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1.
The interactions of the phenolic acids cinnamic acid (CNA), ferulic acid (FA), caffeic acid (CA) and chlorogenic acid (CLA) with bovine serum albumin (BSA) were investigated and compared using affinity capillary electrophoresis (ACE) and the fluorescence quenching methods. ACE gives binding constants (K b) and thermodynamic parameters. The thermodynamic parameters show that each of four phenolic acids bind to BSA mainly by hydrogen bonds, electrostatic and hydrophobic interactions. The fluorescence quenching method provided quenching constant K sv, binding site number n and K b. The fluorescence results indicate that BSA fluorescence quenching is mainly a static quenching process. The binding constants (K b) of CNA, FA, CA and CLA were from 2.52×104 to 7.90×104 L⋅mol−1 from ACE experiments and 1.19×104 to 5.21×104 L⋅mol−1 from fluorescence, their increase corresponded to the increase in the number of hydroxyl groups. These results imply that molecular structure and the number of hydroxyl groups of phenolic acids play act key roles in the affinity of natural phenolic acids towards BSA.  相似文献   

2.
Heterogeneous reactions of gaseous methanesulfonic acid (MSA) with calcium carbonate (CaCO3) and kaolinite particles at room temperature were investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatography (IC). Methanesulfonate (MS?) was identified as the product in the condensed phase, in accordance with the product of the reaction of gaseous MSA with NaCl and sea salt particles. When the concentration of gaseous MSA was 1.34 × 1013 molecules cm?3, the uptake coefficient was (1.21 ± 0.06) × 10?8 (1σ) for the reaction of gaseous MSA with CaCO3 and (4.10 ± 0.65) × 10?10 (1σ) for the reaction with kaolinite. Both uptake coefficients were significantly smaller than those of the reactions of gaseous MSA with NaCl and sea salt particles.  相似文献   

3.
The kinetics of the hydrogen–deuterium (H–D) exchange at both the methine (alpha) and methylene (gamma) positions of glutamic acid in deuterated hydrochloric acid solution has been studied in the temperature range of 383–433 K by 1H NMR detection. The reaction rates of H–D exchange at the two positions were described by applying multivariable linear regression (MLR) analysis and are determined as v = k[Glu]3.3[D3O+]1.5 mol L?1 h?1 with k = 3.52 × 1016 × exp (–1.37 × 105/RT) mol?3.8 L h?1 for the alpha position as well as v = k[Glu]1.0[D3O+]0.45 mol L?1 h?1 with k = 1.77 × 1012 × exp (–0.99 × 105/RT) mol?0.45 L h?1 for the gamma position. The Arrhenius activation energy (Ea) at the gamma position is less than that at the alpha position, which implies that the deuteration reaction at the gamma position proceeded more easily.  相似文献   

4.
Formic acid is considered a promising energy carrier and hydrogen storage material for a carbon‐neutral economy. We present an inexpensive system for the selective room‐temperature photocatalytic conversion of formic acid into either hydrogen or carbon monoxide. Under visible‐light irradiation (λ>420 nm, 1 sun), suspensions of ligand‐capped cadmium sulfide nanocrystals in formic acid/sodium formate release up to 116±14 mmol H2 gcat?1 h?1 with >99 % selectivity when combined with a cobalt co‐catalyst; the quantum yield at λ=460 nm was 21.2±2.7 %. In the absence of capping ligands, suspensions of the same photocatalyst in aqueous sodium formate generate up to 102±13 mmol CO gcat?1 h?1 with >95 % selectivity and 19.7±2.7 % quantum yield. H2 and CO production was sustained for more than one week with turnover numbers greater than 6×105 and 3×106, respectively.  相似文献   

5.
Methylmaleic (citraconic, CTA) acid and methylfumaric (measaconic, MSA) acid in aqueous sulfuric acid solution undergo bromine-catalyzed reversible cis-trans isomerization in the presence of ceric and bromide ions. The positional isomerization of CTA or MSA to itaconic acid (ITA) is not observed. The method of high performance liquid chromatography (HPLC) was applied to study the kinetics of this catalyzed isomerization. The major catalytic species is best expressed as the Br?2 · radical anion. Under suitable catalytic conditions, there is a tendency for the [MSA]/[CTA] ratio to reach an equilibrium value of 4.10 at 25° for the CTA+Br?2 · ? MSA+Br?2 · reaction. Chloromaleic (CMA) and chlorofumaric (CFA) acids undergo similar isomerization with an equilibrium [CFA]/[CMA] ratio of 10.3 at 25°. The isomerization of maleic acid (MA) to fumaric acid (FA) is essentially irreversible with 50 as the lower limit of the equilibrium [FA]/[MA] ratio. The substituent has an important effect on the reversibility of this catalyzed isomerization of butenedicarboxylic acids. The thermodynamic parameters ΔH° and ΔS° at 25° for the CTA+Br?2 · ? MSA+Br?2 · reaction were found to be ?5.1±0.7 kj/mol and ?6.0±3.3 J/mol K, respectively. The present method gives a plausible way to measure the differences in enthalpy and entropy between the trans- and cis-isomers of butenedicarboxylic acids (CRCO2H=CR'CO2H) in aqueous solution.  相似文献   

6.
This contribution describes the development and demonstration of the ambient‐temperature, high‐speed living polymerization of polar vinyl monomers (M) with a low silylium catalyst loading (≤ 0.05 mol % relative to M). The catalyst is generated in situ by protonation of a trialkylsilyl ketene acetal (RSKA) initiator (I) with a strong Brønsted acid. The living character of the polymerization system has been demonstrated by several key lines of evidence, including the observed linear growth of the chain length as a function of monomer conversion at a given [M]/[I] ratio, near‐precise polymer number‐average molecular weight (Mn, controlled by the [M]/[I] ratio) with narrow molecular weight distributions (MWD), absence of an induction period and chain‐termination reactions (as revealed by kinetics), readily achievable chain extension, and the successful synthesis of well‐defined block copolymers. Fundamental steps of activation, initiation, propagation, and catalyst “self‐repair” involved in this living polymerization system have been elucidated, chiefly featuring a propagation “catalysis” cycle consisting of a rate‐limiting C? C bond formation step and fast release of the silylium catalyst to the incoming monomer. Effects of acid activator, catalyst and monomer structure, and reaction temperature on polymerization characteristics have also been examined. Among the three strong acids incorporating a weakly coordinating borate or a chiral disulfonimide anion, the oxonium acid [H(Et2O)2]+[B(C6F5)4]? is the most effective activator, which spontaneously delivers the most active R3Si+, reaching a high catalyst turn‐over frequency (TOF) of 6.0×103 h?1 for methyl methacrylate polymerization by Me3Si+ or an exceptionally high TOF of 2.4×105 h?1 for n‐butyl acrylate polymerization by iBu3Si+, in addition to its high (>90 %) to quantitative efficiencies and a high degree of control over Mn and MWD (1.07–1.12). An intriguing catalyst “self‐repair” feature has also been demonstrated for the current living polymerization system.  相似文献   

7.
Human saliva quantitative monitoring of clarithromycin (CLA) by chemiluminescence (CL) with flow injection analysis was proposed for the first time, which was based on the quenching effect of CLA on luminol–bovine serum albumin (BSA) CL system with a linear range from 7.5?×?10?4 to 2.0 ng/ml. This proposed approach, offering a maximum sample throughput of 100 h?1, was successfully applied to the quantitative monitoring of CLA levels in human saliva during 24 h after a single oral dose of 250 mg intake, with recoveries of 95.2~109.0 % and relative standard deviations lower than 6.5 % (N?=?7). Results showed that CLA reached maximum concentration of 2.28?±?0.02 μg/ml at approximately 3 h, and the total elimination ratio was 99.6 % in 24 h. The pharmacokinetic parameters including absorption rate constant (0.058?±?0.006 h?1), elimination rate constant (0.149?±?0.009 h?1) and elimination half-life time (4.66?±?0.08 h) were obtained. A comparison of human saliva and urine monitoring was also given. The mechanism study of BSA–CLA interaction revealed the binding of CLA to BSA is an entropy driven and spontaneous process through hydrophobic interaction, with binding constant K BSA–CLA of 4.78?×?106 l/mol and the number of binding sites n of 0.82 by flow injection–chemiluminescence model. Molecular docking analysis further showed CLA might be in subdomain IIA of BSA, with K BSA–CLA of 6.82?×?105 l/mol and ΔG of ?33.28 kJ/mol.  相似文献   

8.
Proton transfer reactions under anhydrous conditions have attracted remarkable interest due to chemical energy conversions in polymer electrolyte membrane fuel cells. In this work, 1H‐1,2,4‐triazole (Tri) was used as a proton solvent in different polymer host matrices such as Poly(vinylphosphonic acid) (PVPA), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) (PAMPS). PVPATrix and PAMPSTrix electrolytes were investigated where x is the molar ratio of Tri to corresponding polymer repeat unit. The interaction between polymer and Tri was studied via FTIR spectroscopy. Thermogravimetry analysis and differential scanning calorimetry were employed to examine the thermal stability and homogeneity of the materials, respectively. PVPATri1.5 showed a maximum water‐free proton conductivity of 2.3 × 10?3 S/cm at 120 °C and that of PAMPSTri2 was 9.3 × 10?4 S/cm at 140 °C. The results were interpreted in terms of different acidic functional groups and composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3315–3322, 2006  相似文献   

9.
Doped polyaniline (PANI) was synthesized by an “in situ doping polymerization” method in the presence of different sulfonic acids, such as methanesulfonic acid (MSA), p‐methylbenzene sulfonic acid (MBSA), β‐naphthalenesulfonic acid (β‐NSA), α‐naphthalenesulfonic acid (α‐NSA), 1,5‐naphthalenedisulfonic acid (1,5‐NSA), and 2,4‐dinitronaphol‐7‐sulfonate acid (NONSA). Morphology, solubility in m‐cresol, and electrical properties of the doped PANI were measured with the variation of the molecular structure of the selected sulfonic acids. Granular morphology was obtained when the sulfonic acids without a naphthalene ring, such as MSA and MBSA, were used. Regular tubular morphology was obtained only when β‐NSA was used. The tubular morphology can be modified by changing the substitutes, the number, and location of sulfo‐group(SOH) on the naphthalene ring. These results indicated that naphthalene ring in the selected sulfonic acids plays an important role in forming the tubular morphology of the doped PANI by the “in situ doping polymerization” method. All resulting PANI salts were soluble in m‐cresol, with the solubility depending on the molecular structure of the selected dopants. Room‐temperature conductivity for the doped PANI ranges from 10−1 to 100S/cm. Temperature dependence of conductivity shows a semiconductor behavior, and it can be expressed by one dimenson Variable Range Hopping (VRH) model. 1 © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1277–1284, 1999  相似文献   

10.
Two new complexes, namely [Cu6L6] ( 1 ) and [Zn(HL)2] ( 2 ) (H2L = N‐(1‐phenyl‐3‐methyl‐4‐propenylidene‐5‐pyrazolone)‐2‐furancarboxylic acid hydrazide), have been synthesized and characterized. Single crystal X‐ray analysis indicates that complex 1 has a hexanuclear structure and complex 2 exhibits a mononuclear structure. The DNA/bovine serum albumin (BSA) binding properties of complexes 1 and 2 were investigated by absorption spectroscopy and fluorescence quenching. Both complexes could effectively intercalate to DNA with calculated quenching constants of 2.6 × 105 and 1.25 × 105 M?1, respectively. The quenching mechanism of the intrinsic fluorescence of BSA by the complexes was found to be a static one. The cytotoxicities of 1 and 2 were investigated in two human tumor cell lines, human esophageal cancer cells (Eca‐109) and cervical cancer cells (HeLa). Complex 1 exhibits higher antitumor activity than 2 . Furthermore, 1 can inhibit HeLa cells by inducing apoptosis and G0/G1 phase cell cycle arrest. All results demonstrate that 1 and 2 both have DNA/BSA binding capacity and antitumor activity.  相似文献   

11.
Stability constant for mercury binding by commercial and natural humic acids (HA) were determined using a new potentiometric mercury(II) sensor based on dithiosalicylic acid modified carbon paste electrode. The sensor present a high selective and sensitive response to mercury(II) ions, and a low detection limit of 1.8×10?8 M. The potentiometric titrations curves of humic acids against mercury(II) ions were modeled. For 1.00×10?7 to 3.00×10?4 M mercury(II) ion concentration levels the results are consistent with the presence of two different binding sites in the humic acid macromolecule. The strongest binding sites (log K1 ranging from 10.1 to 6.8) are probably due to interaction with carboxylic acid and amine groups in the molecule, whereas weakest binding sites (log K2 ranging from 8.8 to 4.5) can be associated to phenolic groups.  相似文献   

12.
Based on the linear enhancement of formaldehyde (FA) within 7.0 ~ 1000 pmol l?1 on luminol—bovine serum albumin (BSA) chemiluminescence (CL) system, FA determination in air and beer samples using CL with flow injection (FI) was proposed. The detection limit was 2.5 pmol l?1 (3σ) and the relative standard deviations were less than 4.5% (n = 7). At a flow rate of 2.0 mL min?1, a whole analysis from sampling to washing only needed 32 s, offering a sample throughput of 112 h?1. This proposed method was successfully utilized to determine FA vapor pressure in liquid (121.8 ± 3.8 Pa), FA content in real air sample (8.93 ± 0.03 mg m?3), and FA levels in beer (199.5 ± 5.6 ~ 225.2 ± 3.5 mg l?1), giving determination recoveries from 90.7% to 109.3%. The mechanism of BSA—FA interaction was also investigated, showing FA binding to BSA was a spontaneous process mainly through hydrogen bonding and van der Waals force by FI‐CL, with binding constant K of 1.89 × 106 l mol?1 and the number of binding sites n of 0.86. Molecular docking analysis further revealed FA could enter into the pocket at subdomain IIA of BSA, with K of 1.71 × 105 l mol?1 and ΔG of ‐29.68 kJ mol?1.  相似文献   

13.
Abstract

A new binuclear complex, [Zn2L2Cl4]·2H2O {L?=?N-aldehyde-N-(4-(benzyloxy)benzyl)-1,4,7triazacyclononane}, was synthesized and characterized by X-ray, elemental analysis, infrared and electronic spectroscopy, and mass spectrometry. The central ion is bridged by the L and lies in a tetrahedral configuration with Zn···Zn distance of 6.283 Å. The complex crystallizes in the triclinic space group Pī. ESI-MS of the complex indicates that the protonated ligand HL+ is the active species. The interaction of HL+ with calf thymus–DNA (CT–DNA) and bovine serum albumin (BSA) was studied by means of various spectroscopic methods, which revealed that HL+ could interact with CT–DNA through groove-binding mode and could quench the intrinsic fluorescence of BSA in a static quenching process. DNA–cleavage experiments indicate that HL+ exhibits efficient DNA–cleavage activity in the presence of H2O2, hydroxyl radical (HO?) may serve as the major cleavage active species, and the pseudo-Michaelis–Menten kinetic parameters (Kcat, KM, Vmax); 2.47?h?1, 2.70?×?10?4 M and 6.68?×?10?4 Mh?1.  相似文献   

14.
When the concentration of dodecyl benzene sulfonic acid sodium salt (SDBS) is 0.7 mmol·L?1, the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)32+‐chlorpheniramine maleate (CPM) system at the Au electrode were studied. The results showed that compared with the absence of SDBS, enhancement of the ECL intensity was 14‐fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode. Under the optimum experimental condition, the enhanced ECL intensities had good linear relationship with the concentration of CPM in the range of 1.0×10?4–1.0×10?7 mol·L?1, and a linear regression equation was obtained as follows: I (counts)=48.805×106c+394.03 (r=0.9975), the detection limit for CPM was 1.4×10?8 mol·L?1. The RSD for 5 times determinations of 1.0×10?5 mol·L?1 CPM was 3.2%. The results of recovery test were between 96.3%–102.5%, and the RSD of recovery test (n=5) was 2.7%. In addition, eleven kinds of tertiary amines‐Ru(bpy)32+ systems were investigated in the absence and presence of SDBS. The results showed that the enhancement of SDBS on ECL intensity of tertiary amines‐Ru(bpy)32+ systems was universal.  相似文献   

15.
Summary: A novel production route for nylon-6 out of 6-aminocapronitrile has been investigated. Hydrolysis of 6-aminocapronitrile using a solid porous ZrO2 catalyst is the key step in this novel route. Nylon-6 with a number average molecular weight of 10 · 103 g · mol−1 can be produced from the hydrolyzed 6-aminocapronitrile. The reactor set up for the polycondensation can in broad outline be the same as the continuously operated reactor used for the ε-caprolactam based production of nylon-6. For the hydrolysis of 6-aminocapronitrile a number of parallel batchwise operated loop reactors is recommended. A fixed bed of catalyst particles is part of each recirculation loop. Intraparticle mass transport limitation can be avoided by using catalyst particles made of a shell of active ZrO2 and a massive inert core. An annual production of 50 · 106 kg nylon-6 demands for 5.3 m3 zirconia.  相似文献   

16.
The interaction between CdTe quantum dots (QDs) and bovine serum albumin (BSA) was systematically investigated by fluorescence, UV‐vis absorption and circular dichroism (CD) spectroscopy under physiological conditions. The experimental results showed that the fluorescence of BSA could be quenched by CdTe QDs with a static quenching mechanism, indicating that CdTe QDs could react with BSA. The quenching constants according to the modified Stern‐Volmer equation were obtained as 1.710×106, 1.291×106 and 1.010×106 L·mol?1 at 298, 304, and 310 K, respectively. ΔH, ΔS and ΔG for CdTe QDs‐BSA system were calculated to be ?33.68 kJ·mol?1, 6.254 J·mol?1·K?1 and ?35.54 kJ·mol?1 (298 K), respectively, showing that electrostatic interaction in the system played a major role. According to F?rster theory, the distance between Trp‐214 in BSA and CdTe QDs was given as 2.18 nm. The UV‐vis, synchronous fluorescence and CD spectra confirmed further that the conformations of BSA after addition of CdTe QDs have been changed.  相似文献   

17.
An analytical method consisting of flow injection sampling and chemiluminescence detection for the determination of thyroxine hormone is described. It is based on the weak chemiluminescent reaction of KMnO4 ‐ Na2SO3 in acidic medium, which is enhanced by the addition of thyroxine hormone. The chemiluminescence intensity was correlated linearly with concentration of thyroxine in the range of 1.0 × 10?7 – 2.0 × 10?6 mol L?1 (r2 = 0.9976) with a relative standard deviation (n = 4) in the range of 1.0 – 1.9%. The limit of detection (3σ blank) is 5.0 × 10?9 mol L?1 with a sample throughput of 180 h?1. The method has been applied to the determination of thyroxine in pharmaceutical preparations and the results are in good agreement with the value reported. Metal and non‐metal ions and some organic compounds commonly present in tablets and some amino acids were also studied for thyroxine determination.  相似文献   

18.
Styrene (St) and methyl methacrylate (MMA) were polymerized by azobisisobutyronitrile at 50°C. in the presence of silanes such as tetramethylsilane, trimethylcholorosilane, dimethyldichlorosilane, methyltrichlorosilane, and tetrachlorosilane. The polymerization rates of both St and MMA in the presence of silanes were nearly equal to those in the absence of silanes. On the other hand, the molecular weights decreased gradually as the concentration of chlorosilane increased. The chain transfer constants of all the silanes in the polymerization of St and MMA at 50°C. were calculated by Mayo's equation. The chain transfer constants of Me4Si, Me3SiCl, Me2SiCl, MeSiCl3, and SiCl4 were 0.31 × 10?3, 1.25 × 10?3, 1.78 × 10?3, 1.92 × 10?3, and 2.0 × 10?3, for St and 0.13 × 10?3, 0.22 × 10?3, 0.245 × 10?3, 0.27 × 10?3, and 0.30 × 10?3, for MMA, respectively. From these results, it was found that the Si? Cl bond was radically cleaved. The Qtr values of the silanes, in the same order as above, were found to be 1.03 × 10?4, 2.33 × 10?4, 2.83 × 10?4, 3.10 × 10?4, and 3.35 × 10?4, respectively and the etr values were +0.58, +1.30, +1.50, +1.48, and +1.43, respectively.  相似文献   

19.
The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, kh were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10?5 M–2.2×10?3 M and 1.5×10?5 M–3.2×10?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10?5 M and 1.4×10?6 M by CV and DPV methods.  相似文献   

20.
The esterification reaction of n-butanol and acetic acid has been performed in batch reactor in the presence of different homogeneous acid catalyst, namely sulfuric acid, nitric acid, and para toluene sulfonic acid (p-TSA). The objective of present research work is to investigate kinetic behavior of esterification reaction over the temperature range of 60°C–80°C. The effect of reaction parameter such as catalyst loading varied from 1% to 5% v/v and acid to alcohol molar ratio of 1:1, 1:3, and 1:5 has been observed. A pseudo homogeneous kinetic model has been applied. Kinetic parameters such as equilibrium constant, reaction rate constant, enthalpy, activation energy, and entropy were calculated by the experimental data for different acid catalyst system. It was observed that sulfuric acid gives higher conversion 73% than p-TSA 68.5% and nitric acid 66.25% at temperature of 80°C, 1:1 molar ratio and 3% catalyst concentration. The activation energy was estimated 36448.49, 23324.31 and 19060.156 J/mol K for three different catalyst sulfuric acid, nitric acid and p-TSA respectively. The enthalpy and entropy of the esterification reaction of acetic acid with n-butanol over three different catalysts has been calculated (Enthalpy: 25.788 KJ/mol, 12.256 KJ/mol, 28.320 KJ/mol, Entropy: 88.1 J/mol K, 45.298 J/mol K, 91.44 J/mol K) and found enthalpy is having positive value that shows reaction is endothermic.  相似文献   

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