Sulfite Formation in Isolated Soy Proteins

ABSTRACT: Defatted soybean flour contained 2820 parts per million (ppm) inorganic sulfate. The corresponding laboratory isolated soy proteins (ISP) contained 1364 ppm sulfate bound to a greater than 3000 molecular weight fraction. Defatted soy flour contained 0.98 nmoles of adenosine triphosphate (ATP) per 0.1 g. ATP levels decreased when the defatted flour was hydrated under a variety of conditions. Neither adenosine-5'-phosphosulfate or 3'-phosphoadenosine-5'-phosphosulfate could be detected in defatted soybean flour or in aqueous extracts of defatted flour. Defatted soy flour contained 1034 ppm reduced glutathione and 647 ppm reduced homogluatathione. These levels dropped to 62 and 13 ppm, respectively, immediately after the isoelectric precipitation step of ISP processing. No oxidized glutathione or homoglutathione were detected. Defatted flour contained 106 ppm cysteine-S-sulfonate, alkaline extracts of defatted flour contained 329 to 579 ppm and ISP contained 0 to 43 ppm. Neither sulfite nor methanethiol were detected until after the soluble components at pH 4.6 were separated from the precipitated soy proteins. These findings indicate that cysteine-S-sulfonate is present in defatted flour and increases during ISP processing. Also, the formation of sulfite during the final stages of ISP processing corresponds to elevated methanethiol levels.     

ZSM-5/MgO质量比对复合催化剂物化性质及合成甲硫醇反应的影响

采用介孔碱性MgO对微孔酸性ZSM-5分子筛进行复合改性,利用液相沉淀包覆技术制备了ZSM-5/MgO复合催化剂,研究了ZSM-5与MgO质量比对复合催化剂物化性质和合成甲硫醇催化性能的影响。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、比表面积及孔隙分析仪(BET)和化学吸附分析仪(CO₂/NH₃-TPD)等手段对不同复合催化剂的晶相组成、微观形貌、孔结构及表面酸碱性进行分析表征。结果表明：ZSM-5/MgO质量比对ZSM-5/MgO复合催化剂的物化性质和催化性能影响较大。过高或过低ZSM-5/MgO质量比制得复合催化剂中MgO结晶度都有所降低,且未形成包覆相结构;ZSM-5/MgO质量比为1/3时制得复合催化剂形成了均匀包覆相结构和微 介孔结构(总比表面积为162 m²/g,总孔体积0.46 cm³/g),同时具有酸碱特性;在反应压力1.0 MPa、反应温度370  ℃、H2S/CH₃OH摩尔比2/1、N₂流速80 mL/min、H₂S流速4.9 mL/min反应条件下合成甲硫醇,复合催化剂表现出优越的催化性能、稳定性及寿命,CH₃OH转化率、CH₃SH选择性和CH₃SH收率分别达到90.48%、90.04%和81.47%,催化剂寿命达到18 h。与单一ZSM-5分子筛相比,复合催化剂寿命延长了7 h,CH₃SH收率提高了13.97百分点。     

Intrinsic sulfite content of isolated soy proteins

Commercial isolated soy proteins (ISP) contain 22 and 31 ppm sulfite as measured by the optimized Monier-Williams method (Sulfites in Foods, Official Methods of Analysis, 16th edn., AOAC, Washington, DC, 1995, Official Method 990.28). A method was developed to cryogenically trap and quantify the sulfur dioxide produced by this method using GC-MS. The same commercial ISP samples were found to contain 17 and 26 ppm sulfite, respectively, with GC-MS. ISP prepared in the laboratory contained 33 ppm sulfur dioxide, and defatted soybean flakes contained only a trace. Adding dithiothreitol after beginning the boiling step of the Monier-Williams assay had no significant effect on the sulfite content of a commercial ISP, whereas adding dithiothreitol prior to bringing the sample to a boil reduced the sulfite content from 17 to about 1 ppm.     

On methanethiol synthesis from H2S‐containing syngas over K2MoS4/SiO2 catalysts promoted with transition metal oxides

The catalysts K₂MoS₄/SiO₂ promoted with transition metal oxides Fe₂O₃, CoO, NiO and MnO₂ were prepared and used to catalyze the synthesis of methanethiol from H₂Scontaining syngas. The results of activity assay show that the catalysts promoted with Fe₂O₃, CoO and NiO can remarkably increase the hour space yield of methanethiol. Nevertheless, MnO₂ was found to have a disadvantageous effect on the selectivity of methanethiol. The results of XRD and XPS characterization indicate that the addition of the transition metal oxides promoters is in favor of the formation of a Mo–S–K active phase and also retards the decomposition of K₂MoS₄ to MoS₂, thereby suppressing both the deep reduction of Mo species and the formation of (S–S)² species, which are reflected by the increment of the concentration ratios of both Mo⁶⁺/Mo⁴⁺ and S²/(S–S)².     

载体酸碱性对高硫合成气制甲硫醇的K-Mo-Co催化剂结构和性能的影响

选取3种酸碱性不同的载体(γ-Al2O3,SiO2,MgO)制备由高硫合成气制甲硫醇的负载型K-Mo-Co催化剂。它们的活性高低顺序为:K2MoCo0.35O/SiO2>K2MoCo0.35O/γ-Al2O3>K2MoCo0.35O/MgO;程序升温脱附表征结果显示,这3种不同载体的催化剂与载体的酸碱性强弱顺序一致,弱酸性载体制备的催化剂对合成甲硫醇有利;H2程序升温还原和激光Raman光谱表征结果显示,碱性载体制备的催化剂中,Mo以易于还原和硫化的八面体构型存在,硫化后主要以MoS2存在;弱酸性载体制备的催化剂中,Mo以难于还原和硫化的四面体构型存在,硫化后主要以氧硫钼物种存在,这些物种与合成甲硫醇密切相关。     

Factors Influencing the Occurrence of Methanethiol in Aqueous Slurries of Soy Protein Concentrates

: Aqueous slurries of 6 commercial soy protein concentrate (SPC) contained from 9.8 to 21.7 ppb methanethiol, which corresponds to odor values (in water) of 49 to 108. Effects of temperature (5.5, 24, and 65°C), pH (4.8,6.6, and 9.0), transition metals (FeCl₃, FeCl₂, and CuCl₂), lipoxygenase, and EDTA on methanethiol levels in SPC slurries were investigated. Higher temperature (65°C), basic pH (9.0), transition metals, lipoxygenase, and EDTA caused significant increases in methanethiol compared with the control. CuCl₂ caused greater increases in methanethiol than FeCl₃ and FeCl₂. In contrast, treatments with lower temperature (5.5°C) or acidic pH (4.8) resulted in lower levels of methanethiol in all commercial SPC samples examined.     

1-(并二甲硫基)甲基-4-甲氧基苯的合成

０．１５ｍｏｌ茴香醛和０．６ｍｏｌ甲硫醇在９ｍｍｏｌ对甲苯磺酸催化下发生反应，合成了相应的缩硫醛，产率８３．７％。通过红外光谱、元素分析、核磁共振检测对产物结构进行了确证。此外，浓硫酸、氯化锌也是反应的催化剂。     

Headspace Evaluation of Methanethiol and Dimethyl Trisulfide in Aqueous Solutions of Soy-protein Isolates

Volatile compounds from 2 samples of aqueous soy‐protein isolates (SPI) (7%) were analyzed using both static and dynamic headspace methods. Based on dynamic headspace analyses, the most powerful odorants were (1) dimethyl trisulfide, (2) methanethiol, (3) hexanal, (4) an unidentified charred, sweaty feet‐like odor, (5) 2‐pentyl furan, (6) 2,3‐butadione, and (7) an unknown burnt‐like odor. The most powerful odorants by static headspace analyses were (1) dimethyl trisulfide, (2) hexanal, (3) methanethiol, and (4) 2‐pentyl furan. Using deuterium labeled DMTS as an internal standard, DMTS was quantified at 60.1 and 45.5 ppb in the SPIs. This corresponds to odor values of 6014 and 4554, respectively. Using a cool, on‐column technique, direct injection of concentrated‐headspace volatiles and solvent‐recovered volatiles with an internal standard of d₆‐DMTS detected both methanethiol and DMTS at similar levels as with the traditional injection methods.     

Olfactory Perception of Major Odorants Found in the Headspace of Aqueous Soy Protein Isolate Slurries

ABSTRACT: Concentrations of hexanal, methanethiol, 2‐pentyl furan and dimethyl trisulfide (DMTS) in the headspace above aqueous soy protein isolates (SPI) slurries were quantified through gas chromatography/ mass spectrometry (GC/MS). Simulation of the characteristic odor of SPI was attempted by combining these 4 odorants in water to recreate headspace concentrations found above the aqueous slurries of SPI. Sensory characteristics of the combined odorants were compared with each individual odorants. The mixture of combined odorants was perceived to possess more resemblance to the characteristic odor of SPI than any individual odorant and was rated a 5 on a 10‐point scale. A 2nd sensory evaluation showed that 2‐pentyl furan suppressed the perceived intensity of DMTS.     

Sulfite-radical anions in isolated soy proteins

ABSTRACT:  Aqueous mixtures of manganese and sulfite, at levels found in isolated soy proteins (ISP) and defatted soy flakes, spontaneously react in the presence of oxygen to produce methanethiol from the 1-electron oxidation of methionine. The carbon and sulfur of methanethiol originate from the methyl-carbon and sulfur of methionine. Similar aqueous mixtures of sulfite, manganese, and oxygen also produce sufficient levels of free radicals to degrade fluorescein. The degradation of methionine by free radicals generated in the sulfite, manganese, and oxygen reaction mixture is inhibited by the free radical spin trapping agent 5,5-dimethyl-1-pyrroline N-oxide. Processing ISP with either L-cystine or potassium iodate reduces the free sulfite content of ISP and reduces the headspace methanethiol from aqueous ISP slurries to nondetectable levels. ISP processed without additives contained sufficient levels of free radicals to generate methanethiol from the oxidation of added methionine. There were no detectable levels of methanethiol produced when methionine was added to ISP processed with iodate.