2019 Volume 36 Issue 9

Application Progress of Doping in Organic Field-Effect Transistors
QIU Yuming , JIANG Yihang , LU Guanghao
2019, 36(9): 977-995  doi: 10.11944/j.issn.1000-0518.2019.09.190141
[Abstract](592) [FullText HTML] [PDF 1319KB](6)
Abstract:
Organic field-effect transistors(OFETs) as a new type of electronic devices have attracted wide attention due to their flexibility and large scale and simple fabrication. However, OFETs are confronted with problems such as inadequate device performance and complex control methods. Researchers endeavor to solve these problems by doping. In this review, we summarize the application of doping technology in OFETs based on the related work of our group and prospect the future development.
Synergetic Modification of Polybutylene Succinate and Poly(epichlorohydrin-co-ethylene oxide) Elastomer in Toughening Poly(lactic acid)
HU Kuan , JIANG Hai , HUANG Dong , LIU Chang , ZHANG Kunyu , PAN Li
2019, 36(9): 996-1002  doi: 10.11944/j.issn.1000-0518.2019.09.190096
[Abstract](511) [FullText HTML] [PDF 1100KB](2)
Abstract:
A ternary blend system was prepared via melt blending poly(lactic acid)(PLA) with renewable poly(butylene succinate)(PBS) and poly(epichlorohydrin-co-ethylene oxide) copolymer(ECO) to toughen PLA. The results of dynamic mechanical analysis(DMA) and scanning electron microscopy(SEM) showed that the ECO component improved the miscibility between PBS and PLA. The mechanical test proved that ECO and PBS could synergistically toughen the PLA matrix. The highest elongation at break was 280% for PLA/PBS/ECO(70/20/10) while the impact strength of PLA/PBS/ECO(70/10/20) blend was up to 23.7 kJ/m2 which is 12 times as much as that of neat PLA. In the ternary blend, ECO plays a dual role as both the compatibilizer and the toughening agent, resulting in a favorable synergistic effect with PBS. Blending PLA with flexible biopolyester and bioelastomer is proved to be a simple and efficient way to obtain high performance biobased materials.
Preparation of Electroactive and Bioactive DOPA-Jointed Insulin-Like Growth Factor-1@Poly(glycolide-lactide)/Poly(3-hexylthiophene) Electrospinning Fiber and Its Application in Neural Tissue Engineering
ZHANG Shouyan , HU Jianglei , SHI Xincui , ZHANG Peibiao , ITO Yoshihiro
2019, 36(9): 1003-1014  doi: 10.11944/j.issn.1000-0518.2019.09.190027
[Abstract](654) [FullText HTML] [PDF 1559KB](5)
Abstract:
An ideal biomaterial for nerve repair should have the properties of similar electrical properties to normal nerve, biomimetic extracellular matrix structure and the release of specific growth factors. In this study, composite fibers with electroactive and bionic structures were prepared by electrospinning process by incorporating various mass fractions(0, 3%, 5%, 10%) poly(3-hexylthiophene)(P3HT) into the poly(glycolide-lactide)(PLGA) polymer. DOPA-jointed insulin-like growth factor-1(DOPA-IGF-1) with different concentrations(10, 50, 100 ng/mL) was bound to the fiber surface using tyrosine hydroxylase to achieve long-term and stable release of growth factor. The fiber diameter and surface hydrophilic properties of the material were characterized by scanning electron microscopy and contact angle measurement, respectively. The biocompatibility and bioactivity of the fibers in vitro were evaluated by cell culture and fluorescence staining experiments. It was found that the electroactive fiber could effectively promote the proliferation of rat adrenal pheochromocytoma cells(PC12 cells), and PLGA/P3HT-5% fiber showed better cell responsiveness. Fibers incorporated with DOPA-IGF-1 with a concentration of 10 ng/mL were more conducive to PC12 cell adhesion and growth. The results showed that DOPA-IGF-1@PLGA/P3HT with both electrical and biological activity had potential application in neural tissue repair.
Near-infrared Absorbing Non-fullerene Acceptors with Dithienopyrrole as π Spacer for Organic Solar Cells
ZHANG Xiaomei , LI Miaomiao , WANG Qi , JIANG Yu , GENG Yanhou
2019, 36(9): 1023-1034  doi: 10.11944/j.issn.1000-0518.2019.09.190048
[Abstract](574) [FullText HTML] [PDF 992KB](3)
Abstract:
A series of non-fullerene acceptors with dithieno[3, 2-b:2', 3'-d]pyrrole(DTP) π bridge to link indacenodithiophene(IDT) core and 3-(dicyanomethylidene)indan-1-one(IC) or difluorinated IC(2F-IC) terminals, i.e. IDTDTP-C2C2-H and IDTDTP-C2C2-F with 1-ethylpropyl on DTP, IDTDTP-C6C6-H and IDTDTP-C6C6-F with 1-hexylheptyl on DTP, and IDTDTP-C12-H and IDTDTP-C12-F with n-dodecyl on DTP, was designed and synthesized. These molecules achieved low optical band gaps(1.37~1.44 eV). Compared with the IC-terminated molecules(IDTDTP-C2C2-H, IDTDTP-C6C6-H and IDTDTP-C12-H), IDTDTP-C2C2-F, IDTDTP-C6C6-F and IDTDTP-C12-F with 2F-IC as terminals show red-shifted absorption spectra and down-shifted the highest occupied molecular orbitals(HOMO) and the lowest unoccupied molecular orbitals(LUMO) energy levels owing to the electron-withdrawing ability of F substituents. Organic solar cells(OSCs) based on these acceptors were fabricated with the wide-bandgap polymer poly[2, 6-(4, 8-bis(5-(2-ethylhexyl))thiophen-2-yl)-benzo[1, 2-b:4, 5-b']dithiophene-alt-5, 5-(1', 3'-di-2-thienyl)-5', 7'-bis(2-ethylhexyl)-benzo[1', 2'-c:4', 5'-c']dithiophene-4, 8-dione](PBDB-T) as the donor. Owing to the higher and more balanced hole and electron mobilities, and a proper phase-separated morphology in the blend film, IDTDTP-C6C6-F with 1-hexylheptyl on DTP unit achieved a maximum power conversion efficiency(PCE) of 6.94% with an open-circuit voltage(Voc) of 0.86 V, a short circuit current density(Jsc) of 13.56 mA/cm2 and a fill factor(FF) of 59.5%.
Theoretical Investigation and Ultrafast Third-Order Nonlinear Optical Response of Novel Isomeric Pyrenyl Chalcones
SHI Yufang , BAI Yang , SUN Jinyu , LI Jun , ZHAO Minggen
2019, 36(9): 1035-1043  doi: 10.11944/j.issn.1000-0518.2019.09.190018
[Abstract](244) [FullText HTML] [PDF 796KB](2)
Abstract:
Three nevol isomeric pyrenyl chalcone 1-(pyren-1-yl)-3-(pyridin-2-yl) prop-2-en-1-one(3a), 1-(pyren-1-yl)-3-(pyridin-3-yl) prop-2-en-1-one(3b) and 1-(pyren-1-yl)-3-(pyridine-4-yl) prop-2-en-1-one(3c) were successfully synthesized and characterized by nuclear magnetic resonance(NMR), Fourier transform infrared spectrometer(FTIR), and liquid chromatography-mass spectrometer(LC-MS). Their thermal stability was measured by differential scanning calorimetry(DSC). The linear optical properties and third-order nonlinear optical(NLO), absorption were studied by ultraviolet visible(UV-Vis) spectrum and Z-scan technique, respectively. The experiment shows that compounds 3a-3c are all able to exhibit ultrafast third-order NLO response with 180 fs laser pulses at 532 nm. The nonlinear absorption coefficient of compound 3c is 1.14 and 2.67 times of compounds 3b and 3a, respectively. The non-linear optical properties and the electron transition properties of compounds 3a-3c were calculated by density functional theory method. The results indicate that molecule 3c has the largest static first hyperpolarizability(2830.9 a.u.) and the smallest energy gap(3.11 eV) between highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO), and also has the smallest transition energy(ΔE)(2.67 eV), which is related to the position of N atom on the pyridine ring. There are charge transfer phenomena inside the molecules of 3a-3c. Three compounds have no absorption at more than 450 nm but show good thermal stability implying potential application in the laser protection.
Solubility Properties of 1-Alkyl-4-amino-1, 2, 4-triazolium Energetic Ionic Liquids
GAO Bo , YANG Hongwei , TIAN Shaopeng , ZHAO Yuzhen , Tian TIAN
2019, 36(9): 1044-1052  doi: 10.11944/j.issn.1000-0518.2019.09.190036
[Abstract](425) [FullText HTML] [PDF 822KB](5)
Abstract:
Based on NO3-, ClO4-, N(CN)2-, [2, 4, 5-TNI]-, [3, 5-DNTZ]- anions, a series of 1-alkyl-4-amino-1, 2, 4-triazolium energetic ionic liquids(EILs) were synthesized. The structures were characterized by 1H NMR spectroscopy. The interaction energies of EILs-solvents and dipole moment of the 1-alkyl-4-amino-1, 2, 4-triazolium EILs were calculated using ab initio at MP2/6-311G++(2d, p). The relationships between the solubility and molecular structure, common solvents, and the interaction energies of EILs-solvents, etc., were discussed systematically. The results showed that the|ΔE|between[BATZ]NO3 and water had the biggest value of 40.7 kJ/mol with the different cations and the|ΔE|of[BATZ] [3, 5-DNTZ] and water possessed the biggest value of 45.1 kJ/mol with the same cation. The dipole moment of the above EILs was in the following order:[BATZ] [3, 5-DNTZ] > [BATZ] [2, 4, 5-TNI] > [BATZ]N(CN)2 > [BATZ]ClO4 > [RATZ]NO3. The solubility of the title energetic ionic liquids increased with decreasing dielectric constant of solvent. With the increase of the alkyl chain length, the interaction energies of EILs-solvents, the anion size, and the solubility in polar solvents all decreased. The solubility in polar solvents was in the following order:[BATZ] [3, 5-DNTZ] > [BATZ] [2, 4, 5-TNI] > [BATZ]NO3 > [BATZ]ClO4 > [BATZ]N(CN)2 > [PATZ]NO3 > [HATZ]NO3 > [DATZ]NO3, and[BATZ] [2, 4, 5-TNI] had the highest solubility of 10.0327 g/10 g in water.
A Coumarin-Based Fluorescent Probe for Rapid Detection of Endogenous Formaldehyde
GAO Man , HE Xin , CUI Jingnan , LIU Tao , TIAN Zhenhao , HE Shengui
2019, 36(9): 1053-1060  doi: 10.11944/j.issn.1000-0518.2019.09.190023
[Abstract](255) [FullText HTML] [PDF 879KB](3)
Abstract:
A coumarin-based formaldehyde(FA) fluorescent probe Coun was designed and synthesized. The mechanism of this fluorescent probes for FA is based on blocking electron transfer between hydrazine and the dye upon FA nucleophilic addition. The results show that the optimal reaction time of Coun and FA is 4 min, which greatly improved the detection efficiency with detection limit of 5×10-6 μmol/L. In addition, the probe has good cell membrane permeability, and can be used in the biological field to detect endogenous formaldehyde.
A Comparative Study on the Formation of Nitrosamines of Ethanolamines
HU Xueyi , LUO Minmin , FANG Yun , LI Junguo , SUN Yang , LI Huashan
2019, 36(9): 1061-1068  doi: 10.11944/j.issn.1000-0518.2019.09.190029
[Abstract](616) [FullText HTML] [PDF 680KB](6)
Abstract:
To investigate the reasonability and feasibility to substitute fatty acid diethanolamide by monoethanolamide and methylethanolamide in surfactant production and application, the nitrosation of methylethanolamine or monoethanolamine was compared with diethanolamine. In this study, nitrosamines were prepared from three ethanolamines by nitrosating agents of both tert-butyl nitrite and nitrous acid. The products of nitrosation by tert-butyl nitrite were identified to reveal nitrosation mechanisms, while the yields of the nitrosamines formed by nitrous acid were used to evaluate the easiness of nitrosation among three ethanolamines. Mechanism analysis of nitrosation shows that diethanolamine or methylethanolamine forms the corresponding nitrosamines, while monoethanolamine solely forms trace amount of N-nitroso-diethanolamine owing to the formation of intermediate diethanolamine by disproportionation of monoethanolamine. The experimental results also reveal that methylethanolamine and monoethanolamine are more difficult to form nitrosamines than diethanolamine. Therefore, it is reasonable and feasible to substitute fatty acid diethanolamide by monoethanolamide and methylethanolamide in surfactant production and application, which has theoretical and practical significance for safeguarding human health and safety.
One-Step Synthesis of TiO2-Au Composite and Its Performance for Photocatalytic Hydrogen Evolution
LIU Bing , GONG Huili , LIU Rui , HU Changwen
2019, 36(9): 1076-1084  doi: 10.11944/j.issn.1000-0518.2019.09.190017
[Abstract](612) [FullText HTML] [PDF 1039KB](2)
Abstract:
Titanium powders as the reductant and HAuCl4 were used as the oxidant to prepare TiO2-Au composite in the hydrothermal reactor at 180℃. Finally, the surface of TiO2 with 800 nm diameter was evenly coated by gold nanoparticles with 20 nm diameter. The specific surface area is about 3.5 m2/g. The structures and properties of the samples were characterized by X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), X-ray photoelectron spectroscopy(XPS), ultraviolet-visible diffuse reflectance spectroscopy, photocurrent density and photocatalytic hydrogen production performance. The morphology of the catalyst synthesized by the one-step method is regular. The final TiO2 is anatase. The catalyst has a strong absorption in the visible region, benefitting from the local surface plasmon resonance(LSPR) of gold nanoparticles. The hydrogen production performance of the catalyst increases firstly and then decreases with the increase of Au. Under visible light, the maximum hydrogen production rate is 0.1 μmol/(g·h) and the photocatalyst has good stability.
Multilayered Anode Catalytic Electrode in High-Temperature Proton Exchange Membrane Fuel Cell
LIU Shiwei , Liang LIANG , LI Chenyang , LIU Changpeng , XING Wei , DONG Xiandui
2019, 36(9): 1085-1090  doi: 10.11944/j.issn.1000-0518.2019.09.190034
[Abstract](465) [FullText HTML] [PDF 1037KB](7)
Abstract:
High temperature proton exchange membrane fuel cell is a promising energy conversion device with the advantages of toxicity resistance and good stability. In this report, the multilayered catalytic structure was designed to improve anode electrode catalytic activity of fuel cell. Poly vinylidene fluoride co-hexafluoropropylene(PVDF-HFP) and polybenzimidazoles(PBI) are used as electrode binders to adjust the wettability of the diffusion electrode interface. The surface morphology and wettability of the electrode catalyst have been characterized. It was found that the porosity and roughness of the electrode layer were improved. The wettability distinction between layers(contact angles:149° for PVDF-HFP and 19° for PBI) was conducive to produce more stable three-phase reaction interfaces. The catalytic performance of fuel cells shows that the peak power density is enhanced by about 22%, and it has retained 82.1% and 71.4% in H2 fuel containing CO at the concentrations of 10000 mg/m3 and 30000 mg/m3, respectively. It is concluded that the catalytic layer with such structure could increase the catalyst utilization and still maintain good toxic resistance to CO impurity inside fuel gas.
Synthesis of Copper Modified Porous Nickel Self-supported Electrode and Its Catalytic Oxidation of Glucose
CHE Tinghua , TAN Xiao , YAN Jiawei , SONG Fengdan , ZHANG Hongmei , QI Suitao
2019, 36(9): 1091-1098  doi: 10.11944/j.issn.1000-0518.2019.09.190005
[Abstract](1084) [FullText HTML] [PDF 904KB](5)
Abstract:
Porous Ni(nickel foam, NF) self-supported electrodes modified by Cu2O/Cu were fabricated by hydrothermal method. Their morphology and structure were characterized by X-ray diffraction(XRD) and field-emission scanning electron microscopy(FESEM). The resulted surface of porous Ni is completely covered with octahedral Cu2O/Cu composites of different sizes. The maximum diameter of the octahedron is about 5 μm. The glucose catalytic oxidation activity of Cu2O/Cu-NF was measured by cyclic voltammetry and constant potential amperometric method in alkaline medium with three-electrode system. The results show that the Cu2O/Cu-NF fabricated at 150℃ has the strongest electrocatalytic activity. The linear relationship of response current and glucose concentration could be observed clearly in the range of 3.7×10-3~1.1 mmol/L and 1.4~5.0 mmol/L, with sensitivity of 6929 μA/(mmol·L-1·cm2) and 706.1 μA/(mmol·L-1·cm2), respectively. Satisfyingly, the Cu2O/Cu-NF electrode is successfully employed to eliminate the interferences from uric acid(UA), acid ascorbic(AA) and L-proline(L-P) during the catalytic oxidation of glucose. The response current of Cu2O/Cu-NF electrode for glucose electrocatalytic oxidation could reach 91.6% of the original current after one month. The Cu2O/Cu-NF electrode allows highly sensitive, excellently selective, stable, and fast amperometric sensing of glucose and thus is promising for the future development of nonenzymatic glucose sensors.
Synthesis and Antiproliferative Activity of Novel Indazole-Chalcone Hybrids
GONG Yilin , SHI Jiantao , WANG Yang , CHEN Ye , DING Shi , LIU Yang , LIU Ju
2019, 36(9): 1015-1022  doi: 10.11944/j.issn.1000-0518.2019.09.190045
[Abstract](224) [FullText HTML] [PDF 511KB](2)
Abstract:
Nine novel indazole-chalcone hybrids(4a-4i) have been synthesized by condensation of substituted 4-(3-oxo-3-phenylprop-1-en-1-yl) benzoic acid with 4-morpholino-1H-indazol-3-amine prepared from 2, 6-difluorobenzonitrile by amination with morpholine and then cyclisation with hydrazine hydrate. Their chemical structures were confirmed by Fourier transform infrared spectrometer(FTIR), nuclear magnetic resonance spectroscopy(NMR), mass spectrometry(MS) and elemental analysis. Compounds(4a-4i) were screened for in vitro antiproliferative activities against human gastric cancer cell line(MKN45) and human lung adenocarcinoma cell line(A549). Most of the designed compounds were found to exhibit potential antiproliferative activities. Among them, compounds 4a and 4d exhibited remarkable inhibitory activity against MKN45 cell lines with IC50 value of 2.65 and 3.55 μmol/L, respectively, which were more potent than that of the positive control sorafenib(IC50=4.69 μmol/L).
Stability of Aluminum Hydride Etherates and Its Solid-State Conversion to Alpha-Aluminum Hydride
ZHU Zhaoyang , JIANG Aifeng , XIA Debin , WANG Ping , LIN Kaifeng , FAN Jizhuang , FAN Ruiqing , YANG Yulin
2019, 36(9): 1069-1075  doi: 10.11944/j.issn.1000-0518.2019.09.190032
[Abstract](237) [FullText HTML] [PDF 1101KB](2)
Abstract:
The problem of whether α-AlH3 crystallized by aluminum hydride etherates(AlH3·nEt2O) stored for varying time is systematically studied. First, AlH3·nEt2O was prepared by a conventional method and stored under a nitrogen atmosphere for 1 to 20 days, and then α-AlH3 was prepared by a solid phase and vacuum crystallizing technique based on the AlH3·nEt2O. XRD, TGA and SEM analysis show that the ether composition gradually decreases during storage and α-AlH3 with higher purity can be prepared within 10 days of storage. However, after 10 days, γ-AlH3 with smaller particle size appeared. Finally, we confirm that the amount of ether in AlH3·nEt2O is directly related to the quality of prepared α-AlH3. Another highlight of this paper is the abandonment of the toxic reagent toluene used in conventional processes. This also provides a possibility for the kilogram preparation of α-AlH3.
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