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1.
The kinetics of degradation of tobramycin (Ne-De-Ka) in aqueous solution was studied as a function of pH. Tobramycin hydrolyzes in acidic solution to yield kanosamine (Ka-OH) and nebramine (Ne-De-OH) with a pseudo first-order rate constant of 2.7 × 10-6 s-1 in 1 N HCl at 80°C. The activation energy for the acid catalyzed hydrolysis is 32 kcal mol-1. In basic solution, the hydrolysis products are deoxystreptamine (De-OH), nebramine (Ne-De-OH) and deoxystreptamine-kanosaminide (HO-De-Ka). The pseudo first-order rate constant for the hydrolysis in 1 N KOH is 1 × 10-8 s-1 at 80°C. The activation energy for the base catalyzed hydrolysis is 15 kcal mol-1. Tobramycin is very stable towards hydrolysis at neutral pH; however, it rapidly oxidizes giving several products including De-OH, Ne-De-OH, and HO-De-Ka. In pH 7 phosphate buffer (0.01 M), the t90 value is 70 hr at 80°C.  相似文献   

2.
The degradation kinetics of somatostatin (somatotropin release inhibiting factor), a cyclic tetradecapeptide, was investigated as a function of temperature, pH, ionic strength, buffer type, and buffer concentration. In addition, the effect of different container materials in which the solutions were stored and the presence of an antimicrobial agent for in vitro use was examined. The degradation of somatostatin followed first-order kinetics under all investigated conditions. The pH-stability profile showed a well-defined stability optimum around pH 3.7. The degradation was accelerated at higher buffer concentrations, phosphate buffer being significantly more detrimental than acetate buffer. The ionic strength and the drug concentration had virtually no effect on the degradation rate. When general purpose glass vials were used as storage containers, degradation was faster due to release of alkali from the container material. The solution properties, i.e., pH, buffer type, buffer capacity, and the experimental setup such as container material and sterile conditions need to be carefully selected or maintained, in order to avoid accelerated degradation.  相似文献   

3.
Degradation products of mycophenolate mofetil in aqueous solution   总被引:1,自引:0,他引:1  
The thermal and peroxide-catalyzed degradation products of mycophenolate mofetil (1) were studied in aqueous solution at pH 2.0, 3.5, 6.0, and 8.2. The major thermal degradation product observed was mycophenolic acid (2). At pH 6.0 and 8.2, 2 was the only product observed in the absence of peroxide, while at pH 2.0 and 3.5, the lactone analogue of mycophenolic acid (5), a hydroxylactone due to oxygenation of the double bond (6), and an unidentified product were formed. Compound 6 degraded to 4-hydroxy-6-methoxy-7-methyl-3-oxo-1,3-dihydro-isobenzofuran-5-carbaldehyde (9) on prolonged storage and was present in the sample stressed at pH 2. Mycophenolic acid (2), the N-oxide of mycophenolate mofetil (3), the hydroxylactone of mycophenolic acid (6), and the erythro form of 4-methoxy-5-methyl- 2-(2-methyl-5-oxo-tetrahydro-furan-2-yl)-3,6-dihydro-2H-1,7-dioxa-as-indacen-8- one (8) were observed in the presence of hydrogen peroxide at pH 3.5, 6.0, and 8.2. In addition, at pH 8.2, 4-hydroxy-4-(4-methoxy-5-methyl-8-oxo-2,3,6,8-tetrahydro-1,7-dioxa-as-indacen-2-yl)-pentanoic acid (7) was seen. Peroxide-stressed samples at pH 2.0 gave no major degradation peaks, but a small amount of the hydroxylactone of mycophenolic acid (6) was formed.  相似文献   

4.
The degradation kinetics of fluorouracil-acetic-acid-dextran conjugate (FUAC-dextran) was investigated in various buffer solutions with different pH value and physiological saline solution at 60°C and 37°C, respectively. The hydrolytic reaction displayed pseudo-first-order degradation kinetics. Hydrolytic rate constant obtained was the function of pH value and independent of species of buffering agents. The smallest rate constant was observed at pH round 3.00. The activation energy of the hydrolytic reaction was estimated from Arrhenius equation as 88.73 ± 6.00 kJ·mol-1. The special base catalytic degradation of the conjugate was observed from acidic to slight alkaline condition and the special base catalytic rate constants were calculated. The conjugate was more stable in physiological saline than that in buffer solution at pH 7.00 or 9.00 at 37°C. The results revealed that the conjugate was stable in acidic condition and will degrade in alkaline condition.  相似文献   

5.
Degradation of 17alpha-ethinylestradiol in aqueous solution by ozonation   总被引:1,自引:0,他引:1  
This study investigates the ozonation of 17alpha-ethinylestradiol (EE(2)) in aqueous solution. The affecting factors on the degradation of EE(2) were studied and described in details, such as initial EE(2) concentration, initial pH value and ozone concentration. In addition, some parameters such as pH, electrical conductivity, mineralization efficiency and degradation products were monitored during the process. The mineralization efficiency of EE(2) could reach 53.9%. During the ozonation process the rapid decrease of pH and the sharp increase of electrical conductivity indicated the formation of acidic by-products, small fragments and ions which were confirmed by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC/MS) analysis. Results showed that there were intermediate products of smaller molecule with higher polarity produced during the course of EE(2) degradation. Then a possible reaction pathway for EE(2) degradation involving all intermediates detected is proposed. During the ozonation process EE(2) was first oxidized into hydroxyl-semiquinone isomers which were subsequently degraded into low molecular weight compounds such as oxalic acid, malonate, glutarate, and so on. Furthermore, these organic acids are easily oxidized by ozone into carbon dioxide (CO(2)). This work shows that ozonation process is promising for the removal of EE(2). The results can provide some useful information for the potential treatment of EE(2) by ozonation in aqueous solution.  相似文献   

6.
The degradation of alachlor aqueous solution by using hydrodynamic cavitation was systematically investigated. It was found that alachlor in aqueous solution can be deomposed with swirling jet-induced cavitation. The degradation can be described by a pseudo-first-order kinetics and the degradation rate was found to be 4.90 × 10−2 min−1. The effects of operating parameters such as fluid pressure, solution temperature, initial concentration of alachlor and medium pH on the degradation rates of alachlor were also discussed. The results showed that the degradation rates of alachlor increased with increasing pressure and decreased with increasing initial concentration. An optimum temperature of 40 °C existed for the degradation rate of alachlor and the degradation rate was also found to be slightly depend on medium pH. Many degradation products formed during the process, and some of them were qualitatively identified by GC–MS.  相似文献   

7.
Samples of zirconium(IV)iodotungstate have been synthesized under varying mixing order and ratios of aqueous solution of potassium iodate, sodium tungstate and zirconium oxychloride at pH 1. A tentative formula was proposed on the basis of chemical composition, FTIR and thermogravimetric studies. The material shows a capacity of 0.68 meq g−1 (for K+) which can be retained up to 200 °C. pH titration data reveal its monofunctional behavior. The distribution coefficient values of metal ions have been determined in various solvent systems. A number of important and analytically difficult quantitative separations of metal ions have been achieved using columns packed with this exchanger. In order to demonstrate practical utility of this material, Hg2+ and Pb2+ have been selectively separated and determined in the synthetic mixtures. Assay of Al3+ and Mg2+ in commercial tablets and analysis of lead in the standard reference material have also been attempted.  相似文献   

8.
Degradation of malachite green in aqueous solution by Fenton process   总被引:1,自引:0,他引:1  
In this study, advanced oxidation process utilizing Fenton's reagent was investigated for degradation of malachite green (MG). The effects of different reaction parameters such as the initial MG concentration, initial pH, the initial hydrogen peroxide concentration, the initial ferrous concentration and the reaction temperature on the oxidative degradation of MG have been investigated. The optimal reacting conditions were experimentally found to be pH 3.40, initial hydrogen peroxide concentration=0.50mM and initial ferrous concentration=0.10mM for initial MG concentration of 20mg/L at 30 degrees C. Under optimal conditions, 99.25% degradation efficiency of dye in aqueous solution was achieved after 60 min of reaction.  相似文献   

9.
Degradation of diuron in aqueous solution by dielectric barrier discharge   总被引:2,自引:0,他引:2  
Degradation of diuron in aqueous solution was conducted in a dielectric barrier discharge (DBD) reactor and the proposed degradation mechanism was investigated in detail. The factors that affect the degradation of diuron were examined. The degradation efficiency of diuron and the removal of total organic carbon (TOC) increased with increasing input power, and the degradation of diuron by DBD fitted first-order kinetics. Both strong acidic and alkaline solution conditions could improve diuron degradation efficiency and TOC removal rate. Degradation of diuron could be accelerated or inhibited in the presence of H2O2 depending on the dosage. The degradation efficiency increased dramatically with adding Fe2+. The removal of TOC and the amount of the detected Cl-, NO3- and NH4+ were increased in the presence of Fe2+. The concentrations of oxalic and acetic acids were almost the same in the absence and presence of Fe2+, but high concentration of formic acid was accumulated in the presence of Fe2+. The main degradation pathway of diuron by DBD involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes.  相似文献   

10.
p-Nitrotoluene (PNT) is a nitroaromatic compound that is hazardous to humans and is a suspected hormone disrupter. The degradation of PNT in aqueous solution by ozonation (O(3)) combined with sonolysis (US) was investigated in laboratory-scale experiments in which pH, initial concentration of PNT, O(3) dose and temperature were varied. The degradation of PNT followed pseudo-first-order kinetics, and degradation products were monitored during the process. The maximum degradation was observed at pH 10.0. As the initial concentration of PNT decreased, the degradation rate increased. Both temperature and ozone dose had a positive effect on the degradation of PNT. Of the total organic carbon (TOC) reduction, 8, 68, and 85% were observed with US, O(3), and a combination of US and O(3) after reaction for 90 min, respectively, proving that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone. Major by-products, including p-cresol, 4-hydroxybenzaldehyde, 4-hydroxybenzoic acid, 4-(oxomethylene) cyclohexa-2,5-dien-1-one, but-2-enedioic acid, and acetic acid were detected by gas chromatography coupled with mass spectrometry.  相似文献   

11.
The present study investigates the degradation of atrazine (2-chloro-4-(ethyl amino)-6-isopropyl amino-s-triazine) in aqueous solution by a developed new method, namely by means of a microwave-assisted electrodeless discharge mercury lamp (MW-EDML). An experimental design was conducted to assess the influence of various parameters: pH value, initial concentration, amount of EDML, initial volume and coexisted solvent. Atrazine was degraded completely by EDML in a relatively short time (i.e. t(1/2)=1.2 min for 10 mg/l). Additionally, the identification of main degradation products during atrazine degradation process was conducted by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). This study proposes the degradation mechanism including four possible pathways for atrazine degradation according to the degradation products.  相似文献   

12.
A hybrid photoelectroreaction system has been developed in this study, which consists of three functional electrodes: a TiO2/Ti sheet as the anode, a steel (Fe) sheet as another anode in parallel and a piece of graphite felt (GF) as the cathode. While an electrical current is applied between the Fe anode and GF cathode and UV light is irradiated on the surface of TiO2/Ti anode, both of E-Fenton reaction and photoelectrocatalytic (PEC) reaction are involved simultaneously. The integration of E-Fenton and PEC reactions was evaluated in terms of 2,4-dichlorophenol (2,4-DCP) degradation in aqueous solution. In the meantime, the current distribution between two anodes and pH influence on the 2,4-DCP degradation were studied and optimized. Experimental results confirmed that 2,4-DCP in aqueous solution was successfully degraded by 93% and mineralized by 78% within 60 min in such a hybrid oxidation process. When a current intensity of 3.2 mA was applied, the current efficiency for H2O2 generation on the GF cathode was determined to be 61%. Furthermore, the experiments demonstrated that combination of E-Fenton reaction with photocatalytic reaction let the process be less pH sensitive and would be more favorable to water and wastewater treatment in practice.  相似文献   

13.
A series of titanium dioxide (TiO(2)/Ti) film electrodes were prepared from titanium (Ti) metal mesh by an improved anodic oxidation process and were further modified by photochemically depositing gold (Au) on the TiO(2) film surface as Au-TiO(2)/Ti film electrodes. The morphological characteristics, crystal structure and photoelectroreactivity of both the TiO(2)/Ti and Au-TiO(2)/Ti electrodes were studied. The experiments confirmed that the gold modification of TiO(2) film could enhance the efficiency of e(-)/h(+) separation on the TiO(2) conduction band and resulted in the higher photocatalytic (PC) and photoelectrocatalytic (PEC) activity under UV or visible illumination. To further enhance the TiO(2) PEC reaction, a reticulated vitreous carbon (RVC) electrode was applied in the same reaction system as the cathode to electrically generate H(2)O(2) in the aqueous solution. The experiments demonstrated that such a H(2)O(2)-assisted TiO(2) PEC reaction system could achieve a much better performance of BPA degradation in aqueous solution due to an interactive effect among TiO(2), Au, and H(2)O(2). It may have good potential for application in water and wastewater treatment in the future.  相似文献   

14.
The degradation kinetics of neostigmine were studied in aqueous solutions with varied pH from 1.5 to 9.9 under accelerated storage conditions. The stability of neostigmine in solutions containing propylene glycol or polyethylene glycol 400 was also investigated. The reaction order of neostigmine in these aqueous and solvent systems followed pseudo-first-order degradation kinetics. The degradation rates of neostigmine under various buffer concentrations within the investigated pH range were obtained. They indicated that the degradation was independent of the species of buffering agent. Maximum stability of neostigmine was determined at pH 5.0 buffer species conditions. The activation energy could be estimated from the Arrhenius plot as 15.72 kcal/mole. The half-life of 883.7 days was estimated at room temperature in 0.1 M, pH 4.9 acetate buffer solution (mu = 0.5). Ultraviolet (UV) irradiation at 254 nm of the neostigmine solutions in pH 4.9 acetate buffer showed an accelerated degradation in comparison with light-protected samples. Incorporation of propylene glycol into the neostigmine solution at pH 4.9 enhanced the stability; however, an adverse effect on the stability of neostigmine was noted when a polyethylene glycol 400 solvent system was used.  相似文献   

15.
The study examined the effect of operating conditions (zinc oxide concentration, pH and irradiation time) of the UV/ZnO photocatalytic process on degradation of amoxicillin, ampicillin and cloxacillin in aqueous solution. pH has a great effect on amoxicillin, ampicillin and cloxacillin degradation. The optimum operating conditions for complete degradation of antibiotics in an aqueous solution containing 104, 105 and 103 mg/L amoxicillin, ampicillin and cloxacillin, respectively were: zinc oxide 0.5 g/L, irradiation time 180 min and pH 11. Under optimum operating conditions, complete degradation of amoxicillin, ampicillin and cloxacillin occurred and COD and DOC removal were 23.9 and 9.7%, respectively. The photocatalytic reactions under optimum conditions approximately followed a pseudo-first order kinetics with rate constant (k) 0.018, 0.015 and 0.029 min?1 for amoxicillin, ampicillin and cloxacillin, respectively. UV/ZnO photocatalysis can be used for amoxicillin, ampicillin and cloxacillin degradation in aqueous solution.  相似文献   

16.
The rates of hydrolysis of valganciclovir to ganciclovir and L-valine and isomerization of the R and S diastereomers of valganciclovir in aqueous buffer solution from pH 3.8 to 11.5 were determined at 37 degrees C. The kinetics of hydrolysis were first order for at least two half-lives in neutral and basic solutions. In acidic solutions where less than 10% degradation occurred, the rate of hydrolysis was determined assuming a first-order loss in drug. At 37 degrees C and pH 7.08, the half life is 11 h. The maximum stability at the pH values studied occurred at pH 3.81 with a half life of 220 days. The kinetics of the approach to equilibrium for the isomerization were first order and the ratio of the R:S isomer at equilibrium was 52:48. Isomerization was approximately 10 fold faster than hydrolysis over the pH range studied with a half-life at pH 7.01 of 1 h. The maximum stability toward isomerization (t1/2>533 h) occurs at a pH below 3.8. The pH-rate profile for the hydrolysis and the isomerization reaction are best described by hydroxide ion catalyzed mechanisms. In acidic and neutral solutions, the hydroxide reacts with the protonated form of the drug, while in basic solutions, the hydroxide reacts with the neutral form of the drug.  相似文献   

17.
18.
The chemical degradation of curcumin (CU) in aqueous solution and on silver nanoparticles was studied by means of ultraviolet (UV)-visible absorption and surface-enhanced Raman (SERS) spectroscopy at different pH levels and upon light irradiation. CU undergoes a chemical degradation in aqueous solution mainly when the pH is increased. The CU degradation is catalytically enhanced in the presence of Ag nanoparticles. In general, CU degradation implies two steps: (1) the breakdown of the interring chain connecting the two CU aromatic side rings, producing smaller phenolic compounds rich in carboxylate groups, and (2) polymerization of the resulting phenolic products, giving rise to phenolic polymeric products. The degradation-polymerization mechanism can be modulated depending on the experimental conditions. The chemical photoproducts resulting from the visible light irradiation are similar to the polycatechol products obtained when catechol is adsorbed on Ag nanoparticles.  相似文献   

19.
Ozonation of p-chlorophenol in aqueous solution.   总被引:1,自引:0,他引:1  
The ozonation of p-chlorophenol (CHP) in aqueous solution has been studied in the pH range 2.0-8.0, in the presence of tert-butyl alcohol, which prevents the activation of the radical mechanism of oxidation. Results indicate that the pH influences the system reactivity and that only a partial chlorine release is observed for lengthy ozonation too, after the complete substrate disappearance. For adopted experimental conditions the oxidation process develops under a quasi-diffusional regime of absorption with reaction, a transition domain between kinetic and diffusional regimes in which ozone and dissolved substances react exclusively in the liquid film. A proper mathematical model has been developed and used to simulate the system behaviour  相似文献   

20.
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