Exchange of carbonyl sulfide (COS) between wheat soil and atmosphere

The exchange of COS between wheat soil and atmosphere was investigated by using a dynamic enclosure. The investigated soil type acted as a significant sink for the trace gas COS. Atmospheric COS mixing ratios and temperature were found to be the physicochemical parameters controlling the uptake. The uptake reached maximum about 0.6×10~(-12) mol ?g~(-1) ?h~(-1) at 15-20℃ under natural ambient atmospheric conditions. The measured uptake values agree well with that calculated by Guenther algorithm.     

Analysis of wheat extracts for ochratoxin A by molecularly imprinted solid-phase extraction and pulsed elution

A molecularly imprinted solid-phase extraction (MISPE) method has been developed for the rapid analysis of wheat extracts for ochratoxin A (OTA). Molecularly imprinted polymer (MIP) particles were synthesized from N-phenylacrylamide (PAM) and slurry-packed into a micro-column for selective solid-phase extraction (SPE) of OTA. With water flowing at 0.5 mL min^–1, a total binding capacity of 30 ng OTA was determined for the 20 mg of MIP particles. MISPE conditions were optimized using OTA in methanol/acetic acid (99:1 v/v). Nearly 100% binding could be achieved from one 20-L injection of sample containing up to 30 ng of OTA. Pulsed elution (PE) using methanol/triethylamine (99:1 v/v) was good for the quantitative desorption of OTA. The MISPE–PE method, with fluorescence detection at _ex=385 nm and _em=445 nm, afforded a detection limit of 5.0 ng mL^–1 (or 0.1 ng in 20 L of sample injected) for OTA. Recovery of OTA from wheat extracts was 103±3%. Each MISPE–PE analysis required less than 5 min to complete.     

An in vitro experiment on the interaction of charcoal or wheat bran with 11-nor-9-carboxy-Δ9-tetrahydrocannabinol and its glucuronide

The rather long yet variable terminal half-lives and detection times since last use of urinary cannabinoids may partly be attributed to their enterohepatic circulation which generally can be interrupted or restricted by chemical adsorbents. Therefore, an in vitro experiment was performed to study the adsorption/binding of 11-nor-9-carboxy-Δ⁹-tetrahydrocannabinol (THC-COOH) and its glucuronide to activated charcoal and wheat bran; remaining concentrations were determined by liquid chromatography/tandem mass spectrometry. Adsorption/binding of 1,000 ng/mL of free or conjugated THC-COOH was complete using as little as 5 mg of charcoal whereas adsorption/binding to wheat bran increased with increasing amounts. Taking of remedies affecting enterohepatic recycling of THC-COOH and its glucuronide may challenge interpretation of cannabinoid concentrations used to detect or assess frequency of drug use or the time since last drug consumption.

Production of β-galactosidase by Trichoderma reesei FTKO-39 in wheat bran

Trichoderma reesei FTKO-39 grown at 35°C for 5 d on wheat bran supplemented with MgCl₂ and lactose as the carbon source produced two isozymes of β-galactosidase: BGT I and BGT II. These isozymes were partially purified on a DEAE-Trisacryl column. Both BGT I and BGT II fractions exhibited optimum activity at 65°C, but the pH optima were 4.0 and 6.5, respectively. The isozymes also showed similar thermal stability. However, BGT I was more stable than BGT II in a pH range of 3.0–10.0. At least two different β-galactosidases are produced by T. reesei, as revealed by the two bands seen on a 6% polyacrylamide gel stained for activity.     

Fourth-derivative spectrophotometric determination of fungicide ferbam (iron(III) dimethyldithiocarbamate) in a commercial sample and wheat grains using 2,2′-bipyridyl

A procedure has been developed for the direct fourth-derivative spectrophotometric determination of iron(III) dimethyldithiocarbamate by converting it into an iron(II) 2,2'-bipyridyl complex, which is then dissolved in Triton X-100. Beer's law is obeyed over the concentration range 0.5-20 microg mL(-1 )in the final solution. Various parameters such as the effect of pH and interference of large number of ions on the determination of ferbam have been studied in detail. The method is sensitive, highly selective and can be used for the determination of ferbam in a commercial sample and in mixtures with various dithiocarbamates (ziram, zineb, maneb, etc.) and from wheat grains.     

Effect of γ-ray irradiation on the germinating characteristics of wheat seed

Few researches have been reported on the long-term germination characteristics and the effect of high gamma radiation dose on cereal seeds. In this paper, to observe the effects of gamma irradiation (0-3 kGy) on the germination of wheat seed in long-term (within 20 months), wheat seed was dried after irradiation and the germination experiment during storage time was conducted. It was found that the lengths of buds of irradiated wheat seeds diminished, the roots of irradiated wheat seeds disappeared, and no germinations in irradiated wheat seed was found. The influence of γ-ray irradiation on roots was more significant than that on buds. After long-term storage, the germination of irradiated wheat seeds increased.     

DSC studies of γ -irradiation influence on amylose-lipid complex transition in wheat flour

DSC studies were carried out in the heating-cooling cycles for non-irradiated and irradiated with -rays (⁶⁰Co) using 30 kGy dose wheat flour. The differences between gelatinisation and reversible transition of amylose-lipid complexes occurring in suspensions of non-irradiated and the irradiated flour (characterized by a dry matter to water ratio of 1:1 and 1:3) depend on the conditions applied in DSC measurements (concentration, heating/cooling rate) and on the preceding treatment of samples. An essential decrease in the temperature of amylose-lipid complex transition was discovered after irradiation. Retrogradation is inhibited in the dense gels of the irradiated samples as compared to the initial ones. The results are discussed in terms of radiation-induced destruction of the polysaccharide chains and lipid modification.     

Miniaturized liquid–liquid extraction coupled with ultra-performance liquid chromatography/tandem mass spectrometry for determination of topramezone in soil,corn, wheat,and water

A rapid and simple miniaturized liquid–liquid extraction method has been developed for the determination of topramezone in soil, corn, wheat, and water samples using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-electrospray ionization (ESI)/MS/MS). The established method for the extraction and purification procedure was based on liquid–liquid partitioning into an aqueous solution at a low pH (pH ≈ 2.5), followed by back-partitioning into water at pH > 9. Two precursor, product ion transitions for topramezone were measured and evaluated to provide the maximum degree of confidence in the results. Under negative ESI conditions, quantitation was achieved by monitoring the fragment at m/z = 334 and the qualitative fragment at m/z = 318, whereas also collecting the corresponding parent ion at m/z = 362. Chromatographic separation was achieved using gradient elution with a mobile phase consisting of methanol and a 0.01% aqueous ammonium hydroxide solution. Recovery studies for soil, corn, wheat, and water were conducted at four different topramezone concentrations (5 or 10, 50, 100, and 1,000 μg kg⁻¹); the overall average recoveries ranged from 79.9% to 98.4% with intra-day relative standard deviations (RSD) of 3.1~8.7% and inter-day RSD of 4.3~7.5%. Quantitative results were determined from calibration curves of topramezone standards containing 1–500 μg L⁻¹ with an R ² ≥ 0.9994. Method sensitivities expressed as limits of quantitation were typically 6, 8, 9, and 1 μg kg⁻¹ in soil, corn, wheat, and water, respectively. The results of the method validation confirmed that this proposed method was convenient and reliable for the determination of topramezone residues in soil, corn, wheat, and water.     

Updated estimates of the selenomethionine content of NIST wheat reference materials by GC–IDMS

Updated estimates of the selenomethionine content of four NIST wheat reference materials have been obtained by use of a revised gas chromatography–stable-isotope dilution mass spectrometric method. The revised method makes use of digestion with methanesulfonic acid, which enables more complete recovery of endogenous selenomethionine than was previously achieved by overnight denaturing treatment in 0.1 mol L⁻¹ HCl. The NIST wheat reference materials each contain approximately 55% of their total Se content as selenomethionine. Information about forms of Se in reference materials adds value to these materials in Se speciation studies. Estimates of selenomethionine content are also provided for other wheat samples, including several grown under conditions of exposure to high Se levels. These samples also contain approximately 55% of their total Se content as selenomethionine. The consistent level of 55% of total selenium occurring in the form of selenomethionine when the total selenium content varies by a factor of 500 is suggestive of an active mechanism of incorporation of selenium into wheat grain. Figure Selenomethionine content of wheat samples     

Interfacial behaviour of wheat puroindolines: monolayers of puroindolines at the air–water interface

Puroindolines are among the major basic and cysteine-rich lipid binding proteins of wheat seeds. The interfacial properties of puroindoline-a (PIN-a) and puroindoline-b (PIN-b) are important both from a biological and a technological point of view. In the work reported here, the interfacial characteristics of spread monolayers of wheat puroindolines at the air–water interface were studied at varying subphase compositions using a Langmuir–Blodgett film balance. The compression isotherms (π–A _Sp) were recorded at constant barrier speed (3.3 cm/min). It was observed that both PIN-a and PIN-b form stable monolayers at the air–water interface. The stability of the monolayers was found to be dependent on the subphase composition as well as on the concentration of protein in the spreading solution. When the ionic strength of the subphase is below 0.50, the compression isotherms of both PIN-a and PIN-b remains unaffected with the change in the ionic strength of the subphase; however, when the ionic strength is above 0.50, the compression isotherms of both PIN-a and PIN-b undergo significant change with an increase in the ionic strength of the subphase. A gradual increase in the values of the collapse pressure (π_C) and the limiting area (A ₀) was observed due to an increase in the ionic strength of the subphase from 0.5 to 4.0, which may be correlated with the salt-induced conformational changes of the protein molecule. The presence of NaCl and KCl (ionic strength 1.0) in the subphase has a comparable effect on the compression isotherms of both PIN-a and PIN-b; however, the presence of CaCl₂ (ionic strength 1.0) in the subphase leads to an increase in the values of π_C and A ₀. A change in the pH of the subphase from 3.0 to 7.2 was to have a significant effect on the values of π_C and A ₀, which may be due to the pH-induced alteration of the protein conformation. Received: 8 August 2000 Accepted: 15 December 2000     

Alteration in <Emphasis Type="Italic">α</Emphasis>-tocopherol,some minerals,and fatty acid contents of wheat through sprouting

In this study, two wheat cultivars (cvs Demir 2000 and Konya 2002) were sprouted at 17°C and 85% relative humidity for 9 days. Then the wheat sprouts were dried and ground. The wheats and their sprouts were analyzed for α-tocopherol, some minerals, and fatty acid contents during the sprouting. The α-tocopherol contents of cvs Demir 2000 and Konya 2002 were 26.99 and 23.77 mg/kg, respectively, and these values reached 54.62 and 47.19 mg/kg for their sprouts, respectively. Mineral analyses showed that the mineral contents of the sprouts also increased with sprouting. Fatty acids, e.g., 4:0, 6:0, 8:0, and 10:0, could not be detected in the sprouts while some of them, e.g., cis-18:1 and cis,cis-18:2, were decreasing during sprouting, but an increase in 18:3 n3 (0-3) contents was noted. The results showed that sprouting of wheat grains leads to an increase in some significant functional components.     

FT-IR spectroscopic imaging microscopy of wheat kernels using a Mercury–Cadmium–Telluride focal-plane array detector

A 64×64 Mercury–Cadmium–Telluride (MCT) focal-plane array detector attached to a Fourier transform infrared (FT-IR) microscope was used to spectroscopically image 8-μm-thick cross-sections of wheat kernels in the fingerprint region of the infrared spectrum. After fast-Fourier transformation of the raw image interferograms, the data can be displayed as either a series of spectroscopic images collected at individual wavelengths, or as a collection of IR spectra obtained at each pixel position in the image. Image contrast is achieved due to the intrinsic chemical nature of the sample at each pixel location in the image. Individual cell layers near the outer portion of the wheat kernel, as well as the primary root within the germ, can be clearly differentiated in the IR images as a result of this enhanced chemical contrast.     

Novel aspects of quantitation of immunogenic wheat gluten peptides by liquid chromatography–mass spectrometry/mass spectrometry

A novel, specific and sensitive non-immunological liquid chromatography–mass spectrometry (LC–MS) based assay has been developed to detect and quantify trace levels of wheat gluten in food and consumer products. Detection and quantification of dietary gluten is important, because gluten is a principle trigger of a variety of immune diseases including food allergies and intolerances. One such disease, celiac sprue, can cause intestinal inflammation and enteropathy in patients who are exposed to dietary gluten. At present, immunochemistry is the leading analytical method for gluten detection in food. Consequently, enzyme-linked immunosorbent assays (ELISAs), such as the sandwich or competitive type assays, are the only commercially available methods to ensure that food and consumer products are accurately labeled as gluten-free. The availability of a comprehensive, fast and economic alternative to the immunological ELISA may also facilitate research towards the development of new drugs, therapies and food processing technologies to aid patients with gluten intolerances and for gluten-free labeling and certification purposes. LC–MS is an effective and efficient analytical technique for the study of cereal grain proteins and to quantify trace levels of targeted dietary gluten peptides in complex matrices. Initial efforts in this area afforded the unambiguous identification and structural characterization of six unique physiologically relevant wheat gluten peptides. This paper describes the development and optimization of an LC–MS/MS method that attempts to provide the best possible accuracy and sensitivity for the quantitative detection of trace levels of these six peptides in various food and consumer products. The overall performance of this method was evaluated using native cereal grains. Experimental results demonstrated that this method is capable of detecting and quantifying select target peptides in food over a range from 10 pg/mg to 100 ng/mg (corresponding to approximately 0.01–100 ppm). Limits of detection (LOD) and quantification (LOQ) for the six target peptides were determined to range from 1 to 30 pg/mg and 10–100 pg/mg respectively. Reproducibility of the assay was demonstrated by evaluation of calibration data as well as data collected from the analysis of quality control standards over a period of four consecutive days. The average coefficient of determination (R²) for each peptide was consistently found to be >0.995 with residuals ranging from approximately 80% to 110%. Spike recovery data for each peptide in various matrices was evaluated at a concentration level near the approximate LOQ for each, as well as at higher concentration levels (30 and 60 ng/mg). The average range of accuracy of detection for all peptides at the lower concentration level was determined to be 90% (±11), while accuracy at the 30 and 60 ng/mg levels was 98% (±5%) and 98% (±3%), respectively. The usefulness and capabilities of this method are presented in a practical application to prospectively screen a variety of common commercially available (native and processed) gluten-containing and gluten-free foods and products.     

Synthesis and characterization of di- and trivalent pyrazolylborate β-diketonates and cyanometalates

The syntheses, structures, and magnetic properties of a series of di- and trivalent hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) cyanomanganates are described. Treatment of tris(acetylacetonate)manganese(III) [Mn(acac)(3)] with KTp* and tetra(ethyl)ammonium cyanide affords [NEt(4)][(Tp*)Mn(II)(κ(2)-acac)(CN)] (1), as the first monocyanomanganate(II) complex; attempted oxidation of 1 with iodine affords {(Tp*)Mn(II)(κ(2)-acac(3-CN))}(n) (2) as a one-dimensional chain and bimetallic {[NEt(4)][(Tp*)Mn(II)(κ(2)-acac(3-CN))](2)(μ-CN) (3) as the major and minor products, respectively. A fourth complex, [NEt(4)][(Tp*)Mn(II)(η(2)-acac(3-CN))(η(1)-NC-acac)] (4), is obtained via treatment of Mn(acac(3-CN))(3) with KTp* and [NEt(4)]CN, while [NEt(4)](2)[Mn(II)(CN)(4)] (5) was prepared from manganese(II) trifluoromethanesulfonate and excess [NEt(4)]CN. Tricyanomanganate(III) complexes, [cat][(Tp*)Mn(III)(CN)(3)] [cat = NEt(4)(+), 7; PPN(+), 8], are prepared via sequential treatment of Mn(acac(3-CN))(3) with KTp*, followed by [NEt(4)]CN, or [cat](3)[Mn(III)(CN)(6)] with (Tp*)SnBu(2)Cl. Magnetic measurements indicate that 1, 2, and 4 contain isotropic Mn(II) (S = (5)/(2); g = 2.00) centers, and no long-range magnetic ordering is found above 1.8 K. Compounds 7 and 8 contain S = 1 Mn(III) centers that adopt singly degenerate spin ground states without orbital contributions to their magnetic moments.     

Automatically and electronically controllable hydrogel based valves and microvalves – design and operating performance

This paper describes automatically and electronically controlled valves and microvalves based on smart hydrogels. The operating performance of such devices will be discussed in dependence on various design parameters. Furthermore, it will be shown that hydrogel based valves are showing an outstanding possibility of miniaturization, a leakage free switching behavior up to a pressure drop of 8.4 bar, and a pronounced particle tolerance.     

Syntheses and characterizations of trinuclear and dinuclear “half-sandwich” zirconocene phosphates and phosphonates

A series of six-coordinate “half-sandwich” zirconocene phosphates and phosphonates have been synthesized by the reaction of Cp₂ZrCl₂ with (diphenyl-, dibenzyl-)phosphate and methylphenylphosphinic acid under different conditions. All of the complexes were characterized by elemental analysis, FT-IR and NMR (¹H, ¹³C) spectroscopy. Except for complex 3, the structures of complexes 1, 2, 4, 5, and 6 were confirmed by X-ray crystallography. The structure analyses reveal that complexes 1, 2, and 3 are trinuclear complexes with fascinating μ₃-oxygen bridging ligands, central to a Zr–O backbone (Cp₂ZrCl₂:ligand is 1:1) while complexes 4, 5, and 6 are centrosymmetric dinuclear complexes built up about the trapezoidal Zr₂(μ₂-OH)₂ unit (Cp₂ZrCl₂:ligand is 1:2).     

Synthesis and electrochemical properties of mono- and (±)-1,2-dialkylferrocenes and alkylferrocenium hexafluorophosphates in aqueous and micellar media

Absract Simple methods have been developed for the preparation of a series ofn-alkylferrocenes H(CH₂) _n Fc (n = 3, 5–8, or 12) based on Friedel-Crafts acylation of ferrocenes followed by reduction of the corresponding ketones with Zn amalgam. The properties of H(CH₂) _n Fc and the corresponding ferrocenium ions in micellar aqueous solutions and the behavior of water-soluble cations H(CH₂) _n Fc⁺ in the absence of micelles were studied by cyclic voltammetry. In all cases, the formal redox potentials of ferrocenes (E ^o) increase linearly asn increases up to 8. Whether micelles are present or not, the corresponding correlation equation has the following form:E ^o= + n, where = 29 mV in all cases. The synthesis of (±)-1-ethyl-2-methylferrocene from racemic -dimethylaminoethylferrocene is reported.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2575–2581, October 1996.     

Synthesis and properties of cross-conjugated ��,�ء�-bis-dimethylamino ketones and dinitriles with N-acetyl- and N-benzylpiperidine cycles

Reactions of N-acetyl- and N-benzyl-4-piperidones with aminal of ??-dimethylaminoac-rolein yielded ketocyanines bearing piperidine cycle. Reaction of 3-dimethylamino-1,1,3-trimethoxypropane with 1-acetylpiperidin-4-ylidenemalononitrile in the presence of ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF₄), resulted in cross-conjugated ??,???-dimethylamino dinitrile. Protonation of ketocyanines bearing N-acetyl- and N-benzyl-piperidine cycles with Et₂O·HBF₄ (1 equiv.) furnished piperidinium salts, while protonation of the latter with Et₂O·HBF₄ (2 equiv.) afforded doubly charged 4-hydroxypolymethine salts. Unlike protonation, reaction of 3,5-bis(3-dimethylaminoprop-2-enylidene)-1-acetylpiperidin-4-one with Me₂SO₄ involved only the oxygen atom and led to a singly charged 4-methoxypolymethine salt. Methylation of 3,5-bis(3-dimethylaminoprop-2-enylidene)-1-benzylpiperidin-4-one with Me₂SO₄ (1 equiv.) involved cyclic nitrogen atom and resulted in piperidinium salt; heating of the latter with the excess of Me₂SO₄ afforded doubly charged bis-methoxysulfonate. Starting from 4-methoxytetrahydropyridinium salts, meso-methoxythiapentacarbocyanine dyes were synthesized.     

Di- and Trinuclear σ-Aryl Iron and Manganese Complexes

Reactions of p- and m-diiodobenzenes, p,p'-diiodobiphenyl, and 1,3,5-triiodobenzene with anions derived from dicarbonyl(cyclopentadienyl)iron and pentacarbonylmanganese, catalyzed by palladium complexes, provide a successful route to mono-, di-, and trinuclear -aryl iron and manganese complexes.