Asymmetric α‐Hydroxylation of a Lactone with Vinylogous Pyridone by Using a Guanidine–Urea Bifunctional Organocatalyst: Catalytic Enantioselective Synthesis of a Key Intermediate for (20S)‐Camptothecin Analogues

We have developed a catalytic asymmetric synthesis of (S)‐4‐ethyl‐6,6‐(ethylenedioxy)‐7,8‐dihydro‐4‐hydroxy‐1H‐pyrano[3,4‐f]indolizine‐3,10(4H)dione ( 5 a ), a synthetic intermediate for (20S)‐camptothecin analogues. A key step in this synthesis is an asymmetric α‐hydroxylation of a lactone with a vinylogous pyridone structure ( 8 a ) by using a guanidine–urea bifunctional organocatalyst. The present oxidation was successfully applied to the synthesis of C20‐modified derivatives of (+)‐C20‐desethylbenzylcamptothecin ( 13 ).     

sdg Interacting boson model: hexadecupole degree of freedom in nuclear structure

Thesdg interacting boson model (sdgIBM), which includes monopole (s), quadrupole (d) and hexadecupole (g) degrees of freedom, enables one to analyze hexadecupole (E4) properties of atomic nuclei. Various aspects of the model, both analytical and numerical, are reviewed emphasizing the symmetry structures involved. A large number of examples are given to provide understanding and tests, and to demonstrate the predictiveness of thesdg model. Extensions of the model to include proton-neutron degrees of freedom and fermion degrees of freedom (appropriate for odd mass nuclei) are briefly described. A comprehensive account ofsdgIBM analysis of all the existing data on hexadecupole observables (mainly in the rare-earth region) is presented, includingβ ₄ (hexadecupole deformation) systematics,B(IS4; 0 _GS ⁺ →4 _γ ⁺ ) systematics that give information about hexadecupole component in γ-vibration,E4 matrix elements involving few low-lying 4⁺ levels,E4 strength distributions and hexadecupole vibrational bands in deformed nuclei. The survey of literature for this review was concluded in December 1991.     

Instanton counting on blowup. II. K-theoretic partition function

We study Nekrasov's deformed partition function $Z(\varepsilon_1,\varepsilon_2,\vec{a};\mathfrak q,\boldsymbol\beta)$ of 5-dimensional supersymmetric Yang-Mills theory compactified on a circle. Mathematically it is the generating function of the characters of the coordinate rings of the moduli spaces of instantons on $\mathbb R^4$. We show that it satisfies a system of functional equations, called blowup equations, whose solution is unique. As applications, we prove (a) $F(\varepsilon_1,\varepsilon_2,\vec{a};\mathfrak q,\boldsymbol\beta) = \varepsilon_1\varepsilon_2 \log Z(\varepsilon_1,\varepsilon_2,\vec{a};\mathfrak q,\boldsymbol\beta)$ is regular at $\varepsilon_1 = \varepsilon_2 = 0$ (a part of Nekrasov's conjecture), and (b) the genus $1$ parts, which are first several Taylor coefficients of $F(\varepsilon_1,\varepsilon_2,\vec{a};\mathfrak q,\boldsymbol\beta)$, are written explicitly in terms of $\tau = d^2 F(0,0,\vec{a};\mathfrak q,\boldsymbol\beta)/da^2$ in rank $2$ case.     

IBA,macroscopic SU(3) and microscopic description of ground state bands in rotational nuclei

The number of bosons deduced from variational calculations of spectra and intrinsic mass quadrupole moments of heavy deformed nuclei are compared with predictions of IBA in the SU(3) limit. The differenct between the two suggest the need for including l > 2 bosons in IBA.     

Studies on the goodness of IBA group symmetries. I. Centroids,widths and partial widths for irreducible representations of IBA group symmetries

We present explicit analytic expressions for the centroids, widths and partial widths of the eigenvalue distribution over an irreducible representation corresponding to various group symmetries of the interacting boson approximation model of Arima and Iachello. As an example we present a study of the goodness of IBA group symmetries for Sm isotopes.     

Determination of musty odorants, 2-methylisoborneol and geosmin, in environmental water by headspace solid-phase microextraction and gas chromatography--mass spectrometry.

A simple and sensitive method for the determination of musty odorants, 2-methylisoborneol (MIB) and geosmin (GSM), in environmental water was developed by headspace solid-phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry. MIB and GSM were separated within 10 min using a DB-1 capillary column and detected in the selective ion monitoring mode. HS-SPME using a polydimethylsiloxane/divinylbenzene fiber provided effective sample enrichment, and was carried out by fiber exposition at 70 degrees C for 30 min. Using this method, the calibration curves of MIB and GSM were linear in the range of 0-500 pg/mL, with a correlation coefficient above 0.9977 (n=24). The detection limits (S/N=3) of MIB and GSM were 0.9 and 0.6 pg/mL, respectively. This method was successfully applied to the analysis of environmental water samples without interference peaks.     

Local physical quantities for spin based on the relativistic quantum field theory in molecular systems

Local physical quantities for spin are investigated on the basis of the four‐ and two‐component relativistic quantum theory. In the quantum field theory, local physical quantities for spin such as the spin angular momentum density, spin torque density, zeta force density, and zeta potential play important roles in spin dynamics. We discuss how to calculate these local physical quantities based on the two‐component relativistic quantum theory. Some different types of relativistic numerical calculations of local physical quantities in Li atom and C₆H₆ are demonstrated and compared. Local physical quantities for each orbital are also discussed, and it is seen that a total local zeta potential is given as a result of some cancellation of large contributions from each orbital. © 2016 Wiley Periodicals, Inc.     

Hydration process of Na2- in small water clusters: photoelectron spectroscopy and theoretical study of Na2- (H2O)n

Photoelectron spectroscopy (PES) of Na2- (H2O)n (n < or = 6) was investigated to examine the solvation of sodium aggregates in small water clusters. The PES bands for the transitions from the anion to the neutral ground and first excited states derived from Na2 (1(1)Sigmag+) and Na2 (1(3)Sigmau+) shifted gradually to the blue, and those to the higher-excited states correlated to the 3(2)S + 3(2)P asymptote dropped down rapidly to the red and almost degenerated on the 1(3)Sigmau+-type band at n = 4. Quantum chemical calculations for n up to 3 showed that the spectra can be ascribed to structures where one of the Na atoms is selectively hydrated. From the electron distributions, it is found that the Na- -Na+(H2O)n- -type electronic state grows with increasing cluster size, which can be regarded as a sign of the solvation of Na2- with ionization of the hydrated Na.     

Regeneration of levulinic acid from loaded-organic phase: equilibrium,kinetic studies and process economics

Regeneration of carboxylic acids from the loaded-organic phase is an essential step to complete the reactive extraction process. A study on the regeneration of levulinic acid from loaded-organic phase (methyl isobutyl ketone + tri-n-octylamine + acid) was carried out using various techniques including NaOH, temperature swing, diluent swing, and tri-methylamine methods. Equilibrium data obtained show that among all the methods, the recovery of acid is the highest for the tri-methylamine method when the molar ratio of tri-methylamine to levulinic acid concentrations is greater than 1. Kinetic studies performed for the tri-methylamine method showed that there are no changes in the specific rate of extraction with changes in stirrer speed rate and phase volume ratio (V _aq/V _org), and the overall order of reaction is 1.5. Based on the effects of stirrer speed and phase volume ratio on the specific rate of extraction, the reaction was concluded to occur in the fast regime. Also, about 80% of acid was recovered by the evaporation of tri-methylamine phase at 104–140 °C. A detailed economic evaluation for the recovery of levulinic acid using reactive extraction for a feed rate of 2 m³ h^?1 shows that the payback period for recovering capital investment is 0.49 years.     

Synthesis of 1,2-naphthalenediol derivatives by Rh-catalyzed intermolecular OH insertion reaction of 1,2-diazonaphthoquinones with water and alcohols

Rh(II)-catalyzed OH insertion reaction of diazonaphthoquinones with water or alocohols proceeded to yield 1,2-naphthalenediol derivatives.