Size distribution and characteristics of chemical components in ambient particulate matter.

Ambient particulate matter and gas in Kyoto were investigated by gravimetric analysis, X-ray fluorescence spectrometry, and ion chromatography in order to clarify their behavior and origin. The size distribution and characteristics of the chemical components in ambient particulates collected on PTFE membrane filters using an Andersen air sampler were examined from August 2001 to April 2004. A four-stage filter pack method was used to sample the atmosphere for the determination of gas (SO2, HNO3, HCl, NH3) and particulate matter (SO42, NO3, Cl-, Na+, K+, Ca2+, Mg2+, NH4+) concentrations from October 2002 to April 2004. The concentration of SPM mass was in the range of 6.7 - 80.2 microg/m3. The size distributions of SPM mass were bimodal, peaking at around 0.65 - 1.1 and 3.3 - 4.7 microm, and 40 - 85% of SPM mass was fine particles (< 2.1 microm). Na, Mg, Al, Si, Ca, Cl, and Fe were mainly present in coarse particles (2.1 to 11.0 microm), while S was present in fine particles. The concentrations of Al, Si, Ca, Mg, and Fe in fine particles increased from March to April in 2002, and those in coarse particulates increased in November 2002 and from March to April in 2004. This may be the effect of the continental yellow sand "Kosa." The differences in the size distributions of Al, Si, Ca, Mg, and Fe in particles may depend on differences in their place of occurrence and course of transport from China to Japan. The concentration of HCl gas was higher than that of particulate chloride ion in summer. Nitric acid gas existed at higher concentrations in summer, but fine particulate nitrate ion was observed in winter. The gaseous-to-fine aerosol nitrate fraction became higher at warmer temperatures. Coarse sulfate was below 10%, and SO2 gas and fine particulate sulfate were above 90%.     

Dynamic kinetic resolution of amino acid amide catalyzed by D-aminopeptidase and alpha-amino-epsilon-caprolactam racemase

Amino acid amide racemizing activity was discovered in alpha-amino-epsilon-caprolactam (ACL) racemase (EC 5. 1. 1. 15) from Achromobacter obae. The enzymatic synthesis of d-alanine from l-alanine amide has been demonstrated by use of d-aminopeptidase (DAP; EC 3. 4. 11. 19) from Ochrobactrum anthropi C1-38 and ACL racemase. The conversion of 45 mM l-alanine amide was carried out at 30 degrees C for 7 h; l-alanine amide was completely converted to d-alanine, and no l-alanine was detected. The result of successive enzymatic reaction shows that the combination of ACL racemase and DAP can be applied for dynamic kinetic resolution of dl-amino acid amides to yield d-amino acids.     

Specific heat and neutron diffraction study on quaternary sulfides BaNd2CoS5 and BaNd2ZnS5

Magnetic and electrical properties are investigated for quaternary neodymium sulfides BaNd₂TS₅ (T=Co, Zn) through the specific heat, neutron diffraction, and electrical conductivity measurements. Their electrical conductivities show semiconductive behavior, which follows the Arrhenius temperature dependence with the activation energy of E_a=1.46 eV for BaNd₂ZnS₅ and E_a=1.19 eV for BaNd₂CoS₅. The specific heat of BaNd₂ZnS₅ has a λ-type anomaly at 2.8 K due to the antiferromagnetic ordering of the Nd³⁺ moments and a Schottky-type anomaly at around 60 K, which results from the crystal field splitting of the ⁴I_9/2 ground state of the Nd³⁺ ion. The specific heat of BaNd₂CoS₅ shows two λ-type anomalies at 5.7 K due to the antiferromagnetic ordering of Nd³⁺ and at 58 K due to the antiferromagnetic ordering of Co²⁺. The latter overlaps with the Schottky-type anomaly due to the crystal field splitting of the Nd³⁺ ion. Neutron diffraction measurements for BaNd₂CoS₅ show that a magnetic arrangement of the Co²⁺ moments has a collinear antiferromagnetic structure, while that of the Nd³⁺ moments has a noncollinear one.     

Study on multimers and their structures in molecular association mixture

Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed.     

Preparation of dry powder inhalation with lactose carrier particles surface-coated using a Wurster fluidized bed

An attempt was made to produce carrier particles for dry powder inhalation with lactose carrier particles surface-coated using a Wurster fluidized bed. The lactose carrier particles were coated with lactose aqueous solution containing hydroxypropyl methyl cellulose (HPMC) as a binder using a Wurster coating apparatus. Drug/carrier powder mixtures were prepared consisting of micronized salbutamol sulfate and lactose carriers under various particle surface conditions. These powder mixtures were aerosolized by a Jethaler((R)), and the in vitro deposition properties of salbutamol sulfate were evaluated by a twin impinger. The in vitro inhalation properties of the powder mixture prepared using the coated lactose carrier differed significantly compared with those of the powder mixture prepared using the uncoated lactose carrier, indicating improvements in in vitro inhalation properties of sulbutamol sulfate. In vitro inhalation properties increased with the surface coating time. This surface coating system would thus be valuable for increasing the in vitro inhalation properties of dry powder inhalation with lactose carrier particles.     

Conformational peculiarities of alcohols incorporated in lyotropic and thermotropic liquid crystals

Conformational characteristics of 1-butanol incorporated not only in hexagonal and lamellar aggregates formed by a lyotropic liquid crystal composed of sodium octanoate, 1-butanol, and water but also in a thermotropic liquid crystal, 4'-methoxybenzylidene-4-n-butylaniline (MBBA), have been investigated from 2H NMR quadrupolar splittings of the perdeuterated and partially deuterated compounds. In the lyotropic phases, 1-butanol shows strong trans preferences and renders itself extended, and octanoate decreases the trans fraction toward the methyl terminal to fill the inner space of the aggregate on behalf of 1-butanol. In MBBA, 1-butanol prefers globular conformations. This tendency was also indicated from the phase behaviors of 1-butanol/MBBA and 1-decanol/MBBA systems. In the nematic field, two successive C-C bonds of 1-butanol mostly adopt g+/-g+/- conformations, which are formed in the vicinity of the headgroup of 1-decanol in the lamella of the sodium octanoate/1-decanol/water system. A large degree ofconformational freedom near the hydroxyl group of alcohols, being shown by ab initio molecular orbital calculations at the Gaussian-2 level, permits them to change conformation for each environment.     

Estimation of biotinylated lectin by isoelectric focusing

Concanavalin A (Con A) was biotinylated to various degrees using N-biotinyl-omega-aminocaproic-acid-N-hydroxy succinimide ester as the biotinylation reagent, and then analyzed by isoelectric focusing using PhastGel IEF 3-9. The isoelectric points of biotinylated ConAs were found to decrease with increasing concentration of the biotinylation reagent. Analysis by isoelectric focusing followed by dot blotting clearly indicated that the biotinylated ConA with an isoelectric point lower than that of the original ConA by 2.2 +/- 0.6 had the strongest binding activity for ovalbumin.     

Controlled kinetics of non-enzymatic chemiluminescence reactions for simple imaging of DNA and protein

A robust and sensitive non-enzymatic chemiluminescence (CL) imaging method is presented. In the method a fast-emitting CL reaction is tuned to furnish a slower-emitting reaction suitable for simple CL imaging. Typically, non-enzymatic CL reactions between luminol or fluorescein and oxygen species generated by KCN as catalyst, were rather fast and unsuitable for CL imaging; the speed of the reactions could, however, be reduced substantially by changing KCN for CH(3)CN or benzonitrile. Light emission from the tuned CL reaction was intense and long-lived, and even with a simple arrangement high sensitivity could be achieved. The maximum CL peak was reached after approximately 1.5 min in the presence of 25% acetonitrile, and as little as 16 fmol commercial isoluminol-labeled streptavidin was detected and visualized on either microplate or membrane. The approach was further illustrated by imaging of DNA on a membrane and of antibody on a microplate by use of biotin-streptavidin chemistry. Overall, this simple, economical, and sensitive CL imaging system is expected to be very useful in biochemical analysis, and greatly complements currently used enzyme-based CL imaging methods, especially in routine applications.     

Optically active copolyamides by melt and solution condensation polymerization

The melt and solution condensation copolymerization of nylon salts which were prepared from d-camphoric acid and adipic acid with hexamethylenediamine were carried out, and optically active copolyamides were obtained. The copolyamides obtained had a positive specific rotation. The specific rotations for the copolyamides increased with increasing content of d-camphoryl units in the copolymers. The optical rotatory dispersion of the copolyamides had positive curves and were found to fit the simple Drude equation. The λ_c values of the polymers obtained by the melt and solution condensation polymerization were 241 mμ and 245 mμ, respectively.