The Polarographic Determination of Tenoxicam in the Pharmaceutical Preparations

Abstract

In this study, the polarographic behaviour and the optimum polarographic conditions for the determination of TNX using DC (direct current), DP (differential pulse), SCAP (superimposed constant amplitude pulse) and SIAP (superimposed increasing amplitude pulse) polarographic techniques are described based on the reduction of enol group of the molecule on the dropping mercury electrode. The experiments were conducted in the aqueous supporting electrolyte solution containing 0.2 M KCl and 0.2 M buffer solution. Single waves were obtained at various pH values. The limiting currents were decreased and E_1/2 values were linearly shifted to more negative potentials with an increase in the pH. The system was irreversible at both the acidic and the basic media and it was adsorptional in the acidic medium and diffusional at pH 10.8. The variation in the limiting current was found to be 0.86 μA/°C. Good relations were obtained for DC, DP, SCAP and SIAP polarographic techniques at pH 10.8. The determination of TNX in pharmaceutical preparations, namely Tilcotil® tablets, containing 20 mg of TNX were tested employing DC, DP, SCAP, SIAP polarographic techniques. The results were compared to those of HPLC and the standard deviations (SD) were found to be in the range of 0.14 and 0.22 for the techniques employed for filtered and unfiltered solutions. The polarographic techniques used for the determination of TNX seem to be accurate, rapid and practical. Therefore, the suggested method may be promising in the routine analysis.

     

氧化铈纳米粒子光催化降解亚甲基蓝的动力学和机理

 CeO2 nanocrystals were synthesized by a simple precipitation method and calcination at 600 °C. (NH4)2Ce(NO3)6 and ammonia were used as precursors. The CeO2 nanoparticles were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and N2 adsorption. The photodegradation of methylene blue catalyzed by CeO2 nanoparticles was studied under UV and sunlight irradiation. The highest degradation was obtained with 1.0 g/L CeO2 at pH 11 within 125 min. The pseudo first order rate constants of dye bleaching were calculated as 16.2x10-3 and 15.7x10-3 min-1 under UV and sunlight irradiation, respectively. The effect of iso-PrOH, iodide ion, and H2O2 was studied to predict the pathway of dye degradation. The obtained results indicate the effect of photogenerated holes in the degradation mechanism of the dye. Also, the photocatalytic activity of the prepared photocatalyst was studied in the presence of several negative ions.     

Cyclodextrin-Cross-Linked Hydrogels for Adsorption and Photodegradation of Cationic Dyes in Aqueous Solution

Possessing three-dimensional porous structures and tunable mechanical strengths, cyclodextrin-containing polymeric hydrogels are one of the most promising water-based adsorbent materials due to their easy availability, simple chemical modification and environmental friendliness. In this work, two kinds of hydrogels were prepared via the copolymerization with acrylic acid and vinyl-derivatized β-cyclodextrins in water. These two gels have showed good adsorption performance towards cationic dyes through the noncovalent interactions with their anionic backbones and porous network. Meanwhile, pseudo-second-order model was selected to clarify the adsorption kinetics process. Moreover, nano-scaled TiO₂ was doped into these resultant cyclodextrins-based hydrogels to achieve efficient degradation of dyes upon light irradiation. The obtained TiO₂-loaded hydrogels could exhibit improved adsorption performance and make the adsorbed dyes photo-degraded with the decolorization rates above 95%. It can be envisioned that such cyclodextrin-based soft materials may find applications in dye clearance and water treatment.     

Stress Cracking and Photodegradation: The Combination of Two Major Causes of HIPS Failure

Summary: This work investigates the effects of photodegradation on the stress cracking resistance of high impact polystyrene (HIPS). Injection moulded samples were exposed to the ultraviolet light for various times in the laboratory prior to solvent contact. The bars were then stressed with several different loads in a tensile testing machine under the presence of several types of alcohols (mostly butanol). During this period, the stress relaxation was monitored and, after unloading, the ultimate properties were evaluated. Complementary tests were done by size exclusion chromatography, and scanning electron microscopy. The results indicated that both photodegradation and butanol causes significant modification in HIPS properties, with reduction in mechanical properties. The previously degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison to the undegraded ones. The synergistic action of photodegradation and stress cracking in polystyrene may be a consequence of the chemical changes caused by oxidation and the reduction in molecular sizes.     

水环境中红霉素和罗红霉素抗生素光降解的研究

采用固相萃取分离富集,LC—MS-MS为检测平台,研究了水环境中低浓度（10mg／L）红霉素和罗红霉素的光降解效率及其影响因素。结果表明,在接近中性（pH=7．5）的水溶液中,经过1h的光照,两种抗生素的光降解率在30％以下;而在有2000mg／LTiO2催化剂存在时,光照15min,二者的降解率即可分别达95．5％和97．2%,此时溶液的pH值对光催化降解的影响不大。实验也表明,光直接降解反应和光催化降解反应均符合一级反应动力学。     

Identification of New Photodegradation Byproducts of the Antifouling Agent Irgarol in Seawater Samples

Abstract

A photodegradation study for Irgarol was carried out in order to investigate several products of degradation formed in different environmental matrices and under different conditions. Deionized water, groundwater and seawater samples, spiked at 30–100 μg/L with Irgarol, were irradiated using a xenon are lamp and/or sunlight. Aliquots of the spiked water samples were taken at different times of irradiation and compounds were isolated from the water samples by means of solid-phase extraction (SPE) using either C₁₈ or PLRP-s cartridges. Separation and detection of the compounds was accomplished by several analytical methodologies such as liquid chromatography-diode array detection (LC-DAD), liquid chromatography-electrospray ionization/mass spectrometry (LC-ESI/MS) and gas chromatography-mass spectrometry (GC-MS). Four new byproducts, with molecular weights of 167, 197, 207 and 213, were identified in this photodegradation study. When the photolysis was carried out with xenon lamp, half-lives of Irgarol were 103.8, 125.4 and 107.5 minutes in deionized water, groundwater and seawater, respectively. In seawater samples, a 98% of degradation was observed for Irgarol, after 217 hours of solar irradiation, being the main byproduct formed that corresponding to M_w = 213. On the other hand, the use of two different sensitizers -(TiO₂/H₂O₂), (FeCI₃/H₂O₂)- was also evaluated in deionized water samples containing Irgarol. These experiments were carried out in order to evaluate the use of these two sensitizers for decontamination of polluted waters.     

Homogeneous Photodegradation of PVC by Tungstophosphoric Acid

The photocatalytic degradation of polyvinyl chloride (PVC) films by tungstophosphoric acid (HPW) was investigated. The main reason for highly enhanced photodegradation of HPW-doped PVC film was studied and discussed.     

土壤悬浮液中双酚A的光降解研究

实验研究了双酚A在土壤表面的吸附特征及在土壤悬浮液中的光降解.研究结果表明,双酚A在土壤表面的吸附为单分子的化学吸附,用Langmuir模型或Freundlich模型拟合时相关性较好.在高压汞灯(λ=300nm)照射下,双酚A在土壤悬浮液中能快速降解,降解速度随酸度的增大而加快.在此体系中双酚A光降解动力学遵循Langmuir-Hinshelwood(H-L)方程,在土壤量不超过10g/L的条件下,降解率随土壤量增加而增加,加入腐殖酸可以促进双酚A的光解,同时增大光照强度有利于双酚A的降解.     

杂多酸光催化降解有机污染物

本文综述了杂多酸对有机污染物的光催化降解,包括自身光致催化作用,半导体协同光催化作用,H₂O₂存在下的类Fenton反应和超声辅助催化作用。杂多酸与有机物反应的机理主要是电子-空穴对的产生和·OH等自由基的生成。概述了杂多酸的结构类型和杂多酸光催化作用的优点和局限性,提出利用掺杂调变杂多酸的晶体结构,降低其能带宽度,提高光催化作用反应的量子效率;探索杂多酸与其它电子受体的组合,特别是与具有可见光活性的物质的组合,以扩大光响应范围,实现可见光催化反应。     

Photodegradation actuated shape-changing hydrogels

Hydrogels are attractive materials for generating 4D shapes due to their ability to undergo pronounced volume changes in response to several stimuli, including light. We previously reported shape-changing hydrogels actuated by long-wave UV and visible light in the presence of live cells using poly(ethylene glycol) macromers incorporating different photodegradable ortho-nitrobenzyl (o-NB) groups. In this comprehensive study, we determine the effect of chemical structure of different o-NB macromers (which influences molar absorptivity and rate constant of degradation), composition (macromer weight percent), fabrication design (initial gel thickness) and environment (ionic strength of solution) on light-induced hydrogel folding. We demonstrate successful photopolymerization and subsequent photodegradation of hydrogels, multistep folding, and live-cell encapsulation. This hydrogel system may be useful as new tool in stem cell differentiation and developmental biology research, facilitating the in vitro investigation of processes that are sensitive to both physical and temporal stimuli.     

The Incorporation of Titania into Modified Silicates for Solar Photodegradation of Aqueous Species

A new class of sol-gel-derived photocatalytic materials has been synthesized and used in solar-assisted photodegradation studies. The materials are comprised of a homogeneous dispersion of commercial TiO₂ powder into silica and organically modified silicate (Ormosil) hosts. The efficiency of the photocatalytic properties of these TiO₂-containing materials was determined by their relative performance in the solar photodecomposition of aqueous rhodamine B. The improved adsorption properties of the modified materials compared to commercial TiO₂ increase the photodecomposition rate and the buoyancy properties, although excess hydrophobicity decreases the wetted section of the catalyst and its photocatalytic performance. These materials can be used as floatable catalysts for solar-assisted water purification.     

Site‐Specific Acid–Base Properties of Tenoxicam

The Hammett approach, as a new deductive tool, was introduced to characterize the otherwise inaccessible minor protonation pathway of tenoxicam ( 1 ), the non‐steroidal anti‐inflammatory drug. A total of eight compounds, constituting a systematic series of side chain‐substituted analogues of tenoxicam and piroxicam ( 2 ), were synthesized and studied in terms of acid? base properties and Hammett constants to identify the ideal replacement of the unprotonated pyridin‐2‐yl group, a key moiety in both molecules. Hammett constants of the phenyl substituents have been found to be in a linear correlation with the experimental log K values of the enolate sites, the basic moiety of the extended conjugated system in this family of piroxicam derivatives. Then, a similar correlation was observed for the analogous tenoxicam derivatives. After identifying the 2‐aza Hammett constant of the pyridin‐2‐yl group and the corresponding log K value, the site‐specific acid–base properties of tenoxicam could be quantitated. This novel method is assessed to be a fine‐tuning tool to find the ideal substituent by using analogue‐based deductive method to obtain site‐specific constants of the minor protonation/deprotonation pathway in drugs and biomolecules. The tenoxicam microconstant values indicate that the enolate moiety is of extremely low basicity (reflected by the =3.70 and =1.09 values), which can, however, be interpreted in terms of the peculiar ring system and the overwhelming electron‐withdrawing effects of the adjacent heteroatoms. A diagram depicting the pH‐dependent distribution of 1 microspecies is also presented.     

对乙酰氨基酚在Fe（Ⅲ）／草酸盐体系中的光降解

药品和个人护理用品(Pharmaceuticals and Personal Care Products,简称PPCPs)作为潜在环境污染物,在近几年成为新的环境热点问题[1,2].对乙酰氨基酚(APAP)作为一种典型的药品和个人护理用品被用作阿司匹林的替代物,主要起到减轻疼痛的作用.     

Study of the Photodegradation of PBDEs in Water by UV-LED Technology

Polybrominated diphenyl ethers (PBDEs) are persistent organic pollutants that can arrive to water bodies from their use as flame retardants in a wide range of applications, such as electric and electronic devices or textiles. In this study, the photodegradation of PBDEs in water samples when applying UV-LED radiation was studied. Irradiation was applied at three different wavelengths (255 nm, 265 nm and 285 nm) and different exposure times. The best degradation conditions for spiked purified water samples were at 285 nm and 240 min, resulting in degradations between 67% and 86%. The optimized methodology was applied to real water samples from different sources: river, marine, wastewater (effluent and influent of treatment plants) and greywater samples. Real water samples were spiked and exposed to 4 hours of irradiation at 285 nm. Successful photodegradation of PBDEs ranging from 51% to 97% was achieved for all PBDE congeners in the different water samples with the exception of the marine one, in which only a 31% of degradation was achieved.     

Preliminary Study of a Potential Post-Column Photodegradation Reaction Scheme for the Detection of Organophosphorus Compounds

Abstract

The photodegradation of organophosphorus compounds has been studied using triethylphosphate as a model compound, A 150 W xenon lamp was used in conjunction with ammonium peroxydisulfate to achieve high yields of orthophosphate in a 100-second irradiation time. The effects of the pH of the reaction medium and the initial concentrations of a peroxydisulfate and triethylphosphate on the extent of reaction were determined. A survey of potential interferences was performed, Copper (II) ion was found to catalyze the reaction, The effect of varying the Cu (II) concentration and the pH dependence of the catalyzed reaction were determined, Organic solvents were found to interfere with the photo degradation, but the reaction shows good potential for incorporation into a post-column detection system for the liquid chromatographic determination of organophosphorus compounds where totally aqueous mobile phases can be used.     

The Thermodynamic Driving Force for Kinetics in General and Enzyme Kinetics in Particular

The thermodynamic driving force of a reaction is usually taken as the chemical potential difference between products and reactants. The forward and backward reaction rates are then related to this force. This procedure is of very limited validity, as the resulting expression contains no kinetic factor and gives little information on reaction kinetics. The transformation of the reaction rate as a function of concentration (and temperature) into a function of chemical potential should be more properly performed, as illustrated by a simple example of an enzymatic reaction. The proper thermodynamic driving force is the difference between the exponentials of the totaled chemical potentials of reactants and products.     

Polymerization Kinetics of Water-Soluble N-Vinyl Monomers in Aqueous and Organic Solution

Summary: Free-radical batch polymerization (FRP) of N-vinyl pyrrolidone (NVP) and N-vinyl formamide (NVF) monomers in aqueous solution as well as NVP polymerization in organic (n-butanol) solution has been studied. The differences found in rate of monomer conversion with monomer and solvent choice correlates well with the differences in values of the propagation rate coefficients (k_p) and their variation with monomer concentration measured in independent pulsed-laser polymerization studies, a result demonstrating that a generalized understanding of water-soluble vinyl monomers can be obtained once their k_p differences have been accounted for. A reasonable representation of polymer molecular mass averages and the complete molecular mass distributions for the three systems was obtained by assuming that the rate coefficient for transfer to monomer, polymer, and organic solvent also vary as a function of monomer concentration.     

TiO2/ACF的制备及光催化降解四氯乙烯性能

以钛酸四丁酯为前驱物,活性炭纤维(ACF)为载体,蔗糖为胶粘剂,采用真空吸附水解的方法制得了TiO₂/ACF催化剂.采用BET、XRD、SEM等手段对其物理化学特性进行表征,以四氯乙烯光降解反应为探针反应,考察了TiO₂/ACF催化剂的光催化降解性能.实验结果表明,采用真空吸附水解法可以将TiO₂很好地负载到活性炭纤维表面上.通过优化条件制备的TiO₂/ACF催化剂在光照2h条件下,可以将水中溶解量的四氯乙烯降解90%以上.催化剂可以多次循环使用,光催化反应活性不变.     

基于GM（1,1）的TiO2光催化降解苯胺的动力学研究

采用溶液浸渍法制备TiO2并将其担载到瓷砖上,通过添加过渡金属离子和H2O2,来考察对TiO2光催化降解苯胺的影响,其动力学过程利用GM（1,1）模型进行模拟.结果表明,添加Cu2＋、Mn2＋和Co2＋均能提高TiO2催化活性,且提高程度为Cu2＋〉Mn2＋〉Co2＋;掺杂Ni2＋反而降低其活性.H2O2能提高瓷砖固载...     

离子色谱法测定硝基苯光降解产物中邻、间、对硝基苯酚及硝酸根

研究了离子色谱法同时测定硝基苯光降解的中间产物邻硝基苯酚、间硝基苯酚、对硝基苯酚及硝酸根的分析方法.采用7.5mmol/L的碳酸氢钠,1.5mmol/L的碳酸钠混合溶液为淋洗液,紫外检测波长215nm.回收率在96.8%～101.3%之间;RSD小于1.5%;检出限在8.5×10-4以下.