Downstream processing of pectinase produced by Aspergillus niger in solid state cultivation and its application to fruit juices clarification

In this work, a protocol for the formulation of an enzyme concentrated product to be applied in fruit juice treatment is described. Downstream processing conditions for the recovery and concentration of pectinases produced by the new strain Aspergillus niger LB-02-SF in solid state cultivation were assessed. The solid-liquid ratio in the extraction step of pectinases recovery from the cultivated media was evaluated and the highest activity was obtained with a solid-liquid ratio of 1:10. The crude extract was concentrated by ultrafiltration and the total pectinase (TP) activity was 73.6-fold concentrated in relation to the crude extract, and a final TP titer of 663 U mL–1 was obtained with 73.7% of recovery yield. KCl and different glycerol concentrations were added to the concentrated extract and the stability of pectinases during the storage at 5°C for 59 weeks was tested. The formulation with 50% w/w glycerol was applied to the treatment of apple and grape juices and the results of these tests were statistically comparable to those obtained with two high-quality commercial preparations.

Enhanced extraction of phenolic compounds from coffee industry’s residues through solid state fermentation by Penicillium purpurogenum

Abstract The use of agroindustrial residues is an economical solution to industrial biotechnology. Coffee husk and pulp are abounding residues from coffee industry which can be used as substrates in solid state fermentation process, thus allowing a liberation and increase in the phenolic compound content with high added value. By employing statistical design, initial moisture content, pH value in the medium, and the incubation temperature were evaluated, in order to increase the polyphenol content in a process of solid state fermentation by Penicillium purpurogenum. The main phenolic compounds identified through HPLC in fermented coffee residue were chlorogenic acid, caffeic acid, and rutin. Data obtained through HPLC with the radical absorbance capacity assay suggest the fermented coffee husk and pulp extracts potential as a source of phenolic acids and flavonoids. Results showed good perspectives when using P. purpurogenum strain to enhance the liberation of phenolic compounds in coffee residues.

Hypercalcemia and acute kidney injury caused by abuse of a parenteral veterinary compound containing vitamins A, D, and E

A previously healthy 19 year-old male presented to the hospital with anorexia, nausea, and vomiting. Laboratory studies were significant for hypercalcemia (peak calcium value of 14.8 mg/dL) and acute kidney injury (peak serum creatinine of 2.88 mg/dL). He admitted to using a parenteral formulation of vitamins A, D and E restricted for veterinary use containing 20,000,000 IU of vitamin A; 5,000,000 IU of vitamin D3; and 6,800 IU of vitamin E per 100 mL vial. The patient stated to have used close to 300 mL of the product over the preceding year. Interestingly, the young man was not interested in the massive amounts of vitamins that the product contained; he was only after the local effects of the oily vehicle. The swelling produced by the injection resulted in a silicone-like effect, which gave the impression of bigger muscles. Nevertheless, the product was absorbed and caused hypervitaminosis. The serum level of 25(OH) vitamin D was clearly elevated at 150 ng/mL (reference range from 30 to 60 ng/mL), but in most published cases of vitamin D toxicity, serum levels have been well above 200 ng/mL. His PTH level was undetectable and other potential causes of hypercalcemia were excluded. Therefore, we posit that the severity of the hypercalcemia observed in this case was the result of a synergistic effect of vitamins A and D. The patient was treated with normal saline, furosemide and zolendronic acid, with rapid normalization of calcium levels and renal function.

Post-transaction brand and model line-up integration in the automotive industry: Case studies of European companies as target of acquisitions by Chinese and Indian multinational corporations

Corporations practice company acquisitions in order to create shareholder’s value. During the last few decades, the companies in emerging markets have become active in the acquisition business. During the last decade, large and significant acquisitions have occurred especially in automotive industry. While domestic markets have become too competitive and companies are lacking required capabilities, they seek possibilities to expand into Western markets by attaining valuable assets through acquisitions of developed country corporations. This study discusses the issues and characteristics of these acquisitions through case studies. The purpose of this study was to identify the acquisition motives and strategies for post-transaction brand and product integration as well as analyze the effect of the motives to the integration strategy. The cases chosen for the research were Chinese Geely acquiring Swedish Volvo in 2010 and Indian Tata Motors buying British Jaguar Land Rover in 2008. The main topics were chosen according to their significance for companies in automotive industry as well as those are most visible parts for consumers. The study is based on qualitative case study methods, analyzing secondary data from academic papers and news articles as well as companies’ own announcements e.g. stock exchange and press releases. The study finds that the companies in the cases mainly possessed asset-seeking and market-seeking motives. In addition, the findings refer to rather minimal post-acquisition brand and product integration strategies. Mainly the parent companies left the target company autonomous to make their own business strategies and decisions. The most noticeable integrations were in the product development and production processes. Through restructuring the product architectures, the companies were able to share components and technology between product families and brands, which results in cutting down costs and in increase of profitability and efficiency. In the Geely- Volvo case, the strategy focused more on component sharing and product development know-how, whereas in Tata Motors-Jaguar Land Rover case, the main actions were to cut down costs through component sharing and combine production and distribution networks especially in Asian markets. However, it was evident that in both cases the integration and technology sharing were executed cautiously to prevent on harming the valuable image of the luxury brand. This study has concluded that the asset-seeking motives have significant influence on the posttransaction brand and model line-up integration strategies. By taking a cautious approach in acquiring assets, such as luxury brand, the companies in the cases have implemented a successful post-acquisition strategy and managed to create value for the shareholders at least in short-term. Yritykset harjoittavat yritysostoja luodakseen osakkeenomistajille lisäarvoa. Viimeisten muutamien vuosikymmenien aikana yritykset kehittyvissä maissa ovat myös aktivoituneet yritysostoissa. Viimeisen vuosikymmenen aikana erityisesti autoteollisuudessa on esiintynyt suuria ja merkittäviä yritysostoja. Koska kilpailu kotimaan markkinoilla on kiristynyt ja yritykset ovat vailla vaadittavia valmiuksia, ne etsivät mahdollisuuksiaan laajentaa länsimaisiin markkinoihin hankkimalla arvokkaita etuja kehittyneiden maiden yrityksistä yritysostojen avulla. Tämä tutkimus pohtii näiden yritysostojen olennaisia kysymyksiä ja ominaisuuksia casetutkimuksien kautta. Tutkimuksen tarkoitus oli tunnistaa sekä yritysostojen motiiveja ja brändi- ja mallisto-integraation strategioita että analysoida kyseisten motiivien vaikutusta integraatiostrategiaan. Tapaus-tutkimuksiksi valittiin kiinalaisen Geelyn yritysosto ruotsalaisesta Volvosta vuonna 2010 ja intialaisen Tata Motorsin yritysosto englantilaisesta Jaguar Land Roverista vuonna 2008. Tutkimus on kvalitatiivinen case-tutkimus ja siinä analysoidaan toissijaista tietoa sekä akateemisten ja uutisartikkeleiden että yritysten omien ilmoitusten, kuten pörssi- ja lehdistötiedotteiden, kautta. Tutkimuksen tulokset osoittavat, että tutkittujen yritysten toiminnat perustuivat motiiveihin, joita ajoivat etujen and uusien markkinoiden tarve. Sen lisäksi tutkimustulokset osoittivat, että yritysoston jälkeinen brändi- ja mallisto-integraatio pidettiin minimaalisena. Pääasiallisesti kohdeyrityksille jätettiin autonomia tehdä omat liikkeenjohdolliset päätökset yritysstrategioihin liittyen. Huomattavimmat integraatiot koskivat tuotekehityksellisiä ja tuotannollisia prosesseja. Kehittämällä uudelleen tuotearkkitehtuureja, yritykset pystyivät jakamaan komponentteja ja teknologiaa tuoteperheiden ja brändien välillä. Tämä mahdollisti kustannusleikkauksia sekä kannattavuuden ja tehokkuuden parantamista. Geely-Volvo –tapauksessa integraatiostrategia keskittyi komponenttien jakamiseen yhteisten tuotearkkitehtuurien avulla ja tuotekehityksen ammattitaitoon, kun taas Tata Motors-JLR –tapauksessa päätoiminnat olivat kustannuksien leikkaus sekä tuotannon ja jakeluverkoston yhdistäminen erityisesti Aasian maissa. Yhteistä yrityskaupoissa oli, että brändi- ja mallisto-integraatio sekä teknologian jakaminen suoritettiin varoen ehkäistäkseen arvokkaiden luksus-brändien tuotekuvan vahingoittamista. Tutkimuksen lopputulokset osoittavat, että yrityskaupan motiiveilla on huomattava vaikutus brändija mallisto-integraation strategiaan. Toteuttamalla varovaista lähestymistapaa luksus-brändin hankinnassa ja integraatiossa, yritykset ovat onnistuneet luomaan lisäarvoa osakkeenomistajille vähintään lyhyellä aikavälillä.

Lean Product Management – Enhancing Product Managers' Ability to Create Value

The purpose of this master’s thesis was to study the opportunity to apply Lean practices to product management function which happens in an office environment. Since product management plays an important role in the company’s success story, it’s important to have it functioning as effectively as possible. The goal was to find those Lean tools and methods that fit the best to the needs of product management. The research was conducted as a qualitative action research which comprises a comprehensive literature review and a single case study. Theoretical information about Lean Thinking and product management was collected from articles, literature and Internet sources. Moreover, empirical data was collected by conducting interviews in the Case Company’s product management department in order to gain an in-depth understanding of product management’s problematics. The results indicate that most of the product management challenges could be overcome by applying Lean practises. Based on the usability rate, which has been discussed in the empirical part of this study, the most suitable Lean practises for product management function are: value stream mapping, Kanban and KPIs.

The role of product features on buyer-supplier collaboration in packaging industry

The thesis presents the study relative to the collaboration between suppliers and buyers in packaging industry with the impact of product features. The main purpose of this study is to examine the importance of product characteristics on collaboration to develop better packaging and to figure out how buyer-supplier collaboration in the supply chain perspectives is conducted and managed in packaging industry. The theoretical part reviewed some basic frameworks of collaboration including the scopes and levels of collaboration, risks as well as powers of collaboration, relationship and some key factors for successful collaboration. Followed by the overviews of packaging industry with the main issues related to product characteristics in packaging. By using the qualitative method, secondary data consisting of articles, reports, websites and primary data through interviewing some well-known packaging companies and case companies are collected in the thesis. The empirical result emphasized the importance of product features’ analysis in packaging industry since it plays a central role in the materials, design process, production and innovation with the role of collaboration. Collaboration in packaging is vital for packaging companies to survive and grow in the competitive environment. Finally, some key factors for effective collaboration were summarized based on the perspectives of packaging companies. It is highly recommend building a long-run collaboration with their customers due to undeniable benefits With increasingly importance of collaboration in packaging industry, further studies may be conducted.

Exploring the impact of celebrity endorsement and product class involvement on advertising effectiveness: an eye tracking approach

Celebrity endorsement has increased in popularity over the past decades and companies are willing to spend increasingly excessive amounts of money into it. Even though multiple studies support celebrity endorsement, further research on its impact on advertising effectiveness is called for. Fur-ther, the role of consumers’ product class involvement in advertising needs to be further studied. The purpose of this study is to explore if consumers’ product class involvement and exposure to celebrity endorsers affect consumers brand recall. Supported by earlier studies, brand recall was used as a measure for advertising effectiveness in this study. In general, a psychological approach was chosen for building the theoretical framework. Concept of classical conditioning was presented in order to understand why people act how they do. Balanced theory and meaning transfer model were presented in order to study how celebrities can be used effectively in advertising context. Further, the importance of product class involvement in advertising effectiveness was evaluated. Hypotheses were formulated based on a literature review of the existing research. Because of the versatility of the research design, a mixed methods approach for this study was adopted. Empirical part of the study was conducted in three stages. First, a pre-test was conducted in order to choose suitable product endorsers for the advertisement stimuli used in the experiment. Second, an eye-tracking experiment with 30 test subjects was conducted in order to study how people view advertisements and whether the familiarity of the product endorser and consumers’ product class involvement affects brand recall. For the experiment, a fictional brand was created in order to avoid bias on brand recall. Third, qualitative interviews for 15 test subjects were conducted in the post-experiment stage in order to gain deeper understating of the phenomenon and to make sense of the findings from the experiment. Findings from this study support celebrity endorsement by suggesting that a famous spokesperson does not steal attention from brand information more than a non-celebrity product endorser. As a result, the use of a celebrity endorser did not decrease brand recall. Results support earlier research as consumer’ higher product class involvement resulted in a better brand recall. Findings from the interviews suggest that consumers have positive perceptions of celebrity endorsement in general. However, the celebrity–brand congruence is a crucial factor when creating attitudes towards the advertisement. Future research ideas were presented based on the limitations and results of this study

Impact of Product-harm Crisis on Brand Equity: the Moderating Role of Corporate Social Performance

There is an increasing amount of product-harm crisis in the past few years; and the impact of a product-harm crisis becomes more and more influential due to the high increasing speed of globalization. And it is believed that the negative damages to a firm leading to a loss of the intangible assets is bigger than other costs such as the cost of the product recall. Brand equity is a very important and valuable intangible asset for a firm; and it is particularly vulnerable during the crisis. And CSP (CSP) is a hot concept associated with product-harm crisis and brand equity. The aim of this study is to understand how product-harm crisis influences by simultaneously involving CSP as a moderator in a consumer-based level. An experimental study was conducted through an online questionnaire among 198 students in Finland. The questionnaire mainly assessed the consumers’ attitudes towards CSP and brand before/after a fictional product-harm crisis. The results shows that the brand equity was negatively related to the product-harm crisis. And the extent level of crisis’s severity was positively related to the loss of the brand equity; whereas, acknowledged blame was more useful to compensate the loss of brand equity in the low-severity crisis. CSP acted as a moderator role which could compensate the loss of brand equity caused by the product-harm crisis. Managerial implications are also offered for crisis managers, brand managers, and CSR managers.

Product recall process development for exported nonfood consumer products

The purpose of this research is to examine the different opportunities that companies operating on international level has for conducting a product recall. The main subject of the research is strategic decision-making of recall and product recall process. The theoretical framework, core of the research, is based on research questions. The research is performed as qualitative case study and the material has been collected by combining results of previous studies and by observing the case company. Different opportunities for conducting a recall are examined in the empirical part of this study. As a result, different product recall models have been created, which all require deep cooperation between different entities of the supply chain.

An investigation into the oxidation of organic sulphides, organic selenides and simple hydrocarbons by Mortierella isabellina NRRL 1757

The work presented in this thesis is divided into three separate sections 4!> Each' 'section is involved wi th a different problem, however all three are involved with a microbial oxidation of a substrate~ A series of 'aryl substituted phenyl a.nd be,nzyl methyl sulphides were oxidized to the corre~pondi~g sulphoxides by 'Mo:rtierellai's'a'b'e'llina NRR.L17'S7 @ For this enzymic Qxidation, based on 180 labeled experiments, the oxygen atom is derived fr'orn the atmosphere and not from water. By way of an u~.traviolet analysis, the rates of oxidation, in terms of sulphox~ de appearance, were obtained and correlated with the Hatnmett p s~grna constants for the phenyl methyl sulphide series. A value of -0.67 was obtained and, is interpreted in terms of a mechanism of oxidation that involves an electrophilic attack on the sulphide sulphur by an enzymic ironoxygen activated complex and the conversion of the resulti!lg sulphur cation to sulphoxide. A series of alkyl phenyl selen~des have been incubated with the fu~gi, Aspergillus niger ATCC9l42, Aspergillus fO'etidus NRRL 337, MIIJisabellina NF.RLl757 and'He'lminth'osparium sp'ecies NRRL 4671 @l These fu?gi have been reported to be capable of carrying out the efficient oxidation of sulphide to sulphoxide, but in no case was there any evidence to supp'ort the occurrence of a microbialox,idation. A more extensive inves·t~gation was carried out with'M,e 'i's'a'b'e'l'l'i'na, this fu~gus was capable of oxidizing the correspondi~g sulphides to sulphoxi.de·s·$ Usi:ng a 1abel.edsubstra.te, [Methyl-l4c]-methyl phenyl selenide, the fate of this compound was invest~gated followi!lg an i'ncubation wi th Me isabellina .. BeSUldes th. e l4C-ana1YS1Q S-,'. a quant"ltta"lve selen'lum ana1Y"S1S was carried out with phenyl methyl selenide. These techniques indicate that thesel'enium was capable of enteri!1g thefu!1gal cell ef'ficiently but that s'ome metabolic cleav~ge of the seleni'um-carbon bond' may take plac'e Ie The l3c NMR shifts were assigned to the synthesized alkyl phenyl sulphides and selenides@ The final section involved the incubation ofethylben~ zene and p-e:rtr.hyltoluene wi th'M ~ 'isab'e'llina NRRL 17574b Followi~ g this incubation an hydroxylated product was isolated from the medium. The lH NMR and mass spectral data identify the products as I-phenylethanol and p-methyl-l-phenylethanol. Employi!lg a ch'iral shift re~gent,tri~ (3-heptafluorobutyl-dcamphorato)'- europium III, the enantiomeric puri ty of these products was invest~gated. An optical rotation measurement of I-phenylethanol was in ~greement with the results obtained with the chiral shift re~gen,te 'M.isabe'l'lina is capable of carryi~g out an hydroxylation of ethylbenzene and p-ethyltoluene at the ~ position.

Biotransformation of polycylic aromatic compounds by fungi and an investigation into the oxidation of alkylbenzenes by Mortierella isabellina NRRL 1757

Incubations of several polycyclic heteroaromatic compounds and two polycyclic aromatic hydrocarbons with a series of common fungi have been performed. The fungi Cunninghamella elegans ATCC 26269, Rhizopus arrhizus ATCC 11145, and Mortierella isabellina NRRL 1757 were studied in this regard. Of the aza heteroaromatics, only dibenzopyrrole gave a ring hydroxylated product following the incubation with C. elegans. From the thio heteroaromatics studied, dibenzothiophene was metabolized by all the three fungi and thioxanthone by C. elegans and M. isabellina giving sulfones and sulphoxides. Thiochromanone was metabolized stereoselectively to the corresponding sulphoxide by C. elegans. Methyl substituted thioxanthones on incubation with C. elegans produced oxidative products, arising from S -oxidation and hydroxylation at the methyl group. Of the cyclic ketones studied, only fluorenone was reduced to hydroxyfluorene and this metabolism is compared with that reported with cytochrome P-450 monooxygenases of hepatic microsomes. A series of para-substituted ethylbenzenes has been transformed stereoselectively to the 1-phenylethanols by incubation with M. isabellina. Comparisons of the enantiomeric purities obtained from products with their respective para substituent of the same steric size but different electronic properties indicate that the stereoselectivity of hydroxylation at benzylic carbon may be susceptible to electron donating or withdrawing factors in some cases, but that observation is not va lid in all the comparisons. The stereochemistry of the reaction is discussed in terms of three possible steps, ethylbenzene ---) 1-phenylethanol ---) acetophenone ---) 1-phenylethanol. This metabolic pathway could account for the inconsistencies observed in the comparisons of optical purities and electronic character of para substituents. Furthermore, formation of 2-phenylethanol (in some cases), l-(p-acetylphenyl)ethanol from p-diethylbenzene, and N-acetylation of p-ethylaniline was observed. n-Propylbenzene was also converted to optically active 1-phenylpropanol. Acetophenone, p-ethylacetophenone, and o(,~,~-trifluoroacetophenone were transformed to 1-phenylethanol, l-(p-ethylphenyl)ethanol, and 1-phenyl-2,2,2-trifluoroethanol, respectively, with high chemical and excellent optical yields. The 13 C NMR spectra of several substrates and metabolic products have been reported and assigned for the first time.

The 21-dehydroxylation of corticosteroids: evidence for an enol intermediate and the hydroxylation of steroids by fungal cyto-chrome P450: evidence for a stepwise mechanism

Two enzyme mechanisms were examined: the 21-dehydroxylation of corticosteroids by the anaerobe Eubacterium l en tum, and the hydroxylation of steroids by fungal cytochrome P450. Deuterium labelling techniques were used to study the enzymic dehydroxylation. Corticosteroids doubly labelled (2H) at the C-21 position were incubated with a culture of Eubacterium lentum. It was found that t he enzymic dehydroxylation proceeded with the loss of one 2H f rom C-21 per molecule of substrate. The kinetic isotope ef fect f or the reaction was found to be k~kD = 2. 28. These results suggest that enzyme/substr ate binding in this case may proceed via t he enol form of the substrate. Also , it appears that this binding is, at least in part, the rate determining step of t he reaction. The hydroxylation of steroids by fungal cytochrome P450 was examined by means of a product study. Steroids with a double bond at the A8 (9), ~( lO ), or ~ (ll) position were synthesized. These steroids were then incubated with fungal strains known to use a cytochrome P450 monooxygenase to hydroxylate at positions allylic to these doubl e bonds. The products formed in these incubations indicated that the double bonds had migrated during allylic hydroxylat ion. This suggests that a carbon centred radical or ion may be an intermediate i n the cytochrome P450 cat alytic cycle.

The regulation of oat coleoptile phosphoenolpyruvate carboxylase and malic enzyme by Hâ ½ and metabolites : kinetic evidence for and against a cytosolic pH-stat

Phosphoenolpyruvate carboxylase (PEPC) and malic enzyme activities in soluble protein extracts of Avena coleoptiles were investigated to determine whether their kinetics were consistent with a role in cytosol pH regulation. Malic enzyme activity was specific for NADP+ and Mn2+. Maximal labelled product formation from [14C]-substrates required the presence of all coenzymes, cofactors and substrates. Plots of rate versus malate concentration, and linear transformations there- 2 of, indicated typical Michaelis-Menten kinetics at non-saturating malate levels and substrate inhibition at higher malate levels. pH increases between 6.5 and 7.25 increased near-optimal activity, decreased the degree of substrate inhibition and the Kmapp(Mn2+) but did not affect the Vmax or Kmapp(malate). Transformed data of PEPC activity demonstrated non-linear plots indicative of non-Michaelian kinetics. pH increases between 7.0 and 7.6 increased the Vmax and decreased the Km app (Mg2+) but did not affect the Kmapp(PEP). Various carboxylic acids and phosphorylated sugars inhibited PEPC and malic enzyme activities, and these effects decreased with pH increases. Metabolite inhibited malic enzyme activity was non-competitive and resulted mainly from Mn2+ chelation. In contrast, metabolite inhibited PEPC activity was unique for each compound tested, being variously dependent on the PEP concentration and the pH employed. These results indicate that fluctuations in pH and metabolite levels affect PEPC and malic enzyme activities similarly and that 3 the in vitro properties of PEPC are consistent with its proposed role in a pH-stat, whereas the in vitro properties of the malic enzyme cannot be interpreted in terms of a role in pH regulation.

Biotransformation of aromatic hydrocarbons and organic sulphides by fungi

Toluene is converted to benzyl alcohol by the fungi Mortierella isabellina and Helminthosporium species; in the latter case, the product is further metabolized. Toluene-a -d 1 , toluene-a,a-d2, and toluene-a,a,a-d 3 have been used with Mortierellaisabellina in a series of experiments to determine both primary and secondary deuterium kinetic isotope effects for the enzymic benzylic hydroxylation reaction. The values obtained, intermolecular primary kH/kD = intramolecular p rim a r y kH r kD = 1. 0 2 + O. 0 5, and sec 0 n dar y k H I kD = 1. 37 .:!. 0.05, suggest a mechanism for the reaction involving benzylic proton removal from a radical intermediate in a non-symmetrical transition state. 2H NMR (30.7 MHz) studies using ethylbenzene-l,1-d 2 , 3 -fluoroethylbenzene-l,1-d 2 , 4 -fluoroethylbenzene-l,1-d 2 , and toluene-dB as substrates with Mortierella isabellina suggest, based on the observable differences in rates of conversion between the substrates, that the hydroxylation of hydrocarbons at the benzylic position proceeds via a one electron abstraction from the aromatic ring, giving a radical cation. A series of 1,3-oxathiolanes (eight) were incubated with Mortierella isabellina , Helminthosporium , Rhizopus arrhizus , and Aspergillus niger . Sulphoxides were obtained from Mortierella isabellina and Rhizopus arrhizus using the substrates 2-phenyl-, 2-methyl-2-phenyl-, and 2-phenyl-2-tert. butyl-l,3-oxathiolane. The relative stereochemistry of 2-methyl-2-phenyl-l,3-oxathiolan-l-oxide was assigned based on lH decoupling, n.O.e, 1 and H NMR experiments. The lH NMR (200 MHz) of the methylene protons of 2-methyl-2-phenyl-l,3-oxathiolan-l-oxide was used as a diagnostic standard in assigning the relative stereochemistry of 2-phenyl-l,3-oxathiolan-l-oxide and 2-phenyl-2-tert. butyl-l,3-oxathiolan-l-oxide. The sulphoxides obtained were consistent with an oxidation occurring from the opposite side of the molecule to the phenyl substituent.

Kinetic and product studies for the oxidtion of organic sulfides and sulfoxides in the presence of transition metal complexes

Rates and products of the oxidation of diphenyl sulfide, phenyl methyl sulfide, p-chlorophenyl methyl sulfide and diphenyl sulfoxide have been determined. Oxidants included t-Bu02H alone, t-Bu02H plus molybdenum or vanadium catalysts and the molybdenum peroxo complex Mo0(02)2*HMPT. Reactions were chiefly carried out in ethanol at temperatures ranging from 20° to 65°C. Oxidation of diphenyl sulfide by t-Bu02H in absolute ethanol at 65°C followed second-order kinetics with k2 = 5.61 x 10 G M~1s"1, and yielded only diphenyl sulfoxide. The Mo(C0)g-catalyzed reaction gave both the sulfoxide and the sulfone with consecutive third-order kinetics. Rate = k3[Mo][t-Bu02H][Ph2S] + k^[Mo][t-Bu02H][Ph2S0], where log k3 = 12.62 - 18500/RT, and log k^ = 10.73 - 17400/RT. In the absence of diphenyl sulfide, diphenyl sulfoxide did not react with t-Bu02H plus molybdenum catalysts, but was oxidized by t-Bu02H-V0(acac)2. The uncatalyzed oxidation of phenyl methyl sulfide by t-Bu02H in absolute ethanol at 65°C gave a second-order rate constant, k = 3.48 x 10~"5 M^s""1. With added Mo(C0)g, the product was mainly phenyl methyl sulfoxide; Rate = k3[Mo][t-Bu02H][PhSCH3] where log k3 = 22.0 - 44500/RT. Both diphenyl sulfide and diphenyl sulfoxide react readily with the molybdenum peroxy complex, Mo0(02)2'HMPT in absolute ethanol at 35°C, yielding diphenyl sulfone. The observed features are mainly in agreement with the literature on metal ion-catalyzed oxidations of organic compounds by hydroperoxides. These indicate the formation of an active catalyst and the complexation of t-Bu02H with the catalyst. However, the relatively large difference between the activation energies for diphenyl sulfide and phenyl methyl sulfide, and the non-reactivity of diphenyl sulfoxide suggest the involvement of sulfide in the production of an active species.