Login In
2017 Volume 34 Issue 3
2017, 34(3): 245-261
doi: 10.11944/j.issn.1000-0518.2017.03.160438
Abstract:
Ion-conducting block copolymers(BCPs) as conducting materials have attracted significant interests in solid state lithium batteries. BCP self-assembly offers promise for designing ordered materials with nanoscale domains. Such nanostructures provide a facile method for introducing sufficient mechanical stability into polymer electrolyte membranes, while maintaining the ionic conductivity at levels similar to corresponding solvent-free homopolymer electrolytes. This ability to simultaneously control conductivity and mechanical integrity provides opportunities for the fabrication of sturdy, yet easily processable, solid-state lithium batteries. This review presents a brief overview of recent progress in ion-conducting block copolymers base on polyoxyethylene and single ion conductors. We also summarize some experimental studies of BCP electrolytes with respect to the effects of morphology on ionic conductivity. Finally, we present some remaining challenges for BCP electrolytes and highlight several important areas for future research.
Ion-conducting block copolymers(BCPs) as conducting materials have attracted significant interests in solid state lithium batteries. BCP self-assembly offers promise for designing ordered materials with nanoscale domains. Such nanostructures provide a facile method for introducing sufficient mechanical stability into polymer electrolyte membranes, while maintaining the ionic conductivity at levels similar to corresponding solvent-free homopolymer electrolytes. This ability to simultaneously control conductivity and mechanical integrity provides opportunities for the fabrication of sturdy, yet easily processable, solid-state lithium batteries. This review presents a brief overview of recent progress in ion-conducting block copolymers base on polyoxyethylene and single ion conductors. We also summarize some experimental studies of BCP electrolytes with respect to the effects of morphology on ionic conductivity. Finally, we present some remaining challenges for BCP electrolytes and highlight several important areas for future research.
2017, 34(3): 262-268
doi: 10.11944/j.issn.1000-0518.2017.03.160239
Abstract:
Owing to the shortage of lithium resources, we investigated the sodium-ion storage device using MoO3 as the negative electrode materials. MoO3 was prepared through a simple method and characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). MoO3 was used as the negative electrode materials for electric energy storage devices using Na+-based organic electrolytes. The charge storage mechanism at the MoO3 negative electrode was investigated by cyclic voltammetry and galvanostatic charge-discharge tests. A new type of electric energy storage devices was constructed with MoO3 as negative materials and activated carbon(or graphite) as positive materials. The electrochemical properties were studied in 1 mol/L NaPF6-propylene carbonate(PC). The MoO3/AC and MoO3/graphite devices owns the voltage ranges of 0~3.2 V and 0~3.5 V, energy densities of 31.6 Wh/kg and 53 Wh/kg, respectively. The long-cycling stabilities of both devices are superior to the AC/AC symmetric capacitor obviously. This kind of energy storage devices would be a good substitute for lithium-ion batteries.
Owing to the shortage of lithium resources, we investigated the sodium-ion storage device using MoO3 as the negative electrode materials. MoO3 was prepared through a simple method and characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). MoO3 was used as the negative electrode materials for electric energy storage devices using Na+-based organic electrolytes. The charge storage mechanism at the MoO3 negative electrode was investigated by cyclic voltammetry and galvanostatic charge-discharge tests. A new type of electric energy storage devices was constructed with MoO3 as negative materials and activated carbon(or graphite) as positive materials. The electrochemical properties were studied in 1 mol/L NaPF6-propylene carbonate(PC). The MoO3/AC and MoO3/graphite devices owns the voltage ranges of 0~3.2 V and 0~3.5 V, energy densities of 31.6 Wh/kg and 53 Wh/kg, respectively. The long-cycling stabilities of both devices are superior to the AC/AC symmetric capacitor obviously. This kind of energy storage devices would be a good substitute for lithium-ion batteries.
2017, 34(3): 269-275
doi: 10.11944/j.issn.1000-0518.2017.03.160214
Abstract:
To provide a theoretical basis for designing natural gas hydrate inhibitors and understanding the inhibition mechanism, and to analyze the nature and characteristics of the interactions between amphiphilic polyamides and water, water soluble poly(1,3-propylene citramide) was synthesized and based upon which, a new amphiphilic polymer was prepared by the modification with cyclohexyl isocyanate. The structure and properties of the product were characterized by proton nuclear magntic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry. The results show that the modified polymer forms nonfreezable bound water(NFBW) and the amount of the NFBW is twice the level in traditional kinetic gas hydrate inhibitors such as poly(N-vinylcaprolactam) or poly(N-vinylpyrrolidone). The specific heat capacities of water in the modified polymer increases remarkably by 36%. The hydrophobic interaction force between the polymer and water is enhanced, resulting in significant hydrophobic hydration restricted in the polymer. The modified polymers show strong hydrophobicity, leading to high levels of tightly bound water molecules and providing a necessary environment for increasing amount of NFBW.
To provide a theoretical basis for designing natural gas hydrate inhibitors and understanding the inhibition mechanism, and to analyze the nature and characteristics of the interactions between amphiphilic polyamides and water, water soluble poly(1,3-propylene citramide) was synthesized and based upon which, a new amphiphilic polymer was prepared by the modification with cyclohexyl isocyanate. The structure and properties of the product were characterized by proton nuclear magntic resonance spectroscopy, gel permeation chromatography and differential scanning calorimetry. The results show that the modified polymer forms nonfreezable bound water(NFBW) and the amount of the NFBW is twice the level in traditional kinetic gas hydrate inhibitors such as poly(N-vinylcaprolactam) or poly(N-vinylpyrrolidone). The specific heat capacities of water in the modified polymer increases remarkably by 36%. The hydrophobic interaction force between the polymer and water is enhanced, resulting in significant hydrophobic hydration restricted in the polymer. The modified polymers show strong hydrophobicity, leading to high levels of tightly bound water molecules and providing a necessary environment for increasing amount of NFBW.
2017, 34(3): 276-281
doi: 10.11944/j.issn.1000-0518.2017.03.160195
Abstract:
Condensation polymerization of 2,2'-bis(trifluoromethyl)-4,4'-diamino biphenyl(TFDB) and 3,3',4,4'-tetracarboxydiphthalic ether dianhydride(ODPA) gives a soluble polyimide. The effect of the degree of chemical imidization on positive photosensitive polyimide performance was investigated by adjusting the content of α-picoline in the imidization reagent to control the extent of the imide. The results show that the photosensitive polyimide has the best developing performance when the mole ratio of α-picoline to acetic anhydride is 1 to 5 in the process of chemical imidization.
Condensation polymerization of 2,2'-bis(trifluoromethyl)-4,4'-diamino biphenyl(TFDB) and 3,3',4,4'-tetracarboxydiphthalic ether dianhydride(ODPA) gives a soluble polyimide. The effect of the degree of chemical imidization on positive photosensitive polyimide performance was investigated by adjusting the content of α-picoline in the imidization reagent to control the extent of the imide. The results show that the photosensitive polyimide has the best developing performance when the mole ratio of α-picoline to acetic anhydride is 1 to 5 in the process of chemical imidization.
2017, 34(3): 282-290
doi: 10.11944/j.issn.1000-0518.2017.03.160237
Abstract:
Carbon nanotubes(CNTs) composited sodium polyacrylate(PAA-Na) superabsorbent polymer was prepared by solution polymerization of acrylic acid(AA), where ammonium persulfate(APS) was used as an initiator, N,N'-methylene-bisacrylamide(MBA) as a crosslinker in the presence of carbon nanotubes. Effects of the amount of CNTs, initiator, crosslinker and the reaction temperature on water absorbency were studied. The results show that the synthetic resins have the best water absorbency when the mass ratio of the crosslinker to AA is 0.04%, the initiator to AA is 0.3%, the CNTs to AA is 0.3% and the reaction temperature at 75℃. After the addition of carbon nanotubes, the CNTs/PAA-Na shows rough surface and porous structure, which may lead to changes in water absorbency. The water absorbence and the swelling rate by the CNTs/PAA-Na are significantly improved than those by PAA-Na. The highest water absorbence of CNTs/PAA-Na reaches 1423 g/g and 104 g/g in distilled water and in saline water, respectively. The CNTs/PAA-Na composite maintains 76.0% of its water absorbency after repeated five times, and the water absorbent capacity is 1081.5 g/g.
Carbon nanotubes(CNTs) composited sodium polyacrylate(PAA-Na) superabsorbent polymer was prepared by solution polymerization of acrylic acid(AA), where ammonium persulfate(APS) was used as an initiator, N,N'-methylene-bisacrylamide(MBA) as a crosslinker in the presence of carbon nanotubes. Effects of the amount of CNTs, initiator, crosslinker and the reaction temperature on water absorbency were studied. The results show that the synthetic resins have the best water absorbency when the mass ratio of the crosslinker to AA is 0.04%, the initiator to AA is 0.3%, the CNTs to AA is 0.3% and the reaction temperature at 75℃. After the addition of carbon nanotubes, the CNTs/PAA-Na shows rough surface and porous structure, which may lead to changes in water absorbency. The water absorbence and the swelling rate by the CNTs/PAA-Na are significantly improved than those by PAA-Na. The highest water absorbence of CNTs/PAA-Na reaches 1423 g/g and 104 g/g in distilled water and in saline water, respectively. The CNTs/PAA-Na composite maintains 76.0% of its water absorbency after repeated five times, and the water absorbent capacity is 1081.5 g/g.
2017, 34(3): 291-299
doi: 10.11944/j.issn.1000-0518.2017.03.160213
Abstract:
A high quality PVA/CdS QDs nanocomposites modified by thiol-functionalized polyvinylalcohol (PVA) was prepared by aqueous synthetic approaches at low temperature. The samples were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TG), photoluminescence spectroscopy (PL) and ultraviolet-visible spectroscopy (UV-Vis). The results show that CdS QDs in the nanocomposites are spherical particles with a cubic crystal structure and a diameter size of about 5 nm. PVA/CdS nanocomposites have good stability, high dispersibility and excellent luminescence properties. Meanwhile, the fluorescent responses of as-prepared PVA/CdS to different metal ions were studied. Based on the fluorescence quenching behavior of PVA/CdS quantum dots, we established a method for the fluorescent detection of Cu2+. When the concentration of Cu2+ is in the range of 1~1000 nmol/L, the fluorescence intensity linearly decreases with the increase of Cu2+ concentration. The linear correlation coefficient is 0.9923 and the detection limit reaches 0.12 nmol/L. The method provides high sensitivity, simplicity of operation and low detection limit, and is successfully applied to the determination of trace copper in the Yellow River samples.
A high quality PVA/CdS QDs nanocomposites modified by thiol-functionalized polyvinylalcohol (PVA) was prepared by aqueous synthetic approaches at low temperature. The samples were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TG), photoluminescence spectroscopy (PL) and ultraviolet-visible spectroscopy (UV-Vis). The results show that CdS QDs in the nanocomposites are spherical particles with a cubic crystal structure and a diameter size of about 5 nm. PVA/CdS nanocomposites have good stability, high dispersibility and excellent luminescence properties. Meanwhile, the fluorescent responses of as-prepared PVA/CdS to different metal ions were studied. Based on the fluorescence quenching behavior of PVA/CdS quantum dots, we established a method for the fluorescent detection of Cu2+. When the concentration of Cu2+ is in the range of 1~1000 nmol/L, the fluorescence intensity linearly decreases with the increase of Cu2+ concentration. The linear correlation coefficient is 0.9923 and the detection limit reaches 0.12 nmol/L. The method provides high sensitivity, simplicity of operation and low detection limit, and is successfully applied to the determination of trace copper in the Yellow River samples.
2017, 34(3): 300-307
doi: 10.11944/j.issn.1000-0518.2017.03.160406
Abstract:
A chelating fiber which contains large amount of sulfur atoms was prepared through two step reactions by microwave assisted method using polyacrylonitrile fibers (PANF) as the matrix and diethylenetriamine (DETA) and sodium sulphide as functional agents. The influence of pH, the initial concentration of metal ion, adsorption time and temperature were investigated thoroughly. The results show that microwave assisted method exhibits a highly efficient, energy saving, economic and eco-friendly way for the preparation of chelating fibers. The modification processes were performed in nontoxic water environment and the consumed amount of reaction agents were reduced remarkably, along with significantly decreased functionalization time. The pseudo-second-order model and Langmuir isotherm model were found to provide the best fit to the experiment data for the adsorption process of mercury. The obtained chelating fiber shows high affinity towards mercury with the maximum adsorption capacity of 333.1 mg/g at pH=7, in dicating its potential for the removal of mercury from aqueous solution.
A chelating fiber which contains large amount of sulfur atoms was prepared through two step reactions by microwave assisted method using polyacrylonitrile fibers (PANF) as the matrix and diethylenetriamine (DETA) and sodium sulphide as functional agents. The influence of pH, the initial concentration of metal ion, adsorption time and temperature were investigated thoroughly. The results show that microwave assisted method exhibits a highly efficient, energy saving, economic and eco-friendly way for the preparation of chelating fibers. The modification processes were performed in nontoxic water environment and the consumed amount of reaction agents were reduced remarkably, along with significantly decreased functionalization time. The pseudo-second-order model and Langmuir isotherm model were found to provide the best fit to the experiment data for the adsorption process of mercury. The obtained chelating fiber shows high affinity towards mercury with the maximum adsorption capacity of 333.1 mg/g at pH=7, in dicating its potential for the removal of mercury from aqueous solution.
2017, 34(3): 308-315
doi: 10.11944/j.issn.1000-0518.2017.03.160352
Abstract:
Sixteen novel double-heterocyclic modified amide sulfide derivatives containing 1,2,4-triazole and 1,3,4-thiadiazole were designed and synthesized, and their structures were characterized. The inhibitory activities of synthesized molecules against cell division cycle 25B(Cdc25B) of protein tyrosine phosphatase 1B(PTP1B) were evaluated. The results show that all target molecules exhibit good inhibitory activity against PTP1B. Compounds 8-C-d and 8-D-c have the optimal inhibition. Their half maximal inhibitory concentration(IC50) values are (1.19±0.22) mg/L and (1.08±0.09) mg/L, respectively, which are lower than that of positive reference oleanolic acid(IC50=(1.27±0.19) mg/L). They are expected to be anti-diabetic drug leading compounds. The target molecules also exhibit good inhibitory activities against Cdc25B. The IC50 values of compounds 8-A-d, 8-C-d and 8-D-c are higher than that of positive reference Na3VO4(IC50=(1.25±0.14) mg/L), which are expected to be anticancer drug leading compounds.
Sixteen novel double-heterocyclic modified amide sulfide derivatives containing 1,2,4-triazole and 1,3,4-thiadiazole were designed and synthesized, and their structures were characterized. The inhibitory activities of synthesized molecules against cell division cycle 25B(Cdc25B) of protein tyrosine phosphatase 1B(PTP1B) were evaluated. The results show that all target molecules exhibit good inhibitory activity against PTP1B. Compounds 8-C-d and 8-D-c have the optimal inhibition. Their half maximal inhibitory concentration(IC50) values are (1.19±0.22) mg/L and (1.08±0.09) mg/L, respectively, which are lower than that of positive reference oleanolic acid(IC50=(1.27±0.19) mg/L). They are expected to be anti-diabetic drug leading compounds. The target molecules also exhibit good inhibitory activities against Cdc25B. The IC50 values of compounds 8-A-d, 8-C-d and 8-D-c are higher than that of positive reference Na3VO4(IC50=(1.25±0.14) mg/L), which are expected to be anticancer drug leading compounds.
2017, 34(3): 316-323
doi: 10.11944/j.issn.1000-0518.2017.03.160219
Abstract:
In order to explore novel green pesticide with potent biological activities, a series of novel 1, 4-pentadien-3-one oxime ester derivatives bearing heterocycle moiety, derived from curcumin, was designed and synthesized. Their structures were confirmed by infrared spectroscopy, proton nuclear magnetic resonance spectroscopy (1H NMR), 13C NMR, and high resolution mass spectroscopy (HRMS). The bioassays indicate that inhibition rates of compound 5d against G.zeae, F.ox-ysporum and C.mandshurica at 50 mg/L are 64.75%, 52.05% and 69.68%, respectively, and compounds 5d, 5e and 5f have good curative and deactivation activities against tobacco mosaic virus at 500 mg/L, with the inhibition rates of 56.93% and 86.89%, 53.08% and 83.51%, and 53.40% and 89.01%, respectively. These indicate that 1, 4-pentadien-3-one oxime ester is a valuable scafford to develope new compounds poessessing high biological activities such as potential antifungal and antiviral activities.
In order to explore novel green pesticide with potent biological activities, a series of novel 1, 4-pentadien-3-one oxime ester derivatives bearing heterocycle moiety, derived from curcumin, was designed and synthesized. Their structures were confirmed by infrared spectroscopy, proton nuclear magnetic resonance spectroscopy (1H NMR), 13C NMR, and high resolution mass spectroscopy (HRMS). The bioassays indicate that inhibition rates of compound 5d against G.zeae, F.ox-ysporum and C.mandshurica at 50 mg/L are 64.75%, 52.05% and 69.68%, respectively, and compounds 5d, 5e and 5f have good curative and deactivation activities against tobacco mosaic virus at 500 mg/L, with the inhibition rates of 56.93% and 86.89%, 53.08% and 83.51%, and 53.40% and 89.01%, respectively. These indicate that 1, 4-pentadien-3-one oxime ester is a valuable scafford to develope new compounds poessessing high biological activities such as potential antifungal and antiviral activities.
2017, 34(3): 324-329
doi: 10.11944/j.issn.1000-0518.2017.03.160243
Abstract:
Benzoxazole derivatives are well known for their applications in medicinal, industrial and synthetic organic chemistry. Numerous effects has been focused on developing efficient methods for the synthesis of it. The benzoxazole derivatives was synthesised by condensation of 2-aminophenol and benzaldehyde in presence of glycerol under focused microwave-irradiation conditions. Reaction conditions:2-aminothiophenol(1.0 mmol), benzaldehyde(1.0 mmol), glycerol(2 mL), irradiating under focused microwave for several minutes at 20 W and 110℃. The corresponding products was obtained in 80% to 91% yield. The present method has the advantages of mild conditions, green solvent, simple operation, easily available reaction substrates, and excellent product yields, which make it a useful and important supplement to the existing methods.
Benzoxazole derivatives are well known for their applications in medicinal, industrial and synthetic organic chemistry. Numerous effects has been focused on developing efficient methods for the synthesis of it. The benzoxazole derivatives was synthesised by condensation of 2-aminophenol and benzaldehyde in presence of glycerol under focused microwave-irradiation conditions. Reaction conditions:2-aminothiophenol(1.0 mmol), benzaldehyde(1.0 mmol), glycerol(2 mL), irradiating under focused microwave for several minutes at 20 W and 110℃. The corresponding products was obtained in 80% to 91% yield. The present method has the advantages of mild conditions, green solvent, simple operation, easily available reaction substrates, and excellent product yields, which make it a useful and important supplement to the existing methods.
2017, 34(3): 330-337
doi: 10.11944/j.issn.1000-0518.2017.03.160220
Abstract:
A radical cyclization reaction of benzamides toward isoquinolinedione bearing α-substituted quaternary carbon was developed. Using alkyl azo compounds as tertiary radical sources, N-alkyl-N-methacryloylbenzamides underwent cascade radical addition/cyclization/C-C bond formation in the presence of Cu catalyst and air, and constructed triple-fold carbon-carbon bonds in a single step, leading to a series of isoquinolinediones in 41% to 71% yield. Notably, this work discovered a new type of radical precursor to α-functional tertiary radical and a protocol to incorporate two α-functional tertiary alkyl moieties. The broad substrate scope and high efficiency allow this method a cheap, simple and rapid catalytic synthetic entry to pharmaceutically interesting isoquinolindiones.
A radical cyclization reaction of benzamides toward isoquinolinedione bearing α-substituted quaternary carbon was developed. Using alkyl azo compounds as tertiary radical sources, N-alkyl-N-methacryloylbenzamides underwent cascade radical addition/cyclization/C-C bond formation in the presence of Cu catalyst and air, and constructed triple-fold carbon-carbon bonds in a single step, leading to a series of isoquinolinediones in 41% to 71% yield. Notably, this work discovered a new type of radical precursor to α-functional tertiary radical and a protocol to incorporate two α-functional tertiary alkyl moieties. The broad substrate scope and high efficiency allow this method a cheap, simple and rapid catalytic synthetic entry to pharmaceutically interesting isoquinolindiones.
2017, 34(3): 338-344
doi: 10.11944/j.issn.1000-0518.2017.03.160304
Abstract:
Two kinds of novel polyesters containing 8-hydroxyquinoline side groups (P5, P6) were synthesized by multistep reactions. Subsequently, polyesters P5 and P6 reacted with zinc acetate and aluminum chloride to get zinc complexes (P5-Zn, P6-Zn) and aluminum complexes (P5-Al, P6-Al). The structures and properties of polyesters and metal complexes were characterized by elemental analysis, IR, UV-Vis, 1H NMR, GPC, TG and fluorescence spectroscopy. Polyesters P5 and P6 can be easily dissolved in many solvents such as tetrahydrofurane (THF), N, N-dimethyl formamide (DMF), N, N-dimethyl acetamide (DMAC), dimethylsulfoxide (DMSO), and N-methyl pyrrolidone (NMP) at room temperature. Complexes P5-Zn, P6-Zn, P5-Al and P6-Al can be partially dissolved in DMF, DMAc, DMSO and NMP. The mass mean relative molecular mass (Mw) and polydispersity index (PDI) of P5 and P6 are 41200, 54200 and 1.50, 1.40, respectively. The 5% mass loss temperatures of P5, P6, P5-Zn, P6-Zn, P5-Al and P6-Al are 261.4, 291.1, 307.7, 306.2, 286.3 and 297.8℃, respectively. Fluorescence emission peaks of P5 and P6 in DMF solution appear at 432 and 429 nm, emitting weak purple light. Fluorescence emission peaks of P5-Zn, P6-Zn, P5-Al and P6-Al in solid state emerge at 550, 556, 531, 535 nm, emitting strong green light, which are all red-shifted to some extent, compared with their emission peaks in DMF solution located at 540, 537, 517 and 522 nm.
Two kinds of novel polyesters containing 8-hydroxyquinoline side groups (P5, P6) were synthesized by multistep reactions. Subsequently, polyesters P5 and P6 reacted with zinc acetate and aluminum chloride to get zinc complexes (P5-Zn, P6-Zn) and aluminum complexes (P5-Al, P6-Al). The structures and properties of polyesters and metal complexes were characterized by elemental analysis, IR, UV-Vis, 1H NMR, GPC, TG and fluorescence spectroscopy. Polyesters P5 and P6 can be easily dissolved in many solvents such as tetrahydrofurane (THF), N, N-dimethyl formamide (DMF), N, N-dimethyl acetamide (DMAC), dimethylsulfoxide (DMSO), and N-methyl pyrrolidone (NMP) at room temperature. Complexes P5-Zn, P6-Zn, P5-Al and P6-Al can be partially dissolved in DMF, DMAc, DMSO and NMP. The mass mean relative molecular mass (Mw) and polydispersity index (PDI) of P5 and P6 are 41200, 54200 and 1.50, 1.40, respectively. The 5% mass loss temperatures of P5, P6, P5-Zn, P6-Zn, P5-Al and P6-Al are 261.4, 291.1, 307.7, 306.2, 286.3 and 297.8℃, respectively. Fluorescence emission peaks of P5 and P6 in DMF solution appear at 432 and 429 nm, emitting weak purple light. Fluorescence emission peaks of P5-Zn, P6-Zn, P5-Al and P6-Al in solid state emerge at 550, 556, 531, 535 nm, emitting strong green light, which are all red-shifted to some extent, compared with their emission peaks in DMF solution located at 540, 537, 517 and 522 nm.
2017, 34(3): 345-353
doi: 10.11944/j.issn.1000-0518.2017.03.160236
Abstract:
2-Aminobenzyl alcohol and its derivatives are a kind of important bifunctional compounds, and has found wide application in organic chemistry and drug synthesis. An efficient and simple method for synthesis of 2-(arylaminoethylamino) benzyl alcohols was described and the fungicidal activities of the target compounds were evaluated in this paper. N-alkylation of 2-aminobenzyl alcohol with bromoacetyl aryl amines produced 2-[(2-hydroxymethylphenyl) amino] acetyl aryl amines 3a~3i, which were reduced by LiAlH4 giving a series of novel 2-(arylaminoethylamino) benzyl alcohols 5a~5i in 76%~95% yields. All the structures of the target compounds were characterized by the infrared spectroscopy (IR), proton nuclear magnetic resonance spectroscopy (1H NMR), 13C NMR and elemental analysis. Most of compounds show moderate to good fungicidal activities under the testing concentration. Compound 5e shows 73% activity of against Phytophythora capsici.
2-Aminobenzyl alcohol and its derivatives are a kind of important bifunctional compounds, and has found wide application in organic chemistry and drug synthesis. An efficient and simple method for synthesis of 2-(arylaminoethylamino) benzyl alcohols was described and the fungicidal activities of the target compounds were evaluated in this paper. N-alkylation of 2-aminobenzyl alcohol with bromoacetyl aryl amines produced 2-[(2-hydroxymethylphenyl) amino] acetyl aryl amines 3a~3i, which were reduced by LiAlH4 giving a series of novel 2-(arylaminoethylamino) benzyl alcohols 5a~5i in 76%~95% yields. All the structures of the target compounds were characterized by the infrared spectroscopy (IR), proton nuclear magnetic resonance spectroscopy (1H NMR), 13C NMR and elemental analysis. Most of compounds show moderate to good fungicidal activities under the testing concentration. Compound 5e shows 73% activity of against Phytophythora capsici.
2017, 34(3): 354-360
doi: 10.11944/j.issn.1000-0518.2017.03.160210
Abstract:
In order to investigate the properties of 3-carboxyl-1,2,4-triazole complexes, a novel complex,[Mn(C3H2N3O2)2(H2O)2], was synthesized by the hydrothermal method. The properties of the complex were characterized by Fourier transform infrared spectroscopy(IR), element analysis, thermal gravimetric anlysis(TGA) and powder X-ray diffraction(PXRD). The single crystal X-ray analysis reveals that the complex is a unique single-core structure and belongs to the monoclinic crystal system in space group P21/c. The coordination number of MnⅡ is six. The MnⅡ atom is located on an inversion centre. Each MnⅡ atom is coordinated by two O atoms and two N atoms from two 3-carboxyl-1,2,4-triazole anions and two coordinated water molecules to form a slightly distorted octahedral geometry. The discrete molecules of the complex are furthermore linked, resulting in a three-dimensional network structure through extensive intermolecular hydrogen bonds and π-π interactions. Solid fluorescence of the complex shows an emission peak at 517 nm. Compared with the ligand, there is a 7 nm blue shift. The research provides a reference for exploiting new metal-organic complex fluorescent materials.
In order to investigate the properties of 3-carboxyl-1,2,4-triazole complexes, a novel complex,[Mn(C3H2N3O2)2(H2O)2], was synthesized by the hydrothermal method. The properties of the complex were characterized by Fourier transform infrared spectroscopy(IR), element analysis, thermal gravimetric anlysis(TGA) and powder X-ray diffraction(PXRD). The single crystal X-ray analysis reveals that the complex is a unique single-core structure and belongs to the monoclinic crystal system in space group P21/c. The coordination number of MnⅡ is six. The MnⅡ atom is located on an inversion centre. Each MnⅡ atom is coordinated by two O atoms and two N atoms from two 3-carboxyl-1,2,4-triazole anions and two coordinated water molecules to form a slightly distorted octahedral geometry. The discrete molecules of the complex are furthermore linked, resulting in a three-dimensional network structure through extensive intermolecular hydrogen bonds and π-π interactions. Solid fluorescence of the complex shows an emission peak at 517 nm. Compared with the ligand, there is a 7 nm blue shift. The research provides a reference for exploiting new metal-organic complex fluorescent materials.
2017, 34(3): 361-366
doi: 10.11944/j.issn.1000-0518.2016.03.160232
Abstract:
A bifuntional cryptate chelate 2, 6-{N, N', N, N'-[bis (2, 2'-bipyridine-6, 6'-dimethyl)]bis (aminomethyl)}-pyridine-3, 5-diethyl diester for homogeneous time-resolved fluorimmunoassay product was synthesized from the raw material diethyl 2, 6-dimethylpyridine-3, 5-dicarboxylate through N-bromobutanimide (NBS) bromination, electrophilic substitution. The structure and property were confirmed by differential thermal analysis (DTA) Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and mass spectrometry (MS). Also, the spectral properties of the Eu (Ⅲ)-cryptate chelate, such as absorption spectra, emission spectra, and fluorescence lifetime, were discussed. The fluorescence spectroscopic properties of Eu (Ⅲ)-cryptate are as follows:the excitation peak is at 322 nm, the narrow emission spectrum peaks are at 597 nm (5D0-7F1) and 618 nm (5D0-7F2), respectively, the Stokes shift is 290 nm, the fluorescence lifetime is 918 μs, and the fluorescence quantum yield is Φ=0.249.
A bifuntional cryptate chelate 2, 6-{N, N', N, N'-[bis (2, 2'-bipyridine-6, 6'-dimethyl)]bis (aminomethyl)}-pyridine-3, 5-diethyl diester for homogeneous time-resolved fluorimmunoassay product was synthesized from the raw material diethyl 2, 6-dimethylpyridine-3, 5-dicarboxylate through N-bromobutanimide (NBS) bromination, electrophilic substitution. The structure and property were confirmed by differential thermal analysis (DTA) Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance spectroscopy (1H NMR) and mass spectrometry (MS). Also, the spectral properties of the Eu (Ⅲ)-cryptate chelate, such as absorption spectra, emission spectra, and fluorescence lifetime, were discussed. The fluorescence spectroscopic properties of Eu (Ⅲ)-cryptate are as follows:the excitation peak is at 322 nm, the narrow emission spectrum peaks are at 597 nm (5D0-7F1) and 618 nm (5D0-7F2), respectively, the Stokes shift is 290 nm, the fluorescence lifetime is 918 μs, and the fluorescence quantum yield is Φ=0.249.
