Template synthesis of novel porous carbons using various types of zeolites

As previously reported, high surface area microporous carbons with long-range order can be synthesized by using zeolite Y as a template. In this work, an attempt is made to synthesize porous carbon using several other types of zeolites (zeolite β, ZSM-5, mordenite and zeolite L). Special attention is paid to whether the structural regularity of each zeolite can be transferred to the carbon structure as well as with the case of zeolite Y. The carbon filling method was then examined to see which gives the highest regularity to the carbon structure. It has been found that the optimum carbon filling method for zeolite Y is not an optimum one for the other zeolites and the degree of the regularity of long-range ordering in the carbons strongly depends on zeolite type. The order of the regularity in the resultant carbons is zeolite β>>zeolite L>mordenite>ZSM-5. The effect of zeolite type on the regularity is discussed in relation to the size and the shape of the zeolite channels.     

Antioxidant effects of chlorophyll and pheophytin on the autoxidation of oils in the dark. I. Comparison of the inhibitory effects

The effects of chlorophyll and pheophytin on the autoxidation of oils in the dark were investigated by oven tests. The results indicated that both chlorophyll and pheophytin show antioxidant activity when methyl linoleate is used as substrate. Furthermore, chlorophyll retarded the oxidative deterioration of triglycerides in rapeseed and soybean oils at 30 C. Among the four chlorophyll derivatives (chlorophylls a and b and pheophytins a and b), chlorophyll a showed the strongest antioxidant activity. The antioxidant effects of chlorophyll and pheophytin depended on the storage temperature and the kinds of oil used as substrate.     

Critical temperature for production of MAG by esterification of different FA with glycerol using <Emphasis Type="Italic">Penicillium camembertii</Emphasis> lipase

Production of MAG by a lipase-catalyzed reaction is known to be effective at low temperature. This phenomenon can be explained by assuming that synthesized MAG are excluded from the reaction system because MAG, which have low m.p., are solidified at low temperatures. Consequently, MAG are efficiently accumulated and do not serve as the precursor of DAG. If this hypothesis is correct, the critical temperature for MAG production, defined as the highest temperature at which DAG synthesis is repressed, should depend on the m.p. of the MAG. Esterification of FFA with glycerol using Candida rugosa, Rhizopus oryzae, and Penicillium camembertii lipases produced MAG efficiently at low temperatures. However, Candida lipase showed very low esterification activity at high temperatures (>20°C), and Rhizopus lipase produced not only MAG but also DAG even at low temperatures. Meanwhile, P. camembertii lipase catalyzed synthesis of MAG only from FFA and glycerol at low temperatures, although the enzyme catalyzed synthesis of DAG from MAG in addition to synthesis of MAG at high temperatures. We thus studied the effect of temperature on esterification of C₁₀−C₁₈ FFA with glycerol using Penicillium lipase as a catalyst and determined the critical temperatures for production of MAG. The critical temperature for production of each MAG showed a linear correlation with m.p. of the MAG, which supported the hypothesis. In addition, because the m.p. of MAG are estimated from that of the constituent FA, the optimal temperature for production of MAG can be predicted from the m.p. of the FFA used as a substrate.     

Preparation of Aluminum Nitride Powder from Aluminum Polynuclear Complexes

AIN powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride and basic aluminum lactate were used as the aluminum polynuclear complexes. These starting materials and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining after drying and precalcining at 800°C under nitrogen gas flow. Then excess carbon was removed by firing in air. Nitridation in the system was investigated and compared with that in the alumina–carbon black system. It was found that in our reaction system nitridation began and proceeded at lower calcination temperatures above 1200°C than in the alumina–carbon black system. Using aluminum polynuclear complexes, AIN was synthesized through the nitridation of γ-alumina and produced in a very fine and sharp particle size distribution.     

A new maritime lifesaving multiple-effect solar still design

This paper presents a new maritime lifesaving multiple-effect solar still design where several extended wicks feed seawater to their evaporating areas by capillary force, and the resulting water vapor diffuses and condenses on facing wicks with the condensate flowing through the wicks into storage bags. A theoretical analysis showed that a temperature drop through diffusion layers between evaporating and condensing wicks slowly increases in the main evaporating areas and rapidly near salt depositions whereas the evaporation rate decreases slowly in the main area and rapidly near salt depositions. These changes are caused by increases in salt concentrations and resulting boiling point elevation. With steady-state transfer analysis, the proposed still is predicted to produce about 15 kg m ⁻²d⁻¹ fresh water on a sunny day of 22 MJm⁻²d⁻¹ solar radiation, showing a potential to be a maritime lifesaving desalinator.     

Low-Temperature Synthesis of ZrC Powder by Cyclic Reaction of Mg in ZrO2–Mg–CH4

We investigated the conditions for low-temperature synthesis of ZrC fine powder from ZrO₂–Mg–CH₄. The synthesis utilizes a thermite-type reaction, with Mg as the reducing agent, and a reaction between Mg and CH₄ gas as a carbon source. The Mg/ZrO₂ molar ratio as well as the heating rate were varied. Because C can be continuously fed into the reaction group by the cyclic reaction of Mg through the formation and decomposition of Mg₂C₃ (2Mg + 3CH₄→ Mg₂C₃+ 6H₂→ 2Mg + 3C), a molar ratio of 2.2 for Mg/ZrO₂ was sufficient for the synthesis of single-phase ZrC. ZrC powders were synthesized under the following conditions: Mg/ZrO₂ molar ratio = 2.2, heating rate = 20°C/min, and temperature maintained at 750°C for 30 min. The amount of reaction heat produced in the reduction reaction of ZrO₂ by Mg depended on the Mg/ZrO₂ molar ratio, specifically, the amount of ZrO₂ contained. Moreover, the cyclic reaction of Mg-Mg₂C₃–Mg was influenced by the amount of reaction heat described above and by the heating rate. The ZrC fine powder showed little aggregation and high dispersibility.     

New class of cellulose fiber spun from the novel solution of cellulose by wet spinning method

A novel cellulose solution, prepared by dissolving an alkali-soluble cellulose, which was obtained by the steam explosion treatment on almost pure natural cellulose (soft wood pulp), into the aqueous sodium hydroxide solution with specific concentration (9.1 wt %) was employed for the first time to prepare a new class of multifilament-type cellulose fiber. For this purpose a wet spinning system with acid coagulation bath was applied. The mechanical properties and structural characteristics of the resulting cellulose fibers were compared with those of regenerated cellulose fibers such as viscose rayon and cuprammonium rayon commercially available. X-ray analysis shows that the new cellulose fiber is crystallographically cellulose II, and its crystallinity is higher but its crystalline orientation is slightly lower than those of other commercial regenerated fibers. The degree of breakdown of intramolecular hydrogen bond at C₃[X_am(C₃)] of the cellulose fiber, as determined by solid-state cross-polarization magic-angle sample spinning (CP/MAS) ¹³C NMR, is much lower than other, and the NMR spectra of its dry and wet state were significantly different from each other, indicating that cellulose molecules in the new cellulose fiber are quite mobile when wet. This phenomenon has not been reported for so-called regenerated cellulose fibers.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

Double organic modification by 3‐chloropropyl and methyl groups on pure silica MCM‐41 and Ti‐MCM‐41: efficient catalyst for epoxidation of cyclododecene

Simultaneous surface modification by 3‐chloropropyl and methyl groups on the same Si atoms resulted in hydrophobic and highly ordered mesoporous silica with a very high surface area. ¹³C and ²⁹Si MAS NMR spectra indicate homogeneous grafting of chloropropyl and methyl groups in the silica matrix and this organically modified Ti‐MCM‐41 shows outstanding catalytic performance in the epoxidation of cyclododecene using tert‐butyl hydroperoxide as oxidant. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.