Prostaglandin analogs modified at the 10 and 11 positions

A simplified methodology for the building of prostaglandins substituted at the 10 and 11 positions is presented.     

Synthesis of hydrothermally stable and long-range ordered Ce-MCM-48 and Fe-MCM-48 materials

The hydrothermally stable and long-range ordered Ce-MCM-48 and Fe-MCM-48 were conveniently synthesized at 393 K for 24 h by directly adding fluoride ions to the initial gel without posttreatment and pH adjustment. The Ce-MCM-48 with a Si/Ce of 200 and 100, which were prepared by directly adding fluoride ions, could still maintain their mesoporous structures after refluxing in boiling water for 3 days. The incorporation of Ce into MCM-48 could enhance the hydrothermal stability of MCM-48 in the absence of fluoride ions; however, the incorporation of Fe into MCM-48 materials barely improved the hydrothermal stability of MCM-48 materials. The effect of adding NaF was much more efficient in enhancement of hydrothermal stability than that of the incorporation of Ce. The addition of fluoride ions mainly improves the degree of polymerization of silicates. The Ce(4+) ions in Ce-MCM-48 appear to be present partly in tetrahedral coordination in the framework and partly as CeO(2) particles on the surface of framework. The Ce positioned on the surface of pore walls and in the framework both provide the protection against water attack.     

Clove oil prevents glycyrrhizin gel formation in aqueous solution

One persistent problem with using therapeutic concentrations of glycyrrhizin (GZ) is that, at these high concentrations, it forms a gel in an aqueous solution. We previously solved this problem by dissolving GZ in a highly concentrated phosphate buffer. Unfortunately, the resulting GZ solution has a hyperosmotic pressure that renders it unsuitable for use in patients. The aim of this study was to prepare a highly concentrated GZ solution having an osmotic pressure ratio of 1 and a pH of 7.4. By adding small amounts of oil and using a 100 mM phosphate buffer, we achieved an emulsified GZ solution that is stable at room temperature and has a physiological osmotic pressure and pH. When clove oil was used as an emulsifier, the gel formation temperature of GZ solution decreased appreciably compared to that of GZ solution without clove oil. Using scanning electron microscopy (SEM), we examined the detailed characteristics of GZ gels prepared from solutions with or without clove oil. SEM of cross sections of GZ gels revealed an irregular structure in gels prepared with clove oil, indicating that clove oil prevented the formation of the intermolecular GZ networks typically characterized by gels derived from pure GZ solutions.     

Remote asymmetric induction with vinylketene silyl n,o-acetal

A highly regio- and diastereoselective TiCl4-mediated vinylogous Mukaiyama aldol reaction using the chiral vinylketene silyl N,O-acetal has been developed. The present vinylogous Mukaiyama aldol reaction provides a unique and effective means of controlling remote asymmetric induction. The methyl group at the alpha-position is important in achieving a high level of stereoselectivity. From a synthetic point of view, this methodology can provide a one-step construction of delta-hydroxy-alpha,gamma-dimethyl-alpha,beta-unsaturated carbonyl unit that is seen in many natural polyketide products.     

Improved surface morphology of flow-modulated MOVPE grown AIN on sapphire using thin medium-temperature AIN buffer layer

High-temperature (HT) AIN films were grown on (0 0 0 1) sapphire by low-pressure flow-modulated (FM) metal organic vapor phase epitaxy (MOVPE) with and without inserting a thin medium-temperature (MT) AIN layer. To suppress parasitic reactions between the sources of trimethylaluminum (TMA) and ammonia (NH₃), TMA and NH₃ was introduced to the reactor of MOVPE by alternating supply way. Surface morphology and crystalline quality were characterized by a scanning electronic microscopy (SEM), atomic force microscopy (AFM) and X-ray rocking curve (XRC) measurements of (0 0 0 2) and (10-12) diffractions. The AFM and SEM measurements indicated that the thin MT-AIN layer had a strong influence on the surface morphology of the HT-AIN films. The surface morphology became quite smooth by inserting the thin MT-AIN layer and surface RMS roughness values were 0.84 nm and 13.4 nm for the HT-AIN films with and without inserting the thin MT-AIN buffer layer, respectively. By etching the samples in aqueous KOH solution, it was found that the polarity of AIN films was different, the HT-AIN film with the thin MT-AIN layer could not be etched, indicating that the film had an Al-polar surface; however, the film without the MT-AIN layer was etched, which was explained that that film had a N- or mixed-polar surface. The mechanism for the origin of the different polarity of HT-AIN with and without the thin MT-AIN layer was proposed and discussed in detail.     

Thermogravimetric analysis in steam and oxygen with gas chromatograph mass spectrometry for basic study of biomass gasification

We modified a commercially available thermogravimetric analyzer to introduce helium alone or with steam, oxygen or both, atmosphere of which was controllable to be similar to that in a fixed-bed or an entrained-flow type gasifier, for studying basic properties of biomass gasification. We also connected it to a gas chromatograph-mass selective detector for identifying materials produced during the thermogravimetric analyses. Thermogravimetric analyses of Japanese cedar wood and identifications of the produced materials at around 365 °C were measured as demonstrations.     

Selective separation of water–ethanol mixture through synthetic polymer membranes having carboxylic acid as a functional group

Separation of water–ethanol mixture through a membrane was carried out by pervaporation using a membrane which provided a hydrogen-bonding interaction. A membrane obtained from poly(acrylic acid-co-acrylonitrile) was effective for a selective separation of water from aqueous ethanol solution by pervaporation technique. Spectroscopic and flux analyses verified that this high selectivity toward water was attributed to the hydrogen-bonding interaction between water and acrylic acid (carboxylic acid) unit in the membrane. On the other hand, a membrane from poly(acrylic acid-co-styrene) preferentially permeated ethanol in the low water feed concentration region.     

Acid anhydrides as alternatives to acid chlorides in the palladium‐catalyzed reaction with silacyclobutanes

The palladium‐catalyzed reaction of acid anhydrides with silacyclobutane gives a mixture of cyclic silyl enol ether, carboxy(propyl)silane, and 3‐(carboxysilyl)ketone. In the presence of N,N‐dicyclohexylcarbodiimido (DCC), the reaction preferentially provides a cyclic silyl enol ether in a good yield. In addition, the palladium‐catalyzed reaction of benzoic acid with silacyclobutane in the presence of two equivalents of DCC also affords a cyclic silyl enol ether in a moderate yield. Copyright © 2001 John Wiley & Sons, Ltd.