a log odds ratio of 0.359 (95% CI 0.1111 to 0.5294), which differed significantly from zero (z = 3.103, p = 0.002). The results of this study identified fluvoxamine as effective in preventing clinical deterioration, and subgrouping analysis suggests that earlier treatment with a dose of 200 mg or above provides the best outcomes. We hope the outcomes of this study can help design future studies into respiratory viral infections and potentially improve clinical outcomes.


Asunto(s)
Tratamiento Farmacológico de COVID-19 , COVID-19 , Fluvoxamina , SARS-CoV-2 , Fluvoxamina/uso terapéutico , Humanos , COVID-19/mortalidad , SARS-CoV-2/aislamiento & purificación , SARS-CoV-2/efectos de los fármacos , Resultado del Tratamiento , Deterioro Clínico , Inhibidores Selectivos de la Recaptación de Serotonina/uso terapéutico , Inhibidores Selectivos de la Recaptación de Serotonina/efectos adversos , Inhibidores Selectivos de la Recaptación de Serotonina/administración & dosificación
18.
Mol Divers ; 2024 May 13.
Artículo en Inglés | MEDLINE | ID: mdl-38739229

RESUMEN

To discover new Werner (WRN) helicase inhibitors, a series of N-aryl-2-trifluoromethyl-quinazoline-4-amine derivatives were designed and synthesized through a structural optimization strategy, and the anticancer activities of 25 new target compounds against PC3, K562, and HeLa cell lines were evaluated by the MTT assay. Some of these compounds exhibited excellent inhibitory activity against three different cancer cell lines. Compounds 6a, 8i, and 13a showed better antiproliferative activity against K562 cells, with IC50 values of 3871.5, 613.6 and 134.7 nM, respectively, than did paclitaxel (35.6 nM), doxorubicin (2689.0 nM), and NSC 617145 (20.3 nM). To further verify whether the antiproliferative activity of these compounds is dependent on WRN, PC3 cells overexpressing WRN (PC3-WRN) were constructed to further study their antiproliferative potency in vitro, and the inhibition ratio and IC20 values showed that compounds 6a, 8i, and 13a were more sensitive to PC3-WRN than were the control group cells (PC3-NC). The IC20 ratios of compounds 6a, 8i, and 13a to PC3-NC and PC3-WRN were 94.3, 153.4 and 505.5, respectively. According to the docking results, the compounds 6a, 8i, and 13a overlapped well with the binding pocket of 6YHR. Further study demonstrated that among the tested compounds, 13a was the most sensitive to PC3-WRN. In summary, our research identified a series of N-aryl-2-trifluoromethyl-quinazoline-4-amine derivatives as potential WRN-dependent anticancer agents.

19.
Front Chem ; 12: 1398946, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38800577

RESUMEN

Amino acid-derived quaternary ammonium salts were successfully applied in the asymmetric aza-Henry reaction of nitromethane to N-Boc trifluoromethyl ketimines. α-Trifluoromethyl ß-nitroamines were synthesized in good to excellent yields with moderate to good enantioselectivities. This reaction is distinguished by its mild conditions, low catalyst loading (1 mol%), and catalytic base. It also proceeded on a gram scale without loss of enantioselectivity. The products were transformed to a series of adamantane-type compounds containing chiral trifluoromethylamine fragments. The potent anticancer activities of these compounds against liver cancer HepG2 and melanoma B16F10 were evaluated. Six promising compounds with notable efficacy have potential for further development.

20.
ACS Appl Mater Interfaces ; 16(21): 27439-27449, 2024 May 29.
Artículo en Inglés | MEDLINE | ID: mdl-38764253

RESUMEN

The charge transfer efficiency of the solid electrolyte depends on the number of lithium ions that can be effectively transported and participate in the electrode reaction. However, limited by the strong coupling relationship between Li+ and Lewis basic sites on the polymer chain, the Li+ transference number (tLi+) of the solid polymer electrolyte (SPE) based dual-ion conductor is typically low, resulting in excessive anion aggregation at the electrode side and inducing concentration polarization. In this study, we present a functionalized modified polymer electrolyte (FMPE) with selective cation transport, which was synthesized by embedding 4-(trifluoromethyl)styrene (TFS) functionalized groups onto the poly(diethylene glycol diacrylate) polymer chain. The TFS group formed noncovalent couplings with TFSI- anions through hydrogen bondings and dipole-dipole interactions, which effectively limited the migration of the anions and contributed to the elevated tLi+ of the FMPEs to 0.595 and 0.699 at 25 and 60 °C, respectively. Density functional theory (DFT) calculations were performed to verify the increased anion migration barriers for different noncovalent interactions and revealed that the conjugated system formed by the delocalized π electrons of the benzene ring and the C═O groups helped to disperse the electron distribution of the polymer chains. Consequently, the decrease in the degree of Li+ immobilization promotes the decoupling and migration of Li+ between the polymer chains. Benefiting from optimized Li+ transport behavior, the lithium metal batteries (LMBs) assembled by FMPEs and LiFePO4 exhibit excellent rate performance (discharge specific capacity of 88.8 mAh g-1 at 5 C) and stable long-term cycle performance (capacity decay rate of only 0.064% per cycle for 500 cycles at 25 °C and 0.5 C).

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