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2021 Volume 40 Issue 5
2021, 40(5): 533-539
doi: 10.14102/j.cnki.0254–5861.2011–3157
Abstract:
Electrochemical oxygen reduction reaction (ORR) with 2-electron process is an alternative for decentralized H2O2 production, but it remains high challenging to develop highly active and selective catalysts for this process. In this work, we present a selective and efficient nonprecious electrocatalyst, prepared through an easily scalable mild oxidation of single-walled carbon nanotubes (SWNTs) with different oxidative acids including sulfur acid, nitride acid and mixed sulfuric/nitric acids, respectively. The high-degree oxidized SWNTs treated by mixed acids exhibit the highest activity and selectivity of electroreduction of oxygen to synthesize H2O2 at low overpotential in alkaline and neutral media. Spectroscopic characterizations suggested that the C–O is vital for catalyzing 2-electron ORR, providing an insightful understanding of defected carbon surface as the active catalytic sites for 2-electron ORR.
Electrochemical oxygen reduction reaction (ORR) with 2-electron process is an alternative for decentralized H2O2 production, but it remains high challenging to develop highly active and selective catalysts for this process. In this work, we present a selective and efficient nonprecious electrocatalyst, prepared through an easily scalable mild oxidation of single-walled carbon nanotubes (SWNTs) with different oxidative acids including sulfur acid, nitride acid and mixed sulfuric/nitric acids, respectively. The high-degree oxidized SWNTs treated by mixed acids exhibit the highest activity and selectivity of electroreduction of oxygen to synthesize H2O2 at low overpotential in alkaline and neutral media. Spectroscopic characterizations suggested that the C–O is vital for catalyzing 2-electron ORR, providing an insightful understanding of defected carbon surface as the active catalytic sites for 2-electron ORR.
2021, 40(5): 540-548
doi: 10.14102/j.cnki.0254–5861.2011–2990
Abstract:
Excited-state intramolecular proton transfer (ESIPT) reactions of three ortho-hydroxylated oxazolines, 2-(4, 4-dimethyl-4, 5-dihydro-oxazol-2-yl)-phenol (DDOP), 4-(4, 4-dimethyl-4, 5-dihydro-oxazol-2-yl)-[1, 1΄-biphenyl]-3-ol (DDOP-C6H5) and 4-(4, 4-dimethyl-4, 5-dihydrooxazol-2-yl)-3-hydroxy-benzonitrile (DDOP-CN), have been systematically explored by density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. Two stable configurations (enol and keto forms) are found in the ground states (S0) for all the compounds while the enol form only exists in the first excited states (S1) for the compound modified with electron donating group (-C6H5). In addition, the calculated absorption and emission spectra of the compounds are in good agreements with the experiments. Infrared vibrational spectra at the hydrogen bond groups demonstrate that the intramolecular hydrogen bond O(1)−H(2)···N(3) in DDOP-C6H5 is strengthened in the S1 states, while the frontier molecular orbitals further reveal that the ESIPT reactions are more likely to occur in the S1 states for all the compounds. Besides, the proton transfer potential energy curves show that the enol forms can barely convert into keto forms in the S0 states because of the high energy barriers. Meanwhile, intramolecular proton transfer of all the compounds could occur in S1 states. The ESIPT reactions of the ortho-hydroxylated oxazolines are barrierless processes for unsubstituted DDOP and electron withdrawing substituted DDOP-CN, while the electron donating substituted DDOP-C6H5 has a small barrier, so the electron donating is unfavorable to the ESIPT reactions of ortho-hydroxylated oxazolines.
Excited-state intramolecular proton transfer (ESIPT) reactions of three ortho-hydroxylated oxazolines, 2-(4, 4-dimethyl-4, 5-dihydro-oxazol-2-yl)-phenol (DDOP), 4-(4, 4-dimethyl-4, 5-dihydro-oxazol-2-yl)-[1, 1΄-biphenyl]-3-ol (DDOP-C6H5) and 4-(4, 4-dimethyl-4, 5-dihydrooxazol-2-yl)-3-hydroxy-benzonitrile (DDOP-CN), have been systematically explored by density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. Two stable configurations (enol and keto forms) are found in the ground states (S0) for all the compounds while the enol form only exists in the first excited states (S1) for the compound modified with electron donating group (-C6H5). In addition, the calculated absorption and emission spectra of the compounds are in good agreements with the experiments. Infrared vibrational spectra at the hydrogen bond groups demonstrate that the intramolecular hydrogen bond O(1)−H(2)···N(3) in DDOP-C6H5 is strengthened in the S1 states, while the frontier molecular orbitals further reveal that the ESIPT reactions are more likely to occur in the S1 states for all the compounds. Besides, the proton transfer potential energy curves show that the enol forms can barely convert into keto forms in the S0 states because of the high energy barriers. Meanwhile, intramolecular proton transfer of all the compounds could occur in S1 states. The ESIPT reactions of the ortho-hydroxylated oxazolines are barrierless processes for unsubstituted DDOP and electron withdrawing substituted DDOP-CN, while the electron donating substituted DDOP-C6H5 has a small barrier, so the electron donating is unfavorable to the ESIPT reactions of ortho-hydroxylated oxazolines.
2021, 40(5): 549-564
doi: 10.14102/j.cnki.0254–5861.2011–2982
Abstract:
Acetaldehyde dehydrogenase 1A1 is a hopeful therapeutic target to ovarian cancer. In this present work, 3D-QSAR, molecular docking and molecular dynamics (MD) simulations were implemented on a series of quinoline-based ALDH1A1 inhibitors to investigate novel acetaldehyde dehydrogenase 1A1 inhibitors as anti-cancer adjuvant drugs for ovarian cancer. Two reliable CoMFA (Q2 = 0.583, R2 = 0.967) and CoMSIA (Q2 = 0.640, R2 = 0.977) models of ALDH1A1 inhibitors were established. Novel ALDH1A1 inhibitors were predicted by the 3D-QSAR models. Molecular docking reveals important residues for protein-compound interactions, and the results revealed ALDH1A1 inhibitors had stronger electrostatic interaction and binding affinity with key residues of protein, such as Phe171, Val174 and Cys303. Molecular dynamics simulations further verified the results of molecular docking. The above information provided significant guidance for the design of novel ALDH1A1 inhibitors.
Acetaldehyde dehydrogenase 1A1 is a hopeful therapeutic target to ovarian cancer. In this present work, 3D-QSAR, molecular docking and molecular dynamics (MD) simulations were implemented on a series of quinoline-based ALDH1A1 inhibitors to investigate novel acetaldehyde dehydrogenase 1A1 inhibitors as anti-cancer adjuvant drugs for ovarian cancer. Two reliable CoMFA (Q2 = 0.583, R2 = 0.967) and CoMSIA (Q2 = 0.640, R2 = 0.977) models of ALDH1A1 inhibitors were established. Novel ALDH1A1 inhibitors were predicted by the 3D-QSAR models. Molecular docking reveals important residues for protein-compound interactions, and the results revealed ALDH1A1 inhibitors had stronger electrostatic interaction and binding affinity with key residues of protein, such as Phe171, Val174 and Cys303. Molecular dynamics simulations further verified the results of molecular docking. The above information provided significant guidance for the design of novel ALDH1A1 inhibitors.
2021, 40(5): 565-575
doi: 10.14102/j.cnki.0254–5861.2011–2960
Abstract:
In this study, CoMFA, CoMSIA and HQSAR techniques were used to study the important characteristic activities of thieno [2, 3-d] pyrimidine derivatives for effective antitumor activity. The q2 value of cross validation of CoMFA model was 0.621, and r2 value of non-cross validation was 0.959. The best cross validation q2 value of CoMSIA model was 0.522, while the r2 value of non-cross validation was 0.961. The most effective HQSAR model was obtained by taking atoms and bonds as fragments: the q2 value of cross validation is 0.535, the r2 value of non-cross validation is 0.871, the standard error of prediction is 0.488, and the optimal hologram length is 199. The statistical parameters from the model show that the data fit well and have high prediction ability. In addition, molecular docking is used to study the binding requirements between ligands and receptor proteins, including several hydrogen bonds between thieno [2, 3-d] pyrimidine and active site residues. The results obtained from these QSAR modeling studies can be used to design promising anticancer drugs.
In this study, CoMFA, CoMSIA and HQSAR techniques were used to study the important characteristic activities of thieno [2, 3-d] pyrimidine derivatives for effective antitumor activity. The q2 value of cross validation of CoMFA model was 0.621, and r2 value of non-cross validation was 0.959. The best cross validation q2 value of CoMSIA model was 0.522, while the r2 value of non-cross validation was 0.961. The most effective HQSAR model was obtained by taking atoms and bonds as fragments: the q2 value of cross validation is 0.535, the r2 value of non-cross validation is 0.871, the standard error of prediction is 0.488, and the optimal hologram length is 199. The statistical parameters from the model show that the data fit well and have high prediction ability. In addition, molecular docking is used to study the binding requirements between ligands and receptor proteins, including several hydrogen bonds between thieno [2, 3-d] pyrimidine and active site residues. The results obtained from these QSAR modeling studies can be used to design promising anticancer drugs.
2021, 40(5): 588-594
doi: 10.14102/j.cnki.0254–5861.2011–2986
Abstract:
A new coordination polymer containing mixed ligands, namely [Ni(S2COiBu)2(DBPMF)·(CHCl3)]∞ (DBPMF = 2, 7-dibromo-9, 9-(4-pyridylmethyl)fluorine), has been synthesized and structurally characterized by elemental analysis and single-crystal X-ray diffractions. X-ray structural analysis reveals that each Ni atom is coordinated by two isobutyl xanthogenate molecules and two nitrogen atoms from two DBPMF ligands to form octahedral coordination geometry. DBPMF acts as a bridge to form a coordination polymer. Fluorescence property of this coordination polymer displays a broad emission band at λ = 413 nm. Thermal analysis shows that the solvent molecule CHCl3 can be stabilized in the crystal structure until 140 ℃.
A new coordination polymer containing mixed ligands, namely [Ni(S2COiBu)2(DBPMF)·(CHCl3)]∞ (DBPMF = 2, 7-dibromo-9, 9-(4-pyridylmethyl)fluorine), has been synthesized and structurally characterized by elemental analysis and single-crystal X-ray diffractions. X-ray structural analysis reveals that each Ni atom is coordinated by two isobutyl xanthogenate molecules and two nitrogen atoms from two DBPMF ligands to form octahedral coordination geometry. DBPMF acts as a bridge to form a coordination polymer. Fluorescence property of this coordination polymer displays a broad emission band at λ = 413 nm. Thermal analysis shows that the solvent molecule CHCl3 can be stabilized in the crystal structure until 140 ℃.
2021, 40(5): 595-602
doi: 10.14102/j.cnki.0254–5861.2011–2989
Abstract:
Two copper(Ⅱ) coordination polymers {[Cu(bib)(nip)]·1.5H2O}n (1) and [Cu2(bib)(glu)2]n (2) (bib = 1, 4-bis(2-methyl-imidazol-1-yl)butane, H2nip = 5-nitroisophthalic acid, H2glu = glutaric acid) were synthesized by the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analyses, IR and solid-state diffuse-reflection spectra. 1 forms a 2D network with the point symbol of (44·62) and 2D → 2D polythreaded network. 2 constructs the 6-connected 3D network based on the [Cu2(COO)2] dimer with the point symbol of (44·610·8). The energy band gaps (Eg) of 1 and 2 were 2.453 and 2.162 eV, respectively. 1 and 2 present high photocatalytic activity for the degradation of methylene blue under visible light irradiation.
Two copper(Ⅱ) coordination polymers {[Cu(bib)(nip)]·1.5H2O}n (1) and [Cu2(bib)(glu)2]n (2) (bib = 1, 4-bis(2-methyl-imidazol-1-yl)butane, H2nip = 5-nitroisophthalic acid, H2glu = glutaric acid) were synthesized by the hydrothermal method and characterized by single-crystal X-ray diffraction, elemental analyses, IR and solid-state diffuse-reflection spectra. 1 forms a 2D network with the point symbol of (44·62) and 2D → 2D polythreaded network. 2 constructs the 6-connected 3D network based on the [Cu2(COO)2] dimer with the point symbol of (44·610·8). The energy band gaps (Eg) of 1 and 2 were 2.453 and 2.162 eV, respectively. 1 and 2 present high photocatalytic activity for the degradation of methylene blue under visible light irradiation.
2021, 40(5): 610-614
doi: 10.14102/j.cnki.0254–5861.2011–2992
Abstract:
Constructed from 2, 5-bis(4-pyridyl) thiazolo[5, 4-d]thiazole (Py2TTz), sulfate anions and metal ions Cd(II), a new 3D luminescent metal-organic framework (LMOF) with good water stability is synthesized under solvothermal condition. [Cd(Py2TTz)(SO4)]n (Py2TTz = 2, 5-bis(4-pyridyl) thiazolo[5, 4-d]thiazole). It crystallizes in tetragonal space group P421m with a = 6.830(3), b = 6.830(3), c = 17.676(12) Å, V = 824.5(8) Å3, Z = 4, Mr = 504.83, Dc = 2.033 g·cm-3, F(000) = 496, GOOF = 1.088, the final R = 0.0434 and wR = 0.0948 for 6301 reflections with I > 2σ(I). Upon excitation at 370 nm, the emission peak of the compound appears at 455 nm, which has a slight redshift compared to the free ligand Py2TTz. The compound has potential to be a luminescence sensing material.
Constructed from 2, 5-bis(4-pyridyl) thiazolo[5, 4-d]thiazole (Py2TTz), sulfate anions and metal ions Cd(II), a new 3D luminescent metal-organic framework (LMOF) with good water stability is synthesized under solvothermal condition. [Cd(Py2TTz)(SO4)]n (Py2TTz = 2, 5-bis(4-pyridyl) thiazolo[5, 4-d]thiazole). It crystallizes in tetragonal space group P421m with a = 6.830(3), b = 6.830(3), c = 17.676(12) Å, V = 824.5(8) Å3, Z = 4, Mr = 504.83, Dc = 2.033 g·cm-3, F(000) = 496, GOOF = 1.088, the final R = 0.0434 and wR = 0.0948 for 6301 reflections with I > 2σ(I). Upon excitation at 370 nm, the emission peak of the compound appears at 455 nm, which has a slight redshift compared to the free ligand Py2TTz. The compound has potential to be a luminescence sensing material.
2021, 40(5): 615-624
doi: 10.14102/j.cnki.0254–5861.2011–2987
Abstract:
Three lanthanide complexes [LnL3(H2O)]PMo12O40·CH3CN (Ln = Dy3+ for 1, Ln = Ho3+ for 2, Ln = Lu3+ for 3, L = tetraethyl ethylenediphosphonate) have been synthesized, and characterized by single-crystal X-ray diffraction, elemental analysis, IR, PXRD, thermogravimetric analysis and terahertz time-domain spectroscopy (THz-TDS). Structural analysis results show that they have the same coordination mode and similar steric structures. Complexes 1~3 all crystallize in the monoclinic crystal system with space group P21/c. The centered Ln(Ⅲ) obtained a seven-coordinated mononuclear structure by linking with three tetraethyl ethylenediphosphonates and one water molecule, resulting in a three-dimensional supramolecular structure through hydrogen bonding. The three complexes have good adsorption properties for rhodamine B (RhB) in powder state. Moreover, terahertz time-domain spectroscopy (THz-TDS) was applied to represent the structures of complexes and ligands, which will provide useful information for establishing bridge between THz and complex structure in coordination chemistry.
Three lanthanide complexes [LnL3(H2O)]PMo12O40·CH3CN (Ln = Dy3+ for 1, Ln = Ho3+ for 2, Ln = Lu3+ for 3, L = tetraethyl ethylenediphosphonate) have been synthesized, and characterized by single-crystal X-ray diffraction, elemental analysis, IR, PXRD, thermogravimetric analysis and terahertz time-domain spectroscopy (THz-TDS). Structural analysis results show that they have the same coordination mode and similar steric structures. Complexes 1~3 all crystallize in the monoclinic crystal system with space group P21/c. The centered Ln(Ⅲ) obtained a seven-coordinated mononuclear structure by linking with three tetraethyl ethylenediphosphonates and one water molecule, resulting in a three-dimensional supramolecular structure through hydrogen bonding. The three complexes have good adsorption properties for rhodamine B (RhB) in powder state. Moreover, terahertz time-domain spectroscopy (THz-TDS) was applied to represent the structures of complexes and ligands, which will provide useful information for establishing bridge between THz and complex structure in coordination chemistry.
2021, 40(5): 625-630
doi: 10.14102/j.cnki.0254–5861.2011–2976
Abstract:
A Fe-based metal-organic framework, [Fe(INAIP)(DMF)]n·0.5nDMF (1), has been synthesized by the reaction of 5-(isonicotinamido)isophthalic acid (H2INAIP) with FeSO4∙7H2O under DMF reaction solvent. Single-crystal X-ray diffraction analysis indicates that complex 1 displays a two-fold interpenetrated three-dimensional (3D) framework with sra topology. The TG, magnetic and adsorption properties of the complex were also studied.
A Fe-based metal-organic framework, [Fe(INAIP)(DMF)]n·0.5nDMF (1), has been synthesized by the reaction of 5-(isonicotinamido)isophthalic acid (H2INAIP) with FeSO4∙7H2O under DMF reaction solvent. Single-crystal X-ray diffraction analysis indicates that complex 1 displays a two-fold interpenetrated three-dimensional (3D) framework with sra topology. The TG, magnetic and adsorption properties of the complex were also studied.
2021, 40(5): 631-636
doi: 10.14102/j.cnki.0254–5861.2011–3057
Abstract:
A new manganese(II) complex [Mn(C14H9O3)2(C12H8N2)2]·4H2O (1) was synthesized with o-ben- zoylbenzoic acid, manganese sulfate and 1, 10-phenanthroline (phen) in the mixture of acetonitrile and water solvent. It crystallizes (C52H42MnN4O10, Mr = 937.83) in monoclinic, space group P21/n with a = 13.3528(5), b = 17.6963(6), c = 19.7889(7) Å, β = 109.647(4)º, V = 4403.8(3) Å3, Dc = 1.415 g/cm3, Z = 4, F(000) = 1948, μ(MoKα) = 0.368 mm-1, R = 0.0404 and wR = 0.0956. The crystal structure shows that the manganese ion is coordinated with two oxygen atoms from two o-benzoylbenzoic acid molecules and four nitrogen atoms from two phen molecules, forming a distorted octahedral coordination geometry. The TG, spectrum analysis and magnetic properties of 1 were studied.
A new manganese(II) complex [Mn(C14H9O3)2(C12H8N2)2]·4H2O (1) was synthesized with o-ben- zoylbenzoic acid, manganese sulfate and 1, 10-phenanthroline (phen) in the mixture of acetonitrile and water solvent. It crystallizes (C52H42MnN4O10, Mr = 937.83) in monoclinic, space group P21/n with a = 13.3528(5), b = 17.6963(6), c = 19.7889(7) Å, β = 109.647(4)º, V = 4403.8(3) Å3, Dc = 1.415 g/cm3, Z = 4, F(000) = 1948, μ(MoKα) = 0.368 mm-1, R = 0.0404 and wR = 0.0956. The crystal structure shows that the manganese ion is coordinated with two oxygen atoms from two o-benzoylbenzoic acid molecules and four nitrogen atoms from two phen molecules, forming a distorted octahedral coordination geometry. The TG, spectrum analysis and magnetic properties of 1 were studied.
2021, 40(5): 637-645
doi: 10.14102/j.cnki.0254–5861.2011–2995
Abstract:
In this work two isomeric semi-rigid multi-carboxylate ligands 3, 5-bi(3-carboxyphenoxy)benzoic acid (3-H3BCP), 3, 5-bi(4-carboxyphenoxy)benzoic acid (4-H3BCP) and two rigid ligands (bis-triazole 4-(4-(4H-1, 2, 4-triazol-4-yl)phenyl)-4H-1, 2, 4-triazole (L1), 2-(1H-pyrazol-3-yl)pyrazine (L2)) have been employed to react with Cd(II) salts under similar solvothermal reactions. Two novel Cd(II) mixed-ligand coordination polymers, namely, {[Cd3(3-BCP)2(L1)]·3H2O}n (1) and [Cd(4-HBCP)(L2)]n (2), have been isolated. 1 displays a rare 2D cluster-based network while 2 displays a 3D supramolecular network through weak interactions. Solid-state luminescent properties and thermal analyses of 1 and 2 also have been determined, indicating strong fluorescent emissions and good thermal stabilities. Different coordination modes of two semi-rigid multi-carboxylate ligands and L1 and L2 also have been briefly discussed, which also reveal the great potential in the construction of these novel mixed-ligand luminescent frameworks with diverse structural motifs and unique functional properties.
In this work two isomeric semi-rigid multi-carboxylate ligands 3, 5-bi(3-carboxyphenoxy)benzoic acid (3-H3BCP), 3, 5-bi(4-carboxyphenoxy)benzoic acid (4-H3BCP) and two rigid ligands (bis-triazole 4-(4-(4H-1, 2, 4-triazol-4-yl)phenyl)-4H-1, 2, 4-triazole (L1), 2-(1H-pyrazol-3-yl)pyrazine (L2)) have been employed to react with Cd(II) salts under similar solvothermal reactions. Two novel Cd(II) mixed-ligand coordination polymers, namely, {[Cd3(3-BCP)2(L1)]·3H2O}n (1) and [Cd(4-HBCP)(L2)]n (2), have been isolated. 1 displays a rare 2D cluster-based network while 2 displays a 3D supramolecular network through weak interactions. Solid-state luminescent properties and thermal analyses of 1 and 2 also have been determined, indicating strong fluorescent emissions and good thermal stabilities. Different coordination modes of two semi-rigid multi-carboxylate ligands and L1 and L2 also have been briefly discussed, which also reveal the great potential in the construction of these novel mixed-ligand luminescent frameworks with diverse structural motifs and unique functional properties.
2021, 40(5): 646-652
doi: 10.14102/j.cnki.0254–5861.2011–2984
Abstract:
There are currently many materials for treating residual antibiotics in the environment, but none of them can specifically remove antibiotics. In addition, these materials are not sensitive enough to low concentrations of antibiotics. Here we show that a sensitive and specific material was developed by the preparation of magnetic Fe3O4-PAMAM-antibody complexes for treating tetracycline. The prepared antibody complexes can specifically treat tetracycline from aqueous solutions and the tetracycline removal ability by adsorption was also investigated. Controlled experiments were carried out with the effects of solution pH, temperature, and initial concentration of the tetracycline. The tetracycline was completely removed within 35 min at room temperature 30 ℃ with the maximum removal rate of almost 100%. Therefore, this material for specifically combining antigen and antibody to treat tetracycline indicated good application prospects for the waste water treatment.
There are currently many materials for treating residual antibiotics in the environment, but none of them can specifically remove antibiotics. In addition, these materials are not sensitive enough to low concentrations of antibiotics. Here we show that a sensitive and specific material was developed by the preparation of magnetic Fe3O4-PAMAM-antibody complexes for treating tetracycline. The prepared antibody complexes can specifically treat tetracycline from aqueous solutions and the tetracycline removal ability by adsorption was also investigated. Controlled experiments were carried out with the effects of solution pH, temperature, and initial concentration of the tetracycline. The tetracycline was completely removed within 35 min at room temperature 30 ℃ with the maximum removal rate of almost 100%. Therefore, this material for specifically combining antigen and antibody to treat tetracycline indicated good application prospects for the waste water treatment.
2021, 40(5): 653-658
doi: 10.14102/j.cnki.0254–5861.2011–2981
Abstract:
The crystal of (24R)-3β, 5α-dihydroxy-24-ethyl-5α-cholestan-6-one (1) was isolated from the leaves of P. nagi planted in Fujian for the first time with the same skeleton as 26, 27-dinorcholest-5-en-3-β-ol (2) and β-sitosterol (3) that have been reported before. Compound 1 crystallizes in monoclinic, space group P21 with a = 10.8482(4), b = 7.3671(3), c = 33.7860(15) Å, β = 93.103(4)°, V = 2696.21(19) Å3, Z = 75, Mr = 446.70, ρcalc = 1.145 g/cm3, F(000) = 1032, μ = 0.572 mm–1, GOOF = 1.034, the final R = 0.0467 and wR = 0.1129 for 6989 observed reflections with I > 2σ(I). Compound 2 was selected to evaluate for their preliminary in vitro anticancer activity against four cancer cell lines for the first time. The results showed that compound 2 exhibited great inhibition against gastric cancer, breast cancer MCF-7, lung cancer A549 and Helacell lines with the inhibitions of 89.16% ±1.17, 97.02%±0.53, 47.20% ±2.58 and 36.89%±1.22 respectively at the concentration of 1.4×10-2 M, which means that we found the new anticancer compound in this plant medicine.
The crystal of (24R)-3β, 5α-dihydroxy-24-ethyl-5α-cholestan-6-one (1) was isolated from the leaves of P. nagi planted in Fujian for the first time with the same skeleton as 26, 27-dinorcholest-5-en-3-β-ol (2) and β-sitosterol (3) that have been reported before. Compound 1 crystallizes in monoclinic, space group P21 with a = 10.8482(4), b = 7.3671(3), c = 33.7860(15) Å, β = 93.103(4)°, V = 2696.21(19) Å3, Z = 75, Mr = 446.70, ρcalc = 1.145 g/cm3, F(000) = 1032, μ = 0.572 mm–1, GOOF = 1.034, the final R = 0.0467 and wR = 0.1129 for 6989 observed reflections with I > 2σ(I). Compound 2 was selected to evaluate for their preliminary in vitro anticancer activity against four cancer cell lines for the first time. The results showed that compound 2 exhibited great inhibition against gastric cancer, breast cancer MCF-7, lung cancer A549 and Helacell lines with the inhibitions of 89.16% ±1.17, 97.02%±0.53, 47.20% ±2.58 and 36.89%±1.22 respectively at the concentration of 1.4×10-2 M, which means that we found the new anticancer compound in this plant medicine.
2021, 40(5): 659-665
doi: 10.14102/j.cnki.0254–5861.2011–2974
Abstract:
The title compound (4aR, 7aS)-6-benzyl-1-((R)-2-(2-chlorophenyl)-4, 5-dihydrothiazole-4-carbonyl)- hexahydro-5H-pyrrolo[3, 4-b]pyridine-5, 7(6H)-dione (C24H22ClN3O3S) was synthesized, and its chemical structure was confirmed by 1H NMR, 13C NMR and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic system, space group C2/c with a = 28.929(6), b = 7.858(16), c = 22.936(5) Å, β = 125.20(3)°, V = 4221.4(15) Å3, Z = 8, Dc = 1.473 g/cm3, μ(MoKa) = 0.314 mm–1, the final R = 0.0629 and wR = 0.1708 for 2812 observed reflections with I > 2σ(I). The preliminary insecticidal activity indicated that the title compound exhibited good and promising insecticidal activities against Mythimna separata, Plutella xylostella and Culex pipiens pallens. Moreover, the calcium imaging experiment indicated that the title compound can activate intracellular calcium channels to release the stored calcium ion from endoplasmic reticulum (ER) to cytoplasm of Mythimna separata.
The title compound (4aR, 7aS)-6-benzyl-1-((R)-2-(2-chlorophenyl)-4, 5-dihydrothiazole-4-carbonyl)- hexahydro-5H-pyrrolo[3, 4-b]pyridine-5, 7(6H)-dione (C24H22ClN3O3S) was synthesized, and its chemical structure was confirmed by 1H NMR, 13C NMR and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic system, space group C2/c with a = 28.929(6), b = 7.858(16), c = 22.936(5) Å, β = 125.20(3)°, V = 4221.4(15) Å3, Z = 8, Dc = 1.473 g/cm3, μ(MoKa) = 0.314 mm–1, the final R = 0.0629 and wR = 0.1708 for 2812 observed reflections with I > 2σ(I). The preliminary insecticidal activity indicated that the title compound exhibited good and promising insecticidal activities against Mythimna separata, Plutella xylostella and Culex pipiens pallens. Moreover, the calcium imaging experiment indicated that the title compound can activate intracellular calcium channels to release the stored calcium ion from endoplasmic reticulum (ER) to cytoplasm of Mythimna separata.
2021, 40(5): 666-674
doi: 10.14102/j.cnki.0254–5861.2011–2991
Abstract:
Fifteen novel N-sulfonyl aromatic amide derivatives were designed and synthesized, and the structures were characterized by 1H- and 13C-NMR, EA and HRMS. The crystal structures of compounds I-8 and I-9 were obtained from X-ray diffraction: I-8 is of triclinic system, Mr = 372.35, space group P21/n with a = 7.9151(10), b = 8.5637(11), c = 12.2022(15) Å, β = 86.865(2)º, V = 807.09(18) Å3, Z = 2, F(000) = 384, Dc = 1.532 g/cm3, the final R = 0.0408 and wR = 0.1068 for 2836 unique reflections with 2435 observed ones (I > 2σ(I)). I-9 belongs to triclinic system, Mr = 407.39, space group P21/n, with a = 8.4911(8), b = 8.6053(9), c = 14.5808(15) Å, β = 77.1190(10)º, V = 995.44(17) Å3, Z = 2, F(000) = 416, Dc = 1.359 g/cm3, the final R = 0.0567 and wR = 0.1779 for 3475 unique reflections with 2392 observed ones (I > 2σ(I)). The preliminary bioassay results indicated that the target compounds showed weak nematicidal activity, while compound I-5 displayed good fungicidal activity against Colletotrichum capsici with the inhibition rate of 61.7%.
Fifteen novel N-sulfonyl aromatic amide derivatives were designed and synthesized, and the structures were characterized by 1H- and 13C-NMR, EA and HRMS. The crystal structures of compounds I-8 and I-9 were obtained from X-ray diffraction: I-8 is of triclinic system, Mr = 372.35, space group P21/n with a = 7.9151(10), b = 8.5637(11), c = 12.2022(15) Å, β = 86.865(2)º, V = 807.09(18) Å3, Z = 2, F(000) = 384, Dc = 1.532 g/cm3, the final R = 0.0408 and wR = 0.1068 for 2836 unique reflections with 2435 observed ones (I > 2σ(I)). I-9 belongs to triclinic system, Mr = 407.39, space group P21/n, with a = 8.4911(8), b = 8.6053(9), c = 14.5808(15) Å, β = 77.1190(10)º, V = 995.44(17) Å3, Z = 2, F(000) = 416, Dc = 1.359 g/cm3, the final R = 0.0567 and wR = 0.1779 for 3475 unique reflections with 2392 observed ones (I > 2σ(I)). The preliminary bioassay results indicated that the target compounds showed weak nematicidal activity, while compound I-5 displayed good fungicidal activity against Colletotrichum capsici with the inhibition rate of 61.7%.
2021, 40(5): 675-681
doi: 10.14102/j.cnki.0254–5861.2011–3080
Abstract:
Tri(o-chlorobenzyl)tin 2, 4, 6-trimethylbenzoate (1) and tri(o-bromobenzyl)tin salicylate (2) were synthesized and characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C and 119Sn), thermogravimetric analysis, and single-crystal X-ray diffraction. The initio calculation and in vitro anticancer activity test were performed for compounds 1 and 2. They are both single tin nucleus structures and the tin atoms were tetracoordinated in a distorted tetrahedral configuration; Compounds 1 and 2 showed stronger anticancer activity than cisplatin in human cervical cancer cells (Hela), liver cancer cells (HuH-7), non-small cell lung cancer cells (A549), lung adenocarcinoma cells (H1975) and breast cancer (MCF-7).
Tri(o-chlorobenzyl)tin 2, 4, 6-trimethylbenzoate (1) and tri(o-bromobenzyl)tin salicylate (2) were synthesized and characterized by elemental analysis, IR spectroscopy, NMR (1H, 13C and 119Sn), thermogravimetric analysis, and single-crystal X-ray diffraction. The initio calculation and in vitro anticancer activity test were performed for compounds 1 and 2. They are both single tin nucleus structures and the tin atoms were tetracoordinated in a distorted tetrahedral configuration; Compounds 1 and 2 showed stronger anticancer activity than cisplatin in human cervical cancer cells (Hela), liver cancer cells (HuH-7), non-small cell lung cancer cells (A549), lung adenocarcinoma cells (H1975) and breast cancer (MCF-7).
