Estimated MP2 and CCSD(T) interaction energies of n-alkane dimers at the basis set limit: comparison of the methods of Helgaker et al. and Feller

The MP2 (the second-order M?ller-Plesset calculation) and CCSD(T) (coupled cluster calculation with single and double substitutions with noniterative triple excitations) interaction energies of all-trans n-alkane dimers were calculated using Dunning's [J. Chem. Phys. 90, 1007 (1989)] correlation consistent basis sets. The estimated MP2 interaction energies of methane, ethane, and propane dimers at the basis set limit [EMP2(limit)] by the method of Helgaker et al. [J. Chem. Phys. 106, 9639 (1997)] from the MP2/aug-cc-pVXZ (X=D and T) level interaction energies are very close to those estimated from the MP2/aug-cc-pVXZ (X=T and Q) level interaction energies. The estimated EMP2(limit) values of n-butane to n-heptane dimers from the MP2/cc-pVXZ (X=D and T) level interaction energies are very close to those from the MP2/aug-cc-pVXZ (X=D and T) ones. The EMP2(limit) values estimated by Feller's [J. Chem. Phys. 96, 6104 (1992)] method from the MP2/cc-pVXZ (X=D, T, and Q) level interaction energies are close to those estimated by the method of Helgaker et al. from the MP2/cc-pVXZ (X=T and Q) ones. The estimated EMP2(limit) values by the method of Helgaker et al. using the aug-cc-pVXZ (X=D and T) are close to these values. The estimated EMP2(limit) of the methane, ethane, propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane dimers by the method of Helgaker et al. are -0.48, -1.35, -2.08, -2.97, -3.92, -4.91, -5.96, -6.68, -7.75, and -8.75 kcal/mol, respectively. Effects of electron correlation beyond MP2 are not large. The estimated CCSD(T) interaction energies of the methane, ethane, propane, and n-butane dimers at the basis set limit by the method of Helgaker et al. (-0.41, -1.22, -1.87, and -2.74 kcal/mol, respectively) from the CCSD(T)/cc-pVXZ (X=D and T) level interaction energies are close to the EMP2(limit) obtained using the same basis sets. The estimated EMP2(limit) values of the ten dimers were fitted to the form m0+m1X (X is 1 for methane, 2 for ethane, etc.). The obtained m0 and m1 (0.595 and -0.926 kcal/mol) show that the interactions between long n-alkane chains are significant. Analysis of basis set effects shows that cc-pVXZ (X=T, Q, or 5), aug-cc-pVXZ (X=D, T, Q, or 5) basis set, or 6-311G** basis set augmented with diffuse polarization function is necessary for quantitative evaluation of the interaction energies between n-alkane chains.     

Carboxylic acid catalyzed three-component aza-Friedel-Crafts reactions in water for the synthesis of 3-substituted indoles

[reaction: see text] The carboxylic acid catalyzed three-component aza-Friedel-Crafts reactions of aldehydes, primary amines, and indoles in water have been developed. The aza-Friedel-Crafts products could be easily transformed to various 3-substituted indoles including biologically active compounds. This system offers a novel efficient method for the synthesis of 3-substituted indoles.     

Magnitude and directionality of interaction in ion pairs of ionic liquids: relationship with ionic conductivity

The intermolecular interaction energies of nine ion pairs of room temperature ionic liquids were studied by MP2/6-311G level ab initio calculations. The magnitude of the interaction energies of 1-ethyl-3-methylimidazolium (emim) complexes follows the trend CF(3)CO(2)(-) > BF(4)(-) > CF(3)SO(3)(-) > (CF(3)SO(2))(2)N(-) approximately PF(6)(-) (-89.8, -85.2, -82.6, -78.8, and -78.4 kcal/mol, respectively). The interaction energies of BF(4)(-) complexes with emim, ethylpyridinium (epy), N-ethyl-N,N,N-trimethylammonium ((C(2)H(5))(CH(3))(3)N), and N-ethyl-N-methylpyrrolidinium (empro) are not very different (-85.2, -82.8, -84.6, and -84.4 kcal/mol, respectively), while the size of the orientation dependence of the interaction energies follows the trend emim > epy approximately (C(2)H(5))(CH(3))(3)N > empro. Comparison with the experimental ionic conductivities shows that the magnitude and directionality of the interaction energy of the ion pairs play a crucial role in determining the ionic dissociation/association dynamics in the ionic liquids. The electrostatic interaction is the major source of attraction between ions. The induction contribution is small but not negligible. The hydrogen bonding with the C(2)-H of imidazolium is not essential for the attraction in the ion pair. The interaction energy of the BF(4)(-) complex with 1-ethyl-2,3-dimethylimidazolium (em2im) (-81.8 kcal/mol) is only 4% smaller than that of the emim complex.     

Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids

[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization.     

Heteroatom-guided torquoselective olefination of alpha-oxy and alpha-amino ketones via ynolates

Ynolates were found to react with alpha-alkoxy-, alpha-siloxy-, and alpha-aryloxyketones at room temperature to afford tetrasubstituted olefins with high Z selectivity. Since the geometrical selectivity was determined in the ring opening of the beta-lactone enolate intermediates, the torquoselectivity was controlled by the ethereal oxygen atoms. From experimental and theoretical studies, the high Z selectivity is induced by orbital and steric interactions rather than by chelation. In a similar manner, alpha-dialkylamino ketones provided olefins with excellent Z selectivity. These products can be easily converted into multisubstituted butenolides and gamma-butyrolactams in good yield.     

Host-guest interactions in the supramolecular incorporation of fullerenes into tailored holes on porphyrin-modified gold nanoparticles in molecular photovoltaics

Novel gold nanoparticles modified with a mixed self-assembled monolayer of porphyrin alkanethiol and short-chain alkanethiol were prepared (first step) to examine the size and shape effects of surface holes (host) on porphyrin-modified gold nanoparticles. The porphyrin-modified gold nanoparticles with a size of about 10 nm incorporated C60 molecules (guest) into the large, bucket-shaped holes, leading to the formation of a supramolecular complex of porphyrin-C60 composites (second step). Large composite clusters with a size of 200-400 nm were grown from the supramolecular complex of porphyrin-C60 composites in mixed solvents (third step) and deposited electrophoretically onto nanostructured SnO2 electrodes (fourth step). Differences in the porphyrin:C60 ratio were found to affect the structures and photoelectrochemical properties of the composite clusters in mixed solvents as well as on the SnO2 electrodes. The photoelectrochemical performance of a photoelectrochemical device consisting of SnO2 electrodes modified with the porphyrin-C60 composites was enhanced relative to a reference system with small, wedged-shaped surface holes on the gold nanoparticle. Time-resolved transient absorption spectroscopy with fluorescence lifetime measurements suggest the occurrence of ultrafast electron transfer from the porphyrin excited singlet states to C60 or the formation of a partial charge-transfer state in the composite clusters of supramolecular complexes formed between porphyrin and C60 leading to efficient photocurrent generation in the system. Elucidation of the relationship between host-guest interactions and photoelectrochemical function in the present system will provide valuable information on the design of molecular devices and machines including molecular photovoltaics.     

A practical asymmetric synthesis of trans-4,5-benzhydrindan-1-ones as a precursor of A-nor B-aromatic steroidal compounds

The enantio-controlled synthesis of trans-4,5-benzhydrindan-1-ones was achieved by means of a stereoselective [4+2] cycloaddition of o-quinodimethanes generated by a thermal cleavage of benzocyclobutene derivatives as a key step. The chiral substrates of the thermal reaction were synthesized by a diastereoselective Grignard addition to the chiral O-isopropylideneglyceroketones connected to a benzocyclobutene ring, which were simply prepared from D-mannitol as a chiral source. This approach can provide a new efficient access to A-nor B-aromatic steroidal compounds.     

Coenzyme models. 32. Catalytic activity of polymer-bound thiazolium ions as estimated by flavin trapping technique

Three thiazolium-containing polymers, Th-7, Th-33, and Th-18-Py [where Th-x and Py mean x mol % thiazolium unit and pyridinium unit (54 mol %), respectively], were synthesized from partially p-chloromethylated polystyrene. The catalytic activities of these polymer catalysts in acyloin condensation of aldehydes and decarboxylation of α-keto acids were estimated kinetically by oxidative trapping of the key intermediate by flavin (flavin-trapping technique). In aqueous solution at 30°C, the catalytic activity of Th-18-Py and Th-33 in condensation of p-chlorobenzaldehyde was comparable with that of the cationic-micelle-bound thiazolium ion, whereas Th-7 and a monomeric thiazolium compound (N-benzylthiazolium bromide) scarcely exhibited any catalytic activity. The catalysis of the polymer-bound thiazolium ions was sensitively suppressed by increased ionic strength. These results suggest that the pendent thiazolium ion is activated by the relatively high charge density along the polymer chain: the cationic environment is able to facilitate dissociation of the thiazolium ion to the ylid form and deprotonation of the thiazolium-aldehyde adduct to the key intermediate.     

Visualization of acetylcholine distribution in central nervous system tissue sections by tandem imaging mass spectrometry

Metabolite distribution imaging via imaging mass spectrometry (IMS) is an increasingly utilized tool in the field of neurochemistry. As most previous IMS studies analyzed the relative abundances of larger metabolite species, it is important to expand its application to smaller molecules, such as neurotransmitters. This study aimed to develop an IMS application to visualize neurotransmitter distribution in central nervous system tissue sections. Here, we raise two technical problems that must be resolved to achieve neurotransmitter imaging: (1) the lower concentrations of bioactive molecules, compared with those of membrane lipids, require higher sensitivity and/or signal-to-noise (S/N) ratios in signal detection, and (2) the molecular turnover of the neurotransmitters is rapid; thus, tissue preparation procedures should be performed carefully to minimize postmortem changes. We first evaluated intrinsic sensitivity and matrix interference using Matrix Assisted Laser Desorption/Ionization (MALDI) mass spectrometry (MS) to detect six neurotransmitters and chose acetylcholine (ACh) as a model for study. Next, we examined both single MS imaging and MS/MS imaging for ACh and found that via an ion transition from m/z 146 to m/z 87 in MS/MS imaging, ACh could be visualized with a high S/N ratio. Furthermore, we found that in situ freezing method of brain samples improved IMS data quality in terms of the number of effective pixels and the image contrast (i.e., the sensitivity and dynamic range). Therefore, by addressing the aforementioned problems, we demonstrated the tissue distribution of ACh, the most suitable molecular specimen for positive ion detection by IMS, to reveal its localization in central nervous system tissues.     

Evolved gas analysis of Ti(C5H5)2Cl2 by means of Li+ ion attachment mass spectrometry

Characterization of the compound Ti(C(5)H(5))(2)Cl(2) was studied using Li(+) ion attachment mass spectrometry (IAMS) as an analytical methodology. Since this target compound is used as an anticancer drug in the treatment of leukemia, accurate and rapid monitoring methods for the determination of titanium drugs in a hospital environment are desirable. A quadrupole mass spectrometry system along with a Li(+) ion attachment technique and a direct inlet probe (DIP) produced the Li(+) adduct of Ti(C(5)H(5))(2)Cl(2), Ti(C(5)H(5))(2)Cl(2)Li(+). The DIP also was used to study the temperature-resolved behavior of this compound. The slope of the plot of signal intensity of Ti(C(5)H(5))(2)Cl(2)Li(+) versus temperature for Ti(C(5)H(5))(2)Cl(2) sublimation from 60 to 100 °C was used to determine an apparent activation energy (E(a)) of 124.43 kJ/mol for the sublimation of Ti(C(5)H(5))(2)Cl(2). This value is comparable to the reported value of 118.8 kJ/mol for molar enthalpy of sublimation of Ti(C(5)H(5))(2)Cl(2). These results demonstrate that the IAMS methodology can be used to study the enthalpy of sublimation for d-metal complex materials.