Stable molecular isomers were calculated for the azobenzene crown ether p-tert-butylcalix[4]arene (1) in the host and their alkali-metal-ion complexes. The structures of two distinct isomers (cis and trans) have been optimized using DFT B3LYP/6-31G(d,p) method. Trans isomer of 1 is found to be 11.69 kcal/mol more stable than cis analogue. For two different kinds of complexation mode, the alkali-metal-cation in the crown-ether moiety (exo) has much better complexation efficiency than in the benzene-rings (endo) pocket for both isomers of 1. Sodium ion has much better complexation efficiency than potassium ion in all kinds of complexation mode with host 1. The Na+ complexation efficiency of the trans-complex (1) in the exo-binding mode is 8.24 kcal/mol better than cis-exo analogue.

The title compound of nicotinato lead(II) complex [Pb$(C_5H_4NCOO)_2$] has been optimized at B3LYP/LANL2DZ and HF/LANL2DZ levels of theory. The calculated results show that the lead(II) ion adopts 2- coordinate geometry, which is the same as its crystal structure and different from the 4-coordinate geometry of isonicotinato lead(II) complex. Atomic charge distributions indicate that during forming the title compound, each nicotinic acid ion transfers their negative charges to central lead(II) ion. The electronic spectra calculated by B3LYP/LANL2DZ level show that there exist two absorption bands, which have some red shifts compared with those of isonicotinato lead(II) complex and the electronic transitions are mainly derived from intraligand $\pi$ -$\pi$ transition and ligand-to-metal charge transfer (LMCT) transition. CIS-HF method is not suitable for the system studied here. The thermodynamic properties of the title compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained. The second order optical nonlinearity was calculated, and the molecular hyperpolarizability was $1.147754{\times}10^{-30}$ esu.

An improved HPLC method for the separation of madecassoside isomers (madecassoside and asiaticoside-B) has been developed. The isomers can be separated with high resolution from extracts of Centella asiatica by HPLC using $\beta$-cyclodextrin as a mobile phase added on a $C_{18}$ column. The result shows that the isomers can be separated with a mobile phase consisting of methanol:water (50:50, v/v) with 4 mmol/L $\beta$-CD. To elucidate the mechanism of the separation of madecassoside and asiaticoside-B, this paper studied the separation of their aglycon parts (madecassic acid and terminolic acid), another pair of isomers. The isomers can also be separated with high resolution with a mobile phase consisting of methanol:water (65:35, v/v) with 4 mmol/L $\beta$-CD and the pH of the mobile phase was adjusted to 4. The paper also studied the separation of the two isomers by HPLC using $\alpha$-CD and Glucosyl-$\beta$-CD as a mobile phase additive in order to elucidate the mechanism of the separation process.

In air stripping of ammonia from the aqueous solution, a new removal model was presented considering the equilibrium principles for the ammonia in aqueous solution and between the aqueous and air phase. The effects of pH, temperature and airflow rate on the ammonia removal were evaluated with the model. In addition, the saturation degree of ammonia in air was defined and used to evaluate the effect of each experimental factor on the removal rate. As pH (8.9 to 11.9) or temperature (20 to 50 oC) was increased, the overall removal rate constants in all cases were appeared to be increased. Our presented model shows that the degrees of saturation were about the same (0.45) in all cases when the airflow condition remains the same. This result indicates that the effect of pH and temperature were directly taken into consideration in the model equation. As the airflow increases, the overall removal rate constants were increased in all cases as expected. However, the saturation degree was exponentially decreased with increasing the airflow rate in the air phase (or above-surface) aeration. In the subsurface aeration the saturation degree remains a constant value of 0.65 even though the airflow rate was increased. These results indicate that the degree of saturation is affected mainly by the turbulence of the aqueous solution and remains the same above a certain airflow rate.

Reaction of AgNO3 with triethanolaminetriisonicotinate (L) produces 1 D coordination polymer of [Ag3(L)2](NO3)3 and the same treatment of Cu(NO3)2 with L gives 1D coordination polymer of [Cu(L)2](NO3)2. The nonrigid triethanolaminetriisonicotinate acts as a m 3-bridged tridentate for [Ag3(L)2](NO3)3 and a m 2-bridged bidentate for [Cu(L)2](NO3)2 to produce unusual motifs. The NO3- anions can be smoothly exchanged by PF6- anions in an aqueous suspension without destruction of the skeletal structure.

A new pyrene appended diaza-18-crown-6 ether derivative 1 has been prepared and its fluoroionophoric properties toward transition metal ions were investigated. Compound 1 exhibited a high Hg2+-selectivity over other transition metal ions as well as alkali and alkaline earth metal ions in aqueous acetonitrile solution. The ratiometric analysis of the monomer and excimer emissions of pyrene successfully signals the presence of Hg2+ ions. The detection limit for Hg2+ ions was found to be 3.1 ´ 10-6 M in 50% aqueous acetonitrile solution at pH 8.1. Competition experiments also suggest that the compound could be utilized as a selective and sensitive fluorescent chemosensor for the analysis of micromolar Hg2+ ions in physiological and environmental samples.

The well-known Cu2+-selective chemodosimetric behavior of rhodamine B hydrazide was successfully switched to selectivity for Hg2+. The fluorescence signaling is remarkably selective toward Hg2+ ions compared to other common biologically and environmentally important metal ions, including Cu2+ ions. The detection limit was 0.2 mM in an acetate-buffered aqueous 10% methanol solution at pH 5. The OFF-ON type of signaling is due to the selective Hg2+-induced hydrolysis of the lactam ring of the hydrazide as has been reported for the standard Cu2+-signaling process of the same compound. A simple change in medium resulted in clear switching of selective signaling from Cu2+ to Hg2+, which extends the applicability of the easily accessible hydrazide derivative.

Second-order rate constants (kN) have been measured spectrophotometrically for reactions of Y-substituted phenyl benzoates (1a-h) with azide ion (N3) in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the azidolysis exhibits a downward curvature, i.e., the slope (b lg) changes from 0.97 to 0.20 as the basicity of the leaving group decreases. The pKao (defined as the pKa at the center of the Brnsted curvature) is 4.8, which is practically identical to the pKa of the conjugate acid of N3 ion (4.73). Hammett plots correlated with s o and s constants exhibit highly scattered points for the azidolysis. On the contrary, the corresponding Yukawa-Tsuno plot results in an excellent linear correlation with r = 2.45 and r = 0.40, indicating that the leaving group departs in the rate-determining step. The curved Brnsted-type plot has been interpreted as a change in the rate-determining step in a stepwise mechanism. The microscopic rate constants (k1 and k2/k1 ratio) have been calculated for the azidolysis and found to be consistent with the proposed mechanism.

Second-order rate constants (kN) have been measured for reactions of Y-substituted phenyl 2-thiophenecarboxylates (6a-h) with morpholine and piperidine in 80 mol % H2O/20 mol % DMSO at 25.0 0.1 oC. The Brnsted-type plot for the reactions of 6a-h with morpholine is linear with b lg = 1.29, indicating that the reactions proceed through a tetrahedral zwitterionic intermediate (T?). On the other hand, the Brnsted-type plot for the reactions of 6a-h with piperidine exhibits a downward curvature, implying that a change in the rate-determining step occurs on changing the substituent Y in the leaving group. Dissection of kN into microscopic rate constants (i.e., k1 and k2/k1 ratio) has revealed that k1 is smaller for the reactions of 6a-h than for those of Y-substituted phenyl 2-furoates (5a-h), while the k2/k1 ratio is almost the same for the reactions of 5a-h and 6a-h. It is also reported that modification of the nonleaving group from the furoyl (5a-h) to the thiophenecarbonyl (6a-h) does not influence pKao (defined as the pKa at the center of the Brnsted curvature) as well as the k2/k1 ratio.

The inclusion complexes of cyclodextrins (CDs) with flavones in aqueous solution were investigated by phase solubility measurements. The effect of b -cyclodextrin (b -CD), heptakis (2,6-di-O-methyl) b -cyclodextrin (DM-b -CD) and 2-hydroxypropyl-b -cyclodextrin (HP-b -CD) on the aqueous solubility of three flavones, namely, chrysin, apigenin and luteolin was investigated, respectively. Solubility enhancements of all flavones obtained with three CDs followed the rank order: HP-b -CD > DM-b -CD > b -CD, and besides, CDs show higher stability constant on luteolin than that on others flavones. 1H-nuclear magnetic resonance (NMR) spectroscopy and molecular modeling was used to help establish the model of interaction of the CDs with luteolin. NMR spectroscopic analysis suggested that A-C ring, and part of the B ring of luteolin display favorable interaction with the CDs, which was also confirmed by docking studies based on the molecular simulation. The observed augmentation of solubility of luteolin by three CDs was explained by the difference of electrostatic interaction of each complex, especially hydrogen bonding.

Emodin (3-methyl-1,6,8-trihydroxyanthraquinone) is a natural chemotherapeutic compound with diverse biological properties including an antitumor activity. Emodin, a specific inhibitor of the protein tyrosine kinase, has a number of cellular targets in related to it. Its inhibition activity affects the mammalian cell cycle regulation in specific oncogene. Practically, it has been proven to inhibit HER-2/neu tyrosine kinase expressing breast cancer cells as an anticancer agent. 2-[123I]iodoemodin has been synthesized and evaluated human breast cancer cells (MDA-MB-231, MCF-7, fibroblast as a control) which express basal levels of HER-2/neu tyrosine kinase to investigate its suitability as a breast cancer imaging agent and 2-iodoemodin has been synthesized as a standard compound. The radiochemical yield of the 2-[123I]iodoemodin was about 72% and its radiochemical purity was over 97% after purification. The radioactivity of the 2-[123I]iodoemodin was increased in a time dependent manner in both cell lines and the ratio of MDA-MB-231 and MCF7 to fibroblast was 2.9 and 1.7, respectively.

The complexes Pd(nbmtp)Cl2 and Pt(nbmtp)Cl2 (nbmptp = 1-nonyl-3,4-bis(methylthio)pyrrole) were prepared and their x-ray structures were determined at room temperature. The four-coordinated metal unit and the pyrrole ring formed a nearly planar geometry. The free ligand dissolved in CH2Cl2 produced two luminescence bands associated with the lone-pair electron of S (l max = 525 nm) and the pyrrole p electron (l max = 388 nm). When the two complexes were dissolved in CH2Cl2, these two luminescence bands were also observed, although the low-energy band was blueshifted. For the crystalline Pt(II) complex, only the strong charge transfer band (l max = 618 nm) from the d* orbital of Pt resulted from excitation of the lone-pair electron of S.

A series of N-alkenyl pyrrolidine-2-thiones were synthesized by the reaction between pyrrolidine-2-thione and various aldehydes such as n-propanal, isopropanal, n-butanal, n-hexanal, n-octanal and phenylacetaldehyde in 32-86% yields using microwave irradiation technique. Only one structural E isomers were predominantly formed within 15 minutes in chlorobenezene?/p-toluenesulfonic acid monohydrate.

A periodic mesoporous organosilica material was synthesized by microwave heating (PMO-M) using 1,2-bis(trimethoxysilyl)ethane as a precursor in a cationic surfactant solution, and textural properties were compared with those of the product produced by conventional convection heating (PMO-C). These synthesized materials were characterized using XRD, TEM/SEM, N2 adsorption isotherm, 29Si and 13C NMR, and TGA, which confirmed their good structural orders and clear arrangements of uniform 3D-channels. Synthesis time was reduced from 21 h in PMO-C to 2-4 h in PMO-M. PMO-M was made of spherical particles of 1.5-2.2 m m size, whereas PMO-C was made of decaoctahedron-shaped particles of ca. 8.0 m m size. Effect of synthesis temperature, time, and heating mode on the PMO particle morphology was examined. The particle size of PMO-M could be controlled by changing the heating rate by adjusting microwave power level. PMO-M demonstrated improved separation of selected organic compounds compared to PMO-C in a reversed phase HPLC experiment. Ti-grafted PMO-M also resulted in higher conversion in liquid phase cyclohexene epoxidation than by Ti-PMO-C.

Eight triterpenoids, six lanostanes 1-6, one lupenane 7, and one oleanane 8, were isolated by bioactivity-guided fractionation of the ethylacetate extract from roots of Glycine max (L.) Merr. All isolated compounds were examined for their inhibitory activities against human ACAT-1 (hACAT-1) and human ACAT-2 (hACAT-2). Among them, three triterpenoids showed potent hACAT inhibitory activities, (24R)-ethylcholest-5-ene-3,7-diol (1) and 3b -hydroxylup-20(29)-en-28-oic acid (7) exhibited more potent inhibitory activity against hACAT-1 (1: IC50 = 25.0 1.2 and 7: IC50 = 11.5 0.4 m M) than hACAT-2 (1: IC50 = 102.0 5.4 and 7: IC50 = 33.9 3.7 m M), respectively. Interestingly, 5a ,8a -epidioxy-24(R)-methylcholesta-6,22-diene-3b -ol (4) has proven to be a specific inhibitor against hACAT-1 (IC50 = 38.7 0.8 m M) compared to hACAT-2 (IC50 >200). In conclusion, this is the first study to demonstrate that triterpenoids of G. max have potent inhibitory activities against hACAT-1 and hACAT-2.

A new thiacalix[4]arene diamide (TCAm) has been prepared and its electrochemical property and complexation behavior toward various metal ions have been investigated by voltammetry. p-tert-Butylthiacalix[4]arene diamide (TCAm) exhibited selectivity toward Sr2+ ion over alkali, alkaline earth and transition metal ions while conventional calix[4]arene diamides showed selective binding property with Ca2+ ion. This is probably due to the bigger size of thiacalix[4]arene than those of calix[4]arene.

Spin-coating electrostatic self-assembly (SCESA) is utilized to fabricate a single layer of carboxylic-acid-coated Pd nanoparticles (NPs) (D??5 nm) on an oppositely charged surface. The packing density of a NP monolayer formed on a rotating solid substrate (3000 rpm) was examined with regards to various parameters, including the particle concentration, the pH, and the ionic strength of the solution. Initially, the packing density grew exponentially with increases in the particle concentration, up to a maximum value (of 8.4 ´ 1011/cm2) at 1.2 wt%. The packing density was also found to increase drastically as the pH decreased and the ionic strength of the solution increased; these trends can be attributed to a reduction in the interparticle repulsions among the NPs in the solution and on the substrate. The best result of this study was achieved in a 1.2 wt% solution at pH 8; under these conditions, an NP monolayer with the highest density (namely, 1.6 ´ 1012/cm2) was obtained.

The geometrical structures, atomic charges, and relative energies of tetracoordinated Pd complexes [PdCl3Z (Z = Cl-, Br-, OH?-, H2O, NH3, PH3), PdCl2Z2 (Z = Br-, OH?-, H2O, NH3, PH3), PdZ?2X (Z = Cl-, OH?-, H2O, NH3, PH3; X = oxalate, O2-?CCO2-), and PdZ2Y (Z = Cl?-, OH?-, H2O, NH3, PH3; Y = succinate, CO2-?CHCHCO2-?)] and the ligand exchange reactions of the Pd complexes were investigated using the ab initio second order Mller-Plesset perturbation (MP2) and Density Functional Theory (DFT) methods. The geometrical characteristics of the tetracoordinated Pd(II) complexes with mono- and bidentate ligands, the effects of the atomic charges for the charged and uncharged ligands, the (dz2-p ) interactions between the dz2-orbital of Pd(II) and the p -orbital of bidentates, and the relative stabilities between the isomers of PdCl2Z2 and PdZ2Y were investigated in detail. The potential energy surfaces for the ligand exchange reactions used for the conversions of {[PdCl2(NH3)2] + H2O} to {[PdCl(NH3)2(H2O)]+ + Cl?-?} and {[PdCl2(PH3)2] + H2O} to {[PdCl(PH3)2(H2O)]+ + Cl?-?]} were investigated. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes were also examined quantitatively.

Equilibrium molecular dynamics simulations in a canonical ensemble are performed to evaluate the transport coefficients of several Lennard-Jones (LJ) mixtures at a liquid argon states of 94.4 K and 1 atm via modified Green-Kubo formulas. Two component mixture of A and B is built by considering the interaction between A and A as the attractive (A) potential, that between A and B as the attractive potential (A), and that between B and B as the repulsive potential (R), labelled as AAR mixture. Three more mixtures - ARA, ARR, and RAR are created in the same way. The behavior of the LJ energy and the transport properties for all the mixtures is easily understood in terms of the portion of attractive potential (A %). The behavior of the thermal conductivities by the translational energy transport due to molecular motion exactly coincides with that of diffusion constant while that of the thermal conductivities by the potential energy transport due to molecular motion is easily understood from the fact that the LJ energy of AAR, ARR, and RAR mixtures increases negatively with the increase of A % from that of the pure repulsive system while that of ARA changes rarely.

Microsomal prostaglandin E2 synthase (mPGES-1) is a potent target for pain and inflammation. Various QSAR (quantitative structure activity relationship) analyses used to understand the factors affecting inhibitory potency for a series of MK886 analogues. We derived four QSAR models utilizing various quantum mechanical (QM) descriptors. These QM models indicate that steric, electrostatic and hydrophobic interaction can be important factors. Common pharmacophore hypotheses (CPHs) also have studied. The QSAR model derived by best-fitted CPHs considering hydrophobic, negative group and ring effect gave a reasonable result (q2 = 0.77, r2 = 0.97 and Rtestset = 0.90). The pharmacophore-derived molecular alignment subsequently used for 3D-QSAR. The CoMFA (Comparative Molecular Field Analysis) and CoMSIA (Comparative Molecular Similarity Indices Analysis) techniques employed on same series of mPGES-1 inhibitors which gives a statistically reasonable result (CoMFA; q2 = 0.90, r2 = 0.99. CoMSIA; q2 = 0.93, r2 = 1.00). All modeling results (QM-based QSAR, pharmacophore modeling and 3D-QSAR) imply steric, electrostatic and hydrophobic contribution to the inhibitory activity. CoMFA and CoMSIA models suggest the introduction of bulky group around ring B may enhance the inhibitory activity.

Antagonists of the d -opioid receptor are effective in overcoming resistance against analgesic drugs such as morphine. To identify novel antagonists of the d -opioid receptor that display high potency and low resistance, we performed 3D-QSAR analysis using chemical feature-based pharmacophore models. Chemical features for d -opioid receptor antagonists were generated using quantitative (Catalyst/HypoGen) and qualitative (Catalyst/HipHop) approaches. For HypoGen analysis, we collected 16 peptide and 16 non-peptide antagonists as the training set. The best-fit pharmacophore hypotheses of the two antagonist models comprised identical features, including a hydrophobic aromatic (HAR), a hydrophobic (HY), and a positive ionizable (PI) function. The training set of the HipHop model was constructed with three launched opioid drugs. The best hypothesis from HipHop included four features: an HAR, an HY, a hydrogen bond donor (HBD), and a PI function. Based on these results, we confirm that HY, HAR and PI features are essential for effective antagonism of the d -opioid receptor, and determine the appropriate pharmacophore to design such antagonists.