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1.
Three poly(N‐vinylcarbazole) (PVK)‐based polymer electrets were synthesized through Friedel‐Crafts postfunctionalization for the function of charge storage in nonvolatile organic field effect transistor (OFET) memory devices. The bulky side chain effect of these stacked polymer electrets on the morphology, water contact angles, and memory characteristics were examined with regard to those of precursor PVK. The introduction of steric hindrance groups could interrupt the large length of π‐stacked structures in PVK and block the form of region‐regular structures from region‐random on external electric field. As a result, the memories based on the three modified polymers exhibited approximate memory windows of 32 V increased by 13 V with respect to PVK. Besides, the write‐read‐erase‐read cycles stability of the modified polymers was superior to that of PVK. Furthermore, we found that the holes were mainly located in the region of local π‐stacked structures and bulky π‐conjugated groups also acted as additional electron trapping sites. Molecular engineering of charge trapping site with tunneling polymers will be a promise strategy for the advance of transistor memory. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3554–3564  相似文献   

2.
We report the memory characteristics of n‐type N,N′‐bis(2‐phenylethyl)‐perylene‐3,4:9,10‐tetracarboxylic diimide‐based organic field‐effect transistors (OFET) using a series of donor–acceptor (D–A) polyimide electrets of poly[4,4′‐diamino‐4″‐methyltriphenylamine‐hexafluoroisopropylidenediphthal imide] ( PI(AMTPA‐6FDA) ), poly[N,N‐bis‐(4‐aminophenyl)‐aminonaphthalene‐hexafluoroisopropylidenediphthalimide] ( PI(APAN‐6FDA) ), and poly[N,N‐bis‐(4‐aminophenyl)‐aminopyrene‐hexafluoroisopropylidenediphthalimide] ( PI(APAP‐6FDA) ). Among the polymer electrets, the OFET memory device based on PI(APAP‐6FDA) exhibits the largest memory window of 40.63 V and the best charge retention ability (maintained for over 104 s with the ON/OFF current ratio about 103) due to introducing polycyclic arene functionality of pyrene into the electron donating moiety. With the excellent carrier delocalization, pyrene successfully enhanced the charge storage ability and sustained the CT complex. Besides, PI(APAP‐6FDA)‐based OFET memory also performed well in the write‐read‐erase‐read tests for over 100 cycles. Our finding may provide a new approach for the preparation of high performance nonvolatile OFET memories with electrets of D–A polyimide systems. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 139–147  相似文献   

3.
With the rapid advances in organic memory, organic field‐effect transistor (OFET) memory has been recognition of the value over the past few years. Although the functional polymer with the Donor‐Acceptor (D‐A) structure has been widely investigated, little research has been carried out to clarify the relationships among D‐A structure of the polymer, capability of charge‐transfer, and memory performance. Here, we report the nonvolatile memory characteristics of pentacene‐based OFET memory using random copolyimides, poly[4,4′‐diaminotriphenylamine‐hexafluoroisopropylidenediphthalimide‐co‐4‐(N,N‐bis(p‐aminophenyl)amino)‐4′‐nitroazobenzene‐hexafluoroisopropylidenediphthalimide) (PI(TPA‐6FDA‐DACx)), with feeding ratios of DAC to TPA set as x (where x = 0,10, 30,50,70,100). The OFET memory performance based on the molar ratio of DAC to TPA equal to 30:70 represents the best results with the proper charge mobility, on/off current ratio, and memory window. Intriguingly, the memory performance can be enhanced by introducing more D‐A monomer in polymer electrets, yet the concomitant inferior growth of pentacene decreases the charge mobility, attributed to the intrinsically destructive arrangement of polymer backbone. Our conclusion points out the importance of polymer arrangement and capability of charge‐transfer to the OFET performance and memory characteristics. The comparable results can also be applied for advanced OFET memory devices. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1113–1121  相似文献   

4.
Three random copolymers comprised pendant styrene and 4‐(1‐pyrenyl)‐styrene (PyS) moieties in different molar ratios (21.4:1 ( P1 ), 3.9:1 ( P2 ), and 1.4:1 ( P3 )) were synthesized and employed as charge storage polymeric electret for nonvolatile organic field‐effect transistor (OFET) memory application. The impact of varying the molar ratio in side‐chain electron‐donating pyrene moieties on the thermal, optical, photophysical, electrochemical, and electrical properties of the resulting pendant copolymers was evaluated to establish structure–property relationship. The OFET memory with P3 electret layer exhibits a largest memory window of 41.8 V, long retention time of 104 s with memory ratio of 105, and stable reversibility of at least 100 cycles due to enhanced field‐induced holes trapping ability from higher PyS composition ratio. Therefore, polymer electret with pendant functional moieties shows potential for use as trapping layer in OFET memory devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 910–917  相似文献   

5.
We report pentacene‐based organic field‐effect transistor memory devices utilizing supramolecular electrets, consisting of a polyimide, PI(6FOH‐ODPA), containing hydroxyl groups for hydrogen bonding with amine functionalized aromatic rings (AM) of 1‐aniline (AM1), 2‐naphthylamine (AM2), 2‐aminoanthracene (AM3), and 1‐aminopyrene (AM4). The effect of the phenyl ring size and composition of AM1–AM4 on the hole‐trapping capability of the fabricated devices was investigated systematically. Under an operating voltage under ±40 V, the prepared devices using the electrets of 100 % AM1–AM4/PI ratios exhibited a memory window of 0, 8.59, 25.97, and 29.95 V, respectively, suggesting that the hole‐trapping capability increased with enhancing phenyl ring size. The memory window was enhanced as the amount of AM in PI increased. Furthermore, the devices showed a long charge‐retention time of 104 s with an ON/OFF current ratio of around 103–104 and multiple switching stability over 100 cycles. This study demonstrated that the electrical characteristics of the OFET memory devices could be manipulated through the chemical compositions of the supramolecular electrets.  相似文献   

6.
A new polythiophene derivative was synthesized by both chemical and electrochemical oxidative polymerization of 1‐(1‐phenylethyl)‐2,5‐di(2‐thienyl)‐1H‐pyrrole (PETPy). Of which the chemical method produces a polymer that is completely soluble in organic solvents. The structures of both the monomer and the soluble polymer were elucidated by nuclear magnetic resonance (1H and 13C NMR) and Fourier transform infrared (FTIR) spectroscopy. The average molecular weight has been determined by gel permeation chromatography to be Mn = 3.29 × 103 for the chemically synthesized polymer. Polymer of PETPy was synthesized via potentiostatic electrochemical polymerization in acetonitrile (AN)/NaClO4/LiClO4 (0.1 M) solvent–electrolyte couple. Characterizations of the resulting polymer were performed by cyclic voltammetry, FTIR, scanning electron microscopy, and UV–vis spectroscopy. Four‐probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the polymer films were investigated. In addition, dual‐type polymer electrochromic devices based on P(PETPy) with poly(3,4‐ethylenedioxythiophene) were constructed. Spectroelectrochemistry, electrochromic switching, and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts, and optical memories. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2215–2225, 2006  相似文献   

7.
Poly(2‐ureidoethylmethacrylate) (PUEMn) was synthesized via reversible addition‐fragmentation chain transfer (RAFT) radical polymerization and following polymer reaction. We prepared two PUEMn samples with different degrees of polymerization (n = 100 and 49). The polymers exhibited upper critical solution temperature (UCST) in phosphate‐buffered saline (PBS) solution. The phase separation temperature (Tp) in PBS can be controlled ranging from 17 to 55 °C by changing molecular weight of the polymer, polymer concentration, and adding NaCl concentration. The polymers in PBS formed coacervate drops by liquid–liquid phase separations below Tp. Results of the dielectric relaxation measurement, the hydration number per monomeric unit was 5 above Tp. Based on a fluorescence study, the polymer formed slightly hydrophobic environments below Tp. The liquid–liquid phase separation was occurred presumably because of weak hydrophobic interactions and intermolecularly hydrogen bonding interactions between the pendant ureido groups. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2845–2854  相似文献   

8.
Sugar fluorides were found to undergo powder‐to‐powder polycondensation without any catalyst at 110–160 °C under vacuum, giving highly branched polysaccharides (Conv. = 40–95%, Mw = 1400–20,000). The cross‐polarized optical microscopy at 110 °C disclosed that the crystal shape of α‐glucosyl fluoride ( FGlc ) was unchanged throughout the polymerization in spite of producing the amorphous polymer ( Poly‐FGlc ). The solid‐state post polymerization of Poly‐FGlc (Mw: 2700) at 180 °C increased the higher molecular weight (Mw: 8900). The product polysaccharide was per‐O‐methylated and subjected to structure analyses. Acid‐hydrolysis, which gave a variety of the partially O‐methylated monosaccharides, suggested that the product polysaccharides had a highly branched structure consisting of all of the possible glycosidic linkages. MALDI‐TOF mass analysis revealed that the 1,6‐anhydride terminal unit was formed and participated to the polymerization. Interestingly, α‐maltosyl fluoride hydrate ( FMal·H 2 O ) was polymerized at the lower temperature (100 °C) than the anhydrate ( FMal ), which required 160 °C for the polymerization. They produced different structure polymers even from the same monomer. The polymer from the former consisted of the disaccharide‐repeating unit, while the repeating unit of the polymer from the latter was the monosaccharide, which was formed by the acetal exchange reaction. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3851–3860, 2007  相似文献   

9.
A novel strategy for the synthesis and characterization of branched polymer brushes by sequential light‐mediated controlled radical polymerizations is described. Initially, linear brushes are prepared by surface‐initiated copolymerization of methyl methacrylate and 2‐hydroxyethyl methacrylate (HEMA). In a subsequent step, the HEMA side chains are functionalized with initiating groups for secondary graft polymerization, leading to hierarchical, branched architectures. The increased steric bulk due to the polymer side chains results in a dramatic increase in film thickness when compared to the starting linear brushes. This strategy also allows chemical gradient and complex three‐dimensional structures to be obtained by employing grayscale photomasks in combination with controlled radical polymerization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2276–2284  相似文献   

10.
I n this study, we successfully synthesized water/methanol soluble random copolymers with a high dielectric constant, poly(n‐(hydroxymethyl) acrylamide‐co‐5‐(9‐(5‐(diethylamino)pentyl)?2‐(4‐vinylphenyl)?9H‐fluorene(P(NMA‐co‐F6NSt)), which contained chemical crosslinkable segment (NMA) and hole trapping building block (F6NSt). The feeding molar ratios of two monomers (NMA:F6NSt) were set as 100:0, 95:5, 80:20, and 67:33 for the copolymers of P1 , P2 , P3, and P4 , respectively. The crosslinked P(NMA‐co‐F6NSt) thin film could serve as both dielectric and charge storage layers in organic field‐effect transistor (OFET) memory device and exhibited high k (i.e., 4.91–6.47) characteristics, leading to a low voltage operation and a small power consumption. Devices based on the P1 ‐ P4 dielectrics showed excellent insulating properties and good charge storage performance under a low operating voltage in a range of ±5V because of tightly network structures and well‐dispersed trapping cites. In particular, P3 ‐based memory device exhibited a large memory window of 4.13 V with stable data retention stability over 104 s, a large on/off ratio of 104, and good endurance characteristics as high as 200 cycles. The above results suggested that a high‐performance OFET memory device could be facilely achieved using the novel crosslinkable high‐k copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3224–3236  相似文献   

11.
A simple diamine (TetraPEDA) containing rigid nonplanar conjugated tetraphenylethylene (TetraPE) moieties was designed and synthesized through Wittig–Horner and Suzuki coupling reactions. Four kinds of high‐performance functional polyimides (PI) were thus prepared by the polymerization of TetraPEDA and four dianhydrides, respectively. Because of the introduction of the aromatic rigid nonplanar TetraPE structure, the PI exhibited special fluorescent characteristics, as the maximum fluorescence emission of the four PI was observed at 425–505 nm in NMP solution and at 470–491 nm in film state. Also these organo‐soluble PI showed outstanding properties, such as low dielectric constant (even without fluorinated substituent), light color, high glass transition temperatures (382–443 °C) and thermal stability in air (Td5% up to 565 °C), and excellent mechanical properties. The polymer memory devices with the configuration of indium tin oxide/PI/aluminum (ITO/PI/Al) exhibited distinct volatile memory characteristics of static random access memory, with an ON/OFF current ratio of 1 × 104 to 1 × 105. These functional PI showed attractive potential applications in the field of high performance flexible polymer photoconducting devices or fluorescent polymer memory devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013  相似文献   

12.
The new thermal radical initiators (TRIs) with linear and cyclic type groups based on derivatives of O‐imino‐isourea have been designed and synthesized. The radical polymerization property of the synthesized TRI derivatives as a radical initiator in n‐butyl acrylate was monitored by differential scanning calorimetry analysis. TRI derivatives with linear type groups, such as 3‐PenDCC, 3‐HexDCC, and 4‐HepDCC, showed peak temperatures (Tpeak) of 80–84 °C, whereas those with cyclic type groups, such as C‐PenDCC, C‐HexDCC, and C‐HepDCC, exhibited a wide Tpeak distribution in the 74–87 °C range. The polymerization efficiency using new TRIs in n‐butyl acrylate was elaborately identified from the molecular weights and conversion obtained using gel permeation chromatography analysis and NMR spectroscopy. To consider their possible application to automotive clearcoats, the real‐time evolution of the rheological properties of clearcoat resins during the crosslinking process with newly synthesized TRI derivatives was measured, confirming the different crosslinking kinetics of TRI derivatives in real thermal curing process. The results were found to be well correlated with data from the radical polymerization experiments of TRIs. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3593–3600.  相似文献   

13.
Branched and star‐branched polymers were successfully synthesized by the combination of two successive controlled radical polymerization methods. A series of linear and star poly(n‐butyl acrylate)‐co‐poly(2‐(2‐bromoisobutyryloxy) ethyl acrylate) statistical copolymers, P(nBA‐co‐BIEA)x, were first synthesized by nitroxide‐mediated polymerization (NMP at T > 100 °C). The subsequent polymerization of n‐butyl acrylate by single electron transfer‐living radical polymerization (SET‐LRP at T = 25 °C), initiated from the brominated sites of the P(nBA‐co‐BIEA)x copolymer, produced branched or star‐branched poly(n‐butyl acrylate) (PnBA). Both types of polymerizations (NMP and SET‐LRP) exhibited features of a controlled polymerization with linear evolutions of logarithmic conversion versus time and number‐average molar masses versus conversion for final Mn superior to 80,000 g mol?1. The branched and star‐branched architectures with high molar mass and low number of branches were fully characterized by size exclusion chromatography. The Mark–Houwink Sakurada relationship and the analysis of the contraction factor (g′ = ([η]branched/[η]linear)M) confirmed the elaboration of complex PnBA. The zero‐shear viscosities of the linear, star‐shaped, branched, and star‐branched polymers were compared. The modeling of the rheological properties confirmed the synthesis of the branched architectures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

14.
We successfully synthesized new D‐A copolymers that employ 1,10‐bithienopyrrolodione (biTPD), thiophene, and selenophene‐based donor monomeric units. Two polymers, PBTPDEBT and PBTPDEBS , exhibited high degrees of crystallinity and unique polymer chain arrangements on the substrate, which is attributed to their enhanced coplanarity and intermolecular interactions between the polymer chains. Among the thin‐film transistor devices made of PBTPDEBT and PBTPDEBS , the annealed PBTPDEBS device displayed relatively high hole mobility, which was twice that of the PBTPDEBT ‐based device. In addition, an organic photovoltaic device based on a PBTPDEBS :PC71BM blend displayed the maximum power conversion efficiency of 3.85%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1228–1235  相似文献   

15.
A systematic comparison between the grafting‐to (convergent) and grafting‐from (divergent) synthetic routes leading to cyclic peptide–polymer conjugates is described. The reversible addition–fragmentation chain transfer (RAFT) process was used to control the polymerizations and the couplings between cyclic peptide and polymer or RAFT agent were performed using N‐hydroxysuccinimide (NHS) active ester ligation. The kinetics of polymerization and polymer conjugation to cyclic peptides were studied for both grafting‐to and grafting‐from synthetic routes, using N‐acryloyl morpholine as a model monomer. The cyclic peptide chain transfer agent was able to mediate polymerization as efficiently as a traditional RAFT agent, reaching high conversion in the same time scale while maintaining excellent control over the molecular weight distribution. The conjugation of polymers to cyclic peptides proceeded to high conversion, and the nature of the carbon at the α‐position to the NHS group was found to play a crucial role in the reaction kinetics. The study was extended to a wider range of monomers, including hydrophilic and temperature responsive acrylamides, hydrophilic and hydrophobic acrylates, and hydrophobic and pH responsive methacrylates. Both approaches lead to similar peptide–polymer conjugates in most cases, while some exceptions highlight the advantages of one or the other method, thereby demonstrating their complementarity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1003–1011  相似文献   

16.
A series of 2‐aminopyridine Ni(II) complexes bearing different substituent groups {(2‐PyCH2NAr)NiBr, Ar = 2,4,6‐trimethylphenyl ( 3a) , 2,6‐dichlorophenyl ( 3b ), 2,6‐dimethylphenyl ( 3c) , 2,6‐diisopropylphenyl ( 3d ), 2,6‐difluorophenyl ( 3e ); (2‐PyCH2NHAr)2NiBr2, Ar = 2,6‐diisopropylphenyl ( 4a )} have been synthesized and investigated as precatalysts for ethylene polymerization in the presence of methylaluminoxane (MAO). High molecular weight branched polymers as well as short‐chain oligomers were simultaneously produced with these complexes. Enhancing the steric bulk of the ortho‐aryl‐substituents of the catalyst resulted in higher ratio of solid polymer to oligomer and higher molecular weight of the polymer. With ortho‐haloid‐substitution, the catalysts afforded a product with low polymer/oligomer ratio ( 3b ) and even only oligomers ( 3e ) in which C14H28 had the maximum content. Compared with complex 3d containing ionic ligand, complex 4a containing neutral ligand exhibited obviously low catalytic activity for ethylene polymerization. The molecular weight, molecular weight distribution, and microstructure of the resulted polymer were characterized by gel permeation chromatography and 13C NMR spectrogram. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1618–1628, 2008  相似文献   

17.
Two novel acceptors of benzo[c][1,2,5]thiadiazole and quinoxaline with conjugated dithienylbenzothiadiazole pendants were first designed and synthesized for building efficient photovoltaic copolymers. Based on benzo[1,2‐b;3,4‐b′]dithiophene donors and the two acceptors, two new copolymers have been prepared by Stille coupling polymerization. The resulting copolymers were characterized by 1H NMR, gel permeation chromatography, and thermogravimetric analysis. UV–Visible absorption and cyclic voltammetry measurements indicated that the two copolymers possessed strong and broad absorption in the range of 300–700 nm, and deep‐lying energy levels of highest occupied molecular orbitals. The polymer photovoltaic devices based on benzo[c][1,2,5]thiadiazole‐based copolymer/phenyl‐C71‐butyric acid methyl ester exhibited a power conversion efficiency of 2.42%, attributed to its relatively better light‐harvesting ability and active film morphology. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 668–677  相似文献   

18.
Polysilanes upon UV irradiation give rise to silyl macroradicals which are capable to initiate radical polymerization. Hence, chiral block functional polysilanes were synthesized by UV irradiation of poly(methylphenylsilane) (PMPS) with a vinyl chiral monomer, (R)‐N‐(1‐phenylethyl)methacrylamide (R‐NPEMAM). The synthesized copolymer samples were characterized by FTIR, NMR, and UV–vis spectroscopy. The number and weight average molecular weights of PMPS and synthesized chiral‐block‐PMPS were measured by GPC analysis. Two glass transition temperatures (Tg) of the synthesized materials clearly indicate the formation of chiral‐block‐PMPS copolymers. SEM analysis also indicated the synthesized organic–inorganic block copolymers. The optical and chiroptical properties of the synthesized materials were studied. The cotton effect is observed not only at 276 nm due to aromatic ring of the chiral monomer units but also at 325 nm which is associated with the Si–Si conjugation of PMPS block of synthesized functional polysilanes. Such tunable chirality may find potential application in optoelectronics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3626–3634  相似文献   

19.
The functional polyimide (OMe)2TPPA‐6FPI ( PI ) and the polyamide (OMe)2TPPA‐6FPA ( PA ) consisting of electron‐donating N,N′‐bis(4‐aminophenyl)‐N,N′‐di(4‐methoxylphenyl)1,4‐phenylenediamine [(OMe)2TPPA‐diamine] for memory application were prepared in this study. These polyimide and polyamide memory devices were fabricated with the sandwich configuration of indium tin oxide (ITO)/polymer/Al, and could be switched from the initial low‐conductivity (OFF) state to the high‐conductivity (ON) state with high ON/OFF current ratios of 107 and 109, respectively. PI exhibited dynamic random access memory (DRAM) performance, whereas PA showed static random access memory (SRAM) behavior. To get more insight into the memory behaviors of these two different types of polymer memory devices, molecular simulation on the basic unit was carried out. Furthermore, the differences of highest occupied molecular orbital (HOMO) energy level, lowest unoccupied molecular orbital (LUMO) charge density isosurfaces, dipole moment, and linkage conformation between PI and PA were found to affect the volatile memory behavior. Both polymer memory devices revealed excellent stability with long operation time of 104 s at continuous applied voltage of ‐2 V. The effect of polymer thickness on the volatile memory behavior of PA was also investigated in this study. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

20.
A new aromatic host polymer poly{[1,4‐bis(9‐decylcarbazole‐3‐yl)‐2,3,5,6‐tetrafluorobenzene‐3,3′‐diyl]‐alt‐[N‐methylisatin‐2‐one‐3,3‐diyl]} (PICzFB) containing carbazole–tetrafluorinebeneze–carbazole moiety in the π‐conjugated interrupted polymer backbone was synthesized by superacid‐catalyzed metal‐free polyhydroxyalkylation. The resulted copolymer PICzFB showed a comparatively wide band gap up to 3.32 eV and high triplet energy (ET) of 2.73 eV due to confined conjugation by the δ? C bond interrupted polymer backbone. Blue and green light‐emitting devices with PICzFB as host, FIrpic and Ir(mppy)3 as phosphorescent dopants showed the maximum luminous efficiencies of 5.0 and 27.6 cd/A, respectively. The results suggested that the strategy of incorporating bipolar unit into the π‐conjugated interrupted polymer backbone can be a promising approach to obtain host polymer with high triplet level for solution‐processed blue and green phosphorescent polymer light‐emitting diodes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1037–1046  相似文献   

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