We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride（CDBF） loaded poly（acrylonitrile） nanofiber based on an intermolecular charge-transfer complexation.Reversible response a...We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride（CDBF） loaded poly（acrylonitrile） nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.展开更多
The photoacoustic spectra of Eu ( benz)(3) (.) ( phen)(2) ( benz: benzoate, phen: phenanthroline) and Eu-0.(8)Ln(0.2)(benz)(3)(.)(phen)(2)(Ln(3+) : La3+ or Nd3+) were reported. The intermolecular energy transfer proce...The photoacoustic spectra of Eu ( benz)(3) (.) ( phen)(2) ( benz: benzoate, phen: phenanthroline) and Eu-0.(8)Ln(0.2)(benz)(3)(.)(phen)(2)(Ln(3+) : La3+ or Nd3+) were reported. The intermolecular energy transfer processes were studied from the point of the nonradiative transitions. Combined with the fluorescence spectroscopy, photoacoustic spectroscopy reflects the variation of the luminescence efficiencies of solid samples. The luminescence efficiency increases when La3+ is introduced, but it decreases greatly when Nd3+ is added, which is due to the difference of intermolecular energy transfer processes. The models of intramolecular and intermolecular energy transfer and relaxation processes were established.展开更多
For the uracil-BX3 （X = F, Cl） systems, geometries and binding energies have been calculated by using the Lee-Young-Parr correlation functionals （B3LYP） method of density functional theory （DFT） and the second-o...For the uracil-BX3 （X = F, Cl） systems, geometries and binding energies have been calculated by using the Lee-Young-Parr correlation functionals （B3LYP） method of density functional theory （DFT） and the second-order Moller-Plesset （MP2） method of ab initio at the 6- 311 ＋G^＊ or 6-311 ＋＋G^＊ basis set. Four isomers were found for each system, and then the single-point energy evaluations were performed using the larger basis sets of （6-311 ＋G（2df, p） and aug-cc-pVDZ with DFF method. In the most stable isomer of uracil-BF3 or uracil-BCl3, the boron atom of BX3 （X = F, Cl） connects to the carbonyl oxygen O7 of uracil with a stabilization energy of -46.56 or -31.10 kJ/mol at the B3LYP/6-31 1＋G^＊ level （BSSE corrected）. The analyses for combining interaction between BX3 and uracil with the atom-in-molecule theory （AIM） and natural bond orbital method （NBO） have been performed. The results indicate that all isomers were formed with σ-p type interactions between uracil and BX3, in which the carbonyl oxygen offers its lone pair electrons to the empty p orbital of boron atom and the concomitances of charge transfer from uracil to BX3 occur. Moreover, there exists one or two hydrogen bonds in most isomers of uracil-BX3 system and these hydrogen bonds contribute to the stability of the complex systems. Frequency analysis suggests that the stretching vibration of BX3 undergoes a red shift in complexes. Uracil-BF3 complex is more stable than uracil-BCl3 although the distance of B-O is shorter in the latter. Besides, the conversion mechanisms between different isomers of uracil-BF3 have been obtained.展开更多
The rovibrational spectrum of O2–N2O van der Waals complex is measured in the ν1 symmetric stretch region of N2 O monomer using a tunable diode laser spectrometer. The complex is generated by a slit-pulsed supersoni...The rovibrational spectrum of O2–N2O van der Waals complex is measured in the ν1 symmetric stretch region of N2 O monomer using a tunable diode laser spectrometer. The complex is generated by a slit-pulsed supersonic expansion with gas mixtures of O2, N2 O, and He. Both a- and b-type transitions are observed. The effective Hamiltonian for an open-shell complex consisting of a diatomic molecule in a ^3Σ electronic state and a closed-shell partner is used to analyze the observed spectrum. Molecular constants in the vibrationally excited state are determined accurately. The band-origin of the spectrum is determined to be 1284.7504（25） cm^-1, red-shifted from that of the N2 O monomer by ～ 0.1529 cm^-1.展开更多
Exploring the factors to control Znsalen aggregation is of importance to design functional materials in catalysis, optical materials and biological imaging. In this work, we synthesized and characterized four cryptand...Exploring the factors to control Znsalen aggregation is of importance to design functional materials in catalysis, optical materials and biological imaging. In this work, we synthesized and characterized four cryptand type tri Znsalen complexes and found that cryptand structure could efficiently minimize intermolecular Zn…O interaction. More importantly, encapsulated by PLGA nanoparticles, cryptand tri Znsalen 1 displayed visible intracellular fluorescence whereas monomeric Znsalen 5 could not. These results provide a new access to design new luminescent materials with the potential application in optics and biological studies.展开更多
Geometries and binding energies were predicted at the B3LYP/6-311＋G＊ level for the guanine-BX3 （X = F, Cl） systems and four isomers with no imaginary frequencies have been obtained for both guanine-BF3 and guanine...Geometries and binding energies were predicted at the B3LYP/6-311＋G＊ level for the guanine-BX3 （X = F, Cl） systems and four isomers with no imaginary frequencies have been obtained for both guanine-BF3 and guanine-BCl3, respectively. Single energy calculations using much larger basis sets （6-311＋G（2df, p） and aug-cc-pVDZ were carded out as well. It was found that the most stable isomer of guanine-BF3 is BF3 connected to N3 of guanine with the stabilization energy of-19.93 kcal/mol （BSSE corrected）, while that of guanine-BC13 is BC13 connected to O10 of guanine having stabilization energy of -15.02 kcal/mol at the same level. The analyses for the combining interaction between BX3 and guanine with the atom-in-molecules theory （AIM） and natural bond orbital （NBO） methods have been performed. The results indicated that all the isomers are formed with σ-p type interactions between guanine and BX3, in which pyridine-type nitrogen or carbonyl oxygen or nitrogen atom of amino group offers its lone pair electrons to the empty p orbital of boron atom and the concomitance of charge transfer from guanine to BX3 has occurred. Still, one or two hydrogen bonds exist in some isomers of guanine-BX3 system and contribute to the stability of complex systems. Frequency analysis suggested that the stretching vibration of BX3 undergoes a red shift in complexes. Guanine-BF3 complex is more stable than guanine-BC13 although the B-Y （Y=N, O） bond distance in the latter is shorter.展开更多
研究了以2,2′-亚甲基双(4,6-二叔丁基苯酚)(简称双酚Z)与三氯化磷为原料,经一级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)亚磷酸酯一氯化物;与异辛醇二级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)异辛烷氧基亚磷酸酯(简称HP-...研究了以2,2′-亚甲基双(4,6-二叔丁基苯酚)(简称双酚Z)与三氯化磷为原料,经一级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)亚磷酸酯一氯化物;与异辛醇二级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)异辛烷氧基亚磷酸酯(简称HP-10)。一级酯化工艺条件:n(双酚Z)∶n(三氯化磷)=1.0∶1.3,催化剂0.2g,反应时间2.0h,温度85.0℃;二级酯化工艺条件:异辛醇6.5g,缚酸剂13.0g,反应时间4.0h,温度85.0℃。合成HP-10收率达84.3%,熔点147.5～148.2℃,经IR1、H NMR、13 C NMR、LC-MS谱图解析,与HP-10结构相符,产物质量分数大于97.0%。展开更多
基金supported by Basic Science Research Program through the National Research Foundation(NRF) grant funded by the Korea Government(MEST)(No.2011-0001084)supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by the Ministry of Knowledge Economy, Republic of Korea
文摘We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride（CDBF） loaded poly（acrylonitrile） nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.
文摘The photoacoustic spectra of Eu ( benz)(3) (.) ( phen)(2) ( benz: benzoate, phen: phenanthroline) and Eu-0.(8)Ln(0.2)(benz)(3)(.)(phen)(2)(Ln(3+) : La3+ or Nd3+) were reported. The intermolecular energy transfer processes were studied from the point of the nonradiative transitions. Combined with the fluorescence spectroscopy, photoacoustic spectroscopy reflects the variation of the luminescence efficiencies of solid samples. The luminescence efficiency increases when La3+ is introduced, but it decreases greatly when Nd3+ is added, which is due to the difference of intermolecular energy transfer processes. The models of intramolecular and intermolecular energy transfer and relaxation processes were established.
基金This work was supported by the National Natural Science Foundation of China (No. 20171031)
文摘For the uracil-BX3 （X = F, Cl） systems, geometries and binding energies have been calculated by using the Lee-Young-Parr correlation functionals （B3LYP） method of density functional theory （DFT） and the second-order Moller-Plesset （MP2） method of ab initio at the 6- 311 ＋G^＊ or 6-311 ＋＋G^＊ basis set. Four isomers were found for each system, and then the single-point energy evaluations were performed using the larger basis sets of （6-311 ＋G（2df, p） and aug-cc-pVDZ with DFF method. In the most stable isomer of uracil-BF3 or uracil-BCl3, the boron atom of BX3 （X = F, Cl） connects to the carbonyl oxygen O7 of uracil with a stabilization energy of -46.56 or -31.10 kJ/mol at the B3LYP/6-31 1＋G^＊ level （BSSE corrected）. The analyses for combining interaction between BX3 and uracil with the atom-in-molecule theory （AIM） and natural bond orbital method （NBO） have been performed. The results indicate that all isomers were formed with σ-p type interactions between uracil and BX3, in which the carbonyl oxygen offers its lone pair electrons to the empty p orbital of boron atom and the concomitances of charge transfer from uracil to BX3 occur. Moreover, there exists one or two hydrogen bonds in most isomers of uracil-BX3 system and these hydrogen bonds contribute to the stability of the complex systems. Frequency analysis suggests that the stretching vibration of BX3 undergoes a red shift in complexes. Uracil-BF3 complex is more stable than uracil-BCl3 although the distance of B-O is shorter in the latter. Besides, the conversion mechanisms between different isomers of uracil-BF3 have been obtained.
基金Project supported by the National Natural Science Foundation of China(Grants Nos.11174098,11304023,and 11304095)
文摘The rovibrational spectrum of O2–N2O van der Waals complex is measured in the ν1 symmetric stretch region of N2 O monomer using a tunable diode laser spectrometer. The complex is generated by a slit-pulsed supersonic expansion with gas mixtures of O2, N2 O, and He. Both a- and b-type transitions are observed. The effective Hamiltonian for an open-shell complex consisting of a diatomic molecule in a ^3Σ electronic state and a closed-shell partner is used to analyze the observed spectrum. Molecular constants in the vibrationally excited state are determined accurately. The band-origin of the spectrum is determined to be 1284.7504（25） cm^-1, red-shifted from that of the N2 O monomer by ～ 0.1529 cm^-1.
基金supported by the National Scientific Foundation of China(No.20971007)National Key Basic Research Support Foundation of China(NKBRSFC)(Nos.2013CB933402,2015CB856300)
文摘Exploring the factors to control Znsalen aggregation is of importance to design functional materials in catalysis, optical materials and biological imaging. In this work, we synthesized and characterized four cryptand type tri Znsalen complexes and found that cryptand structure could efficiently minimize intermolecular Zn…O interaction. More importantly, encapsulated by PLGA nanoparticles, cryptand tri Znsalen 1 displayed visible intracellular fluorescence whereas monomeric Znsalen 5 could not. These results provide a new access to design new luminescent materials with the potential application in optics and biological studies.
基金the National Natural Science Foundation of China (No. 20171031 and 20471033)
文摘Geometries and binding energies were predicted at the B3LYP/6-311＋G＊ level for the guanine-BX3 （X = F, Cl） systems and four isomers with no imaginary frequencies have been obtained for both guanine-BF3 and guanine-BCl3, respectively. Single energy calculations using much larger basis sets （6-311＋G（2df, p） and aug-cc-pVDZ were carded out as well. It was found that the most stable isomer of guanine-BF3 is BF3 connected to N3 of guanine with the stabilization energy of-19.93 kcal/mol （BSSE corrected）, while that of guanine-BC13 is BC13 connected to O10 of guanine having stabilization energy of -15.02 kcal/mol at the same level. The analyses for the combining interaction between BX3 and guanine with the atom-in-molecules theory （AIM） and natural bond orbital （NBO） methods have been performed. The results indicated that all the isomers are formed with σ-p type interactions between guanine and BX3, in which pyridine-type nitrogen or carbonyl oxygen or nitrogen atom of amino group offers its lone pair electrons to the empty p orbital of boron atom and the concomitance of charge transfer from guanine to BX3 has occurred. Still, one or two hydrogen bonds exist in some isomers of guanine-BX3 system and contribute to the stability of complex systems. Frequency analysis suggested that the stretching vibration of BX3 undergoes a red shift in complexes. Guanine-BF3 complex is more stable than guanine-BC13 although the B-Y （Y=N, O） bond distance in the latter is shorter.
文摘研究了以2,2′-亚甲基双(4,6-二叔丁基苯酚)(简称双酚Z)与三氯化磷为原料,经一级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)亚磷酸酯一氯化物;与异辛醇二级酯化反应生成2,2′-亚甲基双(4,6-二叔丁基苯基)异辛烷氧基亚磷酸酯(简称HP-10)。一级酯化工艺条件:n(双酚Z)∶n(三氯化磷)=1.0∶1.3,催化剂0.2g,反应时间2.0h,温度85.0℃;二级酯化工艺条件:异辛醇6.5g,缚酸剂13.0g,反应时间4.0h,温度85.0℃。合成HP-10收率达84.3%,熔点147.5～148.2℃,经IR1、H NMR、13 C NMR、LC-MS谱图解析,与HP-10结构相符,产物质量分数大于97.0%。
