In-situ spectroelectrochemical evidences for the copolymerization of o-toluidine with diphenylamine-4-sulphonic acid by UV-visible spectroscopy.

In-situ spectroelectrochemical studies on the copolymerization of o-toluidine (OT) with diphenylamine-4-sulfonic acid (DPASA) were carried out on ITO electrode in 0.5 M H2SO4 for different feed ratios of OT and DPASA. The early stages of copolymerization of OT with DPASA have been identified through spectroelectrochemical techniques. The results revealed the formation of a head-to-tail dimer type of intermediate at the initial stages of copolymerization. This N-phenyl-paraphenylene diamine (PPD) type of intermediate was assigned to have a peak at 550 nm in UV-visible spectra and confirmed via derivative cyclic voltabsorptogram (DCVA). Constant potential electropolymerization results also supported the formation of intermediate with an absorption maximum at 550 nm.     

Studies on monitoring the composition of the copolymer by cyclic voltammetry and in situ spectroelectrochemical analysis

Electrochemical copolymerization of diphenylamine (DPA) with ortho-toluidine (OT) was carried out in 4 M sulphuric acid medium by cyclic voltammetry. Cyclic voltammograms (CVs) of the copolymer films were recorded to deduce the electrochemical characteristics. In situ UV-visible spectroelectrochemical studies on copolymerization were carried out using indium tin oxide (ITO) coated glass plate as working electrode for different feed ratios of DPA and OT. UV-visible spectral characteristics show clear dependencies on the molar feed composition of DPA or OT used in electropolymerization. Derivative cyclic voltabsorptogram (DCVA) was deduced at the wavelength corresponding to the absorption by the intermediate species and used to identify the intermediates generated during the electropolymerization. The molar composition of DPA and OT units in the copolymer for the copolymers synthesized with different molar feed ratios of DPA and OT was determined by UV-visible spectroscopy. Reactivity ratios of DPA and OT were deduced by using Fineman-Ross and Kelen-Tudos methods and the observed differences in the composition of DPA/OT in the copolymers were correlated with CV characteristics and results obtained from in situ spectroelectrochemical studies.     

Copolymer Formation Between Two N‐Substituted Anilines—Electrochemical and Spectroelectrochemical Studies

Abstract

Electrochemical polymerization of diphenylamine, DPA with N‐methyl aniline, NMA was performed using cyclic voltammetry in a 4?M sulfuric acid medium. The electrochemical parameters representing the polymer deposition showed a strong dependence on the molar concentration ratios of DPA or NMA in the feed. In situ spectroelectrochemical studies were performed during the electropolymerization with different molar concentration feed ratios of DPA. The results reveal the formation of intermediates together with DPA and NMA units. Derivative cyclic voltabsorptograms (DCVAs) were deduced at the wavelength of absorbance corresponding to the intermediates and explained with redox characteristics in cyclic voltammogram. Results from cyclic voltammetry and spectroelectrochemical studies favor copolymer formation between DPA and NMA. Copolymers were prepared for different molar concentrations feed ratios of DPA and the composition of the monomer units in the copolymers were determined. Reactivity ratios of DPA and NMA were deduced using Fineman–Ross and Kelen–Tudos methods and correlated with the results from cyclic voltammetry and spectroelectrochemical studies.     

In situ UV-visible spectroelectrochemical studies on the copolymerization of diphenylamine with ortho-methoxy aniline

UV-visible spectroelectrochemical studies on copolymerization of diphenylamine (DPA) with ortho-methoxy aniline (OMA) were carried out for different feed ratios of DPA and OMA using indium tin oxide (ITO)-coated glass as working electrode. The UV-visible spectra show clear dependencies on the molar feed composition of DPA or OMA used in electropolymerization. Derivative cyclic voltabsorptogram (DCVA) was deduced at the wavelengths corresponding to the absorption by the intermediate species and used to confirm the intermediates generated during the electropolymerization. The composition of DPA and OMA in the copolymer for the copolymers synthesized with different molar feed ratios of DPA and OMA was determined by UV-visible spectroscopy. Reactivity ratios of DPA and OMA were deduced by using Fineman-Ross and Kelen-Tudos methods and correlated with spectroelectrochemical results.     

2-羟基-1,4-萘醌的电化学氧化还原机理研究

利用现场红外光谱电化学方法、 红外光谱循环伏吸法(CVA)和导数循环伏吸法(DCVA)研究了2-羟基-1,4-萘醌(2-HNQ)在乙腈溶剂中的电子转移机理. 在扫描范围为0.2~-1.8 V时, 2-HNQ的循环伏安(CV)图中有2对氧化还原峰. 在扫描范围为1.0~-2.0 V时, CV图在更正的电位下会出现1个氧化峰. 通过分析循环伏安扫描过程中1656, 1495, 1549和1325 cm^-1等峰的变化, 观察到整个电化学过程中存在2种中间状态, 去质子化醌(Q-O^-)还原生成的自由基二价阴离子会继续发生电化学反应, 即Q-O^-的还原遵循电化学-电化学反应机理(EE机理). 红外分析结果表明, 2-HNQ的电化学过程中存在较强的氢键作用.     

Copolymerization of luminol on screen-printed cells for single-use electrochemiluminescent sensors

An efficient electrochemiluminescent (ECL) single-use sensor for H(2)O(2) is presented based on an electropolymerized film prepared on screen-printed gold electrode (gold SPE). A study of the copolymerization of luminol in the presence of different monomers was carried out. The polymeric films were grown potentiodynamically with a potential interval between -0.2 and 1.0 V in 0.2 M H(2)SO(4) and were characterized by their electrochemical, electrochemiluminescent, and superficial features. The polymer with the most efficient growth and ECL emission was poly(luminol-3,3',5,5'-tetramethylbenzidine) at 1:5 ratio. These prepared SPE cells present good mechanical and photoemissive properties. A semi-logarithmic linearization shows a noticeable four decade-width concentration range with a limit of detection (LOD) of 2.6 × 10(-9) M and a precision of 10.2% (n = 5; as relative standard deviation, RSD) in the medium range level. The described SPE ECL sensors will be useful for the determination of oxidase substrates in ECL single-use biosensors.     

On the Role Played by Dimers of Radical Cations in the Process of Electrochemical Oxidation–Reduction of Polyaniline: The Data that Were Obtained Using the Method of Cyclic Voltabsorptometry in the Presence of Counteranions of a Diverse Nature

The electrochemical oxidation–reduction of films of polyaniline is studied in the presence of various counteranions. The differential cyclic voltabsorptometric (DCVA) curves (dA/dt relative to potential, where A is the optical absorption) are recorded at characteristic wavelengths corresponding to individual spectrum components previously isolated with the Alentsev–Fok method. The DCVA curves for aqueous solutions of HCl, HClO₄, and H₂SO₄ at different potential scan rates are compared to traditional cyclic voltammograms. For the DCVA curves obtained at 665 nm discovered is one broad peak of dA/dt in the region of potentials between the first and second stages of polyaniline oxidation (0.6 V vs. Ag/AgCl). An assumption is made about a chemical nature of the process of generation of absorption in this spectral region, which, more likely than not, is connected with the emergence of dimers of radical cations of polyaniline. It is discovered that the electrochemical processes in the region of potentials that correspond to the first stage of oxidation give rise to variations in the absorption inside several regions of spectrum: 435 nm (radical cations) and 755 nm (localized polarons). An assumption is made that the first peak of the current corresponds to several successive processes that occur in a polyaniline molecule in the course of oxidation as well as to the existence of heterogeneous regions where the generation of localized polarons proceeds at different rates.     

A new black to highly transmissive switching bilayer polymer composite films with electroactive pEA as a color buffer layer for improving electrochromic stability

Two reported D-A-D monomers based on 3,4-ethylenedioxythiophene (EDOT) were selected for electrochemical copolymerization to obtain copolymer film, named pRG. Then, a soluble polymer poly[3,4-ethylenedioxythiophene-alt-3,4-bis([2-ethylhexyl]oxy)thiophene] (pEA) based on the EDOT derivative was screened out, which is complementary to the absorption trough of the pRG film in visible region and matched with its working potential. The bilayer composite film pRG/pEA was obtained by spinning pEA basement membrane on fluorine doped tin oxide (FTO) coated glass surface, and then in situ electrochemical polymerization of pRG film. Compared to the pRG monolayer film, the bilayer composite film shows a more saturated black color in the neutral state and significant improvement on cyclic stability (only decreased by 1.7% after 250 cycles, while pRG film decreased by 17.1%). The introduction of pEA buffer layer not only achieves the full spectral absorption of the composite film in the visible region, but also significantly improves the cyclic stability of the bilayer composite film. The assembled EC prototype device based on the pRG/pEA composite film exhibits a “black to high transmission” reversible switch. Finally, this method combining electrochemical copolymerization, spin-coating, lamination and other methods provides a new research idea for designing and preparing black to transmissive electrochromic materials.     

联苯胺类共轭共聚物的金属配合物催化法合成及性质

联苯二胺 ,3,3′ 二甲基联苯二胺在次氯酸钠介质中氧化制备了相应的N ,N′ 二氯联苯醌二亚胺 ,3,3′ 二甲基 N ,N′ 二氯联苯醌二亚胺 .通过红外 (FT IR) ,核磁共振 (1 H NMR)等进行了表征 .研究了此化合物在二价镍配合物存在下 ,与 2 ,5 二溴噻吩制成的Grignard试剂共聚的方法 ,并得到了联苯醌二亚胺与噻吩交替共聚的共轭聚合物 .该合成方法所得聚合物的纯收率分别为 6 3% ,88% .循环伏安测定表明该类聚合物具有一定的电化学活性 ,紫外 可见光谱中分别在 310nm ,4 5 0nm处 (共聚物Ⅰ )和 2 90nm ,4 30nm处 (共聚物Ⅱ )出现吸收峰 .根据聚合物的粉末X 射线衍射图 (XRD) ,对所得聚合物的结晶性也做了初步探讨 .     

Grafting onto Gelatin. II. Graft Copolymerization of Ethyl Acrylate and Methyl Methacrylate onto Gelatin in the Presence of Ce4+ as Redox Initiator

In order to initiate a comprehensive study of graft copolymerization of vinyl monomers onto soluble protein-gelatin, we have studied grafting of ethyl acrylate (EA) and methyl methacrylate (MMA) onto gelatin using eerie ammonium nitrate (CAN) and eerie ammonium sulfate (CAS) as the redox initiator in an aqueous medium. A small amount of mineral acid (HNO₃ with CAN and H2SO4 with CAS) was found to catalyze the graft copolymerization. Graft copolymerization reactions were carried out at different temperatures. Maximum grafting occurred at 65°C both with EA and MMA. Percentage grafting has been determined as function of 1) concentration of monomer (EA and MMA), 2) concentration of initiator (CAN and CAS), 3) concentration of acid (HNO3 and H2SO4), 4) time, and 5) temperature.     

Edge plane sites on highly ordered pyrolytic graphite as templates for making palladium nanowires via electrochemical decoration

An approach for the fabrication of metal nanowires is presented. Palladium wires with diameters less than 50 nm were produced by electrochemical decoration of step edge sites on the surface of highly ordered pyrolytic graphite via the following three steps. First an electrochemical activation step was used to oxidize the edge plane sites on highly ordered pyrolytic graphite surfaces in 0.5 M Na(2)SO(4). Second, a potential cycling step in a 1 mM PdCl(2) solution in 0.1 M H(2)SO(4) was used to form palladium oxide (s) and/or complexes of Pd on the step edges. Third, Pd nanowires were formed by electroreduction after transfer of the graphite to 0.1 M H(2)SO(4). The resulting wires showed a high degree of uniformity. A merit of this approach is that it allowed metal nanowires to be fabricated without the simultaneous formation of nanoparticles on the basal plane terraces, in contrast to other studies of this type. The mesoscopic palladium wires are shown to be useful for the electrochemical sensing of hydrazine.     

Structure and electrochemistry of 4,4'-dithiodipyridine self-assembled monolayers in comparison with 4-mercaptopyridine self-assembled monolayers on Au(111)

4,4'-Dithiodipyridine (PySSPy) monolayers on Au(111) were investigated by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and in situ scanning tunneling microscopy (STM). The studies were performed in solutions of different anions and pHs (0.1 M H2SO4, 0.1 M HClO4, 0.1 and 0.01 M Na2SO4, 0.1 and 0.01 M NaOH). The cyclic current-potential curves in H2SO4 show current peaks at about 0.4 V, which are absent for all other electrolytes at this potential. The XPS data suggest that PySSPy adsorbs via the S endgroup on the gold surface and the S-S bond breaks during adsorption. From the chemical shift of the N(ls) peak, it is concluded that in acidic media the self-assembled monolayer (SAM) is fully protonated, whereas in basic solution it is not. The pKa is estimated to be 5.3. STM studies reveal the existence of highly ordered superstructures for the SAM. In Na2SO4 and H2SO4, a (7 x mean square root of 3) structure is proposed. However, whereas in Na2SO4 solutions the superstructure does not change with potential, in 0.1 M H2SO4 the superstructure is observed only negative of the current peak at +0.4 V. At more positive potentials, the film becomes disordered. The results are compared to those for 4-mercaptopyridine (PyS) SAMs. XPS experiments and current-potential curves indicate that both molecules adsorb in the same manner on Au(111), that is, even in the case of PySSPy the adspecies is PyS. The STM results, however, call for a more subtle interpretation. While in Na2SO4 solutions the observed superstructures are the same for both SAMs, markedly different structures are found for PySSPy and PyS SAMs in 0.1 M H2SO4.     

电解质溶液对聚吡咯电聚合中过氧化行为的影响

分别以硫酸/水和高氯酸锂/乙腈为电解质溶液, 采用循环伏安法在铂基底电极上电聚合制备了聚吡咯, 研究了电解质溶液对聚吡咯电聚合过程中过氧化行为的影响. 与硫酸/水溶液相比, 在高氯酸锂/乙腈溶液中电聚合制备的聚吡咯发生过氧化的峰电位正移了0.42 V. 采用原位傅里叶变换红外(in situ FTIR)光谱技术检测, 结果表明, 电聚合制备的聚吡咯在2种电解质溶液中均发生了过氧化反应, 其β-C经氧化生成C-OH或CO. 在硫酸/水溶液中, 部分聚吡咯发生电氧化降解生成CO₂, 致使其共轭结构被破坏, 电导率迅速下降. 而在高氯酸锂/乙腈溶液中, 在更高的电位范围内, 聚吡咯并没有氧化降解成CO₂.     

Synthesis and optical limiting properties of axially bridged phthalocyanines: [(tBu4PcGa)2O] and [(tBu4PcIn)2O

Highly soluble [(tBu(4)PcM)(2)O] phthalocyanine dimers (M=Ga(III) (3), In(III) (4)) were prepared by the reaction of [tBu(4)PcMCl] (M=Ga(III) (1), In(III) (2)) with excess of concentrated H(2)SO(4) at -20 degrees C. The Mbond;Obond;M linkages in 3 and 4 are not stable against concentrated H(2)SO(4) at room temperature, 6 n HCl at reflux, or during isolation under column chromatographic conditions (e.g. silica gel/toluene). The stability of 3 in solution is considerably higher than that of 4. The mu-oxo-bridged phthalocyanine dimers 3 and 4 have a more intense photoluminescence emission in the red region than the monomers 1 and 2. The gallium phthalocyanines 1 and 3 have fluorescence lifetimes of a few nanoseconds, while those of the indium phthalocyanines 2 and 4 last for only several hundred picoseconds. Comparison of the fluorescence lifetimes of monomers 1 and 3 with dimers 2 and 4, reveals that the dimers have longer lifetimes of the excited singlet states. The transient absorption spectrum is similar for all of the compounds, and the transient absorption band at about 520 nm, observed by nanosecond laser irradiation, can be assigned to the transition from the lowest triplet excited state to the upper triplet excited states (T-T absorption). The magnitude of the optical limiting exhibited by 1, 2, 3, and 4 in toluene at 532 nm laser pulse irradiation is in the order: 4>3>2>1 [corrected]. The values of the imaginary third-order nonlinear susceptibility Im[chi((3))] of the above compounds at 532 nm in toluene are also reported. These results demonstrate that these compounds are candidates for optical limiting applications.     

对硝基苯酚在质子惰性溶剂中的氧化还原机理

利用现场红外光谱电化学法、红外光谱循环伏吸法(CVA)和导数循环伏吸法(DCVA)研究了对硝基苯酚(PNP)在乙腈中的氧化还原机理,并结合B3LYP方法在6-311++G*水平上计算得出反应中自由基阴离子和二聚体可能的结构.通过循环伏安曲线(CV)和快速扫描红外光谱验证了在电化学还原过程中PNP在乙腈溶剂中发生较复杂的自质子化反应,并且PNP的电化学行为受其浓度的影响.当PNP浓度较高时,PNP在还原成自由基阴离子后发生自质子化作用,然后自由基阴离子与质子化产物得到电子发生二聚反应,随后PNP阴离子还原成二价阴离子;当PNP浓度较低时,电化学还原机理会发生改变,二聚现象消失,阴离子自由基继续还原.     

Model system for the study of 2D phase transitions and supramolecular interactions at electrified interfaces: hydrogen-assisted reductive desorption of catechol-derived adlayers from Pt(111) single-crystal electrodes

Classical electroanalytical techniques and in situ FTIR are used to study the oxidative chemisorption of catechol (o-H(2)Q) and the hydrogen-assisted reductive desorption of catechol-derived adlayers (o-Q((ads))) at nearly defect-free Pt(111) single-crystal electrodes in 0.5 M H(2)SO(4). At near equilibrium conditions (lim(upsilon-->0)) the cyclic voltammetric response does not conform to the behavior expected from classical models of molecular adsorption at electrochemical interfaces. Instead, attractive interactions play a controlling role, i.e., hydrogen-assisted displacement of o-Q((ads)) takes place as an electrochemically reversible two-dimensional (2D) phase transition controlled by collision-nucleation-growth phenomena in the presence of 2 mM o-H(2)Q((aq)). In contrast, different desorption dynamics are observed when the reductive desorption of the adlayers is carried out in clean (0 mM o-H(2)Q((aq)) supporting electrolyte. Donor-acceptor (DA) interactions between the Pt(111)/o-Q((ads)) surface adduct and o-H(2)Q((aq)) are postulated as a possible intervening mechanism leading to the observed differences in the macroscopic electrochemical responses. The results also demonstrate that in aqueous solutions it is thermodynamically feasible to shift the formal oxidation potential of catechol-metal adducts to potentials near those of molecular hydrogen via chemically reversible, nondissociative interactions, taking place as a 2D phase transition.     

不同电解质溶液对聚吡咯修饰膜性质的影响

以对甲基苯磺酸钠(p-TSNa)为掺杂剂在不锈钢电极表面恒电位合成聚吡咯(PPy)修饰膜, 采用循环伏安法在-1.6 - 0.8 V大范围扫描研究了修饰膜在H2SO4、Na2SO4、NaOH电解质溶液中的氧化还原行为. 结果表明, 在H2SO4溶液中, 以H+的脱出(氧化)/嵌入(还原)为特征, 并发现聚吡咯在酸性溶液中所特有的质子还原峰. 在Na2SO4和NaOH溶液中, 以Na+的脱出(氧化)/嵌入(还原)峰为特征. FT-IR吸收光谱显示, 经NaOH处理后, 聚吡咯膜的长共轭结构被完全破坏, 而经H2SO4和Na2SO4处后, 膜的共轭结构未发生变化.     

Electrochemically controlled chemically reversible transformation of alpha-tocopherol (vitamin E) into its phenoxonium cation

Alpha-tocopherol (alpha-TOH) can be electrochemically oxidized in CH(3)CN containing Bu(4)NPF(6) in a chemically reversible two-electron/one-proton (ECE) process to form the phenoxonium cation (alpha-TO(+)) that is stable for at least several hours at 243 K. In the presence of up to approximately 1% CF(3)SO(3)H, alpha-TO(+) exists in equilibrium with the alpha-tocopherol cation radical (alpha-TOH(+)(*)), whereas at concentrations between approximately 1-3% CF(3)SO(3)H the electrochemical oxidation of alpha-TOH occurs by close to one-electron to form alpha-TOH(+)(*).alpha-TOH(+)(*) can be further oxidized in a one-electron process to form the alpha-tocopherol dication (alpha-TOH(2+)). The identity and stability of the phenolic cationic compounds were determined by a combination of electrochemical (cyclic voltammetry and controlled potential electrolysis) and in situ spectroscopic (UV-vis-NIR, FTIR, EPR, and NMR) analysis.     

Synthesis and photophysical processes of an anthracene derivative containing hole transfer groups

A novel luminescent compound 9,10-di-(N-carbazovinylene)anthracene (DCVA) was synthesized by Heck reaction of 9,10-dibromoanthracene and N-vinylcarbazole. The structure was characterized by MS, 1H NMR and Elemental analysis. The photoluminescent properties of DCVA have been carefully investigated by UV-vis absorption and fluorescence emission spectra. The results showed that the luminescent quantum yield of DCVA was 0.73 in THF and it emitted blue-light with the band gap of 3.60 eV estimated from the onset absorption. In addition, the light-emission of DCVA can be quenched by electron acceptor (dimethyl terephthalate), however, the fluorescent intensities of DCVA were slowly increased with the addition of electron donor (N,N-dimethylaniline). Furthermore, the molecular interactions of DCVA with fullerene (C60) and carbon nanotubes (CNTs) were also investigated, which indicated the organic luminescent compound can be used as new fluorescent probe.     

Role of the anion in the underpotential deposition of cadmium on a Rh(111) electrode: probed by voltammetry and in situ scanning tunneling microscopy

In situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) were employed to examine the underpotential deposition (UPD) of cadmium on a rhodium(111) electrode in sulfuric and hydrochloric acids. The (bi)sulfate and chloride anions in the electrolytes played a main role in controlling the number and arrangement of Cd adatoms. Deposition of Cd along with hydrogen adsorption occurred near 0.1 V (vs reversible hydrogen electrode) in either 0.05 M H2SO4 or 0.1 M HCl containing 1 mM Cd(ClO4)2. These coupled processes resulted in an erroneous coverage of Cd adatoms. The process of Cd deposition shifted positively to 0.3 V and thus separated from that of hydrogen in 0.05 M H2SO4 containing 0.5 M Cd2+. The amount of charge (80 microC/cm2) for Cd deposition in 0.5 M Cd2+ implied a coverage of 0.17 for the Cd adatoms, which agreed with in situ STM results. Regardless of [Cd2+], in situ STM imaging revealed a highly ordered Rh(111)-(6 x 6)-6Cd + HSO4- or SO42- structure in sulfuric acid,. In hydrochloric acid, in situ STM discerned a (2 x 2)-Cd + Cl structure at potentials where Cd deposition commenced. STM atomic resolution showed roughly one-quarter of a monolayer of Cd adatoms were deposited, ca. 50% more than in sulfuric acid. Dynamic in situ STM imaging showed potential dependent, reversible transformations between the (6 x 6) Cd adlattices and (square root 3 x square root 7)-(bi)sulfate structure, and between (2 x 2) and (square root 7 x square root 7)R19.1 degrees -Cl structures. The fact that different Cd structures observed in H2SO4 and HCl entailed the involvement of anions in Cd deposition, i.e. (bi)sulfate and chloride anions were codeposited with Cd adatoms on Rh(111).