The correlation between the water and N-methylacetamide (NMA) intramolecular vibrational frequencies and the hydrogen-bond length in a variety of NMA-H₂O and NMA-D₂O complexes was investigated by carrying out ab initio calculations. As the hydrogen-bond length decreases, the frequencies of bending and stretching modes of the hydrogen-bonding water increases and decreases, respectively, and the amide I and II (III) mode frequencies of the NMA decreases and increases, respectively. In this paper, correlation maps among the amide (I, II, and III) modes of NMA and three intramolecular water modes are thus established, which in turn can be used as guidelines for interpreting two-dimensional vibrational spectra of aqueous NMA solutions.

A theoretical description and experimental demonstration of homodyne-detected two-color transient grating (2-C TG) signal are presented. By treating the coupled bath degrees of freedom as a collection of harmonic oscillators and using a short-time expansion method, approximated nonlinear response functions were obtained. An analytic expression for the two-color transient grating signal was obtained by carrying out relevant Gaussian integrals. The initial rising and decaying parts of the 2-C TG signal is shown to be critically dependent on the ultrafast inertial component of the solvation correlation function. The experimental results confirm the predictions of the theoretical model.

We have investigated femtosecond coherent vibrational motions of Zn(II)-5,15-diphenylporphyrin in toluene using chirp-controlled ultrashort pulses. The oscillatory features superimposed on the temporal profiles of the pump-probe transient absorption signal are affected by the chirping and energy of excitation pulses. Using chirp- and excitation energy-controlled femtosecond pulses, we are able to obtain information on the structural changes between the electronic ground and excited states based on a comparative analysis of the Fouriertransformed frequency-domain spectra retrieved from the oscillatory components with the ground state resonance Raman spectra and normal mode calculations.

Two different electronically resonant two-dimensional spectroscopies are described. The first, two-color photon echo peak shift spectroscopy, is sensitive to correlations in transition frequency between the initial and probed (final) states. It provides new insight into the mechanism of ultrafast solvation and should prove useful for characterizing dynamics in inhomogeneous systems in general. The second technique, fifth order threepulse scattering, contains two coherence periods whose durations are controlled. The entire two-dimensional surface was recorded for a dye molecule in dilute solution and a photosynthetic light-harvesting complex. The data provide insight into the short-time dynamics of solvation and exciton relaxation, respectively.

The effects of different polarization conditions on vibrational echo signals are systematically explored for the rigid cyclic dipeptide 2,5-diazabicyclo[2,2,2]octane-3,6-dione. An anharmonic vibrational Hamiltonian is constructed by computing energy derivatives to fourth order using density functional theory. Molecular frame transition dipole orientations are then used to calculate polarization dependent orientational factors corresponding to various Liouville space pathways. Enhancement and elimination of specific peaks in twodimensional correlation plots is accomplished by identifying appropriate pulse configurations.

The cubic and quartic anharmonic force field of malonaldehyde is calculated using density functional theory at the B3LYP/6-31G(d,p) level, and used to simulate coherent infrared vibrational spectra. 12 normal modes are included in the simulation, and the Arnoldi method is employed for the diagonalization of the Hamiltonian. The calculated three pulse infrared signals in the k1 + k2 - k3 direction show signatures of the intramolecular hydrogen bond couplings between the C=O stretch, H-O-C bend and O-H stretch vibrations.

In our previous work we developed the Finite Field method in order to calculate the fifth-order Raman response. The method was applied to calculate various polarization components of the two-dimensional response of liquid $CS_2$. So far, all calculations relied on the dipole-induced dipole. Accurate time-dependent density functional theory calculations have shown that this model has big discrepancies, when molecules are close together as in the liquid. We now report results of investigations on the importance of multipole and electron overlap effects on the polarizability and the fifth-order Raman response. It is shown that these collision effects, especially the induced multipoles, are crucial in the description of the fifth-order response. The impact is found to be especially pronounced for the χ_{mmzzzz}^{(5)}$response that is solely due to interaction induced effects. The calculated response will be compared with various experimental results.

Valuable insight into the nonlinear dynamics of a system can be gleaned from its response to a single intense short pulse. We derive expressions for the corresponding nonlinear response functions and show that the fluctuation-dissipation theorem may be extended beyond the linear response limit to an arbitrary pulse intensity. As an illustrative example, we calculate response functions up to 11th order for the regular Lorentz gas in two dimensions.

We present one-color nonlinear wavepacket interferometry (WPI) signal calculations for a system of two electronic levels and one vibrational degree of freedom. We consider two cases, a displaced harmonic oscillator system, which can be treated analytically, and a model photodissociative system, whose WPI signal must be calculated by numerical wavepacket propagation. We show how signals obtained with different combinations of intrapulse-pair phase shifts can be combined to isolate the complex-valued overlap between a given onepulse target wavepacket and a variable three-pulse reference wavepacket. We demonstrate that with a range of inter- and intrapulse-pair delays the complex overlaps and variable reference states can be used to reconstruct the target wavepacket. We compare our results with previous methods for vibronic state reconstruction based on linear WPI and discuss further generalizations of our method.

Coherent multidimensional vibrational spectroscopy is a new technique for establishing correlations between features in vibrational spectra that are caused by intra- and intermolecular interactions. These interactions cause cross-peaks between vibrational transitions that reflect the coupling. In this paper, we use Doubly Vibrationally Enhanced Infrared Spectroscopy (DOVE-IR) and DOVE-Raman processes to obtain coherent two dimensional vibrational spectra. The spectra are fitted to obtain the dephasing rates and third order susceptibilities $(χ^{(3)})$ for the nonlinear processes. We show that the DOVE $χ^{(3)}$ values are directly related to the molar absorptivities and Raman $χ^{(3)}$. We then use these relationships to obtain estimates for the $χ^{(3)}$ of the stimulated photon echo and $χ^{(5)}$ of the six wave mixing spectroscopies, respectively. We also predict the ratio of the cascaded four wave mixing signal to the six wave mixing signal.

The signals obtained from the $5^{th}$-order (two-dimensional) Raman spectrum of a liquid can depend dramatically on the polarizations of the various light beams, but to date there has been no evidence presented that different polarization conditions probe any fundamentally different aspects of liquid dynamics. In order to explore the molecular significance of polarization we have carried out a molecular dynamics simulation of the $5^{th}$-order spectrum of a dilute solution of CS₂ in liquid Xe, perhaps the simplest system capable of displaying a full range of polarization dependencies. By focusing on the 5 distinct rotational invariants revealed by the different polarizations and by comparing our results with those from liquid Xe, a liquid whose spectrum has no significant polarization dependence, we discovered that the polarization experiments do, in fact, yield valuable microscopic information. With different linear combinations of the experimental response functions one can separate the part of the signal derived from the purely interaction-induced part of the many-body polarizability from the portion with the largest contributions from single-molecule polarizabilities. This division does not directly address the underlying liquid dynamics, but it significantly simplifies the interpretation of the theoretical calculations which do address this issue. We find that the different linear combinations differ as well in whether they exhibit nodal lines. Despite the absence of nodes with the atomic liquid Xe, observing the resilience of our solution's nodes when we artificially remove the anisotropy of our solute leads us to conclude that there is no direct connection between nodes and specifically molecular degrees of freedom.

The kinetics and mechanism of the pyridinolysis $(XC_5H_4N)$ of Y-aryl phenyl isothiocyanophosphates (1;$(YC_6H_4O)\;(C_6H_5O)$P(=O)NCS) are investigated in acetonitrile at 55.0 ℃. The Hammett plots for substituent (Y) variations in the substrate (log k₂ vs σY) exhibit a convex upward biphasic type with breaks at Y = H. For electron-donating Y groups the Hammett coefficients, ρY, are positive and cross-interaction constant ρXY is negative, while those for electron-withdrawing Y groups ρY values are negative with a positive ρXY. These results are interpreted to indicate mechanistic change at the breakpoint (σY = 0) from a concerted to a stepwise mechanism with rate-limiting expulsion of the $^-NCS$ group from a trigonal bipyramidal pentacoordinated (TBP-5C) intermediate. Biphasic plots of log k₂ vs σX or $pK_a$(X) with steeper slopes for the more basic nucleophiles are obtained suggesting an equatorial nucleophilic attack in contrast to an apical attack for the less basic nucleophiles with smaller magnitude of ρX or βx.

The structures and gas-phase ionization energies (ΔG°) of Meldrum's acid (I) and related cyclic (II-VI) and acyclic compounds (VII-IX) are investigated theoretically at the MP2/6-31+$G^*$, B3LYP/6-31+$G^*$, B3LYP/6- 311+$G^{**}$, B3LYP/6-311++G(3df,2p) and G3(+)(MP2) levels. Conformations of three neutral cyclic series vary gradually from boat (Meldrum's acid, I), to twisted chair (II) and to chair (III) as the methylene group is substituted for the ether oxygen successively. The preferred boat form of I can be ascribed to the two strong $n_O$ → σ* c-c antiperiplanar vicinal charge transfer interactions and electrostatic attraction between negatively charged C¹ and positively charged C⁴at the opposite end of the boat. All the deprotonated anionic forms have half-chair forms due to the two strong $n_C$ → π* c=0 vicinal charge transfer interactions. The dipole-dipole interaction theory cannot account for the higher acidity of Meldrum's acid (I) than dimedone (III). The origin of the anomalously high acidity of I is the strong increase in the vicinal charge transfer ($n_C$ → π* c=0) and 1,4-attrative electrostatic interactions (C¹↔C⁴) in the ionization (I → $I^-$ + $H^+$). In the acyclic series (VII-IX) the positively charged end atom, C⁴, is absent and the attractive electrostatic stabilization (C¹↔C⁴) is missing in the anionic form so that the acidities are much less than the corresponding cyclic series.

The reactions of [Ni(L)(H₂O)₂]Cl₂ (L = 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) with terephtalate (tp) and 2,5-pyridinedicarboxylate (pdc) generate one-dimensional nickel(II) complexes, [Ni(L)(H₂O)₂](tp) · ₄H₂O (1) and [Ni(L)(H₂O)₂](pdc)·₄H₂O (2). The structures have been characterized by X-ray crystallography, magnetic susceptibility and spectroscopy. The crystal structures of 1 and 2 show a distorted octahedral coordination geometry around the Ni(II) ion, with secondary amines of the macrocycle and two water molecules at the trans position. Complexes 1 and 2 display the one-dimensional hydrogen-bonded infinite chains. The magnetic behavior of all compounds exhibits weak interchain antiferromagnetic interactions with J values of -1.09(3) for 1 and -1.14(2) cm-1 for 2.

Nanocrystalline semiconductor film electrodes have been prepared by sintering three different sizes of TiO₂ nanoparticle sols on conducting indium-tin-oxide (ITO) glass substrate. The electrochemical and photoelectrochemical properties of the prepared electrodes were comparatively investigated. The particle sizes, surface morphologies and crystallinities of the films were studied by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Cyclic voltammetry and capacitance measurements in the dark implies the formation of depletion layer in the semiconductor films which was usually neglected in the previous studies and shows that flat band potential ($E_{fb}$

The structures of molecular species of galactolipids, such as monogalactosyl diacylglycerol (MGDG) and digalactosyl diacylglycerol (DGDG), isolated from wheat flour have been investigated using negative-ion electrospray ionization (ESI) mass spectrometry interfaced with high performance liquid chromatography (HPLC). According to the result of HPLC analysis, MGDG and DGDG were found to consist of mixtures of five and four molecular species, respectively. The galactolipids have been also analyzed to determine their fatty acid compositions, using HPLC/ESI-MS combined with in-source (or cone voltage) fragmentation. HPLC/ ESI-MS is very useful for one-step analysis of mixtures of galactolipids with a small sample quantity. Especially, the carboxylate anions produced in in-source fragmentations of the negative-ion of each component separated by HPLC provide valuable information on the composition of its fatty acyl chains.

A stable derivative of L-ascorbic acid, 2-O-[(3-aminopropyl)phosphinooxy]-L-ascorbic acid (LAAP), was synthesized in moderate yield and its chemical stability and effects on melanin synthesis were investigated. LAscorbic acid was decomposed completely within about 1 hour, while 93% of LAAP remained even after 10 days. Treatment of L-ascorbic acid and LAAP decreased melanin content in normal human melanocytes to 33.8% and 49.1% of control at 2 mM, respectively. Considering chemical instability of L-ascorbic acid, LAAP is a much better whitening agent.

This study aims to investigate the applicability of Sd/StFFF and to develop a method for size characterization of urban airborne particles, focusing primarily on particles larger than about 1 mm. It was found that the airborne concentration vary with time, although no particular seasonal trend was observed. When averaged over time, the airborne concentration was the lowest in the park areas with 99 ㎍/m³. The apartment, industrial, and central city area showed similar levels of the airborne concentrations with 166, 170, and 171 ㎍/m³, respectively. The housing area showed the highest airborne concentration with 201 μg/m³ among all tested areas. A power-programmed Sd/StFFF was used for size analysis of airborne particles with the initial field strength of 300 rpm, $t_a$ = 4, $t_i$ = -16, p = 8, and the flow rate of 7 mL/min. It was found that urban airborne samples were mostly populated by particles having diameters between about 5 to 20 ㎛, although all have broad size distributions ranging up to about 50 ㎛. Under the Sd/StFFF condition used in this study, no significant differences were found in size distributions among the airborne particles collected at different urban sites, and also among those collected at different times.

Thallium is quantitatively retained by 1,10-phenanthroline and tetraphenylborate onto benzophenone in the pH range 0-11 from a large volumes of aqueous solutions of various samples. After filtration, the solid mass consisting of thallium complex and benzophenone is dissolved with 5 mL of dimethylformamide and the metal was determined by flame atomic absorption spectrometric. About 0.4 ㎍ of thallium can be concentrated from 400 mL of aqueous sample, where its concentration is as low as 1.0 ng/mL. Eight replicate determinations of 8.0 ㎍/mL of thallium in final dimethylformamide solution gave a mean absorbance of 0.160 with a relative standard deviation of 1.7%. The sensitivity for 1% absorption was 0.22 ㎍/mL. The interference of a large number of anions and cations has been studied and the optimized conditions developed were utilized for the trace determination of thallium in various alloys and biological samples.

Condensation of 4-cyano-5,6-dimethyl-3-pyridazinone 1 with aromatic aldehydes gave the novel styryl derivatives 2a-c. Refluxing of compound 2a with phosphorus oxychloride furnished 3-chloropyridazine derivative 3. Compound 3 was reacted with thiourea and produced pyridazine-3(2H)thione 4. Thieno[2,3-c]- pyridazines 5a-e were achieved by cycloalkylation of compound 4 with halocompounds in methanol under reflux and in the presence of sodium methoxide. Also, refluxing of compound 4 with N-substituted chloroacetamide in the presence of potassium carbonate afforded thienopyridazines 6a-e. Cyclization of compound 6 with some electrophilic reagents as carbon disulfide and triethyl orthoformate furnished the novel pyrimido[4',5':4,5]thieno[2,3-c]pyridazines 12 and 13a-c, respectively. Diazotisation of compound 6 with sodium nitrite in acetic acid produced the pyridazino[4',3':4,5]thieno[3,2-d][1,2,3]triazines 14a-c. Ternary condensation of compound 1, aromatic aldehydes and malononitrile in ethanol containing piperidine under reflux afforded the novel phthalazines 16a-c. Compound 3 was subjected to some nucleophilic substitution reactions with amines and sodium azide and formed the aminopyridazines 17a, b and tetrazolo[1,5-b]-pyridazine 19, respectively. The structures of the synthesized compounds were established by elemental and spectral analyses.

In order to study the role of residue in the active site of glutathione S-transferase (GST), Tyr 108 residue in human GST P1-1 was replaced with alanine, phenylalanine and tryptophan by site-directed mutagenesis to obtain mutants Y108A, Y108F and Y108W. These three mutant enzymes were expressed in Escherichia coli and purified to electrophoretic homogeneity by affinity chromatography on immobilized GSH. The substitutions of Tyr108 significantly affected $K_m^{CDNB}$ and $K_m^{ETA}$, whereas scarcely affected $K_m^{GSH}$. The substitutions of Tyr108 also significantly affected $I_{50}$ of ETA, an electrophilic substrate-like compound. The effect of these substitutions on kinetic parameters and the response to inhibition suggests that tyrosine 108 in hGST P1-1 contributes to the binding of the electrophilic substrate and a major determinant in the binding of CDNB is the aromatic ring of Tyr108, not its hydroxyl group.

Palladium-catalyzed heteroannulation of 2-amino-3-iodoquinoline derivatives and 1-trimethylsilyl internal alkynes provided highly regioselective pyrrolo[2,3-b]quinolines with trimethylsilyl group next to the nitrogen atom in the pyrrole ring.

Patterning of biological molecules was attempted on both gold and glass using fourth generation (G4) poly(amidoamine) (PAMAM) dendrimer as an interfacing layer between solid surfaces and biomolecules. As for the patterning of avidin and anti-biotin antibody on gold, PAMAM dendrimers representing amine functionalities were firstly printed onto the 11-mercaptoundecanoic acid SAM by microcontact printing, followed by biotinylation, and reacted with fluorescence-labeled avidin or anti-biotin antibody. Fluorescence microscopic analysis revealed that the patterns of avidin and anti-biotin antibody were well constructed with the resolution of < 2 ㎛. The PAMAM dendrimers were also printed onto aldehyde-activated slide glass and reacted directly with anti-BSA antibodies, which had been oxidized with sodium periodate. As a result, distinct patterns of the anti-BSA antibodies were also obtained with a comparable edge resolution to that of avidin patterns on gold. These results clearly show that PAMAM dendrimers can be adopted as an interfacing layer for the patterning of biological molecules on solid surfaces with micrometer resolution.

Analysis of health-related microbes called probiotics was performed by capillary electrophoresis. A rapid and easy characterization for two important probiotics, Saccharomyces cerevisiae and Enterococcus feacalis, was obtained in the running buffer containing poly(ethylene oxide). Quantitation of probiotic (Saccharomyces cerevisiae) shows a good linearity between the peak area versus the concentration of microbe. From the comparison of electropherograms of antidiarrhea, it was found that capillary electrophoresis could be employed for the quality control and quality assurance for the production of a medicine containing the probiotics.

The effect of solvent structure on the slope in the plot of ln K vs. solute carbon number was examined. It was found that the free energy of methylene group transfer from the gas phase into a solvent was always negative and that the absolute magnitude of interaction free energy between the methylene group and the solvent was always larger than the absolute magnitude of cavity formation free energy of the methylene group in the solvent. Thus, the slope in the plot of ln K vs. solute carbon number was always positive and its value decreases with increase of solvent polarity since the cavity formation energy of the CH₂ unit increases with increase of solvent polarity while the dispersive interaction energy of the CH₂ unit is virtually invariant. We also examined the effect of sequential addition of CH₂ unit to a solvent molecule upon ln K for three homologous series of solvents: n-alkanes, n-alcohols, and n-nitriles. Characteristic trends in the plots of ln K vs. solvent carbon number were observed for individual solvent groups. A decrease of ln K with solvent carbon number was observed for n-alkanes. An abrupt increase in ln K followed by levelling off was observed for n-alcohols while a final slight decrease in ln K after an abrupt increase followed by rapid levelling off was noted for n-nitriles. All of theses phenomena were found related to variation in cavity formation energy. It was clearly shown that a structural change of a polar solvent by sequential addition of CH₂ units causes an abrupt polarity decrease initially, then gradual levelling off, and finally, conversion to a virtually nonpolar solvent if enough CH₂ units are added.

The anomalies that appear at every multiple of 15 ℃ in the viscosity of a thin liquid film of water and of water near solid interfaces are explained in this paper by comparing the thermal wavelength and molecular free volume of water, and quantum numbers are found. The possibility that these anomalies are related to the preferred and/or lethal temperatures of organisms is considered. The toxicity of heavy water (D₂O) can also be explained with this approach.

An analysis of the bonding situation in CaM₂P₂ (M=Fe, Ni) with ThCr₂Si₂ structure is made in terms of DOS and COOP plots. The main contributions to covalent bonding are due to M-P and P-P interactions in both compounds. Particularly, the interlayer P-P bonding by variation in the transition metal is examined in more detail. It turns out that the shorter P-P bonds in CaNi₂P₂ form as a result of the decreasing electron delocalization into ${{\sigma}_p}^*$ of P₂ due to the weaker bonding interaction between the metal d and ${{\sigma}_p}^*$ as the metal d band is falling from Fe to Ni.