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1.
The chromaticity of poly(o-anisidine) (POAN) doped with different acids (HA), HA-doped POAN, has been studied by the spectrophotometric technique and the results were substantiated by molecular mechanics (MM+) calculations. The observed absorbance decrease (λ around 720 nm, dark green coloration) with increasing concentration of the inorganic oxidizing agent (KMnO4) can be attributed to the oxidative hydrolysis mechanism. The oxidative hydrolysis constant (K h) is highly dependent on the strength of the acid used. The HClO4-doped POAN matrix has the ability to store about 128.878 kJ⋅g−1 chromogenic energy (CE) at the wavelength 720 nm in a condensed lightweight form. MM+ calculations suggest that the potential energy (PE) in kJ⋅mol−1 of the optimum molecular geometric (OMG) structure of the HClO4-doped POAN matrix is at least two (2.052) times more stable than the OMG of the base form (POAN-EB) of the POAN matrix. Kinetic parameters of the oxidative hydrolysis reaction of the HA-doped POAN matrix were deduced from absorbance variations with time. The results of computer-oriented kinetic analysis indicate that the rate-controlling step for HA-doped POAN oxidative hydrolysis is governed by the Ginstling-Bronshein equation that represents three-dimensional diffusion (D4). Activation parameters for the oxidative hydrolysis of the HClO4-doped POAN matrix were computed and discussed.  相似文献   

2.
From a rheological study of emeraldine base (EB)/N‐methyl‐2‐pyrrolidinone (NMP)/2‐methyl‐aziridine (2MA) solutions, a correlation between the solution concentration and solution viscosity was found. We investigated the rheokinetic mechanism of the EB dissolution process and determined the reaction rate, activation energy, equilibrium constant, and Gibbs free energy (ΔGo) for the complexation between 2MA and EB tetrameric molecules ({EB}). The low rate constant (~3.0 × 10?4 mol?2 L2 min?1 at 298 K) indicates that the process of EB/NMP/2MA solution formation is slow. The {EB} and 2MA molecules need approximately 76 kJ/mol energy to form the complexes, and this implies that stable bonds may need to be broken before the complexes can form. Therefore, increasing the temperature can accelerate solution formation. The equilibrium constant increases with temperature, and this indicates that EB · 2MA complexation is endothermic. A positive value of ΔGo (5.26 kJ/mol) indicates that EB · 2MA complexation is a thermodynamically unfavorable reaction; therefore, the concentrated EB/NMP/2MA solutions eventually gel. Furthermore, we find that the activation energy of EB/NMP viscous flow is 80 kJ/mol, which is about 3–4 times the energy of ? N? H? hydrogen bonding. This suggests that at least three hydrogen bonds can form between two {EB} molecules, which might be responsible for the poor solubility of EB in organic solvents. The effects of the temperature, EB concentration, and 2MA:{EB} molar ratio on the gelation process have also been investigated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2702–2713, 2002  相似文献   

3.
Thermokinetic parameters of the solid-state of poly(o-toluidine) (POT) doped with perchloric (HClO4) acid was studied by thermogravimetric analysis (TG) and differential thermal analysis (DTA) under non-isothermal conditions. Molecular mechanics (MM) calculations suggest that the optimal geometric structure (OMG) of the HClO4-doped POT is at least four orders of magnitude more stable than the molecular geometric (MG) structure. These calculations indicate that the potential energy (PE/kJ mol−1) of the OMG is about four (1.09·104) orders of magnitude lower than the MG structure of the same matrix. The empirical formula of the doped polymer is best represented by [POT-2HClO4·2H2O]n as substantiate by elemental analysis and MM calculations. The full polymer decomposition and degradation were found to occur in three stages during the temperature increase. The decomposition activation energy (E d) of HClO4-doped POT matrix was calculated by employing different approximations. The heating rate (α) of the decomposition and the frequency factor (K o) were calculated. A number of equations were used to evaluate the kinetic parameters. The mechanism of the degradation of the conducting polymer is explained on the basis of their kinetic parameters. A remarkable heating rate dependence of the decomposition rate was observed.  相似文献   

4.
《化学:亚洲杂志》2017,12(19):2597-2603
In this paper, an Ag‐doped WO3 (and MoO3) composite has been prepared by following a simple micelle‐directed method and high‐temperature sintering route. The as‐prepared samples were characterized by X‐ray diffraction, inductively coupled plasma, transmission electron microscopy, X‐ray photoelectron spectroscopy, UV/Vis diffuse reflectance spectroscopy, Brunauer–Emmett–Teller, photoluminescence spectroscopy, and electrochemical impedance spectroscopy techniques. The photocatalytic experiments reveal that their oxygen‐production rates are up to 95.43 μmol (75.45 μmol) for Ag‐doped WO3 (MoO3), which is 9.5 (7.3) times higher than that of pure WO3: 9.012 μmol (MoO3: 9.00 μmol) under visible‐light illumination (λ ≥420 nm), respectively. The improvement of their photocatalytic activity is attributed to the enhancement of their visible‐light absorption and the separation efficiency of photogenerated carriers by Ag doping. Moreover, Ag‐doped WO3 (MoO3) also shows excellent adsorption of rhodamine B (RhB) and methylene blue (MB) in aqueous solution, with maximum adsorption capacities towards RhB and MB of 822 and 820 mg g−1 for Ag‐doped WO3, and 642 and 805 mg g−1 for Ag‐doped MoO3, respectively.  相似文献   

5.
The photophysical properties of a Keggin‐type polyoxometalate (POM) covalently bounded to a benzospiropyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features (λ em (closed form)=530 nm, λ em (open form)=670 nm) and that the fluorescence of the BSPR unit of the hybrid is considerably enhanced compared to BSPR parent compounds. While the fluorescence excitation energy of the BSPR reference compounds (370 nm) is close to the intense absorption responsible of the photochromic character (350 nm), the fluorescence excitation of the hybrid is shifted to lower energy (400 nm), improving the population of the emissive state. Combined NOESY NMR and theoretical calculations of the closed form of the hybrid give an intimate understanding of the conformation adopted by the hybrid and show that the nitroaryl moieties of the BSPR is folded toward the POM, which should affect the electronic properties of the BSPR.  相似文献   

6.
《化学:亚洲杂志》2017,12(18):2486-2493
A new class of phenanthrene‐fused BF2 azadipyrromethene (azaBODIPY) dyes have been synthesized through a tandem Suzuki reaction and oxidative ring‐fusion reaction, or a palladium‐catalyzed intramolecular C−H activation reaction. These phenanthrene‐fused azaBODIPY dyes are highly photostable and display markedly redshifted absorption (up to λ =771 nm) and emission bands (λ ≈800 nm) in the near‐infrared region. DFT calculations and cyclic voltammetry studies indicate that, upon annulation, more pronounced stabilization of the LUMO is the origin of the bathochromic shift of the absorption and high photostability.  相似文献   

7.
Various ladder‐like structured poly(phenyl‐co‐methacryl silsesquioxane)s (LPMSQ)s with high molecular weight (Mw = 10,000 ~ 40,000) were synthesized by direct hydrolysis and polymerization in the presence of base catalyst at 25 °C. Synthesized LPMSQs mainly showed ladder‐like structure and photo‐cure reaction by 100 mW/cm2 (360 nm) for 10 s without any photo‐cure initiators. Chemical composition and structural analysis of the obtained LPMSQs were characterized using 1H NMR, 29Si NMR, Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and X‐ray diffraction (XRD). Physical properties of LPMSQs before and after photcuring were analyzed by Nanoindentation. Surface modulus increased to 8GPa and hardness of thin films increased from 100 to 400 MPa. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

8.
Various protonated poly(o‐anisidine) (PoAN)/poly(vinyl alcohol) (PVA) composites were prepared with different types of acids: sulfuric (SA), p‐toluene sulfonic (TSA), camphor sulfonic (CSA), and p‐dodecylbenzene sulfonic (DBSA). In the visible spectrum of each composite in dimethyl sulfoxide, three absorption peaks were observed at 440, 620, and 860 nm. The peaks at 440 and 860 nm, which were enhanced with the increasing content of acid‐doped PoAN in the PVA matrix, were attributed to the radical cation and localized polaron generated in the conducting polymer. However, the peak at 620 nm was ascribed to the emeraldine base (EB) form of PoAN; that is, a portion of the acid was detached from the conducting polymer to form EB‐PoAN and free acid. The linear dependence of the logarithmic electrical conductivity on the variation of humidity, which was observed for all the composites, was caused by the salt–base transition of the conducting polymer, that is, by the movement of free acid between the active sites of the conducting polymer and the strongly bound water existing in PVA, which in turn depended directly on the environmental humidity. The response time of the composites to humidity was shortened with a decrease in the size of the dopant anions: DBSA > CSA > TSA > SA. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4343–4352, 2000  相似文献   

9.
The tetrabutylammonium (TBA+) salts of square‐planar monoanionic gold complexes of the unsymmetrically substituted Ar,H‐edt2? 1,2‐dithiolene ligands (Ar,H‐edt2?=arylethylene‐1,2‐dithiolato; Ar=phenyl ( 1 ?), 2‐naphthyl ( 2 ?), and 1‐pyrenyl ( 3 ?)) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species ( 1 , 2 , and 3 , respectively) were obtained in CH2Cl2 solution at room temperature by diiodine oxidation. The single‐crystal X‐ray diffraction structural data collected for (TBA+)( 2 ?), supported by DFT theoretical calculations, are consistent with the ene‐1,2‐dithiolate form of the ligand and the AuIII oxidation state. All complexes feature intense near‐IR absorptions (at about 1.5 μm) in their neutral states and Vis‐emitting properties in the 400–550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3 ?/ 3 couple. The spectroscopic and electrochemical features of 1 x? and 2 x? (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time‐dependent (TD) DFT calculations.  相似文献   

10.
The influence of temperature (77–230 K) on the fate of pyrene (Py) radical ions and Py excited states in irradiated poly(dimethylsiloxane) (PDMS) doped with Py is described. At 77 K, the Py radical ions seem to be stable, whereas the Py excited states [fluorescence (λ = 395 nm) and phosphorescence (λ = 575–650 nm)] are generated via tunneling charge transfer. In the range of the glass‐transition temperature (Tg = 152–153 K), the Py radical ions start to decay, taking part in a recombination process and leading to the Py monomer and Py excimer fluorescence (λ = 475 nm). The wavelength‐selected radiothermoluminescence (WS RTL) observed at approximately 395, 475, and 600 nm has helped us to identify the Tg range (152–153 K). The absorption maximum at approximately 404 nm, found in the temperature range under consideration, is thought to represent PyH?, cyclohexadienyl‐type radicals produced as a result of the reaction of Py?? with protonated PDMS macromolecules. With the initial‐rise method of evaluating the activation energy (Ea) with the WS RTL peaks observed in the Tg range, Ea values of 123–151 kJ mol?1 have been found. Such high Ea values can be explained by the contribution of energy connected to the molecular relaxation of the matrix in the Tg range. The well‐known Williams–Landel–Ferry equation, with universal constants C1 = 17.4 and C2 = 12.7, has been successfully applied to the interpretation of old pulse‐radiolysis/viscosity data found for crosslinked PDMS doped with Py. The mechanisms involved in these phenomena are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6125–6133, 2004  相似文献   

11.
Two synthetic nanographenes (NGs), N‐H7H and C‐H7H , were prepared. N‐H7H is doped with nitrogen, and C‐H7H is the all‐carbon analogue. Both are hexapole [7]helicenes (H7Hs), and their structures were identified by single‐crystal X‐ray diffraction. Sharp contrasts in absorption (absλmax, 683 vs. 593 nm), emission (emλmax, 894 vs. 777 nm), and electrochemical behavior (oxE1, 0.28 vs. 0.53 V) were observed between N‐H7H and C‐H7H , and the origin of these differences was rationalized by theoretical calculations. Studies on N‐H7H and C‐H7H set a clear example to elucidate the remarkable effects of N‐doping on the physical properties of NGs.  相似文献   

12.
The title compound, [Nd(C7H3O6S)(H2O)]n or [Nd(SSA)(H2O)]n (H3SSA is 5‐sulfosalicylic acid), was synthesized by the hydrothermal reaction of Nd2O3 with H3SSA in water. The compound forms a three‐dimensional network in which the asymmetric unit contains one NdIII atom, one SSA ligand and one coordinated water mol­ecule. The central NdIII ion is eight‐coordinate, bonded to seven O atoms from five different SSA ligands [Nd—O = 2.405 (4)–2.612 (4) Å] and one aqua O atom [Nd—OW = 2.441 (4) Å].  相似文献   

13.
A series of amphiphilic silica/fluoropolymer nanoparticles of SiO2g‐P(PEGMA)‐b‐P(12FMA) were prepared by silica surface‐initiating atom transfer radical polymerization (SI‐ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA) and poly dodecafluoroheptyl methacrylate (P12FMA). Their amphiphilic behavior, lower critical solution temperature (LCST), and surface properties as protein‐resistance coatings were characterized. The introduction of hydrophobic P(12FMA) block leads SiO2‐g‐P(PEGMA)‐b‐P(12FMA) to form individual spherical nanoparticles (~150 nm in water and ~170 nm in THF solution) as P(PEGMA)‐b‐P(12FMA) shell grafted on SiO2 core (~130 nm), to gain obvious lower LCST at 36–52 °C and higher thermostability at 290–320 °C than SiO2‐g‐P(PEGMA) (LCST = 78–90 °C, Td = 220 °C). The water‐casted SiO2‐g‐P(PEGMA)‐b‐P(12FMA) films obtain much rougher surface (125.3–178.4 nm) than THF‐casted films (11.5–16.9 nm) and all SiO2‐g‐P(PEGMA) films (26.8–31.3 nm). Therefore, the water‐casted surfaces exhibit obvious higher water adsorption amount (Δf = ?494 ~ ?426 Hz) and harder adsorbed layer (viscoelasticity of ΔDf = ?0.28 ~ ?0.36 × 10?6/Hz) than SiO2‐g‐P(PEGMA) films, but present loser adsorbed layer than THF‐casted films (ΔDf = ?0.29 ~ ?0.63 × 10?6/Hz). While, the introduction of P(12FMA) segments does not show obviously reduce in the protein‐repelling adsorption of SiO2‐g‐P(PEGMA)‐b‐P(12FMA) films (△f = ?15.7 ~ ?22.3 Hz) compared with SiO2‐g‐P(PEGMA) films (△f = ?8.3 ~ ?11.3 Hz) and no obvious influence on water adsorption of ancient stone. Therefore, SiO2‐g‐P(PEGMA)‐b‐P(12FMA) is suggested to be used as protein‐resistance coatings. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 381–393  相似文献   

14.
Phosphorus‐doped hexagonal tubular carbon nitride (P‐TCN) with the layered stacking structure was obtained from a hexagonal rod‐like single crystal supramolecular precursor (monoclinic, C2/m). The production process of P‐TCN involves two steps: 1) the precursor was prepared by self‐assembly of melamine with cyanuric acid from in situ hydrolysis of melamine under phosphorous acid‐assisted hydrothermal conditions; 2) the pyrolysis was initiated at the center of precursor under heating, thus giving the hexagonal P‐TCN. The tubular structure favors the enhancement of light scattering and active sites. Meanwhile, the introduction of phosphorus leads to a narrow band gap and increased electric conductivity. Thus, the P‐TCN exhibited a high hydrogen evolution rate of 67 μmol h?1 (0.1 g catalyst, λ >420 nm) in the presence of sacrificial agents, and an apparent quantum efficiency of 5.68 % at 420 nm, which is better than most of bulk g‐C3N4 reported.  相似文献   

15.
The photophysical properties of two energy‐transfer dyads that are potential candidates for near‐infrared (NIR) imaging probes are investigated as a function of solvent polarity. The dyads ( FbC‐FbB and ZnC‐FbB ) contain either a free base (Fb) or zinc (Zn) chlorin (C) as the energy donor and a free base bacteriochlorin (B) as the energy acceptor. The dyads were studied in toluene, chlorobenzene, 1,2‐dichlorobenzene, acetone, acetonitrile and dimethylsulfoxide (DMSO). In both dyads, energy transfer from the chlorin to bacteriochlorin occurs with a rate constant of ~(5–10 ps)?1 and a yield of >99% in nonpolar and polar media. In toluene, the fluorescence yields (Φ f = 0.19) and singlet excited‐state lifetimes (τ~5.5 ns) are comparable to those of the benchmark bacteriochlorin. The fluorescence yield and excited‐state lifetime decrease as the solvent polarity increases, with quenching by intramolecular electron (or hole) transfer being greater for FbC‐FbB than for ZnC‐FbB in a given solvent. For example, the Φ f and τ values for FbC‐FbB in acetone are 0.055 and 1.5 ns and in DMSO are 0.019 and 0.28 ns, whereas those for ZnC‐FbB in acetone are 0.12 and 4.5 ns and in DMSO are 0.072 and 2.4 ns. The difference in fluorescence properties of the two dyads in a given polar solvent is due to the relative energies of the lowest energy charge‐transfer states, as assessed by ground‐state redox potentials and supported by molecular‐orbital energies derived from density functional theory calculations. Controlling the extent of excited‐state quenching in polar media will allow the favorable photophysical properties of the chlorin–bacteriochlorin dyads to be exploited in vivo. These properties include very large Stokes shifts (85 nm for FbC‐FbB , 110 nm for ZnC‐FbB ) between the red‐region absorption of the chlorin and the NIR fluorescence of the bacteriochlorin (λ f = 760 nm), long bacteriochlorin excited‐state lifetime (~5.5 ns), and narrow (≤20 nm) absorption and fluorescence bands. The latter will facilitate selective excitation/detection and multiprobe applications using both intensity‐ and lifetime‐imaging techniques.  相似文献   

16.
Near‐monodisperse Bi‐doped anatase TiO2 nanospheres with almost uniform diameters in the range of 117 to 87 nm were prepared simply by introducing different amounts of bismuth nitrate pentahydrate into the reaction system and subsequent calcinations. X‐ray diffraction, UV‐visible diffuse reflectance spectra, and X‐ray photoelectron spectroscopy confirm that the doped ions substitute some of the lattice titanium atoms, and furthermore, Bi3+ and Bi4+ ions coexist. All the Bi‐doped TiO2 samples show much better photocatalytic activity than pure TiO2 in the degradation of rhodamine B (RhB) under the irradiation of visible light (λ>420 nm), and, interestingly, it was found that the degradation mechanism is different from the conventional one, which has already been reported elsewhere. The detailed mechanism is discussed in this article.  相似文献   

17.
两种含5-取代苯并-10-氮杂-15-冠-5的Schiff碱锰(III)、钴(II)配合物( , )及其吗啉基取代的类似物( , ) 用于催化α-吡啶甲酸对硝基苯酯(PNPP)水解。探讨了氮杂冠醚Schiff 碱配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型;考察了配合物结构、反应温度、缓冲溶液pH值等对PNPP水解反应的影响。结果表明,在25℃条件下随着缓冲溶液pH值的增大,催化PNPP水解速率提高;含取代苯并-10-氮杂-15-冠-5的Schiff碱配合物表现出更高的催化活性。根据阿累尼乌斯公式和不同温度下的表观一级常数求出水解反应的表观活化能。  相似文献   

18.
Establishing an effective design principle in solid‐state materials for a blue‐light‐excited Eu2+‐doped red‐emitting oxide‐based phosphors remains one of the significant challenges for white light‐emitting diodes (WLEDs). Selective occupation of Eu2+ in inorganic polyhedra with small coordination numbers results in broad‐band red emission as a result of enhanced crystal‐field splitting of 5d levels. Rb3YSi2O7:Eu exhibits a broad emission band at λmax=622 nm under 450 nm excitation, and structural analysis and DFT calculations support the concept that Eu2+ ions preferably occupy RbO6 and YO6 polyhedra and show the characteristic red emission band of Eu2+. The excellent thermal quenching resistance, high color‐rendering index Ra (93), and low CCT (4013 K) of the WLEDs clearly demonstrate that site engineering of rare‐earth phosphors is an effective strategy to target tailored optical performance.  相似文献   

19.
《Electroanalysis》2006,18(17):1696-1702
A novel electrochemical immunosensor for human chorionic gonadotrophin (hCG) was proposed by immobilization of hCG in gold nanoparticles doped three‐dimensional (3D) sol‐gel matrix and an interfacial competitive immunoreaction. The 3D organized composite structure was prepared by assemble of gold nanoparticles into a hydrolyzed (3‐mercaptopropyl)‐trimethoxysilane sol‐gel matrix, which showed good biocompatibility. After the interfacial competitive immunoreaction the formed HRP‐labeled immunoconjugate showed good enzymatic activity for the oxidation of o‐phenylenediamine by H2O2. With a competitive format, a method comprising of o‐phenylenediamine‐H2O2‐immobilized HRP labeled hCG immunoconjugate system for immunoassay of hCG from 5.0 to 30.0 mIU mL?1 was developed. The immunosensor showed good precision, high sensitivity, acceptable stability and reproducibility and could be used for detection of hCG in human serum with the consistent results in comparison with those obtained by a commercial analyzer.  相似文献   

20.
In the crystal structure of 3‐amino‐1,2,4‐triazine, C3H4N4, the mol­ecules form hydrogen‐bonded chains that are almost parallel to the b axis (3.2°), and which are inclined to the a and c axes by ~21 and ~69°, respectively. The distortion of the 1,2,4‐triazine ring in the crystal is compared with gas‐phase ab initio molecular‐orbital calculations.  相似文献   

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