Solid-phase extraction of the chromium(III)-diphenylcarbazone complex prior to ion-pair chromatography and application to geological samples

A method for the pre-treatment of acid samples prior to ion chromatography is described. In a strong acid medium, Cr(VI) oxidizes diphenylcarbazide, the resulting products forming a stable complex which can be transferred in a methanolic medium by solid-phase extraction using polyethylene as sorbent. This methanolic sample solution can be injected directly into a chromatographic system with a silica-based column. The separation and determination of the chromium complex can be performed by HPLC-using a mobile phase of 15% (v/v) acetonitrile containing 1 mmol/L tetrabutyl ammonium hydroxide (TBAH). The detection limit is estimated to be 2 g/L chromate and the linear range is at least 0.05–2 mg/L chromate.     

Speciation of Cr(III) and Cr(VI) and separation of common anions by ion pair chromatography with trans-1,2-diaminecyclohexane-N,N,N',N'-tetraacetic acid

A reversed phase ion pair chromatographic method for the simultaneous determination of Cr species and common anions on a C(18)-bonded stationary phase was developed by using acetonitrile-water (2:98 v/v) containing 1.0 mM tetrabutylammonium hydroxide and 0.5 mM trans-1,2-diaminecyclohexane-N,N,N',N'-tetraacetic acid (DCTA) at pH 6.5 as mobile phase and UV-detection at 210 nm. Chromatographic parameters were optimized for separation of Cr(III)-DCTA complex, chromate and other anions. The detection limits were found as 8 ng/ml for Cr(III) and 35 ng/ml for Cr(VI). Under the optimum conditions, most other ions did not interfere. The method can be applied to separate a number of common anions simultaneously with the separation of Cr(III) and Cr(VI).     

Spectrophotometric studies on oxidation of some primary alcohols by 2,2′-bipyridinium chromate. A kinetic study

Some primary alcohols were oxidized by 2,2-bipyridinium chromate (BPC) in the presence of oxalic acid and TsOH giving aldehyde as major product. The reactions were carried out in 80% MeCN-DMF (v/v) medium under varied experimental conditions. The rate depends on the first power of the concentration of BPC and fractional power on the concentrations of alcohol, oxalic acid and TsOH.     

Bacterial Reduction of Chromium

A mixed culture was enriched from surface soil obtained from an eastern United States site highly contaminated with chromate. Growth of the culture was inhibited by a chromium concentration of 12 mg/L. Another mixed culture was enriched from subsurface soil obtained from the Hanford reservation, at the fringe of a chromate plume. The enrichment medium was minimal salts solution augmented with acetate as the carbon source, nitrate as the terminal electron acceptor, and various levels of chromate. This mixed culture exhibited chromate tolerance, but not chromate reduction capability, when growing anaerobically on this medium. However, this culture did exhibit chromate reduction capability when growing anaerobically on TSB. Growth of this culture was not inhibited by a chromium concentration of 12 mg/L. Mixed cultures exhibited decreasing diversity with increasing levels of chromate in the enrichment medium. An in situ bioremediation strategy is suggested for chromate contaminated soil and groundwater.

     

Control of carboxylic acid and ester groups on chromium (VI) binding to functionalized silica/water interfaces studied by second harmonic generation

Resonantly enhanced surface second harmonic generation (SHG) measurements carried out at pH 7 and room temperature were performed to study how surface-bound carboxylic acid and methyl ester functional groups control the interaction of chromate ions with fused silica/water interfaces. These functional groups were chosen because of their high abundance in humic and fulvic acids and related biopolymers commonly found in soils. They were anchored to the silica surface using organosilane chemistry to avoid competing complexation processes in the aqueous solution as well as competitive adsorption of the organic compounds and chromate. The SHG experiments were carried out at room temperature and pH 7 while using environmentally representative chromate concentrations ranging from 1 x10(-6) to 2 x 10(-4) M. Chromate is found to bind to the acid- and ester-functionalized silica/water interfaces in a reversible fashion. In contrast to the plain silica/water interface, chromate binding studies performed on the functionalized silica/water interfaces show S-shaped adsorption isotherms that can be modeled using the Frumkin-Fowler-Guggenheim (FFG) model. This model predicts a coverage-dependent binding constant of K(ads) x exp(gtheta). Values for g are found to be 3.2(2), 2.1(2), and 1.3(2) for the carboxylic acid-, the ester-, and the nonfunctionalized silica/water interfaces, respectively, and are consistent with stabilizing lateral adsorbate-adsorbate interactions among the Cr(VI) species adsorbed to the functionalized surfaces. The FFG model allows for the parametrization of the solid-liquid partition coefficient and chromate retardation factors in silica-rich soil particles whose surfaces contain organic adlayers rich in carboxylic acid and methyl ester groups. The straightforward model presented here predicts that chromate retardation increases by up to 200% when carboxylic acid functional groups are present at the silica/water interface. Increases up to 50% are predicted for methyl ester-containing organic adlayers, and the retardation factor remains effectively near unity for the plain silica/water interface (no siloxanes present).     

超高效液相色谱-串联质谱法同时测定不同饲料中30种真菌毒素

采用QuEChERS前处理技术,建立了超高效液相色谱-串联质谱(UHPLC-MS/MS)检测不同饲料样品(预混料、浓缩料和配合料)中30种真菌毒素含量的分析方法。饲料样品经5 mL水和5 mL含1%(v/v)甲酸的乙腈溶液提取后,取上清液氮吹至近干,残渣经1 mL 5 mmol/L醋酸铵水溶液-乙腈(80∶20,v/v)复溶后,上机测定。采用基质匹配标准曲线结合同位素内标法进行定量分析。在低、中、高3个添加水平下,30种真菌毒素的平均加标回收率为72.0%~118.4%(n=5),30种真菌毒素在各自的线性范围内线性关系良好,相关系数(r 2)≥0.99,检出限(LOD,S/N=3)和定量限(LOQ,S/N=10)分别为0.7~20μg/L和2~50μg/L。该法简单、快速、实用性强,适用于预混料、浓缩料和配合料中30种真菌毒素的定量分析。     

钢铁及合金中钨测定的高氯酸氧化法

在磷酸介质中,冒烟高氯酸氧化钨成高价,并消除溶液中存在的还原物质的影响,用氯化亚锡及三氯化钛还原铁和钨,约3．6mol／L盐酸介质中,硫氰酸铵与钨（V）生成黄色络合物,通过测其吸光义可定量测定钨含量。由于较多量冒烟高氯酸的氧化作用,还原不需铁作催化剂,消除了基体铁的影响。测定质量分数范围为0．05％－10％。     

Selective extraction of calcium on tri-n-butyl phosphate plasticized selective extraction of calcium on tri-n-butyl phosphate plasticized polyurethane foam for its spectrophotometric determination in glass and ceramics.

The present paper describes the application of a solid phase extraction system in order to separate traces of calcium from glass and ceramics for its spectrophotometric determination. The method is based on the extraction of calcium from sodium hydroxide solution by tri-n-butyl phosphate (TBP) loaded polyurethane foam (PUF), followed by its elution in hydrochloric acid. The spectrophotometric measurement of the absorbance of calcium complex with calconcarboxylic acid (2-hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-3-naphthoic acid) takes place at pH 12. The following parameters were studied: effects of sodium hydroxide concentration and temperature on the extraction of calcium, time of equilibration for quantitative calcium extraction, effect of TBP concentration, effect of hydrochloric acid concentration for quantitative elution of calcium from PUF, effect of pH and concentration of calconcarboxylic acid for quantitative formation of the complex with calcium, effect of acetone on the stability of calcium-calconcarboxylic acid complex and influence of diverse ions on calcium sorption by TBP-loaded PUF. The results show that calcium traces can be separated onto TBP-loaded PUF from 0.25 mol L(-1) NaOH at 30 +/- 5 degrees C within 30 min. PUF was loaded with TBP in CCl4 (40% v/v). Elution of calcium was done in 1.0 mol l(-1) HCl. The calcium formed a complex with calconcarboxylic acid at pH 12 and absorbance was measured at 560 nm in acetone-water medium. Molar absorptivity was found to be 1.082 x 10(4) l mol(-1) cm(-1). The method obeys Beer's law from 0.10 to 5.0 microg ml(-1) Ca. The validity of the method was established by its successful application in NIST standard reference materials. The method proposed was applied to determine calcium in glass and ceramic materials. The results of the proposed method are comparable with the results of ICP-AES analysis and they are found to be in good agreement.     

In vitro accelerated mass propagation and ex vitro evaluation of Aloe vera L. with aloin content and superoxide dismutase activity

An innovative protocol on accelerated in vitro propagation and acclimatisation was developed in Aloe vera L. Culture was initiated with rhizomatous stem where Murashige and Skoog (MS) medium fortified with 0.5?mg?L(-1) α-naphthalene acetic acid and 1.5?mg?L(-1) N(6)-benzylaminopurine (BAP) promoted earliest shoot induction. Maximum shoot multiplication was achieved in MS medium supplemented with 2.5?mg?L(-1)BAP. The best in vitro rooting was observed in the MS medium with 0.5?mg?L(-1) indole-3-acetic acid plus 2?g?L(-1) activated charcoal. The simple acclimatisation process, primarily with a combination of sand and soil (1?:?1 v/v) and finally with a blend of sand, soil and farm yard manure (2?:?1?:?1 v/v), ensured a 98% survival rate. Overall, 192 true-to-type plantlets were achieved from a single explant within 85 days. Morphologically, in vitro generated plants performed better than conventionally propagated plants; nevertheless the similarity in aloin content, gel content and superoxide dismutase activity was corroborated.     

Optimization of seed production for a simultaneous saccharification cofermentation biomass-to-ethanol process using recombinantZymomonas

The five-carbon sugard-xylose is a major component of hemicellulose and accounts for roughly one-third of the carbohydrate content of many lignocellulosic materials. The efficient fermentation of xylose-rich hemicellulose hydrolyzates (prehydrolyzates) represents an opportunity to improve significantly the economics of large-scale fuel ethanol production from lignocellulosic feedstocks. The National Renewable Energy Laboratory (NREL) is currently investigating a simultaneous saccharification and cofermentation (SSCF) process for ethanol production from biomass that uses a dilute-acid pretreatment and a metabolically engineered strain ofZymomonas mobilis that can coferment glucose and xylose. The objective of this study was to establish optimal conditions for cost-effective seed production that are compatible with the SSCF process design. Two-level and three-level full factorial experimental designs were employed to characterize efficiently the growth performance of recombinantZ. mobilis CP4:pZB5 as a function of nutrient level, pH, and acetic acid concentration using a synthetic hardwood hemicellulose hydrolyzate containing 4% (w/v) xylose and 0.8% (w/v) glucose. Fermentations were run batchwise and were pH-controlled at low levels of clarified corn steep liquor (cCSL, 1-2% v/v), which were used as the sole source of nutrients. For the purpose of assessing comparative fermentation performance, seed production was also carried out using a “benchmark” yeast extract-based laboratory medium. Analysis of variance (ANOVA) of experimental results was performed to determine the main effects and possible interactive effects of nutrient (cCSL) level, pH, and acetic acid concentration on the rate of xylose utilization and the extent of cell mass production. Results indicate that the concentration of acetic acid is the most significant limiting factor for the xylose utilization rate and the extent of cell mass production; nutrient level and pH exerted weaker, but statistically significant effects. At pH 6.0, in the absence of acetic acid, the final cell mass concentration was 1.4 g dry cell mass/L (g DCM/L), but decreased to 0.92 and 0.64 g DCM/L in the presence of 0.5 and 1.0% (w/v) acetic acid, respectively. At concentrations of acetic acid of 0.75 (w/v) or lower, fermentation was complete within 1.5 d. In contrast, in the presence of 1.0% (w/v) acetic acid, 25% of the xylose remained after 2 d. At a volumetric supplementation level of 1.5–2.0% (v/v), cCSL proved to be a cost-effective single-source nutritional adjunct that can support growth and fermentation performance at levels comparable to those achieved using the expensive yeast extract-based laboratory reference medium.     

Imino-phenolic-pyridyl conjugates of calix[4]arene (L1 and L2) as primary fluorescence switch-on sensors for Zn2+ in solution and in HeLa cells and the recognition of pyrophosphate and ATP by [ZnL2

Pyridyl-based triazole-linked calix[4]arene conjugates, viz. L(1) and L(2), were synthesized and characterized. These two conjugates were shown to be selective and sensitive for Zn(2+) among the 12 metal ions studied in HEPES buffer medium by fluorescence, absorption, and visual color change with the detection limit of ~31 and ~112 ppb, respectively, by L(1) and L(2). Moreover, the utility of the conjugates L(1) and L(2) in showing the zinc recognition in live cells has also been demonstrated using HeLa cells as monitored by fluorescence imaging. The zinc complexes of L(1) and L(2) were isolated, and the structure of [ZnL(1)] has been established by single-crystal XRD and that of [ZnL(2)] by DFT calculations. TDDFT calculations were performed in order to demonstrate the electronic properties of receptors and their zinc complexes. The isolated zinc complexes, viz. [ZnL(1)] and [ZnL(2)], have been used as molecular tools for the recognition of anions on the basis of their binding affinities toward Zn(2+). [ZnL(2)] was found to be sensitive and selective toward phosphate-bearing ions and molecules and in particular to pyrophosphate (PPi) and ATP among the other 18 anions studied; however, [ZnL(1)] was not sensitive toward any of the anions studied. The selectivity has been shown on the basis of the changes observed in the emission and absorption spectral studies through the removal of Zn(2+) from [ZnL(2)] by PPi. Thus, [ZnL(2)] has been shown to detect PPi up to 278 ± 10 ppb at pH 7.4 in aqueous methanolic (1/2 v/v) HEPES buffer.     

有机膨润土对水中苯、甲苯、乙苯、二甲苯和铬酸根离子的吸附性能

污水处理;有机膨润土对水中苯、甲苯、乙苯、二甲苯和铬酸根离子的吸附性能     

Production and optimisation of rosmarinic acid by Satureja hortensis L. callus cultures

In this study, production and optimisation of rosmarinic acid, a phenolic acid and an economically important metabolite, was investigated in the callus cultures established from the mature seeds of Satureja hortensis L. (summer savory) plant. Gamborg's B5 basal medium, supplemented with indol butyric acid (IBA) (1.00 mg L(-1)), N6-benzyl aminopurine (6-BA) (1.00 mg L(-1)) and sucrose (2.5%, w/v), was employed for the establishment and maintenance of the callus cultures. Applications were individually prepared by preparing the media containing different IBA/6-BA combinations and sucrose concentrations. All of the applications were carried out in the continuous dark. In the applications, where the effects of IBA/6-BA combinations on the growth and rosmarinic acid accumulation were assayed (1-15 applications), the highest biomass yield was obtained from the medium supplemented with 1.00 mg L(-1) IBA and 5.00 mg L(-1) 6-BA. In the case of the rosmarinic acid accumulation, an opposite relationship was determined between the growth and rosmarinic acid production. While the highest biomass yield was obtained from the medium containing 1.00 mg L(-1) IBA and 5.00 mg L(-1) 6-BA, the highest rosmarinic acid accumulation was obtained from the medium supported with 1.00 mg L(-1) IBA and 1.00 mg L(-1) 6-BA. In the applications where the effects of sucrose concentrations on the growth and rosmarinic acid accumulation were examined, the highest biomass yield was obtained from the medium which is supplemented with 5.0% (w/v) sucrose. In this category, the highest rosmarinic acid accumulation was obtained from the medium which is supported with 3.0% (w/v) sucrose. According to the experiments carried out with the wild S. hortensis, it is found to have 25.02+/-1.21 mg g(-1) rosmarinic acid. No differentiation was observed in any callus during the course of this study.     

Effects of pH, sample size, and solvent partitioning on recovery of soluble phenolic acids and isoflavonoids in leaves and stems of red clover (Trifolium pratense cv. Kenland)

Several extraction parameters were tested to determine optimal conditions for extracting phenolics from leaves and stems of red clover (Trifolium pratense L. cv. Kenland), with the goal of using extracts in bioassays and in assessment of phenolic profiles. HPLC-UV profiles were compared before and after partitioning a methanolic extract of soluble phenolics with ethyl acetate-ethyl ether (1:1, v/v). The effect of extract pH on the partitioning of phenolics into the ethyl acetate-ethyl ether (EtOAc-Et2O) phase was evaluated, and several tissue weights were extracted to determine a minimum amount that could be extracted without loss of information. HPLC profiles of soluble phenolics were similar in the methanolic extracts and the partitioned EtOAc-Et2O extracts. However, recoveries in unpartitioned extracts were 2- to 4-fold greater than in the acidified, partitioned extracts. Also, recovery was considerably affected by the pH to which extracts were adjusted prior to partitioning. In extracts acidified to pH 2, recoveries were 2- to 7-fold higher than in extracts partitioned at pH 6. In extracts prepared from 250, 120, or 60 mg of tissue, peak areas of methanolic extracts were directly proportional to the amount of tissue extracted.     

Determination and locational variations in the quantity of hydroxyanthraquinones and their glycosides in rhizomes of Rheum emodi using high-performance liquid chromatography

Locational variations in the quantity of five hydroxyanthraquinone derivatives (emodin glycoside (1), chrysophanol glycoside (2), emodin (3), chrysophanol (4) and physcion (5)) in the rhizomes of Rheum emodi are described. A simple and reliable method was developed for quantitation of compounds (1-5) in the methanolic extract of rhizomes of R. emodi using reverse-phase high-performance liquid chromatography (HPLC) with photo-diode array detector (PDA). The separation was carried out using a Purospher((R))-Star RP-18 e column (4.6mm i.d.x 250 mm, 5 microm) under the following conditions: acetonitrile:methanol (95:5, v/v) (solvent A) and water:acetic acid (99.9:0.1, v/v) (solvent B) as mobile phase with a linear gradient elution at a flow rate of 0.8 mL/min. The detection wavelength was set at 290 nm. Regression equation revealed a linear relationship (r(2)>0.9901) between the mass of hydroxyanthraquinone derivatives injected and the peak areas. The detection limits (S/N=3) ranged from 0.56 to 3.50 ng/mL and the recoveries ranged from 95.7 to 103.5% for five hydroxyanthraquinone derivatives. Compound 2 was found in maximum quantity (up to 2.23%) in the rhizomes from all the three locations (L(1), L(2) and L(3)) while compound 5 was found in the least quantity (up to 0.19%).     

Capillary electrophoresis direct enantioseparation of aromatic amino acids based on mixed chelate-inclusion complexation of aminoethylamino-beta-cyclodextrin

6(A)-(2-Aminoethylamino)-6(A)-deoxy-beta-cyclodextrin (CDen) was synthesized and formed a binary complex with Cu(II) which was shown to be an effective chiral selector for separation of underivatized amino acid enantiomers in capillary electrophoresis (CE). Moreover, the chiral resolution was greatly enhanced by the presence of polyethyl glycol (PEG) and tert-butyl alcohol in the running buffer. The optimum experimental conditions were 20 mmol/L CDen, 20 mmol/L CuSO(4).5H(2)O, 5.0 mg/mL PEG20000 and 1.0% v/v tert-butyl alcohol, pH 5.80. With the proposed method, the four selected aromatic chiral amino acid pairs were separated in less than 15 min.     

Contributions to the basic problems of complexometry—XIII Determination of aluminium and tervalent chromium in the presence of chromate

Aluminium can be determined in the presence of tervalent chromium and chromate using 1,2-diaminocyclohexanetetra-acetic acid (DCTA), which forms a complex with aluminium even in the cold. This phenomenon enables a successive determination to be made of aluminium (iron) and tervalent chromium in the presence of hexavalent chromium. This procedure cannot be carried out with the commonly used ethylenediaminetetra-acetic acid (EDTA).     

Contributions to the basic problems of complexometry-XXIV Determination of aluminium in the presence of very large amounts of manganese

A simple complexometric determination of aluminium in the presence of a large amount of manganese has been developed. For such determinations only triethylenetetraminehexa-acetic acid (TTHA) can be used. In slightly acidic medium TTHA forms with aluminium a binuclear complex Al(2)L. The complex is formed almost immediately at room temperature. The excess of TTHA is backtitrated with copper sulphate at pH about 5.3, with Glycinecresol Red as indicator. Reliable results were obtained for Mn:Al ratios up to at least 20. The sum of Al + Fe can be determined by the same method. Very large amounts of calcium and magnesium do not interfere.     

Synthesis and Photophysical Properties of Hetero‐Bischelated Complexes of Rhodium(III) Containing Phenyl‐Pyridin‐2‐Ylmethylene‐Amine

Three new hetero‐bischelated rhodium (III) complexes of cis‐[Rh(PA)(L)Cl₂]Cl (where PA = phenylpyridin‐2‐ylmethylene‐amine; L = 2,2′‐bipyridine, 2,2′‐dipyridylamine and 1,10‐phenanthroline) have been successfully prepared and characterized. Each complex shows high intensity bands in the UV region, and these are assigned to spin‐allowed π‐π* transitions. The medium‐intensity absorption band profile in the lower energy region can be explained by convolution of spin‐allowed CT and d‐d* transitions. The emission spectra at low temperature (77 K) of these complexes in EtOH/MeOH (4:1 v/v) are virtually identical. They all exhibit a broad, symmetric, and structureless red emission with a microsecond lifetime and hence are assigned as the d‐d* phosphorescence.     

Speciation of butyl- and phenyltin compounds in sediments using pressurized liquid extraction and liquid chromatography-inductively coupled plasma mass spectrometry

A liquid chromatographic method with inductively coupled plasma mass spectrometry is proposed for the speciation of butyl- (monobutyltin, dibutyltin, tributyltin) and phenyl- (monophenyltin, diphenyltin, triphenyltin) tin compounds in sediments. After evaluation of different additives in the mobile phase, the use of 0.075% (w/v) of tropolone and 0.1% (v/v) of triethylamine in a mobile phase of methanol-acetic acid-water (72.5:6:21.5) allowed the best chromatographic separation of the six compounds. Pressurized liquid extraction (PLE) with a methanolic mixture of 0.5 M acetic acid and 0.2% (w/v) of tropolone was suitable for the quantitative extraction of butyl- and phenyltin compounds with recovery values ranging from 72 to 102%. This analytical approach was compared to conventional solvent extraction methods making use of acids and/or organic solvent of medium polarity. The main advantages of PLE over conventional solvent extraction are: (i) the possibility to extract quantitatively DPhT and MPhT from sediments, which could not be done by a solvent extraction approach; (ii) to preserve the structural integrity of the organotin compounds; (iii) to reduce the extraction time from several hours in case of solvent extraction techniques to just 30 min. For spiked sediments, limits of detection ranged from 0.7 to 2 ng/g of tin according to the compound. The relative standard deviations were found to be between 8 and 15%. The developed analytical procedure was validated using a reference material and was applied to various environmental samples.