Synthetic studies toward the PPAP natural products, prolifenones A and B and hyperforin: an Effenberger cyclization approach

A synthetic approach toward the geranylated PPAP natural products, prolifenones A and B. employing Effenberger cyclization as the key step, is delineated. The efficacy of this approach is further expanded through access to an advanced precursor of hyperforin. (C) 2010 Elsevier Ltd. All rights reserved.

In-situ crystallization studies of gels in the ZrO2---SiO2 system

The in-situ investigation of amorphous gels is important in understanding the evolution of structures and the influence of environmental factors on crystallization. In this paper, the ZrO2---SiO2 system has been studied in-situ under electron beam heating. The study reveals that both the size of the ZrO2 particles and the presence of hydroxyl ions influence the nature of the crystalline phase of the ZrO2 particles formed.

Studies on the biosynthesis of cytochrome P-450 in rat liver—A probe with phenobarbital

Cytochrome P-450 has been purified from phenobarbital-treated rat livers to a specific content of 17 nmol/mg protein. The major species purified has a molecular weight of 48,000. Using the purified antibody for the cytochrome P-450 preparation it has been shown that the major product synthesized in vivo and in the homologous cell-free system in vitro is the 48,000 molecular weight species. Poly(A)-containing RNA isolated from phenobarbital-treated animals codes for the synthesis of the 48,000 molecular weight species in the wheat germ and reticulocyte lysate cell-free systems. It is concluded that cytochrome P-450 synthesis does not involve processing of a polyprotein precursor, although certain minor modifications including glycosylation of the primary translation product are not ruled out. Phenobarbital treatment of the animal results in a significant increase in the cytochrome P-450 messenger activity as measured in the wheat germ cell-free system.

Bridging East and West : The Establishment of the International Institute for Applied Systems Analysis (IIASA) in the United States Foreign Policy of Bridge Building, 1964-1972.

The dissertation examines the foreign policies of the United States through the prism of science and technology. In the focal point of scrutiny is the policy establishing the International Institute for Applied Systems Analysis (IIASA) and the development of the multilateral part of bridge building in American foreign policy during the 1960s and early 1970s. After a long and arduous negotiation process, the institute was finally established by twelve national member organizations from the following countries: Bulgaria, Canada, Czechoslovakia, Federal Republic of Germany (FRG), France, German Democratic Republic (GDR), Great Britain, Italy, Japan, Poland, Soviet Union and United States; a few years later Sweden, Finland and the Netherlands also joined. It is said that the goal of the institute was to bring together researchers from East and West to solve pertinent problems caused by the modernization process experienced in industrialized world. It originates from President Lyndon B. Johnson s bridge building policies that were launched in 1964, and was set in a well-contested and crowded domain of other international organizations of environmental and social planning. Since the distinct need for yet another organization was not evident, the process of negotiations in this multinational environment enlightens the foreign policy ambitions of the United States on the road to the Cold War détente. The study places this project within its political era, and juxtaposes it with other international organizations, especially that of the OECD, ECE and NATO. Conventionally, Lyndon Johnson s bridge building policies have been seen as a means to normalize its international relations bilaterally with different East European countries, and the multilateral dimension of the policy has been ignored. This is why IIASA s establishment process in this multilateral environment brings forth new information on US foreign policy goals, the means to achieve these goals, as well as its relations to other advanced industrialized societies before the time of détente, during the 1960s and early 1970s. Furthermore, the substance of the institute applied systems analysis illuminates the differences between European and American methodological thinking in social planning. Systems analysis is closely associated with (American) science and technology policies of the 1960s, especially in its military administrative applications, thus analysis within the foreign policy environment of the United States proved particularly fruitful. In the 1960s the institutional structures of European continent with faltering, and the growing tendencies of integration were in flux. One example of this was the long, drawn-out process of British membership in the EEC, another is de Gaulle s withdrawal from NATO s military-political cooperation. On the other hand, however, economic cooperation in Europe between East and West, and especially with the Soviet Union was expanding rapidly. This American initiative to form a new institutional actor has to be seen in that structural context, showing that bridge building was needed not only to the East, but also to the West. The narrative amounts to an analysis of how the United States managed both cooperation and conflict in its hegemonic aspirations in the emerging modern world, and how it used its special relationship with the United Kingdom to achieve its goals. The research is based on the archives of the United States, Great Britain, Sweden, Finland, and IIASA. The primary sources have been complemented with both contemporary and present day research literature, periodicals, and interviews.

Conformational studies of the triphenylphosphazenyl side chain in cyclophosphazenes. I. Crystal and molecular structure of N3P3C15(NPPh3)

The title compound, C t8H~sC15NaP4, crystallizes in the monoclinic space group P2~/n with a = 20.14 (2), b = 8.69 (1), c = 14.92 (2) A, fl = 98.8 (3) ° , Z = 4. The structure was determined from visual data and refined to R = 0-069 for 1450 reflections. The cyclophosphazene ring is non-planar. The exocyclic NPPh 3 group exhibits type I conformation [R. A. Shaw (1975). Pure Appl. Chem. 44, 317-341] in which the N-P bond is perpendicular to the adjacent P-CI bond.

X-ray studies on crystalline complexes involving amino acids and peptides XIX. Effects of change in chirality in the complexes of succinic acid with dl- and l-arginine

Crystals of dl-arginine hemisuccinate dihydrate (I)(monoclinic; P21/c; a = 5.292, b = 16.296, c = 15.203 Å; α= 92.89°; Z = 4) and l-arginine hemisuccinate hemisuccinic acid monohydrate (II) (triclinic; P1; a = 5.099; b = 10.222, c = 14.626 Å; α= 77.31, β= 89.46, γ= 78.42°; Z = 2) were grown under identical conditions from aqueous solutions of the components in molar proportions. The structures were solved by direct methods and refined to R = 0.068 for 2585 observed reflections in the case of (I) and R = 0.036 for 2154 observed reflections in the case of (11). Two of the three crystallographically independent arginine molecules in the complexes have conformations different from those observed so far in the crystal structures containing arginine. The succinic acid molecules and the succinate ions in the structures are centrosymmetric and planar. The crystal structure of (II) is highly pseudosymmetric. Arginine-succinate interactions in both the complexes involve specific guanidyl-carboxylate interactions. The basic elements of aggregation in both the structures are ribbons made up of alternating arginine dimers and succinate ions. However, the ribbons pack in different ways in the two structures. (II) presents an interesting case in which two ionisation states of the same molecule coexist in a crystal. The two complexes provide a good example of the effect of change in chirality on stoichiometry, conformation, aggregation, and ionisation state in the solid state.

Studies on Unsteady Pressure Fields in the Region of Separating and Reattaching Flows

Experimental studies on the measurement of pressure fields in the region of separating and reattaching flows behind several two-dimensional fore-bodies and one axisymmetric body are reported. In particular, extensive measurements of mean pressure, surface pressure fluctuation, and pressure fluctuation within the flow were made for a series of two-dimensional fore-body shapes consisting of triangular nose with varying included angle. The measurements from different bodies are compared and one of the important findings is that the maximum values of rms pressure fluctuation levels in the shear layer approaching reattachment are almost equal to the maximum value of the surface fluctuation levels.

Laboratory studies on ball wear in the grinding of a hematite-magnetite ore

Marked-ball grinding tests were carried out under different grinding conditions and environments. Three types of balls were used, namely, cast hyper steel, high chrome cast iron and EN-31 (forged), which cover a wide range of chemical composition, microstructure and media hardness. The effect of pulp density on ball wear and grinding efficiency was also studied. Relative pulp viscosities at different percent solids for the ore slurry were also determined. As the Kudremukh ore contained about 0.2% pyrite, the effect of addition of pyrite on ball wear was studied separately. Results of marked-ball grinding tests indicated that ball wear increased with time and showed a sharp increase for wet grinding over dry grinding. Ball wear under wet grinding conditions was also influenced by the gaseous atmosphere in the mill. At 70% solids, the best results in terms of reduced ball wear coupled with satisfactory grinding efficiency were obtained. The influence of oxygen on the corrosive wear of grinding balls was increasingly felt only if sulphide minerals such as pyrite were also present in the ore. The various ball materials could be arranged in the following order with respect to their overall wear resistance: high chrome cast iron > EN-31 (forged) > cast hyper steel.Possible ball wear mechanisms involved in the grinding of Kudremukh ore are discussed.

CD and NMR studies on the aggregation of amphotericin-B in solution

We report in this paper the aggregation properties of amphotericin-B (amp-B) in solution using CD and 1H-NMR techniques. Our results indicate that the preferred structure of amp-B in dimethylsulfoxide is a monomer at low concentrations (10−4M and below) and a stable dimer at higher concentrations (range 5 · 103 M to 10−2M). In a DMSO/ethanol mixture (1:1 (v/v)), the antibiotic is monomeric, irrespective of the concentration within the range studied. We propose a head-to-tail model based on NMR data. An understanding of the head-to-tail dimer, is, we believe important, particularly in view of the recent report wherein it is proposed that the drug inserts into bilayers as head-to-tail oligomers.

Interest in university studies : Its role and relation to other motivational variables

This dissertation empirically explored interest as a motivational force in university studies, including the role it currently plays and possible ways of enhancing this role as a student motivator. The general research questions were as follows: 1) What role does interest play in university studies? 2) What explains academic success if studying is not based on interest? 3) How do different learning environments support or impede interest-based studying? Four empirical studies addressed these questions. Study 1 (n=536) compared first-year students explanations of their disciplinary choices in three fields: veterinary medicine, humanities and law. Study 2 (n=28) focused on the role of individual interest in the humanities and veterinary medicine, fields which are very different from each other as regards their nature of studying. Study 3 (n=52) explored veterinary students motivation and study practices in relation to their study success. Study 4 (n=16) explored veterinary students interest experience in individual lectures on a daily basis. By comparing different fields and focusing on one study field in more detail, it was possible to obtain a many-sided picture of the role of interest in different learning environments. Questionnaires and quantitative methods have often been used to measure interest in academic learning. The present work is based mostly on qualitative data, and qualitative methods were applied to add to the previous research. Study 1 explored students open-ended answers, and these provided a basis for the interviews in Study 2. Study 3 explored veterinary students portfolios in a longitudinal setting. For Study 4, a diary including both qualitative and quantitative measures was designed to capture veterinary students interest experience. Qualitative content analysis was applied in all four studies, but quantitative analyses were also added. The thesis showed that university students often explain their disciplinary choices in terms of interest. Because interest is related to high-quality learning, the students seemed to have a good foundation for successful studies. However, the learning environments did not always support interest-based studying; Time-management and coping skills were found to be more important than interest in terms of study success. The results also indicated that interest is not the only motivational variable behind university studies. For example, future goals are needed in order to complete a degree. Even so, the results clearly indicated that it would be worth supporting interest-based studying both in professionally and generally oriented study fields. This support is important not only to promote high-quality learning but also meaningful studying, student well-being, and life-long learning.

Studies on the 14α-hydroxylation of progesterone in mucor piriformis

Cell-free extracts with high 14?-hydroxylase activity were prepared from induced vegetative cell cultures of Mucor piriformis by grinding in potassium phosphate buffer (0.05 M, pH 8.0) containing glucose (0.25 M), KCl (1 mM), glutathione (1.0 mM) and glycerol (10%). Although the ideal pH for preparing the cell-free extract from vegetative cells was 8.0, the pH optimum of the hydroxylase was found to be 7.6. Microsomes (2.0 mg) prepared from the crude cell-free extract hydroxylated progesterone to 14?-hydroxyprogesterone in not, vert, similar60% yields in 30 min in the presence of NADPH and O2. Microsomes prepared from the uninduced cells did not contain any 14?-hydroxylase activity. The hydroxylase activity was inhibited to a significant extent by CO and p-chloromercuribenzoate whereas moderate inhibition was noticed in the presence of SKF-525A, metyrapone and N-methylmaleimideindicating the possible involvement of the cytochromeP-450 system in the reaction. The membrane bound hydroxylase was solubilized using Triton X-100 and the solubilized fraction contained nearly 35% of the original hydroxylase activity.

Studies on the metabolism of a monoterpene ketone, R-(+)-pulegone-a hepatotoxin in rat: isolation and characterization of new metabolites

1. The metabolic disposition of R-(+)-pulegone (1) was examined in rats following four daily oral doses (250 mg/kg). 2. Six metabolites, namely pulegol (II), 2-hydroxy-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone (III), 3,6-dimethyl-7a-hydroxy-5,6,7,7a-tetrahydro-2(4H)-benzofuranone (IV), menthofuran (V), 5-methyl-2-(1-methyl-1-carboxyethylidene)cyclohexanone (VI), and 5-methyl-5-hydroxy-2-(1-hydroxy-1-carboxyethyl)cyclohexanone (VII) have previously been isolated from rat urine, and identified (Moorthy et al. (1989a). Eight new metabolites have now been isolated from rat urine, namely, 5-hydroxy-pulegone (VIII), piperitone (IX), piperitenone (X), 7-hydroxy-piperitone (XI), 8-hydroxy piperitone (XII), p-cresol (XIII), geranic acid (XIV) and neronic acid (XV). These were identified by n.m.r., i.r. and mass spectrometry. 3. Based on these results, metabolic pathways for the biotransformation of R-(+)-pulegone in rat have been proposed.