Academic literature on the topic 'Sulfur-containing organic compounds'

Background: Sulfur-containing compounds represent an important class of chemical compounds due to their wide range of biological and pharmaceutical properties. Moreover, sulfur-containing compounds may be applied in other fields, such as biological, organic, and materials chemistry. Several studies on the activities of sulfur compounds have already proven their anti-inflammatory properties and use to treat diseases, such as Alzheimer’s, Parkinson’s, and HIV. Moreover, examples of sulfur-containing compounds include dapsone, quetiapine, penicillin, probucol, and nelfinavir, which are important drugs with known activities. Objective: This review will focus on the synthesis and application of some sulfur-containing compounds used to treat several diseases, as well as promising new drug candidates. Results: Due to the variety of compounds containing C-S bonds, we have reviewed the different synthetic routes used toward the synthesis of sulfur-containing drugs and other compounds.

The paper discusses selection of a set of metals for an electrochemical test system used for the detection of sulfur-containing organic substances. Analytical studies of organic sulfur compounds are very important since these compounds are widely used in medicine, biology, oil refining industry, etc. Quantitative determination and identification of sulfur-containing substances is essential for solving environmental problems. The electrochemical test system for analysis of organic substances is a solution containing a set of cations of various metals that have the ability to form complex compounds with analytes. Thereby, a single electrode can be used to carry out electrochemical multisensory analysis because metal cations play the role of sensors. Thus, there is no need to use a set of several working (indicator) electrodes, the number of which determines the number of informative parameters. Since sets of metals for test systems may slightly differ from each other, we need to select an optimal set for a specific problem. According to the study results, a set of metals for sulfur-containing organic substances consists of zinc, gallium and copper. The test system composed of these metals gives reliable results of electroanalytical determination of organic compounds of this class. The expediency of using such a test system is confirmed by comparative estimation of the Euclidean distances between the vector representations of the analytes and sulfur-containing organic compounds presented in the previously created database. Software for experimental data processing, visualization, and comparative analysis of the vector representations and the database components is developed.

Purpose This study aims to investigate the compositional characteristics of aromatic hydrocarbons extracted from coals and to describe how the sulfur content influences the properties of coals and whether widely accepted maturity parameters are suitable for medium- to high-sulfur coal. Design/methodology/approach Four samples of medium- to high-sulfur coal were obtained from Fenxi, Shanxi Province, and studied using gas chromatography and gas chromatography–mass spectrometry (GC-MS). Findings The GC-MS results showed that there were five series of compounds were identified in the aromatic fractions: naphthalenes, phenanthrenes, oxygen-containing compounds, biphenyls and sulfur-containing compounds. The substituent group was mainly methyl. The content of dibenzothiophenes was high, which was attributed to their high thermodynamic stability. The presence of sulfur reduced the content of oxygen-containing compounds. A depositional environment that facilitated the formation of organic sulfur compounds led to a higher content of naphthalenes. Originality/value The development of methods for removing organic sulfur compounds would benefit from a study of their nature, which would be important for improving the use of coal.

The corrosion inhibition performance of pyridine derivatives (4-methylpyridine and its quaternary ammonium salts) and sulfur-containing compounds (thiourea and mercaptoethanol) with different molar ratios on carbon steel in CO2-saturated 3.5 wt.% NaCl solution was investigated by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy, and scanning electron microscopy. The synergistic corrosion inhibition mechanism of mixed inhibitors was elucidated by the theoretical calculation and simulation. The molecules of pyridine derivative compounds with a larger volume has priority to adsorb on the metal surface, while the molecules of sulfur-containing compounds with a smaller volume fill in vacancies. A dense adsorption film would be formed when 4-PQ and sulfur-containing compounds are added at a proper mole ratio.

ABSTRACT DAMASCENOLIDETM [1, 4-(4-methylpent-3-en-1-yl)furan-2(5H)-one], which is isolated from damask rose, is a useful aroma compound with a citrus-like odor. We have previously reported on the synthesis and odor properties of 34 analogs of 1 as part of our new aroma compound development project. In order to develop better aroma compounds and to gather more information on structure–odor relationships, 6 novel sulfur-containing analogs of 1 were synthesized. Odor evaluation revealed that their odors differed significantly from those of the corresponding sulfur-free compounds. The introduction of a sulfur atom does not necessarily result in a sulfur-like odor. In particular, the 2(5H)-thiophenone analogs gave waxy, oily, and lactone-like odors that are uncharacteristic of sulfur-containing compounds. In many synthesized analogs, the introduction of a sulfur atom led to an increase in odor intensity, as expected.

Abstract. Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gaseous and particulate phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at Storm Peak Laboratory near Steamboat Spring, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh resolution mass spectra of the samples after using a reverse phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen containing compounds (CHNO compounds), sulfur containing compounds (CHOS and CHNOS compounds) and other oxygen containing compounds (CHO compounds) with molecular weights up to 700 Da were observed. Average oxygen-to-carbon ratios of ~0.6 indicate a slightly more oxidized composition than most water-soluble organic carbon identified in aerosol studies, which may result from aqueous oxidation in the clouds. The AOM composition indicates significant influences from biogenic secondary organic aerosol (SOA) and residential wood combustion. We observed 60% of the cloud water CHO molecular formulas to be identical to SOA samples of α-pinene, β-pinene, d-limonene, and β-caryophyllene ozonolysis. CHNO compounds had the highest number frequency and relative abundances and are associated with residential wood combustion and NOx oxidation. We observed multiple nitrogen atoms in the assigned molecular formulas for the nighttime cloud sample composite indicating the significance of nighttime emissions or NOx oxidation on the AOM composition. Several CHOS and CHNOS compounds with reduced sulfur (in addition to the commonly observed oxidized sulfur containing compounds) were also observed, however further investigation is needed to determine the origin of the reduced sulfur containing compounds. Overall, the molecular composition determined using ultrahigh resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry provides an unambiguous identification of the cloud water organic composition in the Rocky Mountain area which could help to improve the understanding of aqueous phase processes.

This thesis documents the development of novel methodologies for access to sulfur-containing compounds, including sulfones, sulfonamides and benzoisothiazoles. Chapter 1 provides an overview of the applications and the synthesis of sulfonyl-containing compounds. A comprehensive introduction to the development of sulfur dioxide surrogates and their applications in transition metal-catalysed organic chemistry is given. Chapter 2 describes the development of a one-step copper(I)-catalysed sulfonylative Suzuki-Miyaura cross coupling reaction. A wide range of aryl and alkenyl boronic acids are coupled with aryl and alkenyl iodides to give the corresponding sulfones. A two-step one-pot sulfination/derivatisation method was also developed, allowing access to compounds including β-hydroxy sulfones, sulfonamides and sulfonyl fluorides. Chapter 3 illustrates a one-step copper(II)-catalysed sulfonamide synthesis using boronic acids, amines and SO2. Various aryl and alkenyl boronic acids as well as amines and anilines are compatible, including active pharmaceutical ingredients such as amoxapine and desloratadine. Chapter 4 details an aryne-based selective formation of substituted benzoisothiazoles. Different substitution pattern of the aryne precursor and the thiadiazole are employed, with the target heterocycles being obtained in good to excellent yields. Chapter 5 summarises the research and the future work. Chapter 6 documents the experimental procedures and data.

A systematic investigation has been carried out on the rhodium(I) catalyzed carbonylation of heterocyclic and acyclic compounds containing two heteroatoms at the 1,3-positions. The regioselectivities of carbon monoxide insertion are different in cyclic and acyclic compounds. When there is a choice between C-S and C-N bonds, in acyclic compounds, carbonylation of the C-N bond is more facile and the C-S bond is more easily carbonylated in acyclic compounds. When there is a possibility of ring or side chain carbonylation, it appears that the C-X bond of the side chain is more reactive. Rhodium(I) was also used to catalyze the carbonylation reaction of the N-O bond of isoxazolidine derivatives. When Ir-complexes were used as catalysts, the carbonylation occured and was followed by hydrogen transfer affording tetrahydro-1,3-oxazines as the final products. It was also found that substituents on the isoxazolidines have a dramatic effect on the reactivity of these substrates.

Abstract The work in this thesis concentrates on finding more active and durable catalysts for the demanding environmental application of the oxidation of sulfur-containing volatile organic compounds (S-VOCs). This application is challenging due to the high purification levels required and the catalyst deactivating nature of sulfur. In this thesis, dimethyldisulfide (DMDS) was used as the model molecule to represent S-VOCs since it is often present in odorous emissions and it is more difficult to treat than most of the other S-VOCs. It was found that the addition of a very small amount of Pt (0.3%) especially improves the selectivity of copper oxide based catalysts towards complete oxidation products ((carbon dioixide (CO2), water (H2O) and sulfur dioxide (SO2)) in DMDS oxidation. Catalyst characterization by transmission electron microscopy, temperature programmed reduction and X-ray photoelectron spectroscopy analyses suggests that this promoting effect is most likely due to the close interaction between Cu and Pt species on the bimetallic PtCu/γ-Al2O3 catalyst. The drawback of using the Al2O3 support is that it is not resistant towards sulfur poisoning. The deactivation of the self-made catalysts was studied with the help of an accelerated ageing procedure that was developed based on the information from the industrially aged volatile organic compound (VOC) catalysts. Industrial deactivation was caused by the sintering of the support and active metals and by the formation of metal sulfates with the support. After accelerated ageing, the silica doped alumina (Al2O3)0.8(SiO2)0.2 supported catalyst, showed remarkably promising results in terms of stability towards sulfur poisoning and the activity in DMDS oxidation was very close to that of the most active PtCu/Al2O3. The addition of less than 20% of SiO2 on the Al2O3 support led to a catalyst that is more selective and resistant to sulfur poisoning
Tiivistelmä Väitöskirjassa tuotetaan uutta tietoa rikkipitoisten orgaanisten yhdisteiden (S-VOC) hapetukseen soveltuvien uusien katalyyttisten materiaalien synteesistä ja karakterisoinnista. S-VOC-yhdisteiden käsittely on vaativa katalyyttisen polton sovellus, koska näiden päästöjen käsittely edellyttää korkeaa puhdistustehoa, ja lisäksi yhdisteiden sisältämä rikki on katalyyttimyrkky. Tässä väitöskirjassa valittiin S-VOC-yhdisteitä edustavaksi malliaineeksi dimetyylisulfidi (DMDS), koska se on usein mukana käsiteltävissä S-VOC-päästöissä ja sen käsittely on vaativampaa kuin useiden muiden S-VOC-yhdisteiden käsittely. Tutkimustulosten mukaan hyvin pieni Pt-lisäys (0.3 %) parantaa erityisesti kuparioksidikatalyyttien selektiivisyyttä DMDS:n kokonaishapetustuotteiksi (CO2, H2O, SO2). Katalyyttien karakterisoinnin (läpäisyelektronimikroskopia, lämpötilaohjattu pelkistysreaktio, röntgensädefotoelektronispektroskopia) perusteella voidaan esittää parannuksen syyksi kuparin ja platinan läheinen kontakti bimetallisen PtCu/γ-Al2O3-katalyytin pinnalla. Al2O3-tukiaineen heikkoutena on sen deaktivoitumisherkkyys rikkiyhdisteiden läsnä ollessa. Väitöskirjatyössä valmistettujen katalyyttien deaktivitumista tutkittiin laboratoriomittakaavassa nopeutettujen ikäytyskokeiden avulla, jotka kehitettiin teollisessa käytössä deaktivoituneen katalyytin karakterisointien avulla saadun tiedon perusteella. Teollisessa käytössä olleen katalyytin deaktivoitumisen syyksi havaittiin tukiaineen ja aktiivisten metallien sintrautuminen sekä metallisulfidien muodostuminen tukiaineen kanssa. Nopeutettujen ikäytyskokeiden tulosten perusteella havaittiin, että piidioksidin lisäys alumiinioksiditukiaineeseen paransi tukiaineen rikin kestoa merkittävästi. Tutkimuksissa havaittiin myös, että piidioksidilla muokatun katalyytin aktiivisuus oli hyvin lähellä vastaavaa PtCu/γ-Al2O3-katalyytin aktiivisuutta. DMDS:n hapetuksessa selektiivisempi ja stabiilimpi katalyytti voidaan aikaansaada alle 20 %:n SiO2-lisäyksellä Al2O3-tukiaineeseen

Дисертація присвячена вирішенню важливої науково-технічної проблеми: підвищенню корозійної стійкості та експлуатаційно-технічних властивостей металевих виробів, устаткування та пристроїв шляхом використання синергетичних адсорбційних інгібіторів корозії широкого спектру захисної дії. Розроблено науково-обґрунтований підхід до створення ефективних інгібіторів корозії на основі поліфункціональних органічних сполук та комбінацій органічних сполук і солей металів. Підхід базується на комплексному дослідженні процесів адсорбції, встановленні взаємозв’язку між будовою органічних сполук, їх адсорбційними захисними властивостями, визначенні особливостей кінетики парціальних реакцій конкретних видів корозії і шляхів впливу на них інгібіторів, врахуванні ефектів внутрішньомолекулярного і міжмолекулярного синергізму, які виникають при інгібуванні корозії. Досліджено закономірності адсорбції та захисної дії при кислотній корозії заліза та вуглецевих сталей різних за хімічним складом монофункціональних і поліфункціональних органічних сполук. Виявлена роль амінних, піридинієвих, карбонільних, тіокарбонільних, карбоксильних груп в захисній дії цих інгібіторів. Розвинені сучасні наукові положення щодо механізму захисної дії органічних інгібіторів корозії та ролі різних частинних ефектів її інгібування. Запропоновано і експериментально обґрунтовано рівняння, яке встановлює взаємозв’язок між кінетичними параметрами корозійних процесів, захисною дією інгібіторів та їх адсорбційними властивостями з урахуванням механізму анодного розчинення заліза. Досліджено і науково обґрунтовано ефекти внутрішньомолекулярного і міжмолекулярного синергізму, які виникають при інгібуванні корозії металів поліфункціональними органічними сполуками з атомами Нітрогену, Оксигену, Сульфуру та сумішами органічних і неорганічних сполук різного механізму захисної дії. Встановлено, що амінні та піридинові фрагменти поліфункціональних органічних сполук забезпечують їх захисну дію за енергетичним механізмом при невисоких температурах, а тіокарбонільних та карбоксильних – при підвищених. Висвітлено взаємозв’язок між характером сил взаємодії між адсорбованими частинками та їх захисною дією при кислотній корозії заліза. Запропоновано новий тип синергетичних інгібіторів кислотної, сольової та лужної корозії цинку на основі сумішей органічних сполук і катіонів металів. Встановлено роль модифікації поверхневих властивостей цинку, що відбувається внаслідок протікання різних електрохімічних процесів в захисній дії цього типу інгібіторів корозії. Розроблена модель адсорбції органічних сполук на металах, заснована на уявленнях про утворення комплексів з частинним переносом заряду та прогнозуванні її протікання з використанням принципу ЖМКО Пірсона. На підставі застосування запропонованої моделі адсорбції розроблено напрямки створення нових ефективних інгібіторів корозії, засновані на врахуванні адсорбційних властивостей металів, специфіки механізмів корозії, ефектів синергізму їх захисної дії. Розроблено нову серію органічних інгібіторів корозії на основі четвертинних піридинієвих солей з карбонільними групами широкого спектру дії і поліфункціонального призначення (кислотна корозія, мікробна корозія металів в умовах бактеріальної сульфатредукції, кислотне корозійно-механічне руйнування сталей). Досліджено взаємозв’язок між захисною дією органічних сполук, електронними та стеричними властивостями їх замісників та природою додаткових функціональних угрупувань, схильних до безпосередньої адсорбції на сталі. Виявлено роль біологічного та електрохімічного факторів при інгібуванні корозії металів в умовах бактеріальної сульфатредукції. Науково обґрунтовано ефект синергізму захисної дії органічних сполук під впливом продуктів метаболізму бактерій (HS - , H S). Досліджено вплив інгібіторів на саморозряд, електричні та розрядні 2 характеристики цинкових та кадмієвих анодів хімічних джерел струму. На підставі використання розроблених інгібіторів корозії запропоновано удосконалені свинцево-цинкові та свинцево-кадмієві елементи з кислотними електролітами, марганцево-цинкові елементи водно-сольової та водно-лужної системи. Встановлена перспективність застосування комбінованого протикорозійного захисту вуглецевих сталей в водних агресивних середовищах на основі сумісного використання дифузійних покриттів та інгібіторів корозії.

博士
國立中山大學
環境工程研究所
95
DMSO (dimethyl sulfoxide) is a liquid with a high boiling point (189 oC) that has been extensively utilized in various industries owing to its ability to dissolve various organic and inorganic compounds. DMSO is increasingly being adopted as a detergent or a photo-resistant stripping solvent in manufacturing semiconductors and liquid crystal displays (LCD). Therefore, DMSO is now a major component of wastewater. The biological treatment of DMSO-containing wastewater generates noxious DMS (dimethyl sulfide) and other compounds that may cause odor problems. Also having a high water solubility and a moderate boiling point (110 oC), tetrafluoro propanol (TFP) has been extensively applied in the manufacture of CD-R and DVD-R, due to its ability to dissolve organic dyes. The spin coating process produces a large amount of wastewater containing TFP. No reports have been written on the biodegradability of TFP to the authors’ knowledge. Additionally, HMDS (hexamethyldisilazane) has been extensively used in life science microscopy and material science. For instance, the semiconductor industry employs HMDS to promote the adhesion of photo-resistant material to oxide(s). HMDS is classified as a carcinogen, and has an ammonia odor. Condensing incinerators have been found to be unsuitable for treating HMDS-containing waste gases, because of the formation of silicon dioxide, which blocks porous adsorbents. Biological treatment also appears to be unpromising due to its low water solubility and limited biodegradability. This investigation evaluates the feasibility, effectiveness and oxidation characteristics of aqueous DMSO, TFP and gaseous HMDS (hexamethyldisilazane) by UV/O3 processes. A reactor made entirely of acrylic plastic with an effective volume of 10 L was employed for the reactions. The tested VOCs concentrations were adjusted to 400–890mg/L and 772–887 mg/L for DMSO and TFP, respectively, and the gas (ozone-enriched air) flow rate was controlled at 3L/min. The effects of various solution pH values (acidic, alkaline, uncontrolled), solution temperatures (26 oC, 37 oC, 48 oC and 60 oC), and UV wavelengths (254 nm and 185+254 nm) on the removal of tested VOCs were studied . Additionally, the operation costs of treating DMSO and TFP by UV/O3 were estimated. Experimental results demonstrate that acidic conditions (pH = 3.6) favored the degradation of DMSO, and that the removal efficiency could reach 95% at a volumetric UV intensity P/V of 2.25 W/L and a reaction time of 120 min. However, alkaline conditions (pH = 9.5) favored the decomposition of TFP, with the removal efficiency reaching 95% at P/V = 2.5 W/L and a reaction time of 60 min. Both DMSO and TFP exhibited zero-order degradation kinetics when sufficient ozone was supplied. Raising the oxidation temperature did not increase the UV/O3 oxidation of TFP in the tested concentration and temperature ranges. Operation costs of the UV/O3 per unit volume of wastewater with DMSO or TFP are comparable to those of the methods described in the literature. For the gaseous HMDS oxidation, two batch reactors with effective volumes of 1.2 and 5.8 L were used employed with the decomposition occurred under UV (185+254 nm) irradiation and UV (254 nm)/O3 processes. Tests were performed with initial HMDS concentrations of 32–41mg/m3 under various initial ozone dosages (O3 (mg)/HMDS (mg) =1–5), atmospheres (N2, O2, and air), temperatures (28 oC, 46 oC, 65 oC and 80 oC), relative humilities (20%, 50%, 65% and 99%) and volumetric UV power inputs (0.87 W/L, 1.74 W/L, 4.07 W/L and 8.16 W/L) to assess their effects on the HMDS degradation rate. Results of this study demonstrate that the decomposition rates for the UV (185+254 nm) irradiation exceeded those for the UV (254 nm)/O3 process for all conditions. UV (185+254 nm) decompositions of HMDS displayed apparent first-order kinetics. A process with irradiation of UV (185+254 nm) to HMDS in air saturated with water at temperatures of 46–80 oC favors the HMDS degradation. With the above conditions and a P/V of around 8 W/L, k≈ 0.20 s−1, and over 90% of the initial HMDS was degraded in a time of 12s. The main mechanisms for the HMDS in wet air streams irradiated with UV (185+254 nm) were found to be caused by OH free radical oxidation produced from photolysis of water or O (1D) produced from photolysis of oxygen. Economic evaluation factors of UV (185+254 nm) and UV (254 nm)/O3 processes at various UV power inputs were also estimated.

腐乳是中國傳統豆類發酵製品，具有綿軟的口感和特殊的風味。其是豆腐通過真菌固態發酵，并加入鹽，米酒和香料等進行後期熟化而成的產品。本文的研究分為兩部份，第一部份對腐乳發酵過程中的毛胚，鹽胚，熟化第一天，熟化一個月以及熟化六個月的腐乳樣本進行採樣，并採用傳統微生物培養法和克隆文庫法對每個階段真菌和細菌的生態結構和動態變化進行研究。第二部份重點比較了四株腐乳產品中分離的微生物和購自台灣生物資源保存及研究中心的四株細菌的產揮發性含硫化合物能力，并挑選了最高產的一株微生物進行紫外誘變，最後獲得理想的突變株。本研究的結論如下：
1. 真菌和細菌的總數均是在毛胚階段為最高，在進入熟化階段后開始下降。在傳統微生物培養方法下分別分離出了三株真菌和九株細菌，通過18S rDNA和16 rDNA測序，發現絲孢酵母屬（Trichosporon spp.）是真菌中的優勢菌種，蠟狀芽孢桿菌（Bacillus cereus）和解澱粉芽孢桿菌（Bacillus amyloliquefaciens）為細菌中的優勢菌種；
2. 本研究建立了五個真菌18S rDNA克隆文庫和五個細菌16 rDNA克隆文庫用于研究真菌和細菌的生態結構和動態變化。通過聚合酶鏈式反應-限制性片段長度多態性（PCR-RFLP）的研究，分別在真菌和細菌克隆文庫中發現23和38種圖譜類型，并計算其相應比例。在進行真菌細菌測序之後，對優勢菌群進行了定性和定量分析；
3. 在對比傳統微生物培養方法和克隆文庫技術的結果后發現，二者的結果存有差異，有些在克隆文庫中鑒定到的微生物在傳統培養方法中未能分離鑒定，而有些微生物則只能在傳統培養方法中被分離鑒定。因此，本研究中將這兩種方法結合有助於我們更為全面、客觀地研究腐乳發酵過程中真菌和細菌的生態結構和多樣性。
4. 對四株腐乳中分離純化的微生物和四株外來購入細菌的產揮發性含硫化合物能力進行比較，結果發現，從腐乳產品中分離純化的B-1菌株擁有最高的產揮發性含硫化合物能力，通過紫外誘變后，突變株#3在產揮發性含硫化合物以及L-蛋氨酸代謝酶活力都比初始菌株有了顯著的提升。B-1菌經測序比對后鑒定為絲孢酵母（Trichosporon sp.）。
本研究結果對于傳統腐乳發酵的有效控制和現代腐乳生產工藝的建立有一定指導意義，並且對於腐乳產品中的風味物質，特別是揮發性含硫化合物的產生和優化提供信息。
Sufu (fermented soybean curd) is a soft creamy cheese-type product with a pronounced flavor and is made by fungal solid state fermentation of tofu (soybean curd) followed by aging in brine containing salt and alcohol. In first part of this research, the eco-structure and the dynamic changes of microbes during sufu production process (Pehtze, Salted pehtze, 0 Month sufu, 1 Month sufu and 6 Month sufu sample) were studied by combined microbiology techniques, including plate culture, 16S rDNA and 18S rDNA clone library and restriction fragment length polymorphism (RFLP) analysis. The second part of this research focus on the comparison of volatile sulfur-containing compounds (VSCs) production ability within isolated strains in sufu product and bacteria purchased commercially, the strain that possessed highest ability was selected and followed by a UV mutation experiment, finally obtained the desired mutant. The results of this research are as followed:
1. The population of both fungi and bacteria were all at highest number in Pehtze stage and started to decrease in ripening stages. A combined total of three and nine living strains of fungi and bacteria were obtained from the plate culture, respectively. Through 18S rDNA and 16S rDNA sequencing, Trichosporon spp. was the dominant fungi and Bacillus cereus and Bacillus amyloliquefaciens were the dominant bacteria;
2. Five 18S rDNA clone libraries and five 16S rDNA clone libraries from different stages of sufu production were constructed to analyze the structure and dynamic changes of fungi and bacteria. A total of 23 and 38 RFLP patterns were found, and the ratio of each pattern were calculated. After sequencing, qualitative and quantitative analysis on the dynamic changes of dominant strains was performed;
3. After comparing the results of plate culture and clone library, it was found that there were some differences between the two. Some strains were only found in clone library while some only found in plate culture approach. Therefore, the combination of the two microbiology methods will help us to objectively and completely analyze the structure and dynamic changes of microbes in the sufu production process;
4. The ability to produce VSCs within four strains (B-1, B-2, B-3 & B-4) isolated from a commercial sufu manufacturing process and four commercial strains (B. acetylicum, L. Lactics, S. thermophilus and L. Paracasei) were compared. Results showed that B-1 possessed both the highest VSCs production ability and L-methionine metabolism enzymatic activities among the eight strains. After UV light mutagenesis of B-1 strain, its mutant #3 significantly increased in DMDS and DMTS production and all four L-methionine-related enzymatic activities in reference to that of the starting strain (B-1). B-1 was identified as Trichosporon sp. by sequencing.
These results would make a profound significance on the control of traditional sufu production and the development of new technology for modern sufu manufacturing. They will also help to provide some important information of optimal production of VSCs in sufu ripening and the overall flavor in sufu product.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Detailed summary in vernacular field only.
Huang, Ruolan.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2012.
Includes bibliographical references (leaves 106-117).
Abstracts also in Chinese.
Abstract --- p.i
摘要 --- p.iii
Acknowledgement --- p.v
Table of contents --- p.vi
List of Figures --- p.x
List of Tables --- p.xiii
Chapter Chapter 1 --- : Introduction --- p.1
Chapter 1.1 --- Sufu --- p.1
Chapter 1.1.1 --- Classification --- p.1
Chapter 1.1.1.1 --- Classified by processing technology --- p.1
Chapter 1.1.1.2 --- Classified by color and flavor --- p.1
Chapter 1.1.1.3 --- Other classifications --- p.2
Chapter 1.1.2 --- Typical commercial manufacturing process --- p.2
Chapter 1.1.2.1 --- Production process of naturally fermented sufu --- p.2
Chapter 1.2.2.2 --- Production process of traditional mold-based sufu --- p.5
Chapter 1.2.2.3 --- Production process of traditional bacteria-based sufu --- p.5
Chapter 1.2.2.4 --- Acceleration of sufu ripening process --- p.6
Chapter 1.1.3 --- Important ingredients in sufu production --- p.6
Chapter 1.1.4 --- Flavor components in sufu --- p.7
Chapter 1.1.4.1 --- Volatile flavor components --- p.7
Chapter 1.1.4.2 --- Essential odor in sufu product --- p.8
Chapter 1.1.4.3 --- Volatile sulfur compounds in sufu --- p.9
Chapter 1.1.4.4 --- Using Head Space-Solid phase Microextraction (HS-SPME) to analyze the volatile sulfur components --- p.9
Chapter 1.1.5 --- Relationship between microbes and sufu --- p.12
Chapter 1.1.5.1 --- Microbes involved in fermentation process --- p.13
Chapter 1.1.5.2 --- Microbial changes during the production of sufu --- p.14
Chapter 1.1.6 --- Study on microbial ecology in food product --- p.15
Chapter 1.1.6.1 --- PCR-based molecular techniques --- p.16
Chapter 1.1.6.2 --- Non-PCR based molecular techniques --- p.16
Chapter 1.1.6.3 --- The common techniques used in microbial ecology research --- p.17
Chapter 1.1.6.4 --- Microbial ecology study by molecular biological techniques --- p.18
Chapter 1.2 --- Objectives --- p.19
Chapter Chapter 2 --- : Analysis of fungi diversity during sufu fermentation process --- p.21
Chapter 2.1 --- Introduction --- p.21
Chapter 2.2 --- Materials and methods --- p.21
Chapter 2.2.1 --- Sample collection and preparation --- p.22
Chapter 2.2.2 --- Plate count of fungi during sufu fermentation process --- p.22
Chapter 2.2.3 --- Change of pH values and moisture content --- p.22
Chapter 2.2.4 --- Total DNA extraction from fungi --- p.23
Chapter 2.2.5 --- Preparation of competent cell --- p.23
Chapter 2.2.6 --- 18S rDNA PCR amplification and construction of 18S rDNA clone library --- p.24
Chapter 2.2.7 --- RFLP analysis of 18S rDNA clone library --- p.25
Chapter 2.2.8 --- DNA sequencing for fungi identification --- p.26
Chapter 2.2.9 --- Analysis of the diversity of 18S clone library --- p.26
Chapter 2.2.10 --- Frequency percentage analysis --- p.27
Chapter 2.2.11 --- Enzyme Solutions --- p.27
Chapter 2.2.12 --- Determination of protease activity --- p.28
Chapter 2.2.13 --- Determination of lipase activity --- p.29
Chapter 2.2.11 --- Microtox test --- p.30
Chapter 2.2.12 --- Statistical analysis --- p.30
Chapter 2.3 --- Results and discussion --- p.30
Chapter 2.3.1 --- Fungi growth on plate counting result --- p.30
Chapter 2.3.2 --- Changes in pH and moisture content of sufu during production --- p.33
Chapter 2.3.3 --- Construction and selection of 18S rDNA clone library --- p.35
Chapter 2.3.4 --- Fungal diversity based on 18S rDNA clone library analysis --- p.38
Chapter 2.3.5 --- Protease and lipase activities in Actinomucor elegans and Trichosporon japonicum --- p.45
Chapter 2.3.5.1 --- Protease activity --- p.46
Chapter 2.3.5.2 --- Lipase activity --- p.47
Chapter 2.3.6 --- Toxicity of Actinomucor elegans and Trichosporon japonicum --- p.49
Chapter 2.3.7 --- Analysis of fungi eco-structure and function during sufu fermentation process --- p.50
Chapter 2.3.8 --- The influence of PCR bias and artifact --- p.53
Chapter 2.2 --- Summary --- p.55
Chapter Chapter 3 --- : Analysis of bacteria diversity during sufu fermentation process --- p.57
Chapter 3.1 --- Introduction --- p.57
Chapter 3.2 --- Materials and methods --- p.57
Chapter 3.2.1 --- Sample collection and preparation --- p.57
Chapter 3.2.2 --- Plate count of bacteria during sufu fermentation process --- p.57
Chapter 3.2.3 --- Total DNA extraction from bacteria --- p.58
Chapter 3.2.4 --- Preparation of competent cell --- p.58
Chapter 3.2.5 --- 16S rDNA PCR amplification and construction of 16S rDNA clone library --- p.58
Chapter 3.2.6 --- RFLP analysis of 16S rDNA clone library --- p.59
Chapter 3.2.7 --- DNA sequencing for bacteria identification --- p.60
Chapter 3.2.8 --- Analysis of the diversity of 16S rDNA clone library --- p.60
Chapter 3.3 --- Results and discussion --- p.60
Chapter 3.3.1 --- Bacteria growth on plate counting result --- p.60
Chapter 3.3.2 --- Construction and selection of 16S rDNA clone library --- p.63
Chapter 3.3.3 --- 16S rDNA clone library analysis of bacteria diversity --- p.65
Chapter 3.3.4 --- Analysis of bacteria eco-structure and function during sufu fermentation process --- p.74
Chapter 3.4 --- Summary --- p.77
Chapter Chapter 4 --- : Screening the mutant possess higher capacity of forming volatile sulfur compounds (VSCs) from non-starter microbes of sufu product --- p.80
Chapter 4.1 --- Introduction --- p.80
Chapter 4.2 --- Materials and methods --- p.82
Chapter 4.2.1 --- Strains and culture conditions --- p.82
Chapter 4.2.2 --- Head space-solid phase microextraction (HS-SPME) analysis --- p.83
Chapter 4.2.3 --- Gas Chromatography-Mass Spectrometry (GC-MS) analysis --- p.84
Chapter 4.2.4 --- UV mutation --- p.85
Chapter 4.2.5 --- Ellman’s method --- p.86
Chapter 4.2.6 --- Preparation of cell-free extracts (CFE) for enzymatic assays --- p.86
Chapter 4.2.7 --- Enzymatic assay --- p.86
Chapter 4.2.7.1 --- L-methionine aminotransferase activity assay --- p.86
Chapter 4.2.7.2 --- L-methionine demethiolase activity assay --- p.87
Chapter 4.2.7.3 --- α-keto acid decarboxylase activity assay --- p.87
Chapter 4.2.7.4 --- C-S lyase activity --- p.88
Chapter 4.2.8 --- Statistical analysis --- p.88
Chapter 4.3 --- Results and discussion --- p.89
Chapter 4.3.1 --- Optimization of SPME extraction condition --- p.89
Chapter 4.3.2 --- Selecting the start strain --- p.90
Chapter 4.3.4.1 --- Comparison of VSCs production ability --- p.90
Chapter 4.3.4.2 --- Comparison of enzymatic activity in L-methionine metabolism --- p.92
Chapter 4.3.3 --- Optimization of UV exposure time --- p.95
Chapter 4.3.4 --- Screening the mutants --- p.96
Chapter 4.3.4.1 --- Comparison of VSCs production ability among the mutants --- p.96
Chapter 4.3.4.2 --- Comparison of the L-methionine related enzymatic activities among the mutants --- p.99
Chapter 4.3.4.3 --- Identified of strian B-1 --- p.101
Chapter 4.4 --- Summary --- p.102
Chapter Chapter 5 --- : General conclusions and future work --- p.103
References --- p.106

碩士
中原大學
環境工程學系
105
The objective of this study is to develop an adsorbent that can simultaneously adsorb dichromate and chromium ion. Various concentrations of organic compounds, such as ethyl xanthate, L-cysteine and dodecyl sulfate, containing sulfur atom were used to intercalate Mg-Al layered double hydroxides (Mg-Al LDHs) through a co-precipitation method. The produced adsorbents were used to adsorb dichromate and chromium ion under pH 4 and 5. The adsorbents were characterized by XPS, SEM, FTIR and XRD. The adsorption capacity of target contaminants was calculated by adsorption equilibrium and the possible adsorption mechanism was discussed. The results indicated the Mg-Al LDHs intercalated with ethyl xanthate, L-cysteine and dodecyl sulfate can effectively adsorb dichromate and chromium (III) ion. The adsorption mechanism for chromium ion was regarded as complexation reaction. Because carbonate was found in the interlayer, the adsorption mechanism for dichromate was assumed as anion exchange. The demonstrated the synthesized adsorbents can remove cationic and anionic heavy metal ions. The adsorbents produced by the modification are in addition to the poor adsorption effect obtained after the dodecyl sulfonate intercalation, and the other two anionic organisms can produce high adsorption capacity for the contaminants. For the heavy metal solution at two pH values, the LDHs intercalated by dodecyl sulfonate adsorbs cationic heavy metal contaminants at pH= 5, and the LDHs intercalated by ethyl xanthate removed cationic and anionic heavy metals at pH4 and pH5. The LDHs intercalated by L-cysteine can generate a better effect for the cationic and anionic heavy metal ions at pH5. The overall efficiency of the adsorbent is decrease as the following order: ethyl xanthate-LDHs> cysteine-LDHs> dodecylsulfonate-LDHs.

碩士
國立中山大學
環境工程研究所
100
Neighboring northern Kaohsiung with a dense population of petrochemical and petroleum industrial complexes included China Petroleum Company (CPC) refinery plant, Renwu and Dazher petrochemical industrial plants. In recent years, although many scholars have conducted regional studies, but are still limited by the lack of relevant information evidences (such as odorous matters identification and VOCs fingerprint database), while unable to clearly identify the causes of poor ambient air quality. By sampling and analyzing VOCs, we will be able to understand the major sources of VOCs in northern Kaohsiung and their contribution, and to provide the air quality management and control countermeasures for local environmental protection administration. In this study, we sampled and analyzed the speciation of VOCs and sulfur-containing odorous matters (SOMs) in the CPC refinery plants, Renwu and Dazher petrochemical complexes simultaneously with stack sampling. The sampling of VOCs and SOMs were conducted on January 7th, 14th, and 19th, 2011 (dry season) and May 6th, 13rd, and 23rd, 2011 (wet season). We established the emission source database, investigated the characteristics of VOC fingerprints, and estimate the emission factor of each stack. It helps us understand the temporal and spatial distribution of VOCs and ascertain major sources and their contribution of VOCs. Major VOCs emitted from the stacks of the CPC refinery plant were toluene and acetone. It showed that petroleum refinery processes had similar VOCs characteristics and fingerprints. The fingerprints of stack emissions at Renwu and Dashe industrial complexes varied with their processes. Hydrogen sulfide was the major sulfur-containing odorous matter in all petrochemical plants. Compared to other petrochemical complexes, Renwu industrial complex emitted a variety of SOMs species as well as relatively high concentrations of sulfur-containing odorous matters. The petrochemical industrial complexes in the industrial ambient of VOCs analysis results showed that isobutane, butane, isopentane, pentane, propane of alkanes, propene of alkenes, toluene, ethylbenzene, xylene, styrene of aromatics, 2-Butanone (MEK), acetone, of carbonyls are major species of VOCs. In addition, ethene+acetylene+ethane (C2), 1,2-dichloroethane, chloromethane, dichloromethane, MTBE were also occasionally found. Sulfur-containing odorous matter (SOMs) analytical results showed that major odorous matters included hydrogen sulfide, methanethiol, dimethyl sulfide, and carbon disulfide. The highest hydrogen sulfide concentration went up to 5.5 ppbv. In this study, the species of VOCs were divided into alkanes, alkenes, aromatics, carbonyls, and others. The temporal and spatial distribution of various types of VOCs strongly correlated with near-surface wind direction. The most obvious contaminants were alkanes, aromatics, and carbonyls of the dispersion to the downwind. Generally, the ambient air surrounding the petrochemical industrial complexes was influenced by various pollutants in the case of high wind speeds. It showed that stack emission and fugitive sources had an important contribution to ambient air quality. TSOMs and hydrogen sulfide emitting mainly from local sources resulted in high concentration of TSOMs and hydrogen sulfide surrounding the petrochemical industrial complex. Principal component analysis (PCA) results showed that the surrounding areas of petrochemical industrial complexes, regardless of dry or wet seasons, were mainly influenced by the process emissions and solvent evaporation. The impact of traffic emission sources ranked the second. Chemical mass balance receptor modeling showed that stack emissions from the CPC refinery plants contributed about 48 %, while fugitive emission sources and mobile sources contributed about 30 % and 11%, respectively. The stack emissions from Renwu industrial complex contributed about 75 %, while fugitive emission sources and mobile sources contributed about 17 % and 5 %, respectively. The stack emissions from Dazher industrial complex contributed about 68 %, while fugitive emission sources and mobile sources contributed about 21 % and 2 %, respectively.

This article describes the synthesis, characterization and environmental applications of nanocrystalline zeolites. It begins by considering the use of nanocrystalline zeolites as building blocks in the preparation of hierarchical zeolite structures, followed by a discussion of the synthesis of silicalite-1 with systematically varied crystal sizes, along with the synthesis of nanocrystalline aluminosilicates, NaZSM-5 and NaY. It then looks at the various applications of nanozeolites and hierarchical zeolite structures for environmental catalysis, adsorption of volatile organic compounds and other environmental contaminants, selective catalytic reduction of nitrogen oxide, and decontamination of organic phosphorus and sulfur-containing compounds. It also examines the unique properties and reactivity of nanocrystalline zeolites and concludes by assessing their potential for future environmental applications.

The synergistic antiwear and friction reducing properties of oils containing nor-sulfur nor-phosphoruorganic molybdenum compound (MC) with zinc dialkyldithiophosphate (ZnDDP) were evaluated by four ball tester. The results show that the combination of organic molybdenum compound and ZDDP exhibits good synergistic antiwear and friction reducing properties. Moreover, at the same concentration of ZDDP with different alkyl groups, there was an different optimum MC concentration for better antiwear and friction reducing properties. When MC concentration exceed this optimum valves, the antiwear and friction reducing properties of lubricants were not improved obviously. However, These properties were affected significantly by ZDDP type, while the effect of ZDDP type on these properties became small at higher MC/ZDDP ratios. Especially, the combination of MC with ZDDP containg primary C8 alkyl groups is very effective on tribological behaviours under lower dosage of MC added to oils. Finally, the surface analysis indicated that Mo, S atoms are distributed evenly on the wear scar, which contribute to improve the tribological properties of lubricants.

A feasibility study was conducted, aiming to explore the potential effectiveness of UV/TiO2/O3 photooxidation technologies for simultaneous treatment of odorant and pathogen emissions from livestock and poultry operations. Several key parameters were tested in laboratory (US) and semi-pilot (Israel) scale conditions including: the effects of light energy dose (treatment time and light intensity), relative humidity and air temperature, UV wavelength, presence of photocatalyst (TiO2) and the presence of ozone. Removal and conversion of odor, target gases (sulfur-containing volatile organic compounds S-VOCs, volatile fatty acids (VFAs), phenolics, and ammonia), and airborne pathogens was tested. Up to 100% removal (below method detection level) of S-VOCs, VFAs, and phenolics, the overall odor, and up to 64.5% of ammonia was achieved with optimized treatment. Treatments involving deep UV band (185 nm) and photocatalyst (TiO2) were more efficient in removal/conversion of odorous gases and odor. The estimate of the operational cost of treatment was based on measured emissions of several odorous VOCs from full scale, commercial swine farm ranges from $0.15 to $0.59 per finisher pig. This figure represents significantly lower cost compared with the cost of biofiltration or air scrubbing.

The objective of this research is to study the nature of the competition for cysteine (Cys), the first organic sulfur-containing compound, between its two main metabolites, glutathione (GSH) and methionine (Met). GSH plays a central role in protecting plants during various stresses, while Met, an essential amino acid, regulates essential processes and metabolites in plant cells through its metabolite S-adenosyl-Met. Our results, which are based on flux analysis and measurements of Met- metabolites, show that the flux towards Met synthesis is high during non-stress conditions, however the flux is significantly reduced under stress conditions, when there is high synthesis of GSH. Under oxidative stress the expression level of the regulatory enzyme of Met synthesis, cystathionine g-synthase (CGS) was reduced. By using three different systems, we have found that that GSH down regulates the expression level of CGS, thus reducing Met synthesis. We have found that this regulation occurs at the post-transcriptional level, and further studies have shown that it occurs at post-translationaly. To reveal how oxidative stress affects the flux towards Met and GSH, flux analysis was performed. We have found that the level of Met is significantly reduced, while the level of glutathione significantly increases during stress. Under stress conditions most of the glutathione is converted from GSH to GSSG (the oxidised form of glutathione). These results suggest that under normal growth conditions, Cys is channelled towards both pathways to support GSH accumulation and the synthesis of growth-essential Met metabolites. However, during oxidative stress, when a high level of GSH is required to protect the plants, the levels of GSH increase while those of CGS are reduced. This reduction leaves more Cys available for GSH synthesis under stress conditions. In addition we have also studied the effects of high GSH level on the transcriptome profile. The analysis revealed that GSH affects the expression level of many major genes coding to enzymes or proteins associated with photosynthesis, starch degradation, hormone metabolism (especially genes associated with jasmonate), biotic stress (especially genes associated with PR-proteins), cytochrome P450 genes, regulation of transcription and signaling (especially genes associated with receptor kinases and calcium). These results suggest that indeed GSH levels affect different pathways and metabolites in plants.