The effect of post harvest handling on selected native food plants

A commercial issue currently facing native plant food producers and food processors, and identified by the industry itself, is that of delivering quality products consistently and at reasonable cost to end users based on a sound food technology and nutrition platform. A literature survey carried out in July 2001 by the DPI&F’s Centre for Food Technology, Brisbane in collaboration with the University of Queensland to collect the latest information at that time on the functional food market as it pertained to native food plants, indicated that little or no work had been published on this topic. This project addresses two key RIRDC sub program strategies: to identify and evaluate processes or products with prospects of commercial viability and to assist in the development of integrated production, harvesting, processing and marketing systems. This project proposal also reflects a key RIRDC R&D issue for 2002-2003; that of linking with prospective members of the value chain. The purpose of this project was to obtain chemical data on the post harvest stability of functional nutritional components (bio actives) in commercially available, hand harvested bush tomato and Kakadu plum. The project concentrated on evaluating bioactive stability as a measure of ingredient quality.

Purification and characterization of assimilatory nitrite reductase from Candida utilis

Nitrate assimilation in many plants, algae, yeasts and bacteria is mediated by two enzymes, nitrate reductase (EC 1.6.6.2) and nitrite reductase (EC 1.7.7.1). They catalyse the stepwise reduction of nitrate to nitrite and nitrite to ammonia respectively. The nitrite reductase from an industrially important yeast, Candida utilis, has been purified to homogeneity. Purified nitrite reductase is a heterodimer and the molecular masses of the two subunits are 58 and 66 kDa. The native enzyme exhibits a molecular mass of 126 kDa as analysed by gel filtration. The identify of the two subunits of nitrite reductase was confirmed by immunoblotting using antibody for Cucurbita pepo leaf nitrite reductase. The presence of two different sized transcripts coding for the two subunits was confirmed by (a) in vitro translation of mRNA from nitrate-induced C. utilis followed by immunoprecipitation of the in vitro translated products with heterologous nitrite reductase antibody and (b) Northern-blot analysis. The 66 kDa subunit is acidic in nature which is probably due to its phosphorylated status. The enzyme is stable over a range of temperatures. Both subunits can catalyse nitrite reduction, and the reconstituted enzyme, at a higher protein concentration, shows an activity similar to that of the purified enzyme. Each of these subunits has been shown to contain a few unique peptides in addition to a large number of common peptides. Reduced Methyl Viologen has been found to be as effective an electron donor as NADPH in the catalytic process, a phenomenon not commonly seen for nitrite reductases from other systems.

Hyperexpression of chicken riboflavin carrier protein: Antibodies to the recombinant protein curtail pregnancy in rodents

Chicken riboflavin carrier protein (RCP) is a phosphoglycoprotein present in the egg white and yolk of egg-laying animals and in the sera of laying hens and of estrogenized chicks. The RCP cDNA, encoding a protein of predictedMr27,000, has been cloned into a T7 polymerase-driven vector, and high-level expression was observed on induction with IPTG inEscherichia coli.The protein was largely localized in inclusion bodies when expressed at 37°C but was present in the cytosolic fraction when induced at 22°C. At 37°C, two major bands were detected in whole-cell lysates of the strain expressing the protein. N-terminal sequence analysis indicated that the two proteins represented translated products with and without the pelB leader sequence encoded in the pET20b vector, but both included an additional 10 amino acids generated during cloning procedures. The inclusion body obtained at 37°C, on extraction with detergent, led to preferential solubilization of the protein without the pelB signal sequence. The solubilized recombinant RCP was recognized by polyclonal antisera to native RCP but radioimmunoassay revealed quantitative differences in the epitopes exhibited by the recombinant protein. Thus, sequence-specific monoclonal antibodies to chicken RCP also cross-reacted with the recombinant protein with almost equal efficiency, but antibodies which recognize conformation-dependent epitopes showed relatively reduced cross-reactivity with the recombinant protein. Polyclonal antibodies to recombinant RCP were able to recognize both the native and the denatured RCP. Administration of recombinant RCP antisera to pregnant mice led to embryonic resorption leading to early pregnancy termination. These findings reveal that the recombinant protein will be useful for investigations related to the mechanism of pregnancy termination on immunoneutralization of RCP in mammals, as well as in unraveling folding properties of RCP in terms of its ligand binding and antigenetic determinants exposed at its surface.

Liberty relighting, 20 years later

Recognized around the world as a powerful beacon for freedom, hope, and opportunity, the Statue of Liberty's light is not just metaphorical: her dramatic illumination is a perfect example of American ingenuity and engineering. Since the statue's installation in New York Harbor in 1886, lighting engineers and designers had struggled to illuminate the 150-foot copper-clad monument in a manner becoming an American icon. It took the thoughtful and creative approach of Howard Brandston-a legend in his own right-to solve this lighting challenge. In 1984, the designer was asked to give the statue a much-needed lighting makeover in preparation for its centennial. In order to avoid the shortcomings of previous attempts, he studied the monument from every angle and in all lighting conditions, discovering that it looked best in the light of dawn. Brandston determined that he would need 'one lamp to mimic the morning sun and one lamp to mimic the morning sky.' Learning that no existing lamps could simulate these conditions, Brandston partnered with General Electric to develop two new metal halide products. With only a short time for R&D, a team of engineers at GE's Nela Park laboratories assembled a 'top secret' testing room dedicated to the Statue of Liberty project. After nearly two years of work to perfect the new lamps, the 'dawn's early light' effect was finally achieved just days before the centennial celebrations were to take place in 1986. 'It was truly a labor of love,' he recalls.

ZnO nanocrystalline thin films: a correlation of microstructural, optoelectronic properties

The compositional, structural, microstructural, dc electrical conductivity and optical properties of undoped zinc oxide films prepared by the sol-gel process using a spin-coating technique were investigated. The ZnO films were obtained by 5 cycle spin-coated and dried zinc oxide films followed by annealing in air at 600 A degrees C. The films deposited on the platinum coated silicon substrate were crystallized in a hexagonal wurtzite form. The energy-dispersive X-ray (EDX) spectrometry shows Zn and O elements in the products with an approximate molar ratio. TEM image of ZnO thin film shows that a grain of about 60-80 nm in size is really an aggregate of many small crystallites of around 10-20 nm. Electron diffraction pattern shows that the ZnO films exhibited hexagonal structure. The SEM micrograph showed that the films consist in nanocrystalline grains randomly distributed with voids in different regions. The dc conductivity found in the range of 10(-5)-10(-6) (Omega cm)(-1). The optical study showed that the spectra for all samples give the transparency in the visible range.

Parametrized actor-critic algorithms for finite-horizon MDPs

Due to their non-stationarity, finite-horizon Markov decision processes (FH-MDPs) have one probability transition matrix per stage. Thus the curse of dimensionality affects FH-MDPs more severely than infinite-horizon MDPs. We propose two parametrized 'actor-critic' algorithms to compute optimal policies for FH-MDPs. Both algorithms use the two-timescale stochastic approximation technique, thus simultaneously performing gradient search in the parametrized policy space (the 'actor') on a slower timescale and learning the policy gradient (the 'critic') via a faster recursion. This is in contrast to methods where critic recursions learn the cost-to-go proper. We show w.p 1 convergence to a set with the necessary condition for constrained optima. The proposed parameterization is for FHMDPs with compact action sets, although certain exceptions can be handled. Further, a third algorithm for stochastic control of stopping time processes is presented. We explain why current policy evaluation methods do not work as critic to the proposed actor recursion. Simulation results from flow-control in communication networks attest to the performance advantages of all three algorithms.

Yrittäjyyden arvottaminen akateemisten nuorten argumentoinnissa

Evaluation of entrepreneurship in the speech of academic students and newly qualified young academics a summary of a qualitative attitude study. In Finland very few university students plan to become entrepreneurs. The aim of this research was to examine entrepreneurial attitudes expressed in speech. The material was gathered from interviews with university students and newly qualified young academic adults. The interviewees commented on twelve different sentences with claims formulated using research literature and views that have appeared in public discussions. The interviewees were divided into three different groups based on their self-expressed entrepreneurial intentions. The method of qualitative attitude research (Vesala & Rantanen 1999, 2007) was used in the interviews. The research material was studied using two interpretative theories: (1) The planned behaviour theory (Ajzen 1985, 1991a, b), which makes it possible to focus on the separate elements (attitude towards an act, subjective norms and perceived feasibility) necessary for intentions to develop; and (2) The theory of the two images of entrepreneurship (Vesala 1996), where individualism and relationism can be seen as resources for evaluating entrepreneurship. The subject of the research was how university students and newly qualified young adults viewed entrepreneurship as a general phenomen and in relation to the academic world. A second focus was on the attitudes expressed toward entrepreneurial university education and the possibility of combining entrepreneurship and academic knowledge. Of interest were also questions such as whether academic studies, knowledge and the university itself are resources or barriers to entrepreneurial intentions and entrepreneurship whether university students received any support for their entrepreneurial ambitions from the university and their fellow academic students. The problems tackled by this research were thus the following: How was entrepreneurship seen, both as a general phenomen and in an academic context, when it was evaluated positively, negatively or neutrally by the interviewees? In what way was entrepreneurship constructed in the interviewees attitudes? How were entrepreneurship and the academic world related in the interviewees attitudes? What kind of role did the university as an academic context play in the interviewees attitudes for example were university education and academic knowledge seen as resources or barriers to their entrepreneurial intentions. Traditional attitude studies claim that attitudes are a stable property of an individual. In contrast, rhetorical social psychological and qualitative attitude studies emphasize the contextual and linguistic aspects of attitude, and they offered an alternative viewpoint for this research. The study was based on two general assumptions: attitudes have objects and are evaluative. Here attitude was defined as an evaluative interpresentation made towards an object; adopting an attitude is a contextual process in the sense that attitudes are always concerned with the action context of the persons presenting them. Entrepreneurship, both as a general phenomen and in an academic context, was specified as the object to which an attitude was taken. From a theoretical point of view, qualitative methods suited the general structure of this research well. In a particular, qualitative approach which emphasized contextual elements proved to be both empirically valid and useful for avoiding the problematic assumptions associated with traditional attitude study. The subject of the analysis was the argumentative speech produced by the interviewees. The results of the study show the subjects responses to three main ways of viewing entrepreneurships. The first was an individualistic, ideal image of entrepreneurship. This was mostly evaluated positively and gained wide approval especially among interviewees who included entrepreneurship among their employment choices. Entrepreneurship was seen as the decision to earn one s living independently. In this individualistic image of entrepreneurship, the social context was hardly ever mentioned. Elements which were seen to threaten this ideal image were evaluated negatively. When entrepreneurship was evaluated negatively using the individualistic image of entrepreneurship, it was mentioned that it forced one into a never ending cycle of work and uninterested duties. The relationistic image of entrepreneurship was used as a speech resource when the social context was constructed as an economic resource or a threat to the ideal image of entrepreneurship. In the second view, entrepreneurship was characteristically seen as being based on economics, which was seen as a threat to the ideal individualistic image of entrepreneurship. The risk of economic failure was seen as a limiting factor to entrepreneurial ambitions as it forced entrepreneurs to work around the clock. The third view concerned the relationship between entrepreneurship and the academic world. Entrepreneurship as an employment choice for university educated persons was evaluated as relevant, and thus positively, when university education was constructed as a resource for entrepreneurship - and irrelevant and thus negatively when it was construed as an obstacle, too wide, or when successful entrepreneurship was seen as being mostly based on an individual s personal characteristics. The interviewees with no entrepreneurial intentions expressed the view that academic education didn t provide the proper skills and knowledge for entrepreneurship. The interviewees also expressed interest in university entrepreneurship education, although none had experience on this. The interviewees emphasized the fact that the University didn t encourage them to consider entrepreneurship as a relevant employment choice. The assumption made by this study was that becoming an entrepreneur is a conscious decision, the environment may influence an individual s decisions on how to make a living as it tends to socialise people to act in accordance with cultural traditions. Keywords: Entrepreneurship, Attitudes towards entrepreneurship, Intentional behaviour, Entrepreneurial intention, University entrepreneurship education, Qualitative attitude research (Vesala & Rantanen 1999, 2007), Rhetorical social psychology (Billig 1986), The theory of entrepreneuship s two images: individualism and relationism (Vesala 1996 ), The planned behaviour theory (Ajzen 1985, 1991a, b)

Enzymatic cross-linking of β-casein and its impact on digestibility and allergenicity

Protein modification via enzymatic cross-linking is an attractive way for altering food structure so as to create products with increased quality and nutritional value. These modifications are expected to affect not only the structure and physico-chemical properties of proteins but also their physiological characteristics, such as digestibility in the GI-tract and allergenicity. Protein cross-linking enzymes such as transglutaminases are currently commercially available, but also other types of cross-linking enzymes are being explored intensively. In this study, enzymatic cross-linking of β-casein, the most abundant bovine milk protein, was studied. Enzymatic cross-linking reactions were performed by fungal Trichoderma reesei tyrosinase (TrTyr) and the performance of the enzyme was compared to that of transglutaminase from Streptoverticillium mobaraense (Tgase). Enzymatic cross-linking reactions were followed by different analytical techniques, such as size exclusion chromatography -Ultra violet/Visible multi angle light scattering (SEC-UV/Vis-MALLS), phosphorus nuclear magnetic resonance spectroscopy (31P-NMR), atomic force (AFM) and matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF MS). The research results showed that in both cases cross-linking of β-casein resulted in the formation of high molecular mass (MM ca. 1 350 kg mol-1), disk-shaped nanoparticles when the highest enzyme dosage and longest incubation times were used. According to SEC-UV/Vis-MALLS data, commercial β-casein was cross-linked almost completely when TrTyr and Tgase were used as cross-linking enzymes. In the case of TrTyr, high degree of cross-linking was confirmed by 31P-NMR where it was shown that 91 % of the tyrosine side-chains were involved in the cross-linking. The impact of enzymatic cross-linking of β-casein on in vitro digestibility by pepsin was followed by various analytical techniques. The research results demonstrated that enzymatically cross-linked β-casein was stable under the acidic conditions present in the stomach. Furthermore, it was found that cross-linked β-casein was more resistant to pepsin digestion when compared to that of non modified β-casein. The effects of enzymatic cross-linking of β-casein on allergenicity were also studied by different biochemical test methods. On the basis of the research results, enzymatic cross-linking decreased allergenicity of native β-casein by 14 % when cross-linked by TrTyr and by 6 % after treatment by Tgase. It can be concluded that in addition to the basic understanding of the reaction mechanism of TrTyr on protein matrix, the research results obtained in this study can have high impact on various applications like food, cosmetic, medical, textile and packing sectors.

Stereoselectivity in the addition of hydrogen chloride to cyclohex-1-enecarbonitrile: Possible role of chlorine lone pair-nitrile π-orbital pseudoallylic A1, 3 interaction

The (overall trans) addition of hydrogen chloride to cyclohex-1- enecarbonitrile in anhydrous alcoholic media proceeds to give cis-2-chlorocyclohexanecarboxylate (together with some cis-2- chlorocyclohexanecarboxamide): no corresponding products with the trans-configuration are detectable. In anhydrous ether the addition proceeds to give a single isomer, presumably cis-, of 2-chlorocyclohexanecarbonitrile, indicating that the configuration of the products may not be equilibrium-controlled in alcoholic media. An examination of the steric factors indicates that the transition state for protonation of the presumed intermediate, 2-chlorocyclohexylidenemethylideneimine, leading to cis-product is favoured if interaction between the lateral π-orbital of the C-N double bond and the lone-pairs on the chlorine atom at the 2-position is large. Consideration of interactions in the transition states meets Zimmerman's criticism that invoking A1, 3 interaction existing in ground states to explain product configuration takes insufficient account of the Curtin-Hammett principle.

Purification and characterization of endo-1,4-β-xylanase from Paecilomyces varioti Bainier

An endo-xylanase (1,4-β-d-xylanxylanohydrolase EC 3.2.1.8) was isolated from the culture filtrate of Paecilomyces varioti Bainier. The enzyme was purified 3.2 fold with a 60% yield by gel filtration and ion exchange chromatography. The purified enzyme had a molecular weight of 25,000 with a sedimentation coefficient of 2.2 S. The isoelectric point of the enzyme was 3.9. The enzyme was obtained in crystalline form. The optimum pH range was 5.5–7.0 and the temperature, 65°C. The Michaelis constant was 2.5 mg larchwood xylan/ml. The enzyme was found to degrade xylan by an endo mechanism producing arabinose, xylobiose, xylo- and arabinosylxylo-oligosaccharides, during the initial stages of hydrolysis. On prolonged incubation, xylotriose, arabinosylxylotriose and xylobiose were the major products with traces of xylotetraose, xylose and arabinose.

Afrikkalaisen sikaruton mahdollisia maahantuloreittejä

Afrikkalainen sikarutto on lakisääteisesti vastustettava helposti leviävä sikojen ja villisikojen virustauti, jolla on myös vakavia sosioekonomisia vaikutuksia. Akuutissa tautimuodossa eläimillä esiintyy syömättömyyttä, korkeaa kuumetta, verenpurkaumia iholla, veristä ulostetta sekä mahdollisesti ripulia. Kuolleisuus on lähes 100 % ja tauti johtaa kuolemaan 7-10 vrk tartunnan jälkeen. Tauti ei tartu ihmisiin. Tautia esiintyy sekä kesy- että villisioissa suurimmassa osassa Saharan eteläpuolista Afrikkaa ja Sardiniassa. Vuodesta 2007 lähtien tautia on esiintynyt Kaukasuksen alueella ja vuonna 2011 lähellä Suomen rajaa: Leningradin alueella ja Kuolan niemimaalla. Tässä riskiprofiilissa kartoitetaan reitit ja tapahtumasarjat, jotka voivat johtaa siihen, että afrikkalainen sikarutto tulee Suomeen ensimmäisen kerran. Näistä oleellisimmat ovat: maahantulo infektioalueella matkustaneiden ihmisten mukana, infektoituneen lihan tai lihatuotteen mukana, elävien kesysikojen ja sperman mukana, kontaminoituneiden eläinkuljetusajoneuvojen mukana, kansainvälisen liikenteen ruokajätteen mukana ja Suomeen vaeltavan infektoituneen villisian mukana. Tilatason tautisuojaus sekä tehokas ja kohdennettu tiedottaminen taudin vaaroista ovat avainasemassa, kun halutaan suojata Suomen sikaelinkeinoa afrikkalaiselta sikarutolta.

Dietary aspects of cow's milk allergy in young children

Cow s milk allergy (CMA) affects about 2-6% of infants and young children. Environmental factors during early life are suggested to play a role in the development of allergic diseases. One of these factors is likely to be maternal diet during pregnancy and lactation. The association between maternal diet and development of CMA in offspring is not well known, but diet could contain factors that facilitate development of tolerance. After an established food allergy, another issue is gaining tolerance towards an antigen that causes symptoms. The strictness of the elimination depends on the individual level of tolerance. This study aimed at validating a questionnaire used to inquire about food allergies in children, at researching associations between maternal diet during pregnancy and lactation and subsequent development of cow s milk allergy in the offspring, and at evaluating the degree of adherence to a therapeutic elimination diet of children with CMA and factors associated with the adherence and age of recovery. These research questions were addressed in a prospective birth cohort born between 1997 and 2004 at the Tampere and Oulu University Hospitals. Altogether 6753 children of the Diabetes Prediction and Prevention (DIPP) Nutrition cohort were investigated. Questionnaires regarding allergic diseases are often used in studies without validation. High-quality valid tools are therefore needed. Two validation studies were conducted here: one by comparing parentally reported food allergies with information gathered from patient records of 1122 children, and the other one by comparing parentally reported CMA with information in the reimbursement records of special infant formulae in the registers of the Social Insurance Institution for 6753 children. Both of these studies showed that the questionnaire works well and is a valid tool for measuring food allergies in children. In the first validation study, Cohen s kappa values were within 0.71-0.88 for CMA, 0.74-0.82 for cereal allergy, and 0.66-0.86 for any reported food allergy. In the second validation study, the kappa value was 0.79, sensitivity 0.958, and specificity 0.965 for reported and diagnosed CMA. To investigate the associations between maternal diet during pregnancy and lactation and CMA in offspring, 6288 children were studied. Maternal diet during pregnancy (8th month) and lactation (3rd month) was assessed by a validated, 181-item semi-quantitative food frequency questionnaire (FFQ), and as an endpoint register-based information on diagnosed CMA was obtained from the Social Insurance Institution and complemented with parental reports of CMA in their children. The associations between maternal food consumption and CMA in offspring were analyzed by logistic regression comparing the highest and lowest quarters with two middle quarters of consumption and adjusted for several potential confounding factors. High maternal intake of milk products (OR 0.56, 95% CI 0.37-0.86 p = 0.002) was associated with a lower risk of CMA in offspring. When stratified according to maternal allergic rhinitis or asthma, a protective association of high use of milk products with CMA was seen in children of allergy-free mothers (OR 0.30, 95% CI 0.13 - 0.69, p < 0.001), but not in children of allergic mothers. Moreover, low maternal consumption of fish during pregnancy was associated with a higher risk of CMA in children of mothers with allergic rhinitis or asthma (OR 1.47, 95% CI 0.96 - 2.27 for the lowest quarter, p = 0.043). In children of nonallergic mothers, this association was not seen. Maternal diet during lactation was not associated with CMA in offspring, apart from an inverse association between citrus and kiwi fruit consumption and CMA. These results imply that maternal diet during pregnancy may contain factors protective against CMA in offspring, more so than maternal diet during lactation. These results need to be confirmed in other studies before giving recommendations to the public. To evaluate the degree of adherence to a therapeutic elimination diet in children with diagnosed CMA, food records of 267 children were studied. Subsequent food records were examined to assess the age at reintroduction of milk products to the child s diet. Nine of ten families adhered to the elimination diet of the child with extreme accuracy. Older and monosensitized children had more often small amounts of cow s milk protein in their diet (p < 0.001 for both). Adherence to the diet was not related to any other sociodemographic factor studied or to the age at reintroduction of milk products to the diet. Low intakes of vitamin D, calcium, and riboflavin are of concern in children following a cow s milk-free diet. In summary, we found that the questionnaires used in the DIPP study are valid in investigating CMA in young children; that there are associations between maternal diet during pregnancy and lactation and the development of CMA in offspring; and that the therapeutic elimination diet in children with diagnosed CMA is rigorously adhered to.

Consumers' attitudes towards food prices

High food prices can be a barrier to healthy eating because some of the food products may be perceived as expensive. Understanding the role of price in food purchase situations is important, but only a few studies document attitudes towards expensiveness or cheapness in foods. In this thesis, the role of food price in food choice and consumers attitudes towards food prices were investigated and the aim was to measure the food price attitudes. Food price attitudes were hypothesized to have an impact on consumers willingness to pay judgements and their willingness to buy premium-priced food products. First, using qualitative data consisting of 40 thematic interviews the experiences of the expensiveness and cheapness in foods were explored by using functional food products as a target product category. Second, a Food Price Attitude Scale was developed using four quantitative surveys representing Finnish consumers (2001 N=1158; 2002 N=1156; 2004a N=1113; 2004b N=1027). Food price attitudes were confirmed to compose a multidimensional construct and consumers may perceive positive and negative attitudes towards both high and low food prices. Finnish consumers were clustered into four groups based on their food price attitudes. In the first group, 29% of respondents were negative towards high food prices and they were willing to seek low food prices, whereas respondents in another group (22%) were positive towards high food prices. Additionally, in the third group consumers (17%) were willing to pay for high quality but still looked for low food prices. In the fourth group, consumers (32%) were willing to look for low food prices, unwilling to pay for high quality, but high-priced food was appreciated if offered to others. It was found in qualitative data that consumers willingness to accept high prices in foods was connected to price fairness and to justifications. Feelings of fairness or unfairness might be a core element of food price attitudes. Using quantitative methods, it was confirmed that positive attitudes towards high food prices in terms of high quality enhanced consumers willingness to buy food products with certain benefits (e.g., a health claim). Additionally, the favourable attitude towards low food prices lowered the willingness to pay estimates. This type of tendency, however, can create a possible bias in small convenient samples. In the food price-related research, it is advisable to take into account food price attitudes as possible background variables. The Food Price Attitude Scale needs further development to increase construct validity even though, in the present study, it was shown to be a reliable measure with good predictive and discriminant validity. The theoretical and managerial implications of the results for a better understanding of the role of price in consumers food purchases are discussed.

Oxidation of substituted benzylic hydrocarbons and naphthalenes by peroxydisulphate in the presence of metal ions

Oxidations of various substituted benzylic hydrocarbons with peroxydisulphate in the presence of metal ion catalysts like iron, nickel, copper, cobalt, silver and cerium were examined. Among the metal ions copper (II) catalysed reaction gives products in excellent yield, whereas oxidation of naphthalene and substituted naphthalenes gives low to moderate yield of the products with peroxydisulphate- copper (II).

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.