Fosfazinomycin A(1), methyl valylarginylmethylhydrazinohydroxyphosphonohydro xyacetate, has been synthesized. N-Carbobenzyloxyvalylnitroarginine(6) was reacted with methyl methylhydrazinobenzyloxyphosphonobenzyloxyacet ate(10) which has carbon-phosphorus bond, to give a coupled product of methyl N-Carbobenzyloxyvalylnitroarginylmethylhydrazinob enzyloxyphosphonobenzyloxyacetate(11). The deprotection of (11) by hydrogenation yielded Fosfazinomycin A(1).

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

Laser Raman spectroscopy has been used to study the interaction of $MoO_3$ with $TiO_2$. The bulk molybdenum oxide appeared to spread on the surface of titania under the submonolayer coverage. The surface polymolybdate was observed to be very stable with respect to the repeated treatment of reduction and subsequent calcination. Owing to the interaction of molybdate and titania, the phase transformation of $TiO_2$ seemed to be strongly retarded. The additives such as Co and Ni reacted readily with $MoO_3$ to form the corresponding molybdate salts. Nevertheless, the polymolybdate species appeared to be more stable on the titania surface than the molybdate salts.

In the unhydrated and hydrated states, conformational free energies of L-ascorbic acid anion (AAA) were computed with an empirical potential function and the hydration shell model (a program CONBIO). The conformational energy was minimized from possible starting conformations expressed with five torsion angles of the molecule. The conformational entropy of each low energy conformation in both states was computed using a harmonic approximation. As found in L-ascorbic acid (AA), intramolecular hydrogen bonds (HBs) are proved to be of significant importance in stabilizing the overall conformations of AAA in both states, and give the folded conformations, which are quite different from those in crystal. There are competitions between HBs and hydration around O3 atom of the lactone ring and hydroxyls of the acyclic side chain. Especially, the whole conformation of AAA is strongly dependent on the water-accessibility of O3 atom. Though there is a significant effect of the hydration on conformational surface, the lowest energy conformation of the unhydrated AAA is conserved. The different patterns of HBs and hydration result in the conformations of AAA in both states being different from those of AA. It can be drawn by several feasible conformations obtained in the hydrated state that there exists an ensemble of several conformations in aqueous solution.

Chlorotrimethylsilane reacts with chromic anhydride to form a very reactive neutral chromium (Ⅵ) oxidizing agent. The active oxidizing species is not trimethylsilyl chlorochromate as was previously reported but chromyl chloride generated in equilibrium concentration. This oxidizing agent was proved very suitable for benzylic oxidations of toluenes and alkylbenzenes to benzaldehydes and aralkyl ketones. Dichlorodimethylsilane and trichlormethylsilane also react with chromic anhydride to form chromyl chloride in an equilibrium concentration.

Three humic acids, two from uranium bearing coal shale and one from the neighbouring limey shale region, are extracted from soils by dissolution in 0.1 M NaOH followed by acid precipitation. After purification cycles, they are characterized for their elemental composition, contents of inorganic impurities, molecular size distribution and proton exchange capacities. The results are compared with the data of reference and aquatic humic acids characterized under the project MIRAGE Ⅱ at TUM and also with other literature data. The proton exchange capacity determined by direct titration, is found to be 3.60 and 2.01 meq/g for coal shale and limey shale humic acids, respectively.

The total synthesis of dihydroreynosin (1) and dihydrosantamarine (2) via tandem Cope-Claisen rearrangement has been accomplished starting from (S)-carvone (4).

The photochemical and photophysical properties of N-(2-haloarylmethyl)pyridinium, N-(arylmethyl)-2-halopyridinium, N-(2-haloarylmethyl)-2-halopyridinium salts and N-(2-halobenzyl)-isoquinolinium salt are studied. The pyridinium salts photocyclize to afford isoindolium salts, while the isoquinolium salts do not. In the photocyclization of N-(2-chlorobenzyl)-2-chloropyridinium salts, pyrido[2,1-a]-4-chloroisoindolium salt is formed by the cleavage of chlorine of pyridinium ring. This indicates that the excited moiety is not the phenyl ring, but the pyridinium ring. The triplet states of the pyridinium salts are believed to be largely involved in the photocyclization, since oxygen retards most of the reaction. Some assistance of a ${\pi}$-complex between the excited chlorine moiety of the salt and phenyl plane of the same molecule is required to explain the reactivity of the salts. N-(Benzyl)-2-chloropyridinium salt is two times more reactive than N-(2-chlorobenzyl)pyridinium salt. N-(Benzyl)-2-chloropyridinium salt can form ${\pi}-complex$ effectively because of the electron-rich phenyl group. The ${\pi}$-complex affords an intermediate, phenyl radical by cleaving the chlorine atom. The photocyclized product, isoindolium salt is obtained by losing the hydrogen atom from the phenyl radical. The reactive pyridinium salts 1a, 2a and 3a have a low fluorescence quantum yield (${\Phi}F$ < 0.01) and a higher triplet energy (ET > 68 kcal/mole) than the unreactive quinolinium salt. The unreactivity of isoquinolinium salt can be understood in relation to its high fluorescence quantum yield and its low triplet energy $(E_T = 61 kcal/mole).$.

A lattice mean field theory is developed to investigate the conformational properties of monolayer amphiphiles at the air-water interface. By generalizing Dill and Cantor's method and by extending Whittington's recurrence equation, we derive the supermatrix recurrence equation which is applied to calculation of various segment density profiles and order parameter, etc. In deriving the equation, we incorporated the chain stiffness effect and the chain connectivity which are distinguished features of linear chain molecule. Our result shows that, as the surface coverage $\sigma$ increases the chain ordering process with respect to vertical axis of the lattice system becomes dominant.

The crystal structure of dehydrated fully $Cd^{2+}$-exchanged zeolite A evacuated at $2{\times}10^{-6}$ Torr and $450^{\circ}C (a = 12.225(2){\AA})$ and of its ethylene sorption complex (a = 12.219(2) ${\AA}$) have been determined by single crystal X-ray diffraction techniques in the cubic space group Pm3m at $21(1)^{\circ}$. The structures were refined to final error indices, $R_1$ = 0.063 and $R_2$ = 0.065 with 266 reflections and $R_1$ = 0.055 and $R_2$ = 0.062 with 260 reflections, respectively, for which $I{\gg}3{\sigma}(I)$. In both structures, six $Cd^{2+}$ ions lie at two distinguished three-fold axes of unit cell. Dehydrated $Cd_6$-A sorbs 4 ethylene molecules per unit cell at $25^{\circ}C$ (vapor pressure of ethylene is ca. 100 Torr). Each $Cd^{2+}$ ion forms a lateral ${pi}$ complex with an ethylene molecule. Four $Cd^{2+}$ ions exist in a nearly tetrahedral environment, 2.210(7)${\AA}$ apart from three framework oxygen ions (considering ethylene molecule as a monodentate ligand) and $2.67(6){\AA}$ from each carbon atom of ethylene molecule.

The reactions of aniline with benzyl and phenacyl compounds are studied by the AM1 method. Two types of modeling were adopted: Cation-neutral, in which a proton is attached to the leaving group F and anion-neutral model, in which aniline was replaced by phenoxide with Cl as the leaving group. The cation-neutral model represented the reactvery well, reproducing the various solution-phase experimental results. In the benzyl system, the ${\pi}$-electrons of the two rings (X-ring in the nucleophile and Y-ring in the substrate) interact conjugatively in the transition state (TS) resulting in a bond contraction of the $C_{\alpha}-C_{Y1}$ bond (benzylic effect), whereas in the phenacyl system the ${\pi}$ electrons of the X-ring delocalizes more efficiently into the carbonyl group than into the Y-ring (resonance shunt effect) with a bond contraction of the $C_{\alpha}-C_{\beta}$ bond. The bond contraction in the benzylic effect was substantially greater than that in the resonance shunt effect. The TS was rather loose for benzyl while it was tighter for phenacyl system. Various bond length changes with substituents in the TS were, however, found to be irregular.

A series of compounds that contain varying numbers of the same mesogenic structure, biphenyl p-oxybenzoate unit, attached through a pentamethylene spacer to the central benzene ring were prepared and their liquid crystallinity was studied. The mesophase-forming ability of a dimesogenic compound was found to be greatly dependent on whether or not its geometric shape is linear and also on the existence of the pentamethylene spacer between the mesogen and the central core. The presence of the spacer enhanced the capacity of a compound to form a mesophase. In the trimesogenic compound the mesogens were linked to the 1,3,5-positions of the core benzene ring through the spacer. The compound was found to be enantiotropically nematic.

The $^{13}C-NMR$ shifts of a series of para-substituted $8-aryl-tricyclo[3.2.1.0^{2,7}]oct-8-yl$ and $9-aryl-tricyclo[3.3.1.0^{2,8}]-non-9-yl$ cations were measured in $FSO_3H/SO_2ClF\ at\-90^{\circ}$ in order to examine whether the ${\rho}^{C^+}$ values can be used as a measure of the geometric influence on the charge delocalization resulting from ${\rho}$ conjugation in rigid tricyclopropylcarbinyl cations. Plot of the ${\Delta}{\delta}^{C+} shifts against the ${\sigma}^{C+}$ constants revealed excellent linear correlation. The 8-aryl tricyclooctyl systems yielded a ${\rho}^{C+}$ value of -5.00 with r = 0.9962. Previous investigation of the 9-aryl-tricyclononyl systems gave a correlation coefficient of r = 0.9948 with a slope of ${\rho}^{C+}$ = -4.95. A fair parallelism exists between the results of $^{19}F-NMR $ studies and the change of ${\rho}^{C+}$ value in these cations. Consequently, it is established that the ${\rho}^{C+}$ value can be used to explain the mechanism of charge stabilization of the rigid cyclopropylcarbinyl cation such as tricyclo $[3.2.1.0^{2,7}]oct-8-yl$ cation.

Attempts were made to develop new protecting groups for 1,6-lactam function of 2-N-acyl guanine in oligodeoxyribonucleotide synthesis. Several acyl groups, aryl groups, and carbamoyl groups were tested. Dimethylcarbamoyl and phenylacetyl groups are shown to be a good combination for guanine residue. 6-O-Di-methylcarbamoyl-2-N-pheylacetyl-2'-deoxy guanosine have been successfully used in the synthesis of d[AAGCTT], which is Hind Ⅲ recognition sequence.

A statistical thermodynamic theory of thermotropic main-chain polymeric liquid crystalline melts is developed within the framework of the lattice model by a generalization of the well-known procedure of Flory and DiMarzio. According to the results of Vasilenko et al., the theory of orientational ordering in melts of polymers containing rigid and flexible segments in the main chain is taken into account. When the ordering of flexible segments in the nematic melt is correlated with that of rigid mesogenic groups, the former is assumed to be given as a function of the ordering of rigid mesogenic cores. A free energy density that includes short-range packing contributions is formulated. The properties of the liquid-crystalline transiton are investigated for various cases of the system. The results calculated in this paper show not only the order-parameter values but also the first-order phase transition phenomena that are similar to those observed experimentally for the thermotropic liquid-crystalline polymers and show the transitional entropy terms which actually increase upon orientational ordering. In the orientational ordering values, it is shown that mesogenic groups, flexible segments, and gauche energy (temperature) may be quite substantial. Finally, by using the flexibility term, we predict the highly anisotropic mesophase which was shown by Vasilenko et al.

Ultraviolet spectra of 5-and 6-uracilyl compounds which contain conjugated double bonds were obtained and their characteristic phenomena were examined. 5-Formyluracil and 6-methyl-5-formyluracil showed bathochromic shifts which should be expected from a conjugated carbonyl compound. 6-Formyluracil did not show any shift in absorbing wavelength. 5-and 6-uracilylacrylic acid derivatives, on the other hand, showed absorption at similar wavelengths, indicating the presence of a hexatriene chromophore. The ratio of ${\Delta}ν/J$ in nuclear magnetic resonance spectra of those compounds decreased drastically as the acrylic acids or esters were converted into amides.

The ground state of the oxygen molecule is calculated by various methods of coupled cluster approaches and many body perturbation theory using a double zeta plus polarization basis set and the UHF reference state. All the methods employed are capable of describing the oxygen molecule near the equilibrium bond length and the separated atom, but do not correctly depict the breaking of the multiple bond. For this basis set, including more correlations does not necessarily improve the agreement with experiment for molecular properties such as bond lengths and dissociation energies.

To study the effect of solvents and counterions in Z-DNA crystal of d(5BrC-G-5BrC-G-5BrC-G), we performed the local energy analysis and then molecular dynamics simulations. Since counterions raise serious caging problems in crystal simulations, it is very important to search for the possible positions before simulations. For this purpose, the local energy analysis was done for the whole crystal volume. It is shown from our simulation that counterions along with water molecules play a bridging role to bind adjacent oligomers so as to form the crystal. In this crystal, each water molecule bound to Gua-N2H, either directly or indirectly, hydrates the adjacent anionic phosphate oxygen, and thus assists Gua to be in a syn position. From the simulation, the average root-mean-square deviation of allthe DNA heavy atom coordinates from the X-ray data is $0.99{\AA}$ . The bases are less deviated from the X-ray positions than the phosphates. The temperature factors from the simulation are consistent with those from the X-ray refinement, showing that the phosphates are more mobile than the bases.

New binuclear Ni(Ⅱ) and Cu(Ⅱ) complexes with various alkyl derivatives of 1,2-bis(1,3,6,8,10,13-hexaaza-1-cyclotetradecyl) ethane, in which two fully saturated 14-membered hexaaza macrocyclic subunits are linked together by an ethylene chain, have been synthesized by the one step template condensations of formaldehyde with ethylenediamine and appropriate primary alkyl amines in the presence of the metal ions. Each macrocyclic subunit of the double-ring macrocyclic complexes contains one alkyl pendant arm and has a square planar geometry with a 5-6-5-6 chelate ring sequence. The visible spectra and oxidation properties indicate that the metal-metal interaction of the binuclear complexes are not significant. Synthesis, characterization, and the properties of the complexes are presented.

The "frozen-out" $^{13}C-NMR$ spectrum of cyclooctanone conformer was detected at $-150^{\circ}$ and is reported for the first time. The stable conformation of cyclooctanone deduced by $^{13}C-NMR$ measurements was a unsymmetrical boat-chair conformation.

Generalized multichannel quantum defect theory [C. H. Greene et al. Phys. Rev., A26, 2441 (1982)] is implemented to the vibrational predissociation of triatomic van der Waals molecules. As this is the first one of such an application, the dependences of the quantum defect parameters on energy and radius are examined carefully. Calculation shows that, in the physically important region, quantum defect parameters remain smoothly varying functions of energy for this system as in atomic applications, thus allowing us very coarse energy mesh calculations for the photodissociation spectra. The choice of adiabatic or diabatic potentials as reference potentials for the calculation of quantum defect parameters as done by Mies and Julienne [J. Chem. Phys., 80, 2526 (1984)] can not be used for this system. Physically motivated reference potentials that may be generally applicable to all kinds of systems are utilized instead. In principle, implementation can be done to any other predissociation processes with the same method.