Adsorption of organic acids on TiO2 nanoparticles: effects of pH, nanoparticle size, and nanoparticle aggregation

In this study, the adsorption of two organic acids, oxalic acid and adipic acid, on TiO2 nanoparticles was investigated at room temperature, 298 K. Solution-phase measurements were used to quantify the extent and reversibility of oxalic acid and adipic acid adsorption on anatase nanoparticles with primary particle sizes of 5 and 32 nm. At all pH values considered, there were minimal differences in measured Langmuir adsorption constants, K ads, or surface-area-normalized maximum adsorbate-surface coverages, Gamma max, between 5 and 32 nm particles. Although macroscopic differences in the reactivity of these organic acids as a function of nanoparticle size were not observed, ATR-FTIR spectroscopy showed some distinct differences in the absorption bands present for oxalic acid adsorbed on 5 nm particles compared to 32 nm particles, suggesting different adsorption sites or a different distribution of adsorption sites for oxalic acid on the 5 nm particles. These results illustrate that molecular-level differences in nanoparticle reactivity can still exist even when macroscopic differences are not observed from solution phase measurements. Our results also allowed the impact of nanoparticle aggregation on acid uptake to be assessed. It is clear that particle aggregation occurs at all pH values and that organic acids can destabilize nanoparticle suspensions. Furthermore, 5 nm particles can form larger aggregates compared to 32 nm particles under the same conditions of pH and solid concentrations. The relative reactivity of 5 and 32 nm particles as determined from Langmuir adsorption parameters did not appear to vary greatly despite differences that occur in nanoparticle aggregation for these two different size nanoparticles. Although this potentially suggests that aggregation does not impact organic acid uptake on anatase particles, these data clearly show that challenges remain in assessing the available surface area for adsorption in nanoparticle aqueous suspensions because of aggregation.     

Effect of medium pH on chemical selectivity of oxalic acid biosynthesis by <Emphasis Type="Italic">Aspergillus niger</Emphasis> W78C in submerged batch cultures with sucrose as a carbon source

The pH of the medium is the key environmental parameter of chemical selectivity of oxalic acid biosynthesis by Aspergillus niger. The activity of the enzyme oxaloacetate hydrolase, which is responsible for decomposition of oxaloacetate to oxalate and acetate inside the cell of the fungus, is highest at pH 6. In the present study, the influence of pH in the range of 3–7 on oxalic acid secretion by A. niger W78C from sucrose was investigated. The highest oxalic acid concentration, 64.3 g dm^?3, was reached in the medium with pH 6. The chemical selectivity of the process was 58.6% because of the presence of citric and gluconic acids in the cultivation broth in the amount of 15.3 and 30.2 g dm^?3, respectively. Both an increase and a decrease of medium pH caused a decrease of oxalic acid concentration. The obtained results confirm that pH 6 of the carbohydrate medium is appropriate for oxalic acid synthesis by A. niger, but the chemical selectivity of the process described in this paper was high in comparison to values reported previously in the literature.     

Resonance scattering spectral analysis of chlorides based on the formation of (AgCl)n(Ag)s nanoparticle

A novel resonance scattering spectral method has been proposed for the determination of trace amounts of chlorides in the range of 2 x 10(-7)-8 x 10(-6) mol/l. It was based on the photochemical reaction system of AgNO3-NaCl-sodium oxalic to form the (AgCl)nucleus (n)(Ag)shell (s) nanoparticle. There is a strongest resonance scattering peak at 470 nm and a maximum absorption peak at 425 nm. The concentration of chlorides is proportional to the intensity of resonance scattering at 470 nm. The nonlinear resonance scattering peaks of the nanoparticle system have been also considered, according to the theory of the interaction between the surface electron of nanoparticle and the incidence photon.     

Estimation of atorvastatin calcium and fenofibrate in tablets by derivative spectrophotometry and liquid chromatography

Two simple and accurate methods to determine atorvastatin calcium (ATO) and fenofibrate (FEN) in combined dosage forms were developed using second-derivative spectrophotometry and reversed-phase liquid chromatography (LC). ATO and FEN in combined preparations (tablets) were quantitated using the second-derivative responses at 245.64 nm for ATO and 289.56 nm for FEN in spectra of their solution in methanol. The calibration curves were linear [correlation coefficient (r) = 0.9992 for ATO and 0.9995 for FEN] in the concentration range of 3-15 microg/mL for ATO and FEN. In the LC method, analysis was performed on a Hypersil ODS-C18 column (250 mm x 4.6 mm id, 5 microm particle size) in the isocratic mode using the mobile phase methanol-water (90 + 10, v/v), adjusted to pH 5.5 with orthophosphoric acid, at a flow rate of 1 mL/min. Measurement was made at a wavelength of 246.72 nm. Both drugs were well resolved on the stationary phase, and the retention times were 1.95 min for ATO and 5.50 min for FEN. The calibration curves were linear (r = 0.9985 for ATO and 0.9976 for FEN) in the concentration range of 3-15 microg/mL for ATO and FEN. Both methods were validated, and the results were compared statistically. They were found to be accurate, precise, and specific. The methods were successfully applied to the estimation of ATO and FEN in combined tablet formulations.     

Citric acid adsorption on TiO2 nanoparticles in aqueous suspensions at acidic and circumneutral pH: surface coverage, surface speciation, and its impact on nanoparticle-nanoparticle interactions

Citric acid plays an important role as a stabilizer in several nanomaterial syntheses and is a common organic acid found in nature. Here, the adsorption of citric acid onto TiO(2) anatase nanoparticles with a particle diameter of ca. 4 nm is investigated at circumneutral and acidic pHs. This study focuses on both the details of the surface chemistry of citric acid on TiO(2), including measurements of surface coverage and speciation, and its impact on nanoparticle behavior. Using macroscopic and molecular-based probes, citric acid adsorption and nanoparticle interactions are measured with quantitative solution phase adsorption measurements, attenuated total reflection-FTIR spectroscopy, dynamic light scattering techniques, and zeta-potential measurements as a function of solution pH. The results show that surface coverage is a function of pH and decreases with increasing pH. Surface speciation differs from the bulk solution and is time dependent. After equilibration, the fully deprotonated citrate ion is present on the surface regardless of the highly acidic solution pH indicating pK(a) values of surface adsorbed species are lower than those in solution. Nanoparticle interactions are also probed through measurements of aggregation and the data show that these interactions are complex and depend on the detailed interplay between bulk solution pH and surface chemistry.     

Improvement of chemical analysis of antibiotics. V. A simple method for the analysis of tetracyclines using reversed-phase high-performance liquid chromatography

An isocratic high-performance liquid chromatographic method for the determination of tetracyclines is described using a mobile phase containing oxalic acid and C8- and C18-modified silica gel columns. For good separations of tetracyclines, oxalic acid concentrations of above 0.01 and 0.2 M respectively for parent tetracyclines (group I) and impurities in tetracycline (group II) are required. The optimum pH of the aqueous oxalic acids solution in the mobile phase is 2.0. The combinations of the C8-modified silica gel column with methanol-acetonitrile-0.01 M aqueous oxalic acid solution pH 2.0 (1:1.5:5) and the C18-modified silica gel column with methanol-acetonitrile-0.2 M aqueous oxalic acid solution pH 2.0(1:1:3.5) gave satisfactory results for groups I and II, respectively.     

Extraction de l'acide oxalique par formation de paires d'ions et application au dosage de l'acide oxalique urinaireExtraction of oxalic acid by ion-pair formation with application to the determination of oxalic acid in urine

Extraction of oxalic acid by ion-pair formation with application to the determination of oxalic acid in urineThe yield of ion-pair extraction of oxalic acid by trioctylamine and triisooctylamine in chloroform depends on the pH of the aqueous phase. The optimum pH is 2.7, proving that hydrogenoxalate ion is the extractable form. Extraction yield depends on the acid used for pH adjustment and dissolution of the calcium oxalate formed in complex medium. The best results are obtained with hydrochloric and sulfuric acids and with trioctylamine extraction. This extraction was applied to oxalic acid determination by colorimetry and gas chromatography in urines from twenty healthy patients. Mean excretion was found to be $\text{0.30 mmol}\text{24 h.}$ Extraction yields lie between 94 and 106%.     

草酸改性空气凤梨生物炭吸附甲醛的机理研究

探究草酸改性园林废弃物类生物炭对溶液中甲醛的吸附效率和固定的机理,为园林废弃物类生物炭在甲醛污染控制方面的应用提供科学依据。利用马弗炉在低氧条件下将空气凤梨原材料和草酸改性后的原材料制备成生物炭。然后利用实验室模拟法,研究不同反应时间、甲醛浓度、pH对生物炭吸附效果的影响,并分析草酸改性如何提高园林废弃物类生物炭对甲醛的吸附性能。(1)生物炭对乙酰丙酮和酚试剂两种甲醛检测方法的精度有影响,对乙酰丙酮检测法的影响较小;(2)相比于未改性生物炭,草酸改性通过酸化分解杂质能够使改性生物炭比表面积提高约17倍,孔隙体积增加195.9%;(3)草酸改性后生物炭对甲醛的吸附量为11.6 mg g^-1,比未改性生物炭提高了12.95%,并且在60 min时趋于吸附平衡的状态;(4)Boehm滴定法表明草酸改性能够显著提高制备后生物炭上的官能团(羧基51.8%,羰基13.7%和内酯基35.9%),但酚羟基(4.5%)含量增加不明显,而相关性分析证实比表面积、羧基和内酯基官能团的增加是提高生物炭吸附甲醛的主要因素。实验证明,空气凤梨制备成生物炭用于溶液中甲醛的吸附是可行的,并且草酸改性能够进一步通过官能团提高其吸附能力,这为园林废物资源化利用提供了新的思路。     

草酸在铂基Sb-Pb表面合金电极上的催化还原

将Sb Pb Pt/GC表面合金电极应用于草酸的电催化还原,发现所制备的催化剂电极具有较高的电催化活性,草酸还原的起始电位约－0.4 V,与通常使用的铅阴极相比,正移了大约600 mV.电化学原位红外反射光谱研究,证实所研制的催化剂可在较低的过电位下还原草酸生成乙醛酸,并具有较好的选择性.对于所研制的表面合金电催化剂的实际应用进行了探讨.     

Specific adsorption of simple organic acids on metal(hydr)oxides: a radiotracer approach

The pH dependence of adsorption of (14)C-labeled benzoic and oxalic acids on gamma-Al(2)O(3) and hematite was studied in acid medium in the presence of 0.5 mol dm(-3) NaClO(4) supporting electrolyte. It was found that the adsorption of the organic species starts at pH values where the protonation of the oxide surface takes place. In the case of benzoic acid the extent of adsorption with decreasing pH goes through a sharp maximum at a pH value not far from the pK (4.2) of the acid, while in the case of oxalic acid only a small decrease can be observed at very low pH values (pH<1). In indirect radiotracer studies using (35)S-labeled sulfate ions it was shown that the competitive adsorption of formic, malonic, maleic, and oxalic acids with sulfate ions depends on pH and the effect of the organic acid on the anion adsorption becomes pronounced at pH values about and above the pK of the acid. On the basis of these observations and considerations concerning the dissociation of the organic acids studied it is assumed that the specific adsorption of the anionic form of the acids takes place. It is, however, emphasized that the negative charge of the anions, consequently the electrostatic forces, do not play significant role in the adsorption.     

The determination of oxalic acid in urine by high performance liquid chromatography with electrochemical detection

A system for the determination of oxalic acid in human urine using ion exchange-ion pair, high performance liquid chromatography with electrochemical detection (HPLCEC) is described. Urine is acidified with HCl, and excess CaCl2 is added to precipitate oxalate ion. The precipitate is isolated, redissolved in dilute sulfuric acid, and separated on a strong cation exchange column using an acetic acid-solium acetate-tetrabutylammonium tetrafluoroborate mobile phase adjusted to pH 2.8. Using an electrochemical detector at 1.25 volts vs. the saturated calomel electrode (SCE), oxalic acid exhibits a linear dynamic range from 1 to 1000 mg/liter with a detection limit of 0.1 mg/liter. Quantitative data are obtained by the method of standard addition in the clinically significant range from 5 to 40 mg/liter. Percentage recovery for spiked urine samples was 97.8% with a relative standard deviation of 2.5%.     

光-Fe3+-草酸体系中对氯苯酚的冰相光转化

本文利用室内低温反应装置研究了在模拟太阳光-Fe3+-草酸作用下冰相中对氯苯酚（4-CP）的光转化。结果表明,Fe3+-草酸存在条件对冰相中4-CP的光转化有促进作用。Fe3+和草酸初始浓度、Fe3+与草酸的初始浓度比以及初始pH值对体系中4-CP的转化率具有较大影响。当溶液初始pH值为6.50,Fe3+和草酸的初始浓度比是1/5,草酸初始浓度为0.80mmol/L时,4-CP光照7.5h转化率可达39.1%。在光转化过程中,TOC的转化率滞后于4-CP的光转化率。4-CP的光转化符合一级动力学模型。分别利用直接萃取法和衍生化法富集了反应中间产物,并采用GC-MS进行了分析,据此推断了冰相中模拟太阳光-Fe3+-草酸作用下4-CP光转化的反应机理。     

Determination of trace amount of oxalic acid with zirconium(IV)-(DBS-arsenazo) by spectrophotometry

A novel method is proposed for the determination of trace amount of oxalic acid in the present article. In 1.0M hydrochloric acid medium, oxalic acid can react with the zirconium(IV) in Zr(IV)-(DBS-arsenazo) complex and replaces the DBS-arsenazo to produce a hyperchromic effect at 520 nm. The hyperchromic degree is proportional to the concentration of the oxalic acid added over a defined range. Based on this property, a new method for the spectrophotometric determination of trace oxalic acid was developed. Beer's law is held over the concentration range of 9.0 x 10(-6) to 5.0 x 10(-4)M for oxalic acid with a correlation coefficient of 0.9995. The apparent molar absorptivity of the method is epsilon520 nm = 1.16 x 10(3)L mol(-1)cm(-1) and the detection limit for oxalic acid is 0.815 microg/mL. The developed method was directly applied to the determination of oxalic acid in tomato samples with satisfactory results.     

ATR-FTIR measurements and quantum chemical calculations concerning the adsorption and photoreaction of oxalic acid on TiO2

The adsorption and photoreaction of oxalic acid on the surface of anatase and rutile TiO2 nanoparticles have been studied using a combined experimental and theoretical approach. In the dark, the experimental adsorption reaches an equilibrium state that can be described as a mixture of adsorbed water and oxalic acid molecules, with the latter forming two different surface complexes on anatase and one on rutile particles. When the system is subsequently illuminated with UV(A) light, the surface becomes enriched with absorbed oxalic acid, which replaces photo-desorbed water molecules, and one of the adsorbed oxalic acid structures on anatase is favoured over the other.     

结冰过程对溶解性有机质典型组分还原Cr(Ⅵ)的影响

研究了结冰过程对溶解性有机质(DOM)的4种典型组分草酸、 酒石酸、 苹果酸和柠檬酸还原Cr(Ⅵ)的影响. 结果表明, 在低浓度下Cr(Ⅵ)在水溶液中不能被4种有机酸所还原; 而在冰中, 不同的有机酸对Cr(Ⅵ)的去除均有促进作用, 且去除效果随着有机酸浓度的增大逐渐增强. 4种有机酸的作用效果强弱顺序为草酸>酒石酸>苹果酸>柠檬酸. 通过使用不同浓度的无机盐和无机酸可以改变冰表面上类似液体层的厚度来抑制Cr(Ⅵ)的还原, 作用效果与无机盐种类无关. 溶液的初始pH值和有机酸结构是影响Cr(Ⅵ)还原的重要因素. 实验条件下冷冻浓缩效应的富集倍数至少可达10³, 对冰中草酸去除Cr(Ⅵ)有明显的促进作用.     

结冰过程对溶解性有机质典型组分还原Cr(Ⅵ)的影响

研究了结冰过程对溶解性有机质(DOM)的4种典型组分草酸、酒石酸、苹果酸和柠檬酸还原Cr(Ⅵ)的影响.结果表明,在低浓度下Cr(Ⅵ)在水溶液中不能被4种有机酸所还原;而在冰中,不同的有机酸对Cr(Ⅵ)的去除均有促进作用,且去除效果随着有机酸浓度的增大逐渐增强.4种有机酸的作用效果强弱顺序为草酸酒石酸苹果酸柠檬酸.通过使用不同浓度的无机盐和无机酸可以改变冰表面上类似液体层的厚度来抑制Cr(Ⅵ)的还原,作用效果与无机盐种类无关.溶液的初始pH值和有机酸结构是影响Cr(Ⅵ)还原的重要因素.实验条件下冷冻浓缩效应的富集倍数至少可达10~3,对冰中草酸去除Cr(Ⅵ)有明显的促进作用.     

Determination of oxalate in urine, using an amperometric biosensor with oxalate oxidase immobilized on the surface of a chromium hexacyanoferrate-modified graphite electrode

A novel enzymatic amperometric method is described for the determination of oxalic acid in urine. An amperometric biosensor was made by immobilizing oxalate oxidase on the surface of a chromium(III) hexacyanoferrate-modified graphite electrode by using a bovine serum albumin and glutaraldehyde cross-linking procedure. The enzyme biocatalyzes oxalate decomposition in the presence of oxygen into carbon dioxide and hydrogen peroxide. The oxalate concentration, which is proportional to the amount of hydrogen peroxide, was determined amperometrically by measuring the current resulting in the reduction of hydrogen peroxide at a very low working potential (0.05 V versus the Hg ?Hg2Cl2? 3M KCl electrode), which minimized the influence of the possible interferences present in human urine. All experiments were performed with succinic buffer, pH 3.8, containing 0.1M KCl and 5.4mM ethylenediaminetetraacetic acid. In an aqueous solution of pure oxalic acid, the biosensor showed good linearity in a concentration range of 2.5-100 microM without the use of a dialysis membrane. For untreated urine samples, a high correlation (R2 = 0.9949) was obtained between oxalate concentrations added to urine samples and oxalate recoveries calculated for determinations with the described oxalate biosensor.     

Effect of chelating functional polymer on the size of CdS nanocluster formation

Chelating poly(acrylates-co-2-methylacrylic acid 3-(bis-carboxymethylamino)-2-hydroxy-propyl ester) microspheres of diameter 250-310 nm were prepared by the soap-free emulsion polymerization method for varying amounts of GMA-IDA. Then CdS/copolymer composite was generated by chemical deposition on the surface of the copolymer microspheres. By XRD analysis it is found that the chelated CdS nanoparticles are a pure cubic zinc blende structure. The CdS/copolymer composite is examined by UV-vis absorbance, photoluminescence, and TEM observation. Average CdS nanoparticle size calculated from Henglein's empirical curve is in the range of 3.0-8.0 nm and varies according to the GMA-IDA molar ratio during polymerization, pH value during chelation, and postchelation annealing temperature. Higher ratio of chelating group, pH value, and annealing temperature produce larger CdS nanoparticles. As GMA-IDA ratio increases, photoluminescence exhibits a red shift from 510 to 520 nm, photoluminescence increases, and bandwidth decreases. Photoluminescence of the CdS nanoparticle becomes negligible when diameter exceeds 5 nm.     

Crystal Engineering of Stable Temozolomide Cocrystals

The antitumor prodrug temozolomide (TMZ) decomposes in aqueous medium of pH≥7 but is relatively stable under acidic conditions. Pure TMZ is obtained as a white powder but turns pink and then brown, which is indicative of chemical degradation. Pharmaceutical cocrystals of TMZ were engineered with safe coformers such as oxalic acid, succinic acid, salicylic acid, d,l ‐malic acid, and d,l ‐tartaric acid, to stabilize the drug as a cocrystal. All cocrystals were characterized by powder X‐ray diffraction (PXRD), single crystal X‐ray diffraction, and FT‐IR as well as FT‐Raman spectroscopy. Temozolomide cocrystals with organic acids (pK_a 2–6) were found to be more stable than the reference drug under physiological conditions. The half‐life (T_1/2) of TMZ–oxalic and TMZ–salicylic acid measured by UV/Vis spectroscopy in pH 7 buffer is two times longer than that of TMZ (3.5 h and 3.6 h vs. 1.7 h); TMZ–succinic acid, TMZ–tartaric acid, and TMZ–malic acid also exhibited a longer half‐life (2.3, 2.5, and 2.8 h, respectively). Stability studies at 40 °C and 75 % relative humidity (ICH conditions) showed that hydrolytic degradation of temozolomide in the solid state started after one week, as determined by PXRD, whereas its cocrystals with succinic acid and oxalic acid were intact at 28 weeks, thus confirming the greater stability of cocrystals compared to the reference drug. The intrinsic dissolution rate (IDR) profile of TMZ–oxalic acid and TMZ–succinic acid cocrystals in buffer of pH 7 is comparable to that of temozolomide. Among the temozolomide cocrystals examined, those with succinic acid and oxalic acid exhibited both an improved stability and a comparable dissolution rate to the reference drug.     

Aggregation and dissolution of 4 nm ZnO nanoparticles in aqueous environments: influence of pH, ionic strength, size, and adsorption of humic acid

Metal oxide nanoparticles are used in a wide range of commercial products, leading to an increased interest in the behavior of these materials in the aquatic environment. The current study focuses on the stability of some of the smallest ZnO nanomaterials, 4 ± 1 nm in diameter nanoparticles, in aqueous solutions as a function of pH and ionic strength as well as upon the adsorption of humic acid. Measurements of nanoparticle aggregation due to attractive particle-particle interactions show that ionic strength, pH, and adsorption of humic acid affect the aggregation of ZnO nanoparticles in aqueous solutions, which are consistent with the trends expected from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Measurements of nanoparticle dissolution at both low and high pH show that zinc ions can be released into the aqueous phase and that humic acid under certain, but not all, conditions can increase Zn(2+)(aq) concentrations. Comparison of the dissolution of ZnO nanoparticles of different nanoparticle diameters, including those near 15 and 240 nm, shows that the smallest nanoparticles dissolve more readily. Although qualitatively this enhancement in dissolution can be predicted by classical thermodynamics, quantitatively it does not describe the dissolution behavior very well.