Theoretical and computational studies of organometallic reactions: successful or not?

Theoretical and computational methods are powerful in studying transition metal complexes. Our theoretical studies of C–H σ‐bond activation of benzene by Pd(II)–formate complex and that of methane by Ti(IV)‐imido complex successfully disclosed that these reactions are understood to undergo heterolytic σ‐bond activation and the driving force is the formation of strong O–H and N–H bonds in the former and the latter, respectively. Orbital interactions are considerably different from those of σ‐bond activation by oxidative addition. The transmetallation, which is a key process in the cross‐coupling reaction, is understood to be heterolytic σ‐bond activation. Our theoretical study clarified how to accelerate this transmetallation. Also, we wish to discuss weak points in theoretical and computational studies of large systems including transition metal elements, such as the necessity to incorporate solvation effect and to present quantitatively correct numerical results. The importance of solvation effects is discussed in the oxidative addition of methyliodide to Pt(II) complex which occurs in a way similar to an S_N2 substitution. To apply the CCSD(T) (coupled cluster singles and doubles with perturbative triples correction) method, which is the gold standard of electronic structure theory, to large system, we need to reduce the size of the system by employing a small model. But, such modeling induces neglects of electronic and steric effects of substitutents which are replaced in the small model. Frontier‐orbital‐consistent quantum‐capping potential (FOC‐QCP) was recently proposed by our group to incorporate the electronic effects of the substituents neglected in the modeling. The CCSD(T) calculation with the FOC‐QCP was successfully applied to large systems including transition metal elements. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 10: 000–000; 2010: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900019     

Novelty Filtering Using Phase Conjugate Wave in Organic Dye-Doped Polymer Films

A real-time detection of a moving object was demonstrated by taking the subtraction between cross-polarized phase conjugate waves with fast and slow response times with two kinds of dye-doped phase conjugators. One consists of superposed films of an erythrosin-B-doped film and a methyl-orange-doped film, and the other is a film dispersed with both dyes. The relative phase between cross-polarized phase conjugate waves by the both dye-dispersed films was stable.     

Equivalents of the Riemann hypothesis

We obtain necessary and sufficient conditions for the Riemann hypothesis for the Riemann zeta-function, in terms of the functional distribution of quadratic Dirichlet L-functions. Received: 29 November 2004     

Total Synthesis of (−)‐Isoschizogamine

The total synthesis of (?)‐isoschizogamine was accomplished, featuring the construction of the quaternary carbon center by the modified Johnson–Claisen rearrangement in basic media and the facile assembly of the key tetracyclic quinolone intermediate through a cascade cyclization. The characteristic cyclic aminal was constructed by late‐stage C?H functionalization at the position adjacent to the lactam nitrogen using a combination of CrO₃ and nBu₄NIO₄ and subsequent Bi(OTf)₃‐mediated cyclization.     

Preparation of highly dispersible and tumor-accumulative, iron oxide nanoparticles Multi-point anchoring of PEG-b-poly(4-vinylbenzylphosphonate) improves performance significantly

This paper describes the preparation of iron oxide nanoparticles, surface of which was coated with extremely high immobilization stability and relatively higher density of poly(ethylene glycol) (PEG), which are referred to as PEG protected iron oxide nanoparticles (PEG-PIONs). The PEG-PIONs were obtained through alkali coprecipitation of iron salts in the presence of the PEG-poly(4-vinylbenzylphosphonate) block copolymer (PEG-b-PVBP). In this system, PEG-b-PVBP served as a surface coating that was bound to the iron oxide surface via multipoint anchoring of the phosphonate groups in the PVBP segment of PEG-b-PVBP. The binding of PEG-b-PVBP onto the iron oxide nanoparticle surface and the subsequent formation of a PEG brush layer were proved by FT-IR, zeta potential, and thermogravimetric measurements. The surface PEG-chain density of the PEG-PIONs varied depending on the [PEG-b-PVBP]/[iron salts] feed-weight ratio in the coprecipitation reaction. PEG-PIONs prepared at an optimal feed-weight ratio in this study showed a high surface PEG-chain surface density (≈0.8 chainsnm(-2)) and small hydrodynamic diameter (<50 nm). Furthermore, these PEG-PIONs could be dispersed in phosphate-buffered saline (PBS) that contains 10% serum without any change in their hydrodynamic diameters over a period of one week, indicating that PEG-PIONs would provide high dispersion stability under in vivo physiological conditions as well as excellent anti-biofouling properties. In fact we have confirmed the prolong blood circulation time and facilitate tumor accumulation (more than 15% IDg(-1) tumor) of PEG-PIONs without the aid of any target ligand in mouse tumor models. The majority of the PEG-PIONs accumulated in the tumor by 96 h after administration, whereas those in normal tissues were smoothly eliminated by 96 h, proving the enhancement of tumor selectivity in the PEG-PION localization. The results obtained here strongly suggest that originally synthesized PEG-b-PVBP, having multipoint anchoring character by the phosphonate groups, is rational design for improvement in nanoparticle as in vivo application. Two major points, viz., extremely stable anchoring character and dense PEG chains tethered on the nanoparticle surface, worked simultaneously to become PEG-PIONs as an ideal biomedical devices intact for prolonged periods in harsh biological environments.     

Confinement in carbon nanospace-induced production of KI nanocrystals of high-pressure phase

An outstanding compression function for materials preparation exhibited by nanospaces of single-walled carbon nanohorns (SWCNHs) was studied using the B1-to-B2 solid phase transition of KI crystals at 1.9 GPa. High-resolution transmission electron microscopy and synchrotron X-ray diffraction examinations provided evidence that KI nanocrystals doped in the nanotube spaces of SWCNHs at pressures below 0.1 MPa had the super-high-pressure B2 phase structure, which is induced at pressures above 1.9 GPa in bulk KI crystals. This finding of the supercompression function of the carbon nanotubular spaces can lead to the development of a new compression-free route to precious materials whose syntheses require the application of high pressure.     

Vapour-adsorption and chromic behaviours of luminescent coordination polymers composed of a Pt(II)-diimine metalloligand and alkaline-earth metal ions

Four new bimetallic coordination polymers (CPs), {M[Pt(CN)(2)(5,5'-dcbpy)]·4H(2)O}(n) (M = Mg(2+), Ca(2+), Sr(2+), Ba(2+); 5,5'-H(2)dcbpy = 5,5'-dicarboxy-2,2'-bipyridine) were synthesized using four alkaline-earth metal ions and a Pt(II)-diimine metalloligand [Pt(CN)(2)(5,5'-H(2)dcbpy)]. All four CPs are isomorphous with the Zn complex, {Zn[Pt(CN)(2)(5,5'-dcbpy)]·4H(2)O}(n), which exhibits effective metallophilic interactions between Pt(II) ions. These CPs exhibited colourful thermochromic behaviour and solid-state solvatochromic-like behaviours when suspended in various solvents. Thermogravimetric analysis and vapour-adsorption measurements revealed that the CPs can reversibly adsorb water and MeOH vapours. The emission energy of the triplet metal-metal-to-ligand charge-transfer ((3)MMLCT) state varied markedly upon guest adsorption/desorption. The chromic and vapour-adsorption properties of these CPs depend strongly on the cross-linking M(2+) ions.     

Authenticity assessment of beef origin by principal component analysis of matrix-assisted laser desorption/ionization mass spectrometric data

It has become necessary to assess the authenticity of beef origin because of concerns regarding human health hazards. In this study, we used a metabolomic approach involving matrix-assisted laser desorption/ionization imaging mass spectrometry to assess the authenticity of beef origin. Highly accurate data were obtained for samples of extracted lipids from beef of different origin; the samples were grouped according to their origin. The analysis of extracted lipids in this study ended within 10 min, suggesting this approach can be used as a simple authenticity assessment before a definitive identification by isotope analysis.     

Visualization of phosphatidylcholine,lysophosphatidylcholine and sphingomyelin in mouse tongue body by matrix-assisted laser desorption/ionization imaging mass spectrometry

The mammalian tongue is one of the most important organs during food uptake because it is helpful for mastication and swallowing. In addition, taste receptors are present on the surface of the tongue. Lipids are the second most abundant biomolecules after water in the tongue. Lipids such as phosphatidylcholine (PC), lysophosphatidylcholine (LPC) and sphingomyelin (SM) are considered to play fundamental roles in the mediation of cell signaling. Imaging mass spectrometry (IMS) is powerful tool for determining and visualizing the distribution of lipids across sections of dissected tissue. In this study, we identified and visualized the PC, LPC, and SM species in a mouse tongue body section with matrix-assisted laser desorption/ionization (MALDI)-IMS. The ion image constructed from the peaks revealed that docosahexaenoic acid (DHA)-containing PC, LPC, linoleic acid-containing PC and SM (d18:1/16:0), and oleic acid-containing PC were mainly distributed in muscle, connective tissue, stratified epithelium, and the peripheral nerve, respectively. Furthermore, the distribution of SM (d18:1/16:0) corresponded to the distribution of nerve tissue relating to taste in the stratified epithelium. This study represents the first visualization of PC, LPC and SM localization in the mouse tongue body.     

Solvation structure of coronene-transition metal complex: a RISM-SCF study

Coronene (C(24)H(12)) is a flat polyaromatic hydrocarbon consisting of seven peri-fused benzene rings and attracts lots of attention as a fragment of graphene. Using a hybrid method of quantum chemistry and statistical mechanics called RISM-SCF, which is an alternative to QM/MM, the electronic structure and solvation structure of a coronene-transition metal complex were computed in a self-consistent manner. The binding of a ruthenium complex ([C(5)H(5)Ru](+)) was extensively studied, especially the changing of the solvation structure.