Determination of phosphorus in steel by the combined technique of laser induced breakdown spectrometry with laser induced fluorescence spectrometry

Laser induced breakdown spectrometry (LIBS) combined with laser induced fluorescence spectrometry (LIFS) has been applied for detection of trace-level phosphorus in steel. The plasma induced by irradiation of Nd:YAG laser pulse for ablation was illuminated by the 3rd harmonic of Ti:Sapphire laser tuned to one of the resonant lines for phosphorus in the wavelength region of 253–256 nm. An excitation line for phosphorus was selected to give the highest signal-to-noise ratio. Fluorescence signals, P213.62 and P214.91 nm, were observed with high selectivity at the contents as low as several tens µg g^− 1. Fluorescence intensities were in a good linear correlation with the contents. Fluorescence intensity ratio of a collisionally assisted line (213.62 nm) to a direct transition line (214.91 nm) was discussed in terms of the analytical conditions and experimental results were compared with a calculation based on rate equations. Since the fluorescence signal light in the wavelength range longer than 200 nm can be transmitted relatively easily, even through fiber optics of moderate length, LIBS/LIFS would be a versatile technique in on-site applications for the monitoring of phosphorus contents in steel.     

Structural modeling of beams on elastic foundations with elasticity couplings

A new simplified structural model and its governing equations for beams on elastic foundations with elastic coupling are proposed. This modeling system is simple but appropriate for the initial structural design of large-scale submerged floating-beam structures moored by tension legs spaced at uniform interval along the beam. The model is actually for beam on discrete elastic supports rather than on continuous elastic foundations. Therefore, the governing equations are based on finite difference calculus and solutions for beams on discrete elastic supports with elasticity coupling are also proposed. To clarify the applicability limit of the proposed model, the equivalence between a beam on discrete elastic supports and that on continuous elastic foundation is investigated by comparisons of characteristic solutions.     

Electroreductive intramolecular coupling of aliphatic cyclic imides with ketones and O-methyloximes

The electroreductive intramolecular coupling of aliphatic cyclic imides with ketones in isopropanol gave five- and six-membered cyclized products. Similarly, the electroreductive intramolecular coupling of aliphatic cyclic imides with O-methyloximes afforded five-, six-, and seven-membered cyclized products. These reactions provide a useful method to synthesize azabicyclo[n.m.0] compounds. The bicyclic products were stereoselectively transformed to the corresponding deoxylated compounds by reduction with NaB(CN)H₃ or Et₃SiH/BF₃·Et₂O.     

Catalytic enantioselective 1,3-dipolar cycloadditions of nitrones with propioloylpyrazoles and acryloylpyrazoles induced by chiral π-cation catalysts

A chiral copper(II) complex of 3-(2-naphthyl)-l-alanine amide successfully catalyzes the enantioselective 1,3-dipolar cycloaddition reaction of nitrones with propioloylpyrazole and acryloylpyrazole derivatives. The asymmetric environment created by intramolecular π-cation interaction gives the corresponding adducts in high yields with excellent enantioselectivity. This is the first successful method for the catalytic enantioselective 1,3-dipolar cycloaddition of nitrones with acetylene derivatives. The 1,3-dipolar cycloadducts can be stereoselectively converted to β-lactams via reductive cleavage of the N-O bond using SmI(2).     

Cloud and aerosol contributions to variation in shortwave surface irradiance over East Asia in July during 2001 and 2007

It is important to clarify the contributions of clouds and aerosols to the variation of surface shortwave irradiance (S) for climatological studies. This study examined the contributions of clouds and aerosols to the variation in S over East Asia (75-135°E, 20-55°N) in July during 2001 and 2007 using the index of potential radiative forcing (PRF) to characterize the temporal and geographical variations. After confirming the validity of PRF for multiyear analyses, we performed several temporal analyses of clouds and aerosols over the whole research domain. Changes in the geographical distribution, contribution histograms, and averaged values were studied. In agreement with previous studies that treated single-year cases, we confirmed that the magnitudes of the temporal changes in S variations due to clouds and aerosols were highly variable geographically. As for domain-averaged S variations, we did not observe defined trends for the research period. It was also found that the temporal variation between one parameter and its S variation was negatively correlated, from the point analyses at two locations. Based on these results, we concluded that PRF is a promising tool for research into long-term S variations. This kind of information will be quite valuable as basic data for use in climate modeling.     

Synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids

A convenient synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids (BINSA, 1) was developed. The key was directed ortho-lithiation of BINSA methyl ester 2 with n-BuLi and subsequent reaction with an electrophile. Electrophiles such as Br₂, I₂, Me₃SiOTf, and i-PrOB(Pin) reacted smoothly with 3,3′-dilithiated BINSA methyl ester, and the corresponding 3,3′-dihalo-, 3,3′-bis(trimethylsilyl)-, and 3,3′-diboryl-BINSA derivatives were obtained in yields of 21–78%. This simple synthetic method is highly attractive since the ability to prepare 3,3′-disubstituted BINOLs in advance can be useful.     

Ligand effect of bulky 2,2-dialkyl-1-phosphaethenes on Au-catalyzed cycloisomerization of 1,6-enynes and lactonization of pent-4-ynoic acids

2,2-Dimethyl- and 2-benzyl-2-methyl-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethenes were employed as ligand of mononuclear chlorogold(I) complexes, which catalyzed cycloisomerization of 1,6-enyne affording vinylcyclopentene exclusively in the absence of silver co-catalyst. The reaction mechanisms are discussed based on DFT calculations. In addition to the cycloisomerization, the phosphaalkene-chlorogold(I) complexes catalyzed cyclization of pent-4-ynoic acids providing γ-methylene-γ-lactones under basic conditions.     

Decoupling of the N-soliton solution for a new discrete MKdV equation

We prove that the N-soliton solution for a new discrete MKdV equation can be decoupled into N components. These components satisfy the interacting new discrete MKdV equation, and approach single soliton solutions as t→∞. We present concrete expressions of soliton components in the case of N = 2, and illustrate the results.     

Solvent-dependent conformational switching of the aromatic N-methyl amides depending upon the acceptor properties of solvents

An aromatic N-methyl amide containing N-(2-pyridyl) and 2,6-pyridinedicarboxamide moieties switches its conformation from cis to trans depending upon the acceptor number of solvents.