This diploma thesis was focused on the system of agarose hydrogels with micellar domains. Polysaccharide agarose was used for the preparation of hydrogel matrices. Septonex was chosen as a surfactant. The release of solubilizate from the agarose hydrogel matrix was studied with a hydrophobic dye Sudan III in order to obtain a model system of hydrophobic solubilized drugs. Sudan III was solubilized via surfactant´s micels. Subsequently, this micellar aqueous solution with the dissolved dye was used to prepare the agarose hydrogel. The system was prepared in the environment of deionized water and physiologic solution. The gradual release of the dye into deionized water and physiologic solution was studied for 22 days using the UV-VIS spectrophotometry method. It was found that after 14 days the concentration of the releasing dyes into the deionized water was decreased. The cause is that after 14 and 22 days there was a slight degradation of gels, which was detected using the rheology method. Using the rheology method it was also found that Septonex does not affect the gel formation process.

In dieser Arbeit wird die Herstellung und spektroelektrochemische Charakterisierung von Polymeren aus alkylsubstituierten Anilinderivaten beschrieben. Hierzu wird die zyklische Voltammetrie sowie als in situ-spektroskopische Methoden UV-vis-, FTIR- und Raman-Spektroskopie eingesetzt. Aus allen eingesetzten Monomeren lassen sich elektroaktive und elektrochrome Polymere herstellen. Bei der Mehrzahl der Polymere konnten in situ-Leitfähigkeitsmessungen durchgeführt werden, die eine intrinsische, vom Elektrodenpotential abhängige elektrische Leitfähigkeit zeigen. Der molekulare Aufbau innerhalb der Polymerketten wird durch FTIR- und Raman-Spektroskopie in Analogie zum Polyanilin identifiziert. Er ist wie beim Polyanilin vom Oxidationsgrad abhängig.

Presented Diploma Thesis is focused on electroanalytical determination of genotoxic 4-nitroindane, one of the nitrated polycyclic aromatic hydrocarbons (NPAHs). A hydrocarbon indane (a component of petrol) is a precursor of 4-nitroindane. NPAHs are produced all above by combustion processes in gasoline and diesel engines. It has been shown that NPAHs can be many times more mutagenic or carcinogenic than their parent PAHs, so the analysis of these dangerous pollutants becomes important for modern environmental analytical chemistry. Optimal conditions for determination of 4-nitroindane have been investigated in buffered water-methanolic solutions and electrochemical transformations of 4-nitroindane have been studied by DC voltammetry (DCV), differential pulse voltammetry (DPV) and cyclic voltammetry at a hanging mercury drop electrode (HMDE) and at a mercury meniscus modified silver solid amalgam electrode (m-AgSAE). For voltammetric determination of 4-nitroindane, the following techniques were used: DCV (limit of quantification (LQ) ~ 7. 10-8 mol. l-1 ), DPV (LQ ~ 1. 10-7 mol. l-1 ) and adsorptive stripping voltammetry (AdSV; LQ ~ 7. 10-9 mol. l-1 ) at HMDE, and DCV (LQ ~ 1. 10-7 mol. l-1 ) and DPV (LQ ~ 1. 10-7 mol l-1 ) at m-AgSAE. The applicability of the newly developed...

“Green” explosives are an important sub-family of explosives due to the banning of explosives based on heavy metals, such as lead azide and lead styphnate, according to the REACH list. A substitute to lead azide is potassium 4,6-dinitrobenzofuroxane (KDNBF) which is an alternative “green” explosive. Hence there is an upcoming need for analytical and quality control protocols for KDNBF. In this report is HPLC-UV/VIS, GC-FID and potentiometric titration evaluated for their suitability as methods for testing of KDNBF. The results implies that KDNBF can be analyzed by GC-FID, when dissolved in DMSO and caffeine is used as internal standard. To analyze KDNBF by HPLC-UV/VIS was isocratic mode used together with a porous graphitic carbon (PGC) (Hypercarb ®) column. However, degradation of the analyte was severe and quantitative results were not obtained. Potentiometric titration indicated that KDNBF equilibrate with four hydrogen ions during titration, instead of the one to one ratio with potassium and hydrogen ion, as in previously proposed theory. Despite this and with careful titration is potentiometric titration and GC-FID analysis combined suitable as a quality control protocol for KDNBF.

No description available.

We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner’s group, very good agreement with TD-DFT calculations using local functionals was achieved.

As one of the natural polyphenols, resveratrol possesses hydroxyl substituted trans-stilbene structure and exerts impact on health by inhibiting multiple human enzymes, such as cyclooxygenase, F1 ATPase, and tyrosinase. Resveratrol has to be bound by human serum albumin (HSA) to keep a high concentration in serum, since its solubility is low in water. To improve water solubility and bioavailability, two resveratrol aliphatic acids and their esters have been designed and synthesized. The solubilities of the resveratrol and its derivatives have been measured using a standard procedure. The two aliphatic acids showed better solubilities in pure water and phosphate buffer (pH 7). The binding affinities of resveratrol derivatives for HSA were also measured, and the drug-protein interaction mechanism was investigated using fluorescence, UV-vis, and NMR spectroscopies. Interestingly, resveratrol hexanoic acid (5) was found to be a much better ligand (Ka = (6.70 ± 0.10) × 106 M-1) for HSA than resveratrol (Ka = (1.64 ± 0.07) × 105 M-1), and there was 41-fold improvement for the binding affinity. It was the first time that the increase of fluorescence of resveratrol moiety was observed during the binding to HSA, suggesting that 5 should be bound tightly by HSA. The UV-vis absorption spectroscopy revealed a maximum absorption shift from 318 to 311 nm with decreasing intensity by 20% upon complexation, suggesting that the π-π conjugation of the stilbene structure was impaired during the binding. Although HSA was reported to have only one binding site for resveratrol, the Job's and molar ratio plots suggested that HSA should bind two molecules of 5. NMR study suggested that phenyl group (B ring) in the center of the molecule of 5 should be involved in the π-π stacking interactions with HSA aromatic amino acid residues. Molecular geometry calculation of 5 with Spartan software showed that the stilbene structure had two conformers, orthogonal and planar ones. The former (E = -1.432 KJ/mol) was more stable than the latter (E = -0.128 KJ/mol), suggesting that the former should be the conformer of 5 in the complexation with HSA.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第19378号 / 農博第2148号 / 新制||農||1037(附属図書館) / 学位論文||H28||N4958(農学部図書室) / 32392 / 新制||農||1037 / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 近藤 直, 教授 飯田 訓久, 准教授 小川 雄一 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

No description available.

In dieser Arbeit wird die Herstellung und spektroelektrochemische Charakterisierung von Polymeren aus alkylsubstituierten Anilinderivaten beschrieben. Hierzu wird die zyklische Voltammetrie sowie als in situ-spektroskopische Methoden UV-vis-, FTIR- und Raman-Spektroskopie eingesetzt. Aus allen eingesetzten Monomeren lassen sich elektroaktive und elektrochrome Polymere herstellen. Bei der Mehrzahl der Polymere konnten in situ-Leitfähigkeitsmessungen durchgeführt werden, die eine intrinsische, vom Elektrodenpotential abhängige elektrische Leitfähigkeit zeigen. Der molekulare Aufbau innerhalb der Polymerketten wird durch FTIR- und Raman-Spektroskopie in Analogie zum Polyanilin identifiziert. Er ist wie beim Polyanilin vom Oxidationsgrad abhängig.