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2019 Volume 82 Issue 7
2019, 82(7): 579-584
Abstract:
Molecular imprinting mimic enzyme is a man-made polymer which has the specific catalytic activity for the target molecule by using molecular imprinting technology. It also shows good chemical and physical stability, structural predetermination and practicality. This paper mainly presents the construction strategy of the molecular imprinting mimic enzyme:transition state analogs imprinting, substrate or structural analogs imprinting and other construction approaches. The recent research progress in the preparation method was reviewed in this paper. The catalytic reactions with the enzyme mimics which relate to the catalysis for organic synthesis, decomposition of hazardous substances for food safety, degradation of environmental pollutants and examination in clinical medicine etc were summarized.
Molecular imprinting mimic enzyme is a man-made polymer which has the specific catalytic activity for the target molecule by using molecular imprinting technology. It also shows good chemical and physical stability, structural predetermination and practicality. This paper mainly presents the construction strategy of the molecular imprinting mimic enzyme:transition state analogs imprinting, substrate or structural analogs imprinting and other construction approaches. The recent research progress in the preparation method was reviewed in this paper. The catalytic reactions with the enzyme mimics which relate to the catalysis for organic synthesis, decomposition of hazardous substances for food safety, degradation of environmental pollutants and examination in clinical medicine etc were summarized.
2019, 82(7): 585-589
Abstract:
SAPO-34 molecular sieve is widely used in the reaction of methanol to olefin (MTO). Traditional SAPO-34 molecular sieve is prone to carbon deposition and coking in the catalytic process, which lead to molecular sieve deactivation and short service life. Nano-scale SAPO-34 molecular sieves have smaller crystal size, higher specific surface area, less diffusion limitation, stronger catalyst activity center and anti-carbon deposition ability. In this paper, the preparation methods of nano-scale SAPO-34 were introduced from the perspectives of seed assist, additive addition, double template agent and optimization of crystallization conditions, and the effects of different conditions on the size of nano crystals were further studied and analyzed. Meanwhile, the catalytic performance of different nano-sized SAPO-34 in MTO was discussed. The current research problems and future development directions are put forward.
SAPO-34 molecular sieve is widely used in the reaction of methanol to olefin (MTO). Traditional SAPO-34 molecular sieve is prone to carbon deposition and coking in the catalytic process, which lead to molecular sieve deactivation and short service life. Nano-scale SAPO-34 molecular sieves have smaller crystal size, higher specific surface area, less diffusion limitation, stronger catalyst activity center and anti-carbon deposition ability. In this paper, the preparation methods of nano-scale SAPO-34 were introduced from the perspectives of seed assist, additive addition, double template agent and optimization of crystallization conditions, and the effects of different conditions on the size of nano crystals were further studied and analyzed. Meanwhile, the catalytic performance of different nano-sized SAPO-34 in MTO was discussed. The current research problems and future development directions are put forward.
2019, 82(7): 590-597
Abstract:
In the recent years, counter-current chromatography based on hydrodynamic has been widely used in the separation of natural products and biochemical drugs. And column design is the core of the chromatographic system, the geometry and installation of the pipe, the position and volume of the separation column, and other factors will produce significant affect on the chromatographic behavior and separation efficiency. In this paper, the development and application of modern counter-current chromatographic separation column based on hydrodynamics are reviewed, and the prospect of future counter-current chromatography is also presented.
In the recent years, counter-current chromatography based on hydrodynamic has been widely used in the separation of natural products and biochemical drugs. And column design is the core of the chromatographic system, the geometry and installation of the pipe, the position and volume of the separation column, and other factors will produce significant affect on the chromatographic behavior and separation efficiency. In this paper, the development and application of modern counter-current chromatographic separation column based on hydrodynamics are reviewed, and the prospect of future counter-current chromatography is also presented.
2019, 82(7): 598-605, 597
Abstract:
Sulfur fumigation is a traditional drying method to prevent Chinese medicine materials from insects, molds and erosion etc, and can be used to bleach them. In recent years, investigations have found that the certain active components of traditional Chinese medicine (TCM) can be transformed into sulfur-containing derivatives in the process of sulfur fumigation, resulting in changes of metabolism and pharmacodynamics in the body, and even production of toxic reactions. This paper comprehensively summarizes the various morphologies of sulfur elements, chemical transformation rules of TCM and the toxicological studies in sulfur-fumigation. The review would provide valuable references for further evaluating the rationality of sulfur fumigation process of TCM.
Sulfur fumigation is a traditional drying method to prevent Chinese medicine materials from insects, molds and erosion etc, and can be used to bleach them. In recent years, investigations have found that the certain active components of traditional Chinese medicine (TCM) can be transformed into sulfur-containing derivatives in the process of sulfur fumigation, resulting in changes of metabolism and pharmacodynamics in the body, and even production of toxic reactions. This paper comprehensively summarizes the various morphologies of sulfur elements, chemical transformation rules of TCM and the toxicological studies in sulfur-fumigation. The review would provide valuable references for further evaluating the rationality of sulfur fumigation process of TCM.
2019, 82(7): 606-611
Abstract:
A novel Cu(I) coordination complex[CuI(L1)4](ClO4)2, (L1=4-ethylenedithiotetr-athiafulvalenylpyridine) was synthesized by coordination-driven self-assemble method through a solution process and characterized with micro and bulk crystals forms. The purity of the micro crystals was confirmed by the elemental analysis and XRD results. In the bulk crystal form, the complex[CuI(L1)4](ClO4)2 is mononuclear and further assembles into a 3D supramolecular network through S…S noncovalent interactions. Moreover, the supramolecular chain[CuI(L1)4]∞ forms an one-dimensional microporous framework along c axis (8.05×7.67Å). Due to the construction of an one-dimensional uniform array of the TTF+1/4 along the c axis, a semiconducting behavior is observed in complex[CuI(L1)4](ClO4)2 with σrt=9.1×10-2 S·cm-1 and an activation energy of Ea=50meV.
A novel Cu(I) coordination complex[CuI(L1)4](ClO4)2, (L1=4-ethylenedithiotetr-athiafulvalenylpyridine) was synthesized by coordination-driven self-assemble method through a solution process and characterized with micro and bulk crystals forms. The purity of the micro crystals was confirmed by the elemental analysis and XRD results. In the bulk crystal form, the complex[CuI(L1)4](ClO4)2 is mononuclear and further assembles into a 3D supramolecular network through S…S noncovalent interactions. Moreover, the supramolecular chain[CuI(L1)4]∞ forms an one-dimensional microporous framework along c axis (8.05×7.67Å). Due to the construction of an one-dimensional uniform array of the TTF+1/4 along the c axis, a semiconducting behavior is observed in complex[CuI(L1)4](ClO4)2 with σrt=9.1×10-2 S·cm-1 and an activation energy of Ea=50meV.
2019, 82(7): 612-617
Abstract:
A series of compounds with twisted intramolecular charge transfer (TICT) based on aromatic ketone derivatives were synthesized and characterized. The effects of different conjugated groups and substituent positions on the spectral properties of these compounds were studied by characterization of their linear photophysical and two-photon absorption properties. Additionally, the intramolecular charge transfer properties of these compounds were also studied by solvent effect. Combined with theoretical calculations, the results showed that the molecular conjugated skeleton and the position of substituents can significantly affect the intramolecular charge transfer characteristics. Fluorenone based compounds exhibite strong two-photon absorption and aggregation-induced fluorescence enhancement effects, which have potential applications in biological imaging.
A series of compounds with twisted intramolecular charge transfer (TICT) based on aromatic ketone derivatives were synthesized and characterized. The effects of different conjugated groups and substituent positions on the spectral properties of these compounds were studied by characterization of their linear photophysical and two-photon absorption properties. Additionally, the intramolecular charge transfer properties of these compounds were also studied by solvent effect. Combined with theoretical calculations, the results showed that the molecular conjugated skeleton and the position of substituents can significantly affect the intramolecular charge transfer characteristics. Fluorenone based compounds exhibite strong two-photon absorption and aggregation-induced fluorescence enhancement effects, which have potential applications in biological imaging.
2019, 82(7): 618-622
Abstract:
Probe L was synthesized by using 1, 4-diethyl-7-hydroxytetrahydroquinoxaline-6-carboxaldehyde and 2-methylbenzothiazole salt as starting materials, and its structure was characterized. The probe L can recognize H2S with fast fluorescence "off-on" response, high selectivity and good anti-interference ability in DMSO solution. The detection limit of probe L for H2S was 2.5×10-6mol/L. The fluorescence color of L changed from non-fluoresce to greenyellow strong fluorescence after adding H2S by irradiating with a 365nm UV lamp. Moreover, the color of the solution turned from blueviolet to colorless, thereby suggesting H2S can be detected by the naked eye.
Probe L was synthesized by using 1, 4-diethyl-7-hydroxytetrahydroquinoxaline-6-carboxaldehyde and 2-methylbenzothiazole salt as starting materials, and its structure was characterized. The probe L can recognize H2S with fast fluorescence "off-on" response, high selectivity and good anti-interference ability in DMSO solution. The detection limit of probe L for H2S was 2.5×10-6mol/L. The fluorescence color of L changed from non-fluoresce to greenyellow strong fluorescence after adding H2S by irradiating with a 365nm UV lamp. Moreover, the color of the solution turned from blueviolet to colorless, thereby suggesting H2S can be detected by the naked eye.
2019, 82(7): 623-629
Abstract:
A series of novel tetrahydrobenzo[4', 5']thieno[3', 2':5, 6]pyrido[4, 3-d]pyrimidine derivatives were designed and synthesized via a tandem aza-Wittig reaction, and their anti-tumor activities in vitro were evaluated for CNE2, KB, MGC-803, MCF-7 and PC3 cells by MTT assay. The preliminary biological results showed that these conjugates display significant antiproliferative effect on these five cancer cells, especially for MGC-803. Compound 8c (IC50=0.9±0.25μmol·L-1) stood out as the most potent compound against MGC-803, and is 20 times more active than 5-FU (IC50=18.4±1.43μmol·L-1). Additionally, all compounds were nontoxic to health GES-1 and VERO cells, while 5-FU showed essential toxicity. Tetrahydrobenzo[4', 5'] thieno[3', 2':5, 6] pyrido[4, 3-d] pyrimidine compounds displayed good anti-tumor activity and deserved further research.
A series of novel tetrahydrobenzo[4', 5']thieno[3', 2':5, 6]pyrido[4, 3-d]pyrimidine derivatives were designed and synthesized via a tandem aza-Wittig reaction, and their anti-tumor activities in vitro were evaluated for CNE2, KB, MGC-803, MCF-7 and PC3 cells by MTT assay. The preliminary biological results showed that these conjugates display significant antiproliferative effect on these five cancer cells, especially for MGC-803. Compound 8c (IC50=0.9±0.25μmol·L-1) stood out as the most potent compound against MGC-803, and is 20 times more active than 5-FU (IC50=18.4±1.43μmol·L-1). Additionally, all compounds were nontoxic to health GES-1 and VERO cells, while 5-FU showed essential toxicity. Tetrahydrobenzo[4', 5'] thieno[3', 2':5, 6] pyrido[4, 3-d] pyrimidine compounds displayed good anti-tumor activity and deserved further research.
2019, 82(7): 630-635
Abstract:
Fifteen novel paeonol thiazole derivatives were synthesized using paeonol as starting material and their structures were confirmed by IR, 1H NMR, 13C NMR and MS. All of them were evaluated for their cytotoxicity against three human cancer cell lines (MGC-803, LOVO and T-24) in vitro by standard MTT assay. The results presented that some of the target compounds exhibit significant cytotoxic activity, such as compounds 4b, 4e, 4f, 4h, 4l exhibite better antitumor activity than the positive reference cisplatin against MGC-803. In particular, compound 4b shows the most potent antitumor activities with IC50 values of 11.39±4.46 μg/mL, 2.06±1.27 μg/mL and 6.03±0.86 μg/mL against MGC-803, LOVO and T-24 tumor cell lines, respectively. It suggestes that compound 4b might be the candidate for further investigation.
Fifteen novel paeonol thiazole derivatives were synthesized using paeonol as starting material and their structures were confirmed by IR, 1H NMR, 13C NMR and MS. All of them were evaluated for their cytotoxicity against three human cancer cell lines (MGC-803, LOVO and T-24) in vitro by standard MTT assay. The results presented that some of the target compounds exhibit significant cytotoxic activity, such as compounds 4b, 4e, 4f, 4h, 4l exhibite better antitumor activity than the positive reference cisplatin against MGC-803. In particular, compound 4b shows the most potent antitumor activities with IC50 values of 11.39±4.46 μg/mL, 2.06±1.27 μg/mL and 6.03±0.86 μg/mL against MGC-803, LOVO and T-24 tumor cell lines, respectively. It suggestes that compound 4b might be the candidate for further investigation.
2019, 82(7): 636-641
Abstract:
Three novel chalcone derivatives of ferrocenyl, 1-ferrocenyl-3-(5-Bromothiophen-2-yl)-2-propen-1-one (1), 1-ferrocenyl-3-(4-bromothiophen-2-yl)-2-propen-1-one (2) and 1-ferrocenyl-3-(5-chlorthiophen-2-yl)-2-propen-1-one (3) were synthesized and characterized by 1H NMR, 13C NMR and HR-MS. The thermal properties of compounds 1~3 were measured. Their molecular orbital energies and polarizabilities were calculated by density functional theory method, and then the electronic cloud figures of the molecular orbitals were obtained. Their linear and nonlinear optical properties were investigated using UV-Vis absorption spectra and Z-scan technique (532 nm, 180 fs), respectively. The maximum absorption wavelength of compounds 1~3 increases significantly, and the nonlinear absorption amplitude, polarizability and molecular hyperpolarizability of compound 1 is the largest one. There is distinct intramolecular charge transfer phenomenon within these compounds, which results to interesting ultrafast third-order nonlinear optical response.
Three novel chalcone derivatives of ferrocenyl, 1-ferrocenyl-3-(5-Bromothiophen-2-yl)-2-propen-1-one (1), 1-ferrocenyl-3-(4-bromothiophen-2-yl)-2-propen-1-one (2) and 1-ferrocenyl-3-(5-chlorthiophen-2-yl)-2-propen-1-one (3) were synthesized and characterized by 1H NMR, 13C NMR and HR-MS. The thermal properties of compounds 1~3 were measured. Their molecular orbital energies and polarizabilities were calculated by density functional theory method, and then the electronic cloud figures of the molecular orbitals were obtained. Their linear and nonlinear optical properties were investigated using UV-Vis absorption spectra and Z-scan technique (532 nm, 180 fs), respectively. The maximum absorption wavelength of compounds 1~3 increases significantly, and the nonlinear absorption amplitude, polarizability and molecular hyperpolarizability of compound 1 is the largest one. There is distinct intramolecular charge transfer phenomenon within these compounds, which results to interesting ultrafast third-order nonlinear optical response.
2019, 82(7): 642-648
Abstract:
In order to obtain highly active, novel integrase strand transfer inhibitors (INSTIs), three-dimensional quantitative structure-activity relationship of 32 naphthyridine INST inhibitors were studied using CoMFA and CoMSIA leading to reliable models. The cross-validation coefficients were q2=0.809 and q2=0.816, the fitting verification coefficients were r2=0.998 and r2=0.981, indicating the predictive ability of the established models. Molecular docking was also performed to investigate the binding mode of small molecule compounds to INSTIs. The binding mode indicated that naphthyridines bind to INSTIs mainly via hydrophobic interactions and hydrogen bonding. Finally, the docking results were further verified by molecular dynamics simulation, and it was found that the binding mode of the docking was consistent with the results obtained by molecular dynamics simulation. The comprehensive models and inferences obtained in this study can provide an important theoretical information for the development of new and effective HIV INSTIs.
In order to obtain highly active, novel integrase strand transfer inhibitors (INSTIs), three-dimensional quantitative structure-activity relationship of 32 naphthyridine INST inhibitors were studied using CoMFA and CoMSIA leading to reliable models. The cross-validation coefficients were q2=0.809 and q2=0.816, the fitting verification coefficients were r2=0.998 and r2=0.981, indicating the predictive ability of the established models. Molecular docking was also performed to investigate the binding mode of small molecule compounds to INSTIs. The binding mode indicated that naphthyridines bind to INSTIs mainly via hydrophobic interactions and hydrogen bonding. Finally, the docking results were further verified by molecular dynamics simulation, and it was found that the binding mode of the docking was consistent with the results obtained by molecular dynamics simulation. The comprehensive models and inferences obtained in this study can provide an important theoretical information for the development of new and effective HIV INSTIs.
2019, 82(7): 649-654
Abstract:
The mechanism for the reaction of HO2 with HONO and its isomers was investigated at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(3d, 2p) level. The results showed that HONO has three different isomers, labeled as cis-HONO, trans-HONO and HNO2, and HNO2 is the most stable in them. The energy barrier of HO2+HNO2 is lower by 8.2~13.8 kcal·mol-1 than that of the other two reactions of cis-HONO+HO2 and trans-HONO+HO2. The rate constants of these three reactions were calculated by the traditional transition state theory with Wigner correction in the temperature range of 240~425 K. The calculated results showed that the rate constant of HO2+HNO2 reaction is larger by 4~9 orders of magnitude than those of cis-HONO+HO2 and trans-HONO+HO2, indicating that the total rate constants for the reaction of HO2 with HONO and its isomers mainly lie on the contribution of HO2+HNO2 reaction.
The mechanism for the reaction of HO2 with HONO and its isomers was investigated at the CCSD(T)/aug-cc-pVTZ//M06-2X/6-311+G(3d, 2p) level. The results showed that HONO has three different isomers, labeled as cis-HONO, trans-HONO and HNO2, and HNO2 is the most stable in them. The energy barrier of HO2+HNO2 is lower by 8.2~13.8 kcal·mol-1 than that of the other two reactions of cis-HONO+HO2 and trans-HONO+HO2. The rate constants of these three reactions were calculated by the traditional transition state theory with Wigner correction in the temperature range of 240~425 K. The calculated results showed that the rate constant of HO2+HNO2 reaction is larger by 4~9 orders of magnitude than those of cis-HONO+HO2 and trans-HONO+HO2, indicating that the total rate constants for the reaction of HO2 with HONO and its isomers mainly lie on the contribution of HO2+HNO2 reaction.
2019, 82(7): 655-658
Abstract:
Antifouling surfaces exhibit a promising future in wide applications. This paper reports the good antifouling performance of the polydopamine (rPDA) coatings prepared with a shaking-assisted method. The rPDA coatings were measured to have a contact angel lower than 15°, showing super hydrophilicity. With bovine serum albumin (BSA) as model protein, and grampositive Staphylococcus aureus and gram-negative Escherichia coli as model bacteria, it was found that the rPDA coatings could exhibit good anti-adsorption toward BSA and Staphylococcus aureus and Escherichia coli. Overall, the preparation method is facile, and the obtained rPDA coatings have good antifouling performances.
Antifouling surfaces exhibit a promising future in wide applications. This paper reports the good antifouling performance of the polydopamine (rPDA) coatings prepared with a shaking-assisted method. The rPDA coatings were measured to have a contact angel lower than 15°, showing super hydrophilicity. With bovine serum albumin (BSA) as model protein, and grampositive Staphylococcus aureus and gram-negative Escherichia coli as model bacteria, it was found that the rPDA coatings could exhibit good anti-adsorption toward BSA and Staphylococcus aureus and Escherichia coli. Overall, the preparation method is facile, and the obtained rPDA coatings have good antifouling performances.
2019, 82(7): 659-662
Abstract:
A new method for the determination of glutathione content was established by using the nanoenzyme effect of carboxylated graphene oxide (GO-COOH). The reaction time, pH, and H2O2 concentration were optimized. Under optimal conditions, the linear range of glutathione (GSH) standards was 1~50 μmol/L. The method was applied to the determination of practical sample, and verified by high performance liquid chromatography. The results showed that the content of glutathione tablets was easily and accurately measured with the relative error of 1.8%, indicating that the method is simple and intuitive, and can accurately measure the content of glutathione tablet.
A new method for the determination of glutathione content was established by using the nanoenzyme effect of carboxylated graphene oxide (GO-COOH). The reaction time, pH, and H2O2 concentration were optimized. Under optimal conditions, the linear range of glutathione (GSH) standards was 1~50 μmol/L. The method was applied to the determination of practical sample, and verified by high performance liquid chromatography. The results showed that the content of glutathione tablets was easily and accurately measured with the relative error of 1.8%, indicating that the method is simple and intuitive, and can accurately measure the content of glutathione tablet.
2019, 82(7): 663-665
Abstract:
Trans-4-(hydroxymethyl)piperidin-3-ol, a key intermediate of novel 5-hydroxytryptamine receptor agonist candidate, was synthesized by 4-hydroxymethylpyridin as starting material through four reaction steps including benzyl group protection, reduction with sodium borohydride, hydroboration-oxidation, deprotection of benzyl group. The total yield was up to 55.7%. The reaction products were characterized by IR, 1H NMR and MS, and the synthetic process was also optimized.
Trans-4-(hydroxymethyl)piperidin-3-ol, a key intermediate of novel 5-hydroxytryptamine receptor agonist candidate, was synthesized by 4-hydroxymethylpyridin as starting material through four reaction steps including benzyl group protection, reduction with sodium borohydride, hydroboration-oxidation, deprotection of benzyl group. The total yield was up to 55.7%. The reaction products were characterized by IR, 1H NMR and MS, and the synthetic process was also optimized.
2019, 82(7): 666-671
Abstract:
Academician Liang Jingkui died of illness in January 19, 2019. His series of research work on phase diagrams is considered to be a fruitful and high-level work in the field of phase diagrams in China. It has good theoretical and practical value, so his research results are remarkable. This article shows Liang Jingkui's life, his study experience and his contribution to physical chemistry.
Academician Liang Jingkui died of illness in January 19, 2019. His series of research work on phase diagrams is considered to be a fruitful and high-level work in the field of phase diagrams in China. It has good theoretical and practical value, so his research results are remarkable. This article shows Liang Jingkui's life, his study experience and his contribution to physical chemistry.
