Selectivity of reagents used to extract iron from soil

The selectivity of the Tamm and Mehra-Jackson reagents to iron (hydr)oxides was verified chemically by comparing the efficiencies of the two methods of iron extraction: parallel (commonly adopted) and sequential, i.e., by calculating the difference ΔFe = [Fe_dit ? (Fe_ox(paral) + Fe_dit(seq))]. The expected equality of the extracted iron (i.e., ΔFe ～ 0) is rarely observed. A positive balance reaching ΔFe = (0.5?0.8)% predominates upon iron extraction from forest soils of the Cis-Ural region. This is probably due to the stable Fe(II)-oxalate forming in the course of the Tamm extraction, which is incompletely dissolved by the dithionite-citrate-bicarbonate (DCB). On the contrary, a negative balance with ΔFe reaching ?0.4% predominates in the steppe soils of the Stavropol region. This may be caused by Fe(II) minerals (pyrite and siderite) acting as catalyzers in Tamm’s extract, while being weakly soluble in the DCB. To follow the additivity principle for the Tamm and Mehra-Jackson extracts, we suggest a modification of the Schwertmann criterion K_Sch = (Fe_ox: Fe_dit(paral)), which sometimes exceeds 1, to K _Sch ^m = Fe_ox: (Fe_ox + Fe_dit(seq)), which is always less than 1. The values of the modified Schwertmann criterion better agree with the color of the Cis-Ural forest soils expressed in the CIE-L*a*b* optical system as compared with the initial Schwertmann criterion. In the steppe soils, the use of the modified criterion makes it possible to replace the illogical values of K_Sch = 1.11?1.37 by the quite acceptable K _Sch ^m = 0.68?0.83.     

Comparison of three colorimetric reagents in the determination of methanol with alcohol oxidase. Application to the assay of pectin methylesterase

Three colorimetric reagents for the determination of formaldehyde, the Nash reagent (ammonia plus acetylacetone), Purpald (4-amino-3-hydrazino-5-mercapto-1,2,4-triazole), and N-methylbenzothiazolinone-2-hydrazone (MBTH), were compared for the determination of methanol when used in conjunction with alcohol oxidase. The combination of alcohol oxidase plus the commonly used Nash reagent was specific for methanol versus ethanol, but had the lowest sensitivity of the three reagents tested. Substituting Purpald for the Nash reagent increased the sensitivity 3-fold while still maintaining a high (59-fold) selectivity for methanol versus ethanol. Using MBTH increased the sensitivity still further, but with a loss of the selectivity toward methanol. Since MBTH reacted with aldehydes under neutral conditions, it could be included along with the alcohol oxidase to act as an aldehyde trap. This prevented further oxidation reactions by alcohol oxidase and allowed for extended incubations. A procedure for assaying low levels of pectin methylesterase activity that relies on this trapping ability is described. In addition, alcohol oxidase plus Purpald is shown to be a simple and sensitive way to measure the methanol released from plant material following the thermal activation of endogenous pectin methylesterase.     

Extraction of active aluminum from acid soils in Japan with different reagents

The paper deals with methods of determining active aluminum in acid soils. Extraction reagents examined were 4 acids, 4 salts, and 11 compounds of chelating agents. The effects of different conditions, such as pH, temperature, shaking time and the ratio of solution to soil were observed. Barium salicylate solutions, in which the normal concentration of barium and the molar concentration of salicylate were 1.0 and 0.1 respectively, were found promising as extractants. Initial pH of the solution, shaking time and the ratio of solution to soil were set at 7.0, 2 hours and 50:1, respectively. Ammonium salicylate and ammonium EDTA also extracted active aluminum but amounts varied according to different conditions. The most promising procedure was applied to a few kinds of soils and to soil treated with either lime or phosphate. The amounts of aluminum extracted from soils high in humus were larger than those from soils low in humus. Liming or phosphate application decreased the amounts of aluminum extracted.     

Use of chrome azurol S reagents to evaluate siderophore production by rhizosphere bacteria

Summary Siderophores produced by rhizosphere bacteria may enhance plant growth by increasing the availability of Fe near the root or by inhibiting the colonization of roots by plant pathogens or other harmful bacteria. To examine the populations of siderophore-producing bacteria colonizing the roots of two grass species that differed in their susceptibility to Fe deficiency, we inoculated serial dilutions of root samples onto chrome azurol S (CAS) agar and several other selective and non-selective culture meida. CAS agar effectively differentiated bacteria that were capable of excreting large amounts of siderophore, but the composition of the medium limited its usefulness for ecological studies. A large proportion (71–79%) of the bacterial population that grew on a non-selective medium (tryptic soy agar) failed to grow on CAS agar, and several isolates that showed no sign of siderophore production on CAS agar produced siderophore in liquid culture. Similar populations of siderophore-producing bacteria were observed on roots of St. Augustine grass, which frequently exhibits Fe chlorosis, and bermuda grass, which does not. Roots of both grasses were colonized by bacteria that produced siderophore in vitro at concentrations ranging from 100 to 230 M. The CAS assay solution was also used to compare siderophore production by Pseudomonas fluorescens Q6, an isolate from bermuda grass, and by P. putida B 10, a plant growth-promoting pseudomonad. P. fluorescens Q6 produced 2.4 times more siderophore in vitro than P. putida B 10.     

Colorimetric determination of certain phenothiazine drugs by using morpholine and iodine-potassium iodide reagents

A colorimetric method was developed for the quantitative estimation of 11 phenothiazine drugs. The method is based on the interaction of unsulfoxidized drug with morpholine and iodine-potassium iodide reagents. The interaction for all studied phenothiazine drugs yields a blue product with 2 absorption maxima: one in the range of 620-640 nm with lower molar absorptivity and the other in the range of 662-690 nm with higher molar absorptivity. The color was stable for at least 10 h. The reproducibility and recovery of the method were excellent. The method was applied successfully to the analysis of various commercially available phenothiazines in different dosage forms. The results were comparable to those obtained by official procedures. The suitability of the method for detection and estimation of promethazine excreted in urine has been suggested by preliminary experiments. Reaction products have been isolated and identified.     

Desorption of myo‐inositol hexakisphosphate and phosphate from goethite by different reagents

Inositol phosphates are abundant organic phosphates found widely in the environment. The sorption and desorption of organic phosphate (P_o) are important processes in controlling the mobility, bioavailability and fate of phosphorus (P) in soil and sediment. The desorption characteristics of myo‐inositol hexakisphosphate (IHP) and inorganic phosphate (P_i) from goethite were studied by pre‐sorption of IHP or P_i followed by desorption by KCl, H₂O, and citrate. Batch experiments and in situ attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy were used to investigate the desorption of IHP/P_i. The desorption percentage of IHP/P_i by citrate was much higher than that by H₂O/KCl. The desorption of P by citrate was mainly achieved through ligand exchange, and the desorption increased with decreasing pH. Desorption by H₂O was slightly greater than that by 0.02 M KCl because the electrostatic repulsion between the P molecules is larger in H₂O. Due to the higher affinity of IHP for goethite than that of P_i, the maximum desorption of IHP was lower than that of P_i. Desorption curves (desorption concentration in solution vs. sorption density) of IHP or P_i on goethite by KCl or H₂O was well fitted by an exponential equation, while those by citrate were well fitted by a linear equation. The desorption amounts of P in the first cycle account for more than 58% of the total desorption followed by substantial decreases in the second and third cycles. There was a re‐sorption of P_i from solution in the late stage of desorption by KCl and H₂O, resulting in a sharp decrease in desorption. Re‐sorption of IHP did not occur, which is probably due to its poor diffusion into goethite. The initial desorption rate of P_i with KCl and H₂O decreased with increasing pre‐sorption time, whereas that of IHP was opposite. This study indicates that strong sorption on and weak desorption of IHP from iron (hydr)oxides may explain the accumulation of IHP in soils.     

Instability studies of porcine somatotropin in aqueous solutions and the possible reagents for its stabilization

The instability of porcine somatotropin (pST) in various solutions and possible stabilization of the hormone by sugars and mild detergents were studied. Aggregation and decomposition of the hormone molecules in various pH solutions and under presence of sugar or detergent were monitored by gel permeation chromatography (GPC) or ultraviolet spectroscopy (UV). The pST is a very unstable hormone in an aqueous environment. It was found in this project that the peptide hormone underwent aggregation or decomposition quickly in acidic and alkaline solutions but slowly in neutral pH solutions. High losses of pST monomers were seen in concentrated solutions of the hormone. On the other hand, pST monomers were stabilized to a certain degree in glucose solutions and at a low concentration of urea. These results should facilitate the development of efficient controlled-release systems which are essential for commercializing porcine somatotropin.     

振动深松技术与生化制剂在苏打盐碱土改良中的应用

振动深松与生化制剂的有机结合旨在探求一种改良苏打盐碱土壤、快速修复草原生态环境的新方法.该文根据田间观测及室内试验,获得了盐碱土改良前后土壤物理化学指标的变化趋势.采用土壤水分特征指标法,定量了振动深松后深松层的土壤蓄水容量.利用方差分析方法分析了改良区增产效果.结果表明,集成技术对苏打盐碱土的改土、增产效果十分明显.其结论是采用振动深松技术改善了牧草生长的土壤环境,提高了降水有效利用率:与生化制剂的结合运用,降低盐碱对牧草根系的毒害,土壤中全氮、全磷和有机质等含量明显增加,提高了土壤肥力;经治理后的3～4a,改良区变为优质草场.     

Beta-D-glucosyl and alpha-D-galactosyl Yariv reagents: syntheses from p-nitrophenyl-D-glycosides by transfer reduction using ammonium formate

Yariv beta-D-glucosyl (4a) and Yariv alpha-d-galactosyl (4b) reagents are multivalent phenylglycosides. The beta-D-glucosyl reagent is considered diagnostic for arabinogalactan proteins (AGPs) to which it can reversibly bind, stain, and precipitate. The alpha-D-galactosyl reagent does not bind AGPs and is used as a control. In a new strategy, we accomplished the large scale synthesis of the Yariv reagents in one continuous step by a transfer reduction method and without a need for any specialized apparatus. As the starting material, p-nitrophenyl-D-glycosides (1) were reduced to p-aminophenyl-D-glycosides (2) using ammonium formate as the hydrogen donor. The excess formate was converted to formic acid and ammonia, which then were removed from the reaction by simple distillation. Without isolation, p-aminophenyl-D-glycosides were diazotized (3) and coupled to phloroglucinol to give the Yariv reagents in approximately 40% yield. AGPs are a major component of gum arabic, an emulsifying agent widely used in the food and pharmaceutical industries. Increasing interest in AGPs prompted the development of a relatively easy and inexpensive method for the synthesis of these reagents.     

Rapid microchemical identification of four phenothiazine antiemetics with gold bromide and iodine-potassium iodide reagents: collaborative study

A microchemical method was developed for the rapid identification of 4 phenothiazine antiemetics. Perphenazine, promethazine, thiethylperazine, and triflupromazine were positively identified and differentiated with the aid of a gold bromide reagent and an iodine-potassium iodide reagent. Only promethazine and triflupromazine yielded microcrystalline derivatives with gold bromide; only perphenazine and thiethylperazine reacted with iodine-potassium iodide. For each pair of positive reactions, the crystalline products were morphologically distinguishable under a microscope. The 2 tests were collaboratively studied by 7 independent laboratories and found to be simple, rapid, and effective for identifying the phenothiazines of interest. The method has been adopted official first action.     

Evaluation of two derivatization reagents for the determination by LC-MS/MS of ammonia in cigarette mainstream smoke

Ammonia in cigarette mainstream smoke was quantified by LC-MS/MS after derivatization. Two different reagents, fluorescamine and dansyl chloride, were investigated, but only the latter gave stable derivatives; therefore, it was considered the most appropriate choice. Smoke samples were collected on a Cambridge filter pad followed by an impinger containing a solution of hydrochloric acid. Ammonia was then derivatized with a 18.5 mM solution of dansyl chloride in acetonitrile at 70 °C for 30 min in a vial with the internal standard, (15)ND(4)Cl. The resulting derivative was analyzed by LC-MS/MS detection with an atmospheric pressure chemical ionization (APCI) interface in the positive ionization mode using multiple-reaction monitoring (MRM). Good linearity was obtained in the concentration range of 0.02-1.65 μg/mL (r(2) ≥ 0.999), and the limit of detection (LOD) was established at 0.006 μg/mL. This method has the advantage of being sensitive, efficient, and reliable and is not hindered by interferences from the sample matrix. It should thus be considered a reference method of choice for the determination of ammonia in smoke.     

A new green analytical procedure for monitoring sub-nanogram amounts of chlorpyrifos on fruits using flow injection chemiluminescence with immobilized reagents

A novel green method using flow injection chemiluminescence with controlled-reagent-release technology has been investigated for the rapid and sensitive monitoring of sub-nanogram amounts of chlorpyrifos. The analytical reagents involved in chemiluminescence (CL) reaction, luminol and periodate, were both immobilized on an anion-exchange column. The CL signals produced by the reaction between luminol and periodate, which were eluted from the column through water injection, were decreased in the presence of chlorpyrifos. The decrease of CL intensity was linear over the logarithm of concentration of chlorpyrifos ranging from 0.48 to 484.0 ng x mL(-1) (r(2) = 0.9969), and the limit of detection was 0.18 ng x mL(-1) (3sigma). At a flow rate of 2.0 mL x min(-1), the determination of chlorpyrifos, including sampling and washing, could be performed in 0.5 min with a relative standard deviation of less than <3.0%. The proposed method was applied successfully in an assay of remnant chlorpyrifos on fruits such as orange and shaddock with the recovery of 94.4-107.4%. The change of the concentration of chlorpyrifos in a water sample was also investigated, and the variation rate was 99.96% during 35 h in the open air.     

Gas-liquid chromatographic determination of selenium in biological materials, using 4-bromo- and 4-chloro 1,2-diaminobenzene as derivatizing reagents

A method is described for the gas-liquid chromatographic determination of traces of selenium in marine biological materials. The method is based on the reaction of Se(IV) with bromo- and chloro-substituted 1,2-diaminobenzenes. The benzoselenadiazoles so formed are sensitive to electron capture detection. The sample is digested in a nitric-perchloric acid mixture and selenium is reduced to the IV oxidation state. Different aliquots of the digest solution are reacted with either 4-bromo- or 4-chloro-1,2-diaminobenzene to quantitatively form the corresponding 2,1,3-benzoselenadiazole. Recovery of added selenite to a fish meal sample was 95% for the bromo derivative and 101% for the chloro derivative. Different portions of a well mixed fish meal sample were analyzed in independent laboratories by the fluorometric method and by atomic absorption spectrophotometry (hydride generation). The following mean values (microgram/g) were found: present method 1.89, fluorometric method 1.91, atomic absorption method 2.1. The lower limit of detection for the method described was 13 ng, using the bromo derivative, and 27 ng, using the chloro derivative.     

The acid-base buffer capacity of podzolic soils and its changes under the impact of treatment with the Mehra-Jackson and Tamm reagents

The acid-base buffer capacity before and after the treatment with the Mehra-Jackson and Tamm reagents was assessed by continuous potentiometric titration for the main genetic horizons of two profiles of podzolic soils in the Central Forest State Reserve. The total buffer capacity was calculated in the pH range from the initial titration point (ITP) to 3 for the acid titration and from the ITP to 10 for the base titration, as well as the buffer capacities in the pH intervals of 0.25. It was found that both treatments abruptly decreased the base buffer capacity, which reached 70–90% in the E horizons. The high direct linear correlation of the difference between the total base buffer capacities before and after each treatment with the content of Fe in the Tamm extract was revealed. From the results obtained, a conclusion was drawn that finely dispersed Fe hydroxides were the main solid-phase constituents ensuring the base buffer capacity, and the deprotonation of hydroxyl groups on the surface of Fe hydroxides was the essential buffer reaction during the base titration.     

Spectrophotometric determination of ascorbic acid in canned fruit juices, cordials, and soft drinks with iron(III) and 1,10-phenanthroline as reagents

A simple and accurate spectrophotometric method has been developed for the determination of ascorbic acid in canned fruit juices, cordials, and soft drinks, based on the reduction of iron(III) by ascorbic acid to iron(II), which is then complexed with 1,10-phenanthroline. Background correction is necessary for most samples and can be achieved by copper(II)-catalyzed oxidation of the acid. The calibration graph was linear from 0 to 8 micrograms/mL of ascorbic acid with a slope of 0.12/ppm. The precision for the determination of ascorbic acid in a lemon drink containing 210 micrograms/mL of the acid was 0.9%. Many ingredients commonly found in fruit juices, cordials, and soft drinks do not interfere; however, tannic acid, pyrogallol, and sulfite interfere with the method. A wide range of samples was analyzed for ascorbic acid content by the proposed method. The samples included mango and lemon tea drinks and also grapefruit juices, for which no background correction is needed.     

Electrochemical modifications of proteins. 1. Glycitolation.

When an electrochemical method is tentatively applied for N-alkylation of proteins, some Maillard reactions occur on the counter electrode. A low level of reductive N-alkylation of casein was obtained on a cathodic electrode, but the method unfortunately remains poorly efficacious in comparison with those using a hydride donor such as sodium cyanoborohydride. Electroassisted reductive N-alkylation is suitable only for basic proteins such as histones or lysozyme. For other proteins, an alternative consists of either methylating carboxylic residues to increase the value of their isoelectric pH or coating them with a cationic detergent.