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Dye-sensitized solar cells (DSSCs) have emerged as a promising alternative for renewable energy conversion. The synthesis and characterization of the 2-acetonitrile-benzoxazole (BOA) sensitizer MSW-1-4 are presented along with their chemical structures. Four new organic dyes, MSW-1 through MSW-4, were synthesized using BOA as the main building block, with different additional donor groups. The dyes were characterized and their photophysical and electrochemical properties were studied. Computational modeling using density functional theory (DFT) was performed to investigate their potential as sensitizers/co-sensitizers for photovoltaic applications. The modeling showed a distinct charge separation between the donor and acceptor parts of the molecules. For dye-sensitized solar cells, MSW-4 performed the best out of MSW-1-3 and was also better than the reference dye D-5. Moreover, MSW-3 was co-sensitized along with a typical highly efficient bipyridyl Ru(ii) sensitizer, N719, reference dye D-5, and metal-free dye MSW-4, to induce light harvesting over the expanded spectral region and hence improve the efficiency. Co-sensitizer (MSW-3 + N719) showed an improved efficiency of 10.20%. This outperformed a solar cell that used only N719 as the sensitizer, which had an efficiency of 7.50%. The appropriate combined dye loading of MSW-3 + N719 enabled good light harvesting and maximized the photoexcitation. The synergistic effect of using both MSW-3 and N719 as co-sensitizers led to enhanced solar cell performance compared with using N719 alone.
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Design and virtual screening of a set of non-acidic 4-methyl-4-phenyl-benzenesulfonate-based aldose reductase 2 inhibitors had been developed followed by chemical synthesis. Based on the results, the synthesized compounds 2, 4a,b, 7a-c, 9a-c, 10a-c, 11b,c and 14a-c inhibited the ALR2 enzymatic activity in a submicromolar range (99.29-417 nM) and among them, the derivatives 2, 9b, 10a and 14b were able to inhibit ALR2 by IC50 of 160.40, 165.20, 99.29 and 120.6 nM, respectively. Moreover, kinetic analyses using Lineweaver-Burk plot revealed that the most active candidate 10a inhibited ALR2 potently via a non-competitive mechanism. In vivo studies showed that 10 mg/kg of compound 10a significantly lowered blood glucose levels in alloxan-induced diabetic mice by 46.10 %. Moreover, compound 10a showed no toxicity up to a concentration of 50 mg/kg and had no adverse effects on liver and kidney functions. It significantly increased levels of GSH and SOD while decreasing MDA levels, thereby mitigating oxidative stress associated with diabetes and potentially attenuating diabetic complications. Furthermore, the binding mode of compound 10a was confirmed through MD simulation. Noteworthy, compounds 2 and 14b showed moderate antimicrobial activity against the two fungi Aspergillus fumigatus and Aspergillus niger. Finally, we report the thiazole derivative 10a as a new promising non-acidic aldose reductase inhibitor that may be beneficial in treating diabetic complications.
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Aldeído Redutase , Desenho de Fármacos , Inibidores Enzimáticos , Aldeído Redutase/antagonistas & inibidores , Aldeído Redutase/metabolismo , Animais , Inibidores Enzimáticos/farmacologia , Inibidores Enzimáticos/síntese química , Inibidores Enzimáticos/química , Camundongos , Relação Estrutura-Atividade , Estrutura Molecular , Diabetes Mellitus Experimental/tratamento farmacológico , Diabetes Mellitus Experimental/induzido quimicamente , Relação Dose-Resposta a Droga , Simulação de Acoplamento Molecular , Masculino , Humanos , Benzenossulfonatos/farmacologia , Benzenossulfonatos/química , Benzenossulfonatos/síntese química , Hipoglicemiantes/farmacologia , Hipoglicemiantes/síntese química , Hipoglicemiantes/químicaRESUMO
The chemicals formed from antipyrines are flexible organic building blocks that are employed in the development of pharmaceuticals. By diazotizing (4-arylazo-3-hydroxy-2-thienyl) 4-antipyrine ketones 1a, 1b and 1c and (4-arylazo-3-methyl-2-thienyl) 4-antipyrine ketones (2a, 2b and 2c) further replaced with six other coupling components, a broad spectrum of hybrid molecules have been created. Mass spectra, NMR, FTIR, and elemental analyses have all been used to confirm the structures of the synthesised compounds. The antimicrobial screening was investigated by agar well diffusion and diluting the broth technique against both Gram-negative and positive-tested bacterial strains. (3-methyl-5-(phenylamino)-4-(4-tolylazo)-2-thienyl) 4-antipyrine ketone (2a) was found to be superior to Ciprofloxacin against test strains: Acinetobacter sp (34.33±1.15â mm), Listeria monocytogenes (29.33±1.15â mm) and Streptococcus sp. (19.33±1.15 mm). Also, good to moderate activities were expressed as minimum inhibitory concentration (MIC) and minimum bacterial concentration (MBC) which were recorded at 9±1 to 59.67±4.51â µg/mL and 16±4 to >512â µg/mL, respectively, using compounds 2a, 2b, and 2c. MBC/MIC ratio showed, that only, 2a and 2b have a bactericidal effect but other antipyrines with bacteriostatic strength. To conclude, it was suggested that the use of these novel synthesized (4-arylazo-3-methyl-2-thienyl) 4-antipyrine ketone derivatives molecules as a new chemical class of antimicrobial agents to perform new drug discovery in pharmaceutical preparations and medicinal research.
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Antibacterianos , Desenho de Fármacos , Cetonas , Testes de Sensibilidade Microbiana , Antibacterianos/farmacologia , Antibacterianos/síntese química , Antibacterianos/química , Cetonas/química , Cetonas/farmacologia , Cetonas/síntese química , Antipirina/farmacologia , Antipirina/química , Antipirina/análogos & derivados , Antipirina/síntese química , Relação Estrutura-Atividade , Estrutura Molecular , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacosRESUMO
In this study, we synthesized new series of 5-oxo-2-phenyl-4-(arylsulfamoyl)sulphenyl) hydrazono)-4,5-dihydro-1H-pyrrole-3-carboxylate hybrids 4a-f with the goal of overcoming sulfonamide resistance and identifying novel therapeutic candidates by chemical changes. The chemical structures of the synthesized hybrids were established over the spectroscopic tools. The frontier molecular orbitals configuration and energetic possessions of the synthesized compounds were discovered utilizing DFT/B3LYP/6-311++ G** procedure. The 3D plots of both HOMO and LUMO showed comparable configuration of both HOMO and LUMO led to close values of their energies. Amongst the prepared analogues, the sulfonamide hybrids 4a-f, hybrid 4a presented potent inhibitory towards S. typhimurium with (IZD = 15 mm, MIC = 19.24 µg/mL) and significant inhibition with (IZD = 19 mm, MIC = 11.31 µg/mL) against E.coli in contrast to sulfonamide (Sulfamethoxazole) reference Whereas, hybrid 4d demonstrated potent inhibition with (IZD = 16 mm, MIC = 19.24 µg/mL) against S. typhimurium with enhanced inhibition against E. Coli, Additionally, the generated sulfonamide analogues'' molecular docking was estimated over (PDB: 3TZF and 6CLV) proteins. Analogue 4e had the highest documented binding score as soon as linked to the other analogues. The docking consequences were fitting and addressed with the antibacterial valuation.
Assuntos
Antibacterianos , Testes de Sensibilidade Microbiana , Simulação de Acoplamento Molecular , Pirróis , Sulfonamidas , Sulfonamidas/química , Sulfonamidas/farmacologia , Sulfonamidas/síntese química , Antibacterianos/farmacologia , Antibacterianos/química , Antibacterianos/síntese química , Pirróis/química , Pirróis/farmacologia , Pirróis/síntese química , Salmonella typhimurium/efeitos dos fármacos , Escherichia coli/efeitos dos fármacos , Modelos Moleculares , Relação Estrutura-Atividade , Estrutura MolecularRESUMO
The aim of this study involves the synthesis novel thiophene analogues that can be used as anticancer medications through a strategic multicomponent reaction connecting ethyl 4-chloroacetoacetate (1), phenyl isothiocyanate, and a series of active methylene reagents, including ethyl acetoacetate (2), malononitrile, ethyl cyanoacetate, cyanoacetamide 6a-c, N-phenyl cyanoacetamide derivatives 13a-c, and acetoacetanilide derivatives 18. This reaction was facilitated by dry dimethylformamide with a catalytic quantity of K2CO3. The resultant thiophene derivatives were identified as 4, 8a-b, 9, 12a-d, 15a-c, and 20a-b. Further reaction of compound 4 with hydrazine hydrate yielded derivative 5, respectively. When compound 1 was refluxed with ethyl 3-mercapto-3-(phenylamino)-2-(p-substituted phenyldiazenyl)acrylate 10a-e in the presence of sodium ethoxide, it produced thiophene derivatives 12a-d. Comprehensive structural elucidation of these newly synthesized thiophene-analogues was accomplished via elemental and spectral analysis data. Furthermore, the study delves into the cytotoxicity of the newly synthesized thiophenes was evaluated using the HepG2, A2780, and A2780CP cell lines. The amino-thiophene derivative 15b exhibited an increased growth inhibition of A2780, and A2780CP with IC50 values 12±0.17, and 10±0.15â µM, respectively compared to Sorafenib with IC50 values 7.5±0.54 and 9.4±0.14. This research opens new avenues for developing thiophene-based anticancer agents.
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Antineoplásicos , Proliferação de Células , Ensaios de Seleção de Medicamentos Antitumorais , Tiofenos , Humanos , Antineoplásicos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Relação Dose-Resposta a Droga , Estrutura Molecular , Relação Estrutura-Atividade , Tiofenos/química , Tiofenos/farmacologia , Tiofenos/síntese químicaRESUMO
New sets of functionalized thiazolidinone and thiadiazole derivatives were synthesized, and their cytotoxicity was evaluated on HepG2, MCF-7, HTC-116, and WI38 cells. The synthetic approach is based on the preparation of 4-(4-acetamidophenyl)thiosemicarbazide (4) and their thiosemicarbazones 5 a-e, which are converted to the corresponding thiazoldin-4-one compounds 6 a-e upon cyclization with ethyl bromoacetate. The thiadiazole compounds 9 and 12 were obtained by reacting 4-(4-acetamidophenyl)thiosemicarbazide with isothiocyanates and/or ethyl 2-cyano-3,3-bis(methylthio)acrylate, respectively. The thiazolidinone compounds 6 c and 6 e exhibited strong cytotoxicity against breast cancer cells, with an IC50 (6.70±0.5â µM) and IC50 (7.51±0.8â µM), respectively, very close to that of doxorubicin (IC50: 4.17±0.2â µM). In addition, the anti-cancer properties of the tested thiazolidinone and thiadiazole scaffolds were further explored by the molecular docking program (MOE)-(PDB Code-1DLS). Compounds 5 d, 5 e, 6 d, 6 e, and 7 have the best binding affinity, ranging from -8.5386â kcal.mol-1 to -8.2830â kcal.mol-1.
Assuntos
Antineoplásicos , Ensaios de Seleção de Medicamentos Antitumorais , Simulação de Acoplamento Molecular , Tiadiazóis , Tiazolidinas , Humanos , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Tiadiazóis/química , Tiadiazóis/farmacologia , Tiadiazóis/síntese química , Tiazolidinas/química , Tiazolidinas/farmacologia , Tiazolidinas/síntese química , Relação Estrutura-Atividade , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Estrutura Molecular , Relação Dose-Resposta a DrogaRESUMO
Various sets of thiazole, thiophene, and 2-pyridone ring structures containing a dimethylaniline component were synthesized. Substituted thiazoles 2-3 and thiophenes 5-7 were produced by reacting thiocarbamoyl compound 4 with α-halogenated reagents in different basic conditions. Also, a series of 2-pyridone derivatives 9a-f substituted with dimethylaniline was synthesized through Michael addition of malononitrile to α,ß-unsaturated nitrile derivatives 8a-f. The synthesized products were structurally proven by spectroscopic methods such as IR, 1H NMR, 13C NMR, and MS data. Furthermore, the anti-cancer efficacy of the compounds was assessed using the MTT assay on two cell lines: hepatocellular carcinoma (HepG-2) and breast cancer (MDA-MB-231). The results showed the highest growth inhibition for derivatives 2, 6, 7, and 9c, which were further examined for their IC50 values. The IC50 for compound 2 showed equipotent activity (IC50 = 1.2 µM) against the HepG-2 cell line compared to Doxorubicin (IC50 = 1.1 µM). Compounds 2, 6, 7 and 9c showed very good ADME assessments for further drug administration. Moreover, the PASS theoretical prediction for the compounds showed high antimitotic and antineoplastic activities for compounds 2, 6, 7, and 9c, as well as potent inhibition activity for the insulysin enzyme (IDE). Molecular docking stimulations were performed on CDK1/CyclinB1/CKS2 (PDB ID: 4y72) and BPTI (PDB ID: 2ra3). When docked into (PDB ID: 4y72), all of the tested compounds showed considerable inhibition, and the 2-pyridone derivative 9d had the maximum binding affinity (- 8.1223 kcal/mol). While thiophene derivative 6 offered the maximum binding affinity (- 7.5094 kcal/mol) when docked into (PDB ID: 2ra3).
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We report on the synthesis and characterization of six novel 2,2'-bithiophene-based organic compounds (3a-c and 5a-c) that are designed to serve as co-sensitizers for dye-sensitized solar cells (DSSCs) based on TiO2. The compounds are linked to various donor and acceptor groups, and we confirm their chemical structures through spectral analyses. Our focus is on enhancing the performance of metal based N3, and the compounds were designed to operate at the nanoscale. We performed absorption and fluorescence emission measurements in dimethylformamide (DMF), where one of our compounds 5a exhibited the longest maximum absorption and maximum emission wavelengths, indicating the significant impact of the para methoxy group as a strong electron-donating group. Our dyes 5a + N3 (η = 7.42%) and 5c + N3 (η = 6.57%) outperformed N3 (η = 6.16%) alone, where the values of short current density (JSC) and open circuit voltage (VOC) for these two systems also improved. We also investigated the charge transfer resistance at the TiO2/dye/electrolyte interface using electrochemical impedance spectroscopy (EIS), which is important in the context of nanotechnology. According to the Nyquist plot, the 5a + N3 cocktail exhibited the lowest recombination rate, resulting in the highest VOC. Our theoretical calculations based on density functional theory (DFT) are also in agreement with the experimental process. These findings suggest that our compounds have great potential as efficient DSSC co-sensitizers. This study provides valuable insights into the design and synthesis of new organic compounds for use as co-sensitizers in DSSCs based on TiO2 and highlights the potential of these compounds for use in efficient solar energy conversion.
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Two cytotoxic sesquiterpene lactones, 17-epichlorohyssopifolin A (1) and chlorjanerin (2), and a monoterpene lactone, loliolide (3) were isolated from Centaurea pseudosinaica. The cytotoxicity of the total extract and terpenoids 1-3 were evaluated against three human cancer cells (HepG2, PC-3, and HT-29), along with the human normal primary epidermal keratinocytes (HEKa) cells. With IC50 values ranging between 0.6 ± 0.04 and 5.0 ± 0.61 µg/mL against HepG2; 0.2 ± 0.01 and 11.9 ± 1.31 µg/mL against PC-3, and 0.04 ± 0.013 and 8.9 ± 0.97 µg/mL against HT-29, the total extract, and lactones 1-3 demonstrated cytotoxic effects. Compound 1 displayed the strongest impact on all cancer cells and a slightly safe effect on the normal cells HEKa. Compound 1 caused accumulation of HepG2 and HT-29 cells in G1 phase as displayed cell cycle analysis. On the other hand, the cell distributions were increased in the S phase in PC-3 cells. Furthermore, 1 caused apoptosis in PC-3 and HePG2 cells with 91.50%, and 79.72 %, respectively. A higher fraction of necrotic cells was observed in HT-29 cells amounting to 23.60%. These results suggested that the promising cytotoxicity exhibited by 1 is brought by the apoptosis induction in the cancer cells, which were evaluated. As the compounds showed antiproliferative effect against the HT-29 cells, the docking simulation was performed aiming at determining how they would interact with the EGFR enzyme, whose PDB: 4I23 is considered one of the two distinct wild types of EGFR enzymes. The antibacterial activity results revealed that 3 showed the most remarkable antibacterial effects, especially against the examined Gram-positive bacteria. The total extract exhibited potent activity against all examined bacteria. The total extract showed a potent antifungal effect against two Candida and two Aspergillus pathogens. The antioxidant activity revealed the potency of the total extract and 3 as antioxidant candidates. The obtained results refer to the importance of Centaurea pseudosinaica as a source of potent antiproliferative agents and the whole plant as an antipathogenic and antioxidant agent.
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The synthesis, description, and demonstration of dye-sensitive solar cell sensitizers containing bifuran/biphenyl derivatives with cyanoacetic acid, barbiturate, thiobarbituric acid, and 4-carboxylcyanoacetamides have been reported. A photovoltaic performance measurement was conducted using the Ru(ii) dye N3 as a reference to examine the effects of different electron acceptor units and replacement of the π-spacer bifuran by biphenyl units on the photophysical, electrochemical, and photovoltaic properties of eight new distinct organic dyes HB-1-8. The new organic dyes HB-1-8 were prepared and compared with the N3 metal dye. Density functional theory calculations were carried out to explore the ground state geometrical structures and electronic structures of the eight dyes. Under standard global AM 1.5 solar condition, the solar cells based on HB-1-8 show the overall power conversion efficiencies of 2.93-5.51%. The presented research shows that the organic dye photovoltaic performances can vary greatly depending on the type of electron donor and acceptor used. Dye HB-3 exhibited the highest efficiency among the eight investigated dyes, reaching 5.51% with a V OC value higher than N3.
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Several pyrazole-benzene sulfonamides were reported as human carbonic anhydrase inhibitors. In this research work, a design of Arylidine-extented 5-oxo-pyrazole benzenesulfonamides (4a-i), (8a-d) and (10a-e) were reported based on tail-approach design. Beside the reported synthetic procedures and confirmation by different analytical procedures, a DFT study was employed to confirm the Z- conformer of the synthesized compounds. In vitro biological assay against four different human carbonic anhydrases took place and based on the results, SAR study was illustrated and selectivity indexes were discussed. Compounds 4g and 8a exhibited the best inhibitory activity among the target compounds with values (hCAIX: KI = 71.2 nM, hCAXII: KI = 22.5 nM), (hCAIX: KI = 34.3 nM, hCAXII: KI = 74.3 nM); respectively. Both of them were subjected to cellular assay against two different cancer cell lines with expressing nature to hCA isoforms under both normoxic and hypoxic conditions. Compound 4g showed the highest cytotoxic activity against MCF-7 cancer cell line (IC50 = 4.15 µM under hypoxic conditions and IC50 = 8.59 µM under normoxic conditions) compared to the reference drug doxorubicin under normoxic, (IC50 = 4.34 µM), and hypoxic, (IC50 = 2.23 µM), conditions. Further cellular investigations were employed to study the effect of this compound on the cell cycle of the affected cell line. Finally, molecular docking supported by molecular dynamic simulation was utilized to understand the mechanism of the inhibitory activity of two of these compounds - as representative examples- based on the designed rational.
Assuntos
Inibidores da Anidrase Carbônica , Sulfonamidas , Humanos , Estrutura Molecular , Relação Estrutura-Atividade , Inibidores da Anidrase Carbônica/farmacologia , Simulação de Acoplamento Molecular , Sulfonamidas/farmacologia , Pirazóis/farmacologia , BenzenossulfonamidasRESUMO
Synthetic strategy for the synthesis of thiophene 2-carboxamide derivatives substituted with hydroxyl, methyl and amino groups at position-3 was proposed. The strategy includes the cyclization of the precursor ethyl 2-arylazo-3-mercapto-3-(phenylamino)acrylate derivatives, 2-acetyl-2-arylazo-thioacetanilide derivatives and N-aryl-2-cyano-3-mercapto-3-(phenylamino)acrylamide derivatives with N-(4-acetylphenyl)-2-chloroacetamide in alcoholic sodium ethoxide. IR, 1H NMR, and mass spectroscopic analyses were used to characterize the synthesized derivatives. In addition, molecular, electronic properties of the synthesized products were studied by the density functional theory (DFT) where they exhibited close HOMO-LUMO energy gap (ΔEH-L) in which the amino derivatives 7a-c have the highest while the methyl derivatives 5a-c were the lowest. Using the ABTS method, the antioxidant properties of the produced compounds were evaluated, where amino thiophene-2-carboxamide 7a exhibit significant inhibition activity 62.0% compared to ascorbic acid The antibacterial activity against two pathogenic Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and two of pathogenic Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) revealed that 7b records the highest activity index compared to ampicillin 83.3, 82.6, 64.0, 86.9%, respectively. Furthermore, the thiophene-2-carboxamide derivatives were docked with five different proteins with the use molecular docking tools and the results explained interactions between amino acid residue of enzyme and compounds. Compounds 3b and 3c showed the highest binding score with 2AS1 protein.
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3-Amino-4,6-dimethylpyrazolopyridine was applied as a precursor for the synthesis of some new pyridopyrazolo-triazine and pyridopyrazolo-triazole derivatives through diazotization, followed by coupling with many 2-cyanoacetamide compounds, ethyl 3-(phenylamino)-3-thioxopropanoate, 3-oxo-N-phenylbutanethioamide, and α-bromo-ketone reagents [namely; 2-bromo-1-(4-fluorophenyl)ethan-1-one, 5-bromo-2-(bromoacetyl)thiophene, 3-(2-bromoacetyl)-2H-chromen-2-one and/or 3-chloroacetylacetone]. The prepared compounds were identified by spectroscopic analyses as IR, 1H NMR, and mass data. The anticancer activity of these pyrazolopyridine analogues was investigated in colon, hepatocellular, breast, and cervix carcinoma cell lines. The pyridopyrazolo-triazine compound 5a substituted with a carboxylate group gave a distinguished value of IC50 = 3.89 µM against the MCF-7 cell line compared to doxorubicin as a reference drug. Also, the pyridopyrazolo-triazine compound 6a substituted with the carbothioamide function gave good activity toward HCT-116 and MCF-7 cell lines with IC50 values of 12.58 and 11.71 µM, respectively. The discovered pyrazolopyridine derivatives were studied theoretically by molecular docking, and this study exhibited suitable binding between the active sides of pyrazolopyridine ligands and proteins (PDB ID: 5IVE). The pyridopyrazolo-triazine compound 6a showed the highest free binding energy (- 7.8182 kcal/mol) when docked inside the active site of selected proteins.
Assuntos
Antineoplásicos , Humanos , Estrutura Molecular , Relação Estrutura-Atividade , Simulação de Acoplamento Molecular , Antineoplásicos/química , Triazinas/farmacologia , Células MCF-7 , Triazóis/química , Proliferação de Células , Ensaios de Seleção de Medicamentos Antitumorais , Linhagem Celular TumoralRESUMO
A new series of pyridine, thiazole, and pyrazole analogues were synthesized. The pyridone analogues 4a-e were synthesized by treating N-aryl-2-cyano-3-(4-(diphenylamino)phenyl)acrylamides 3a-e with malononitrile. Many 4-arylidene-thiazolidin-5-one analogues 6a-d were obtained by Knoevenagel reactions of 4-(diphenylamino)benzaldehyde (1) with their corresponding thiazolidin-5-one derivatives 5a-d. The structural elucidation of the products was proven by the collections of spectroscopic methods such as IR, 1H NMR, 13C NMR, and MS data. Their anti-cancer activity was examined against two cell lines, MDA-MB-231 (mammary carcinomas) and A-549 (lung cancer). Compared with cisplatin as a reference standard drug, 6-amino-4-(4-(diphenylamino)phenyl)-2-oxo-1-(p-tolyl)-1,2-dihydropyridine-3,5-dicarbonitrile (4b) and 6-amino-4-(4-(diphenylamino)phenyl)-1-(4-nitrophenyl)-2-oxo-1,2-dihydropyridine-3,5-dicarbonitrile (4e) exhibited better efficiency against the A-549 cell line, with IC50 = 0.00803 and 0.0095 µM, respectively. Also, these compounds 4b and 4e showed the most potency among the examined compounds against MDA-MB-231 with IC50 = 0.0103 and 0.0147 µM, respectively. The newly synthesized compounds were docked inside the active sites of the selected proteins and were found to demonstrate proper binding. 2-Cyano-2-(4,4-(diphenylamino)benzylidene)-5-oxo-3-phenylthiazolidin-2-ylidene)-N-(p-tolyl)acetamide (6c) offered the highest binding affinity (- 8.1868 kcal/mol) when docked into (PDB ID:2ITO), in addition to 2-cyano-N-(4-(diethylamino)phenyl)-2-(4-(4-(diphenylamino)benzylidene)-5-oxo-3-phenylthiazolidin-2-ylidene)acetamide (6a) gave the highest energy score (- 9.3507 kcal/mol) with (PDB ID:2A4L).
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A new series of metal-free organic dyes (SM1-5) with dual anchors are synthesized for application in dye-sensitized solar cells (DSSC). Here, a simple triphenylamine (TPA) moiety serves as the electron donor, while di-cyanoacrylamide and di-thiazolidine-5-one units serve as the electron acceptors and anchoring groups. To understand the effect of dye structure on the photovoltaic characteristics of DSSCs, the photophysical and electrochemical properties, as well as molecular geometries calculated from density functional theory (DFT), are used for dyes SM1-5. The extinction coefficients of the organic dyes SM1-5 are high (5.36-9.54 104 M-1 cm-1), indicating a high aptitude for light harvesting. The photovoltaic studies indicated that using dye SM4 as a sensitizer showed a power conversion efficiency (PCE) of 6.09% (JSC = 14.13 mA cm-2, VOC = 0.624 V, FF = 68.89%). Interestingly, SM4 showed the highest values of VOC among all dyes, including N-719, due to its maximum dye coverage on the TiO2 surface, enhancing charge recombination resistance in the sensitized cell. The good agreement between the theoretically and experimentally obtained data indicates that the energy functional and basis set employed in this study can be successfully utilized to predict new photosensitizers' absorption spectra with great precision before synthesis. Also, these results show that bi-anchoring molecules have a lot of potentials to improve the overall performance of dye-sensitized solar cells.
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Herein, we present a thorough photovoltaic investigation of four triphenylamine organic sensitizers with D-π-A configurations and compare their photovoltaic performances to the conventional ruthenium-based sensitizer N719. SFA-5-8 are synthesized and utilized as sensitizers for dye-sensitized solar cell (DSSC) applications. The effects of the donor unit (triphenylamine), π-conjugation bridge (thiophene ring), and various acceptors (phenylacetonitrile and 2-cyanoacetamide derivatives) were investigated. Moreover, this was asserted by profound calculations of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy levels, the molecular electrostatic potential (MEP), and natural bond orbital (NBO) that had been studied for the TPA-sensitizers. Theoretical density functional theory (DFT) was performed to study the distribution of electron density between donor and acceptor moieties. The sensitization by the absorption of sensitizers SFA-5-8 leads to an obvious enhancement in the visible light absorption (300-750 nm) as well as a higher photovoltaic efficiency in the range of (5.53-7.56%). Under optimized conditions, SFA-7 showed outstanding sensitization of nanocrystalline TiO2, resulting in enhancing the visible light absorption and upgrading the power conversion efficiency (PCE) to approximately 7.56% over that reported for the N719 (7.29%). Remarkably, SFA-7 outperformed N719 by 4% in the total conversion efficiency. Significantly, the superior performance of SFA-7 could be mainly ascribed to the higher short-circuit photocurrents (Jsc) in parallel with larger open-circuit voltages (Voc) and more importantly, the presence of different anchoring moieties that could enhance the ability to fill the gaps on the surface of the TiO2 semiconductor. That could be largely reflected in the overall enhancement in the device efficiency. Moreover, the theoretical electronic and photovoltaic properties of all studied sensitizers have been compared with experimental results. All the 2-cyanoacrylamide derivative sensitizers demonstrated robust photovoltaic performance.
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Fourteen new thienylnicotinamidines and their analogs 5a-5k, 12, 13a, and 13b were prepared and their antiproliferative potential was evaluated against the growth of 60 cancer cell lines. The tested compounds had a strong antiproliferative efficacy against almost all cancer cell lines, with the average GI50 at ~2.20 µM. The effect of the thienylnicotinamidines on the growth of normal lung fibroblast cells (WI-38) indicated that these derivatives are safe to the normal cells. The selectivity index (SI) ranges from 5.5- to 42.0-fold. The conceivable mechanisms of action of the effective compounds 5d, 5f, 5g, 5i, 5j, and 5k with high SI were investigated. Although the thienylnicotinamidines are similar in structure, they could be divided into three groups as per their effects on gene expression: The first group (5d and 5f) elevated p53 and caspase 3 expression, the second group (5g and 5i) elevated p53 expression, and the last group (5j and 5k) elevated p53 and reduced topoII expression. Many thienylnicotinamides inhibited the vascular endothelial growth factor receptor-2 (VEGFR-2) in cell lysates at concentrations comparable to or better than pazopanib. The data of caspase 3 expression were confirmed by measuring the protein level by Western blot and the activity of the cleaved active enzyme. The ability to arrest the cell cycle and induce apoptosis was confirmed by flow cytometry. Taken together, two derivatives, 5d and 5f, with a distinctive VEGFR-2 inhibitory activity and a proapoptotic and cell cycle arrest profile merit further investigations.
Assuntos
Antineoplásicos , Receptor 2 de Fatores de Crescimento do Endotélio Vascular , Apoptose , Caspase 3/metabolismo , Pontos de Checagem do Ciclo Celular , Proliferação de Células , Ensaios de Seleção de Medicamentos Antitumorais , Células Hep G2 , Humanos , Niacinamida/química , Relação Estrutura-Atividade , Proteína Supressora de Tumor p53/metabolismo , Proteína Supressora de Tumor p53/farmacologia , Fator A de Crescimento do Endotélio Vascular/metabolismo , Fator A de Crescimento do Endotélio Vascular/farmacologiaRESUMO
Two novel bithienyl fluorobenzamidine derivatives namely, 4-([2,2':5',2''-terthiophen]-5-yl)-2-fluorobenzamidine hydrochloride salt (MA-1615), 5'-(4-amidino-3-fluorophenyl)-[2,2'-bithiophene]-5-carboxamidine dihydrochloride salt (MA-1740) were synthesized, characterized and their corrosion inhibition properties were evaluated by electrochemical methods for carbon steel (C-steel) in 1 M HCl. Experimental investigations revealed that the inhibition effectiveness of the investigated inhibitors (INHs) by the Tafel polarization method followed the order: MA-1740 (96.9%) > MA-1615 (95.6%), demonstrating higher efficiency than inhibitors of similar structure reported in the literature. The investigated bithiophene derivatives exhibit mixed-type corrosion inhibition characteristics by blocking the active sites on the surface of C-steel. EIS study revealed that the INHs behave as interface-type corrosion inhibitors. UV-Visible spectrometric measurements confirmed a complex formation between the Fe2+ cation released during the corrosion reactions and inhibitor molecules.
RESUMO
New phthalonitrile derivatives formed from reactions of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) were considered as the key intermediates for the synthesis of new phthalocyanines. Moreover, new phthalonitrile derivatives 2, 5, 9, 10, 15 and 16 reacted with 1,4-diazabicyclo[2.2.2]octane (DBO) or hydroquinone to afford the corresponding new phthalocyanine dyes 3, 6, 11, 12, 17 and 18. In addition, the cyclotetramerization of phthalic anhydride derivative 20 afforded new phthalocyanine dye 22. Spectral and elemental investigations revealed the structures of the newly synthesized phthalocyanines. The antioxidant and cytotoxic properties of the novel compounds were investigated, and it has been established that compounds 17 and 18 have very strong anticancer and antioxidant action against all cell lines.
RESUMO
The photophysical and electrochemical properties of new targeted 2-cyanoacetanilide-based dyes are illustrated. New cyanoacetanilides SA7-10 were synthesized and employed as co-sensitizers in DSSCs. The chemical structures of these 2-cyanoacetanilides differ according to the substituent at the benzene ring (-H, -Me, -OMe and -NEt2), with the anchoring moiety being the same, a -COOH group. Furthermore, a density functional theory (DFT) calculation has shown an effective intermolecular charge transfer character, the HOMOs of SA7-10 are mainly located on the corresponding donor part, and their LUMOs are located on carboxylic acid moieties as the acceptor. Interestingly, using photosensitizers SA7-10 as co-sensitizers with HD-2 dye causes an improvement in their photovoltaic performances. Among the dyes, SA10 co-sensitized with HD-2 displayed an overall efficiency of 8.25%, a JSC of 19.5 mA cm-2, a VOC of 0.65 V and an FF of 64.35 compared to 7.46%, 19 mA cm-2, 0.64 V and 60.54, respectively, of HD-2 only. Moreover, the electrochemical impedance spectroscopy (EIS) data of SA7-10 and HD-2 were found to be in accordance with the obtained photovoltaic parameters. Finally, the results indicated that 2-cyanoacetanilide-based dyes were utilized as promising co-sensitizers due to their easy preparation methods and their relatively small size.