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  • Chemistry  (407,122)
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  • LUNAR AND PLANETARY EXPLORATION
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  • Islamic Azad University, Science and Research Branch, Tehran, Fisheries  (13)
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  • 1
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19475 | 17408 | 2016-01-25 09:48:26 | 19475 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-06-29
    Description: Fish sauce is a popular fermented product used in south Asian countries which is made from different small fishes in this research work it was attempted to produce fish sauce from kilka of the Caspian sea, the fish sauce was made from three models of kilka ,such as whole kilka , cooked whole kilka and dressed kilka , each of these models treated it four different fashions of fermentation such as:1- Traditional method, 2- Enzymatic method 3- Microbial method, 4- Mixture of enzyme and microb The results of this investigation showed that time of fermentation for the traditional method was six month, enzymatic method one month, microbial method 3 month and the mixture of enzyme and microb 1 month. The rate of fermentation was least for dressed Kilka, microbial and biochemical changes of Kilka fish sauce were evaluated, total bacterial count was 2.1-6.15 log cfu/ml total volatile nitrogen (TVN) in samples recorded was 250 mg /100g, the amount of protein varied between 10-13 percent, the name of commercial enzymes added was Protamex and Flavourzyme, the bacteria added was L act ob acillus and Pediococous, fish sauce containers fish and 20% salt, temperature of keeping for fermentation was 37 degree c for 6 month.
    Description: PhD
    Description: Advisors: S. Moini Counsellors: A. keyvan, Gh. Vosoughi
    Keywords: Aquaculture ; Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
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  • 2
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19311 | 17408 | 2016-02-08 10:25:26 | 19311 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-06-25
    Description: The first aim of this research was to identify fatty acids, amino acids composition of Thunnustonggol roe and their changes during cold storage (-18'C). The second aim was to determinethe changes of moisture, protein, fat and ash contents of the roe during one year cold storage(-18'C). 60 samples of longtail tuna (Thunnus tonggol) ovaries were randomly collected formBandar-e-Abbas landings. The samples were frozen at-30'C and kept in cold store at -18'Cfor one year. According to a time table, the samples were examined for identification offatty acids, amino acids, moisture, protein, fat, ash, peroxide and T.V.N. and their changeswere evaluated during this time. The results showed that 26 fatty acids were identified. Theunsaturated fatty acids (UFA) and saturated fatty acids (SFA) were 62.33 and 37.6%,respectively, in fresh roe. So that, DHA (C22:6) and oleic acid (C18:1) had high amounts(24.79 and 21.88%) among the UFA and palmitic acid (C16:0) was the most content(22.75%) among the SFA. The PUFA/SFA was 0.91. Also, 17 amino acids were identifiedthat essential amino acids (EAA) and nonessential amino acids (NE) were 10478 and 7562mg/100g, respectively, and E/NE was 1.38. Among the EAA and NE, lysine (2110mg/100g)and aspartic acid (1924 mg/100g) were the most contents. Also, results showed that moisture,ash, protein and fat contents were 72.74, 1.8, 19.88 and 4.53%, respectively, in fresh roe. Theeffects of freezing and cold storage on the roes showed that UFA and SFA contents havereached to 49.83 and 48.07%, respectively, at the end of cold storage. It indicated that thesecompounds change to each other during frozen storage. Also, n-3 and n-6 series of fattyacids were 32.75 and 1.61% in fresh roe. But their contents decreased to 22.96 and 1.25% atthe end of period. Among the fatty acids, 22:6 and C16:0 had the most changes. The changesof fatty acids were significantly at 95% level except for C15:1, C18:3(n-3) and C20:4(n-6).All of the amino acids decreased in frozen storage and their changes were significantly(P〈0.05). EAA was 7818 mg/100g and E/NE was 1.27 at the end of storage period. Amongthe amino acids, leucine and lysine had the most changes. Moisture, ash, protein and fatcontents were 70.13, 1.82, 19.4 and 6.51%, respectively, at the end of storage period. Theperoxide value and T.V.N. increased during storage. So that, their contents have reached to5.86 mg/kg and 26.37 mg/100 g, respectively, at the end of frozen storage. The best shelf lifeof Thunnus tonggol roe was 6 or 7 months, because of lipid oxidation and increasing ofperoxide.
    Description: PhD
    Description: Advisors: S. Moeini Counsellors: A. Keyvan, M. Yousefian
    Keywords: Biology ; Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
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  • 3
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19301 | 17408 | 2016-02-01 21:14:27 | 19301 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-14
    Description: Fish protein concentrate (FPC) is a healthy, sustainable and high nutritiveproduct which sanitized produced from fishes in which, protein and othernutrients are more concentrated than in fresh fishes.The aim of this research is to study on the sustainability of FPC producedfrom Kilka (Clupeonella engrauliformis , C. grimmi and C. cultriventris)in two Vaccum Packaging and Modified Atmosphere Packaging atdifferent environmental factors during six months.In our study the analysis of FPC protein showed 91.2%, lipid: 0.5%, ash:3.6%, moisture: 2.3%, Total Volatile Nitrogen: 10 ml/100gr andperoxide: 5meq/kg. Amino acids and fatty acids were also determined.Bacteria and Fungi were lower than 1000 colony. Samples are kept indifferent condition of temperature (5, 20 and 35 degree centigrade),humidity (25, 40 and 90 percent) and light and dark environment in sixmonth.Lipid rate in FPC after 6 months in VP and MAP (60% C02, 30 % N2 and10% O2), packages was decreased but was not significant (P〉0.05). It wasalso detected that increase temperature lead to more decrease in lipidcontent. Protein rate of FPC was decreased from 91.2% to 73.6% duringsix months at 35°C in VP Package and from 91.2% to 69.4% in MAPpackage. These changes were significant (P〈0.05). TVN and PV rate inFPC after 6 months in VP and MAP packages was increased but wassignificant (P〈0.05). Amino acids and fatty acids were also determined.But more changes in MAP packages was detected.
    Description: PhD
    Description: Advisors: Abbas Ali Motalebi Counsellors: Wadud Rzvylar, Aliasghar Khanipoor. The full text document is in Farsi only so it has not been possible for AC Editors to check the metadata input.
    Keywords: Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
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  • 4
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19474 | 17408 | 2016-01-25 09:45:47 | 19474 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-06-29
    Description: At the fishing season, in 2000, samples of species persian sturgeon (A. persicus), Severjuga (A. stellatus) and Mullet (L. aurata), were caught from the southern coasts of Caspian Sea and were freezes and preserved in the cold storage for one year They have also become biometery. The tissue's fillet were identified in order to determined the Fatty Acids. This was done during one year, frequently, fresh, two weeks after freezing and then monthly, respectively. So, after the extraction of lipids from the tissues and methylation, was injected to the gas-liquid Chromatography. After calibration, identified Fatty Acids were compared with standards according to their Retention Times. Peroxid value, lipid content and humidity were controlled. The unsaturated Fatty acids had The most amount, and a plenty of Polyunsaturated Fatty acids (PUFA) were observed, so that linoleic (C18:2), a-linolenic (C18:3), Arashidonic (C20:4), EPA (C20:5) and DHA (C22:6) Fatty acids had high amounts. The w-3, PUFA were more in comparison with w-6. The effects of freezing and cold storing on the fish fatty acids , were evaluated by the statistical tests , like SPSS, Tukey, Homogenous and Anova, and showed that in some species, a group of Fatty acids, specially PUFA, had some variation. The peroxide value that indicates the lipid deterioration, increased during toring. So, the best term if preserving in the cold storage, were determined and their Nutrition value and Medical applications due to their consumption were investigated.
    Description: PhD
    Description: Advisors: Sohrab Moeini Counsellors: Amin Keyvan, Mehdi Yousefian
    Keywords: Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
    Format: application/pdf
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  • 5
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19139 | 17408 | 2016-02-06 09:39:39 | 19139 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: Biodegradable protein-based film was developed by incorporating cinnamon essential oil(CEO) into whey protein concentrate (WPC) at level of 0.8% and 1.5% v/v. Then physicaland mechanical properties of the films were evaluated. Adding CEO to the WPC matrixdecreased the water vapour permeability of the films and water solubility. Films containingCEO showed significant antibacterial activity both gram-positive and gram-negative strainsand exhibited significant inhibitory effect on the studied fungi. In continue, the effect ofwhey coating and whey coating incorporated with 1.5% CEO on quality and shelf life ofHuso huso fillet during refregrated (4±1°C) storage period were also investigated. The controland treated fish samples were analyzed for microbiological (total viable count, psychrophiliccounts), chemical (PV, TBA, FFA, pH, TVB-N), and sensory characteristics in 4-dayintervals up of microbial, chmical and sensoy analyses indicated lower levels of PV, TBA,FFA, pH, TVB-N in coasted sampels and specially, those with CEO while were kept inrefrigerator. Based on results, whey protein edible coating contain 1.5% cinnamon essentialoil could enhance preserving ability Huso huso during storage cold.
    Description: PhD
    Description: Advisors: M. Rezaei Counsellors: M. Soltioni, A. kamali
    Keywords: Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
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  • 6
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19143 | 17408 | 2016-02-06 09:45:48 | 19143 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: The ever-increasing population of the world and the growing need for animal protein has doubled the modern man’s demand for food. Additionally, the improvement in the general public health, and the worsening of environmental/ecological pollution have prompted today’s world to look for ways to procure healthy food. And one such attempt is the use of natural preservatives to decrease the bacterial load in foodstuffs, in other words, to increase their durability.This study evaluates the effects of different concentrations of Zataria multiflora Bioss (EO 0, 0.005, 0.015, 0.045, 0.135, 0.405%) and Nisin (0, 0.25, 0.5, 0.75 μg/ml) and storage time (9 days) on the growth of Lactococcus garvieae Ir-170A(856bp) alone, and their combination in a food model system (fillets of the rainbow trout (Oncorhynchus mykiss). Additionally, the growth of a sample of this bacteria in laboratory conditions was studied.The results of this study showed that different concentrations of Nisin had a significant impact (p〈0.05) on Lactococcus garvieae.With the value of t in 0.75 μg/ml, the effectiveness rose to 65.77%; the biggest effect on Lactococcus garvieae. And the effect at 4 0C exceeded 80C.The study has also demonstrated that all concentrations of Zataria multiflora Bioss were effective against Lactococcus garvieae. However, with the value of t at 0.405%, the effectiveness was 71.91%. This value had the biggest effect on Lactococcus garvieae. At 4 0C, the effect surpassed the one at 80C.The synergistic effects of the EO and Nisin showed that with the value of t at 0.405% EO and 0.75 μg/ml Nisin was 14.62% had the greatest effect on Lactococcus garvieae.In this study, multi-factorial effects for different concentrations of Zataria multiflora Bioss (EO 0, 0.005, 0.015, 0.0025%), three different concentrations of122Nisin (0, 0.25,0.75 μg/ml) and two different levels of PH (5.5 , 7) at two incubation temperatures (15,37) on logp% of Lactococcus garvieae during 43 days in BHI broth were evaluated. Most of the effects on Lactococcus garvieae occurred in PH 5.5 and at a temperature of 150C.
    Description: PhD
    Description: Advisors: Mehdi Soltani, A. Akhondzadeh Basti. counsellor: A. Kamali
    Keywords: Aquaculture ; Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
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  • 7
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19304 | 17408 | 2016-02-08 10:30:38 | 19304 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-14
    Description: The main aim of this research was to identify fatty acids composition of Caspian sea of White fish Rutilus frisi kutum tissue and their changes during one year cold storage (-18Ċ).The secondary aim was to determine the changes of moisture, ash, protein, fat, and to investigate the effects of storage time on peroxide, TBAi, FFA, and extractability of myofibrillar proteins of the fish tissue during one year cold storage (-18 Ċ). 10 samples of (Rutilus frisi kutum) were randomly collected from Anzali landings. The samples were frozen at -30 Ċ and kept in cold storage at -18Ċ for one year. According to time table, the samples were examined. The results showed that 27 fatty acids were identified. The unsaturated fatty acids (UFA) and saturated fatty acids (SFA) were 74/09 and 21/63 %, respectively, in fresh tissue. So that DHA (C22:6) oleic acid (C18:1c) had high amounts (15/07 ,20/57 ) among the UFA and palmitic acid (C16:0) was the most (13/09 %) among the SFA. The effects of freezing and cold storage on fish tissue showed that UFA and SFA contents have reached to 58/79 and 22/17 %, respectively, at the end of cold storage. It indicated that these compound change to each other during frozen storage. Also ω-3 and ω-6 series of fatty acids was 24/22 and 15/56% in fresh tissue, but their contents decreased to 8/68 and 5/11% at the end of period. Among the fatty acids C22:6, C18:1c and C16:0 had the most changes. The changes of fatty acids were significantly at 95% level expected for C18:0. Results showed that moisture, ash, protein, and fat contents were 75/9±0/03, 1/28±0/012, 21/8±0/2, and 4/1±0/01 % respectively, in fresh tissue. The moisture, ash, protein, and fat contents were 72/3±0/04, 1/83±0/05, 1/91±0/01 and 19/9±0/01 % respectively, at the end of storage period. Lipid damage was measured on the basis of free fatty acids (FFA), peroxide value (PV), and Thiobarbituric acid index (TBA-i). PV, TBARS and FFA concentration of frozen Caspian Sea white fish stored at -18 Ċ the temporal variation of these three variables were statistically significant (p〈0.001). Results of White fish myofibrillar proteins showed aggregation of bound reduced for stored at 12 months. SDS-PAGE analysis revealed that, the intensity of the myosin heavy chain and actin bound was reduced with increasing storage time. SDS-PAGE patterns showed that myosin heavy chain was much more susceptible to hydrolysis than actin.Key words: Rutilus frisi kutum, frozen storage, ω-3, ω-6, protein myofibrillar
    Description: PhD
    Description: Advisors: Sohrab Moeini, Nasser Ghaemi Counsellors: A.K. Haghdost
    Keywords: Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
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  • 8
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19186 | 17408 | 2016-02-06 09:46:24 | 19186 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: In this study microbiological , chemical quality and fatty acid composition ofgrass carp (Ctenopharyngodon idella) fillets treated by dipping in sodiumacetate (%1 and %3), nisin (% 0.1 and % 0.2) and combination of sodiumacetate and nisin was evaluated during 16 days of refrigerated of 4°CAntilisterial effect of nisin was enhanced with the increased concentration ofsodium acetate. At day 12 post storage, Listeria monocytogenese count washigher in the control group than the recommended value, however in sodiumacetate and nisin treated samples, the count was lower (5.17-5.91 log cfu/g).With increasing the concentrations of sodium acetate, mesophilic counts werelower. Regarding nisin, better results was obtained by applying %0.1 nisin.Greater inhibition of mesophile bacteria was observed when combinationtreatment was used. The number of lactobacillus was lower when higherconcentrations of sodium acetate and nisin were used.Total Volatile Nitrogen values at the end of the experiment were lower in thesamples treated with both nisin and sodium acetate and the better results wereobtained in combination treatments. Peroxide (PV) at the end of the experimentwas 1.9 meq/kg in control, and the lowest values were observed for thetreatments 3(%0 sodium acetate +% 0.2 nisin) and 9(%3 sodium acetate +% 0.2nisin) between 1.08 and 1.62 meq/kg without significant difference.Thiobarbituric acid (TBA) levels at the end of experiment have been shown tobe 0.46 mg malonaldehyde per kg in the control. On the other hand treatments 9had the TBA values of 0.19 mg malonaldehyde per kg which was significantlylower than that of control.Polyunsaturated fatty acids increased by increasing the sodium acetate dosesand instead saturated fatty acids and n-6/n-3 ratio decreased. The ratio ofUFA/SFA and also C22:6/C16:0 increased when a higher concentration ofsodium acetate has been used. The best result obtained by using 3% of sodiumacetate but no such relation with nisin was observed.
    Description: PhD
    Description: Advisors: Mehdi Soltani, Abolghasem Kamali Counsellors: Mohammad Reza Ghomi, Seyed Ebrahim Hoseini
    Keywords: Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
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  • 9
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19182 | 17408 | 2016-02-06 09:57:11 | 19182 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: Effects of different thawing method i.e. in a refrigerator, in water, at air ambient temperature and in a microwave oven on proximate, chemical (PV, TBA, FFA, TVB-N, SSP, FA), biochemical (pH, WHC,ThL), microbial (total viable, psychrotrophic, coliform, Shewanella and yeast-mould count) and sensory analysis were carried out on frozen whole Caspian sea Kutum (Rutilus frisii kutum) and Rainbow trout (Oncorhynchus mykiss) carcasses. The values of ash, protein, SSP, WHC, PUFA, PUFA/SFA. EPA+DHA/C16:0, pH, and microbial count of thawed samples decreased significantly while fat, PV, TBA, FFA, TVB-N, SFA and MUFA increased compared to the fresh fish (unfrozen) as control samples. Also, sensory evaluation all of thawed samples showed a significant (p〈0.05) quality loss compared to the fresh fish as control samples. The lowest chemical and biochemical values as well as microbial growth were determined in water thawed samples. Therefore, based on this study thawing in water is most suitable for frozen whole rainbow trout.
    Description: PhD
    Description: Advisors: Masoud Rezaei, Mehdi Soltani Counsellors: Mohammad Haghighi, Reza Pourgholam
    Keywords: Aquaculture ; Biology ; Chemistry
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
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  • 10
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19245 | 17408 | 2016-02-08 10:18:48 | 19245 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: There is an increasing demand in developing newer and safer methods in preserving food products.Among which herbal additives seem to attract evermore attention recently.the major advantage of herbal additives is due to their favorable aroma besides their antimicrobial effects and less expensive than chemical additives. Zataria multiflora Boiss is a native Iranian herb which is used vastly as a food preserver essential oils and also medical usage.Metabolites of harmless bacteria, such as Nisin are also known to be safe preservatives that have antimicrobial activity.However to establish the usefulness of natural antimicrobial preservatives, they must be evaluated alone and in combination with other preservation factors to determine whether there are synergistic effects in rigid media .In this study were evaluated the effects of different concentrations of Zataria multiflora (EO 0, 0.005, 0.015, 0.045, 0.135, 0.405 ,0.810 %) and Nisin(0, 0.15, 0.25, 0.75 μg/ml) and Storage time (up to 21 days) on growth of Staphylococcus aureus ATCC 6538 in a food model system(light salted fish of silver carp, Hypophthalmichthys molitrix).The results on growth of S. aureus were evaluated using SPSS 15.0 statistical software (SPSS 15.0 for windows, SPSS Inc.) and analyzed the logarithm of total count of the bacteria by Tukey Test. Results were considered statistically significant when P≤0.05.The growth of Staphylococcus aureus was affected significantly(P〈0.05) by EO and Nisin and also combinations of EO and Nisin.Samples treated with 0.135, 0.405 and 0.810% of thyme essential oil showed a significant decrease on the growth of the bacteria compared with an treated samples(P〈0.05). No significant difference was seen on the growth of S.aureus in samples treated with lower concentrations of Z.multiflora(below 0.045%) and untreated group(P〉0.05).The most inhibitory effects were seen in samples treated with 0.405% and 0.810% of thyme essential oil until 9 and 12 days after storage,respectively.Also there was significant inhibtory effect(P〈0.05) in different concentration of nisin on the organism compared with an treated samples.The synergism effects of the Eo and nisin on the growth rate of the bacteria was significant (P〈0.05) compared with untreated samples and samples treated with the Eo or nisin, only. Synergismic effects was observed at concentration of 0.405 and 0.810% of Z. multiflora essential oil with 0.25 μg/ml Nisin, respectively until 15 days after storage.As expected it is preferred to apply the least possible amounts of additives in food preserving that not only are effective and safe but are economically justifiable.
    Description: PhD
    Description: Advisors: Afshin Akhondzadeh Basti, Mehdi Soltani counsellors: Abbas Matinfar
    Keywords: Aquaculture ; Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
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  • 11
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19144 | 17408 | 2016-02-06 09:40:52 | 19144 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: The present study aimed production of a new product with various texture and sensoryproperties in chase of the impetus for increasing human consumption considering suitableresources of Kilka fish in Caspian Sea. Following deheading, gutting, and brining, commonKilka were battered in two different formulations, i.e. simple batter and tempura batter, viaautomated predusting machinery and then, they were fried through flash frying for 30 secondsat 170°C in sunflower oil after they were breaded with bread crumbs flour. The products weresubjected to continuous freezing at -40°C and were kept at -18°C in cold storage for fourmonths once they were packed. Chemical composition (protein, fat, moisture, and ash), fattyacid profiles (29 fatty acids), chemical indices of spoilage (peroxide value, thiobarbituric acid,free fatty acids, and volatile nitrogen), and microbial properties (total bacteria count andcoliform count) were compared in fresh and breaded Kilka at various times before frying (rawbreaded Kilka), after frying (zero-phase), and in various months of frozen storage (phases 1,2, 3, and 4). Organoleptic properties of breaded Kilka (i.e. odor, taste, texture, crispiness,cohesiveness of batter) and general acceptability in the phases 0, 1, 2, 3, and 4 were evaluated.The results obtained from chemical composition and fatty acid profiles in common Kilkadenoted that MUFA, PUFA, and SFA were estimated to be 36.96, 32.85, and 29.12 g / 100glipid, respectively. Levels of ù-3 and ù-6 were 7.6 and 1.12 g / 100 gr lipid, respectively.Docosahexaonoic acid (20.79%) was the highest fatty acid in PUFA group. ù-3/ù-6 andPUFA/SFA ratios were 7.6 and 1.12, respectively. The high rates of the indices and highpercentage of ù-3 fatty acid in common Kilka showed that the fish can be considered asinvaluable nutritional and fishery resources and commonsensical consumption of the speciesmay reduce the risk of cardiovascular diseases. Frying breaded Kilka affected overall fat andmoisture contents so that moisture content in fried breaded Kilka decreased significantlycompared to raw breaded Kilka, while it was absolutely reverse for fat content. Overall fatcontent in tempura batter treatment was significantly lower than that of simple battertreatment (P≤0.05). Presence of hydrocolloids, namely proteins, starch, gum, and otherpolysaccharides, in tempura batter may prohibit moisture evaporation and placement with oilduring frying process in addition to boosting water holding capacity through confining watermolecules. During frying process, fatty acids composition of breaded Kilka with variousbatters changed so that rates of some fatty acids such as Palmitic acid (C16:0), Stearic acid(C18:0), Oleic acid (C18:1 ù-9cis), and linoleic acid (C18:3 ù-3) increased considerablyfollowing frying; however, ù-3/ù-6, PUFA/SFA, and EPA+DHA/C16:0 ratios (Polyan index)decreased significantly after frying. ù-3/ù-6, PUFA/SFA, and EPA+DHA/C16:0 ratios intempura batter treatment were higher than those of simple batter treatment which is anindicator of higher nutritional value of breaded Kilka with tempura batter. Significantelevations were found in peroxide, thiobarbituric acid, and free fatty acids in fried breaded Kilka samples compared to raw samples which points to fat oxidation during cooking process.Overall microorganism count and coliform count decreased following heating process. Bothbreaded Kilka samples were of high sanitation quality at zero-phase according to ICMSFStandard. The results acquired from organoleptic evaluation declared that odor, cohesiveness,and general acceptability indices, among others, had significant differences between thetreatments (P≤0.05). In all evaluated properties, breaded Kilka with tempura batter indifferent phases gained higher scores than breaded Kilka with simple batter. During coldstorage of various treatments of breaded Kilka, total lipid content, PUFA, MUFA, ù-3, ù-3/ù-6, PUFA/SFA, Polyen index decreased significantly. The mentioned reductions inaddition to significant elevation of spoilage indices, namely peroxide, thiobarbituric acid, andfree fatty acids, during frozen storage, indicate to oxidation and enzymatic mechanismactivity during frozen storage of breaded Kilka. Considering sensory evaluation at the end ofthe fourth month and TVB-N contents exceeded eligible rate in the fourth month, shelf life ofthe products during frozen storage was set to be three months at -18°C. The results obtainedfrom statistical tests indicate to better quality of breaded Kilka processed with tempura battercompared to simple batter in terms of organoleptic evaluation, spoilage indices, and highquality of fat in various sampling phases.
    Description: PhD
    Description: Advisors: Ali Asghar Khanipour, Mehdi Soltani Counsellors: Abbasali Motallebi, Abolghasem Kamali
    Keywords: Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
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  • 12
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19118 | 17408 | 2015-12-14 19:22:20 | 19118 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: The purpose of this study, Evaluation the effect of Rosmarinus officinalis and Thymus vulgaris extracts on the stability of poly unsaturated fatty acids in frozen Silver carp minced. Treatments include:Treatment 1 - Control: frozen meat packaged in conventionalTreatment 2: Frozen Silver carp minced+Thyme 300 mg/kg in normal packagingTreatment 3: Frozen Silver carp minced+Rosemary 200 mg/kg in normal packagingTreatment 4: Frozen Silver carp minced+Rosemary compound (100 mg/kg) and Thyme(100 mg/kg) in normal packagingAfter rapid freezing of samples in the spiral freezer by individual quick freezing method, tomaintain the cold temperature (-18) °C were transferred. Sampling and measurements to determine the fatty acid profile of the zero phase beginning in the first month and then every ten days, and 15 days in the second month of the third month after the monthly test.Identifying, defining and measuring the fatty acid profile by gas chromatography was performed. In this study, levels of both saturated and unsaturated fatty acids in threeexperimental and one control were identified as follows:A: saturated fatty acids: Meristic C14: 0/Palmitic C16: 0/Hepta decaenoic C17: 0/Stearic C18: 0/Arashidic C20: 0/B:Mono unsaturated fatty acids: palmitoleic C16: 1-W7/Oleic C18: 1-W9/Gadoleic C20:1-W9C:Poly unsaturated fatty acids: Linoleic C18: 2-W6/α-Linolenic C18: 3-W3D:High unsaturated fatty acids: Arachidonic C20: 4-W6 Eicosapentaenoic acid C20: 5-EPA/W3 Docosahexaenoic C22: 6-DHA/W3Results of this study was to determine, Thyme and rosemary extracts containing silver carpminced stored in freezing conditions, Stability of different types of fatty acids, monounsaturatedfatty acids, poly-unsaturated fatty acids, omega-3 and omega-6 fatty acids are. So that none of the fatty acids measured were not significant 100% increase or decrease,While changes in the fatty acid oxidation during storage time is minimized. The resultsobtained from the fatty acid profiles and indicators of their and statistical tests show that treatment with rosemary extract More stable during storage (-18) ° C In comparison with the control and other treatments are shown; And at relatively low compared to othertreatments and control samples oleic acid and linoleic acid, palmitic more.According to studies,in Silver carp minced that containing rosemary extract, end of the storage period of six months. Were usable, so even rosemary extract the shelf-lifeexamples to increase more than six months.
    Description: PhD
    Description: Advisors: A. A. Motalebi Moghanjvqy, Seyed Ebrahim Hosseini Counsellors: Ali Asghar Khanipour, Mehdi Soltani
    Keywords: Agriculture ; Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
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  • 13
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    Islamic Azad University, Science and Research Branch, Tehran, Fisheries
    In:  http://aquaticcommons.org/id/eprint/19141 | 17408 | 2016-02-01 21:04:45 | 19141 | Islamic Azad University, Science and Research Branch, Tehran
    Publication Date: 2021-07-13
    Description: Nisin is a widely used naturally occurring antimicrobial effective against many pathogenic and spoilage microorganisms. It has been proposed thatreduced efficacy of nisin in foods can be improved by technologies such as encapsulation to protect it from interferences by food matrix components. Theaim of this study was using of spray dried encapsulated nisin with zein in concentration of (0.15 and 0.25 g/kg) and sodium citrate (1.5 and 2.5%) and treatments with both of them to extent the shelf life of filleted trouts packagedby Modified Atmosphere Packaging (45% CO2, 50% N2 ,5% O2) and stored at 4±1 °C for 20 days. Furthermore, to evaluate the antimicrobial efficiency of encapsulated nisin and soudium citrate the trouts fillets was inoculated withStaphylococcus aureus as an index pathogenic bacteria. Assessment of chemical spoilage indexes such as (Proxide value, Thiobarbituric acid, total volatile basenitrogen and pH) , microbial parameters (Total Plate Count, Psychrotrophic count, Lactic acid bacteria count), Staphylococcus aureus cont in treatments which were inoculated with 5 logcfu/g of this bacteria and sensory evaluation of fillets including (smell, color, texture and total acceptability) was carried out indays of 0, 4, 8, 12, 16 and 20. The results revealed that treatment with both exposure of nisin and sodium citrate showed significantly lower chemicalspoilage indexes in comparison with controls (vaccum packed and MAP)(P〈0.05). Furthermore, (nisin 0.25 g/kg sodium citrate 2.5%) treatment whichwas exposed to the maximal level used of both materials was significantly thelowest treatment with (Proxide value, Thiobarbituric acid, total volatile basenitrogen and pH) of 9.95 (meq O2/kg) , 1.55 (mgMA/kg), 29.65 (mgN/100g) and 6.65 , respectively and according to the maximal recommended level of this indices , shelf life of fillets in this treatment was esstimated 20 days.The control(vaccum packed) treatment was significantly the highest treatment with (Proxide value, Thiobarbituric acid, total volatile base nitrogen and pH) of 15.17 (meq O2/kg), 3.03 (mgMA/kg), 38.4 (mgN/100g) and 6.95 , respectively and according to the maximal recommended level of this indices , shelf life of filletsin this treatment was estimated 11 days. Also, in microbial point of view (nisin0.25 g/kg- sodium citrate 2.5%) treatment was the lowest treatment with TotalPlate Count, Psychrotrophic count, Lactic acid bacteria count andStaphylococcus aureus count of 6.7, 6.83, 5.25 and 6.04 logcfu/g respectively,and conrol (vaccum packed) treatment was the highest treatment with 9.15, 9.41, 7.7 and 9.01 logcfu/g respectively. According to the lower results of chemicaland microbial indices and higher sensory evaluated scores assessed in this research for encapsulated nisin in comparison with free nisin , it was concludedthat encapsulation of nisin with zein capsules may improve the efficiency of nisin. The measuremented values of Mass yield, Total solids content of capsules, Encapsulation efficiency, In vitro release kinetics in 200 hour for encapsulated nisin in this study was 49.89, 62, 98.31 and 69% respectively and Encapsulated particle size was lower than 674.21 μm for 90% of particles. As a consequence, nisin , in particular encapsulated nisin, and sodium citrate alone or together with and Modified Atmosphere packaging might be considered as effective tools in preventing the quality degradation of the fillets, resulting in an extension of their shelf life.
    Description: PhD
    Description: Advisors: Seyed Ebrahim Hosseini, Aboulghassem Kamali Counsellorrs: Abbasali Motallebi, Resa Pourgholam
    Keywords: Aquaculture ; Chemistry ; Fisheries
    Repository Name: AquaDocs
    Type: thesis
    Format: application/pdf
    Format: application/pdf
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  • 14
    Keywords: Chemistry ; Chemistry, Physical organic ; Condensed matter ; Quantum theory
    ISBN: 9781402087073
    Language: English
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  • 15
    Keywords: Chemistry ; Engineering ; Magnetism ; Materials ; Optical materials
    ISBN: 9781402087967
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  • 16
    Keywords: Chemistry ; Chemistry ; Mathematics ; Computer simulation ; Computer software ; Weights and measures
    ISBN: 9781402069451
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  • 17
    Keywords: Biology ; Data processing ; Chemistry ; Chemistry, Physical organic ; Materials ; Nanotechnology
    ISBN: 9781402081897
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    Dordrecht : Springer
    Keywords: Chemistry, Physical organic ; Chemistry, inorganic ; Chemistry ; Mathematics ; Materials ; Mathematics ; Physics
    ISBN: 9781402066603
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    Keywords: Chemistry ; Chemistry, Physical organic ; Chemistry ; Mathematics ; Quantum theory
    ISBN: 9781402085468
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    Dordrecht : Springer
    Keywords: Analytical biochemistry ; Chemistry ; Chemistry, Physical organic ; Crystallography ; Molecular structure ; Nanotechnology
    ISBN: 9781402059414
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  • 21
    Keywords: Biochemistry ; Biology ; Data processing ; Biomedical engineering ; Chemistry ; Chemistry, Physical organic ; Materials
    ISBN: 9781402081842
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    Keywords: Analytical biochemistry ; Chemistry ; Materials ; Nanotechnology
    ISBN: 9781402053726
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    Keywords: Chemistry ; Chemistry ; Mathematics ; Computer graphics ; Nanotechnology
    ISBN: 9781402060205
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  • 24
    Keywords: Biochemistry ; Bioinformatics ; Chemistry ; Chemistry, Organic ; Medicine
    ISBN: 9781402050015
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  • 25
    Keywords: Chemistry ; Chemistry, Physical organic ; Materials ; Molecular structure ; Plasma (Ionized gases) ; Quantum theory
    ISBN: 9781402054600
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    Keywords: Chemistry
    ISBN: 9781402062919
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    Keywords: Biochemistry ; Biochemistry ; Chemistry ; Chemistry, Physical organic
    ISBN: 9781402044076
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    Keywords: Catalysis ; Chemistry ; Chemistry, Organic ; Materials ; Nanotechnology ; Polymers
    ISBN: 9781402060915
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    Keywords: Chemistry ; Mathematics ; Computer science ; Logic design
    ISBN: 9781402042232
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  • 30
    Keywords: Chemistry ; Electric engineering ; Nanotechnology ; Optical materials ; Surfaces (Physics)
    ISBN: 9781402048128
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    Keywords: Chemistry ; Chemistry, Physical organic ; Chemistry ; Mathematics ; Crystallography
    ISBN: 9781402048531
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    Dordrecht : Springer
    Keywords: Chemistry ; Chemistry, Physical organic ; Chemistry, inorganic ; Mechanics, applied ; Molecular structure ; Quantum theory
    ISBN: 9781402036880
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    Keywords: Biology ; Data processing ; Biomedical engineering ; Chemistry
    ISBN: 9781402035876
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    Dordrecht : Springer
    Keywords: Catalysis ; Chemical engineering ; Chemistry ; Chemistry, Physical organic ; Chemistry ; Mathematics ; Surfaces (Physics)
    ISBN: 9781402044052
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    Keywords: Chemistry ; Chemistry, Organic ; Chemistry ; Mathematics
    ISBN: 9781402048513
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    Keywords: Chemistry ; Chemistry ; Chemistry ; Mathematics ; Condensed matter ; Quantum optics
    ISBN: 9781402048500
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    Keywords: Chemical engineering ; Chemistry ; Chemistry, Physical organic ; Polymers ; Thermodynamics ; Water pollution
    ISBN: 9781402043826
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    Keywords: Catalysis ; Chemistry ; Condensed matter ; Materials ; Renewable energy sources
    ISBN: 9781402034985
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    Keywords: Chemistry ; Chemistry, Organic ; Chemistry, Physical organic ; Chemistry, inorganic ; Polymers
    ISBN: 9781402023545
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    Keywords: Chemistry ; Chemistry, Physical organic ; Chemistry ; Mathematics ; Computer simulation
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  • 41
    ISSN: 1434-193X
    Keywords: Triplet recombination ; Electron transfer ; Radical ions ; Photochemistry ; Terpenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The triphenypyrylium tetrafluoroborate (TPT)-sensitized reactions of several terpene donor molecules, including sabinene (1), α-phellandrene (4), α-terpinene (5) and γ-terpinene (6) give rise to significantly different products than reactions induced by other electron-transfer sensitizers, such as 1,4-dicyanobenzene (DCB). The divergent reactions require decidedly different key intermediates; the products obtained with TPT can be explained by dissociative recombination of the intermediate radical-radical cation pair in the triplet state, generating donor-derived biradicals.
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  • 42
    ISSN: 1434-193X
    Keywords: Azides ; Cleavage reactions ; Cycloadditions ; Nitrogen heterocycles ; Polycycles ; Ring expansion ; Synthetic methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---2-Alkyl-1-methylquinazolinium hexafluorophosphates 9 are deprotonated by sodium or potassium hydride to afford solutions of 2-alkylidenedihydroquinazolines 10, which were investigated by NMR spectroscopy. Trapping with methanesulfonyl azide (5a) of 10 in situ or subsequent treatment with trifluoromethanesulfonyl azide (5b) gives mixtures of colourless (15) and intensely yellow N-sulfonylimino-1,4-benzodiazepines 16 along with products due to cleavage of the exocyclic double bond of 10, viz. 11 and 13. The ethylidene compound 10b yields the bicyclic products 18 and 19, apparently by complex sequences of reactions that are triggered by removal of the acidic proton at C-2 of 16b and 16f. The structures of the products are based on spectroscopic evidence and X-ray diffraction analyses performed on 15b, 16d, 16e, and 19.
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  • 43
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1589-1593 
    ISSN: 1434-193X
    Keywords: Azaallenium ions ; Azaallylium ions ; Iminium ion ; Kinetics ; Linear Free Energy Relationships ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The rate constants for the reactions of the 2-azaallenium ion 1b+, the 2-azaallylium ion 2a+ and the iminium ion 3+ with different nucleophiles were determined by 1H NMR spectroscopy. By correlation with the Linear Free Enthalpy Relationship (LFER) lg k20°C = s (E + N), developed by Mayr and Patz, the electrophilicity parameters E(1b+) = -3.7, E(2a+) ≍ -16 and E(3+) = -10.43 were obtained. They show that the relative reactivities of these ions are approximately 1012:1:106. Quantum chemical calculations (ab initio, DFT) of the methyl anion affinities for the ions 1b+,2a+ and3+ are in agreement with the experimental E values. The X-ray structure of 3+·CF3SO3- is reported for the first time; it shows no strong interaction between the cation and the anion.
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  • 44
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1595-1601 
    ISSN: 1434-193X
    Keywords: Oxazoline N-oxide ; Cycloadditions ; Cycloadditions ; Lactams ; Thienamycin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---[3+2] Cycloaddition between a camphor-derived oxazoline N-oxide 9 and the γ,δ-unsaturated enamino ester 11 afforded the single adduct 6. A stereoselective reduction of the enamino ester side chain allowed the control of the absolute configuration of the two additional asymmetric centres. Nitrogen protection and oxidative hydrolysis of the resulting product 13, followed by further functional group manipulations, led to the β-lactam derivative 1, a known precursor of the β-methylthienamycin derivative2a.
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  • 45
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1603-1607 
    ISSN: 1434-193X
    Keywords: Boron ; Cyclotrimerizations ; Nitrogen heterocycles ; Macrocycles ; Subphthalocyanines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The regioselective preparation of ortho-substituted subphthalocyanides was achieved employing 3-substituted phthalonitrile derivatives as starting materials. A mechanistic proposal has been outlined.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99525_s.pdf or from the author.
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  • 46
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1609-1615 
    ISSN: 1434-193X
    Keywords: Terpenoids ; Natural products ; Total synthesis ; Cyclizations ; Rearrangements ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---A new route for the synthesis of 2,7- and 7-functionalized labdanes starts from (R)-carvone (1). 11-Nordrim-7-en-9-one (15) is an appropriate starting material for the total synthesis of hispanone (21), a biologically active furolabdane isolated from the Mediterranean medicinal plant Ballota saxatilis.
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  • 47
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1623-1626 
    ISSN: 1434-193X
    Keywords: Iridoid glucoside ; (8S)-Kingiside ; (8S)-Loganin ; (8S)-7-Ketologanin ; Asymmetric synthesis ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The tetraacetyl derivative 8 of the naturally occurring kingiside (8a) was prepared from aucubin (1). Intermediates in the synthesis were (8S)-tetraacetyl loganin (6) and (8S)-tetraacetyl-7-ketologanin (7), whose free (8R)-epimers occur in many different plants (Caprifoliaceae, Loganiaceae). The 13C NMR spectrum allows the structure to be unequivocally identified.
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  • 48
    ISSN: 1434-193X
    Keywords: Tetrakis(dimethylamino)naphthalenes ; Basicity ; Hydrogen bonds ; Cyclicvoltammetry ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---For comparison to the recently described 2,3,6,7-tetrakis(dimethylamino)naphthalene (1) the three isomers 2,3, and 4 were synthesized. The basicities of this group of isomers are strongly dependent upon the different mutual orientations of the pairs of dimethylamino substituents: only the isomers 3 and, partially, 4, both with dimethylamino groups in adjacent peri-positions of the naphthalene, are strong “proton sponges”. For the isomers 1 and 2 with the same number and kind of twofold dimethylamino substituents in neighbouring ortho-positions, however, no significant basicity increase is observed. To explain this difference between the two groups of isomers it is suggested that in the ortho-pairs of 1 and 2 the C-N bonds diverge considerably, leading to an increased N···N distance and consequently to less stable [N···H···N]+ hydrogen bonds in contrast to the parallel C-N bonds in the peri-substituted isomers 3 and 4. X-ray crystal structure analyses of the bases and of some of the salts derived therefrom were solved and are discussed. Cyclic voltammetry indicates that 1 to 4 are strong electron donors, reacting easily to radical cations or dications which with suitable acids have been obtained as salts.
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  • 49
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1677-1683 
    ISSN: 1434-193X
    Keywords: Radicals ; Cyclizations ; Pyridinethione ; Tetrahydrofurans ; Asymmetric synthesis ; Thiazolethione ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The trisubstituted functionalized tetrahydrofurans 10, 11, 16, 18, and 19 were photochemically prepared from 2,3-syn- and 2,3-anti-configuredN-(3-benzoyloxy-5-hexen-2-oxy)thiazole-2(3H)-thione anti-6, pyridinethiones 7, anti-8, and BrCCl3. The formation of tetrahydrofurans was achieved by an efficient and highly regioselective alkoxyl radical cyclization (5-exo-trig). The 2,3-anti substituted intermediates 9 and 12 cyclize stereoselectively whereas a 2,3-syn-configured O-radical affords both possible diastereomeric addition products in equal amounts. The cyclized tetrahydrofuryl methyl radicals were trapped with the bromine atom donor BrCCl3 to afford the bromomethyl-substituted cyclic ethers 10, 11, 18, and 19 in excellent yields. The utility of this reaction was stressed by conversion of one of the newly prepared tetrahydrofurans in a two-step synthesis into (+)-allo-muscarine (+)-20.Supporting information for this article is available on the WWW under //http://www.wiley-vch.de/contents/jc_2046/2000/99590_s.pdf or from the author.
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  • 50
    ISSN: 1434-193X
    Keywords: Thioketones ; Thiocarbonyl ylides ; Cycloadditions ; Cycloreversions ; Sulfur heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Reactions of diaryl thioketones with diazomethane at room temperature afford 4,4,5,5-tetraaryl-1,3-dithiolanes; the scope of this surprising 2:1 interaction has been studied for decades (Schönberg Reaction). The clue to the mechanism was our observation that the stoichiometry is 1:1 at -78 °C, and 2,5-dihydro-2,2-diaryl-1,3,4-thiadiazoles are formed as primary [2+3] cycloadducts. They lose N2 at -45 °C in first-order reactions generating diaryl thioketone S-methylides which can be intercepted by thioketones (→1,3-dithiolanes), multiple CC bonds, or acids HX. In the absence of trapping reagents, the elusive intermediates either dimerize furnishing 2,2,3,3-tetraaryl-1,4-dithianes or give rise to 2,2-diarylthiiranes by electrocyclization. Beyond thiobenzophenone and diazomethane, our main model reaction, the studies involve fluorene-9-thione, 4,4-dimethoxy- and 4,4-dichlorothiobenzophenone. The ring of 2,5-dihydro-2,2-diphenyl-1,3,4-thiadiazole (8) is opened by LDA at -78 °C and derivatives of anion 12 are obtained. - In summa: The Schönberg reaction consists of two 1,3-dipolar cycloadditions, linked by a 1,3-dipolar cycloreversion.
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  • 51
    ISSN: 1434-193X
    Keywords: Conjugation ; Boron ; Sensors ; Cyclic voltammetry ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---New electropolymerizable aromatic compounds (i.e. pyrrole, thiophene, aniline) bearing boronic acid and ester substituents have been synthesized and their electrochemical behavior has been investigated. Functionalized polythiophene and polypyrrole films could be anodically generated in acetonitrile, whereas the polyaniline derivative was electroformed in an acidic aqueous solution. The electrochemical responses of some of these materials were changed when fluoride ions were added to the electrolytic solutions. The strongest modifications, caused by binding of fluoride by the immobilized boron, were observed for the polypyrrole derivative in hydroorganic media.
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  • 52
    ISSN: 1434-193X
    Keywords: Heterocycles ; Zinc ; Palladium ; Catalysts ; Sulfur ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Organozinc halides derived from Grignard reagents behave differently in their reaction with ethyl (±±)-(2RS,3SR)-tetrahydro-4-methylene-2-phenyl-3-(phenylsulfonyl)furan-3-carboxylate (3) according to the hybridisation of the carbon ligand. During the development of short multi-component reactions for the synthesis of diverse functionalized ethyl 2,5-dihydrofuran-3-carboxylates it was discovered that aryl and vinyl zinc halides undergo clean reaction with 3 in the presence of Pd(PPh3)4. In contrast, when alkyl zinc halides are reacted with 3 in the presence of Pd(PPh3)4, reductive desulfonation of 3 is observed. Remarkably, in the absence of a transition metal catalyst, the allylic substitution of 3 with alkyl zinc halides proceeds cleanly and in moderate to good yield.
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  • 53
    ISSN: 1434-193X
    Keywords: Self-assembly ; Vapor-pressure osmometry ; Resorcin[4]arenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Resorcin[4]arene tetracarboxylic acids 5,6 (A) and resorcin[4]arene tetrapyridines 2,3 (P) self-assemble in chloroform solution to form stable heterotopic AP dimers. Data from NMR titration and dilution experiments, as well as from vapor-pressure osmometry (VPO), indicate that the AP dimer is formed with an association constant greater than 107 M-1. Solid-solution extraction experiments are indicative of the formation of a 2:1 trimer (A2P), while self-associated homotopic species (A2 and A3) can be detected by NMR and VPO. Analysis of the heterotopic noncovalent assembly process over a range of compositions shows that these other species are much less stable than the AP heterodimer, which is the exclusive species at an A/P concentration ratio of 1:1 (〉 99.7% of the total at 10 mM).
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  • 54
    ISSN: 1434-193X
    Keywords: Sulfoxides ; β-Amino sulfones ; Mannich type reaction ; Lithium perchlorate ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The LiClO4-mediated one-pot reaction of aldehydes with (trimethylsilyl)dialkyl amines and the lithium salt of sulfoxides or sulfones, affords the corresponding β-(dialkylamino) sulfoxides and β-(dialkylamino) sulfones in high yields. The aminosulfoxidation reaction of aliphatic or aromatic aldehydes lacks diastereoselectivity, but the diastereomeric sulfoxides can be separated by HPLC or column chromatography for further use.
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  • 55
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 2000 (2000), S. 1741-1744 
    ISSN: 1434-193X
    Keywords: Bridged pyranose derivatives ; Ring enlargement ; Carbenes ; Glycosides ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Addition of dichlorocarbene to the glycal (±±)-2 followed by cyclopropyl-allyl rearrangement leads to the chloro-2H-pyran (±±)-4. Oxidation of (±±)-4 and reduction of the obtained hydroxypyranone (±±)-5 gave the methyl pyranoside (±±)-6. The relative configuration of (±±)-6 was established by X-ray structural analysis of the corresponding acetate (±±)-7. The synthesis of the optically active starting materials (+)-2 and (-)-2 is also reported.
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  • 56
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    Liebigs Annalen 2000 (2000), S. 1745-1758 
    ISSN: 1434-193X
    Keywords: CMP-Neu5Ac analogues ; Enzyme inhibitors ; Substrate analogues ; Transition state analogues ; Transferases ; Carbohydrates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quinic acid was transformed into phosphitamides 16, 25, and 36, which could be readily linked to 5′-O-unprotected cytidine derivative 17. Ensuing oxidation of the obtained phosphite triesters with tBuO2H and hydrogenolytic de-O-benzylation furnished the corresponding phosphate diesters 18, 26, and 38. Base catalyzed removal of acetyl protecting groups, and methyl ester hydrolysis furnished CMP-Neu5Ac analogues 1d, 1e, and 2. Quinic acid was also transformed into 1,2-unsaturated diallyl α-hydroxymethyl-phosphate derivatives (R)- and (S)-46, which on reaction with cytidine phosphitamide 47 afforded the phosphite triesters. Subsequent oxidation with tBuO2H and then treatment with NEt3 gave phosphate diester derivatives (R)- and (S)-48. Deallylation, acetyl group removal, and methyl ester hydrolysis furnished (R)- and (S)-3, respectively. Treatment of (R)- and (S)-48 with DBU as a base led to acetic acid elimination, thus yielding, after de-O-allylation, acetyl group cleavage, and ester hydrolysis, diene derivative (E)-4. Donor substrate analogues 1d and 1e exhibited good α(2-6)-sialyltransferase inhibition (Ki: 2.0·10-4 and 2.0·10-5 M). However, transition state analogues (R)-, and particularly (S)-3 showed excellent inhibition properties (Ki: 1.6·10-6 and 2.7·10-7 M).
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  • 57
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    Liebigs Annalen 2000 (2000), S. 1759-1765 
    ISSN: 1434-193X
    Keywords: Cyclitols ; Aminocyclitols ; Glycosidase inhibitors ; α-Mannosidase inhibitors ; Deoxygenation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Three deoxy derivatives 2-4 of the α-mannosidase inhibitor mannostatin A (1) were synthesized, and their inhibition of Jack bean α-mannosidase was evaluated in order to elucidate the roles of each of the three hydroxyl groups of the inhibitor. The 1- and 2-deoxy derivatives 2 and 3 retained some inhibitory activity, although reduced by a factor of about 100 relative to the parent, whereas it was completely lost with the 3-deoxy derivative 4. Structure and activity relationships are discussed in the light of these findings.
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  • 58
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    Liebigs Annalen 2000 (2000), S. 1767-1772 
    ISSN: 1434-193X
    Keywords: Circular dichroism ; Conformation analysis ; s-Triazines ; Chiral auxiliaries ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---CD data of the optically pure 2-[(R)-1-(9-anthryl)ethylamino]-4-chloro-6-[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2[(R)-1-(9-anthryl)ethylamino]-4,6-bis[(R)-1-(1-naphthyl)ethylamino]-1,3,5-triazine, 2,4-bis[(R)-1-(9-anthryl)ethylamino]-6-chloro-1,3,5-triazine are presented. The analysis of the CD spectra by means of the nonempirical DeVoe approach has afforded the complete conformational characterisation of the three s-triazine derivatives, allowing us to establish how the conformation of these derivatives depends on the nature of the substituent 1-arylethylamino groups.
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  • 59
    ISSN: 1434-193X
    Keywords: Cycloadditions ; Carbenes ; Nitrones ; Nitrilimines ; Pyrazolines ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of tert-butylalkynyl chromium Fischer carbene complex 1 with nitrones 2 affords β-enamino-ketoaldehydes 4 by the light-promoted rearrangement of the corresponding [3+2] cycloadduct carbene complexes 3. On the other hand, [3+2] cycloaddition of chiral nonracemic Fischer alkenyl carbene complexes 19 with nitrilimines 10 yields enantiomerically pure Δ2-pyrazolines with high regio- and diastereoselectivity.
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  • 60
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Zinc ; Transition structures ; QM/MM computations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Trimethylsilyl substitutions of the fenchyl alcohols [(1R,2R,4S)-exo-(2-Ar)-1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, Ar = 2-methoxyphenyl (1) and Ar = 2-(dimethylaminomethyl)phenyl (2)] yield the chiral ligands 3 [Ar = 2-methoxy-3-(trimethylsilyl)phenyl] and 4 [Ar = 2-(dimethylaminomethyl)3-(trimethylsilyl)phenyl]. Increased reactivities and enantioselectivities in diethylzinc additions to benzaldehyde are obtained from 3 (63% ee R) and 4 (93% ee S), relative to 1 (26% ee S) and 2 (73% ee S). X-ray crystal structures of 3 and of its methylzinc complex 3-Zn reveal out-of-plane bending of the methoxy groups as major geometrical consequences of the trimethylsilyl substitutions. Analyses of QM/MM ONIOM μ-O transition-structure models for 1, 2, 3, and 4 show that trimethylsilyl-induced distortions of methoxy and of dimethylaminomethyl groups explain the observed increased enantioselectivities.
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  • 61
    ISSN: 1434-193X
    Keywords: Palladium ; exo-π-Allylpalladium complexes ; Allylic alkylation ; Spiro compounds ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The palladium(0)-catalyzed alkylation of 2,3-bis(acetoxymethyl)bicyclo[2.2.1]hepta-2,5-diene 1 with malonate-type enolates as nucleophiles is investigated. A monoalkylated product is formed first, and undergoes (depending on the nucleophile used) a second intramolecular reaction leading to spirocyclopropane-annulated bicyclo[2.2.1]heptene derivatives 5. The formation of endo spirobicyclic cyclopropanes adducts as major isomer is rationalized by assuming formation of an intermediate exo-(π-allyl)palladium complex.
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  • 62
    ISSN: 1434-193X
    Keywords: Ketones ; Reductions ; Micelles ; Cobalt ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Operationally simple and environmentally benign procedures have been developed to selectively reduce different α,β-unsaturated ketones, 4,4-dimethylcyclohex-2-ene-1-one (1), isophorone (2), benzylideneacetone (3), chalcone (4) by NaBH4 or by the system NaBH4 + CoCl2. Alternative reaction media to the extensively used MeOH have been explored, and new procedures take advantage of the acceleration and chemoselectivity induced by water or by aqueous micellar solutions. It was possible to selectively and quantitatively afford pure products of 1,2 and of 1,4 reduction as well as the totally reduced compounds (yield and selectivity 〉 90%) by simple changes in the experimental conditions.
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  • 63
    ISSN: 1434-193X
    Keywords: C-Glycosides ; Conformation analysis ; Molecular dynamics ; Selectins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The conformational behavior of the C-glycosyl analogue of sialyl-α-(2→3)-galactose, synthesized as a glycosidase inhibitor, has been studied using a combination of NMR spectroscopy (J and NOE data) and molecular dynamics calculations. The obtained results show that the population distribution of conformers with respect to the orientation about the pseudo-glycosidic linkages is mainly controlled by steric interactions. This is in contrast to findings made for O-glycosides. In these natural compounds, the conformational behavior about the glycosidic linkage Φ is mainly governed by the exo-anomeric effect.
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  • 64
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    Liebigs Annalen 2000 (2000), S. 1815-1820 
    ISSN: 1434-193X
    Keywords: Asymmetric synthesis ; Palladium-catalysed couplings ; Palladacycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Chiral C2-symmetric N-benzylazetidines have been conveniently prepared from optically pure anti-1,3-diols without loss of enantiomeric purity. N-Debenzylation led to the corresponding N-unsubstituted azetidines, which were then subjected to palladium-catalysed coupling reactions with aryl bromides to afford chiral N-arylazetidines. (R,R)-N-Benzyl-2,4-dimethylazetidine has been employed in the synthesis of a new cyclopalladated complex, which can be used, for instance, as a chiral recognition agent for phosphorus ligands.
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  • 65
    ISSN: 1434-193X
    Keywords: Cyclizations ; Spiro compounds ; Nucleosides ; Isomerizations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Syntheses of the spiro nucleosides 2′-deoxyhydantocidin 3a and its 1′-epimer 3b are described. The newly developed route involves a Horner-Wadsworth-Emmons condensation of the phosphonate 16 with the erythrose derivative 15 affording a mixture of six isomers which was fully assigned by NMR spectroscopy. The mixture was directly converted into the final compounds in an efficient base-catalyzed cyclization reaction. A base-catalyzed interconversion between the two isomers was observed.
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  • 66
    ISSN: 1434-193X
    Keywords: Benzodiazepines ; Heterocycles ; Azeto[1,2-a]-1,5-benzodiazepines ; Cyclizations ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The reaction of o-phenylenediamine (4) with one, two or three equivalents of p-substituted 3-dimethylaminopropiophenone hydrochlorides 5a-e was studied. 4-Aryl-2,3-dihydro-1H-1,5-benzodiazepine derivatives 6a-e were obtained in good yields, along with the 1:2-adducts 7c-e and the unexpected 1:3-adducts rac-8c-e. The type of adduct formed is determined by the molar ratio of the reactants 4 and 5 and by the nature of the substituent in the para position of the propiophenone 5.
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  • 67
    ISSN: 1434-193X
    Keywords: Cup-shaped PAHs ; Host-guest compounds ; Host-guest chemistry ; Cyclizations ; Semiempirical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Cyclotrimerisation of benzo-polycyclic bromostannylalkenes 8a-d with Cu(NO3)2·3H2O in THF affords benzotri(benzonorbornadienes) 3a-d as a mixture of the syn and anti isomers. The ratio of syn to anti is close to the 1:3 statistical value in most cases (i.e. in cyclotrimers 3a,b,d), but highly in favour of the anti isomer in 3c, where steric hindrance by the methoxy groups plays an important role in the stereochemistry of the cyclotrimerisation. The substrates for the cyclotrimerisation, i.e. the bromostannyl alkenes 8a-d, were prepared from bromoalkenes 7a-d by treatment with base (LDA) and quenching with trimethyltin chloride. In turn, bromoalkenes 7a-d were prepared from alkenes 5a-d by radical bromination-elimination. The reaction conditions used were designed to minimise Wagner-Meerwein rearrangements that would lead to unwanted bromo isomers. The cup-shaped syn cyclotrimers 3a-d exhibit high electron density within the cavity as determined by AM1 semiempirical calculations of their electrostatic potential surfaces and are valuable substrates for supramolecular chemistry. As an example, it is shown that fullerene C60 is drawn into solution in acetonitrile by complexation with both the syn and anti trimer of benzonorbornadiene 3a.
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  • 68
    ISSN: 0935-6304
    Keywords: Capillary HPLC ; gradient elution ; temperature programming ; phenolic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper describes a liquid chromatographic method using a reversed phase capillary column coupled to an UV detector for the quantitation of thirteen pollutant phenols. Chromatographic separation was carried out with gradient elution at 25.0 ± 0.1°C. The two major anisocratic elution modes (gradient elution and temperature programming) were evaluated. The detection limit range was 10-81 pg (100 nL injected). The chromatographic method combined with liquid-liquid extraction was applied to analysis of these compounds in river water. Recoveries of 75-103% were achieved for most of them.
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  • 69
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    Journal of High Resolution Chromatography 23 (2000), S. 389-392 
    ISSN: 0935-6304
    Keywords: Capillary SFC ; zinc dialkyldithiophosphates ; lubricating oils ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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  • 70
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    Journal of High Resolution Chromatography 23 (2000), S. 393-396 
    ISSN: 0935-6304
    Keywords: Supercritical fluid chromatography (SFC) ; micropacked capillary columns ; waxes ; restoring ; objects of art ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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  • 71
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    Journal of High Resolution Chromatography 23 (2000), S. 379-385 
    ISSN: 0935-6304
    Keywords: Aroma ; “lulo del Chocó” ; Solanum topiro ; volatiles ; glycosidically bound volatiles ; glycoside TFA derivatives ; enantioselective gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The volatile constituents of lulo del Chocó (Solanum topiro) fruit pulp obtained by liquid-liquid extraction were analyzed by capillary GC and capillary GC-MS. In total, 30 components were identified with methyl salicylate, hexadecanoic acid, hexanal, guaiacol, ethyl butanoate, and ethyl acetate being the major components. Chirospecific MDGC analysis revealed the predominance of (R)-ethyl-3-hydroxybutanoate (ee 40%) and the presence of racemic mixtures both of δ-octalactone and of δ-decalactone. For γ-hexalactone, γ-octalactone, and γ-decalactone enantiomeric distributions of 22.4 : 77.6, 22.9 : 77.1, and 20.0 : 80.0, (R) : (S), respectively, were determined. Glycosidically bound aroma compounds were identified by capillary GC and capillary GC-MS after isolation of the glycosidic fraction obtained by Amberlite XAD-2 adsorption and methanol elution followed by hydrolysis with a commercial pectinase enzyme. In total 13 bound aroma compounds (aglycones) were identified. These aglycones mainly consisted of compounds exhibiting aromatic structures. Additionally, with the aid of capillary GC and capillary GC-MS (EI and NCI) of trifluoroacetylated derivatives we identified eight glucosides: the novel 3,6-epoxy-7-megastigmen-5,9-diol β-D-glucopyranoside and the hexyl, benzyl, linalyl oxide (furanic), 2-phenylethyl, vomifolyl (isomer 1), (6S,9R)-vomifolyl, and scopoletin β-D-glucopyranosides.
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  • 72
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    Journal of High Resolution Chromatography 23 (2000), S. 409-412 
    ISSN: 0935-6304
    Keywords: Cyclodextrin ; capillary electrophoresis ; system peak ; CHES 1 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a running buffer containing cyclodextrins (CDs) and 2-[N-cyclohexylamino]-ethanesulfonic acid (CHES), positive system peaks were observed in the analysis of a ganglioside mixture by CE-UV. These system peaks were related to CDs in the running buffer because these peaks were also detected when a plug of solution devoid of CDs but having the same CHES concentration and pH as the running buffer was injected. Neutral CDs were separated owing to the formation of inclusion complexes with the anionic CHES ion. One possible explanation for the positive system peaks is that the anionic CD-CHES inclusion complex is displaced by co-ions with higher UV absorptivity.
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  • 73
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    Journal of High Resolution Chromatography 23 (2000), S. 565-566 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; zinc dithiocarbamate ; vulcanization accelerator ; rubber gloves ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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  • 74
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    Journal of High Resolution Chromatography 23 (2000), S. 603-608 
    ISSN: 0935-6304
    Keywords: Solvation parameter model ; ystem constants for poly(dimethyldiphenylsiloxane) HP-5 and poly(ethylene glycol) HP-INNOWax stationary phases ; temperature ; molecular interaction ; retention models ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 75
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    Journal of High Resolution Chromatography 23 (2000), S. 561-564 
    ISSN: 0935-6304
    Keywords: Retention factors ; Cinnamomi ramulus ; high-performance liquid chromatography ; capillary electrophoresis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 76
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    Journal of High Resolution Chromatography 23 (2000), S. 590-594 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; graphitic carbon stationary phases ; anions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Inorganic anions could be separated on porous graphitic carbon stationary phases in ion chromatography. Ion exchange between eluent anions and sample anions on the stationary phase was confirmed by the retention behavior and the possibility of indirect photometric detection. The elution order of anions was different from that observed for commercially available anion exchangers. Chloride, nitrate, and sulfate contained in tap water could be determined in 7 min.
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  • 77
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    Journal of High Resolution Chromatography 23 (2000), S. 485-488 
    ISSN: 0935-6304
    Keywords: Pyrethroids ; solid-phase microextraction ; water analysis ; temperature ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Synthetic pyrethroids are increasingly being used for insect control on field crops because of their advantageous environmental properties such as short field life, broad spectrum of insecticide activity, and relatively low mammalian toxicity. In the present work, experimental conditions were optimized for trace analysis of pyrethroids in water by using solid-phase microextraction followed by capillary gas chromatography. Effects of temperature, SPME-fiber diameter, and matrix were studied. SPME used off-line with a gas chromatograph electron-capture detection (GC-ECD) showed a linear response over a wide concentration range. Our results showed a strong temperature effect on pyrethroid extraction yield. The detection limit after 5 min of SPME-fiber exposure to the samples changed from 1 ppb (at 30°C) to 0.1 ppt (at 90°C), which is a 10000 increase in pyrethroid detection. The standard deviations of the analyte peak area ratios were typically in the range of 1-7% at 30°C and of 3 to 15% at 90°C. Best conditions for pyrethroids analysis were achieved using high temperature solution and a 100 μm polydimethylsiloxane fiber. No matrix (river water) influence was observed on detection of the investigated pyrethroids.
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  • 78
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    Journal of High Resolution Chromatography 23 (2000), S. 19-26 
    ISSN: 0935-6304
    Keywords: Microfabrication ; monolith ; electrochromatography ; peptides ; reactive ion etching ; reversed phase ; nanocolumns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolith columns are generally fabricated by polymerization of monomers within a column. This paper reviews an alternative strategy in which the bed is microfabricated in an inorganic material by ablation. Channels of 1.5 μm width and 10 μm depth were sculpted in quartz by deep reaction ion etching. Using this approach chromatographic beds were constructed in which cubic support structures were created and arranged in rows to mimic particles in a conventional column. Beds ranging from hundreds of thousands to millions of “particles” with volumes of 15 nL to 15 μL were produced. Columns that had been derivatized with an octadecyl silane stationary phase were used to separate both low molecular weight analytes and peptides in the CEC mode. Plate height in the CEC mode was 1.2 μm at maximum efficiency.
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  • 79
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    Journal of High Resolution Chromatography 23 (2000), S. 39-43 
    ISSN: 0935-6304
    Keywords: Monoliths ; CIM® monolithic column ; dynamic binding capacity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The characterization of CIM® DEAE monolithic columns in terms of dynamic binding capacity is presented in this paper. Breakthrough experiments were performed for capacity determination. Bovine serum albumin (BSA) was used as a model protein. It is shown that CIM® monolithic columns have good batch-to-batch reproducibility as well as long-term stability. The experiments performed under different linear velocities demonstrated that the dynamic capacity is unaffected at least up to a linear velocity of 2450 cm/h. Furthermore, the breakthrough curve slope is constant, indicating that the capacity would remain constant at even higher linear velocities. The adsorption isotherm of BSA dissolved in 20 mM Tris-HCl buffer shows a constant capacity of around 30 mg/mL of support down to a concentration of 20 μg/mL. The capacity is substantially influenced by the ionic strength; however, 20% of the maximal capacity is still preserved at 0.3 M NaCl.
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  • 80
    ISSN: 0935-6304
    Keywords: Monolith ; factor VIII ; affinity chromatography ; combinatorial peptide library ; peptide synthesis ; recombinant proteins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: FVIII is a very complex molecule of great therapeutic significance. It is purified by a sequence of chromatographic steps including immunoaffinity chromatography. A peptide affinity chromatography method has been developed using peptides derived from a combinatorial library. Spot technology using cellulose sheets has been applied for this purpose. The dual positional scanning strategy was used for identification of the amino acids in random positions. Approximately 5000 possible candidates found in the first screening round were reduced to a panel of 36. Six candidates have been selected empirically. Five peptides seem to be directed against the light chain of FVIII, one peptide seems to be directed against the heavy chain. The peptides have been immobilized on conventional beaded material and CIM polymethacrylate monoliths. Much better performance with respect to capacity and selectivity has been observed with the monolithic material. Exposure of the ligand and its ensuing accessibility are responsible for these properties.
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  • 81
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    Journal of High Resolution Chromatography 23 (2000), S. 67-72 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic column ; electroosmotic flow ; retention mechanism ; aromatic compound ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically. The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.
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  • 82
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    Journal of High Resolution Chromatography 23 (2000), S. 73-80 
    ISSN: 0935-6304
    Keywords: Continuous-bed ; sol-gel ; octadecylsilica ; mixed-mode stationary phase ; large-pore ; column technology ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Sol-gel bonded packing materials in continuous-bed columns have been prepared for capillary electrochromatography (CEC). Three packing materials were investigated: small-pore Spherisorb ODS1 (3 μm, 80 Å) with octadecyl as stationary phase, small-pore mixed-mode Spherisorb ODS/SCX (3 μm, 80 Å) with octadecyl and propyl sulfonic acid as stationary phases, and large-pore Nucleosil ODS (7 μm, 1 400 Å) with octadecyl as stationary phase. The characteristics of these columns were compared in terms of electroosmotic flow, efficiency, inertness, and retention factors. In contrast to columns containing sol-gel bonded ODS, columns containing sol-gel bonded mixed-mode ODS/SCX generated nearly pH independent electroosmotic flow (EOF) over pH 2-9. Columns containing sol-gel bonded large-pore ODS produced nearly three times lower reduced plate height than those containing small-pore ODS. Efficiencies of 220,000 plates per meter and 175,000 plates per meter were obtained from columns containing sol-gel bonded 7 μm, 1 400 Å ODS and columns containing sol-gel bonded 3 μm, 80 Å ODS, respectively, which are among the highest reported efficiencies for continuous-bed columns. In CEC, over one million plates per meter and pH independent EOF are expected from continuous-bed columns containing sol-gel bonded 1.5 μm particles with large pores and mixed-mode stationary phases.
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  • 83
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    Journal of High Resolution Chromatography 23 (2000), S. 81-88 
    ISSN: 0935-6304
    Keywords: Monolithic chromatography columns ; capillary electrochromatography (CEC) ; micro high performance liquid chromatography ; sol-gel based columns for chromatography ; fritless capillary chromatography columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Particle-loaded (3 μm, octadecylsilica) monolithic sol-gel columns have been prepared and selected characteristics measured. Several electrical properties may be calculated from simple current measurements in the column as a whole. Resistivity in the packed segment is approximately three times that in open segments, resulting in a 60% increase in field strength in the packed regions compared to the capillary with no packing. The surprisingly high specific permeability of these sol-gel columns is characteristic of 8-μm particles, which allows their operation in the microLC mode at pressures as low as 69 kPa where their efficiency is about 50,000 plates per meter and in the CEC mode where efficiency is about 106,000 plates per meter at 5 kV. There is a relatively rapid loss of efficiency with increasing linear velocity beyond 0.2 mm/s in microLC mode, which may be due to additional diffusion processes in the inter-particulate voids. A rapid loss of efficiency above 0.5 mm/s is also observed in the CEC mode, for the same reasons. Chromatographic retention behavior in either separation mode is characteristic of conventional octadecylsilica particles, indicating that analytes have significant access to the surface within the pores of the immobilized bonded phase.
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  • 84
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    Journal of High Resolution Chromatography 23 (2000), S. 89-92 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; packed columns ; fritless columns ; stationary phases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Fritless packed silica gel columns were prepared using sol-gel technology. A part of a 75 μm i.d. fused silica capillary was filled with a mixture of tetramethoxysilane and poly(ethylene glycol). After gelling at 40°C and heating at 300°C, the resultant silica gel was derivatized with dimethyloctadecylchlorosilane. A scanning electron micrograph of a cross-section of the capillary column showed that the gel took the form of a spherical particle aggregate and adhered to the column inner wall. The column performance was evaluated for electrochromatography using acetonitrile-50 mM HEPES buffer (pH 6.6) (60/40 or 40/60, v/v) as the mobile phase. An electroosmotic flow of 1.0 mm/s was generated with (60/40, v/v) acetonitrile/HEPES buffer at a field strength of 546 V/cm. Using a sol-gel-derived packed column at an electroosmotic flow of 0.5 mm/s, efficiencies of up to 1.1×105 plates/m were obtained for retained solutes.
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  • 85
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    Journal of High Resolution Chromatography 23 (2000), S. 93-99 
    ISSN: 0935-6304
    Keywords: HPLC ; monolithic column ; silica rod column ; fast separations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The application of a new silica-based, monolithic-type HPLC-column for fast separations is presented. The column is prepared according to a new sol-gel process, which is based on the hydrolysis and polycondensation of alkoxysilanes in the presence of water soluble polymers. The method leads to “rods” made of a single piece of porous silica with a defined pore structure, i. e. macro- and mesopores. The main feature of silica rod columns is a higher total porosity, about 15% higher than of conventional particulate HPLC columns. The resulting column pressure drop is therefore much lower, allowing operation at higher flow rates including flow gradients. Consequently, HPLC analysis can be performed much faster, as it is demonstrated by various applications.
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  • 86
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    Journal of High Resolution Chromatography 23 (2000), S. 3-18 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic columns ; synthetic polymers ; stationary phase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolithic materials have quickly become a well-established stationary phase format in the field of capillary electrochromatography (CEC). Both the simplicity of their in situ preparation method and the large variety of readily available chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. This review summarizes the contributions of numerous groups working in this rapidly growing area, with a focus on monolithic capillary columns prepared from synthetic polymers. Various approaches employed for the preparation of the monoliths are detailed, and where available, the material properties of the resulting monolithic capillary columns are shown. Their chromatographic performance is demonstrated by numerous separations of different analyte mixtures in variety of modes. Although detailed studies of the effect of polymer properties on the analytical performance of monolithic capillaries remain scarce at this early stage of their development, this review also discusses some important relationships such as the effect of pore size on the separation performance in more detail.
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  • 87
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    Journal of High Resolution Chromatography 23 (2000), S. 100-105 
    ISSN: 0935-6304
    Keywords: Preparative chromatography ; silica monoliths ; PrepROD™ ; productivity ; SMB-chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The use of monolithic silica sorbents for the isolation of substances by preparative liquid chromatography is demonstrated. Preparative liquid chromatography is recognized as a valuable technique for the isolation and purification of substances in the pharmaceutical and fine chemicals industry. The system technology has meanwhile reached a high standard, and the greatest future improvements are expected to arise from new and improved adsorbents. Monolithic silica sorbents offer some unique features for preparative liquid chromatography. They exhibit high efficiencies even at high flow rates due to their fast convective mass transfer and can therefore be used at very high mobile phase velocities, leading to high productivity and hence to maximum process economy. The benefits of this new type of adsorbent are illustrated for an example in batch-chromatographic mode and an example using the continuous simulated moving bed (SMB) technology.
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  • 88
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    Journal of High Resolution Chromatography 23 (2000), S. 106-110 
    ISSN: 0935-6304
    Keywords: Silica ; monolithic column ; aging ; mesopores ; pore size distribution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Mesopore formation in silica gels having continuous macropores has been investigated. The macroporous wet silica gel prepared by the sol-gel process including phase separation was aged in a basic solvent making use of hydrolysis of urea in a closed condition. The mesopore structure was finally obtained by subsequent evaporation drying of solvent and heat-treatment at 600°C for 2 h. The dissolution-reprecipitation kinetics at the interfaces between wet gel skeletons and an external solvent affected the size and volume of pores formed within the skeletons. Below 120°C, mesopores suitable for various chromatographic applications have been formed typically within 24 h. On the other hand, at 200°C, the pore size attained the macropore dimensions (〉50 nm), and the whole macroporous morphology was significantly modified.
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  • 89
    ISSN: 0935-6304
    Keywords: Monolithic column ; silica monolith ; HPLC ; capillary liquid chromatography ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two types of monolithic silica columns derivatized to form an ODS phase, one prepared in a fused silica capillary (SR-FS) and the other prepared in a mold and clad with an engineering plastic (poly-ether-ether-ketone) (SR-PEEK), were evaluated. The column efficiency and pressure drop were compared with those of a column packed with 5-μm ODS-silica particles and of an ODS-silica monolith prepared in a mold and wrapped with PTFE tubing (SR-PTFE). SR-FS gave a lower pressure drop than a column packed with 5-μm particles by a factor of 20, and a plate height of 20 μm at a linear velocity below 1 mm/s. SR-PEEK showed higher flow-resistance than the other monolithic silica columns, but they still showed a minimum plate height of 8-10 μm and a lower pressure drop than popular commercial columns packed with 5-μm particles. The evaluation of SR-FS columns in a CEC mode showed much higher efficiency than in a pressure-driven mode.
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  • 90
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    Journal of High Resolution Chromatography 23 (2000), S. 119-126 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; retention volume ; real gas carrier ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of the calculation and interpretation of the net retention volume with a real gas as carrier is revisited. The properties of the carrier are described by a first order virial equation of state. The net retention volume of a solute is related to the mean flow rate of the carrier, therefore determination of the mean flow rate of a real gas carrier is reviewed. It is shown that the mean flow rate cannot be calculated from the mean column pressure. With a real gas carrier the local capacity factor depends on the local pressure of the real gas. The basic relationship between the net retention volume and the function describing this pressure dependence is also reviewed. Precise formulae as well as practical approximations are presented for the calculation of the mean flow rate, of the mean column pressure, and of a representative pressure related to the mean capacity factor.
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  • 91
    ISSN: 0935-6304
    Keywords: Chemiluminescence ; diol compound ; oxalate ; post-column reaction ; ruthenium complex ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this paper we propose a new post-column detection method for polyols containing 1,2-diol, 1,3-diol, and saccharides. The polyols are oxidized in a photochemical reactor to yield oxalate with subsequent chemiluminescence detection using [Ru(III)(bpy)3]3+. A mixing solution of eluate and oxidizing reagent is delivered to a reaction coil, which is then irradiated with ultraviolet light to promote the oxidation reaction. The detection limits for 1,2-ethanediol (ethylene glycol) and 1,3-propanediol were 38 pmol and 23 pmol, respectively.
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  • 92
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    Journal of High Resolution Chromatography 23 (2000), S. 131-137 
    ISSN: 0935-6304
    Keywords: On-line coupled LC-GC ; nitrogen selective detection ; NPD ; carbazoles ; PANH ; personal exposure measurement ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A coupled LC-GC method for the analysis of carbazole-type PANH has been developed and evaluated. Group separation and isolation of carbazoles from interfering acridines in a complex sample matrix was accomplished by using a back-flush technique and an in situ end-capped dimethylaminopropyl silica column in the HPLC part of the system. On-line injection of the carbazole fraction into the GC column was performed with a loop-type interface utilizing concurrent solvent evaporation technique. An LOD of 1-3 pg of individual carbazole compounds was achieved by nitrogen selective detection using an NPD. The method is shown to be robust and is demonstrated by application to personal exposure measurement in an aluminum reduction plant.
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  • 93
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    Journal of High Resolution Chromatography 23 (2000), S. 138-142 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; nucleosides ; short-end injection ; phenyl-bonded silica ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The influence of several experimental parameters (pH, ionic strength, organic modifier content of hydro-organic buffer) upon EOF, migration time, and retention factor has been studied in CEC with a phenyl-bonded silica column on a model mixture of five nucleosides. This paper illustrates the current interest in CEC as a method of resolving complex mixtures of neutral and ionic solutes and demonstrates the potential of the short-end injection method as a means of reducing analysis time.
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  • 94
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    Journal of High Resolution Chromatography 23 (2000), S. 143-148 
    ISSN: 0935-6304
    Keywords: Analysis of anthraquinones ; capillary electrophoresis ; high-performance liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The separation and determination of twelve anthraquinones, viz. anthraquinone 1, chrysphanol 2, aloe-emodin 3, alizarin 4, anthraquinone-2-carboxylic acid 5, purpurin 6, sennoside B 7, sennoside A 8, emodin 9, quinalizarin 10, rhein 11, and anthraflavic acid 12, were achieved by capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC). Detection at 260 nm with a buffer solution containing 30 mM sodium borate (adjusted to pH = 10.56 with 0.05N NaOH) and acetonitrile (9 : 1) in CE or with a linear gradient elution containing 20 mM KH2PO4 with 0.05% phosphoric acid (pH = 2.91) and methanol in HPLC was found to be the most suitable approach for this separation. Contents of six components (2, 3, 7, 8, 9, 11) in crude Rhei Rhizoma extract could easily be determined within 39 min by CE or 63 min by HPLC. The effects of buffers on this separation and the validation of the two methods were studied.
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  • 95
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    Journal of High Resolution Chromatography 23 (2000), S. 156-157 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; trichlorophenols ; ammonia ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 96
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    Journal of High Resolution Chromatography 23 (2000), S. 149-155 
    ISSN: 0935-6304
    Keywords: Capillary GC ; fast GC ; on-column injection ; narrow-bore column ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this work a fast gas chromatography set-up with on-column injection was optimized and evaluated with a model mixture of C8-C28 n-alkanes. Usual injection volumes when using narrow-bore (e. g., 0.1 mm i.d.) analytical columns are ca. 0.1 μL. The presented configuration allows introduction of 10-30-fold larger sample volumes without any distortion of peak shapes. In the set-up a normal-bore retention gap (1 m×0.32 mm i. d.) was coupled to a narrow-bore (4.8 m×0.1 mm i. d.×0.4 μm film thickness) analytical column using a low dead volume column connector. The effects of the experimental conditions such as inlet pressure, sample volume, initial injection temperature, and oven temperature on a peak focusing are discussed. H-u curves for helium and hydrogen are used to compare their suitability for high speed gas chromatography and to show the dependence of separation efficiency on the carrier gas velocity at high inlet pressures. In the fast gas chromatography system a baseline separation of C10-C28 n-alkanes was achieved in less than 3 minutes.
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  • 97
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    Journal of High Resolution Chromatography 23 (2000), S. 182-188 
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; GC×GC ; thermal modulation ; oil analysis ; petroleum analysis ; analysis of middle-distillate oil fractions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) is an utterly suitable separation technique for the analysis of complex samples, such as oil fractions. Once the two columns and the operating conditions are properly tuned, the technique is able to provide a detailed characterization of such materials. Some considerations applying to the tuning of a GC×GC system for a specific separation are presented and discussed. The authors present a number of different column sets and conditions which allow the separation of a non-aromatic hydrocarbon solvent, a kerosene, the light end of a crude oil, and an olefinic fraction, respectively. The highly structured GC×GC chromatograms, together with chemical knowledge about the samples, provide a much more comprehensive characterization of the samples than hitherto possible.
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  • 98
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; thermal desorption modulator ; temperature programming ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In comprehensive two-dimensional gas chromatography, two individual separations are coupled by means of a rotating thermal desorption modulator interface. The injection pulse introduced via the interface onto the second column should be as short as possible. Parameters affecting the modulator operation are studied. In the set-up used in this study, the temperature of the second column can be programmed independently from that of the first column. Optimization of the second-dimension separation to minimize peak broadening and maximize resolution is discussed and an elegant approach to determine second-dimension retention times using a non-constant modulation frequency is demonstrated. The high separation power of the comprehensive system is demonstrated by the analysis of technical and biota samples containing chlorinated biphenyls and toxaphene.
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  • 99
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    Journal of High Resolution Chromatography 23 (2000), S. 197-201 
    ISSN: 0935-6304
    Keywords: Multidimensional gas chromatography ; comprehensive two-dimensional gas chromatography ; GC×GC ; oxygenates ; MTBE ; reformulated gasoline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) has been applied to the quantitation of oxygenates in reformulated gasoline. Target oxygenates were C1-C4 alcohols, tert-pentanol, methyl tert-butyl ether (MTBE), diisopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). These were separated from the gasoline matrix using a volatility-based selectivity in the first chromatographic dimension, followed by a mixed-phase polarity/shape selectivity in the second dimension. The high resolving power of this stationary phase combination completely separated all oxygenates except DIPE, ETBE, and TAME, which exhibited coelution with other nonpolar gasoline components. Oxygenates quantitation was achieved with the use of an internal standard, an FID detector, and calibration curves. Quantitation results are in good agreement with ASTM and EPA standard methods. When coupled with our previous method for BTEX and aromatics, a single GC×GC method can now quantitate MTBE, alcohols, BTEX, and aromatics in a one-hour analysis.
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  • 100
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    Journal of High Resolution Chromatography 23 (2000), S. 474-478 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Solid-phase extraction, on-line derivatization, and measurement by ion trap mass spectrometry (ITD-MS) were used to investigate the biological degradation of pharmaceutical residues (clofibric acid, ibuprofen, diclofenac). The results of the single steps of sample pretreatment and analytical determination are reported. MS/MS measurements were performed on an ITD-MS by selecting collision induced dissociation of the molecular ions (M+) as parent ions to defined daughter ions. A pilot sewage plant and biofilm reactors operating under oxic and anoxic conditions were run as model systems with synthetic sewage water containing 10 to 50 mg/L dissolved organic carbon (DOC) and pharmaceuticals in concentrations of 10 μg/L. Clofibric acid displayed its persistent character in all cases. The pilot sewage plant and the oxic biofilm reactor showed comparable results for diclofenac and ibuprofen, which both were partly degraded. These results can explain the occurrence of these substances in sewage effluents and in the aquatic environment. A high degree of degradation was found especially for ibuprofen in the oxic biofilm reactor, which was attributed to adaptation of the biofilm to the residue. Two metabolites of ibuprofen could be identified on the basis of their mass spectra and comparison with literature data, viz. hydroxyibuprofen and carboxyibuprofen.
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