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1.
The interaction between N-(4-ethoxyphenyl)-N′-(4-antipyrinyl) thiourea (EPAT) and human serum albumin (HSA) was studied by fluorescence spectroscopy in combination with UV absorption spectroscopy. The intrinsic fluorescence of human serum albumin was quenched by EPAT through a static quenching procedure. The binding constants of EPAT with HSA were estimated according to the fluorescence quenching results at different temperatures. The binding distance was obtained and the binding force was suggested to be mainly hydrophobic force, which was in accordance with the study of molecular model. The effect of common ions on the binding constants was also investigated. A new fluorescence spectroscopy assay of the proteins is presented, and results were very satisfactory.  相似文献   

2.
Polyaniline (PANi), poly(2-iodoaniline) (PIANi), and poly(aniline-co-2-iodoaniline) (co-PIANi) were synthesized using cyclic voltammetry in acetonitrile solution containing tetrabuthylammonium perchlorate (TBAP) and perchloric acid (HClO4) on 304-stainless steel electrodes. Adherent and black polymer films were obtained on the electrodes. The structure and properties of these polymer films were characterized by FTIR and UV-vis spectroscopy and electrochemical method. The corrosion performance of PANi, PIANi, and co-PIANi coated electrodes were investigated in 0.5 M hydrochloric acid (HCl) solutions by potentiodynamic polarization technique, open circuit potential-time curves and electrochemical impedance spectroscopy, EIS. It was found that the PANi film could provide much better protection than PIANi, and co-PIANi and PANi films have barrier property as well as acting as passivator. On the other hand PIANi and co-PIANi films are acting as barrier coatings which were related with the prevention of cathodic reaction taking place at metal\electrolyte interface. EIS measurement shows that every coating gives protection efficiency of greater than 75% after 48 h of immersion time in corrosive test solution.  相似文献   

3.
This paper reports the photosensitivity of poly(methyl methacrylate) (PMMA) and its copolymer doped with trans-4-stilbenemethanol. UV irradiation of the doped-PMMA at 325 nm induced the trans- to cis-isomerization of the dopant. This process was confirmed by 1H NMR spectra of trans-4-stilbenemethanol in CDCL3 solvent before and after irradiation. The isomerization can be initiated by the irradiation with an intensity of 0.62 mW/cm2. Photo-induced refractive index change of −0.0024 was obtained when a PMMA copolymer film doped with 5.1 wt% dopant was exposed to 325 nm light. Lorentz-Lorenz equation was used to estimate the refractive index of a trans-4-stilbenemethanol-PMMA composite and a trans-4-stilbenemethanol-PMMA copolymer composite from the mole refraction and van der Waals volume of each component. A slight elevation of molecular packing coefficient (K) for PMMA and its copolymer containing the dopant implies a denser aggregation as compared to the polymer without the dopant. Long period gratings were created in doped-PMMA films and doped-PMMA copolymer fibers using amplitude mask technique. Gratings were confirmed by microscopic observation and diffraction patterns.  相似文献   

4.
The phenomenon of excited state twisted intramolecular charge transfer (TICT) process in N,N-dimethylaminonaphthyl-(acrylo)-nitrile (DMANAN) has been reported on the basis of steady-state absorption and fluorescence spectroscopy in combination with quantum chemical calculations. The absorption and fluorescence characteristics of DMANAN in solvents of different polarity reveal the presence of a single species in the ground state which forms the intramolecular charge transfer state upon photoexcitation. The observed dual fluorescence is assigned to a high-energy emission from the locally excited or the Franck-Condon state and the red-shifted emission from the charge transfer (CT) state. In polar protic solvents, hydrogen-bonding interaction on CT emission has been established from the linear dependency of the position of the low-energy emission maxima on hydrogen-bonding parameter (α). The experimental findings have been correlated with the theoretical results based on TICT model obtained at density functional theory (DFT) level. The theoretical potential energy surface for the first excited state along both the donor and acceptor twist coordinates in the gas phase obtained by time dependent density functional theory (TDDFT) method and in polar solvent by time dependent density functional theory-polarized continuum model (TDDFT-PCM) method predicts well the experimental spectral properties.  相似文献   

5.
Blend films of poly(N-vinyl-2-pyrrolidone) (PVP) and chitosan (CTS) were prepared by casting method from acetic acid solutions. All blend films obtained are optically clear to the naked eye. The structure and physical properties of the blend films were analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), mechanical testing (Instron) and contact-angle measurements. The ATR-FTIR results indicated that there is no detectable band shifts at 1650 cm−1. From TGA studies, it was found that the onset degradation temperature of the blends almost unchanged due to the presence of a weak interaction between PVP and CTS chains. The DSC analysis showed a single glass transition temperature for all the blends, indicating that these polymers are miscible over the entire composition range. The mechanical properties of the blends, such as breaking stress and elongation at break and Young modulus were greatly affected with increase of CTS content. In addition, we found that the blends exhibit well defined contact angle titration curves from which the surface pKa values were determined. In conclusion, these experimental findings provide fundamental knowledge for the preparation of bioreactive surfaces of controlled reactivity on CTS based blends.  相似文献   

6.
Zn/Zn5(OH)8Cl2·H2O flower-like nanostructures was electrodeposited on the coated Zn with poly (N-methyl pyrrole) in 0.1 M Zn (NO3)2 and 0.1 M KCl solution. The morphology and the structure of the Zn/Zn5(OH)8Cl2·H2O were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction analysis (XRD). The FT-IR results showed special peaks at 908 and 728 cm−1 related to Zn5(OH)8Cl2·H2O. The FESEM results indicated that Zn/Zn5(OH)8Cl2·H2O consists of a flower-like nanostructure and these flower-shaped structures contain many shaped nanopetals with the thickness of 27.8 nm. The XRD result confirmed that the major phase of electrodeposited product in 0.1 M KCl as supporting electrolyte was Zn5(OH)8Cl2·H2O. The ability of PMPy to create a thin film and the existence of several pores in its matrix act as a mold for the growth of Zn/Zn5(OH)8Cl2·H2O flower-like nanostructure. The trapping of Cl and OH within pores can be considered as the reason for the formation of flowerlike Zn/Zn5(OH)8Cl2·H2O nanostructures in 0.1 M KCl.  相似文献   

7.
This study examines the use of some 4H-triazole derivatives, namely 3,5-diphenyl-4H-1,2,4-triazole (DHT), 3,5-bis(4-pyridyl)-4H-1,2,4-triazole (4-PHT) and 3,5-bis(4-methyltiophenyl)-4H-1,2,4-triazole (4-MTHT) for corrosion and dissolution protection of mild steel in normal hydrochloric acid solution. The inhibiting efficiency of the different additives is evaluated by means of weight loss and electrochemical techniques such as ac impedance measurements and polarisation curves. The experimental results obtained reveal that 4-MTHT is the best effective inhibitor and the inhibition efficiency is found to be in the following order: 4-MTHT > 4-PHT > DHT. The variation in inhibitive efficiency mainly depends on the type and nature of the substituents present in the inhibitor molecule. Polarisation curves show that theses triazoles are mixed-type inhibitors in 1 M HCl. The inhibition efficiency increases with 4H-triazole derivatives concentration and attains the maximum value of 99.6% in the case of 4-MTHT at 5 × 10−4 M. The results obtained from weight loss electrochemical studies were in reasonable agreement. The adsorption of 4H-triazole derivatives on the steel surface obeys to the Langmuir isotherm model. The thermodynamic data of adsorption and activation are determined and discussed. The fundamental thermodynamic functions were used to glean important information about the 4H-triazoles inhibitory behaviour. Molecular modeling was used to get better insight, about structural and electronic effects in relation to the inhibition efficiencies.  相似文献   

8.
The several types of sonication methods were applied to access the different morphologies of ZnO nanostructures on the surface of mild steel. To achieve this goal, a sonictor equipped with the probe extender was used as a high intensity ultrasonic apparatus for direct sonication. Furthermore, an ultrasonic bath (low intensity) and a cup-horn system (high intensity) were applied for indirect sonication. To find the effect of the acoustic waves on the ZnO morphology, the micrographs of obtained surfaces were compared to the sample prepared by the conventional method using scanning electron microscopy (SEM). In this work, the beneficial effects of sonication were subjected on the breaking down the agglomerates to smaller size particles, metal surface activation, and on the facile approach to nanostructures synthesis. The influence of the resulting ZnO structures over the corrosion protection of the electroless Ni–P alloy coatings was evaluated by the potentiodynamic polarization technique (Tafel extrapolation).  相似文献   

9.
Y. Liu  J. Y. Lee  L. Hong 《Solid State Ionics》2002,150(3-4):317-326
A new comb-like copolymer, poly(vinylidene fluoride-co-hexafluoropropylene)-g-poly(methyl methacrylate), or [P(VDF-HFP)-g-PMMA], was successfully synthesized through grafting in situ formed PMMA to the P(VDF-HFP) backbone. The composition of the P(VDF-HFP)-g-PMMA copolymer was characterized by Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA) and elemental analysis. X-Ray diffractometry (XRD) and differential scanning calorimetry (DSC) were used to examine the reduction in crystallinity of P(VDF-HFP) due to the anchoring of PMMA segments on it. Gel electrolyte membranes based on the resulting copolymer were prepared by the Bellcore process. The ionic conductivity of Li+ across the membranes and the related transference number were measured. A study of the interfacial stability between Li electrode and the P(VDF-HFP)-g-PMMA gel electrolyte was also conducted to evaluate the suitability of the P(VDF-HFP)-g-PMMA copolymer in rechargeable lithium and lithium-ion battery applications.  相似文献   

10.
Poly(N-methyl pyrrole) coating was successfully electrodeposited on steel substrates in mixed electrolytes of dodecyl benzene sulphonic acid (DBSA) with oxalic acid in the absence and the presence of TiO2 nanoparticles (NPs). The morphology and compositions were characterized by Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform Infrared Spectroscopy (FTIR), Energy-Dispersive X-ray spectroscopy (EDX). X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to calculate the size of nanoparticles. Electrode/polymer/electrolyte system was studied by Electrochemical Impedance Spectroscopy (EIS). The FESEM micrographs suggest that the incorporation of TiO2 nanoparticles affects the morphology of the film significantly and makes the TiO2 to be loosely piled up with PMPy. The results of EIS showed that synthesized PMPy in the presence of TiO2 NPs increases and decreases the Rpo and Cc of the coating respectively. The increase of the area of synthesized PMPy in the presence of nanoparticles can increase its ability to interact with the ions liberated during the corrosion reaction of steel in NaCl solution.  相似文献   

11.
A new compound, 1-[p-(dimethylamino)benzoyl]-4′-phenyl-semicarbazide (1) was synthesized and showed highly selective response to Cu2+ over other metal ions such as Pb2+, Mg2+, Fe2+, Co2+, Zn2+, Cd2+, Hg2+, Ni2+, Ca2+, Ag+, Na+, K+, and Li+. The control compound, 1-[p-(dimethylamino)benzoyl]-4-phenyl-thiosemicarbazide (2), showed different fluorescence spectral response to Cu2+. A 1:1 complex between Cu2+ and 1 was formed while 1:1 and 1:2 complexes between Cu2+ and 2 were formed. The binding model between the receptor (1 or 2) and Cu2+ was supported by IR spectra, mass spectra, and computation model. 1 possessed higher selectivity towards Cu2+ compared with 2 owing to the difference of complexation ability between urea and thiourea groups.  相似文献   

12.
Crystal structure of [Zn(hydet-en)2]·C4O4·H2O (ZHES) (hydet-en is N-(2-hydroxyethyl)ethylenediamine) complex has been synthesized and characterized by analytical, spectroscopic (IR, UV/Vis) and voltammetric techniques. After doping Cu2+ ion, its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystalizes in monoclinic system with space group P21/c and with Z=4. Each hydet-en ligand acts as a tridentate ligand through the two N atoms and the hydroxyl O atom, resulting in a six coordinate Zn(II) ion. The EPR spectra were recorded in three perpendicular planes of Cu2+ doped ZHES single crystal. The calculated g and A values indicated that the paramagnetic center is rhombic symmetry with the Cu2+ ion having distorted octahedral environment. The molecular orbital bond coefficients of the Cu(II) ion in d9 state is also calculated by using EPR and optical absorption parameters. The dianion SQ2− is oxidized reversibly in two consecutive steps to the corresponding radical monoanion and neutral form.  相似文献   

13.
A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications.  相似文献   

14.
Poly(lactic acid) (PLA) is a biodegradable polymer that has a variety of applications, one of which is as biomaterial in surgery or as functional layers on implants, due to its compatibility with living tissue. This paper reports the possibilities of quantification of poly(lactic acid) (PLA) in a polymer matrix such as poly(methyl methacrylate) (PMMA) by micro Raman spectroscopy (MRS). Blends of amorphous poly(DL‐lactic acid) with poly(methyl methacrylate) were prepared by the procedure of dissolution/precipitation. Thermal properties of the blends such as the glass transition temperature (Tg) were characterized by differential scanning calorimetry (DSC). The PLA/PMMA blends exhibited only a single glass transition region, indicating that this system is miscible. The PLA/PMMA system obeys the Gordon–Taylor equation (Tg versus PLA content). Various concentration ratios of PLA blends were prepared to use as a basis for quantitative analysis by MRS. Intensities of the characteristic bands at 813 cm−1 (νCOC of PMMA) and 873 cm−1 (νC―COO of PLA) were used for the calculation. The calibration graph showed a good linear correlation with an R2 value of 0.9985. On the basis of the calibration curve obtained, the determined content of several PLA/PMMA blends was in good agreement when compared with nominal contents. The limit of detection (LOD) and quantification (LOQ) were calculated by the calibration data set as signal‐to‐noise method. The relative standard deviation of this method was lower than 10% and the accuracy better than 4%. This study demonstrated that Raman spectroscopy provides an alternative non destructive method for quantitative analysis of PLA in a PMMA matrix. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

15.
Stimuli-responsive hydrogel nanocomposites comprised of swollen polymer networks, in which magnetic nanoparticles are embedded, are a relatively new class of “smart” soft materials presenting a significant impact on various technological and biomedical applications. A novel approach for the fabrication of hydrogel nanocomposites exhibiting temperature- and magneto-responsive behavior involves the random copolymerization of hexa(ethylene glycol) methyl ether methacrylate (HEGMA, hydrophilic, thermoresponsive) and 2-(acetoacetoxy)ethyl methacrylate (AEMA, hydrophobic, metal-chelating) in the presence of preformed oleic-acid-coated magnetite nanoparticles (OA·Fe3O4). In total, two series of hydrogel nanocomposites have been prepared in two different solvent systems: ethyl acetate (series A) and tetrahydrofuran (series B). The degrees of swelling (DSs) of all conetworks were determined in organic and in aqueous media. The nanocrystalline phase adopted by the embedded magnetic nanoparticles was investigated by X-ray diffraction (XRD) spectroscopy. The obtained diffraction patterns indicated the presence of magnetite (Fe3O4). Deswelling kinetic studies that were carried out at ∼60 °C in water demonstrated the thermoresponsive properties of the hydrogel nanocomposites, attributed to the presence of the hexaethylene glycol side chains within the conetworks. Moreover, thermal gravimetric analysis (TGA) measurements showed that these materials exhibited superior thermal stability compared to the pristine hydrogels. Further to the characterization of compositional and thermal properties, the assessment of magnetic characteristics by vibrational sample magnetometry (VSM) disclosed superparamagnetic behavior. The tunable superparamagnetic behavior exhibited by these materials depending on the amount of magnetic nanoparticles incorporated within the networks combined with their thermoresponsive properties may allow for their future exploitation in the biomedical field.  相似文献   

16.
By copolymerization of monomers containing donor (carbazole) and acceptor (dansyl) fluorophores withN-(2-hydroxypropyl)methacrylamide (HPMA), statistical copolymers with low and high contents of the fluorophores were prepared. The increase in nonradiative energy transfer between copolymers with a low content of fluorophores was probably due to intermolecular penetration of the polymer coils in concentrated solutions.  相似文献   

17.
The opto-electronic properties of native poly(p-phenylene vinylene) (PPV) were tuned by the confinement of the π-conjugation and the incorporation of a sulphur group as a spacer in order to obtain a blue-green emitting polymer (PPVS). The energy band gap of the PPVS thin film has been measured by UV-vis absorption spectroscopy and evaluated to 2.87 eV. Current-voltage characteristics and impedance spectroscopy measurements performed on sandwich structures [ITO/PPVS/Al] are used to elucidate the conduction mechanisms. The static electrical characterisations showed a space charge limited conduction (SCLC) and a conductivity with low power frequency behaviour characteristic of a hopping transport in disordered materials. The impedance spectra can be discussed in terms of an equivalent circuit model designed as a parallel resistor RP and capacitor CP network in series with a resistor RS. We extract numerical values of these parameters by fitting experimental data. Their evolution with bias voltages has shown that the SCLC mechanism is characterised by an exponential trap distribution.  相似文献   

18.
The self-assembled monolayers (SAMs) of n- and t-dodecyl mercaptan on the surface of copper have been obtained. As evidenced by electrochemical impedance spectroscopy (EIS), two kinds of the alkanethiols can self-assemble on the copper surface. But the results of the quartz crystal microbalance (QCM) show that the self-assembled way of the two alkanethiols are different. The SAMs of n-dodecyl mercaptan can increase the weight of the QCM electrode and the SAMs of t-dodecyl mercaptan, on the contrary, make the weight of the QCM electrode decrease. Inspected with the SEM, it is found that a lot of pits spread all over the copper surface after having been modified with t-dodecyl mercaptan. All the results suggest that the self-assemble of t-dodecyl mercaptan on the copper surface can erode and dissolve copper surface sharply.  相似文献   

19.
The binding of 3-(p-bromophenyl)-5-methyl-thiohydantoin (BPMT) with human serum albumin (HSA) was investigated by fluorescence spectroscopy in combination with UV absorption spectrum under physiological conditions. The intrinsic fluorescence of HSA was quenched by BPMT through static quenching mechanism and the fluorescence emission spectrum of HSA exhibited appreciable hypsochromic shift with increasing concentration of BPMT. The binding constants (K) of HSA with BPMT and the number binding sites (n) at different temperatures, thermodynamic parameter enthalpy changes (ΔH) and entropy changes (ΔS) of HSA-BPMT have been calculated according to the relevant fluorescence data, indicating that the hydrophobic interaction played a major role, which was consistent with the result of molecular modeling study.  相似文献   

20.
In order to clarify the dynamical aspects of the peptide structure, N-methylpropionamide (NMPA) was investigated as an example of peptide molecules: XCONHY (X=CH3CH2 and Y=CH3 for NMPA), paying special attention to the internal rotation of the two methyl groups. NMPA was found to have an almost planar skeleton with an extended syn/trans conformation, as indicated by the observed value of Iaa+IbbIcc, and its rotational spectra were interpreted in terms of group G18 consisting of six symmetry species: A1, A2, E1, E2, E3, and E4. The A1 and E2 spectra were observed split in most of b-type transitions, yielding the internal-rotation potential barrier V3 of 796 (21) cm−1 for CH3 in the ethyl group referred to as C-CH3. The spectra of the three E species: E1, E3, and E4 appeared several tens to thousands MHz apart from the corresponding A1 spectra, suggesting the internal-rotation potential barrier of CH3 bonded to the nitrogen, called N-CH3, to be quite low. In sharp contrast with the A1 spectra, which were well fitted to the ordinary asymmetric-rotor spectral pattern, a few higher-order terms were required to reproduce the E1 spectra, presumably because of the low N-CH3 barrier. The spectral analysis thus performed, in fact, led to the V3 of 80.06487 (14) cm−1, an order of magnitude lower than that of C-CH3. The E3 and E4 spectra were found to form triplets with the corresponding E1 lines at the center, and the E3-E1 and E4-E1 splittings were explained essentially by the contributions of the C-CH3 internal rotation combined with the kinetic-energy coupling between the two methyl groups. The torsion around the C-C bond between the ethyl and carbonyl groups was suggested by an ab initio calculation to be of double minimum nature, but the observed A1 spectra did not show any indication of such a double-minimum potential for the C-C torsion, although the possibility of a small hump being present at a planar conformation could not be entirely eliminated. The present results on NMPA along with those obtained on other peptide molecules will be of some significance in clarifying important problems of structural biology such as protein folding and signal transfer through biological systems.  相似文献   

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