四种方法合成单一手性聚苯胺纳米纤维研究

以过硫酸铵或2,3-二氯-5,6-二氰基-1,4-苯醌（DDQ）为氧化剂,单一手性樟脑磺酸作为诱导酸及掺杂剂,在有机溶剂、水-有机溶剂和水溶剂体系中,采用四种不同方法分别进行了单一手性聚苯胺纳米纤维合成研究。通过扫描电子显微镜（SEM）、紫外可见光谱（UV-VIS）、X射线衍射（XRD）和圆二色谱（CD）等手段对自组装法、界面聚合法、低聚物辅助法与二次掺杂法等四种方法制备得到聚苯胺纳米纤维的形貌、结构及光学活性进行表征,对比分析后发现四种方法合成的掺杂态聚苯胺纳米纤维形貌、结构相似,但溶剂体系会影响最终产物的光学活性：水溶剂、有机溶剂体系中,得到的聚苯胺纳米纤维光学活性相反。     

Facile synthesis of polyaniline nanofibers using chloroaurate acid as the oxidant

This work demonstrated a facile route to the synthesis of polyaniline (PANI) nanofibers by polymerization of aniline using chloroaurate acid (HAuCl(4)) as the oxidant. The reduction of AuCl(4)(-) is accompanied by oxidative polymerization of aniline, leading to uniform PANI nanofibers with a diameter of 35 +/- 5 nm and aggregated gold nanoparticles which can precipitate from the liquid phase during the reaction. The resultant PANI nanofibers and gold particles were characterized by means of different techniques, such as UV-vis, FTIR spectroscopy, and scanning and transmission electron microscopy methods. It is found that the gold aggregates are capped with polyaniline, and the conductivity of the fibers is around 0.16 S/cm.     

Antioxidant activity of polyaniline nanofibers

Well-confined uniform polyaniline (PANI) nanofibers were synthesized by using photo-assisted chemical oxidative polymer- ization of aniline in the presence of different dopant acids,and the radical scavenging ability of the produced PANI nanofibers was determined by the DPPH assay.It was found that the antioxidant activity of PANI nanofibers was higher than conventional PANI, and increased with decreasing of averaged diameter of the nanofibers.The enhanced antioxidant activity was concerned with increased surface area of PANI nanofibers.     

A general chemical route to polyaniline nanofibers

Uniform polyaniline nanofibers readily form using interfacial polymerization without the need for templates or functional dopants. The average diameter of the nanofibers can be tuned from 30 nm using hydrochloric acid to 120 nm using perchloric acid as observed via both scanning and transmission electron microscopy. When camphorsulfonic acid is employed, 50 nm average diameter fibers form. The measured Brunauer-Emmett-Teller surface area of the nanofibers increases as the average diameter decreases. Further characterization including molecular weight, optical spectroscopy, and electrical conductivity are presented. Interfacial polymerization is shown to be readily scalable to produce bulk quantities of nanofibers.     

Morphology of polyaniline nanofibers synthesized under different conditions

Polyaniline nanofibers are readily synthesized by bulk polymerization; ammonium per sulphate (APS) is used as oxidizing agent and hydrochloric acid as dopant without any hard or soft templates. A detailed study was conducted on the effect of a variety of synthetic conditions on the size and morphology of the polyaniline nanostructure. These conditions include the concentration of dopant, and the APS-to-aniline and acid-to-aniline molar ratios. The morphology of the nanofibers was confirmed by SEM and TEM. XRD and FT-IR and UV–visible spectroscopy were used for structural characterization of nanofibers. The results showed that not only the microstructure of the polyaniline product, but also other characteristics, for example conductivity, crystallinity, and, more importantly, the efficiency of the process are strongly affected by the synthetic conditions.     

Formation of polyaniline nanofibers: a morphological study

Polyaniline (PANI) powders were prepared by solution precipitation, rapid mixing polymerization, and interfacial polymerization to find the key factors that influence the formation and growth of PANI nanofibers. In chemical oxidative polymerization of aniline, the morphology of the product is mainly determined by aniline concentration. In the case of lower aniline concentration, PANI nanofibers were formed and can be preserved and collected as final product, while in the case of higher aniline concentration, larger sized PANI particles or agglomerates were obtained owing to the growth of the nanofibers. Without participation of the oxidizing step, solid PANI samples with compact structures and dissimilar morphologies were achieved by random accumulation of PANI molecules.     

Copolypeptide-doped polyaniline nanofibers for electrochemical detection of ultratrace trinitrotoluene

This paper demonstrates a new electrochemical method for the detection of ultratrace amount of 2,4,6-trinitrotoluene (TNT) with synthetic copolypeptide-doped polyaniline nanofibers. The copolypeptide, comprising of glutamic acid (Glu) and lysine (Lys) units, is in situ doped into polyaniline through the protonation of the imine nitrogen atoms of polyaniline by the free carboxylic groups of Glu segments, resulting in the formation of polyaniline nanofibers of emeraldine salt. The free amino groups of Lys segments at the surface of nanofibers provide the receptor sites of TNT through the formation of charge-transfer complex between the electron-rich amino groups and the electron-deficient aromatic rings. Adsorptive stripping voltammetry results demonstrate that the poly(Glu-Lys)-doped nanofibers confined onto glassy carbon electrodes exhibit a remarkable enriching effect and thus sensitive electrochemical response to TNT with a linear dynamic range of 0.5-10 μM and a detection limit down to 100 nM. Moreover, other kinds of nitro compounds show different redox behaviors from TNT at the doped nanofibers, and thus do not interfere with the electrochemical detection of TNT. This study essentially offers a new and simple method for electrochemical detection of ultratrace TNT.     

A general synthetic route to nanofibers of polyaniline derivatives

Nanofibrous mats of a wide variety of polyaniline derivatives can be synthesized without the need for templates or functional dopants by simply introducing an initiator into the reaction mixture of a rapidly mixed reaction between monomer and oxidant.     

Synthesis of polyaniline nanofibers by "nanofiber seeding"

Seeding a conventional chemical oxidative polymerization of aniline with even very small amounts of biological, inorganic, or organic nanofibers (usually <1%) dramatically changes the morphology of the resulting doped electronic polymer polyaniline from nonfibrillar (particulate) to almost exclusively nanofibers. The nanoscale morphology of the original seed template is transcribed almost quantitatively to the bulk precipitate. These findings could have immediate impact in the design and development of high-surface area electronic materials.     

Hydrogen sensors based on conductivity changes in polyaniline nanofibers

Hydrogen causes a reversible decrease in the resistance of a thin film of camphorsulfonic acid doped polyaniline nanofibers. For a 1% mixture of hydrogen in nitrogen, a 3% decrease in resistance is observed (DeltaR/R = -3%). The hydrogen response is completely suppressed in the presence of humidity. In contrast, oxygen does not inhibit the hydrogen response. A deuterium isotope effect on the sensor response is observed in which hydrogen gives a larger response than deuterium: (DeltaR/R)H/(DeltaR/R)D = 4.1 +/- 0.4. Mass sensors using nanofiber films on a quartz crystal microbalance also showed a comparable deuterium isotope effect: DeltamH/DeltamD = 2.3 +/- 0.2 or DeltanH/DeltanD = 4.6 +/- 0.4 on a molar basis. The resistance change of polyaniline nanofibers is about an order of magnitude greater than conventional polyaniline, consistent with a porous, high-surface-area nanofibrillar film structure that allows for better gas diffusion into the film. A plausible mechanism involves hydrogen bonding to the amine nitrogens along the polyaniline backbone and subsequent dissociation. The inhibitory effect of humidity is consistent with a stronger interaction of water with the polyaniline active sites that bind to hydrogen. These data clearly demonstrate a significant interaction of hydrogen with doped polyaniline and may be relevant to recent claims of hydrogen storage by polyaniline.     

Biofunctionalized dendritic polyaniline nanofibers for sensitive electrochemical immunoassay of biomarkers

Multi-armed dendritic polyaniline nanofibers (MPANFs) were first synthesized and functionalized with horseradish peroxidase (HRP) and carcinoembryonic antibody (anti-CEA) for highly efficient electrochemical immunoassay of carcinoembryonic antigen (CEA, as a model analyte here) in this work. Transmission electron microscope (TEM) and scanning electron microscope (SEM) techniques were employed to characterize the synthesized MPANFs. By using anti-CEA-conjugated core-shell gold-Fe(3)O(4) nanocomposites (GoldMag) as immunosensing probes and biofunctionalized MPANFs as molecular tags, a new sandwich-type homogeneous immunoassay strategy was developed for the determination of CEA by coupling with a home-made flow-through magneto-controlled microfluidic device. Under optimal conditions, the electrochemical immunoassay exhibited a wide dynamic range of four orders of magnitude from 1.0 pg mL(-1) to 50 ng mL(-1) with a low detection limit of 0.1 pg mL(-1) CEA at 3σ. Intra- and inter-assay coefficients of variation were below 10%. The assayed results for clinical serum specimens with the electrochemical immunoassay were received in good accordance with the results obtained from the referenced enzyme-linked immunosorbent assay (ELISA) method.     

Chirality induction of polyaniline derivatives through chiral complexation

Chirality induction of π-conjugated polyaniline derivatives was achieved by chiral complexation with chiral palladium(II) complexes. The crystal structure of the chiral conjugated complex with a model compound of the polyaniline, N,N-bis(4^′-dimethylaminophenyl)-1,4-benzoquinonediimine, revealed a chiral propeller twist conformation of the π-conjugated moiety.     

聚苯胺纳米纤维的共溶剂界面聚合及储能性能研究

本文采用以盐酸溶液为水相、四氯化碳为有机相的界面聚合法,通过向水相中分别引入具有非对称结构的甲醇和乙醇,以及具有对称结构的异丙醇和丙三醇作为共溶剂,成功制备出聚苯胺纳米纤维.采用场发射扫描电镜、紫外可见光谱和傅里叶红外光谱对其形貌和结构进行了表征分析,并通过循环伏安测试、恒流充放电测试和交流阻抗测试着重研究了不同共溶剂...     

Electrochemical synthesis of polyaniline nanoparticles

Polyaniline nanoparticles were prepared on a highly oriented pyrolytic graphite (HOPG) surface from dilute polyaniline acidic solution (1 mM aniline+1 M HClO₄) using a pulsed potentiostatic method. Electrochemistry, Fourier transform infrared external reflection spectroscopy (FT-IR-ERS), X-ray photoelectron spectroscopy (XPS) and tapping-mode atomic force microscopy (TMAFM) were used to characterize the composition and structure of the polyaniline nanoparticles. FT-IR-ERS and XPS results revealed that the polyaniline was in its emeraldine form. TMAFM measurement showed that the electropolymerized polyaniline nanoparticles dispersed on the HOPG surface with a coverage of about 10¹⁰ cm⁻². These nanoparticles were disk-shaped having a height of 10–30 Å and an apparent diameter varying from 200 to 600 Å. The particle dimensions increased with the electropolymerization charge (Q) over the interval from 5.7 to 19.3 μC cm⁻².     

Chemical synthesis of PEDOT nanofibers

A one-step, room-temperature method is described to chemically synthesize bulk quantities of microns long, 100-180 nm diameter nanofibers of electrically conducting poly(3,4-ethylenedioxythiophene)(PEDOT) in the form of powders, or as optically transparent, substrate-supported films using a V2O5 seeding approach.     

Morphology studies of polyaniline lengthy nanofibers formed via dimers copolymerization approach

In this paper, two different aniline dimers, N-phenyl-1,2-phenylenediamine (2-PPD) and N-phenyl-1,4-phenylenediamine (4-PPD) were used as starting monomers in polyaniline (PANI) synthesis. It was found that 2-PPD dimer alone produced only an amorphous PANI oligomer with a flaky morphology, while the 4-PPD provided either linear nanofiber or a spaghetti-like hollow nanofiber structures comprising of worm-like fibril subunits. By adjusting the molar fed ratio of 4-PPD to 2-PPD in the copolymerization, long PANI nanofibers with length up to tens of microns, bundled together by single PANI fibrils with diameter ca. 3-5 nm, was formed. A possible formation mechanism was proposed taking account of the reactivity difference at positions 4 and 2 on the 4-PPD and 2-PPD, respectively.     

Structural and vibrational characterization of polyaniline nanofibers prepared from interfacial polymerization

This work deals with the structural and vibrational characterization of PANI nanofibers prepared through interfacial polymerization using different concentrations of HCl aqueous solution. The results were compared to those obtained by PANI prepared through the conventional route. X-ray diffraction and small-angle X-ray scattering techniques showed that high concentrations of HCl solutions used in the preparation of the PANI nanofibers reduce their crystallinity. The increase of regions with granular morphology was also observed in the scanning electron microscopy images. The changes in the resonance Raman spectra from 200 to 500 cm (-1), FTIR spectra, and the EPR data of the PANI nanofibers reveal an increase in the torsion angles of C ring-N-C ring segments owing the formation of bipolarons in the PANI backbone higher than the PANI samples prepared by conventional route.