Selective reduction of NOX with C3H6 over Cu incorporated into silicoalumino-phosphate (SAPO)

Cu ion-exchanged SAPO-34 which is a highly active catalyst for selective reduction of NO with C₃H₆, was synthesized and the Cu ion was characterized in the SAPO-34 by ESR, XPS, IR, and XAFS. ESR study indicated that two kinds of Cu(II) with different environments exist in SAPO-34. The Cu(II) species disappeared immediately by C₃H₆ treatment and recovered by oxygen treatment. XAFS study indicated that most of the Cu(II) was reduced to Cu(I) under the presence of C₃H₆. These studies revealed that a selective NO reduction by C₃H₆ over SAPO-34 should proceed by the redox reaction of a copper ion between Cu(I) and Cu(II).     

Total synthesis of deglyco-bleomycin A2

Deglyco-bleomycin A2, the aglycon of bleomycin A2, has been synthesized for the first time.     

Chitin- and Streptavidin-Mediated Affinity Purification Systems: A Screening Platform for Enzyme Discovery

Affinity purification of recombinant proteins is an essential technique in biotechnology. However, current affinity purification methods are very cost-intensive, and this imposes limits on versatile use of affinity purification for obtaining purified proteins for a variety of applications. To overcome this problem, we developed a new affinity purification system which we call CSAP (chitin- and streptavidin-mediated affinity purification) for low-cost purification of Strep-tag II fusion proteins. The CSAP system is designed to utilize commercially available chitin powder as a chromatography matrix, thereby significantly improving the cost-efficiency of protein affinity purification. We investigated the CSAP system for protein screening in 96-well format as a demonstration. Through the screening of 96 types of purified hemoproteins, several proteins capable of the catalytic diastereodivergent synthesis of cyclopropanes were identified as candidates for an abiotic carbene transfer reaction.     

Reaction mechanism of direct episulfidation of caryophyllene and humulene

Direct episulfidations of caryophyllene or humulene with elemental sulfur were examined by means of gas chromatography. Caryophyllene-6,7-episulfide was formed at an early stage in a reaction of the caryophyllene and elemental sulfur at 120 degrees C. Caryophyllene-3,6-sulfide and polymer compounds were formed after the episulfidation. Formations of the these compounds were related to the disappearance of the caryophyllene-6,7-episulfide. Isomerization from the caryophyllene to isocaryophyllene was also observed during the reaction. In the reaction of humulene with elemental sulfur, humulene-6,7-episulfide was initially produced and then converted to humulene-9,10-episulfide. It was assumed that the polymer compound in the reaction of humulene with sulfur was related to the disappearance of the both humulene episulfides.     

Determination of aluminum in large volume parenteral drug products used in total parenteral nutrition therapy by ICP-MS with a dynamic reaction cell

The proposed method was developed for the determination of aluminum (Al) in large volume parenteral (LVP) drug products used in total parenteral nutrition (TPN) therapy. The determination of Al in LVP drug products was performed by an inductively coupled plasma mass spectrometer equipped with a dynamic reaction cell (DRC-ICP-MS). DRC-ICP-MS conditions for the analysis of Al were studied to obtain the best signal to background (S/N) ratios. The interfering polyatomic ions at mass 27 (Al) were reduced by using NH(3) as a reaction gas. The detection limit of Al in a 1% (v/v) HNO(3) aqueous solution was 2 ng/l. The Al contents in LVP drug products obtained by this method were in the range of 1.16-4.33 microg/l and were less than 25 microg/l, that is, the regulation value of Food and Drug Administration (FDA). In order to trace the origin of Al in LVP drug products, each part of the LVP drug product, which is composed of three chambers, was investigated. However, a clear difference of the Al contents in each chamber was not observed. Furthermore, the Al contents in injection bags were quantified. Although the Al contents in injection bags were relatively high (in the range of 27.5-33.6 microg/g), dissolution of Al from the injection bags was not observed in the stability testing. From all of these results, it was concluded that the Al contents in the LVP drug products investigated originated in the amount of the Al in each raw material.     

In situ observation of thermal relaxation of interstitial-vacancy pair defects in a graphite gap

Direct observation of individual defects during formation and annihilation in the interlayer gap of double-wall carbon nanotubes (DWNT) is demonstrated by high-resolution transmission electron microscopy. The interlayer defects that bridge two adjacent graphen layers in DWNT are stable for a macroscopic time at the temperature below 450 K. These defects are assigned to a cluster of one or two interstitial-vacancy pairs (I-V pairs) and often disappear just after their formation at higher temperatures due to an instantaneous recombination of the interstitial atom with vacancy. Systematic observations performed at the elevated temperatures find a threshold for the defect annihilation at 450-500 K, which, indeed, corresponds to the known temperature for the Wigner energy release.     

Catalytic decomposition of CFCs

Catalytic decomposition of CCI₂F₂ was studied over a number of single and complex metal oxides using a fixed-bed reactor. The ZrO₂–Cr₂O₂ catalyst exhibited the highest activity and CO₂ and CCIF₃ were formed at 350–450°C. Selective decomposition of CCI₂F₂ required the presence of both oxygen and water vapor over the catalyst. Catalytic activity gradually declined with time on stream because of the fluorination of ZrO₂. Treatment of the catalyst with both oxygen and water vapor promoted the removal of fluoride ions in sub-surface layers of the catalyst, which is effective for the recovery of the activity. CCI₂F₂ was decomposed at 300–450°C over AIPO₄. No fluorination of the AIPO₄ catalyst took place after the reaction for 1000 h. CH₂FCF₃, an alternative CFC, was completely decomposed over the mixed catalyst of Ce promoted AIPO₄ and Cr₂O₃ at 400–500°C. Catalytic decomposition is a rational method for destruction of used CFCs.