Degradative analysis of aquatic fulvic acid: CuO oxidation versus pyrolysis after tetramethylammonium hydroxide treatments in air and helium atmospheres

The structural composition of Nordic aquatic reference fulvic acid was investigated using chemical and thermal degradation methods: alkaline CuO oxidation and analytical pyrolysis after tetramethylammonium hydroxide (TMAH) pretreatment. Off-line procedures of the TMAH treatments were carried out under both air and helium atmospheres, with the aim of clarifying the effect of oxygen. Irrespective of the fact that the chemical and thermal degradation methods gave qualitatively quite similar basic products (mainly phenols and phenolic acids together with aromatic and aliphatic carboxylic acids), they also revealed their unique selectivity and efficiency for releasing different kinds of structural constituents. The results verify the formation of additional carboxyl functionality in the CuO oxidation. However, some similar oxidative reactions also appeared to take place during the pretreatment procedures of strongly basic TMAH, especially under an air atmosphere. The use of inert and protective atmosphere during the TMAH pretreatment is therefore recommended for producing more relevant structural information about the complex composition of humic substances.     

Use of an injection port for thermochemolysis–gas chromatography/mass spectrometry: Rapid profiling of biomaterials

A simple and direct approach was developed for thermochemolytic analysis of a wide range of biomolecules present in plant materials using an injection port of a gas chromatograph/mass spectrometer (GC/MS) and a novel solids injector consisting of a coiled stainless steel wire placed inside a modified needle syringe. Optimum thermochemolysis (or Thermally Assisted Hydrolysis/Methylation) was achieved by using a suitable methanolic solution of trimethylsulfonium hydroxide (TMSH) or tetramethylammonium hydroxide (TMAH) with an injection port temperature of 350 °C. Intact, methylated flavonoids, saccharides, phenolic and fatty acids, lignin dimers and diterpene resin acids were identified. Samples include tea leaves, hemicelluloses, lignin isolates and herbal medicines. Unexpected chromatographic results using TMAH reagent revealed the presence of intact methylated trisaccharides (658 Da) and structurally informative dimer lignin markers.     

Effects of textured morphology on the short circuit current of single crystalline silicon solar cells: Evaluation of alkaline wet-texture processes

The effect of different surface morphologies obtained by anisotropic etching on the light trapping and short circuit current of single crystalline silicon solar cells was investigated. The anisotropic texturing of a (1 0 0) silicon surface was performed using potassium hydroxide (KOH) solution and/or tetramethylammonium hydroxide (TMAH) solution including isopropyl alcohol (IPA) additive or tertiary butyl alcohol (TBA) additive. Texturing in TMAH solution formed smaller pyramids on the textured surface compared with texturing in KOH solution. Although the textured samples showed similar reflectances (except in the case of the TBA additive), they showed different short circuit currents. Texturing in KOH/TMAH solution led to a 9.6% increase in short circuit current compared with texturing in KOH/IPA solution, a typical etchant in commercial processes. Based on these results, the reflectivity has no simple proportionality relationship to the short circuit current, and the short circuit current of silicon solar cells should be the criterion used in evaluating texturing effects on reducing reflectance and forming a sound junction with high collection efficiency.     

Simple method for the determination of Cu and Fe by electrothermal atomic absorption spectrometry in biodiesel treated with tetramethylammonium hydroxide

A simple analytical procedure for the determination of Cu and Fe in biodiesel samples by electrothermal atomic absorption spectrometry is proposed. An aliquot of the sample is simply mixed with tetramethylammonium hydroxide (TMAH) and heated to 90 °C for 5 min. Pyrolysis and atomization temperatures were optimized through pyrolysis and atomization curves. The high pyrolysis temperature adopted, of 1000 °C, certainly helped minimizing potential interferences. Even though, calibration should be carried out with aqueous standard solutions in the presence of the TMAH. The detection limits (3 s, n = 10), in the sample, were quite low 15 ng g⁻¹ and 24 ng g⁻¹ for Cu and Fe, respectively. Seven biodiesel samples, produced from different raw materials, including vegetable seed, frying oil and animal fat were analyzed. Accuracy was validated by applying the recovery test to two samples, enriching the samples with two concentration levels (recoveries from 105% to 120%). The precision, expressed by the relative standard deviation was less than 3% for Cu and less than 7% for Fe. Copper could be quantified in two and Fe in three of the seven samples. The biodiesel sample from fodder turnip was especially rich in the analytes in comparison to the other samples.     

大体积直接进样离子色谱法检测四甲基氢氧化铵中痕量阳离子

以抑制型电导离子色谱法检测四甲基氢氧化铵溶液中痕量碱金属和碱土金属离子.色谱条件为:IonPac CS12A阳离子交换色谱柱,20mmol/L甲烷磺酸淋洗液等度淋洗,抑制型电导检测.稀释液样品通过Dionex OnGuardⅡ氢型聚苯乙烯基强酸性树脂柱和0.22μm微孔尼龙膜处理.该方法的检测限(S/N=3)在0.024μg/L～0.156μg/L之间,标准曲线在低ng/L到低μg/L范围内呈现良好线性,RSD在10%左右,回收率为88%～115%.     

Analysis of structurally modified polyacrylamides by on-line thermochemolysis-GC–MS

Cationically modified polyacrylamides (cPAA) are commonly used flocculants in sewage water treatment processes. Therefore, those compounds are quantitatively important contaminants in sewage sludges, which were deposited on agricultural soils as fertilizers in the past and even today in many countries. In order to monitor environmental pathways and to correlate ecotoxicological effects with quantitative data, there is a necessity for methodologies for quantitative analyzes of technically applied polyacrylamides. The present investigation provides a fundamental proof of the verifiability of cPAA in particulate samples by on-line thermochemolysis-GC–MS in presence of tetramethyl ammonium hydroxide. This methodological approach induces degradation of cPAA to glutarimide related structures. Experiments were carried out on pure cPAA, spiked sediments and sewage sludges. The results revealed a linear correlation between thermochemically degraded quantities of cPAA and abundances of glutarimide related degradation products as well as a theoretical limit of detection of 250 mg/kg, which is sufficient for corresponding analyzes concerning sewage sludges. Thermochemolysis experiments on polyacrylamide and anionically modified derivates revealed the same glutarimide related degradation products as obtained by degradation of cPAA.     

Towards identification of traditional European and indigenous Australian paint binders using pyrolysis gas chromatography mass spectrometry

We report a pyrolysis GC–MS method capable of analysing Indigenous Australian and European binders typically used in the manufacture of culturally important painted works. Eleven different traditional European binders and ten different Indigenous Australian binders were examined. The method allows discrimination between highly complex and impure lipid, resin, polysaccharide, wax, and protein-based binders. Each was found to have characteristic pyrolysis products that were unique to the binder material, demonstrating the potential for differentiation of these binders on Australian Aboriginal artworks towards identification and conservation of cultural heritage.     

Determination of benzoic acid in soft drinks by gas chromatography with on-line pyrolytic methylation technique

A new application of pyrolytic methylation was developed to determine benzoic acid in soft drinks by gas chromatography (GC) without using any pretreatment procedures and special pyrolyzer. With the on-line pyrolytic methylation by tetramethylammonium hydroxide (TMAH), benzoic acid was converted into its corresponding methyl ester in the injector at 280 °C. Thus, samples containing benzoic acid could be well determined by direct-injection in GC on the medium polar stationary phase column. To obtain optimum methylation conditions, important factors were investigated and then applied to the following experiments. The results were obtained as following: 280 °C as reaction temperature, 2:1 as the proportion of TMAH to benzoic acid. The storage time of mixed solution had no obvious effect on the area of benzoic acid methyl ester peak. With the p-xylene as an inter-standard, GC behaviors were investigated under these optimum conditions. The linear range achieved for benzoic acid was 1-10,000 mg/l with the correlation coefficient of 0.9985. The precision was quite high with the R.S.D. of 2.8% and the limit of detection reached 0.1 mg/l. The potential of the proposed method was assessed by applying it to the determination of benzoic acid in soft drinks. The results obtained coincided with the statement on the labels and all of the detected data were below the maximum permitted concentration of the European Union Legislation. This on-line pyrolytic methylation technique was proved to be simple to implement, sensitive and selective.     

A rugged and transferable method for determining blood cadmium,mercury, and lead with inductively coupled plasma-mass spectrometry

A simple, high-throughput method for determining total cadmium, mercury, and lead in blood in cases of suspected exposure, using inductively coupled plasma-mass spectrometry (ICP-MS), has been developed and validated. One part matrix-matched standards, blanks, or aliquots of blood specimens were diluted with 49 parts of a solution containing 0.25% (w/w) tetramethylammonium hydroxide; 0.05% v/v Triton X-100 (blood cell membranes and protein solubilization); 0.01% (w/v) ammonium pyrolidinedithiocarbamate (mercury memory effect prevention and oxidation state stabilization, solubilization by complexation of all three metals); 1% v/v isopropanol (signal enhancement); and 10 μg/L iridium (internal standard). Thus the final dilution factor is 1 + 49. The method provides the basis for the determination of total cadmium, mercury, and lead for assessment of environmental, occupational, accidental ingestion or elevated exposures from other means. Approximately 80 specimens, including blanks, calibration standards, and quality control materials can be processed in an 8-h day. The method has been evaluated by examining reference materials from the National Institute of Standards and Technology, as well as by participation in six rounds of proficiency testing intercomparisons led by the Wadsworth Center of the New York State Department of Health. This method was developed for the purpose of increasing U.S. emergency response laboratory capacity. To this end, 33 U.S. state, and 1 district health department laboratories have validated this method in their own laboratories.     

TMAH对TiN纳米粉体分散行为的影响

采用四甲基氢氧化铵(TMAH)作为分散剂,利用沉降法、ξ电位、粒度分析、TEM等研究了TiN纳米粉体在水介质中的分散稳定机制,探讨了pH值和分散剂对纳米颗粒分散行为的影响。结果表明：TiN纳米粉体的分散行为遵循静电稳定机制,pH值对TiN纳米粉体的分散性和稳定性有较大影响,在pH=8处TiN纳米粉体有较好的分散效果。有机阳离子型分散剂TMAH能在TiN纳米颗粒表面形成特征吸附,并通过静电作用和空间位阻作用提高TiN纳米颗粒的分散性。在pH=8、TMAH加入量为0.75wt%的条件下,TiN纳米粉体获得无团聚的最佳分散状态,悬浮液稳定时间可达1个月。