京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18093号 / 理博第3971号 / 新制||理||1572(附属図書館) / 30951 / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 丸岡 啓二, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24432号 / 理博第4931号 / 新制||理||1704(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 依光 英樹, 教授 若宮 淳志, 教授 畠山 琢次 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

No description available.

The purpose of this thesis is to examine some of the potential fates of processing reagents in a coal preparation plant.  The focus is specifically on petro-diesel (termed "diesel" in this paper), which is used as a collector in the flotation of fine coal.  Diesel range organics (DRO) and polyaromatic hydrocarbons (PAHs) are measured in aqueous samples using gas chromatography equipped with either a flame ionization detector (GC-FID) or a mass spectrometer (GC-MS).  Samples are subjected to a variety of test conditions in order to understand the behavior of diesel compounds in coal processing streams. Results show that frother and collector reagents are not likely to partition completely to a single fraction of the process slurry.  Further test work has shown that sub-ppm levels of DRO dominated by the water soluble fraction of diesel are expected to be present in process waters; however, PAHs and insoluble DRO may be removed via volatilization and/or degradation.  DRO and PAHs are also expected to be desorbed from coal particles when contacted with fresh water.  Flotation tests have revealed that low levels of DRO are found in both the concentrate and tailings processing streams with slightly higher concentrations being found in the concentrate stream.  From the tests performed in this thesis, it appears as though there is no apparent environmental concern when coal preparation plants are operating under normal conditions. / Master of Science

Daratumumab är en antikropp som används vid behandling av multipelt myelom. Daratumumab är specifik för CD38, ytproteinet som uttrycks i stor mängd på myeloma plasmaceller. Vid antikroppsscreen orsakar daratumumab panreaktivitet då erytrocyter också uttrycker CD38. Dithiothreitol (DTT) behandling av testerytrocyter har visats kunna eliminera panreaktiviteten med daratumumab-antikropparna, detta genom att DTT klyver bort epitopet på CD38 som daratumumab reagerar mot utan att förstöra andra kliniskt relevanta antigen. På Södra Älvsborgs sjukhus skickas prover från daratumumab-behandlade patienter till Sahlgrenska sjukhuset för genotypning för att hitta kompatibelt blod. Förhoppningen är att den nya metoden ska möjliggöra antikroppsscreen på daratumumab-behandlade patienter vid Södra Älvsborgs sjukhus.Syftet med examensarbetet var att verifiera metoden för användning av DTT-behandlade testerytrocyter på plasma från daratumumab-behandlade patienter för att underlätta val av erytrocyter för blodtransfusion.Provmaterialet var venöst tagen patientplasma från 16 daratumumab-behandlade patienter testades mot 0,2 M DTT-behandlade- och obehandlade-testerytrocyter. DTT-behandlade testerytrocyter testades även mot kända antikroppar på plasmaprover från patienter som ej behandlats med daratumumab. Hållbarhetsstudie utfördes med behandlade BAS-testceller.Panreaktivitet sågs hos samtliga patientprover med obehandlade testerytrocyter. Vid test med DTT-behandlade testerytrocyter blev samtliga prover negativa. Behandlade testerytrocyter som testades mot kända antikroppar gav resultat som var oförändrat jämfört med originalscreen. Behandlade testceller var brukbara 25 dagar.DTT behandling av testerytrocyter är effektivt och billigt, resultatet var pålitligt då samtliga patientprover inte uppvisade panreaktivitet efter DTT-behandling av testerytrocyter. De DTT-behandlade erytrocyterna behöll kliniskt relevanta antigen efter behandling och var hållbara 25 dagar. Metoden anses som användbar för Södra Älvsborgs sjukhus. / Daratumumab is an antibody used for treatment of multiple myeloma. The antibody is specific for the surface protein CD38 which is being expressed in high quantity on myeloma plasma cells. Daratumumab is causing pan-reactivity during antibody screening due to regular erythrocytes also express CD38. Dithiothreitol (DTT) treatment of test erythrocytes has shown to eliminate the pan-reactivity caused by the daratumumab antibodies by cleaving the epitope on CD38 that daratumumab is specific to. Södra Älvsborgs hospital are currently sending patient samples from patients treated with daratumumab to Sahlgrenska hospital in Gothenburg for genotyping to find compatible blood.The purpose of the project was to verify the method for use of DTT-treated test erythrocytes on plasma from daratumumab treated patients to screen for antibodies and easier find compatible erythrocytes for blood transfusion at Södra Älvsborgs hospital.Plasma samples from 16 patients treated with daratumumab were tested with DTT-treated and untreated test erythrocytes. DTT-treated test erythrocytes were tested against samples with known antibodies from patients not treated with daratumumab. The cells durability was also tested.Pan-reactivity was shown with all daratumumab samples with non-treated test erythrocytes. Tests with DTT-treated test erythrocytes showed no pan-reactivity. Results from treated test erythrocytes tested against known antibodies were unchanged from original screening. The cells were durable for 25 days.DTT-treatment of test erythrocytes is effective and cheap, test results were reliable, all patient samples had their pan-reactivity eliminated. DTT-treated erythrocytes kept clinically significant antigens. The method is useful for clinical use at Södra Älvsborgs hospital.

No description available.

<p> Under 248 nm laser flash photolysis, the photodecomposition of 1,3,4-trimethyl-1-phenyl-1-germacyclopent-3-ene (28) in dry, deoxygenated hexane solution at 23 °C leads to the prompt formation of two transient species: phenylmethylgermylene (29) and its Ge=Ge doubly bonded dimer, 1,2-dimethyl-1 ,2-diphenyldigemene (30). The formation of 29 proceeds in high chemical yield as shown by the results of steady state trapping experiments with methanol and isoprene. The transient assigned to 29 exhibits λmax = 490 nm and decays with second-order kinetics (τ ~ 2 μs). The second transient, which is formed from the latter, is assigned to digermene 30 and exhibits λmax = 420 nm and a lifetime, τ ~ 8 μs. The assignments are based on comparisons to the spectra of other simple germylenes, such as dimethyl-, diphenyl and dimesitylgermylene as well as on the pattern of reactivity with trapping reagents in solution at room temperature.</p> <p> Reactions studied include N-H, O-H and Sn-H insertion reactions, the [1+2] addition to isoprene and t-butylacetylene, and halogen atom abstraction from carbon tetrachloride.</p> <p> Absolute rate constants for quenching of 29 with the above mentioned scavengers were obtained by direct measurement of the germylene decay kinetics, over the concentration range where the formation of the digermene was more than 70% quenched. This ensures that the decay of 29 was dominated by the reaction with the trapping reagent.</p> <p> Absolute rate constants for reaction of the same reagents with 30 have also been determined for most of the scavengers studied. However, the digermene was found to be considerably less reactive than phenylmethylgermylene in all cases.</p> <p> The trends in spectroscopic properties and reactivity of simple germylenes in solution are discussed.</p> / Thesis / Master of Science (MSc)

<p> Cobalt-clusters are versatile reagents in organometallic chemistry. Their ability to protect an alkyne allows one to selectively manipulate a ligand without undergoing a competitive reaction from the alkyne. Cobalt-clusters geometrically modify linear alkynes to 136-145° degrees, thereby allowing for some non-traditional alkynyl chemistry to occur. In particular, the focus of this dissertation lies upon the chemistry of cobalt-complexed propargyl alkynols, the ability of cobalt to stabilize neighbouring cations generated from these alcohols, and the chemistry that can be accomplished by altering the steric and electronic effects. We have chosen to study the possibility of inducing migration of various substituents from one terminus of the cobalt-complexed alkyne to the alcoholic site of the propargyl group via protonation of the desired complex. While examining various silanes, and altering the propargyl alcohol itself, we have considered both steric and electronic effects, thereby determining the idealized conditions for such transfers to occur. Furthermore, in our attempts to successfully apply these migrations to several systems, we have acquired a diverse synthetic knowledge of propargyl cobalt-clusters and their intricate reactivity.</p> <p> An examination of the potential for allyl migrations in norbornyl derivatives revealed several fascinating transformations. Upon protonation with HBF4, [(2-endo-allyldimethylsilyl)ethynylborneol]Co2(CO)6, 63, suffers elimination of water or propene, to yield [(2-allyldimethylsilyl)ethynylborn-2-ene]Co2(CO)6, 68, [(2-endo-dimethylfluorosilyl)ethynylborneol]Co2(CO)6, 69, respectively, and, surprisingly, the tricobalt complex (2-norbornylidene)CHCCo3(CO)9, 70, In contrast, protonation of the terminal alkyne (2-endo-ethynylborneol)Co2(CO)6, 76, an anticipated precursor to 70, led instead to (2-ethynyl-2-bornene)Co2(CO)6, 78, and the ring-opened species (2-ethynyl-4-isopropyl-1-methylcyclohexa-1,3-diene)Co2(CO)6, 79. However, conversion of 76 to 70 was achievable upon prolonged heating at reflux in acetone, thereby also affording the corresponding alcohol, [2-(2-hydroxybornyl)]CH2CCo3(CO)9, 77. A mechanistic rationale is offered for the formation of RCH2CCo3(CO)9 clusters upon protonation of alkyne complexes of the type (RC≡CH)Co2(CO)6.</p> <p> Our interest in acid-promoted rearrangements in cobalt-clusters led us to novel propargyl radical chemistry induced by using particular solvents. The protonation of (1,1-diphenyl-2-propyn-1-ol)Co2(CO)6, 108, with HBF4 in dichloromethane generates the expected metal-stabilized propargyl cation, and also rearranges to give the tricobalt cluster Ph2C=CH-CCo3(CO)9, 33. In contrast, use of THF as solvent affords the radical (Co2(CO)6)[HC≡C-CPh2·], which dimerizes at the methyne position; subsequent cyclization and carbonylation yields 2,5-bis-(diphenylmethylene)cyclopent-3-en-1-one, 112.</p> <p> Furthermore, use of a fluorenyl substituent, instead of the diphenyl analogue, has uncovered a route to transition-metal peroxides of general synthetic potential. Treatment of benzyl- or vinyl-dimethylsilylethynylfluoren-9-ol[Co2(CO)6], 53 and 54, respectively, with HBF4 in diethyl ether or THF has afforded the very first known bimetallic transition metal peroxides, 124 and 125.</p> <p> Finally, the ability of cobalt-clusters to alter the geometry of cycloalkanes has been investigated. Treatment of 1-[axial]-(trimethylsilylethynyl)cyclohexan-1-ol, 129, with dicobalt octacarbonyl results in a conformational ring flip such that the bulky dicobalt-alkyne cluster moiety now occupies the favored equatorial site. However, when a 4-tert-butyl substituent is present, the coordinated alkynyl group retains its original axial or equatorial position.</p> <p> Complexation of trans-[diaxial]-1,4-bis(triphenylsilylethynyl)cyclohexan-1,4-diol, 142, brings about a chair-to-chair conformational inversion such that both cluster fragments now occupy equatorial sites. In contrast, cis-1,4 bis(triphenylsilylethynyl)cyclohexan-1,4-diol, 143, reacts with Co2(CO)8 to yield the twist-boat conformer, 145, in which the two axial hydroxy substituents exhibit intra-molecular hydrogen bonding. Likewise, the corresponding reaction of cis-1 ,4bis(trimethylsilylethynyl)cyclohexan-1,4-diol, 147, with Co2(CO)8 leads to a twist-boat, 149, but, in this case, the molecules are linked through intermolecular hydrogen bonds. The importance of X-ray crystallography in the unambiguous determination of molecular conformations has been emphasized.</p> / Thesis / Doctor of Philosophy (PhD)

A series of studies are presented in which fluorine tagging reagents are used to analyze complex mixtures for compounds containing active hydrogen functional groups (e.g., hydroxyl, amine, thiol, and carboxylic groups). The existence of these derivatized functional groups is determined by utilizing a number of solution and solid-state nuclear magnetic resonance (NMR) techniques. In solution NMR studies p-fluorobenzoyl chloride was the fluorine tagging reagent of choice because of a large ¹⁹F chemical shift range for the different derivatized substrates (~10 ppm) and generally good reaction yields. Various classes of sterol and amino acid p-fluorobenzoyl derivatives were characterized on the basis of their ¹⁹F NMR isotropic chemical shifts. The presence (or absence) of hydroxyl, amine, and carboxylic acid functional groups in coal extract and pyrolysis products was also determined. The versatility of the p-fluorobenzoyl chloride as the fluorine tagging reagent in ¹⁹F NMR was enhanced by: a) enriching the carbonyl carbon of the acid chloride with labeled ¹³C isotope, thus synthesizing a dual ¹⁹F and ¹³C NMR sensitive reagent and b) using the reagent in conjunction with LC-NMR. The extension to either technique added another dimension to the NMR spectral data obtained from the p-fluorobenzoyl tagging reagent in solution NMR. Finally, preliminary data is presented illustrating how fluorine tagging reagents may be used to study functional groups (and atoms present in the immediate proximity of the group) existing on solid material utilizing solid-state NMR. Functional groups on the solid material are tagged with a fluorinated reagent. The sample is then analyzed using solid-state NMR with cross-polarization (CP), magic angle spinning (MAS), and high-power proton decoupling. The ¹⁹F dipolar coupling interactions, created by the presence of the fluorine tag, attenuate signals for these nuclei in the immediate proximity of the tagged site. A series of 1-adamantanol, steroid, and silica gel fluorinated derivatives show that the effects of the ¹⁹F dipolar interactions were modulated by complex anisotropic molecular motions (i.e., solid system with little motion, exhibiting greater signal attenuations due to ¹⁹F dipolar coupling). / Ph. D. / incomplete_metadata

Call number: LD2668 .T4 1985 M33 / Master of Science