A fast correlated electronic structure method for computing interaction energies of large van der Waals complexes applied to the fullerene-porphyrin dimer

A new implementation of the scaled opposite spin M?ller-Plesset (SOS-MP2) method is briefly described, which exploits the locality and sparsity of expansion coefficients and as a result has computational costs that increase approximately quadratically with molecular size. The performance of SOS-MP2 for describing stacked pi-complexes is carefully investigated using the benzene, ethylene, uracil, and naphthalene dimers as model systems. It is demonstrated that counterpoise-corrected SOS-MP2 results, extrapolated towards the complete basis set (CBS) limit using a two-point extrapolation scheme, can yield association energies that are reasonably close to the best available numbers, when the single scale factor is chosen as 1.55 for extrapolating results at the cc-pVDZ and cc-pVTZ levels. This methodology yields an interaction energy for the fullerene-tetraphenylporphyrin dimer of -31.47 kcal mol(-1) while Hartree-Fock (HF) with the cc-pVTZ basis finds the dimer at the same geometry is unbound by +10.83 kcal mol(-1). This implies that the net binding is a result of substantial correlation effects, presumably long-range London dispersions.     

Delineation of a fundamental alpha-ketoheterocycle substituent effect for use in the design of enzyme inhibitors

The synthesis and examination of a systematic series of 5-substituted 2-keto oxazoles as inhibitors of fatty acid amide hydrolase (FAAH) defined a fundamental substituent effect that led to the discovery of inhibitors with Ki's as low as 400 pM. The intrinsic basis of the relationship (-log Ki vs sigmap), which relates Ki with the Hammett sigmap constant of the substituent, the magnitude of the effect (rho = 3.01), and its predictive value (R2 = 0.91) suggest a widespread applicability in studies beyond FAAH.     

Intermolecular interaction-induced hierarchical transformation in 1D nanohybrids: analysis of conformational changes by 2D correlation spectroscopy

We have examined both self-assembly and confinement effect in room-temperature ionic liquid (RTIL)-aluminum hydroxide hybrids (RAHs) to attain a fundamental understanding of special phenomena in nanoscale spaces as well as to design functional nanomaterials for practical applications. Phase-controlled one-dimensional (1D) RAHs were synthesized through a simple ionothermal process. The RAHs were hierarchically transformed in terms of the molecular structures, morphologies, and phases of the materials during the ionothermal process with respect to the concentration of RTIL. In addition to the hierarchical transformation, the RTIL/aluminum hydroxide nanohybrids revealed unexpected physical behaviors, including thermal transition variation of the RTIL in confined environments and a phase transition from nanosolid to nanoliquid affected by changes of the melting points. More importantly, intermolecular interaction induced-self-assembly and confinement effect of RTILs inside an integrated hybrid system, which have not been clearly explained to date, were analyzed by 2D infrared correlation spectroscopy (2D IR COS); dynamic behaviors of RTILs, i.e., sequentially spatial reorientation and kinetically conformational changes, were attributed to the interactions between RTILs and aluminum hydroxides. 2D IR COS offers a new way to interpret highly complex, veiled systems such as the formation mechanism of nanoparticles, biomineralization, self/supramolecular assembly, and nanoconfinement.     

Conclusive evidence of the trapping of primary ozonides

[reaction: see text] Anomalous ozonolysis of strained bicyclic allylic alcohols yields alpha-hydroxymethyl ketones. The proposed mechanism involves an unusual trapping of the primary ozonide that undergoes a Grob-like fragmentation instead of dissociating into the Criegee intermediates.     

Tandem cyclization of alkynes via rhodium alkynyl and alkenylidene catalysis

A rhodium(I)-catalyzed tandem cyclization of alkynes has been developed. The reaction allows for multiple bond formations to occur at both the alpha- and beta-positions of alkynes under mild conditions to yield a variety of fused ring systems as the products. In the presence of triethylamine and the complex derived from [Rh(COD)Cl]2 and P(4-F-C6H4)3, a terminal alkyne is converted to a rhodium alkynyl species which reacts with a tethered alkyl halide at the beta-position to provide a beta,beta-disubstituted alkenylidene complex. The rhodium alkenylidene species then undergoes additional ring closures with a range of pendent functional groups such as alkene, hydroxyl, and phenyl groups through [2 + 2] cycloaddition, nucleophilic addition, and 6pi-electrocyclization processes, respectively.     

Production of uniform-sized polymer core-shell microcapsules by coaxial electrospraying

Spherical polymeric core-shell microcapsules in uniform size were produced by electrospraying with a coaxial nozzle setup. Contrary to the usual coaxial setup, the inner nozzle was slightly bent to touch the inside wall of the outer nozzle. A polymer solution for the core was introduced through the outer nozzle, and the other solution for the shell was supplied through the inner nozzle. The setup greatly increased reproduction of the same results. As a proof of the concept, core-shell microcapsules consisting of a PS or PMMA core and a PCL shell (PS@PCL, PMMA@PCL) were produced. When the volumetric feed rate of the shell-forming PCL solution was higher than that of the core-forming PS or PMMA solution the core-shell structures in uniform size were readily obtained. In contrast, irregular morphologies were observed when the feed rate of the PCL solution was slower or equal to that of the PS or PMMA solution. The size of the colloid was dependent on the relative feed ratio between the polymer solutions as well as the magnitude of applied voltage.     

Formulation variation and in vitro-in vivo correlation for a rapidly swellable three-layered tablet of tamsulosin HCl

In order to develop a preferable once-a-day oral tablet formulation, various formulations of three-layered tablets containing tamsulosin HCl as a hydrophilic model drug were evaluated and compared with a commercial reference, tamsulosin OCAS?. When the test tablet was exposed to a release medium, the medium quickly permeated to the mid-layer and the two barrier layers swelled surrounding the mid-layer rapidly. Volume expansion showed faster and enough swelling of the three-layered tablet up to 2 h. Larger amount of barrier layers caused reduced release kinetics and a high molecular weight polymer showed more resistance against agitation force. A formulation with water-soluble mid-layer showed fast erosion decreasing its volume significantly. On the pharmacokinetic study, the mean ratio of area under the curve (AUC) and C(max) for the test formulation to the reference was 0.69 and 0.84, respectively, showing that the absorption of the drug was less complete than the reference. Plasma concentration at 24 h of the test formulation was higher than the reference. The Wagner-Nelson method showed that decreased initial dissolution rate might be the cause of the less complete absorption. On considering in vitro-in vivo correlation (IVIVC), level A, the reference (R2=0.981) showed more linear relationship than the test (R2=0.918) due to the decreased dissolution and absorption rate of the formulation. This result suggests that the in vitro dissolution profiles and release kinetics might be useful in correlating absorption kinetics as well as overall plasma drug concentration-time profiles for formulation studies.     

The distinct signaling mechanisms of microbial sensory rhodopsins in Archaea, Eubacteria and Eukarya

Most of the known archaeal-type microbial rhodopsins are retinal-binding ion transporters, such as bacteriorhodopsin (BR) and proteorhodopsin (PR). Their identification is the result of extensive studies of their photochemical and biophysical properties. The cells containing these pigments, however, use other microbial rhodopsins as photosensors to monitor environmental light signals. From the early studies of sensory rhodopsin I (HsSRI) in Halobacterium salinarum and sensory rhodopsin II (NpSRII) in Natronomonas pharaonis, we now know that several microbial sensory rhodopsins in the other major domain of life relay information on light intensity and quality to the cell. Three of the most studied photosensory transduction mechanisms of these microbial rhodopsins are dealt with in this review. We discuss recent progress in the understanding of genomic organization, photochemical properties and photosignaling mechanisms with respect to biological function.     

Preparation, thermal properties, morphology, and microstructure of phosphorus-containing epoxy/SiO2 and polyimide/SiO2 nanocomposites

A phosphorus-containing tri-ethoxysilane (dopo-icteos) reacting from the nucleophilic addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (dopo) and 3-(trieoxysilyl) isocyanate (icteos) was synthesized. The structure of dopo-icteos was confirmed by ¹H, ¹³C, ³¹P NMR and IR spectra. A triethylamine catalyzed mechanism for the dopo-icteos synthesis was proposed and verified by NMR spectra. The phosphorus-containing epoxy/SiO₂ and polyimide/SiO₂ nanocomposites were prepared from the in-situ curing of diglycidyl ether of bisphenol A (DGEBA)/4,4-diaminodiphenylmethane(DDM)/dopo-icteos, and imidization of poly(amic acid) of pyromellitic dianhydride (PMDA)/4,4′-oxydianiline (ODA)/dopo-icteos, respectively. The microstructure and morphology were investigated by ²⁹Si NMR, scanning electron microscope (SEM), EDS (Si and P mapping) analysis and atomic force microscope (AFM). The thermal properties, flame retardancy and dielectric properties of the organic-inorganic hybrids were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), limiting oxygen index (LOI), thermal gravimetric analysis (TGA) and dielectric analyzer (DEA).     

Azobenzene coupled chromogenic receptors for the selective detection of copper(II) and its application as a chemosensor kit

Azobenzene-based receptors 1-4 as colorimetric sensing materials were synthesized and their sensing properties were examined. In solution, the proposed sensing materials give rise to a large cation-induced hypochromic shift for Cu²⁺ resulting in a change from red to pale-yellow, whereas no significant color change was observed upon addition of other selected metal ions. The use of the silica gel plate modified with immobilization of receptor 4 to detect Cu²⁺ was also reported.