Synthesis of a natural product-inspired eight-membered ring lactam library via ring-closing metathesis.

Science.gov (United States)

Brown, Neil; Xie, Baohan; Markina, Nataliya; Vandervelde, David; Perchellet, Jean-Pierre H; Perchellet, Elisabeth M; Crow, Kyle R; Buszek, Keith R

2008-09-01

We have prepared a novel speculative eight-membered lactam demonstration library based on the skeletal structure of the potent antitumor marine natural product octalactin A. The basic scaffold was readily constructed in a convergent fashion via ring-closing metathesis chemistry from the corresponding diene amides. A cursory examination of the biological properties of the library validates the relevance and significance of these structures.

Synthesis of interlocked molecules by olefin metathesis

Science.gov (United States)

Clark, Paul Gregory

polyammonium scaffold. Diolefin polyether fragments were coordinated and "clipped" around the ammonium sites within the polymer backbone using ring-closing olefin metathesis, giving the molecular "charm bracelet". Confirmation of the interlocked nature of the product was achieved via 1H NMR spectroscopy and two-dimensional diffusion ordered NMR spectroscopy. A simple strategy for a one-pot, multi-component synthesis of polyrotaxanes using acyclic diene metathesis polymerization was developed. The polyrotaxanes were characterized by traditional 1H NMR spectroscopy as well as size exclusion chromatography, and the interlocked topology was confirmed using two-dimension diffusion-ordered NMR spectroscopy. The dynamic, self-correcting nature of the ADMET polymerization was also explored through the equilibration of a capped polyammonium polymer in the presence of dibenzo-24-crown-8 ether and olefin metathesis catalysts. The efficiency and ease with which these mechanically interlocked macromolecules can be assembled should facilitate rapid modulation to achieve versatile polyrotaxane architectures. Flexible, switchable [c2]daisy-chain dimers (DCDs) were synthesized, where the macromer ammonium binding site was adjacent to the crown-type recognition structure and separated from the cap by an alkyl chain. A DCD of this topology is expected to have an extended structure in the bound conformation (when the ammonium was coordinated to the crown). Several different macromer candidates were designed to allow access to DCDs with flexible alkyl chains between the ammonium binding site and the cap, and a number of synthetic routes were explored in an effort to access these challenging materials. While the first generation DCD structure proved to be unstable due to a labile ester linkage, work is continuing toward the development of several cap structures in an effort to replace the ester linkage with an ether linkage, which, in the second generation model systems, has proven much more stable

The metathesis of alkynes

Directory of Open Access Journals (Sweden)

H. C. M. Vosloo

1991-07-01

Full Text Available The alkyne metathesis reaction is a direct result of the known and intensively studied alkene or olefin metathesis reaction. Unfortunately this reaction was never studied as intensively as the alkene metathesis reaction, mainly because of a lack of active catalytic systems. In the alkyn metathesis reaction the carbon-carbon triple bonds are broken and rearranged to give a redistribution of alkylidyne groups.

Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization

Directory of Open Access Journals (Sweden)

Jakkrit Suriboot

2016-04-01

Full Text Available Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds. It then discusses in more detail progress in dealing with these issues in ring opening metathesis polymerization chemistry. Such approaches depend on a biphasic solid/liquid or liquid separation and can use either always biphasic or sometimes biphasic systems and approaches to this problem using insoluble inorganic supports, insoluble crosslinked polymeric organic supports, soluble polymeric supports, ionic liquids and fluorous phases are discussed.

Olefin metathesis in nano-sized systems

Directory of Open Access Journals (Sweden)

Denise Méry

2011-01-01

Full Text Available The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM, cross metathesis (CM, enyne metathesis reactions (EYM – for reactions in water without a co-solvent and (ii construction and functionalization of dendrimers by CM reactions.

Acyclicity in edge-colored graphs

DEFF Research Database (Denmark)

Gutin, Gregory; Jones, Mark; Sheng, Bin

2017-01-01

A walk W in edge-colored graphs is called properly colored (PC) if every pair of consecutive edges in W is of different color. We introduce and study five types of PC acyclicity in edge-colored graphs such that graphs of PC acyclicity of type i is a proper superset of graphs of acyclicity of type...

On Acyclicity of Games with Cycles

DEFF Research Database (Denmark)

Andersson, Daniel; Gurvich, Vladimir; Hansen, Thomas Dueholm

2009-01-01

We study restricted improvement cycles (ri-cycles) in finite positional n-person games with perfect information modeled by directed graphs (digraphs) that may contain cycles. We obtain criteria of restricted improvement acyclicity (ri-acyclicity) in two cases: for n = 2 and for acyclic digraphs. We...

Alkane Metathesis

KAUST Repository

Basset, Jean-Marie

2015-03-29

Catalytic activation of alkanes which directly transforms light alkanes into higher homologs is a major area in organometallic chemistry and petrochemical chemistry. This transformation is a chemical challenge considering the inertness of the sp3 carbon-hydrogen bond. It is generally accepted that this catalytic process involves the formation of olefins. This reaction is defined as alkane metathesis. To date, two catalytic systems of alkane metathesis exist: (i) a single catalytic system prepared by surface organometallic chemistry, acting as multifunctional-supported catalyst which transforms any alkanes into a mixture of their lower and higher homologs and (ii) the other catalytic systems employing a tandem strategy with two different metals, one metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two classes of catalysts by looking at their specific reactivity of the catalysts towards alkanes, comparing their performances and studying the mechanism.

Metathesis of alkanes and related reactions

KAUST Repository

Basset, Jean-Marie

2010-02-16

(Figure Presented) The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, (=SiO)2TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of aluminasupported tungsten hydride, W(H)3/Al 2O3, which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis of

Metathesis of alkanes and related reactions.

Science.gov (United States)

Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

2010-02-16

The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of P-Stereogenic, Z-Configured Bicyclo[7.3.1]- and Bicyclo[8.3.1]phosphates.

Science.gov (United States)

Markley, Jana L; Maitra, Soma; Hanson, Paul R

2016-02-05

A phosphate tether-mediated ring-closing metathesis (RCM) study to the synthesis of Z-configured, P-stereogenic bicyclo[7.3.1]- and bicyclo[8.3.1]phosphates is reported. Investigations suggest that C3-substitution, olefin substitution, and proximity of the forming olefin to the bridgehead carbon of the bicyclic affect the efficiency and stereochemical outcome of the RCM event. This study demonstrates the utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol-containing dienes in the generation of macrocyclic phosphates with potential synthetic and biological utility.

Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

KAUST Repository

Riache, Nassima

2015-11-14

Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

Recent applications of ring-rearrangement metathesis in organic synthesis

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2015-10-01

Full Text Available Ring-rearrangement metathesis (RRM involves multiple metathesis processes such as ring-opening metathesis (ROM/ring-closing metathesis (RCM in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008–2014.

Olefin metathesis in air

Directory of Open Access Journals (Sweden)

Lorenzo Piola

2015-10-01

Full Text Available Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance.

Alkane Metathesis

KAUST Repository

Basset, Jean-Marie; Callens, Emmanuel; Riache, Nassima

2015-01-01

metal for alkane (de)hydrogenation and another for olefin metathesis in which the activity of these catalysts is essentially driven by the performance of the (de)hydrogenation steps. In this book chapter, we would focus on the evolution of these two

A tandem cross-metathesis/semipinacol rearrangement reaction.

Science.gov (United States)

Plummer, Christopher W; Soheili, Arash; Leighton, James L

2012-05-18

An efficient and (E)-selective synthesis of a 6-alkylidenebicyclo[3.2.1]octan-8-one has been developed. The key step is a tandem cross-metathesis/semipinacol rearrangement reaction, wherein the Hoveyda-Grubbs II catalyst, or more likely a derivative thereof, serves as the Lewis acid for the rearrangement. Despite the fact that both the starting alkene and the cross-metathesis product are viable rearrangement substrates, only the latter rearranges, suggesting that the Lewis acidic species is generated only after the cross-metathesis reaction is complete.

Acyclic models

CERN Document Server

Barr, Michael

2002-01-01

Acyclic models is a method heavily used to analyze and compare various homology and cohomology theories appearing in topology and algebra. This book is the first attempt to put together in a concise form this important technique and to include all the necessary background. It presents a brief introduction to category theory and homological algebra. The author then gives the background of the theory of differential modules and chain complexes over an abelian category to state the main acyclic models theorem, generalizing and systemizing the earlier material. This is then applied to various cohomology theories in algebra and topology. The volume could be used as a text for a course that combines homological algebra and algebraic topology. Required background includes a standard course in abstract algebra and some knowledge of topology. The volume contains many exercises. It is also suitable as a reference work for researchers.

Zinc Mediated Tandem Fragmentation-Allylation of Methyl 5-Iodopentofuranosides

DEFF Research Database (Denmark)

Hyldtoft, Lene; Madsen, Robert

1999-01-01

In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols.......In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols....

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

2014-01-01

Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

The activation mechanism of Fe-based olefin metathesis catalysts

KAUST Repository

Poater, Albert

2014-08-01

Density functional theory calculations have been used to describe the first turnover for olefin metathesis reaction of a homogenous Fe-based catalyst bearing a N-heterocyclic carbene ligand with methoxyethene as a substrate. Equal to conventional Ru-based catalysts, the activation of its Fe congener occurs through a dissociative mechanism, however with a more exothermic reaction energy profile. Predicted upper energy barriers were calculated to be on average ∼2 kcal/mol more beneficial for Fe catalyzed metathesis. Overall, this present computational study emphasises on advantages of Fe-based metathesis and gives a potential recipe for the design of an efficient Fe-based olefin metathesis catalysts. © 2014 Elsevier B.V.

Acyclicity in edge-colored graphs

DEFF Research Database (Denmark)

Gutin, Gregory; Jones, Mark; Sheng, Bin

2017-01-01

A walk W in edge-colored graphs is called properly colored (PC) if every pair of consecutive edges in W is of different color. We introduce and study five types of PC acyclicity in edge-colored graphs such that graphs of PC acyclicity of type i is a proper superset of graphs of acyclicity of type i......+1, i=1,2,3,4. The first three types are equivalent to the absence of PC cycles, PC closed trails, and PC closed walks, respectively. While graphs of types 1, 2 and 3 can be recognized in polynomial time, the problem of recognizing graphs of type 4 is, somewhat surprisingly, NP-hard even for 2-edge-colored...... graphs (i.e., when only two colors are used). The same problem with respect to type 5 is polynomial-time solvable for all edge-colored graphs. Using the five types, we investigate the border between intractability and tractability for the problems of finding the maximum number of internally vertex...

A Sociolinguistic Analysis of Metathesis in Azeri Language

Directory of Open Access Journals (Sweden)

Biook Behnam

2012-07-01

Full Text Available This study tries to investigate the correlation between sociolinguistic parameters such as sex, age, and social class and the use of metathesis in Azeri. There have been few studies from a sociolinguistic perspective on the use of metathesis. Through studying the stigmatized forms of speech in Azeri, the present study indicates that a significant relationship exists between extralinguistic variables and metathesis as a phonological process. The subjects of the study were Azeri speakers living in different districts of Tabriz categorized by three socioeconomically different groups. The statistical analyses of data indicate that there is an intimate and reciprocal relationship between linguistic behavior and social structure.

Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

Science.gov (United States)

Schrodi, Yann [Agoura Hills, CA

2011-11-29

This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

Comparing Ru and Fe-catalyzed olefin metathesis

KAUST Repository

Poater, Albert; Chaitanya Vummaleti, Sai Vikrama; Pump, Eva; Cavallo, Luigi

2014-01-01

Density functional theory calculations have been used to explore the potential of Fe-based complexes with an N-heterocyclic carbene ligand, as olefin metathesis catalysts. Apart from a less endothermic reaction energy profile, a small reduction in the predicted upper energy barriers (≈ 2 kcal mol -1) is calculated in the Fe catalyzed profile with respect to the Ru catalysed profile. Overall, this study indicates that Fe-based catalysts have the potential to be very effective olefin metathesis catalysts. This journal is © the Partner Organisations 2014.

Development of neutron shielding material using metathesis-polymer matrix

Energy Technology Data Exchange (ETDEWEB)

Sakurai, Yoshinori E-mail: ysakurai@rri.kyoto-u.ac.jp; Sasaki, Akira; Kobayashi, Tooru

2004-04-21

A neutron shielding material using a metathesis-polymer matrix, which is a thermosetting resin, was developed. This shielding material has characteristics that can be controlled for different mixing ratios of neutron absorbers and for formation in the laboratory. Additionally, the elastic modulus can be changed at the hardening process, from a flexible elastoma to a mechanically tough solid. Experiments were performed at the Kyoto University Research Reactor in order to determine the important characteristics of this metathesis-polymer shielding material, such as neutron shielding performance, secondary gamma-ray generation and activation. The metathesis-polymer shielding material was shown to be practical and as effective as the other available shielding materials, which mainly consist of thermoplastic resin.

Ultrasound-assisted self-metathesis reactions of monounsaturated fatty acids

Directory of Open Access Journals (Sweden)

Elmkaddem Mohammed Kamal

2016-09-01

Full Text Available An efficient protocol for the self-metathesis of oleic acid, using ruthenium catalysts is described. The self-metathesis reaction under ultrasonic activation allows the conversion of monoenic fatty acids such as oleic acid, elaidic acid and erucic acid into diacids and olefins with very short reaction times in the presence of Grubbs ruthenium catalysts. These yields and selectivity towards the desired products are influenced by the nature of solvents. This study demonstrated that metathesis reaction carried out in DCM or 1-butanol showed promising results, since it produced a variety of products, like n-alkenes and diacids with good yields (45–75% and high selectivities (75–95%.

Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

KAUST Repository

Riache, Nassima; Callens, Emmanuel; Talbi, Karima; Basset, Jean-Marie

2015-01-01

Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate

A Conversation with Zoltan P. Dienes

Science.gov (United States)

Sriraman, Bharath; Lesh, Richard

2007-01-01

The name of Zoltan P. Dienes (1916- ) stands with those of Jean Piaget, Jerome Bruner, Edward Begle, and Robert Davis as a legendary figure whose work left a lasting impression on the field of mathematics education. Dienes' name is synonymous with the multibase blocks that he invented for the teaching of place value. Among numerous other things,…

Methods for treating a metathesis feedstock with metal alkoxides

Science.gov (United States)

Cohen, Steven A.; Anderson, Donde R.; Wang, Zhe; Champagne, Timothy M.; Ung, Thay A.

2018-04-17

Various methods are provided for treating and reacting a metathesis feedstock. In one embodiment, the method includes providing a feedstock comprising a natural oil, chemically treating the feedstock with a metal alkoxide under conditions sufficient to diminish catalyst poisons in the feedstock, and, following the treating, combining a metathesis catalyst with the feedstock under conditions sufficient to metathesize the feedstock.

Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

KAUST Repository

Hamzaoui, Bilel

2016-02-15

Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

Well-defined silica-supported zirconium–imido complexes mediated heterogeneous imine metathesis

KAUST Repository

Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Basset, Jean-Marie

2016-01-01

Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [(≡Si-O-)Zr(NEt2)3] (1) evolves into an ethylimido complex [(≡Si-O-)Zr(=NEt)NEt2] (2). Reactions of 2 with an imine substrate result in imido/imine (=NRi, R: Et, Ph) exchange (metathesis) with the formation of [(≡Si-O-)Zr(=NPh)NEt2] (3). Compounds 2 and 3 effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis. © The Royal Society of Chemistry 2016.

An Algorithm for Determining Minimal Reduced—Coverings of Acyclic Database Schemes

Institute of Scientific and Technical Information of China (English)

刘铁英; 叶新铭

1996-01-01

This paper reports an algoritm(DTV)for deermining the minimal reducedcovering of an acyclic database scheme over a specified subset of attributes.The output of this algotithm contains not only minimum number of attributes but also minimum number of partial relation schemes.The algorithm has complexity O(|N|·|E|2),where|N| is the number of attributes and |E|the number of relation schemes.It is also proved that for Berge,γ or β acyclic database schemes,the output of algorithm DTV maintains the acyclicity correspondence.

by a solid-state metathesis approach

Indian Academy of Sciences (India)

Wintec

Department of Mechanical Engineering,. † ... A solid-state metathesis approach initiated by microwave energy has been successfully applied for ... and chemical properties of synthesized powders are determined by powder X-ray diffraction, ...

A latent ruthenium based olefin metathesis catalyst with a sterically demanding NHC ligand

KAUST Repository

Leitgeb, Anita; Abbas, Mudassar E.; Fischer, Roland C.; Poater, Albert; Cavallo, Luigi; Slugovc, Christian

2012-01-01

An olefin metathesis catalyst featuring a SIPr NHC and an ester chelating carbene ligand is introduced. In contrast to its previously published SIMes analogue, only the trans dichloro configurated isomer was obtained. The two counterparts are tested in various olefin metathesis reactions, revealing a striking superiority of the new complex in the cross metathesis of olefins with methyl vinyl ketone allowing for full conversion with only 500 ppm catalyst loading. © 2012 The Royal Society of Chemistry.

3000 Horsepower super conductive field acyclic motor

International Nuclear Information System (INIS)

Marshall, R.

1983-01-01

A 3000 hp acyclic motor was assembled and tested utilizing superconducting field coils. The magnet assembly is designed as a quadrupole magnet, utilizing a multifilamentary niobium titanium superconductor. Each magnet coil is 18 inches in diameter and 10 inches long, and operates at rated current of 200 amperes, providing 5.8 tesla in the bore of the coils in the motor configuration. The average winding current density is 10,600 A/cm 2 . The acyclic motor is of a drum-type design with liquid metal current collectors, and is designed to model full-scale machinery for ship propulsion applications. Laboratory test data verified the electrical and electromagnetic design to be within three percent of the calculated values

Metathesis: A "Change-Your-Partners" Dance

Indian Academy of Sciences (India)

Organic chemistry, the chemistry of carbon compounds, is a fascinating subject. ... In general, a chemical reaction is referred to as 'metathesis' or exchange reaction, if it is of .... pounds (alcohols, ketones, aldehydes, etc.), but is stable for long.

Diversity-Oriented Approaches to Polycyclics and Bioinspired Molecules via the Diels-Alder Strategy: Green Chemistry, Synthetic Economy, and Beyond.

Science.gov (United States)

Kotha, Sambasivarao; Chavan, Arjun S; Goyal, Deepti

2015-05-11

We describe diverse approaches to various dienes and their utilization in the Diels-Alder reaction to produce a variety of polycycles. The dienes covered here are prepared by simple alkylation reaction or via the Claisen rearrangement or by enyne metathesis of alkyne or enyne building blocks. Here, we have also included the Diels-Alder chemistry of dendralenes, a higher analog of cross-conjugated dienes. The present article is inclusive of o-xylylene derivatives that are generated in situ starting with benzosultine or benzosulfone derivatives. The Diels-Alder reaction of these dienes with various dienophiles gave diverse polycyclic systems and biologically important targets.

1,4-Disilacyclohexa-2,5-diene

DEFF Research Database (Denmark)

Tibbelin, Julius; Wallner, Andreas; Emanuelsson, Rikard

2014-01-01

2,3,5,6-Tetraethyl-1,4-disilacyclohexa-2,5-dienes with either four chloro (1a), methyl (1b), or trimethylsilyl (TMS) (1c) substituents at the two silicon atoms were examined in an effort to design rigid compounds with strong neutral cross-hyperconjugation between π- and σ-bonded molecular segments......). Furthermore, 1,4-disilacyclohexadiene 1c absorbs strongly at 273 nm (4.55 eV), whereas 1a and 1b have no symmetry allowed excitations above 215 nm (below 5.77 eV). Thus, suitably substituted 1,4-disilacyclohexa-2,5-dienes could represent novel building blocks for the design of larger cross...

Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

KAUST Repository

Szeto, Kaï Chung; Mazoyer, Etienne; Merle, Nicolas; Norsic, Sé bastien; Basset, Jean-Marie; Nicholas, Christopher P.; Taoufik, Mostafa

2013-01-01

Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

KAUST Repository

Szeto, Kaï Chung

2013-09-06

Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

Revisiting the metathesis of 13C-monolabeled ethane

KAUST Repository

Maury, Olivier; Lefort, Laurent; Vidal, Vé ronique; Thivolle-Cazat, Jean; Basset, Jean-Marie

2010-01-01

The metathesis of 13C-monolabeled ethane leads to the parallel occurrence of degenerate and productive reactions, affording the statistical distribution of the various product isotopomers, which can be rationalized in terms of a mechanistic reaction

Mo-catalyzed cross-metathesis reaction of propynylferrocene

Czech Academy of Sciences Publication Activity Database

Bobula, T.; Hudlický, J.; Novák, P.; Gyepes, R.; Císařová, I.; Štěpnička, P.; Kotora, Martin

-, č. 25 (2008), s. 3911-3920 ISSN 1434-1948 Grant - others:GA MŠk(CZ) LC06070 Program:LC Institutional research plan: CEZ:AV0Z40550506 Keywords : alkynes * metallocenes * metathesis * electrochemistry * X-ray diffraction Subject RIV: CC - Organic Chemistry Impact factor: 2.694, year: 2008

The Dienes phenomenon: competition and territoriality in Swarming Proteus mirabilis

NARCIS (Netherlands)

Budding, A. E.; Ingham, C. J.; Bitter, W.; Vandenbroucke-Grauls, C. M.; Schneeberger, P. M.

2009-01-01

When two different strains of swarming Proteus mirabilis encounter one another on an agar plate, swarming ceases and a visible line of demarcation forms. This boundary region is known as the Dienes line and is associated with the formation of rounded cells. While the Dienes line appears to be the

Detecting Elusive Intermediates in Carbohydrate Conversion: A Dynamic Ensemble of Acyclic Glucose-Catalyst Complexes

DEFF Research Database (Denmark)

Meier, Sebastian; Karlsson, Magnus; Jensen, Pernille Rose

2017-01-01

within few seconds prior to reaching a steady state. Exchange between the acyclic intermediates increases at conditions that favor epimerization. Species accounting for less than 0.05% of total glucose can be monitored with sub-second time resolution to allow kinetic analysis of intermediate formation...... and catalytic conversion. Epimerization occurs 2-3 orders of magnitude-fold faster than the binding of acyclic glucose to the catalyst at near-optimum reaction conditions. The current study brings insight in to the nature of acyclic intermediate-catalyst complexes of very low population and into experimental...... strategies for characterizing very minor intermediates in carbohydrate conversion to value-added compounds....

Metathesis synthesis and characterization of complex metal fluoride ...

Indian Academy of Sciences (India)

Administrator

V MANIVANNAN*, P PARHI and JONATHAN W KRAMER. Department of Mechanical Engineering, Campus Delivery 1374, Colorado State University, Fort Collins,. CO 80523, USA. MS received 30 April 2008. Abstract. Metathesis synthesis of complex metal fluorides using mechanochemical activation has been reported.

Specific acyclic isoprenoids as biological markers of methanogenic bacteria in marine sediments.

Science.gov (United States)

Brassell, S C; Wardroper, A M; Thomson, I D; Maxwell, J R; Eglinton, G

1981-04-23

The widespread occurrence of extended hopanoids in sediments and petroleums illustrates the importance of bacterial lipid contributions to geological materials. In archaebacteria, however, hopanoids are absent; their role as structural components of biomembranes is fulfilled by acyclic isoprenoids. Recent studies of the lipid constituents of archaebacteria have greatly extended the range of acyclic isoprenoid skeletons known in organisms (Fig. 1). In particularly, isoprenoids with head-to-head linkages have been identified, and such compounds (for example, 3,7,11,15,18,22,26,30-octamethyldotriacontane, I) have been recognized in petroleum and as degradation products of Messel shale kerogen. Here we report the first recognition of 2,6,10,15,19-pentamethyleicosane (II), a known component of methanogens, in marine sediments of Recent to Cretaceous age (Table 1) and suggest that it and certain other acyclic isoprenoids may be used as biological markers for methanogens.

Synthetic studies on taxanes: A domino-enyne metathesis/Diels ...

Indian Academy of Sciences (India)

Abstract. A domino enyne cross-metathesis/intramolecular Diels-Alder reaction has been successfully used to synthesize a bicyclo[5.3.1] undecene, corresponding to AB-ring of taxol without the gem dimethyl group.

Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

KAUST Repository

Barman, Samir

2017-04-06

Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

Well-Defined Silica Grafted Molybdenum Bis(imido) Catalysts for Imine Metathesis Reactions

KAUST Repository

Barman, Samir; Merle, Nicolas; Minenkov, Yury; De Mallmann, Aimery; Samantaray, Manoja; Le Qué mé ner, Fré dé ric; Szeto, Kai C.; Abou-Hamad, Edy; Cavallo, Luigi; Taoufik, Mostafa; Basset, Jean-Marie

2017-01-01

Novel site-isolated tetracoordinated molybdenum complexes possessing bis(imido) ligands, [(≡Si–O)2Mo(═NR)2] (R = t-Bu, 2,6-C6H3-i-Pr2), were immobilized on partially dehydroxylated silica (SiO2-200) by a rigorous surface organometallic chemistry protocol. The newly developed materials adorned with bis(imido) functional units, which were previously exploited mainly as spectator ligands on silica-supported olefin metathesis molybdenum catalysts, are found to be efficient heterogeneous catalytic systems for imine cross metathesis under mild conditions.

Quantitative analysis of hydroperoxy-, keto- and hydroxy-dienes in refined vegetable oils.

Science.gov (United States)

Morales, Arturo; Marmesat, Susana; Dobarganes, M Carmen; Márquez-Ruiz, Gloria; Velasco, Joaquín

2012-03-16

Quantitative analysis of the main oxidation products of linoleic acid - hydroperoxy-, keto- and hydroxy-dienes - in refined oils is proposed in this study. The analytical approach consists of derivatization of TAGs into FAMEs and direct analysis by HPLC-UV. Two transmethylation methods run at room temperature were evaluated. The reactants were KOH in methanol in method 1 and sodium methoxide (NaOMe) in method 2. Method 1 was ruled out because resulted in losses of hydroperoxydienes as high as 90 wt%. Transmethylation with NaOMe resulted to be appropriate as derivatization procedure, although inevitably also gives rise to losses of hydroperoxydienes, which were lower than 10 wt%, and formation of keto- and hydroxy-dienes as a result. An amount of 0.6-2.1 wt% of hydroperoxydienes was transformed into keto- and hydroxy-dienes, being the formation of the former as much as three times higher. The method showed satisfactory sensitivity (quantification limits of 0.3 μg/mL for hydroperoxy- and keto-dienes and 0.6 μg/mL for hydroxydienes), precision (coefficients of variation ≤ 6% for hydroperoxydienes and ≤ 15% for keto- and hydroxy-dienes) and accuracy (recovery values of 85(± 4), 99(± 2) and 97.0(± 0.6) % for hydroperoxy-, keto- and hydroxy-dienes, respectively). The method was applied to samples of high-linoleic (HLSO), high-oleic (HOSO) and high-stearic high-oleic (HSHOSO) sunflower oils oxidized at 40 °C. Results showed that the higher the linoleic-to-oleic ratio, the higher were the levels of hydroperoxy-, keto- and hydroxy-dienes when tocopherols were completely depleted, i.e. at the end of the induction period (IP). Levels of 23.7, 2.7 and 1.1 mg/g oil were found for hydroperoxy-, keto- and hydroxy-dienes, respectively, in the HLSO when tocopherol was practically exhausted. It was estimated that hydroperoxydienes constituted approximately 100, 95 and 60% of total hydroperoxides in the HLSO, HOSO and HSHOSO, respectively, along the IP. Copyright © 2012

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

KAUST Repository

Urbina-Blanco, Cé sar A.; Poater, Albert; Lé bl, Tomá š; Manzini, Simone; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

2013-01-01

Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

The activation mechanism of Ru-indenylidene complexes in olefin metathesis

KAUST Repository

Urbina-Blanco, César A.

2013-05-08

Olefin metathesis is a powerful tool for the formation of carbon-carbon double bonds. Several families of well-defined ruthenium (Ru) catalysts have been developed during the past 20 years; however, the reaction mechanism for all such complexes was assumed to be the same. In the present study, the initiation mechanism of Ru-indenylidene complexes was examined and compared with that of benzylidene counterparts. It was discovered that not all indenylidene complexes followed the same mechanism, highlighting the importance of steric and electronic properties of so-called spectator ligands, and that there is no single mechanism for the Ru-based olefin metathesis reaction. The experimental findings are supported quantitatively by DFT calculations. © 2013 American Chemical Society.

On Event Detection and Localization in Acyclic Flow Networks

KAUST Repository

Suresh, Mahima Agumbe; Stoleru, Radu; Zechman, Emily M.; Shihada, Basem

2013-01-01

Acyclic flow networks, present in many infrastructures of national importance (e.g., oil and gas and water distribution systems), have been attracting immense research interest. Existing solutions for detecting and locating attacks against

Synthesis of Mono(perfluoroalkyl) Cyclodextrins via Cross Metathesis

Czech Academy of Sciences Publication Activity Database

Řezanka, M.; Eignerová, Barbara; Jindřich, J.; Kotora, M.

-, č. 32 (2010), s. 6256-6262 ISSN 1434-193X R&D Projects: GA AV ČR KAN200200651 Institutional research plan: CEZ:AV0Z40550506 Keywords : metathesis * cyclodextrins * fluorine * alkylation * amphiphiles Subject RIV: CC - Organic Chemistry Impact factor: 3.206, year: 2010

Revisiting the metathesis of 13C-monolabeled ethane

KAUST Repository

Maury, Olivier

2010-12-13

The metathesis of 13C-monolabeled ethane leads to the parallel occurrence of degenerate and productive reactions, affording the statistical distribution of the various product isotopomers, which can be rationalized in terms of a mechanistic reaction scheme combining both processes. © 2010 American Chemical Society.

Understanding the Hydro-metathesis Reaction of 1-decene by Using Well-defined Silica Supported W, Mo, Ta Carbene/Carbyne Complexes

KAUST Repository

Saidi, Aya

2017-12-21

Direct conversion of 1-decene to petroleum range alkanes was obtained using hydro-metathesis reaction. To understand this reaction we employed three different well-defined single site catalysts precursors; [(≡Si-O-)W(CH3)5] 1, [(≡Si-O-)Mo(≡CtBu)(CH2tBu)2] 2 and [(≡Si-O)Ta(=CHtBu)(CH2tBu)2] 3. We witnessed that in our conditions olefin metathesis/isomerization of 1-decene occurs much faster followed by reduction of the newly formed olefins rather than reduction of the 1-decene to decane, followed by metathesis of decane. We found that Mo-based catalyst favors 2+2 cycloaddition of 1-decene forming metallocarbene, followed by reduction of the newly formed olefins to alkanes. However, in the case of W and Ta-based catalysts, a rapid isomerization (migration) of the double bond followed by olefin metathesis and reduction of the newly formed olefins were observed. We witnessed that silica supported W catalyst precursor 1 and Mo catalyst precursor 2 are better catalysts for hydro-metathesis reaction with TONs of 818 and 808 than Ta-based catalyst 3 (TON of 334). This comparison of the catalysts provides us a better understanding that, if a catalyst is efficient in olefin metathesis reaction it would be a better catalyst for hydro-metathesis reaction.

Rare-earth-metal nitridophosphates through high-pressure metathesis

International Nuclear Information System (INIS)

Kloss, Simon David; Schnick, Wolfgang

2015-01-01

Developing a synthetic method to target an broad spectrum of unknown phases can lead to fascinating discoveries. The preparation of the first rare-earth-metal nitridophosphate LiNdP_4N_8 is reported. High-pressure solid-state metathesis between LiPN_2 and NdF_3 was employed to yield a highly crystalline product. The in situ formed LiF is believed to act both as the thermodynamic driving force and as a flux to aiding single-crystal formation in dimensions suitable for crystal structure analysis. Magnetic properties stemming from Nd"3"+ ions were measured by SQUID magnetometry. LiNdP_4N_8 serves as a model system for the exploration of rare-earth-metal nitridophosphates that may even be expanded to transition metals. High-pressure metathesis enables the systematic study of these uncharted regions of nitride-based materials with unprecedented properties. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

National Research Council Canada - National Science Library

Low, Tammy K

2006-01-01

.... Our research goals consisted of employing olefin metathesis in the synthesis of peptidomimetics, and studying the feasibility of this method in dynamic combinatorial chemistry and molecular imprinting of nerve agents...

Metathesis synthesis and characterization of complex metal fluoride ...

Indian Academy of Sciences (India)

Administrator

Sivakumar et al 2004; Mandal and Gopalakrishnan 2005). Although metathesis reactions may initiate spontane- ously .... cal lithography are needed (Sahnoun et al 2005). KMF3 materials with perovskite structures are ... (Knox 1961; Machin et al 1963; Pari et al 1994) and shown in figure 5. The KMF3 compounds are anti-.

Exploiting Confinement Effects to Tune Selectivity in Cyclooctane Metathesis

KAUST Repository

Pump, Eva

2017-08-24

The mechanism of cyclooctane metathesis using confinement effect strategies in mesoporous silica nanoparticles (MSNs) is discussed by catalytic experiments and density functional theory (DFT) calculations. WMe6 was immobilized inside the pores of a series of MSNs having the same structure but different pore diameters (60, 30 and 25 Å). Experiments in cyclooctane metathesis suggest that confinement effects observed in smaller pores (30 and 25 Å) improve selectivity towards the dimeric cyclohexadecane. In contrast, in larger pores (60 Å) a broad product distribution dominated by ring contracted cycloalkanes was found. The catalytic cycle and potential side reactions occurring at [(≡SiO-)WMe5] were examined with DFT calculations. Analysis of the geometries for the key reaction intermediates allowed to rationalize the impact of a confined environment on the enhanced selectivity towards the dimeric product in smaller pores, while in large pores the ring contracted products are favored.

Antiviral acyclic nucleoside phosphonates: New structures and prodrugs

Czech Academy of Sciences Publication Activity Database

Krečmerová, Marcela; Tichý, Tomáš; Pomeisl, Karel; Andrei, G.; Balzarini, J.; Snoeck, R.

2016-01-01

Roč. 1, č. 2 (2016), s. 37 [PharmaMed-2016. International Conference on Medicinal and Pharmaceutical Chemistry . 05.12.2016-07.12.2016, Dubai] R&D Projects: GA ČR(CZ) GA14-00522S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * prodrugs * antivirals * 5-azacytosine Subject RIV: CC - Organic Chemistry

The asymmetric Schrock olefin metathesis catalysts. A computational study

NARCIS (Netherlands)

Goumans, T.P.M.; Ehlers, A.W.; Lammertsma, K.

2005-01-01

The mechanism of the transition metal catalyzed olefin metathesis reaction with the Schrock catalyst is investigated with pure (BP86) and hybrid (B3LYP) density functional theory. On the free-energy surface there is no adduct between ethylene and model catalyst (MeO)

Convergent Synthesis of Pancratistatin from Piperonal and Xylose

DEFF Research Database (Denmark)

Dam, Johan Hygum; Madsen, Robert

2009-01-01

to afford a highly functionalised 1,7-diene, which is then converted into the corresponding cyclohexene by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation and deprotection afford the natural product in a total of 25 steps from the two starting materials. The longest linear...

The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

KAUST Repository

Poater, Albert

2014-10-14

The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

The right computational recipe for olefin metathesis with ru-based catalysts: The whole mechanism of ring-closing olefin metathesis

KAUST Repository

Poater, Albert; Pump, Eva; Vummaleti, Sai V. C.; Cavallo, Luigi

2014-01-01

The initiation mechanism of ruthenium methylidene complexes was studied detailing mechanistic insights of all involved reaction steps within a classical olefin metathesis pathway. Computational studies reached a good agreement with the rarely available experimental data and even enabled to complement them. As a result, a highly accurate computational and rather cheap recipe is presented; M06/TZVP//BP86/SVP (PCM, P = 1354 atm).

Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

KAUST Repository

Manzini, Simone

2015-03-01

The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

Evaluation of an olefin metathesis pre-catalyst with a bulky and electron-rich N-heterocyclic carbene

KAUST Repository

Manzini, Simone; Urbina Blanco, Cé sar A.; Nelson, David J.; Poater, Albert; Lebl, Tomas; Meiries, Sé bastien; Slawin, Alexandra M.Z.; Falivene, Laura; Cavallo, Luigi; Nolan, Steven P.

2015-01-01

The commercially-available metathesis pre-catalyst M23 has been evaluated alongside new complex [RuCl2((3-phenyl)indenylidene)(PPh3)(SIPrOMe)] (1), which bears a para-methoxy-substituted N-heterocyclic carbene ligand. Several model metathesis reactions could be conducted using only parts-per-million levels of ruthenium catalyst. The effects of the different NHC ligands on reactivity have been explored.

Exploring new generations of ruthenium olefin metathesis catalysts: The reactivity of a bis-ylidene ruthenium complex by DFT

KAUST Repository

Poater, Albert; Credendino, Raffaele; Slugovc, Christian; Cavallo, Luigi

2013-01-01

Density functional theory calculations were used to predict the behaviour of a potential novel architecture of olefin metathesis catalysts, in which one of the neutral ligands of classical Ru-based catalysts, e.g. a phosphine or an N-heterocyclic carbene, is replaced by an alkylidene group. Introduction of a second alkylidene ligand favors dissociation of the remaining phosphine and the overall energy profile for the metathesis using ethylene as the probe substrate reveals that the proposed bis-alkylidene complexes might match the requirements of a good performing olefin metathesis catalyst. © 2013 The Royal Society of Chemistry.

Recent advances in the development of alkyne metathesis catalysts

Directory of Open Access Journals (Sweden)

Matthias Tamm

2011-01-01

Full Text Available The number of well-defined molybdenum and tungsten alkylidyne complexes that are able to catalyze alkyne metathesis reactions efficiently has been significantly expanded in recent years.The latest developments in this field featuring highly active imidazolin-2-iminato- and silanolate–alkylidyne complexes are outlined in this review.

Intramolecular cascade rearrangements of enynamine derived ketenimines: access to acyclic and cyclic amidines.

Science.gov (United States)

Chauhan, Dinesh Pratapsinh; Varma, Sreejith J; Gudem, Mahesh; Panigrahi, Nihar; Singh, Khushboo; Hazra, Anirban; Talukdar, Pinaki

2017-06-07

Copper-catalyzed reaction of enynamines with sulfonylazides provides acyclic and cyclic amidines. Nucleophilic addition of the tethered amino group on the in situ generated ketenimine forms a six-membered cyclic zwitterionic intermediate which facilitates migration of the tethered amino group to the C 5 -center giving the acyclic amidine. On the other hand, migration of a substituent on the amino group to C 2 - and C 4 -centers results in the formation of cyclic amidines. Computational studies were carried out to validate the mechanism which indicates that the product distribution of the process depends on the substitutions on the enynamine backbone.

Omega-functionalized fatty acids, alcohols, and ethers via olefin metathesis

Science.gov (United States)

Methyl 17-hydroxy stearate was converted to methyl octadec-16-enoate using copper sulfate adsorbed on silica gel. This compound, possessing unsaturation at the opposite end of the chain from the carboxylate, served as a useful substrate for the olefin metathesis reaction. As a result, several fatt...

Electrochemical selenium- and iodonium-initiated cyclisation of hydroxy-functionalised 1,4-dienes

Directory of Open Access Journals (Sweden)

Philipp Röse

2015-01-01

Full Text Available The cobalt(I-catalysed 1,4-hydrovinylation reaction of allyloxytrimethylsilane and allyl alcohol with substituted 1,3-dienes leads to hydroxy-functionalised 1,4-dienes in excellent regio- and diastereoselective fashion. Those 1,4-dienols can be converted into tetrahydrofuran and pyran derivatives under indirect electrochemical conditions generating selenium or iodonium cations. The reactions proceed in good yields and regioselectivities for the formation of single diastereomers.

Polynomial kernels for deletion to classes of acyclic digraphs

NARCIS (Netherlands)

Mnich, Matthias; van Leeuwen, E.J.

2017-01-01

We consider the problem to find a set X of vertices (or arcs) with |X| ≤ k in a given digraph G such that D = G − X is an acyclic digraph. In its generality, this is Directed Feedback Vertex Set (or Directed Feedback Arc Set); the existence of a polynomial kernel for these problems is a notorious

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

KAUST Repository

Dey, Raju; Samantaray, Manoja; Callens, Emmanuel; Hamieh, Ali Imad Ali; Emwas, Abdul-Hamid M.; Abou-Hamad, Edy; Kavitake, Santosh Giridhar; Basset, Jean-Marie

2016-01-01

Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

Cationic Tungsten(VI) Penta-Methyl Complex: Synthesis, Characterization and its Application in Olefin Metathesis Reaction

KAUST Repository

Dey, Raju

2016-04-13

Tungsten-hexa-methyl readily reacts with B(C6F5)3 in dichloromethane and generates the corresponding well-defined cationic tungsten-penta-methyl complex which was identified precisely by 1H NMR, 13C NMR, 1H-13C NMR correlation spectroscopy. Unlike WMe6, this cationic complex has low energy barrier to form tungsten carbene intermediate, which was further supported by the fact that WMe6 alone has no activity in olefin metathesis reaction whereas the cationic complex shows catalytic activity for self-metathesis of 1-octene.

Towards Optimal Event Detection and Localization in Acyclic Flow Networks

KAUST Repository

Agumbe Suresh, Mahima

2012-01-03

Acyclic flow networks, present in many infrastructures of national importance (e.g., oil & gas and water distribution systems), have been attracting immense research interest. Existing solutions for detecting and locating attacks against these infrastructures, have been proven costly and imprecise, especially when dealing with large scale distribution systems. In this paper, to the best of our knowledge for the first time, we investigate how mobile sensor networks can be used for optimal event detection and localization in acyclic flow networks. Sensor nodes move along the edges of the network and detect events (i.e., attacks) and proximity to beacon nodes with known placement in the network. We formulate the problem of minimizing the cost of monitoring infrastructure (i.e., minimizing the number of sensor and beacon nodes deployed), while ensuring a degree of sensing coverage in a zone of interest and a required accuracy in locating events. We propose algorithms for solving these problems and demonstrate their effectiveness with results obtained from a high fidelity simulator.

Hydro-Metathesis of Long-Chain Olefin (1-decene) using Well-Defined Silica-Supported Tungsten (VI), Molybdenum (VI) and Tantalum (V) Catalysts

KAUST Repository

Saidi, Aya

2016-11-01

Nowadays, catalysis lies at the heart of economy growth mainly in the petroleum industry. Catalysis can offer real and potential solutions to the current challenges for a long-term sustainable energy, green chemistry, and environmental protection. In this context, one of the most important and future prosperity promising catalytic applications in the petrochemical field is hydrocarbons metathesis; it consists on the conversion of both renewable and non-petroleum fossil carbon sources to transportation fuels. Olefin metathesis has become one of the standard methodologies for constructing C-C bonds in many organic transformation reactions. This owed to the numerous types of metathesis reactions that have been developed, for example, enyne, ring-opening and closing, self and cross metathesis, etc. But the one step conversion of olefin to alkanes has not been studied much. Recently, only one such a work has been published for the hydro-metathesis of propylene by tantalum hydride supported on KCC-1 in dynamic reactor. With this knowledge, we thought to study the hydro-metathesis using liquid olefin (1-decene). Another aspect of using 1-decene comes from our previous experience on metathesis of n-decane where the first step is the conversion of decane to 1-decene and subsequently to different chain length alkanes with W-alkyl/alkylidene catalyst. In this way, it would be easy for us to use different catalysts and compare them with parent catalyst concerning TON. We found 100% conversion with TON of 1010 using supported WMe6 onto SiO2-700 [(≡Si-O-)WMe5] against the previous results for n-decane showing 20% conversion and TON of 153. In this work, we disclose the hydro-metathesis reaction of 1-decene using well-defined silica supported W(VI), Mo(VI) and Ta(V) alkyl catalysts in batch reactor condition. This work is divided into three major sections; first chapter contains an introduction to the field of catalysis and surface organometallic chemistry. In second chapter

Rh-Catalyzed rearrangement of vinylcyclopropane to 1,3-diene units attached to N-heterocycles

Directory of Open Access Journals (Sweden)

Alberto Brandi

2011-03-01

Full Text Available Dienes embedded in quinolizidine and indolizidine structures can be prepared in four steps from cyclic nitrones and bicyclopropylidene. The key intermediates α-spirocyclopropanated N-heterocyclic ketones, generated via a domino 1,3-dipolar cycloaddition/thermal rearrangement sequence, were converted by Wittig methylenation to the corresponding vinylcyclopropanes (VCPs, which underwent rearrangement to 1,3-dienes in the presence of the Wilkinson Rh(I complex under microwave heating. The previously unexplored Rh(I-catalyzed opening of the VCP moiety embedded in an azapolycyclic system occurs at high temperature (110–130 °C to afford the corresponding 1,3-dienes in moderate yield (34–53%.

Metathesis in the generation of low-temperature gas in marine shales

Directory of Open Access Journals (Sweden)

Jarvie Daniel M

2010-01-01

Full Text Available Abstract The recent report of low-temperature catalytic gas from marine shales took on additional significance with the subsequent disclosure of natural gas and low-temperature gas at or near thermodynamic equilibrium in methane, ethane, and propane. It is important because thermal cracking, the presumed source of natural gas, cannot generate these hydrocarbons at equilibrium nor can it bring them to equilibrium over geologic time. The source of equilibrium and the source of natural gas are either the same (generation under equilibrium control or closely associated. Here we report the catalytic interconversion of hydrocarbons (metathesis as the source of equilibrium in experiments with Cretaceous Mowry shale at 100°C. Focus was on two metathetic equilibria: methane, ethane, and propane, reported earlier, Q (K = [(C1*(C3]/[(C22], and between these hydrocarbons and n-butane, Q* (K = [(C1*(n-C4]/[(C2*(C3], reported here for the first time. Two observations stand out. Initial hydrocarbon products are near equilibrium and have maximum average molecular weights (AMW. Over time, products fall from equilibrium and AMW in concert. It is consistent with metathesis splitting olefin intermediates [Cn] to smaller intermediates (fission as gas generation creates open catalytic sites ([ ]: [Cn] + [ ] → [Cn-m] + [Cm]. Fission rates increasing exponentially with olefin molecular weight could contribute to these effects. AMW would fall over time, and selective fission of [C3] and [n-C4] would draw Q and Q* from equilibrium. The results support metathesis as the source of thermodynamic equilibrium in natural gas.

Mesoporous molecular sieves as advanced supports for olefin metathesis catalysts

Czech Academy of Sciences Publication Activity Database

Balcar, Hynek; Čejka, Jiří

2013-01-01

Roč. 257, 21-22 (2013), s. 3107-3124 ISSN 0010-8545 R&D Projects: GA AV ČR IAA400400805; GA ČR GBP106/12/G015 Institutional support: RVO:61388955 Keywords : Olefin metathesis * mesoporous molecular sieves * Heterogeneous catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.098, year: 2013

Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

KAUST Repository

Szeto, Kaï Chung; Hardou, Lucie; Merle, Nicolas; Basset, Jean-Marie; Thivolle-Cazat, Jean; Papaioannou, Charalambos; Taoufik, Mostafa

2012-01-01

We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product

Nitro-Grela-type complexes containing iodides – robust and selective catalysts for olefin metathesis under challenging conditions

Directory of Open Access Journals (Sweden)

Andrzej Tracz

2015-10-01

Full Text Available Iodide-containing nitro-Grela-type catalysts have been synthesized and applied to ring closing metathesis (RCM and cross metathesis (CM reactions. These new catalysts have exhibited improved efficiency in the transformation of sterically, non-demanding alkenes. Additional steric hindrance in the vicinity of ruthenium related to the presence of iodides ensures enhanced catalyst stability. The benefits are most apparent under challenging conditions, such as very low reaction concentrations, protic solvents or with the occurrence of impurities.

Synthesis and Ring-Opening Metathesis Polymerization of Second-Generation Dendronized Poly(ether Monomers Initiated by Ruthenium Carbenes

Directory of Open Access Journals (Sweden)

Guzmán Pablo E.

2016-03-01

Full Text Available The Ring-Opening Metathesis Polymerization (ROMP of second-generation dendronized monomers is described. Using the highly active and fast-initiating third-generation ruthenium complex [(H2IMes(pyr2Cl2RuCHPh], moderate to high molecular weight polymers (430-2230 kDa are efficiently synthesized with low dispersities (Ð = 1.01-1.17. This study highlights the power of the metathesis approach toward polymer synthesis in a context where monomer structure can significantly impede polymerization.

Impossibility of an acyclic relativistic electric motor

Energy Technology Data Exchange (ETDEWEB)

Spavieri, G [Universidad de Los Andes, Merida (Venezuela); Cavalleri, G [Milan Univ. (Italy). Ist. di Fisica; Spinelli, G [Padua Univ. (Italy). Ist. di Matematica Applicata

1981-02-11

The relativistic torque acting on a circuit carrying a current and having a uniform translatory motion in a constant and uniform electric field would seem to suggest the possibility of an acyclic relativistic electric motor. However, the net effect on the side parallel to the rotation axis is exactly balanced by the variation of the angular momentum (in the case of an insulating circuit transporting electric charges) or by the external moment due to the magnetic field (in the case of a conducting circuit) acting on the two sides perpendicular to the rotation axis.

On Event Detection and Localization in Acyclic Flow Networks

KAUST Repository

Suresh, Mahima Agumbe

2013-05-01

Acyclic flow networks, present in many infrastructures of national importance (e.g., oil and gas and water distribution systems), have been attracting immense research interest. Existing solutions for detecting and locating attacks against these infrastructures have been proven costly and imprecise, particularly when dealing with large-scale distribution systems. In this article, to the best of our knowledge, for the first time, we investigate how mobile sensor networks can be used for optimal event detection and localization in acyclic flow networks. We propose the idea of using sensors that move along the edges of the network and detect events (i.e., attacks). To localize the events, sensors detect proximity to beacons, which are devices with known placement in the network. We formulate the problem of minimizing the cost of monitoring infrastructure (i.e., minimizing the number of sensors and beacons deployed) in a predetermined zone of interest, while ensuring a degree of coverage by sensors and a required accuracy in locating events using beacons. We propose algorithms for solving the aforementioned problem and demonstrate their effectiveness with results obtained from a realistic flow network simulator.

Metabolism of acyclic and cyclic N-nitroamines by cultured human colon

DEFF Research Database (Denmark)

Autrup, Herman; Harris, Curtis C.; Trump, Benjamin F.

1978-01-01

Cultured human colon mucosa was found to metabolize both acyclic and cyclic N-nitrosamines as measured by 14C-CO2 formation and reaction of the activated moieties with cellular macromolecules. Dimethylnitrosamine and N-nitrosopyrrolidine were metabolized by explants from all patients studied. A p...

Probing Stereoselectivity in Ring-Opening Metathesis Polymerization Mediated by Cyclometalated Ruthenium-Based Catalysts: A Combined Experimental and Computational Study

OpenAIRE

Rosebrugh, L. E.; Ahmed, T. S.; Marx, V. M.; Hartung, J.; Liu, P.; López, J. G.; Houk, K. N.; Grubbs, R. H.

2016-01-01

The microstructures of polymers produced by ring-opening metathesis polymerization (ROMP) with cyclometalated Ru-carbene metathesis catalysts were investigated. A strong bias for a cis,syndiotactic microstructure with minimal head-to-tail bias was observed. In instances where trans errors were introduced, it was determined that these regions were also syndiotactic. Furthermore, hypothetical reaction intermediates and transition structures were analyzed computationally. Combined experimental a...

Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien)2(μ-1κ,2κ2-AsS4)]n (Ln==Sm, Eu, Gd) and [Ln(dien)2(1κ2-AsS4)] (Ln==Tb, Dy, Ho)

International Nuclear Information System (INIS)

Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian

2013-01-01

Solvothermal reactions of Ln 2 O 3 , As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien) 2 (1κ 2 -AsS 4 )] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln 2 O 3 oxides were converted to [Ln(dien) 2 ] 3+ complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS 4 unit. In 1−3, the AsS 4 units interconnect the [Ln(dien) 2 ] 3+ cations via Ln−S bonds as tridentate μ-1κ,2κ 2 -AsS 4 bridging ligands, resulting in the neutral coordination polymers [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n (Ln1). In 4−6, the AsS 4 units coordinate with the Ln 3+ ion of [Ln(dien) 2 ] 3+ as 1κ 2 -AsS 4 chelating ligands to form neutral coordination compounds [Ln(dien) 2 (1κ 2 -AsS 4 )] (Ln2). The Ln 3+ ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln 3+ ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien) 2 (μ-1κ,2κ 2 -AsS 4 )] n and [Ln(dien) 2 (1κ 2 -AsS 4 )] were prepared by solvothermal methods and the soft Lewis basic AsS 4 3– ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS 4 ligand coordinate Ln 3+ ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors with optical band gaps in the range 2.18−3.21 eV

Synthesis of 7-Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

DEFF Research Database (Denmark)

Håkansson, Anders Eckart; Palmelund, Anders; Holm, H.

2006-01-01

from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product....

Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

KAUST Repository

Wappel, Julia

2016-01-28

A straightforward synthesis utilizing the ring-opening metathesis polymerization (ROMP) reaction is described for acid-triggered N,O-chelating ruthenium-based pre-catalysts bearing one or two 8-quinolinolate ligands. The innovative pre-catalysts were tested regarding their behavior in ROMP and especially for their use in the synthesis of poly(dicyclopentadiene) (pDCPD). Bearing either the common phosphine leaving ligand in the first and second Grubbs olefin metathesis catalysts, or the Ru–O bond cleavage for the next Hoveyda-type catalysts, this work is a step forward towards the control of polymer functionalization and living or switchable polymerizations.

Simple activation by acid of latent Ru-NHC-based metathesis initiators bearing 8-quinolinolate co-ligands

KAUST Repository

Wappel, Julia; Fischer, Roland C; Cavallo, Luigi; Slugovc, Christian; Poater, Albert

2016-01-01

A straightforward synthesis utilizing the ring-opening metathesis polymerization (ROMP) reaction is described for acid-triggered N,O-chelating ruthenium-based pre-catalysts bearing one or two 8-quinolinolate ligands. The innovative pre-catalysts were tested regarding their behavior in ROMP and especially for their use in the synthesis of poly(dicyclopentadiene) (pDCPD). Bearing either the common phosphine leaving ligand in the first and second Grubbs olefin metathesis catalysts, or the Ru–O bond cleavage for the next Hoveyda-type catalysts, this work is a step forward towards the control of polymer functionalization and living or switchable polymerizations.

Metathesis of cardanol over Ru catalysts supported on mesoporousmolecular sieve SBA-15

Czech Academy of Sciences Publication Activity Database

Shinde, Tushar; Varga, Vojtěch; Polášek, Miroslav; Horáček, Michal; Žilková, Naděžda; Balcar, Hynek

2014-01-01

Roč. 478, MAY 2014 (2014), s. 138-145 ISSN 0926-860X R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : cardanol * metathesis * supported catalysts Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.942, year: 2014

About morphology in ethylene-propylene(-diene) copolymers-based latexes

NARCIS (Netherlands)

Tillier, D.L.; Meuldijk, J.; Hoehne, G.W.H.; Frederik, P.M.; Regev, O.; Koning, C.E.

2005-01-01

Coatings and engineering plastics often require high impact strength. This property can be achieved with tougheners. For the present paper, core-shell impact modifiers were synthesized using ethylene–propylene copolymers (EPM), ethylene–propylene-diene copolymers (EPDM) or a mixture of both types

In Situ Generated Ruthenium-Arene Catalyst for Photoactivated Ring-Opening Metathesis Polymerization through Photolatent N-Heterocyclic Carbene Ligand.

Science.gov (United States)

Pinaud, Julien; Trinh, Thi Kim Hoang; Sauvanier, David; Placet, Emeline; Songsee, Sriprapai; Lacroix-Desmazes, Patrick; Becht, Jean-Michel; Tarablsi, Bassam; Lalevée, Jacques; Pichavant, Loïc; Héroguez, Valérie; Chemtob, Abraham

2018-01-09

1,3-Bis(mesityl)imidazolium tetraphenylborate (IMesH + BPh 4 - ) can be synthesized in one step by anion metathesis between the corresponding imidazolium chloride and sodium tetraphenylborate. In the presence of 2-isopropylthioxanthone (sensitizer), an IMes N-heterocyclic carbene (NHC) ligand can be photogenerated under irradiation at 365 nm through coupled electron/proton transfer reactions. By combining this tandem NHC photogenerator system with metathesis inactive [RuCl 2 (p-cymene)] 2 precatalyst, the highly active RuCl 2 (p-cymene)(IMes) complex can be formed in situ, enabling a complete ring-opening metathesis polymerization (ROMP) of norbornene in the matter of minutes at room temperature. To the best of our knowledge, this is the first example of a photogenerated NHC. Its exploitation in photoROMP has resulted in a simplified process compared to current photocatalysts, because only stable commercial or easily synthesized reagents are required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new recursive incremental algorithm for building minimal acyclic deterministic finite automata

NARCIS (Netherlands)

Watson, B.W.; Martin-Vide, C.; Mitrana, V.

2003-01-01

This chapter presents a new algorithm for incrementally building minimal acyclic deterministic finite automata. Such minimal automata are a compact representation of a finite set of words (e.g. in a spell checker). The incremental aspect of such algorithms (where the intermediate automaton is

Striking difference between alkane and olefin metathesis using the well-defined precursor [≡Si-O-WMe5]: Indirect evidence in favour of a bifunctional catalyst W alkylidene-hydride

KAUST Repository

Riache, Nassima; Callens, Emmanuel; Espinas, Jeff; Dé ry, Alexandre; Samantaray, Manoja; Dey, Raju; Basset, Jean-Marie

2015-01-01

Metathesis of linear alkanes catalyzed by the well-defined precursor (≡Si-O-WMe5) affords a wide distribution of linear alkanes from methane up to triacontane. Olefin metathesis using the same catalyst and under the same reaction conditions gives a very striking different distribution of linear α-olefins and internal olefins. This shows that olefin and alkane metathesis processes occur via very different pathways.

Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P2[W2(μ-Br3Br6

Directory of Open Access Journals (Sweden)

Despoina Chriti

2015-12-01

Full Text Available The reactivity of the bimetallic complex (Ph4P2[W2(μ-Br3Br6] ({W 2.5 W}7+, a′2e3 towards ring opening metathesis polymerization (ROMP of norbornene (NBE and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA, is presented. Our results show that addition of a silver salt (AgBF4 is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF producing polyphenylacetylene (PPA in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH2Cl2, providing high yields of polymers. 13C Cross Polarization Magic Angle Spinning (CPMAS spectra of insoluble polynorbornadiene (PNBD and polydicyclopentadiene (PDCPD revealed the operation of two mechanisms (metathetic and radical for cross-linking, with the metathesis pathway prevailing.

Ultrasound-assisted catalytic synthesis of acyclic imides in the presence of p-toluenesulfonic acid under solvent free conditions

Directory of Open Access Journals (Sweden)

Nasr-Esfahani Masoud

2012-01-01

Full Text Available A rapid and convenient preparation of acyclic imides by the reaction of aliphatic and aromatic nitriles with acyclic carboxylic anhydride in the presence of catalytic amounts of p-toluenesulfonic acid under thermal or ultrasonic conditions is reported. The advantages of this procedure are moderate reaction times, good to excellent yields, use of inexpensive and ecofriendly catalyst. The reaction of nitriles with aliphatic anhydrides proceeds in thermal conditions, while by the use of ultrasound irradiations these reactions get accelerated.

Existence principles for inclusions of Hammerstein type involving noncompact acyclic multivalued maps

Directory of Open Access Journals (Sweden)

Jean-Francois Couchouron

2002-01-01

Full Text Available We apply Monch type fixed point theorems for acyclic multivalued maps to the solvability of inclusions of Hammerstein type in Banach spaces. Our approach makes possible to unify and improve the existence theories for nonlinear evolution problems and abstract integral inclusions of Volterra and Fredholm type.

Synergy between Two Metal Catalysts: A Highly Active Silica Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane

KAUST Repository

Samantaray, Manoja

2016-06-01

A well-defined, silica supported, bimetallic precatalyst [≡Si-O-W(Me)5 ≡Si-O-Zr(Np)3](4) has been synthesized for the first time via successively grafting two organometallic complexes [W(CH3)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of Zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON: 1436) than the monometallic W hydride (TON: 650) in metathesis of n-decane at 150 0C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation which occurs on Zr. The produced olefin resulting from a ß–H elimination undergoes easy metathesis on W.

Selective conversion of butane into liquid hydrocarbon fuels on alkane metathesis catalysts

KAUST Repository

Szeto, Kaï Chung

2012-01-01

We report a selective direct conversion of n-butane into higher molecular weight alkanes (C 5+) by alkane metathesis reaction catalysed by silica-alumina supported tungsten or tantalum hydrides at moderate temperature and pressure. The product is unprecedented, asymmetrically distributed towards heavier alkanes. This journal is © 2012 The Royal Society of Chemistry.

Secretion of antiretroviral chemokines by human cells cultured with acyclic nucleoside phosphonates

Czech Academy of Sciences Publication Activity Database

Zídek, Zdeněk; Kmoníčková, Eva; Holý, Antonín

2007-01-01

Roč. 574, - (2007), s. 77-84 ISSN 0014-2999 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z50390512; CEZ:AV0Z40550506 Keywords : Acyclic nucleoside phosphonate * Chemokine * Cytokine Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.376, year: 2007

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

KAUST Repository

Martínez, Juan Pablo

2016-04-10

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Silico Olefin Metathesis with Ru-Based Catalysts Containing N-Heterocyclic Carbenes Bearing C60Fullerenes

KAUST Repository

Martí nez, Juan Pablo; Vummaleti, Sai V. C.; Falivene, Laura; Nolan, Steven P.; Cavallo, Luigi; Solà , Miquel; Poater, Albert

2016-01-01

Density functional theory calculations have been used to explore the potential of Ru-based complexes with 1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes) ligand backbone (A) being modified in silico by the insertion of a C60 molecule (B and C), as olefin metathesis catalysts. To this end, we investigated the olefin metathesis reaction catalyzed by complexes A, B, and C using ethylene as the substrate, focusing mainly on the thermodynamic stability of all possible reaction intermediates. Our results suggest that complex B bearing an electron-withdrawing N-heterocyclic carbene improves the performance of unannulated complex A. The efficiency of complex B is only surpassed by complex A when the backbone of the N-heterocyclic carbene of complex A is substituted by two amino groups. The particular performance of complexes B and C has to be attributed to electronic factors, that is, the electronic-donating capacity of modified SIMes ligand rather than steric effects, because the latter are predicted to be almost identical for complexes B and C when compared to those of A. Overall, this study indicates that such Ru-based complexes B and C might have the potential to be effective olefin metathesis catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly selective Ba2+ separations with acyclic, lipophilic di-[N-(X)sulfonyl carbamoyl] polyethers.

Science.gov (United States)

Elshani, Sadik; Chun, Sangki; Amiri-Eliasi, Bijan; Bartsch, Richard A

2005-01-14

New lipophilic acyclic polyethers with two N-(X)sulfonyl carbamoyl groups of "tunable" acidity exhibit remarkable selectivity for Ba2+ over other alkaline earth metal ions in competitive solvent extraction and transport across polymer inclusion membranes.

Comparison of construction algorithms for minimal, acyclic, deterministic, finite-state automata from sets of strings

NARCIS (Netherlands)

Daciuk, J; Champarnaud, JM; Maurel, D

2003-01-01

This paper compares various methods for constructing minimal, deterministic, acyclic, finite-state automata (recognizers) from sets of words. Incremental, semi-incremental, and non-incremental methods have been implemented and evaluated.

Efforts toward rapid construction of the cortistatin A carbocyclic core via enyne-ene metathesis

KAUST Repository

Baumgartner, Corinne; Ma, Sandy; Liu, Qi; Stoltz, Brian M.

2010-01-01

Our efforts toward the construction of the carbocylic core of cortistatin A via an enyne-ene metathesis are disclosed. Interestingly, an attempted S N2 inversion of a secondary mesylate in our five-membered D-ring piece gave a product with retention

New prodrugs of two pyrimidine acyclic nucleoside phosphonates: Synthesis and antiviral activity

Czech Academy of Sciences Publication Activity Database

Krečmerová, Marcela; Dračínský, Martin; Snoeck, R.; Balzarini, J.; Pomeisl, Karel; Andrei, G.

2017-01-01

Roč. 25, č. 17 (2017), s. 4637-4648 ISSN 0968-0896 R&D Projects: GA ČR(CZ) GA14-00522S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * open-ring * PMEO-DAPy * 5-azacytosine * PME-azaC * HPMP-5-azaC Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.930, year: 2016

Metathesis reactions for the synthesis of ring-fused carbazoles

CSIR Research Space (South Africa)

Pelly, SC

2005-12-09

Full Text Available stream_source_info pelly_2005.pdf.txt stream_content_type text/plain stream_size 48007 Content-Encoding ISO-8859-1 stream_name pelly_2005.pdf.txt Content-Type text/plain; charset=ISO-8859-1 Metathesis Reactions... (99). N,Nminute-Di-tert-butyldicarboxylate-2,2minute-biindolyl-3,3minute-divi- nyl 12. Into a 50-mL two-necked oven-dried flask, fitted with a dropping funnel, was placed MePPh3Br (533 mg, 1.49 mmol), and the contents of the flask were blanketed...

Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

KAUST Repository

Samantaray, Manoja; Kavitake, Santosh Giridhar; Morlanes, Natalia Sanchez; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Dey, Raju; Basset, Jean-Marie

2017-01-01

Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.

Unearthing a Well-Defined Highly Active Bimetallic W/Ti Precatalyst Anchored on a Single Silica Surface for Metathesis of Propane

KAUST Repository

Samantaray, Manoja

2017-02-10

Two compatible organometallic complexes, W(Me)(6) (1) and TiNp4 (2), were successively anchored on a highly dehydroxylated single silica support (SiO2-700) to synthesize the well-defined bimetallic precatalyst [(equivalent to Si-O-)W(Me)(5)(equivalent to Si-O-)Ti(Np)(3)] (4). Precatalyst 4 was characterized at the molecular level using advanced surface organometallic chemistry (SOMC) characterization techniques. The strong autocorrelation observed between methyl of W and Ti in H-1-H-1 multiple-quantum NMR spectra demonstrates that W and Ti species are in close proximity to each other. The bimetallic precatalyst 4, with a turnover number (TON) of 9784, proved to be significantly more efficient than the silica-supported monometallic catalyst [(equivalent to Si-O-)W(Me)(5)] (3), with a TON of 98, for propane metathesis at 150 degrees C in a flow reactor. The dramatic improvement in the activity signifies the cooperativity between Ti and W and indicates that the key step of alkane metathesis (C-H bond activation followed by beta-H elimination) occurs on Ti, followed by olefin metathesis, which occurs on W. We have demonstrated the influence and importance of proximity of Ti to W for achieving such a significantly high activity. This is the first report demonstrating the considerably high activity (TON = 9784) in propane metathesis at moderate temperature (150 degrees C) using a well-defined bimetallic system prepared via the SOMC approach.

A cross-metathesis approach to the stereocontrolled synthesis of the AB ring segment of ciguatoxin

OpenAIRE

Kadota, Isao; Abe, Takashi; Uni, Miyuki; Takamura, Hiroyoshi; Yamamoto, Yoshinori

2008-01-01

Synthesis of the AB ring segments of ciguatoxin is described. The present synthesis includes a Lewis acid mediated cyclization of allylstannane with aldehyde, cross-metathesis reaction introducing the side chain, and Grieco-Nishizawa dehydration on the A ring.

Effect of mating types on amorpha-4, 11-diene production in ...

African Journals Online (AJOL)

user

2012-01-26

Jan 26, 2012 ... pYeDP60/GAPDH/ADS harbouring the amorpha-4,11-diene synthase (ADS) gene was transformed into ... cost and an unreliable supply chain for artemisinin ... production mode which could dramatically reduce the cost of ...

Synthesis, structural studies and biological properties of new TBA analogues containing an acyclic nucleotide.

Science.gov (United States)

Coppola, Teresa; Varra, Michela; Oliviero, Giorgia; Galeone, Aldo; D'Isa, Giuliana; Mayol, Luciano; Morelli, Elena; Bucci, Maria-Rosaria; Vellecco, Valentina; Cirino, Giuseppe; Borbone, Nicola

2008-09-01

A new modified acyclic nucleoside, namely N(1)-(3-hydroxy-2-hydroxymethyl-2-methylpropyl)-thymidine, was synthesized and transformed into a building block useful for oligonucleotide (ON) automated synthesis. A series of modified thrombin binding aptamers (TBAs) in which the new acyclic nucleoside replaces, one at the time, the thymidine residues were then synthesized and characterized by UV, CD, MS, and (1)H NMR. The biological activity of the resulting TBAs was tested by Prothrombin Time assay (PT assay) and by purified fibrinogen clotting assay. From a structural point of view, nearly all the new TBA analogues show a similar behavior as the unmodified counterpart, being able to fold into a bimolecular or monomolecular quadruplex structure depending on the nature of monovalent cations (sodium or potassium) coordinated in the quadruplex core. From the comparison of structural and biological data, some important structure-activity relationships emerged, particularly when the modification involved the TT loops. In agreement with previous studies we found that the folding ability of TBA analogues is more affected by modifications involving positions 4 and 13, rather than positions 3 and 12. On the other hand, the highest anti-thrombin activities were detected for aptamers containing the modification at T13 or T12 positions, thus indicating that the effects produced by the introduction of the acyclic nucleoside on the biological activity are not tightly connected with structure stabilities. It is noteworthy that the modification at T7 produces an ON being more stable and active than the natural TBA.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement; Bukhriakov, Konstantin; Bertrand, Olivier; Vu, Khanh B.; Gohy, Jean-Francois; Hadjichristidis, Nikolaos; Rodionov, Valentin

2016-01-01

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

Ring Opening Metathesis Polymerization of Cyclopentene Using a Ruthenium Catalyst Confined by a Branched Polymer Architecture

KAUST Repository

Mugemana, Clement

2016-03-22

Multi-arm polystyrene stars functionalized with Grubbs-type catalysts in their cores were synthesized and used for the ring-opening metathesis polymerization (ROMP) of cyclopentene. The spatial confinement of the catalytic sites and the nanoscale phase separation between polystyrene and the growing polypentenamer chains lead to a dramatic inhibition of the ROMP termination and chain transfer steps. Consequently, cyclopentene polymerizations proceeded fast and with a high degree of conversion even in air. The Grubbs second generation catalyst was oxidatively inactivated under the same conditions. In contrast to conventional small-molecule catalysts, the ultimate degree of conversion of cyclopentene monomer and the polydispersity of the product polypentenamer are not affected by the temperature. This indicates that spatial confinement of the catalyst resulted in a significant change in the activation parameters for the alkene metathesis ring-opening.

N-Branched acyclic nucleoside phosphonates as monomers for the synthesis of modified oligonucleotides

Czech Academy of Sciences Publication Activity Database

Hocková, Dana; Rosenbergová, Šárka; Ménová, Petra; Páv, Ondřej; Pohl, Radek; Novák, Pavel; Rosenberg, Ivan

2015-01-01

Roč. 13, č. 15 (2015), s. 4449-4458 ISSN 1477-0520 R&D Projects: GA ČR GAP207/11/0108; GA ČR GA13-26526S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * oligonucleotides * solid phase synthesis Subject RIV: CC - Organic Chemistry Impact factor: 3.559, year: 2015

A stereoselective synthesis of (+)-physoperuvine using a tandem aza-Claisen rearrangement and ring closing metathesis reaction.

Science.gov (United States)

Zaed, Ahmed M; Swift, Michael D; Sutherland, Andrew

2009-07-07

A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

Diurnal rhythms in gonadotropins and progesterone in lactating and photoperiod induced acyclic hamsters

International Nuclear Information System (INIS)

Bridges, R.S.; Goldman, B.D.

1975-01-01

Levels of LH, FSH, and progesterone in serum were measured in lactating hamsters and in hamsters in which acyclicity was induced with altered photoperiod. Lactating hamsters were found to have low titers of LH, FSH, and progesterone in serum at 0900 (lights on 0500--1900) on Days 4, 9, 14, and 19 of lactation and increased levels of these hormones at 1600. Levels of LH and FSH in serum at both 0900 and 1600 remained relatively constant throughout lactation. In contrast, levels of progesterone in serum obtained at both 0900 and 1600 sampling times increased as lactation progressed. Ovariectomy on Day 9 of lactation reduced serum levels of progesterone at both 0900 and 1600 and eliminated the afternoon surge in progesterone in animals bled 5 days after surgery. The levels and pattern of LH in serum remained unchanged after ovariectomy in lactating hamsters. However, serum FSH levels in the ovariectomized, lactating animals were elevated at both 0900 and 1600 when compared to levels present in intact, lactating hamsters bled at the same times. Females which were acyclic due to altered photoperiod displayed similar patterns of LH, FSH, and progesterone in serum. Levels of LH, FSH, and progesterone in serum were low at 1000 (lights on 0500--1500) and were increased 2 to 10 fold at 1500. Ovariectomy was followed by lower progesterone levels in serum at 1000 and 1500 and eliminated the afternoon rise of this hormone. Serum levels of LH were unaffected by ovariectomy. As in lactating hamsters, levels of FSH in serum were elevated 3--4 days following ovariectomy at both bleeding times, but the levels were higher at 1500. These results indicate that acyclicity induced by lactation or exposure to a short photoperiod is characterized by similar diurnal patterns of circulating hormones in the hamster

Efforts toward rapid construction of the cortistatin A carbocyclic core via enyne-ene metathesis

KAUST Repository

Baumgartner, Corinne

2010-01-01

Our efforts toward the construction of the carbocylic core of cortistatin A via an enyne-ene metathesis are disclosed. Interestingly, an attempted S N2 inversion of a secondary mesylate in our five-membered D-ring piece gave a product with retention of stereochemistry. © 2010 The Royal Society of Chemistry.

Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Bouhoute, Yassine; Szeto, Kai C.; De Mallmann, Aimery; Barman, Samir; Samantaray, Manoja; Delevoye, Laurent; Gauvin, Ré gis M.; Taoufik, Mostafa; Basset, Jean-Marie

2016-01-01

The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst

KAUST Repository

Merle, Nicolas

2016-12-05

The well-defined silica-supported molybdenum oxo alkyl species (SiO−)MoO(CH Bu) was selectively prepared by grafting of MoO(CH Bu)Cl onto partially dehydroxylated silica (silica) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO/SiO olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

Acyclic ketones in the defensive secretion of a "daddy longlegs" (Leiobunum vittatum).

Science.gov (United States)

Meinwald, J; Kluge, A F; Carrel, J E; Eisner, T

1971-07-01

The defensive secretion of the "daddy longlegs" Leiobunum vittatum was analyzed and found to contain the acyclic ketones 4-methylheptan-3-one and E-4,6-dimethyl-6-octen-3-one as its major organic components. Although 4-methylheptan-3-one has been found previously as an alarm substance in certain ant genera, the second component, whose structure is confirmed by synthesis, is new.

Catalytic Enantioselective Synthesis of Naturally Occurring Butenolides via Hetero-Allylic Alkylation and Ring Closing Metathesis

NARCIS (Netherlands)

Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; Zijl, Anthoni W. van; Fletcher, Stephen P.; Minnaard, Adriaan J.; Feringa, Bernard

2011-01-01

An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey

Solvothermal syntheses, crystal structures, and properties of lanthanide(III) thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln==Sm, Eu, Gd) and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln==Tb, Dy, Ho)

Energy Technology Data Exchange (ETDEWEB)

Wang, Fang; Tang, Chunying; Chen, Ruihong; Zhang, Yong; Jia, Dingxian, E-mail: jiadingxian@suda.edu.cn

2013-10-15

Solvothermal reactions of Ln{sub 2}O{sub 3}, As and S in diethylenetriamine (dien) at 170 °C for 6 days afforded two structural types of lanthanide thioarsenates with the general formulae [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} [Ln=Sm(1), Eu(2), Gd(3)] and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] [Ln=Tb(4), Dy(5), Ho(6)]. The Ln{sub 2}O{sub 3} oxides were converted to [Ln(dien){sub 2}]{sup 3+} complex units in the solvothermal reactions. The As atom binds four S atoms, forming a tetrahedral AsS{sub 4} unit. In 1−3, the AsS{sub 4} units interconnect the [Ln(dien){sub 2}]{sup 3+} cations via Ln−S bonds as tridentate μ-1κ,2κ{sup 2}-AsS{sub 4} bridging ligands, resulting in the neutral coordination polymers [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} (Ln1). In 4−6, the AsS{sub 4} units coordinate with the Ln{sup 3+} ion of [Ln(dien){sub 2}]{sup 3+} as 1κ{sup 2}-AsS{sub 4} chelating ligands to form neutral coordination compounds [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] (Ln2). The Ln{sup 3+} ions are in nine- and eight-coordinated environments in Ln1 and Ln2, respectively. The formation of Ln1 and Ln2 is related with ionic size of the Ln{sup 3+} ions. Optical absorption spectra showed that 1−6 have potential use as semiconductors with the band gaps in the range 2.18−3.21 eV. - Graphical abstract: Two types of Ln-thioarsenates [Ln(dien){sub 2}(μ-1κ,2κ{sup 2}-AsS{sub 4})]{sub n} and [Ln(dien){sub 2}(1κ{sup 2}-AsS{sub 4})] were prepared by solvothermal methods and the soft Lewis basic AsS{sub 4}{sup 3–} ligand to Ln(III) centers with polyamine co-ligand was obtained. Display Omitted - Highlights: • Lanthanide thioarsenates were prepared by solvothermal methods. • The soft Lewis basic AsS{sub 4} ligand coordinate Ln{sup 3+} ions with coexistence polyamine ligands. • Two structural types of Ln-thioarsenates with structural turnover at Tb were obtained along Ln series. • The Ln-thioarsenates are potential semiconductors

The olefin metathesis reaction: reorganization and cyclization of organic compounds

International Nuclear Information System (INIS)

Frederico, Daniel; Brocksom, Ursula; Brocksom, Timothy John

2005-01-01

The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances. (author)

Synthesis of novel aryl brassinosteroids through alkene cross-metathesis and preliminary biological study

Czech Academy of Sciences Publication Activity Database

Kořínková, Petra; Bazgier, V.; Oklešťková, Jana; Rárová, L.; Strnad, Miroslav; Kvasnica, Miroslav

2017-01-01

Roč. 127, NOV (2017), s. 46-55 ISSN 0039-128X R&D Projects: GA ČR GJ15-08202Y; GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : Brassinosteroids * BRI1 receptor kinase * Cross-metathesis * Molecular docking * Organic synthesis * Plant bioassays Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 2.282, year: 2016

Using Ring Strain to Control 4π-Electrocyclization Reactions: Torquoselectivity in Ring Closing of Medium-Ring Dienes and Ring Opening of Bicyclic Cyclobutenes.

Science.gov (United States)

Boon, Byron A; Green, Aaron G; Liu, Peng; Houk, K N; Merlic, Craig A

2017-05-05

Syntheses of strained cyclic dienes were accomplished via palladium(II)-catalyzed oxidative cyclizations of terminal bis(vinylboronate esters). The reactions generate strained (E,E)-1,3-dienes that undergo spontaneous 4π-electrocyclizations to form bicyclic cyclobutenes. Formation of the cyclobutenes is driven by the strain in the medium-ring (E,E)-1,3-diene intermediate. Thermal ring openings of the cyclobutenes give (Z,Z)-1,3-diene products, again for thermodynamic reasons. DFT calculations verified the thermodynamic versus kinetic control of the reactions, and kinetic studies are in excellent agreement with the calculated energy changes. An extension of the tandem coupling/4π-electrocyclization pathway was demonstrated by a palladium(II)-catalyzed oxidative homocoupling/8π-electrocyclization cascade.

Ru-Based Complexes with Quaternary Ammonium Tags Immobilized on Mesoporous Silica as Olefin Metathesis Catalysts

Czech Academy of Sciences Publication Activity Database

Pastva, Jakub; Skowerski, K.; Czarnocki, S. J.; Žilková, Naděžda; Čejka, Jiří; Bastl, Zdeněk; Balcar, Hynek

2014-01-01

Roč. 4, č. 9 (2014), s. 3227-3236 ISSN 2155-5435 R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : olefin metathesis * heterogeneous catalysts * mesoporous molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 9.312, year: 2014

Effect of Support on Metathesis of n-Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica-Alumina

KAUST Repository

Samantaray, Manoja

2015-03-11

[WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.

Effect of Support on Metathesis of n-Decane: Drastic Improvement in Alkane Metathesis with WMe5 Linked to Silica-Alumina

KAUST Repository

Samantaray, Manoja; Dey, Raju; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Basset, Jean-Marie

2015-01-01

[WMe6] (1) supported on the surface of SiO2-Al2O3(500) (2) has been extensively characterized by solid-state NMR spectroscopy, elemental analysis, and gas quantification, which clearly reveal the formation of a mixture of monopodal and bipodal species with the migration of methyl from W to Al. The supported species SiO2-Al2O3(500) (2) transformed at 120°C into two types of carbynic centers, one of which is cationic and the other neutral. These species are very efficient for the metathesis of n-decane. Comparison with already-synthesized neutral bipodal tungsten indicates that the high increase in activity is due to the cationic character of the grafted tungsten.

Fe-catalyzed reactions of 2-chloro-1,7-dienes and allylmalonates

Czech Academy of Sciences Publication Activity Database

Nečas, D.; Drabina, P.; Sedlák, M.; Kotora, Martin

2007-01-01

Roč. 48, č. 26 (2007), s. 4539-4541 ISSN 0040-4039 R&D Projects: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclization * C-C bond cleavage * iron * diene * deallylation Subject RIV: CC - Organic Chemistry Impact factor: 2.615, year: 2007

Pregna-5,17(20)-dien-21-oyl amides affecting sterol and triglyceride biosynthesis in Hep G2 cells.

Science.gov (United States)

Stulov, Sergey V; Mankevich, Olga V; Dugin, Nikita O; Novikov, Roman A; Timofeev, Vladimir P; Misharin, Alexander Yu

2013-04-01

Synthesis of series [17(20)Z]- and [17(20)E]-pregna-5,17(20)-dien-21-oyl amides, containing polar substituents in amide moiety, based on rearrangement of 17α-bromo-21-iodo-3β-acetoxypregn-5-en-20-one caused by amines, is presented. The titled compounds were evaluated for their potency to regulate sterol and triglyceride biosynthesis in human hepatoma Hep G2 cells in comparison with 25-hydroxycholesterol. Three [17(20)E]-pregna-5,17(20)-dien-21-oyl amides at a concentrations of 5 μM inhibited sterol biosynthesis and stimulated triglyceride biosynthesis; their regulatory potency was dependent on the structure of amide moiety; the isomeric [17(20)Z]-pregna-5,17(20)-dien-21-oyl amides were inactive. Copyright © 2013 Elsevier Ltd. All rights reserved.

Metal-catalyzed Asymmetric Hetero-Diels-Alder Reactions of Unactivated Dienes with Glyoxylates

DEFF Research Database (Denmark)

Johannsen, Mogens; Yao, Sulan; Graven, Anette

1998-01-01

The development of a catalytic asymmetric hetero-Diels-Alder methodology for the reaction of unactivated dienes with glyoxylates is presented. Several different asymmetric catalysts can be used, but copper-bisoxazolines and aluminium-BINOL give the highest yield, and the best chemo...

Enzymatic study on AtCCD4 and AtCCD7 and their potential to form acyclic regulatory metabolites

KAUST Repository

Bruno, Mark

2016-09-29

The Arabidopsis carotenoid cleavage dioxygenase 4 (AtCCD4) is a negative regulator of the carotenoid content of seeds and has recently been suggested as a candidate for the generation of retrograde signals that are thought to derive from the cleavage of poly-cis-configured carotene desaturation intermediates. In this work, we investigated the activity of AtCCD4 in vitro and used dynamic modeling to determine its substrate preference. Our results document strict regional specificity for cleavage at the C9–C10 double bond in carotenoids and apocarotenoids, with preference for carotenoid substrates and an obstructing effect on hydroxyl functions, and demonstrate the specificity for all-trans-configured carotenes and xanthophylls. AtCCD4 cleaved substrates with at least one ionone ring and did not convert acyclic carotene desaturation intermediates, independent of their isomeric states. These results do not support a direct involvement of AtCCD4 in generating the supposed regulatory metabolites. In contrast, the strigolactone biosynthetic enzyme AtCCD7 converted 9-cis-configured acyclic carotenes, such as 9-cis-ζ-carotene, 9\\'-cis-neurosporene, and 9-cis-lycopene, yielding 9-cis-configured products and indicating that AtCCD7, rather than AtCCD4, is the candidate for forming acyclic retrograde signals.

Enzymatic study on AtCCD4 and AtCCD7 and their potential to form acyclic regulatory metabolites

KAUST Repository

Bruno, Mark; Koschmieder, Julian; Wuest, Florian; Schaub, Patrick; Fehling-Kaschek, Mirjam; Timmer, Jens; Beyer, Peter; Al-Babili, Salim

2016-01-01

The Arabidopsis carotenoid cleavage dioxygenase 4 (AtCCD4) is a negative regulator of the carotenoid content of seeds and has recently been suggested as a candidate for the generation of retrograde signals that are thought to derive from the cleavage of poly-cis-configured carotene desaturation intermediates. In this work, we investigated the activity of AtCCD4 in vitro and used dynamic modeling to determine its substrate preference. Our results document strict regional specificity for cleavage at the C9–C10 double bond in carotenoids and apocarotenoids, with preference for carotenoid substrates and an obstructing effect on hydroxyl functions, and demonstrate the specificity for all-trans-configured carotenes and xanthophylls. AtCCD4 cleaved substrates with at least one ionone ring and did not convert acyclic carotene desaturation intermediates, independent of their isomeric states. These results do not support a direct involvement of AtCCD4 in generating the supposed regulatory metabolites. In contrast, the strigolactone biosynthetic enzyme AtCCD7 converted 9-cis-configured acyclic carotenes, such as 9-cis-ζ-carotene, 9'-cis-neurosporene, and 9-cis-lycopene, yielding 9-cis-configured products and indicating that AtCCD7, rather than AtCCD4, is the candidate for forming acyclic retrograde signals.

Enzymatic study on AtCCD4 and AtCCD7 and their potential to form acyclic regulatory metabolites

Science.gov (United States)

Bruno, Mark; Koschmieder, Julian; Wuest, Florian; Schaub, Patrick; Fehling-Kaschek, Mirjam; Timmer, Jens; Beyer, Peter; Al-Babili, Salim

2016-01-01

The Arabidopsis carotenoid cleavage dioxygenase 4 (AtCCD4) is a negative regulator of the carotenoid content of seeds and has recently been suggested as a candidate for the generation of retrograde signals that are thought to derive from the cleavage of poly-cis-configured carotene desaturation intermediates. In this work, we investigated the activity of AtCCD4 in vitro and used dynamic modeling to determine its substrate preference. Our results document strict regional specificity for cleavage at the C9–C10 double bond in carotenoids and apocarotenoids, with preference for carotenoid substrates and an obstructing effect on hydroxyl functions, and demonstrate the specificity for all-trans-configured carotenes and xanthophylls. AtCCD4 cleaved substrates with at least one ionone ring and did not convert acyclic carotene desaturation intermediates, independent of their isomeric states. These results do not support a direct involvement of AtCCD4 in generating the supposed regulatory metabolites. In contrast, the strigolactone biosynthetic enzyme AtCCD7 converted 9-cis-configured acyclic carotenes, such as 9-cis-ζ-carotene, 9'-cis-neurosporene, and 9-cis-lycopene, yielding 9-cis-configured products and indicating that AtCCD7, rather than AtCCD4, is the candidate for forming acyclic retrograde signals. PMID:27811075

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas

2017-09-25

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Well-defined silica supported bipodal molybdenum oxo alkyl complexes: a model of the active sites of industrial olefin metathesis catalysts

KAUST Repository

Merle, Nicolas; Le Qué mé ner, Fré dé ric; Barman, Samir; Samantaray, Manoja; Szeto, Kai C.; De Mallmann, Aimery; Taoufik, Mostafa; Basset, Jean-Marie

2017-01-01

A well-defined, silica-supported molybdenum oxo alkyl species, ([triple bond, length as m-dash]SiO-)2Mo([double bond, length as m-dash]O)(CH2tBu)2, was prepared by the selective grafting of Mo([double bond, length as m-dash]O)(CH2tBu)3Cl onto a silica partially dehydroxylated at 200 °C using a rigorous surface organometallic chemistry approach. The immobilized bipodal surface species, partly resembling the active species of industrial MoO3/SiO2 olefin metathesis catalysts, exhibited excellent functional group tolerance in conjunction with its high activity in homocoupling, self and ring closing olefin metathesis.

Synthesis of Heavy Fluorous Ruthenium Metathesis Catalysts Using the Stereoselective Addition of Polyfluoroalkyllithium to Sterically Hindered Diimines

Czech Academy of Sciences Publication Activity Database

Hošek, J.; Rybáčková, M.; Čejka, J.; Cvačka, Josef; Kvíčala, J.

2015-01-01

Roč. 34, č. 13 (2015), s. 3327 -3334 ISSN 0276-7333 Institutional support: RVO:61388963 Keywords : ring-closing metathesis * form tetrasubstituted olefins * N-heterocyclic carbene Subject RIV: CC - Organic Chemistry Impact factor: 4.186, year: 2015

Well-defined polyethylene molecular brushes by polyhomologation and ring opening metathesis polymerization

KAUST Repository

Zhang, Hefeng; Gnanou, Yves; Hadjichristidis, Nikolaos

2014-01-01

A novel strategy using polyhomologation and ring opening metathesis polymerization (ROMP) has been developed for the synthesis of well-defined polyethylene (PE) molecular brushes. Polyhomologation was used to afford an OH-terminated PE, which after transformation to the norbornyl PE macromonomer was subjected to ROMP. Kinetics of ROMP of the PE macromonomer was studied by in situ1H NMR monitoring. The brush structure was proved from HT-GPC, 1H NMR and DSC results.

Design and synthesis of novel bis-annulated caged polycycles via ring-closing metathesis: pushpakenediol

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2014-11-01

Full Text Available Intricate caged molecular frameworks are assembled by an atom economical process via a Diels–Alder (DA reaction, a Claisen rearrangement, a ring-closing metathesis (RCM and an alkenyl Grignard addition. The introduction of olefinic moieties in the pentacycloundecane (PCUD framework at appropriate positions followed by RCM led to the formation of novel heptacyclic cage systems.

C-84 Selective Porphyrin Macrocycle with an Adaptable Cavity Constructed Through Alkyne Metathesis

Energy Technology Data Exchange (ETDEWEB)

Zhang, C. X.; Long, H.; Zhang, W.

2012-06-21

A bisporphyrin macrocycle was constructed from a porphyrin-based diyne monomer in one step through alkyne metathesis. The fullerene binding studies (C{sub 60}, C{sub 70} and C{sub 84}) showed the highest binding affinity of the macrocycle for C{sub 84}, which is in great contrast to its bisporphyrin four-armed cage analogue that showed the strongest binding with C{sub 70}.

Outstanding effects on antithrombin activity of modified TBA diastereomers containing an optically pure acyclic nucleotide analogue.

Science.gov (United States)

Scuotto, M; Persico, M; Bucci, M; Vellecco, V; Borbone, N; Morelli, E; Oliviero, G; Novellino, E; Piccialli, G; Cirino, G; Varra, M; Fattorusso, C; Mayol, L

2014-07-28

Herein, we report optically pure modified acyclic nucleosides as ideal probes for aptamer modification. These new monomers offer unique advantages in exploring the role played in thrombin inhibition by a single residue modification at key positions of the TBA structure.

Acyclic nucleoside phosphonate antivirals activate gene expression of monocyte chemotactic protein 1 and 3.

Czech Academy of Sciences Publication Activity Database

Potměšil, Petr; Holý, Antonín; Kmoníčková, Eva; Křížková, Jana; Zídek, Zdeněk

2007-01-01

Roč. 14, č. 1 (2007), s. 59-66 ISSN 1021-7770 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z50390512; CEZ:AV0Z40550506 Keywords : Acyclic nucleoside phosponate * HIV * Monocyte chemotactic protein Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.024, year: 2007

The preparation of 3-H-labeled Acyclic Nucleoside Phosphonates and Study of their Stability

Czech Academy of Sciences Publication Activity Database

Elbert, Tomáš; Břehová, Petra; Holý, Antonín

2010-01-01

Roč. 75, č. 7 (2010), s. 757-766 ISSN 0010-0765 R&D Projects: GA MŠk 1M0508; GA AV ČR IAA400550801 Institutional research plan: CEZ:AV0Z40550506 Keywords : tritium * 3-H NMR * acyclic nucleotide analogues Subject RIV: CC - Organic Chemistry Impact factor: 0.853, year: 2010

Synthesis, spectroscopic and biological activities studies of acyclic and macrocyclic mono and binuclear metal complexes containing a hard-soft Schiff base.

Science.gov (United States)

Abou-Hussein, Azza A A; Linert, Wolfgang

2012-09-01

Mono- and bi-nuclear acyclic and macrocyclic complexes with hard-soft Schiff base, H(2)L, ligand derived from the reaction of 4,6-diacetylresorcinol and thiocabohydrazide, in the molar ratio 1:2 have been prepared. The H(2)L ligand reacts with Co(II), Ni(II), Cu(II), Zn(II), Mn(II) and UO(2)(VI) nitrates, VO(IV) sulfate and Ru(III) chloride to get acyclic binuclear complexes except for VO(IV) and Ru(III) which gave acyclic mono-nuclear complexes. Reaction of the acyclic mono-nuclear VO(IV) and Ru(III) complexes with 4,6-diacetylresorcinol afforded the corresponding macrocyclic mono-nuclear VO(IV) and Ru(IIII) complexes. Template reactions of the 4,6-diacetylresorcinol and thiocarbohydrazide with either VO(IV) or Ru(III) salts afforded the macrocyclic binuclear VO(IV) and Ru(III) complexes. The Schiff base, H(2)L, ligand acts as dibasic with two NSO-tridentate sites and can coordinate with two metal ions to form binuclear complexes after the deprotonation of the hydrogen atoms of the phenolic groups in all the complexes, except in the case of the acyclic mononuclear Ru(III) and VO(IV) complexes, where the Schiff base behaves as neutral tetradentate chelate with N(2)S(2) donor atoms. The ligands and the metal complexes were characterized by elemental analysis, IR, UV-vis (1)H-NMR, thermal gravimetric analysis (TGA) and ESR, as well as the measurements of conductivity and magnetic moments at room temperature. Electronic spectra and magnetic moments of the complexes indicate the geometries of the metal centers are either tetrahedral, square planar or octahedral. Kinetic and thermodynamic parameters were calculated using Coats-Redfern equation, for the different thermal decomposition steps of the complexes. The ligands and the metal complexes were screened for their antimicrobial activity against Staphylococcus aureus as Gram-positive bacteria, and Pseudomonas fluorescens as Gram-negative bacteria in addition to Fusarium oxysporum fungus. Most of the complexes exhibit

Design and Synthesis of Fluorescent Acyclic Nucleoside Phosphonates as Potent Inhibitors of Bacterial Adenylate Cyclases

Czech Academy of Sciences Publication Activity Database

Břehová, Petra; Šmídková, Markéta; Skácel, Jan; Dračínský, Martin; Mertlíková-Kaiserová, Helena; Velasquez, M. P. S.; Watts, V. J.; Janeba, Zlatko

2016-01-01

Roč. 11, č. 22 (2016), s. 2534-2546 ISSN 1860-7179 R&D Projects: GA MV VG20102015046; GA MŠk LO1302 Institutional support: RVO:61388963 Keywords : adenylate cyclase toxin * acyclic nucleoside phosphonates * anthranilic acid Subject RIV: CC - Organic Chemistry Impact factor: 3.225, year: 2016

Acyclic Ketones in the Defensive Secretion of a “Daddy Longlegs” (Leiobunum vittatum)

Science.gov (United States)

Meinwald, J.; Kluge, A. F.; Carrel, J. E.; Eisner, T.

1971-01-01

The defensive secretion of the “daddy longlegs” Leiobunum vittatum was analyzed and found to contain the acyclic ketones 4-methylheptan-3-one and E-4,6-dimethyl-6-octen-3-one as its major organic components. Although 4-methylheptan-3-one has been found previously as an alarm substance in certain ant genera, the second component, whose structure is confirmed by synthesis, is new. PMID:5283937

Hoveyda-Grubbs type metathesis catalyst immobilized on mesoporous molecular sieves MCM-41 and SBA-15

Czech Academy of Sciences Publication Activity Database

Balcar, Hynek; Shinde, Tushar; Žilková, Naděžda; Bastl, Zdeněk

2011-01-01

Roč. 7, January (2011), s. 22-28 ISSN 1860-5397 R&D Projects: GA AV ČR IAA400400805; GA AV ČR KAN100400701 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkene metathesis * catalyst immobilization * hybrid catalysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.517, year: 2011

Study of epoxidation and its influence on the poly dienes behavior

International Nuclear Information System (INIS)

Rocha, Tatiana L.A.C.; Schuster, Robert H.; Meier, Jens; Jacobi, Marly M.; Samios, Dimitrios

2001-01-01

The poly dienes epoxidation is a good method to modify the backbone chain, improving some of its properties. The epoxidation rate changes with the time and reaction temperature, epoxidize agent and polymer microstructure. There are two kinds of different kinetic behavior during the reaction of epoxidation, which are related to the epoxidation of trans 1,4 and cis 1,4 double bonds. An increase in the epoxidation content leads to an increase in the glass temperature (Tg) in all materials studied. Tailor-made linear poly dienes modified by epoxidation also show shifts of the flow region of the viscoelastic spectra to lower frequencies and significant changes in the dynamic mechanical storage and loss moduli. With higher side group density, the plateau modulus decreases due to lower entanglement density and the frequency limits of the rubber elastic region shift to lower values. Higher molecular weights shift the onset of the flow region towards lower frequencies extending the rubbery plateau. The predictions of refined tube models, which are derived directly from molecular considerations are in good correlation with the experimental data. (author)

Investigating temporary acyclicity in a captive group of Asian elephants (Elephas maximus): Relationship between management, adrenal activity and social factors.

Science.gov (United States)

Edwards, Katie L; Trotter, Jessica; Jones, Martin; Brown, Janine L; Steinmetz, Hanspeter W; Walker, Susan L

2016-01-01

Routine faecal steroid monitoring has been used to aid the management of five captive Asian elephant (Elephas maximus) females at Chester Zoo, UK, since 2007. Progestagen analysis initially revealed synchronised oestrous cycles among all females. However, a 14- to 20-week period of temporary acyclicity subsequently occurred in three females, following several management changes (increased training, foot-care and intermittent matriarch removal for health reasons) and the initiation of pregnancy in another female. The aim of this study was to retrospectively investigate whether these management changes were related to increased adrenal activity and disruption of ovarian activity, or whether social factors may have been involved in the temporary cessation of cyclicity. Faecal samples collected every other day were analysed to investigate whether glucocorticoid metabolites were related to reproductive status (pregnant, cycling, acyclic) or management (training, foot-care, matriarch presence). Routine training and foot-care were not associated with adrenal activity; however, intensive foot-care to treat an abscess in one female was associated with increased glucocorticoid concentration. Matriarch presence influenced adrenal activity in three females, being lower when the matriarch was separated from the group at night compared to being always present. However, in the females that exhibited temporary acyclicity, there was no consistent relationship between glucocorticoids and cyclicity state. Although the results of this study do not fully explain this occurrence, the highly synchronised nature of oestrous cycles within this group, and the concurrent acyclicity in three females, raises the question of whether social factors could have been involved in the temporary disruption of ovarian activity. Copyright © 2015 Elsevier Inc. All rights reserved.

Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

KAUST Repository

Tretiakov, Mykyta

2018-03-27

Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104). We demonstrated that the present catalysts are much better than the previously reported (tantalum hydride/KCC-1, TON 786) catalyst. For the first time, we observed the formation of n-decane from propene, which enables us to think of using cheaper raw materials and converting them to petroleum range alkanes using hydro-metathesis reaction.

Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

KAUST Repository

Morandi, Bill

2013-07-26

Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

Regioselective Wacker Oxidation of Internal Alkenes: Rapid Access to Functionalized Ketones Facilitated by Cross-Metathesis

KAUST Repository

Morandi, Bill; Wickens, Zachary K.; Grubbs, Robert H.

2013-01-01

Wacka wacka: The title reaction makes use of a wide range of directing groups (DG) to enable the highly regioselective oxidation of alkenes, and occurs predictably at the distal position. Both E and Z alkenes afford valuable functionalized ketones and cross-metathesis was shown to facilitate the preparation of the starting materials. BQ=benzoquinone.

1,5-Bis (2-Hydroxyphenyl)Pent-1,4-Diene-3-One: A Lead ...

African Journals Online (AJOL)

NJD

occurring chalcone nucleus to design effective antibacterial agents. The present investigation established 1,5-bis(2-hydroxyphenyl)pent-1,4-diene-3-one (1c) as a lead compound with potential against a panel of pathogenic bacterial strains, ...

Energetics of the ruthenium-halide bond in olefin metathesis (pre)catalysts

KAUST Repository

Falivene, Laura; Poater, Albert; Cazin, Catherine S J; Slugovc, Christian; Cavallo, Luigi

2013-01-01

A DFT analysis of the strength of the Ru-halide bond in a series of typical olefin metathesis (pre)catalysts is presented. The calculated Ru-halide bond energies span the rather broad window of 25-43 kcal mol-1. This indicates that in many systems dissociation of the Ru-halide bond is possible and is actually competitive with dissociation of the labile ligand generating the 14e active species. Consequently, formation of cationic Ru species in solution should be considered as a possible event. © 2013 The Royal Society of Chemistry.

SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

KAUST Repository

Qureshi, Ziyauddin

2017-01-05

Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

SOMC-Designed Silica Supported Tungsten Oxo Imidazolin-2-iminato Methyl Precatalyst for Olefin Metathesis Reactions

KAUST Repository

Qureshi, Ziyauddin; Hamieh, Ali Imad Ali; Barman, Samir; Maity, Niladri; Samantaray, Manoja; Ould-Chikh, Samy; Abou-Hamad, Edy; Falivene, Laura; D’ Elia, Valerio; Rothenberger, Alexander; Llorens, Isabelle; Hazemann, Jean-Louis; Basset, Jean-Marie

2017-01-01

Synthesis, structure, and olefin metathesis activity of a surface complex [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4) (ImDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-iminato) supported on silica by a surface organometallic chemistry (SOMC) approach are reported. The reaction of N-silylated 2-iminoimidazoline with tungsten(VI) oxytetrachloride generated the tungsten oxo imidazolin-2-iminato chloride complex [ImDippNW(═O)Cl3] (2). This was grafted on partially dehydroxylated silica pretreated at 700 °C (SiO2-700) to afford a well-defined monopodal surface complex [(≡Si-O-)W(═O)Cl2-ImDippN] (3). 3 underwent alkylation by ZnMe2 to produce [(≡Si-O-)W(═O)(CH3)2-ImDippN] (4). The alkylated surface complex was thoroughly characterized by solid-state NMR, elemental microanalysis, Raman, FT-IR spectroscopies, and XAS analysis. 4 proved to be an active precatalyst for self-metathesis of terminal olefins such as propylene and 1-hexene.

The efficient synthesis of 2-arylpyrimidine acyclic nucleoside phosphonates using Liebeskind-Srogl cross-coupling reaction

Czech Academy of Sciences Publication Activity Database

Břehová, Petra; Česnek, Michal; Dračínský, Martin; Holý, Antonín; Janeba, Zlatko

2011-01-01

Roč. 67, č. 38 (2011), s. 7379-7385 ISSN 0040-4020 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : Liebeskind-Srogl cross - coupling * acyclic nucleoside phosphonates * pyrimidines * arylboronic acids * microwave Subject RIV: CC - Organic Chemistry Impact factor: 3.025, year: 2011

Nitroso Diels-Alder (NDA) Reaction as an Efficient Tool for the Functionalization of Diene-Containing Natural Products

Science.gov (United States)

Carosso, Serena; Miller, Marvin J.

2014-01-01

This review describes the use of nitroso Diels-Alder reactions for the functionalization of complex diene-containing natural products in order to generate libraries of compounds with potential biological activity. The application of this methodology to the structural modification of a series of natural products (thebaine, steroidal dienes, rapamycin, leucomycin, colchicine, isocolchicine and piperine) is discussed using relevant examples from the literature from 1973 onwards. The biological activity of the resulting compounds is also discussed. Additional comments are provided that evaluate the methodology as a useful tool in organic, bioorganic and medicinal chemistry. PMID:25119424

Synthesis of alpha-Branched Acyclic Nucleoside Phosphonates as Potential Inhibitors of Bacterial Adenylate Cyclases

Czech Academy of Sciences Publication Activity Database

Frydrych, Jan; Skácel, Jan; Šmídková, Markéta; Mertlíková-Kaiserová, Helena; Dračínský, Martin; Gnanasekaran, Ramachandran; Lepšík, Martin; Soto-Velasquez, M.; Watts, V. J.; Janeba, Zlatko

2018-01-01

Roč. 13, č. 2 (2018), s. 199-206 ISSN 1860-7179 R&D Projects: GA MV VG20102015046; GA ČR(CZ) GBP208/12/G016; GA MŠk LO1302 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * adenylate cyclase toxin * bisamidates * Bordetella pertussis * prodrugs Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.225, year: 2016

Serendipitous preparation of fac-(acetonitrile-κNtrichlorido[(1,2,5,6-η-cycloocta-1,5-diene]iridium(III

Directory of Open Access Journals (Sweden)

David M. Morris

2015-04-01

Full Text Available A reaction between [(CODIrCl]2 (COD is cycloocta-1,5-diene, HCl and indene failed to provide the hoped for chloridoindenyliridium dimer, but instead produced the title compound, [IrCl3(CH3CN(C8H12], which is an octahedral complex of iridium(III with a chelating cycloocta-1,5-diene ligand, three chloride ligands in a fac arrangement, and one acetonitrile ligand. Attempts to devise a rational synthesis for the title compound were unsuccessful.

Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

KAUST Repository

Saggio, Guillaume; Taoufik, Mostafa; Basset, Jean-Marie; Thivolle-Cazat, Jean

2010-01-01

Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease

Inhibition of hypoxanthine-guanine phosphoribosyltransferase by acyclic nucleoside phosphonates: A new class of antimalarial therapeutics

Czech Academy of Sciences Publication Activity Database

Keough, D. T.; Hocková, Dana; Holý, Antonín; Naesens, L.; Skinner-Adams, T. S.; de Jersey, J.; Guddat, L. W.

2009-01-01

Roč. 52, č. 14 (2009), s. 4391-4399 ISSN 0022-2623 R&D Projects: GA MŠk 1M0508; GA AV ČR 1QS400550501 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * phosphoribosyltransferase * enzyme inhibitors * Plasmodium falciparum Subject RIV: CC - Organic Chemistry Impact factor: 4.802, year: 2009

Dynamic behaviour of tantalum hydride supported on silica or MCM-41 in the metathesis of alkanes

KAUST Repository

Soignier, Sophie

2014-01-01

The metathesis of ethane and propane catalysed by tantalum hydride supported on silica or MCM-41 was studied under static and dynamic conditions. During the reaction, the rate decreased over time, indicating deactivation of the catalyst. The evolution of the catalytic system and surface species over time was monitored by various physico-chemical methods: FTIR, 13C NMR spectroscopy, elemental analysis and chemical reactivity. A carbonaceous deposit composed of unsaturated hydrocarbyl species was observed by 13C NMR. This deposit was responsible for poisoning of the catalyst. The deactivation of the catalyst proved more severe at higher temperatures and under static rather than dynamic conditions. A partial regeneration of the catalyst could be achieved during a series of repeated runs. Mechanistically, the deconvolution of the products\\' distribution over time indicated the occurrence of hydrogenolysis in the early stages of the reaction, while pure metathesis dominated later on. The hydrogen was supplied by the dehydrogenation of hydrocarbyl surface species involved in the deactivation process. © 2014 The Royal Society of Chemistry.

Dynamic behaviour of tantalum hydride supported on silica or MCM-41 in the metathesis of alkanes

KAUST Repository

Soignier, Sophie; Saggio, Guillaume; Taoufik, Mostafa; Basset, Jean-Marie; Thivolle-Cazat, Jean

2014-01-01

The metathesis of ethane and propane catalysed by tantalum hydride supported on silica or MCM-41 was studied under static and dynamic conditions. During the reaction, the rate decreased over time, indicating deactivation of the catalyst. The evolution of the catalytic system and surface species over time was monitored by various physico-chemical methods: FTIR, 13C NMR spectroscopy, elemental analysis and chemical reactivity. A carbonaceous deposit composed of unsaturated hydrocarbyl species was observed by 13C NMR. This deposit was responsible for poisoning of the catalyst. The deactivation of the catalyst proved more severe at higher temperatures and under static rather than dynamic conditions. A partial regeneration of the catalyst could be achieved during a series of repeated runs. Mechanistically, the deconvolution of the products' distribution over time indicated the occurrence of hydrogenolysis in the early stages of the reaction, while pure metathesis dominated later on. The hydrogen was supplied by the dehydrogenation of hydrocarbyl surface species involved in the deactivation process. © 2014 The Royal Society of Chemistry.

Enhanced Topical and Transdermal Delivery of Antineoplastic and Antiviral Acyclic Nucleoside Phosphonate cPr-PMEDAP

Czech Academy of Sciences Publication Activity Database

Vávrová, K.; Kovaříková, P.; Školová, B.; Líbalová, M.; Roh, J.; Čáp, R.; Holý, Antonín; Hrabálek, A.

2011-01-01

Roč. 28, č. 12 (2011), s. 3105-3115 ISSN 0724-8741 R&D Projects: GA MŠk 1M0508 Grant - others:GA ČR(CZ) GAP207/11/0365 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * antivirals * antineoplastics * permeation enhancer * topical skin application * transdermal delivery Subject RIV: CC - Organic Chemistry Impact factor: 4.093, year: 2011

Synthesis of Heterocycles through a Ruthenium‐Catalyzed Tandem Ring‐Closing Metathesis/Isomerization/N‐Acyliminium Cyclization Sequence

DEFF Research Database (Denmark)

Ascic, Erhad; Jensen, Jakob Feldthusen; Nielsen, Thomas Eiland

2011-01-01

Tandem bicycle: In the title reaction double bonds created during ring-closing metathesis isomerize to generate reactive iminium intermediates that undergo intramolecular cyclization reactions with tethered heteroatom and carbon nucleophiles. In this way, a series of biologically interesting hete...... heterocyclic compounds can be made, including a known precursor for the total synthesis of the antiparasitic natural product harmicine....

Metathesis of 2-pentene over Mo and W supported mesoporous molecular sieves MCM-41 and SBA-15

Czech Academy of Sciences Publication Activity Database

Ibrahim, M. A.; Akhtar, M. N.; Čejka, Jiří; Montanari, E.; Balcar, Hynek; Kubů, Martin; Al-Khattaf, S. S.

2017-01-01

Roč. 53, SEP 2017 (2017), s. 119-126 ISSN 1226-086X R&D Projects: GA ČR(CZ) GAP106/12/0189 Institutional support: RVO:61388955 Keywords : metathesis * MCM-41 * SBA-15 Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.421, year: 2016

Structure-Activity Relationships of Acyclic Selenopurine Nucleosides as Antiviral Agents

Directory of Open Access Journals (Sweden)

Pramod K. Sahu

2017-07-01

Full Text Available A series of acyclic selenopurine nucleosides 3a–f and 4a–g were synthesized based on the bioisosteric rationale between oxygen and selenium, and then evaluated for antiviral activity. Among the compounds tested, seleno-acyclovir (4a exhibited the most potent anti-herpes simplex virus (HSV-1 (EC50 = 1.47 µM and HSV-2 (EC50 = 6.34 µM activities without cytotoxicity up to 100 µM, while 2,6-diaminopurine derivatives 4e–g exhibited significant anti-human cytomegalovirus (HCMV activity, which is slightly more potent than the guanine derivative 4d, indicating that they might act as prodrugs of seleno-ganciclovir (4d.

Reaction of acyclic enaminones with methoxymethylene meldrum's acid: synthetic and structural implications

OpenAIRE

Cunha,Silvio; Silva,Viviane C. da; Napolitano,Hamilton B.; Lariucci,Carlito; Vencato,Ivo

2003-01-01

The reaction of acyclic enaminones with methoxymethylene Meldrum's acid afforded N-adduct and/or C-adduct of enaminones in moderate to good yields. The regiochemistry of this reaction depends on the N-amino substituent of the enaminone. The C-adduct is a precursor to 2-pyridones. X-ray analysis of two N-adducts were investigated and the Z-s-Z configuration assigned. A reação de enaminonas com o derivado metoximetilênico do ácido de Meldrum forneceu N-adutos e/ou C-adutos das enaminonas, em...

Synthesis of [diene-"1"4C] curcumin at high specific activity

International Nuclear Information System (INIS)

Filer, Crist N.; Lacy, James M.; Wright, Christopher

2016-01-01

An efficient method is described to label curcumin with "1"4C at high specific activity. - Highlights: • This paper describes the synthesis of ["1"4C] Curcumin at the highest specific activity and total activity amount yet reported. • The "1"4C label was installed in the diene framework of Curcumin. • This paper also describes the characterization of ["1"4C] Curcumin by HPLC and mass spectrometry.

From ruthenium olefin metathesis catalyst to (η5-3- phenylindenyl)hydrido complex via alcoholysis

KAUST Repository

Manzini, Simone; Nelson, David J.; Lé bl, Tomá š; Poater, Albert; Cavallo, Luigi; Slawin, Alexandra M. Z.; Nolan, Steven P.

2014-01-01

The synthesis and characterisation of [Ru(H)(η5-3- phenylindenyl)(iBu-Phoban)2] 4 is reported ( iBu-Phoban = 9-isobutyl-9-phosphabicyclo-[3.3.1]-nonane). 4 is obtained via alcoholysis of metathesis pre-catalyst M11, in a process that was previously thought to be limited to analogous complex [RuCl 2(PPh3)2(3-phenylindenylidene)] (M 10). This journal is © The Royal Society of Chemistry.

Interaction of phosphates of the acyclic nucleoside phosphonates with nucleoside diphosphate kinase from yeast and bovine liver

Czech Academy of Sciences Publication Activity Database

Horská, Květoslava; Votruba, Ivan; Holý, Antonín

2006-01-01

Roč. 71, č. 1 (2006), s. 35-43 ISSN 0010-0765 R&D Projects: GA AV ČR(CZ) IBS4055109 Institutional research plan: CEZ:AV0Z40550506 Keywords : enzymatic phosphorylation * acyclic nucleotide analogs * NTP analogues Subject RIV: CC - Organic Chemistry Impact factor: 0.881, year: 2006

Copper-Catalyzed Heteroarylboration of 1,3-Dienes with 3-Bromopyridines: A cine Substitution.

Science.gov (United States)

Smith, Kevin B; Huang, Yuan; Brown, M Kevin

2018-04-26

A method for the heteroarylboration of 1,3-dienes is presented. The process involves an unusual cine substitution of 3-bromopyridine derivatives to deliver highly functionalized heterocyclic products. Mechanistic studies are included that clarify the details of this unusual process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simple addition of silica to an alkane solution of Wilkinson WMe6 or Schrock W alkylidyne complex give active complex for saturated and unsaturated hydrocarbons metathesis

KAUST Repository

Callens, Emmanuel

2015-08-24

Addition of PDA silica to a solution of the Wilkinson WMe6 as well as the Schrock W neopentilidyne tris neopentyl complex catalyzes linear or cyclic alkanes to produce respectively a distribution of linear alkanes from methane up to triacontane or a mixture of cyclic and macrocyclic hydrocarbons. This single catalytic system transforms also linear α-olefins into higher and lower homologues via isomerization/metathesis mechanism (ISOMET). This complex is also efficient towards functionalized olefins. Unsaturated fatty acid esters (FAEs) are converted into diesters corresponding to self-metathesis products.

Acyclic nucleoside bisphosphonates: Synthesis and properties of chiral 2-amino-4,6-bis[(phosphonomethoxy)alkoxy]pyrimidines

Czech Academy of Sciences Publication Activity Database

Doláková, Petra; Dračínský, Martin; Masojídková, Milena; Šolínová, Veronika; Kašička, Václav; Holý, Antonín

2009-01-01

Roč. 44, č. 6 (2009), s. 2408-2424 ISSN 0223-5234 R&D Projects: GA MŠk 1M0508 Grant - others:NIH(US) 1UC1AIO62540-01 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * pyrimidine * bisphosphonates Subject RIV: CC - Organic Chemistry Impact factor: 3.269, year: 2009

Cyclic phosphopeptides for interference with Grb2 SH2 domain signal transduction prepared by ring-closing metathesis and phosphorylation

NARCIS (Netherlands)

Dekker, Frank J; de Mol, Nico J; Fischer, Marcel J E; Kemmink, Johan; Liskamp, Rob M J; Dekker, Frank

2003-01-01

Cyclic phosphopeptides were prepared using ring-closing metathesis followed by phosphorylation. These cyclic phosphopeptides were designed to interact with the SH2 domain of Grb2, which is a signal transduction protein of importance as a target for antiproliferative drug development. Binding of

Dien Hoetink. 'Bij benadering'. Biografie van een landbouw-juriste in crisis- en oorlogstijd

NARCIS (Netherlands)

Kamp, van J.E.

2005-01-01

A woman with a university degree who makes a career outside of the home was rather exceptional in the first half of the twentieth century. This biography about Dien Hoetink (1904-1945) describes her legal work in Dutch agriculture between 1933 and 1945.It attemps to answer the

Acid-Labile Acyclic Cucurbit[n]uril Molecular Containers for Controlled Release.

Science.gov (United States)

Mao, Dake; Liang, Yajun; Liu, Yamin; Zhou, Xianhao; Ma, Jiaqi; Jiang, Biao; Liu, Jia; Ma, Da

2017-10-02

Stimuli-responsive molecular containers are of great importance for controlled drug delivery and other biomedical applications. A new type of acid labile acyclic cucurbit[n]uril (CB[n]) molecular containers is presented that can degrade and release the encapsulated cargo at accelerated rates under mildly acidic conditions (pH 5.5-6.5). These containers retain the excellent recognition properties of CB[n]-type hosts. A cell culture study demonstrated that the cellular uptake of cargos could be fine-tuned by complexation with different containers. The release and cell uptake of cargo dye was promoted by acidic pH. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low-temperature synthesis of actinide tetraborides by solid-state metathesis reactions

Science.gov (United States)

Lupinetti, Anthony J [Los Alamos, NM; Garcia, Eduardo [Los Alamos, NM; Abney, Kent D [Los Alamos, NM

2004-12-14

The synthesis of actinide tetraborides including uranium tetraboride (UB.sub.4), plutonium tetraboride (PuB.sub.4) and thorium tetraboride (ThB.sub.4) by a solid-state metathesis reaction are demonstrated. The present method significantly lowers the temperature required to .ltoreq.850.degree. C. As an example, when UCl.sub.4 is reacted with an excess of MgB.sub.2, at 850.degree. C., crystalline UB.sub.4 is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl.sub.3 as the initial step in the reaction. The UB.sub.4 product is purified by washing water and drying.

Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

KAUST Repository

Poater, Albert; Correa, Andrea; Pump, Eva; Cavallo, Luigi

2014-01-01

In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

Cis/trans Coordination in olefin metathesis by static and molecular dynamic DFT calculations

KAUST Repository

Poater, Albert

2014-05-25

In regard to [(N-heterocyclic carbene)Ru]-based catalysts, it is still a matter of debate if the substrate binding is preferentially cis or trans to the N-heterocyclic carbene ligand. By means of static and molecular dynamic DFT calculations, a simple olefin, like ethylene, is shown to be prone to the trans binding. Bearing in mind the higher reactivity of trans isomers in olefin metathesis, this insight helps to construct small alkene substrates with increased reactivity. © 2014 Springer Science+Business Media New York.

Olefin cross metathesis based de novo synthesis of a partially protected L-amicetose and a fully protected L-cinerulose derivative

Directory of Open Access Journals (Sweden)

Bernd Schmidt

2014-05-01

Full Text Available Cross metathesis of a lactate derived allylic alcohol and acrolein is the entry point to a de novo synthesis of 4-benzoate protected L-amicetose and a cinerulose derivative protected at C5 and C1.

Dienes AEM as an alternative mathematics teaching aid to enhance Indonesian students’ understanding of algebra concept

Science.gov (United States)

Soro, S.; Maarif, S.; Kurniawan, Y.; Raditya, A.

2018-01-01

The aim of this study is to find out the effect of Dienes AEM (Algebra Experience Materials) on the ability of understanding concept of algebra on the senior high school student in Indonesia. This research is an experimental research with subject of all high school students in Indonesia. The samples taken were high school students in three provinces namely DKI Jakarta Province, West Java Province and Banten Province. From each province was taken senior high school namely SMA N 9 Bekasi West Java, SMA N 94 Jakarta and SMA N 5 Tangerang, Banten. The number of samples in this study was 114 high school students of tenth grade as experimental class and 115 high school students of tenth grade as control class. Learning algebra concept is needed in learning mathematics, besides it is needed especially to educate students to be able to think logically, systematically, critically, analytically, creatively, and cooperation. Therefore in this research will be developed an effective algebra learning by using Dienes AEM. The result of this research is that there is a significant influence on the students’ concept comprehension ability taught by using Dienes AEM learning as an alternative to instill the concept of algebra compared to the students taught by conventional learning. Besides, the students’ learning motivation increases because students can construct the concept of algebra with props.

Comparative reactivity of different types of stable cyclic and acyclic mono- and diamino carbenes with simple organic substrates.

Science.gov (United States)

Martin, David; Canac, Yves; Lavallo, Vincent; Bertrand, Guy

2014-04-02

A series of stable carbenes, featuring a broad range of electronic properties, were reacted with simple organic substrates. The N,N-dimesityl imidazolylidene (NHC) does not react with isocyanides, whereas anti-Bredt di(amino)carbene (pyr-NHC), cyclic (alkyl)(amino)carbene (CAAC), acyclic di(amino)carbene (ADAC), and acyclic (alkyl)(amino)carbene (AAAC) give rise to the corresponding ketenimines. NHCs are known to promote the benzoin condensation, and we found that the CAAC, pyr-NHC, and ADAC react with benzaldehyde to give the ketone tautomer of the Breslow intermediate, whereas the AAAC first gives the corresponding epoxide and ultimately the Breslow intermediate, which can be isolated. Addition of excess benzaldehyde to the latter does not lead to benzoin but to a stable 1,3-dioxolane. Depending on the electronic properties of carbenes, different products are also obtained with methyl acrylate as a substrate. The critical role of the carbene electrophilicity on the outcome of reactions is discussed.

Developing new methods for the mono-end functionalization of living ring opening metathesis polymers.

Science.gov (United States)

Kilbinger, Andreas F M

2012-01-01

In this article we present a review of our recent results in one area of research we are involved in. All research efforts in our group focus on functional polymers and new ways of gaining higher levels of control with regard to the placement of functional groups within these polymers. Here, the living ring opening metathesis polymerization (ROMP) will be reviewed for which end-functionalization methods had been rare until very recently. Polymers carrying particular functional groups only at the chain-ends are, however, very interesting for a variety of industrial and academic applications. Polymeric surfactants and polymer-protein conjugates are two examples for the former and polymer-β-sheet-peptide conjugates one example for the latter. The functionalization of macroscopic or nanoscopic surfaces often relies on mono-end functional polymers. Complex macromolecular architectures are often constructed from macromolecules carrying exactly one functional group at their chain- end. The ring opening metathesis polymerization is particularly interesting in this context as it is one of the most functional group tolerant polymerization methods known. Additionally, high molecular weight polymers are readily accessible with this technique, a feature that living radical polymerizations often struggle to achieve. Finding new ways of functionalizing the polymer chain-end of ROMP polymers has therefore been a task long overdue. Here, we present our contribution to this area of research.

Characterization of E and Z isomers in macrocyclic lactones and acyclic pheromones by NMR spectra

International Nuclear Information System (INIS)

Mahajan, J.R.; Resck, I.S.; Braz Filho, R.; Carvalho, M.G. de

1995-01-01

A large proportion of pheromones, isolated from a variety of insects, constitutes a big list of diversely functionalized acyclic compounds, which have been synthesized by several routes. Catalytic or chemical methods were examined for the Z to E isomerization and their efficiency checked by 1 H and 13 C NMR spectra. Nuclear magnetic resonance has been used to identify and characterize molecular structure of the compounds, besides chemical shifts was analysed

A kinetics and mechanistic study of the OH and NO₂ initiated oxidation of cyclohexa-1,3-diene in the gas phase

DEFF Research Database (Denmark)

Jenkin, M. E.; Andersen, Mads Peter Sulbæk; Hurley, M. D.

2005-01-01

The kinetics and products of the OH and NO2-initiated oxidation of cyclohexa-1,3-diene have been investigated at 296 K and 700 Torr using long path FTIR spectroscopy. Relative rate methods were employed using the photolysis of cyclohexa-1,3-diene/CH3ONO/NO/air mixtures to measure k(OH + cyclohexa...

Classical Example of Total Kinetic and Thermodynamic Control: The Diels-Alder Reaction between DMAD and Bis-furyl Dienes.

Science.gov (United States)

Borisova, Kseniya K; Kvyatkovskaya, Elizaveta A; Nikitina, Eugeniya V; Aysin, Rinat R; Novikov, Roman A; Zubkov, Fedor I

2018-04-20

A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic 1 H NMR spectroscopy.

Carbohydrate carbocyclization by a zinc-mediated tandem reaction and ring-closing enyne metathesis

DEFF Research Database (Denmark)

Poulsen, Carina Storm; Madsen, Robert

2002-01-01

reaction, an amino group can be introduced in the 1,7-enyne products. Addition of 2-TMS-ethynylcerium(III) chloride after the reductive ring-opening produces the corresponding 1,6-enynes. Further annulation of the product 1,3-dienes can be achieved through a Diels-Alder reaction with good control of stereo...

Synthesis and Evaluation of Novel Acyclic Nucleoside Phosphonates as Inhibitors of Plasmodium falciparum and Human 6-Oxopurine Phosphoribosyltransferases

Czech Academy of Sciences Publication Activity Database

Kaiser, Martin Maxmilian; Hocková, Dana; Wang, T. H.; Dračínský, Martin; Poštová Slavětínská, Lenka; Procházková, Eliška; Edstein, M. D.; Chavchich, M.; Keough, D. T.; Guddat, L. W.; Janeba, Zlatko

2015-01-01

Roč. 10, č. 10 (2015), s. 1707-1723 ISSN 1860-7179 R&D Projects: GA MV VG20102015046; GA ČR GAP207/11/0108 Institutional support: RVO:61388963 Keywords : 6-oxopurine * acyclic nucleoside phosphonates * phosphoribosyltransferases * malaria * phosphoramidates Subject RIV: CC - Organic Chemistry Impact factor: 2.980, year: 2015

Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

KAUST Repository

Rouen, Mathieu; Queval, Pierre; Borre, Etienne; Falivene, Laura; Poater, Albert; Berthod, Mikael; Hugues, Francois; Cavallo, Luigi; Basle, Olivier; Olivier-Bourbigou, Helene; Mauduit, Marc

2016-01-01

The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

Selective Metathesis of α-Olefins from Bio-Sourced Fischer–Tropsch Feeds

KAUST Repository

Rouen, Mathieu

2016-10-14

The search for a low-cost process for the valorization of linear alpha-olefins combining high productivity and high selectivity is a longstanding goal for chemists. Herein, we report a soluble ruthenium olefin metathesis catalyst that performs the conversion of linear alpha-olefins to longer internal linear olefins with high selectivity (>99%) under neat conditions at low loadings (50 ppm) and without the need of expensive additives. This robust catalytic process allowed us to efficiently and selectively re-equilibrate the naphtha fraction (C-5-C-8) of a Fischer-Tropsch feed derived from non petroleum resources to a higher-value product range (C-9-C-14), useful as detergent and plasticizer precursors.

Design and synthesis of fused polycycles via Diels–Alder reaction and ring-rearrangement metathesis as key steps

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2015-07-01

Full Text Available Atom efficient processes such as the Diels–Alder reaction (DA and the ring-rearrangement metathesis (RRM have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.

Design and synthesis of fused polycycles via Diels-Alder reaction and ring-rearrangement metathesis as key steps.

Science.gov (United States)

Kotha, Sambasivarao; Ravikumar, Ongolu

2015-01-01

Atom efficient processes such as the Diels-Alder reaction (DA) and the ring-rearrangement metathesis (RRM) have been used to design new polycycles. In this regard, ruthenium alkylidene catalysts are effective in realizing the RRM of bis-norbornene derivatives prepared by DA reaction and Grignard addition. Here, fused polycycles are assembled which are difficult to produce by conventional synthetic routes.

NMR studies of abasic sites in DNA duplexes: Deoxyadenosine stacks into the helix opposite acyclic lesions

International Nuclear Information System (INIS)

Kalnik, M.W.; Chang, Chienneng; Johnson, F.; Grollman, A.P.; Patel, D.J.

1989-01-01

Proton and phosphorus NMR studies are reported for two complementary nonanucleotide duplexes containing acyclic abasic sites. The first duplex, d(C-A-T-G-A-G-T-A-C)·d(G-T-A-C-P-C-A-T-G), contains an acyclic propanyl moiety, P, located opposite a deoxyadenosine at the center of the helix (designated AP P 9-mer duplex). The second duplex, d(C-A-T-G-A-G-T-A-C-)·d(G-T-A-C-E-C-A-T-G), contains a similarly located acyclic ethanyl moiety, E (designated AP E 9-mer duplex). The ethanyl moiety is one carbon shorter than the natural carbon-phosphodiester backbone of a single nucleotide unit of DNA. The majority of the exchangeable and nonexchangeable base and sugar protons in both the AP P 9-mer and AP E 9-mer duplexes, including those at the abasic site, have been assigned by recording and analyzing two-dimensional phase-sensitive NOESY data sets in H 2 O and D 2 O solution between -5 and 5 degree C. These spectroscopic observations establish that A5 inserts into the helix opposite the abasic site (P14 and El14) and stacks between the flanking G4·C15 and G6·C13 Watson-Crick base pairs in both the AP P 9-mer and AP E 9-mer duplexes. Proton NMR parameters for the Ap P 9-mer and AP E 9-mer duplexes are similar to those reported previously. These proton NMR experiments demonstrate that the structures at abasic sites are very similar whether the five-membered ring is open or closed or whether the phosphodiester backbone is shortened by one carbon atom. Phosphorus spectra of the AP P 9-mer and AP E 9-mer duplexes (5 degree C) indicate that the backbone conformation is similarly perturbed at three phosphodiester backbone torsion angles

Understanding the Hydro-metathesis Reaction of 1-decene by Using Well-defined Silica Supported W, Mo, Ta Carbene/Carbyne Complexes

KAUST Repository

Saidi, Aya; Samantaray, Manoja; Tretiakov, Mykyta; Kavitake, Santosh Giridhar; Basset, Jean-Marie

2017-01-01

Direct conversion of 1-decene to petroleum range alkanes was obtained using hydro-metathesis reaction. To understand this reaction we employed three different well-defined single site catalysts precursors; [(≡Si-O-)W(CH3)5] 1, [(≡Si-O-)Mo(≡CtBu)(CH2

Nickel-catalyzed cyclization of alpha, omega-dienes: formation vs. cleavage of C-C bonds

Czech Academy of Sciences Publication Activity Database

Nečas, D.; Turský, M.; Tišlerová, I.; Kotora, Martin

2006-01-01

Roč. 30, č. 4 (2006), s. 671-674 ISSN 1144-0546 R&D Projects: GA MŠk 1M0508; GA ČR GD203/03/H140 Institutional research plan: CEZ:AV0Z40550506 Keywords : catalysis * nickel * cyclization * diene * cyclopentane Subject RIV: CC - Organic Chemistry Impact factor: 2.647, year: 2006

Enantiopurity analysis of new types of acyclic nucleoside phosphonates by capillary electrophoresis with cyclodextrins as chiral selectors

Czech Academy of Sciences Publication Activity Database

Šolínová, Veronika; Kaiser, Martin Maxmilian; Lukáč, Miloš; Janeba, Zlatko; Kašička, Václav

2014-01-01

Roč. 37, č. 3 (2014), s. 295-303 ISSN 1615-9306 R&D Projects: GA ČR(CZ) GAP206/12/0453; GA ČR(CZ) GA13-17224S; GA MV VG20102015046 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * CE * chiral analysis * cyclodextrins * nucleotide analogs Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 2.737, year: 2014

Influence of Acyclic Nucleoside Phosphonate Antivirals on Gene Expression of Chemokine Receptors CCR5 and CXCR4

Czech Academy of Sciences Publication Activity Database

Potměšil, P.; Holý, Antonín; Zídek, Zdeněk

2015-01-01

Roč. 61, č. 1 (2015), s. 1-7 ISSN 0015-5500 R&D Projects: GA ČR GA305/03/1470; GA MŠk 1M0508 Institutional support: RVO:61388963 ; RVO:68378041 Keywords : acyclic nucleoside phosphonate * HIV * CCR5 * CXCR4 * cytokine * RT-PCR Subject RIV: CC - Organic Chemistry; FR - Pharmacology ; Medidal Chemistry (UEM-P) Impact factor: 0.833, year: 2015

Assessment of the role of in situ generated (E)-2,4-diene-valproic acid in the toxicity of valproic acid and (E)-2-ene-valproic acid in sandwich-cultured rat hepatocytes

Energy Technology Data Exchange (ETDEWEB)

Surendradoss, Jayakumar; Chang, Thomas K.H.; Abbott, Frank S., E-mail: frank.abbott@ubc.ca

2012-11-01

Valproic acid (VPA) undergoes cytochrome P450-mediated desaturation to form 4-ene-VPA, which subsequently yields (E)-2,4-diene-VPA by β-oxidation. Another biotransformation pathway involves β-oxidation of VPA to form (E)-2-ene-VPA, which also generates (E)-2,4-diene-VPA by cytochrome P450-mediated desaturation. Although the synthetic form of (E)-2,4-diene-VPA is more hepatotoxic than VPA as shown in various experimental models, there is no conclusive evidence to implicate the in situ generated (E)-2,4-diene-VPA in VPA hepatotoxicity. The present study investigated the effects of modulating the in situ formation of (E)-2,4-diene-VPA on markers of oxidative stress (formation of 2′,7′-dichlorofluorescein; DCF), steatosis (accumulation of BODIPY 558/568 C{sub 12}), necrosis (release of lactate dehydrogenase; LDH), and on cellular total glutathione (GSH) levels in sandwich-cultured rat hepatocytes treated with VPA or (E)-2-ene-VPA. Treatment with either of these chemicals alone increased each of the toxicity endpoints. In VPA-treated hepatocytes, (E)-2,4-diene-VPA was detected only at trace levels, even after phenobarbital (PB) pretreatment and there was no effect on the toxicity of VPA. Furthermore, pretreatment with a cytochrome P450 enzyme inhibitor, 1-aminobenzotriazole (1-ABT), did not influence the extent of VPA toxicity in both PB-pretreated and vehicle-pretreated hepatocytes. However, in (E)-2-ene-VPA-treated hepatocytes, PB pretreatment greatly enhanced the levels of (E)-2,4-diene-VPA and this was accompanied by a further enhancement of the effects of (E)-2-ene-VPA on DCF formation, BODIPY accumulation, LDH release, and GSH depletion. Pretreatment with 1-ABT reduced the concentrations of (E)-2,4-diene-VPA and the extent of (E)-2-ene-VPA toxicity; however, this occurred in PB-pretreated hepatocytes, but not in control hepatocytes. In conclusion, in situ generated (E)-2,4-diene-VPA is not responsible for the hepatocyte toxicity of VPA, whereas it

Learning directed acyclic graphs from large-scale genomics data.

Science.gov (United States)

Nikolay, Fabio; Pesavento, Marius; Kritikos, George; Typas, Nassos

2017-09-20

In this paper, we consider the problem of learning the genetic interaction map, i.e., the topology of a directed acyclic graph (DAG) of genetic interactions from noisy double-knockout (DK) data. Based on a set of well-established biological interaction models, we detect and classify the interactions between genes. We propose a novel linear integer optimization program called the Genetic-Interactions-Detector (GENIE) to identify the complex biological dependencies among genes and to compute the DAG topology that matches the DK measurements best. Furthermore, we extend the GENIE program by incorporating genetic interaction profile (GI-profile) data to further enhance the detection performance. In addition, we propose a sequential scalability technique for large sets of genes under study, in order to provide statistically significant results for real measurement data. Finally, we show via numeric simulations that the GENIE program and the GI-profile data extended GENIE (GI-GENIE) program clearly outperform the conventional techniques and present real data results for our proposed sequential scalability technique.

Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2015-08-01

Full Text Available A simple synthetic strategy to C2-symmetric bis-spiro-pyrano cage compound 7 involving ring-closing metathesis is reported. The hexacyclic dione 10 was prepared from simple and readily available starting materials such as 1,4-naphthoquinone and cyclopentadiene. The synthesis of an unprecedented octacyclic cage compound through intramolecular Diels–Alder (DA reaction as a key step is described. The structures of three new cage compounds 7, 12 and 18 were confirmed by single crystal X-ray diffraction studies.

Construction of Eight-Membered Carbocycles with Trisubstituted Double Bonds Using the Ring Closing Metathesis Reaction

Directory of Open Access Journals (Sweden)

Motoo Tori

2010-06-01

Full Text Available Medium sized carbocycles are particularly difficult to synthesize. Ring closing metathesis reactions (RCM have recently been applied to construct eight-membered carbocycles, but trisubstituted double bonds in the eight-membered rings are more difficult to produce using RCM reactions. In this review, model examples and our own results are cited and the importance of the preparation of suitably designed precursors is discussed. Examples of RCM reactions used in the total synthesis of natural products are also outlined.

A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

KAUST Repository

Maity, Niladri

2018-02-15

A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)(CH-Bu)] was prepared by treatment of highly dehydroxylated silica (SiO: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt][W(=O)(CH-Bu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

A Silica-Supported Monoalkylated Tungsten Dioxo Complex Catalyst for Olefin Metathesis

KAUST Repository

Maity, Niladri; Barman, Samir; Minenkov, Yury; Ould-Chikh, Samy; Abou-Hamad, Edy; Ma, Tao; Qureshi, Ziyauddin; Cavallo, Luigi; D'Elia, Valerio; Gates, Bruce C.; Basset, Jean-Marie

2018-01-01

A well-defined silica-supported monoalkylated tungsten dioxo complex [(Si-O-)W(=O)(CH-Bu)] was prepared by treatment of highly dehydroxylated silica (SiO: silica treated at 700 °C under high vacuum) with an ionic precursor complex [NEt][W(=O)(CH-Bu)]. The identity of the resulting neutral monoalkylated tungsten dioxo surface complex was established by means of elemental microanalysis and spectroscopic studies (IR, solid-state NMR, Raman, and X-ray absorption spectroscopies). The supported tungsten complex was found to act as a precatalyst for the self-metathesis of 1-octene in a batch reactor. The mechanistic implications of this reaction are discussed with the support of DFT calculations highlighting the potential occurrence of thus-far unexplored mechanistic pathways.

Effect of lanthanide contraction on the mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien): Syntheses and characterizations of lanthanide complexes with a tetraelenidoantimonate ligand

International Nuclear Information System (INIS)

Zhao Jing; Liang Jingjing; Pan Yingli; Zhang Yong; Jia Dingxian

2011-01-01

Mixed polyamine systems Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) (Ln=lanthanide, en=ethylenediamine, dien=diethylenetriamine, trien=triethylenetetramine) were investigated under solvothermal conditions, and novel mixed-coordinated lanthanide(III) complexes [Ln(en) 2 (dien)(η 2 -SbSe 4 )] (Ln=Ce(1a), Nd(1b)), [Ln(en) 2 (dien)(SbSe 4 )] (Ln=Sm(2a), Gd(2b), Dy(2c)), [Ln(en)(trien)(μ-η 1 ,η 2 -SbSe 4 )] ∞ (Ln=Ce(3a), Nd(3b)) and [Sm(en)(trien)(η 2 -SbSe 4 )] (4a) were prepared. Two structural types of lanthanide selenidoantimonates were obtained across the lanthanide series in both en+dien and en+trien systems. The tetrahedral anion [SbSe 4 ] 3- acts as a monodentate ligand mono-SbSe 4 , a bidentate chelating ligand η 2 -SbSe 4 or a tridentate bridging ligand μ-η 1 ,η 2 -SbSe 4 to the lanthanide(III) center depending on the Ln 3+ ions and the mixed ethylene polyamines, indicating the effect of lanthanide contraction on the structures of the lanthanide(III) selenidoantimonates. The lanthanide selenidoantimonates exhibit semiconducting properties with E g between 2.08 and 2.51 eV. - Graphical Abstract: Two structural types of lanthanide(III) selenidoantimonates are formed in both en-dien and en-trien mixed polyamines across lanthanide series, indicating the lanthanide contraction effect on the structures of the lanthanide(III) selenidoantimonates. Highlights: → Two structural types of lanthanide selenidoantimonates are prepared across the lanthanide series in both Ln/Sb/Se/(en+dien) and Ln/Sb/Se/(en+trien) systems. → The [SbSe 4 ] 3- anion acts as a mono-SbSe 4 , a η 2 -SbSe 4 or a μ-η 1 ,η 2 -SbSe 4 ligand to the Ln 3+ ions. → The soft base ligand [SbSe 4 ] 3- can be controlled to coordinate to the Ln 3+ ions with en+dien and en+trien as co-ligands.

Method for upgrading diene-containing hydrocarbon mixtures

Energy Technology Data Exchange (ETDEWEB)

Kidwell, L.E. Jr.; Holcomb, D.E.

1984-05-22

There is disclosed a method for upgrading of hydrocarbon mixtures, so as to reduce their content of gum precursors such as diolefins and pseudo-diolefins, and provide a resulting product mixture suitable for mild hydrogenation, for use as a motor fuel or as a feed stock to an extraction unit. The process comprises obtaining a hydrocarbon mixture containing about 60-90 wt. % of aromatic components, about 3-40 wt. % of dienes and pseudodienes, and monoolefins, and up to about 6 wt. % of relatively unreactive organic compounds, reacting this mixture with elemental sulfur in the approximate weight ratio of about 5-95 wt. % of the hydrocarbon mixture with about 95-5 wt. % of elemental sulfur, the reaction being carried out at a temperature in the range of 100/sup 0/-150/sup 0/ C. for about 10 minutes to 24 hours with good mixing, removing the unreacted materials by distillation and separating a sulfur-hydrocarbon reaction product to provide the upgraded hydrocarbon mixture.

FEMA expert panel review of p-mentha-1,8-dien-7-al genotoxicity testing results

NARCIS (Netherlands)

Cohen, Samuel M.; Fukushima, Shoji; Gooderham, Nigel J.; Guengerich, F.P.; Hecht, Stephen S.; Rietjens, Ivonne M.C.M.; Smith, Robert L.; Bastaki, Maria; Harman, Christie L.; McGowen, Margaret M.; Taylor, Sean V.

2016-01-01

p-Mentha-1,8-dien-7-al is a naturally occurring cyclic alpha,beta-unsaturated aldehyde that is used as a flavoring substance throughout the world. Due to the chemical structure and the potential DNA reactivity of the alpha,beta-unsaturated carbonyl moiety, a battery of genotoxicity assays was

Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides.

Science.gov (United States)

Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

2018-02-16

Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

Oxidative cycloaddition of hydroxamic acids with dienes or guaiacols mediated by iodine(III) reagents.

Science.gov (United States)

Shimizu, Hisato; Yoshimura, Akira; Noguchi, Keiichi; Nemykin, Victor N; Zhdankin, Viktor V; Saito, Akio

2018-01-01

[Bis(trifluoroacetoxy)iodo]benzene (BTI) and (diacetoxyiodo)benzene (DIB) efficiently promote the formation of acylnitroso species from hydroxamic acids in the presence of various dienes to give the corresponding hetero-Diels-Alder (HDA) adducts in moderate to high yields. The present method could be applied to the HDA reactions of acylnitroso species with o -benzoquinones generated by the oxidative dearomatization of guaiacols.

Synthesis and biological evaluation of acyclic nucleotide analogues with a furo[2,3-d]pyrimidin-2(3H)-one base

Czech Academy of Sciences Publication Activity Database

Janeba, Zlatko; Holý, Antonín; Pohl, Radek; Snoeck, R.; Andrei, G.; De Clercq, E.; Balzarini, J.

2010-01-01

Roč. 88, č. 7 (2010), s. 628-638 ISSN 0008-4042 R&D Projects: GA MŠk 1M0508 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * Sonogashira reaction * intramolecular cyclization Subject RIV: CC - Organic Chemistry Impact factor: 1.374, year: 2010

Extrudate versus Powder Silica Alumina as Support for Re2O7 Catalyst in the Metathesis of Seed Oil-Derivatives – A Comparison

Directory of Open Access Journals (Sweden)

Bassie B. Marvey

2009-01-01

Full Text Available Self- and cross-metathesis of fatty acid methyl esters (FAMEs was investigated using a silica alumina supported Re2O7 catalyst. Although a 3 wt% Re2O7/SiO2-Al2O3/SnBu4 is already active for the metathesis of unsaturated FAMEs, the results have shown that particle size of silica alumina support has a profound influence on its activity and selectivity. Consequently, high substrate conversions coupled with improved product yields (for mono- and diesters and reaction rates were obtained upon using powder, as opposed to extrudate silica alumina as the support material. Diesters are platform compounds for the synthesis of polymers and fragrances. In this paper a comparative outline of the influence of particle size of silica alumina (extrudate versus powder on catalytic performance of a 3 wt% Re2O7/SiO2-Al2O3/SnBu4 for self- and cross-metathesis of FAMEs is made. Low surface area and diffusion constraints associated with extrudates were identified as some of the factors leading to low catalytic activity and selectivity.

Effect of three 2-allyl-p-mentha-6,8-dien-2-ols on inhibition of mild steel corrosion in 1 M HCl

Directory of Open Access Journals (Sweden)

S. Kharchouf

2014-11-01

Full Text Available 2-Allyl-p-mentha-6,8-dien-2-ols P1−P3 synthesized from carvone P are tested as corrosion inhibitors of steel in 1 M HCl using weight loss measurements, potentiodynamic polarisation and impedance spectroscopy (EIS methods. The addition of 2-allyl-p-mentha-6,8-dien-2-ols reduced the corrosion rate. Potentiodynamic polarisation studies clearly reveal that the presence of inhibitors does not change the mechanism of hydrogen evolution and that they act essentially as cathodic inhibitors. 2-Allyl-p-mentha-6,8-dien-2-ols tested adsorb on the steel surface according to Langmuir isotherm. From the adsorption isotherm some thermodynamic data for the adsorption process are calculated and discussed. EIS measurements show the increase of the charge-transfer resistance with the inhibitor concentration. The highest inhibition efficiency (92% is obtained for P1 at 3 g/L. The corrosion rate decreases with the rise of temperature. The corresponding activation energies are determined.

Effect of support on hydro-metathesis of propene: A comparative study of W(CH 3 ) 6 anchored to silica vs. silica-alumina

KAUST Repository

Tretiakov, Mykyta; Samantaray, Manoja; Saidi, Aya; Basset, Jean-Marie

2018-01-01

Hydro-metathesis of propene was carried out by using well-defined W(CH3)6 supported on silica and silica-alumina. It was observed that W(CH3)6 supported silica-alumina catalyst is much better (TON 4577) than the silica supported catalyst (TON 2104

Competitive solvent extraction of alkaline-earth cations into chloroform by lipophilic acyclic polyether dicarboxylic acids

International Nuclear Information System (INIS)

Kang, S.I.; Czech, A.; Czech, B.P.; Stewart, L.E.; Bartsch, R.A.

1985-01-01

Competitive solvent extraction of alkaline-earth cations from aqueous solutions into chloroform by a series of lipophilic acyclic polyether dicarboxylic acids is reported. The influence of polyether chain length and of terminal carboxylic acid group variation upon extraction selectivity and efficiency is assessed. In the competitive extraction of concentrated magnesium, calcium, strontium and barium chloride solutions, one complexing agent exhibits pronounced selectivity for barium with Ba 2+ /S 2+ = 50, Ba 2+ /Ca 2+ = 250, and no detectable Mg 2+ extraction. 20 references, 3 figures, 1 table

Iron based superconductors and related compounds synthesized by solid state metathesis and high temperature reactions

International Nuclear Information System (INIS)

Frankovsky, Rainer

2013-01-01

The results of this thesis can be divided into three major topics, which can also be seen as different approaches of solid state chemistry to reveal interesting features of known and unknown compounds and to develop alternative synthesis routes. Firstly, known compounds with related structural motifs to the superconducting iron-arsenides were investigated regarding their structural and physical properties. In case of La 3 Pd 4 Ge 4 the influence of Fe doping on the properties was studied, whereas in the series ZrMAs (M=Ti,V) the physical properties have not yet been reported at all and were investigated for the first time. Secondly, an alternative synthesis route has been developed for the synthesis of superconducting LaFeAsO 1-x F x . This solid state metathesis reaction distinctly increased the quality of the samples compared to conventionally prepared products. Furthermore, the reaction pathway was investigated and clarified, which helps to understand the processes during high temperature solid state metathesis reactions in general. Thirdly, this alternative synthesis route was expanded to other systems and new compounds like co-substituted LaFe 1-x Mn x AsO 1-y F y were prepared and thoroughly investigated. This led to a complex study of the interplay of magnetism, electronic and structural conditions and the occurrence of superconducting properties. The investigation and understanding of such complex coherences will probably be decisive for the further understanding of the superconducting mechanism in iron based superconductors.

Design and synthesis of polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis as key steps.

Science.gov (United States)

Kotha, Sambasivarao; Gunta, Rama

2015-01-01

Here, we describe a new and simple synthetic strategy to various polycyclic sulfones via Diels-Alder reaction and ring-rearrangement metathesis (RRM) as the key steps. This approach delivers tri- and tetracyclic sulfones with six (n = 1), seven (n = 2) or eight-membered (n = 3) fused-ring systems containing trans-ring junctions unlike the conventional all cis-ring junctions generally obtained during the RRM sequence. Interestingly the starting materials used are simple and commercially available.

Influence of Two Acyclic Homoterpenes (Tetranorterpenes) on the Foraging Behavior of Anthonomus grandis Boh.

Science.gov (United States)

Magalhães, D M; Borges, M; Laumann, R A; Woodcock, C M; Pickett, J A; Birkett, M A; Blassioli-Moraes, Maria Carolina

2016-04-01

Previous studies have shown that the boll weevil, Anthonomus grandis, is attracted to constitutive and conspecific herbivore-induced cotton volatiles, preferring the blend emitted by cotton at the reproductive over the vegetative stage. Moreover, this preference was paralleled by the release of the acyclic homoterpenes (tetranorterpenes) (E)-4,8-dimethyl-1,3,7-nonatriene (DMNT) and (E,E)-4,8,12-trimethyltrideca-1,3,7,11-tetraene (TMTT) in Delta Opal cotton being higher at the vegetative than at the reproductive stage. Here, we evaluated whether this difference in release of acyclic homoterpenes also occurred in other cotton varieties, and if boll weevils could recognize these compounds as indicators of a specific cotton phenological stage. Results showed that cotton genotypes CNPA TB-90, BRS-293 and Delta Opal all produced higher levels of DMNT and TMTT at the vegetative stage than at the reproductive stage and that these homoterpenes allowed for principal component analysis separation of volatiles produced by the two phenological stages. Electroantennograms confirmed boll weevil antennal responses to DMNT and TMTT. Behavioral assays, using Y-tube olfactometers, showed that adding synthetic homoterpenes to reproductive cotton volatiles (mimicking cotton at the vegetative stage in terms of homoterpene levels) resulted in reduced attraction to boll weevils compared to that to unmodified reproductive cotton. Weevils showed no preference when given a choice between plants at the vegetative stage and the vegetative stage-mimicked plant. Altogether, the results show that DMNT and TMTT are used by boll weevils to distinguish between cotton phenological stages.

Synthesis of amide-functionalized cellulose esters by olefin cross-metathesis.

Science.gov (United States)

Meng, Xiangtao; Edgar, Kevin J

2015-11-05

Cellulose esters with amide functionalities were synthesized by cross-metathesis (CM) reaction of terminally olefinic esters with different acrylamides, catalyzed by Hoveyda-Grubbs 2nd generation catalyst. Chelation by amides of the catalyst ruthenium center caused low conversions using conventional solvents. The effects of both solvent and structure of acrylamide on reaction conversion were investigated. While the inherent tendency of acrylamides to chelate Ru is governed by the acrylamide N-substituents, employing acetic acid as a solvent significantly improved the conversion of certain acrylamides, from 50% to up to 99%. Homogeneous hydrogenation using p-toluenesulfonyl hydrazide successfully eliminated the α,β-unsaturation of the CM products to give stable amide-functionalized cellulose esters. The amide-functionalized product showed higher Tg than its starting terminally olefinic counterpart, which may have resulted from strong hydrogen bonding interactions of the amide functional groups. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrochemical oxidation of cholesterol in acetonitrile leads to the formation of cholesta-4,6-dien-3-one

International Nuclear Information System (INIS)

Hosokawa, Yu-Ya; Hakamata, Hideki; Murakami, Tomonori; Aoyagi, Sakae; Kuroda, Minpei; Mimaki, Yoshihiro; Ito, Ayumi; Morosawa, Sayaka; Kusu, Fumiyo

2009-01-01

Cholesterol was shown to be oxidized at the glassy carbon electrode in an acetonitrile-2-propanol mixture and this oxidation reaction was applied to the determination of serum total cholesterol by high-performance liquid chromatography with electrochemical detection (K. Hojo, H. Hakamata, A. Ito, A. Kotani, C. Furukawa, Y.Y. Hosokawa, F. Kusu, J. Chromatogr. A 1166 (2007) 135-141). To gain insight into the detection mechanisms of cholesterol, an electrolytic product of cholesterol was collected and characterized by infrared spectroscopy, one- and two-dimensional nuclear magnetic resonance, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The three techniques, together with comparisons of literature spectral data, confirmed the formation of cholesta-4,6-dien-3-one. The conversion of cholesterol to cholesta-4,6-dien-3-one, a four-electron, four-proton electrochemical process, has been proposed as an electrochemical oxidation mechanism of cholesterol in acetonitrile.

Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

Science.gov (United States)

Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Del Pozo, Carlos; Fustero, Santos

2015-01-01

A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM-IMDAR protocols.

Isolation of stigmast-5,24-dien-3-ol from marine brown algae Sargassum tenerrimum and its antipredatory activity

Digital Repository Service at National Institute of Oceanography (India)

Majik, M.S.; Adel, H.; Shirodkar, D.; Tilvi, S.; Furtado, J.

In recent years many sterols with potent biological activity have been identified from marine sources. Here we report the isolation of stigmast-5,24-dien-3-ol (fucosterol) as a major metabolite from the bioactive hexane-fraction of Sargassum...

Estimation of apparent binding constant of complexes of selected acyclic nucleoside phosphonates with beta-cyclodextrin by affinity capillary electrophoresis

Czech Academy of Sciences Publication Activity Database

Šolínová, Veronika; Mikysková, Hana; Kaiser, Martin Maxmilian; Janeba, Zlatko; Holý, Antonín; Kašička, Václav

2016-01-01

Roč. 37, č. 2 (2016), s. 239-247 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA13-17224S; GA ČR(CZ) GA15-01948S Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonates * affinity capillary electrophoresis * binding constant * nucleotide analogs * beta-cyclodextrin Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 2.744, year: 2016

The direct oxidative diene cyclization and related reactions in natural product synthesis

Directory of Open Access Journals (Sweden)

Juliane Adrian

2016-09-01

Full Text Available The direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (diastereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

New acyclic secondary metabolites from the biologically active fraction of Albizia lebbeck flowers.

Science.gov (United States)

Al-Massarani, Shaza M; El Gamal, Ali A; Abd El Halim, Mohamed F; Al-Said, Mansour S; Abdel-Kader, Maged S; Basudan, Omer A; Alqasoumi, Saleh I

2017-01-01

The total extract of Albizia lebbeck flowers was examined in vivo for its possible hepatoprotective activity in comparison with the standard drug silymarin at two doses. The higher dose expressed promising activity especially in reducing the levels of AST, ALT and bilirubin. Fractionation via liquid-liquid partition and reexamination of the fractions revealed that the n -butanol fraction was the best in improving liver biochemical parameters followed by the n -hexane fraction. However, serum lipid parameters were best improved with CHCl 3 fraction. The promising biological activity results initiated an intensive chromatographic purification of A. lebbeck flowers fractions. Two compounds were identified from natural source for the first time, the acyclic farnesyl sesquiterpene glycoside1-O-[6-O- α -l-arabinopyranosyl- β -d-glucopyranoside]-(2 E ,6 E -)-farnesol ( 6 ) and the squalene derivative 2,3-dihydroxy-2,3-dihydrosqualene ( 9 ), in addition to eight compounds reported here for the first time from the genus Albizia ; two benzyl glycosides, benzyl 1-O- β -d-glucopyranoside ( 1 ) and benzyl 6-O- α -l-arabinopyranosyl β -d-glucopyranoside ( 2 ); three acyclic monoterpene glycosides, linalyl β -d-glucopyranoside ( 3 ) and linalyl 6-O- α -l-arabinopyranosyl- β -d-glucopyranoside ( 4 ); (2 E )-3,7-dimethylocta-2,6-dienoate-6-O- α -l arabinopyranosyl- β -d-glucopyranoside ( 5 ), two oligoglycosides, n -hexyl- α -l arabinopyranosyl-(1 → 6)- β -d-glucopyranoside (creoside) ( 7 ) and n -octyl α -l-arabinopyranosyl-(1 → 6)- β -d-glucopyranoside (rhodiooctanoside) ( 8 ); and ethyl fructofuranoside ( 10 ). The structures of the isolated compounds were elucidated based on extensive examination of their spectroscopic 1D and 2D-NMR, MS, UV, and IR data. It is worth mentioning that, some of the isolated linalol glycoside derivatives were reported as aroma precursors.

New acyclic secondary metabolites from the biologically active fraction of Albizia lebbeck flowers

Directory of Open Access Journals (Sweden)

Shaza M. Al-Massarani

2017-01-01

Full Text Available The total extract of Albizia lebbeck flowers was examined in vivo for its possible hepatoprotective activity in comparison with the standard drug silymarin at two doses. The higher dose expressed promising activity especially in reducing the levels of AST, ALT and bilirubin. Fractionation via liquid–liquid partition and reexamination of the fractions revealed that the n-butanol fraction was the best in improving liver biochemical parameters followed by the n-hexane fraction. However, serum lipid parameters were best improved with CHCl3 fraction. The promising biological activity results initiated an intensive chromatographic purification of A. lebbeck flowers fractions. Two compounds were identified from natural source for the first time, the acyclic farnesyl sesquiterpene glycoside1-O-[6-O-α-l-arabinopyranosyl-β-d-glucopyranoside]-(2E,6E--farnesol (6 and the squalene derivative 2,3-dihydroxy-2,3-dihydrosqualene (9, in addition to eight compounds reported here for the first time from the genus Albizia; two benzyl glycosides, benzyl 1-O-β-d-glucopyranoside (1 and benzyl 6-O-α-l-arabinopyranosyl β-d-glucopyranoside (2; three acyclic monoterpene glycosides, linalyl β-d-glucopyranoside (3 and linalyl 6-O-α-l-arabinopyranosyl-β-d-glucopyranoside (4; (2E-3,7-dimethylocta-2,6-dienoate-6-O-α-l arabinopyranosyl-β-d-glucopyranoside (5, two oligoglycosides, n-hexyl-α-l arabinopyranosyl-(1 → 6-β-d-glucopyranoside (creoside (7 and n-octyl α-l-arabinopyranosyl-(1 → 6-β-d-glucopyranoside (rhodiooctanoside (8; and ethyl fructofuranoside (10. The structures of the isolated compounds were elucidated based on extensive examination of their spectroscopic 1D and 2D-NMR, MS, UV, and IR data. It is worth mentioning that, some of the isolated linalol glycoside derivatives were reported as aroma precursors.

Acyclic cucurbit[n]uril-type molecular containers: influence of aromatic walls on their function as solubilizing excipients for insoluble drugs.

Science.gov (United States)

Zhang, Ben; Isaacs, Lyle

2014-11-26

We studied the influence of the aromatic sidewalls on the ability of acyclic CB[n]-type molecular containers (1a-1e) to act as solubilizing agents for 19 insoluble drugs including the developmental anticancer agent PBS-1086. All five containers exhibit good water solubility and weak self-association (Ks ≤ 624 M(-1)). We constructed phase solubility diagrams to extract Krel and Ka values for the container·drug complexes. The acyclic CB[n]-type containers generally display significantly higher Ka values than HP-β-CD toward drugs. Containers 1a-1e bind the steroidal ring system and aromatic moieties of insoluble drugs. Compound 1b displays highest affinity toward most of the drugs studied. Containers 1a and 1b are broadly applicable and can be used to formulate a wider variety of insoluble drugs than was previously possible with cyclodextrin technology. For drugs that are solubilized by both HP-β-CD and 1a-1e, lower concentrations of 1a-1e are required to achieve identical [drug].

Asymmetric aza-Diels-Alder reaction of Danishefsky's diene with imines in a chiral reaction medium

Directory of Open Access Journals (Sweden)

Pégot Bruce

2006-09-01

Full Text Available Abstract The asymmetric aza-Diels-Alder reaction of chiral imines with Danishefsky's diene in chiral ionic liquids provides the corresponding cycloadduct with moderate to high diastereoselectivity. The reaction has proved to perform better at room temperature in ionic liquids without either Lewis acid catalyst or organic solvent. Chiral ionic liquids are recycled while their efficiency is preserved.

A novel 3α-p-Nitrobenzoylmultiflora-7:9(11)-diene-29-benzoate and two new triterpenoids from the seeds of zucchini (Cucurbita pepo L).

Science.gov (United States)

Tanaka, Reiko; Kikuchi, Takashi; Nakasuji, Saori; Ue, Yasuhiro; Shuto, Daisuke; Igarashi, Keishi; Okada, Rina; Yamada, Takeshi

2013-06-26

Three novel multiflorane-type triterpenoids, 3α-p-nitrobenzoylmultiflora-7:9(11)-diene-29-benzoate (1), 3α-acetoxymultiflora-7:9(11)-diene-29-benzoate (2), and 3α-acetoxymultiflora-5(6):7:9(11)-triene-29-benzoate (3), along with two known related compounds 4 and 5 were isolated from the seeds of zucchini (Cucurbita pepo L). Their structures were determined on the basis of 1D and 2D NMR spectroscopy and HREIMS. Triterpenoids possessing a nitro group were not isolated previously.

Theoretic derivation of directed acyclic subgraph algorithm and comparisons with message passing algorithm

Science.gov (United States)

Ha, Jeongmok; Jeong, Hong

2016-07-01

This study investigates the directed acyclic subgraph (DAS) algorithm, which is used to solve discrete labeling problems much more rapidly than other Markov-random-field-based inference methods but at a competitive accuracy. However, the mechanism by which the DAS algorithm simultaneously achieves competitive accuracy and fast execution speed, has not been elucidated by a theoretical derivation. We analyze the DAS algorithm by comparing it with a message passing algorithm. Graphical models, inference methods, and energy-minimization frameworks are compared between DAS and message passing algorithms. Moreover, the performances of DAS and other message passing methods [sum-product belief propagation (BP), max-product BP, and tree-reweighted message passing] are experimentally compared.

Sulfonation of vulcanized ethylene-propylene-diene terpolymer membranes

International Nuclear Information System (INIS)

Barroso-Bujans, F.; Verdejo, R.; Lozano, A.; Fierro, J.L.G.; Lopez-Manchado, M.A.

2008-01-01

In the present work, sulfonation of previously vulcanized ethylene propylene diene terpolymer (EPDM) membranes was developed in a swelling solvent with acetyl sulfate. This procedure avoids the need to pre-dissolve the raw polymer. The reaction conditions were optimized in terms of solvent type, reaction time, acetyl sulfate concentration and film thickness to obtain the maximum degree of sulfonation of the polymer. The sulfonation procedure presented in this study yields a degree of sulfonation comparable to the chlorosulfonic acid procedure. Sulfonic acid groups were detected by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, and quantified by titrations. Proton conductivity and water uptake were measured by means of impedance spectroscopy and swelling measurements, respectively, and were correlated with the degree of sulfonation. Tensile strength and Young's modulus of sulfonated EPDM increased with the degree of sulfonation, while elongation at break remained constant. Thermal stability of the sulfonated EPDM was studied by simultaneous thermogravimetry-mass spectroscopy

Mechanism, reactivity, and selectivity of nickel-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes.

Science.gov (United States)

Hong, Xin; Holte, Dane; Götz, Daniel C G; Baran, Phil S; Houk, K N

2014-12-19

Density functional theory (DFT) calculations with B3LYP and M06 functionals elucidated the reactivities of alkynes and Z/E selectivity of cyclodecatriene products in the Ni-catalyzed [4 + 4 + 2] cycloadditions of dienes and alkynes. The Ni-mediated oxidative cyclization of butadienes determines the Z/E selectivity. Only the oxidative cyclization of one s-cis to one s-trans butadiene is facile and exergonic, leading to the observed 1Z,4Z,8E-cyclodecatriene product. The same step with two s-cis or s-trans butadienes is either kinetically or thermodynamically unfavorable, and the 1Z,4E,8E- and 1Z,4Z,8Z-cyclodecatriene isomers are not observed in experiments. In addition, the competition between the desired cooligomerization and [2 + 2 + 2] cycloadditions of alkynes depends on the coordination of alkynes. With either electron-deficient alkynes or alkynes with free hydroxyl groups, the coordination of alkynes is stronger than that of dienes, and alkyne trimerization prevails. With alkyl-substituted alkynes, the generation of alkyne-coordinated nickel complex is much less favorable, and the [4 + 4 + 2] cycloaddition occurs.

Tandem cross enyne metathesis (CEYM–intramolecular Diels–Alder reaction (IMDAR. An easy entry to linear bicyclic scaffolds

Directory of Open Access Journals (Sweden)

Javier Miró

2015-08-01

Full Text Available A new tandem cross enyne metathesis (CEYM–intramolecular Diels–Alder reaction (IMDAR has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM–IMDAR protocols.

Cycloalkyl-based unsymmetrical unsaturated (U2)-NHC ligands: Flexibility and dissymmetry in ruthenium-catalysed olefin metathesis

KAUST Repository

Rouen, Mathieu

2014-01-01

Air-stable Ru-indenylidene and Hoveyda-type complexes bearing new unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands combining a mesityl unit and a flexible cycloalkyl moiety as N-substituents were synthesised. Structural features, chemical stabilities and catalytic profiles in olefin metathesis of this new library of cycloalkyl-based U2-NHC Ru complexes were studied and compared with their unsymmetrical saturated NHC-Ru homologues as well as a set of commercially available Ru-catalysts bearing either symmetrical SIMes or IMes NHC ligands. © 2014 the Partner Organisations.

Acyclic N-halamine-immobilized polyurethane: Preparation and antimicrobial and biofilm-controlling functions

Science.gov (United States)

Luo, Jie; Porteous, Nuala; Lin, Jiajin; Sun, Yuyu

2015-01-01

Hydroxyl groups were introduced onto polyurethane surfaces through 1,6-hexamethylene diisocyanate activation, followed by diethanolamine hydroxylation. Polymethacrylamide was covalently attached to the hydroxylated polyurethane through surface grafting polymerization of methacrylamide using cerium (IV) ammonium nitrate as an initiator. After bleach treatment, the amide groups of the covalently bound polymethacrylamide chains were transformed into N-halamines. The new N-halamine-immobilized polyurethane provided a total sacrifice of 107–108 colony forming units per milliliter of Staphylococcus aureus (Gram-positive bacteria), Escherichia coli (Gram-negative bacteria), and Candida albicans (fungi) within 10 min and successfully prevented bacterial and fungal biofilm formation. The antimicrobial and biofilm-controlling effects were both durable and rechargeable, pointing to great potentials of the new acyclic N-halamine-immobilized polyurethane for a broad range of related applications. PMID:26089593

Consensus pursuit of heterogeneous multi-agent systems under a directed acyclic graph

Science.gov (United States)

Yan, Jing; Guan, Xin-Ping; Luo, Xiao-Yuan

2011-04-01

This paper is concerned with the cooperative target pursuit problem by multiple agents based on directed acyclic graph. The target appears at a random location and moves only when sensed by the agents, and agents will pursue the target once they detect its existence. Since the ability of each agent may be different, we consider the heterogeneous multi-agent systems. According to the topology of the multi-agent systems, a novel consensus-based control law is proposed, where the target and agents are modeled as a leader and followers, respectively. Based on Mason's rule and signal flow graph analysis, the convergence conditions are provided to show that the agents can catch the target in a finite time. Finally, simulation studies are provided to verify the effectiveness of the proposed approach.

Le carcinome parathyroïdien: à propos d’un cas et revue de la literature

Science.gov (United States)

kolsi, Naourez; Jellali, Sondos; Koubaa, Jamel

2017-01-01

Le carcinome parathyroïdien est une tumeur maligne, très rare, de la glande parathyroïde. Cliniquement, ce cancer se présente souvent par un tableau d'hyperparathyroïdie primaire sévère. Le diagnostic est histologique mais n'est pas toujours aisé. Le traitement est basé sur la chirurgie. Femme âgée de 59 ans, aux antécédents d'hypertension artérielle, et de lithiases rénales récidivantes, consultait pour des douleurs osseuses diffuses avec asthénie. L'examen du cou a trouvé une tuméfaction basi-cervicale dure et à bord inférieur non palpable. A la biologie: hypercalcémie à 4,1 mmol/l, une hyperparathyroïdie avec valeur de parathormone (PTH) très élevée à 1088 pg/ml soit 13 fois la normale. La scintigraphie au Technétium-99m-sestamibi a montré une plage de fixation anormale de MIBI en projection de la parathyroïde inférieure gauche. Une parathyroïdectomie inférieure gauche, avec évidement médiastino-récurrentiel homolatéral ont été réalisés. Les suites opératoires étaient marquées par la normalisation de la calcémie et de la PTH. L'anatomopathologie était en faveur d'un carcinome parathyroïdien. Le diagnostic de carcinome parathyroïdien est généralement établi sur la conjonction de signes radiologiques biologiques et histologiques. La gravité de cette pathologie est due à l'hypercalcémie sévère et au risque de récidive et de métastases à distance justifiant la surveillance prolongée. PMID:28819506

Pharmacophore mapping in the laulimalide series: total synthesis of a vinylogue for a late-stage metathesis diversification strategy.

Science.gov (United States)

Wender, Paul A; Hilinski, Michael K; Skaanderup, Philip R; Soldermann, Nicolas G; Mooberry, Susan L

2006-08-31

An efficient synthesis of the macrocyclic core of laulimalide with a pendant vinyl group at C20 is described, allowing for late-stage introduction of various side chains through a selective and efficient cross metathesis diversification step. Representative analogues reported herein are the first to contain modifications to only the side chain dihydropyran of laulimalide and des-epoxy laulimalide. This step-economical strategy enables the rapid synthesis of new analogues using alkenes as an inexpensive, abundantly available diversification feedstock.

Synthesis of the EF-ring of ciguatoxin 3C based on the [2,3]-Wittig rearrangement and ring-closing olefin metathesis.

Science.gov (United States)

Goto, Akiyoshi; Fujiwara, Kenshu; Kawai, Ayako; Kawai, Hidetoshi; Suzuki, Takanori

2007-12-20

The EF-ring segment of ciguatoxin 3C, a causative toxin of ciguatera fish poisoning, was synthesized in three major steps: 1,4-addition for the C20O-C27 bond connection, chirality transferring anti selective [2,3]-Wittig rearrangement for the construction of the anti-2-hydroxyalkyl ether part, and ring-closing olefin metathesis for the F-ring formation.

Cyclooctane metathesis catalyzed by silica-supported tungsten pentamethyl [(ΞSiO)W(Me)5]: Distribution of macrocyclic alkanes

KAUST Repository

Riache, Nassima

2014-10-03

Metathesis of cyclic alkanes catalyzed by the new surface complex [(ΞSiO)W(Me)5] affords a wide distribution of cyclic and macrocyclic alkanes. The major products with the formula CnH2n are the result of either a ring contraction or ring expansion of cyclooctane leading to lower unsubstituted cyclic alkanes (5≤n≤7) and to an unprecedented distribution of unsubstituted macrocyclic alkanes (12≤n≤40), respectively, identified by GC/MS and by NMR spectroscopies.

Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: Structure and application as latent catalyst in olefin metathesis

KAUST Repository

Rouen, Mathieu

2014-09-11

An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions.

Truncated borrelidin analogues: synthesis by sequential cross metathesis/olefination for the southern fragment and biological evaluation.

Science.gov (United States)

Gündemir-Durmaz, Tülay; Schmid, Fabian; El Baz, Yana; Häusser, Annette; Schneider, Carmen; Bilitewski, Ursula; Rauhut, Guntram; Garnier, Delphine; Baro, Angelika; Laschat, Sabine

2016-09-21

The construction of novel borrelidin analogues is reported in which the northern fragment is truncated to a simple hydroxyundecanecarboxylate and the original cyclopentanecarboxylic acid in the southern fragment is replaced with different six-membered rings. The required precursors were prepared by cross metathesis of the appropriate carbocycle-based homoallylic alcohol with crotonaldehyde followed by HWE olefination of the resulting enal with bromocyanophosphonate. The key aldehyde for intramolecular cross coupling was accessible by oxidation of the hydroxy group of the linked undecanecarboxylate unit. Grignard mediated macrocyclization finally yielded the borrelidin related products. The investigation is complemented by SAR studies and quantum-chemical calculations.

Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

Directory of Open Access Journals (Sweden)

Mohamad Irfan Fathurrohman

2015-07-01

Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110 

Antiviral activities of 2,6-diaminopurine-based acyclic nucleoside phosphonates against herpesviruses: In vitro study results with pseudorabies virus (PrV, SuHV-1)

Czech Academy of Sciences Publication Activity Database

Zouharová, D.; Lipenská, I.; Fojtiková, M.; Kulich, P.; Neca, J.; Slaný, M.; Kovařčík, K.; Turanek-Knotigová, P.; Hubatka, F.; Celechovská, H.; Mašek, J.; Koudelka, Š.; Procházka, L.; Eyer, L.; Plocková, J.; Bartheldyová, E.; Miller, A. D.; Růžek, Daniel; Raška, M.; Janeba, Zlatko; Turánek, J.

2016-01-01

Roč. 184, FEB 29 (2016), s. 84-93 ISSN 0378-1135 Institutional support: RVO:60077344 ; RVO:61388963 Keywords : Pseudorabies * Acyclic nucleoside phosphonates * DNA viruses * Cidofovir * Antiviral drugs * DNA polymerase Subject RIV: EE - Microbiology, Virology; CC - Organic Chemistry (UOCHB-X) Impact factor: 2.628, year: 2016

A Directed Acyclic Graph-Large Margin Distribution Machine Model for Music Symbol Classification.

Science.gov (United States)

Wen, Cuihong; Zhang, Jing; Rebelo, Ana; Cheng, Fanyong

2016-01-01

Optical Music Recognition (OMR) has received increasing attention in recent years. In this paper, we propose a classifier based on a new method named Directed Acyclic Graph-Large margin Distribution Machine (DAG-LDM). The DAG-LDM is an improvement of the Large margin Distribution Machine (LDM), which is a binary classifier that optimizes the margin distribution by maximizing the margin mean and minimizing the margin variance simultaneously. We modify the LDM to the DAG-LDM to solve the multi-class music symbol classification problem. Tests are conducted on more than 10000 music symbol images, obtained from handwritten and printed images of music scores. The proposed method provides superior classification capability and achieves much higher classification accuracy than the state-of-the-art algorithms such as Support Vector Machines (SVMs) and Neural Networks (NNs).

The effect of maturation on the configurations of acyclic isoprenoid acids in sediments

Science.gov (United States)

Mackenzie, A. S.; Patience, R. L.; Yon, D. A.; Maxwell, J. R.

1982-05-01

Within a variety of sedimentary rocks of differing maturity, the configurations of a suite of acyclic isoprenoid acids have been examined by gas Chromatographic (in a few cases also by combined gas chromatography-mass spectrometry) analysis of their diastereoisomeric methyl and (-)-menthyl esters. The samples include the Eocene Messel (Germany) and Green River (U.S.) shales, the Permian Irati shale (Brazil) and a number of Lower Toarcian shales from the Paris Basin. The isomer distributions show that isomerisation occurs at the chiral centres with increasing maturation (to increase the number of isomers) and that the rate of isomerisation increases for centres (C-2,C-3) closest to the carboxyl group. These results suggest that adsorption of the carboxyl group to a catalyst surface may control the isomerisation rates by way of access to the catalyst.

A Simple and Efficient Approach to the Synthesis of Endo and Exo Bicyclo[6.1.0]nona-3,5-diene-9-carboxaldehyde

Directory of Open Access Journals (Sweden)

Gholamreza Mashayekhi

2007-10-01

Full Text Available Monobromination of 1,5-cyclooctadiene, followed by cyclopropanation with ethyl diazoacetate, led to the formation of endo and exo ethyl 4,5-dibromobicyclo[6.1.0]nonane-9-carboxylates 3a and 3b. Bis-dehydrobromination of 3a and 3b using 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU afforded the endo and exo ethyl bicyclo[6.1.0]nona-3,5-diene-9-carboxylates 4a and 4b. Reduction of these compounds to the corresponding alcohols 5a and 5b and subsequent oxidation with pyridinium chlorochromate (PCC resulted in the formation of the target compounds endo and exo bicyclo[6.1.0]nona-3,5-diene-9-carboxaldehydes 6a and 6b.

Synthesis of New Acadesine (AICA-riboside Analogues Having Acyclic d-Ribityl or 4-Hydroxybutyl Chains in Place of the Ribose

Directory of Open Access Journals (Sweden)

Gennaro Piccialli

2013-08-01

Full Text Available The antiviral activity of certain acyclic nucleosides drew our attention to the fact that the replacement of the furanose ring by an alkyl group bearing hydroxyl(s could be a useful structural modification to modulate the biological properties of those nucleosides. Herein, we report on the synthesis of some novel acadesine analogues, where the ribose moiety is mimicked by a d-ribityl or by a hydroxybutyl chain.

Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

Science.gov (United States)

Nash, Aaron; Soheili, Arash; Tambar, Uttam K

2013-09-20

Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

Synthesis of LaO1-xFxFeAs (x=0-0.15) via solid state metathesis reaction

Science.gov (United States)

Frankovsky, Rainer; Marchuk, Alexey; Pobel, Roman; Johrendt, Dirk

2012-04-01

LaOFeAs and superconducting LaO1-xFxFeAs have been synthesized via salt metathesis reactions and characterized by X-ray powder diffraction and magnetic susceptibility measurements. The process uses LaOCl and NaFeAs as precursors and yielded very pure samples. Superconductivity was confirmed in samples with x=0.05, 0.10 and 0.15 at critical temperatures of 11 K, 26 K and 9 K, respectively. According to temperature-dependent X-ray diffraction data, the reaction pathway is not topotactic in contrast to earlier suggestions.

Study of ethylene/2-butene cross-metathesis over W-H/Al2O 3 for propylene production: Effect of the temperature and reactant ratios on the productivity and deactivation

KAUST Repository

Mazoyer, Etienne; Szeto, Kaï Chung; Merle, Nicolas; Norsic, Sé bastien; Boyron, Olivier; Basset, Jean-Marie; Taoufik, Mostafa; Nicholas, Christopher P.

2013-01-01

A highly active and selective catalyst based on supported tungsten hydride for the cross-metathesis between ethylene and 2-butenes yielding propylene has been investigated at low pressure with various temperatures and feed ratios. At low temperature

Hybrid macrocycle formation and spiro annulation on cis-syn-cis-tricyclo[6.3.0.02,6]undeca-3,11-dione and its congeners via ring-closing metathesis

Directory of Open Access Journals (Sweden)

Sambasivarao Kotha

2015-07-01

Full Text Available We have developed a simple methodology to transform cis-syn-cis-triquinane derivative 2 into the diindole based macrocycle 6 involving Fischer indolization and ring-closing metathesis (RCM. Various spiro-polyquinane derivatives have been assembled via RCM as a key step.

Optimal allocation of multi-state retransmitters in acyclic transmission networks

International Nuclear Information System (INIS)

Levitin, Gregory

2002-01-01

In this paper, an algorithm for optimal allocation of multi-state elements (MEs) in acyclic transmission networks (ATNs) is suggested. The ATNs consist of a number of positions (nodes) in which MEs capable of receiving and sending a signal are allocated. Each network has a root position where the signal source is located, a number of leaf positions that can only receive a signal, and a number of intermediate positions containing MEs capable of transmitting the received signal to some other nodes. Each ME that is located in a nonleaf node can have different states determined by a set of nodes receiving the signal directly from this ME. The probability of each state is assumed to be known for each ME. The ATN reliability is defined as the probability that a signal from the root node is transmitted to each leaf node. The optimal distribution of MEs with different characteristics among ATN positions provides the greatest possible ATN reliability. The suggested algorithm is based on using a universal generating function technique for network reliability evaluation. A genetic algorithm is used as the optimization tool. Illustrative examples are presented

Evaluation of some antioxidants in radiation vulcanized ethylene-propylene diene (EPDM) rubber

Energy Technology Data Exchange (ETDEWEB)

Abdel-Aziz, M.M.; Basfar, A.A. E-mail: abasfar@kacst.edu.sa

2001-12-01

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) have been used to study the oxidation of {gamma}-ray vulcanized ethylene-propylene diene rubber (EPDM) stabilized with various types of antioxidants. The antioxidants used were pentaerythrityl tetrakis(3,5-di-tert-butyl(-4-hydroxyphenyl))propionate (Irganox 1010), Irganox 1035, Irganox 1520D, as primary antioxidants; Irganox B561 and Irganox B900, as synergistic blends; hindered amine light stabilizer (HALS), i.e. Tinuvin 622 LD; N-isopropyl-N-phenyl-p-phenylene diamine (IPPD) and trimethyl quinoline (TMQ) and their mixtures. The measurements were carried out under atmospheric conditions. The effects of antioxidant type and its selected concentration were determined and mechanism of reaction proposed.

A Directed Acyclic Graph-Large Margin Distribution Machine Model for Music Symbol Classification.

Directory of Open Access Journals (Sweden)

Cuihong Wen

Full Text Available Optical Music Recognition (OMR has received increasing attention in recent years. In this paper, we propose a classifier based on a new method named Directed Acyclic Graph-Large margin Distribution Machine (DAG-LDM. The DAG-LDM is an improvement of the Large margin Distribution Machine (LDM, which is a binary classifier that optimizes the margin distribution by maximizing the margin mean and minimizing the margin variance simultaneously. We modify the LDM to the DAG-LDM to solve the multi-class music symbol classification problem. Tests are conducted on more than 10000 music symbol images, obtained from handwritten and printed images of music scores. The proposed method provides superior classification capability and achieves much higher classification accuracy than the state-of-the-art algorithms such as Support Vector Machines (SVMs and Neural Networks (NNs.

The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

Energy Technology Data Exchange (ETDEWEB)

Grubbs, Robert H

2013-04-05

Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.

Transforming n=1 members of the Ruddlesden-Popper phases to a n=3 member through metathesis: synthesis of a new layered perovskite, Ca2La2CuTi2O10

International Nuclear Information System (INIS)

Sivakumar, T.; Lofland, S.E.; Ramanujachary, K.V.; Ramesha, K.; Subbanna, G.N.; Gopalakrishnan, J.

2004-01-01

We report the formation of a new n=3 Ruddlesden-Popper (R-P) layered perovskite oxide, Ca 2 La 2 CuTi 2 O 10 (I), in the metathesis reaction between NaLaTiO 4 and Ca 2 CuO 2 Cl 2 (n=1 R-P phases) at 700 deg. C in air. Rietveld refinement of powder XRD data shows that I is isostructural with Sr 4 Ti 3 O 10 (space group I4/mmm; a=3.8837(5), c=27.727(6) A), consisting of triple perovskite CuTi 2 O 10 sheets wherein Cu and Ti are ordered at the central and terminal octahedral sites, respectively. Magnetization data provide support for the presence of strong antiferromagnetically coupled CuO 2 sheets in the structure. I is metastable decomposing at higher temperatures (∼950 deg. C) to a mixture of perovskite-like CaLa 2 CuTi 2 O 9 and CaO. Interestingly, the reaction between NaLaTiO 4 and Sr 2 CuO 2 Cl 2 follows a different metathesis route, 2NaLaTiO 4 +Sr 2 CuO 2 Cl 2 →La 2 CuO 4 +2SrTiO 3 +2NaCl, revealing multiplicity of reaction pathways for solid-state metathesis reactions

Antiperovskite nitridophosphate oxide Ho{sub 3}[PN{sub 4}]O by high-pressure metathesis

Energy Technology Data Exchange (ETDEWEB)

Kloss, Simon D.; Weidmann, Niels; Schnick, Wolfgang [Department of Chemistry, University of Munich (LMU), Butenandtstrasse 5-13, 81377, Munich (Germany)

2017-04-03

Rare-earth nitridophosphates are a recently discovered class of materials, which are accessible by high-pressure metathesis. Antiperovskite-type Ho{sub 3}[PN{sub 4}]O was synthesized from HoF{sub 3}, LiPN{sub 2}, Li{sub 3}N, and Li{sub 2}O at 5 GPa and ca. 1025 C by this method and the multianvil technique. Ho{sub 3}[PN{sub 4}]O contains rarely observed isolated PN{sub 4} tetrahedra and can be derived by the hierarchical substitution of the ABX{sub 3} perovskite, in which Ho occupies the X positions, O occupies the B position, and the PN{sub 4} tetrahedra occupy the A position. The structure was refined on the basis of powder diffraction data [I4/mcm, a = 6.36112(3), c = 10.5571(1) Aa, Z = 4, R{sub wp} = 0.04, R{sub Bragg} = 0.01, χ{sup 2} = 2.275] starting from the structural model of isotypic Gd{sub 3}[SiN{sub 3}O]O. To characterize Ho{sub 3}[PN{sub 4}]O, elemental analyses were performed through energy-dispersive X-ray spectroscopy (EDX) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Ho{sub 3}[PN{sub 4}]O is paramagnetic down to low temperatures with μ{sub eff} = 10.43(1) μ{sub B} and a Curie temperature (Θ) of 0.11(4) K. It shows the optical characteristics of Ho{sup 3+} ions and vibrations corresponding to isolated PN{sub 4} tetrahedra. On the basis of DFT calculations [generalized gradient approximation (GGA)], Ho{sub 3}[PN{sub 4}]O has an indirect band gap of 1.87 eV. We demonstrate the versatility of high-pressure metathesis by attaining the low end of the P/N atomic ratio κ = 1/4. This confirms the previous assumption that rare-earth nitridophosphates with κ = 1/2 to 1/4 are feasible by this method. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Pd-Catalyzed N-Arylation of Secondary Acyclic Amides: Catalyst Development, Scope, and Computational Study

Science.gov (United States)

Hicks, Jacqueline D.; Hyde, Alan M.; Cuezva, Alberto Martinez; Buchwald, Stephen L.

2009-01-01

We report the efficient N-arylation of acyclic secondary amides and related nucleophiles with aryl nonaflates, triflates, and chlorides. This method allows for easy variation of the aromatic component in tertiary aryl amides. A new biaryl phosphine with P-bound 3,5-(bis)trifluoromethylphenyl groups was found to be uniquely effective for this amidation. The critical aspects of the ligand were explored through synthetic, mechanistic, and computational studies. Systematic variation of the ligand revealed the importance of (1) a methoxy group on the aromatic carbon of the “top ring” ortho to the phosphorus and (2) two highly electron-withdrawing P-bound 3,5-(bis)trifluoromethylphenyl groups. Computational studies suggest the electron-deficient nature of the ligand is important in facilitating amide binding to the LPd(II)(Ph)(X) intermediate. PMID:19886610

Stereo- and regioselectivity of the hetero-Diels-Alder reaction of nitroso derivatives with conjugated dienes.

Science.gov (United States)

Brulíková, Lucie; Harrison, Aidan; Miller, Marvin J; Hlaváč, Jan

2016-01-01

The hetero-Diels-Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2 H -1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds.

Synthesis of 17α-[(E)-2-[125I]iodoethenyl]androsta-4-6-dien-17β-o l-3-one, an active -site-directed photoaffinity radiolabel for androgen-binding proteins

International Nuclear Information System (INIS)

Diaz Cruz, P.J.; Smith, H.E.; Vanderbilt Univ., Nashville, TN; Danzo, B.J.; Clanton, J.A.; Mason, N.S.

1993-01-01

The active-site-directed photoaffinity radiolabel for androgen-binding proteins, 17α-[(E)-2-[ 125 I]iodoethenyl]androsta-4,6-dien-17β-ol-3-one, was prepared by reaction of 17α-[(E)-2-tributyltin(IV)ethenyl]androsta-4,6-dien-17β-ol-3-one with carrier added sodium iodide-125 in the presence of hydrogen peroxide and acetic acid. Purification by HPLC gave the radiolabeled steroid in 52% radiochemical yield with a specific activity of 27 Ci/mmol and 100% radiochemical purity. (author)

Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis

KAUST Repository

Pump, Eva

2015-06-30

The intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results.

Mechanism of the Ru–Allenylidene to Ru–Indenylidene Rearrangement in Ruthenium Precatalysts for Olefin Metathesis

KAUST Repository

Pump, Eva; Slugovc, Christian; Cavallo, Luigi; Poater, Albert

2015-01-01

The intramolecular allenylidene RuCl2(PR3)2(C═C═CPh2) to indenylidene RuCl2(PR3)2(Ind) rearrangement that occurs during the synthesis of Ru-based precatalysts for olefin metathesis is presented. In the absence of acid, the ring closure via C–H activation was shown to be unfavored for energy barriers up to 70 kcal/mol. Thus, it turned out to be HCl (or other acid) that plays a crucial role during formation of the indenylidene, as the upper energy barrier decreases to a reasonable 35 kcal/mol. Moreover, we proved computationally that depending on the nature of the phosphine the intramolecular rearrangement is either facilitated (PPh3) or slightly hampered (PCy3), which is in line with experimental results.

Morphology-properties relationship on nanocomposite films based on poly(styrene-block-diene-block-styrene copolymers and silver nanoparticles

Directory of Open Access Journals (Sweden)

2011-02-01

Full Text Available A comparative study on the self-assembled nanostructured morphology and the rheological and mechanical properties of four different triblock copolymers, based on poly(styrene-block-diene-block-styrene and poly(styrene-block-diene-block-styrene matrices, and of their respective nanocomposites with 1 wt% silver nanoparticles, is reported in this work. In order to obtain well-dispersed nanoparticles in the block copolymer matrix, dodecanethiol was used as surfactant, showing good affinity with both nanoparticles and the polystyrene phase of the matrices as predicted by the solubility parameters calculated based on Hoftyzer and Van Krevelen theory. The block copolymer with the highest PS content shows the highest tensile modulus and tensile strength, but also the smallest elongation at break. When silver nanoparticles treated with surfactant were added to the block copolymer matrices, each system studied shows higher mechanical properties due to the good dispersion and the good interface of Ag nanoparticles in the matrices. Furthermore, it has been shown that semiempirical models such as Guth and Gold equation and Halpin-Tsai model can be used to predict the tensile modulus of the analyzed nanocomposites.

Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines.

Science.gov (United States)

Pfister, Kai F; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J

2017-06-01

Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering.

Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

KAUST Repository

Chen, Yin; Abou-Hamad, Edy; Hamieh, Ali Imad Ali; Hamzaoui, Bilel; Emsley, Lyndon; Basset, Jean-Marie

2015-01-01

By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

Alkane metathesis with the tantalum methylidene [(≡SiO)Ta(=CH2)Me2]/[(≡SiO)2Ta(=CH2)Me] generated from well-defined surface organometallic complex [(≡SiO)TaVMe4

KAUST Repository

Chen, Yin

2015-01-21

By grafting TaMe5 on Aerosil700, a stable, well-defined, silica-supported tetramethyl tantalum(V) complex, [(≡SiO)TaMe4], is obtained on the silica surface. After thermal treatment at 150 °C, the complex is transformed into two surface tantalum methylidenes, [(≡SiO)2Ta(=CH2)Me] and [(≡SiO)Ta(=CH2)Me2], which are active in alkane metathesis and comparable to the previously reported [(≡SiO)2TaHx]. Here we present the first experimental study to isolate and identify a surface tantalum carbene as the intermediate in alkane metathesis. A systematic experimental study reveals a new reasonable pathway for this reaction.

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

Directory of Open Access Journals (Sweden)

Lucie Brulíková

2016-09-01

Full Text Available The hetero-Diels–Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2H-1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds.

Molecular structure and conformation of two acyclic polythioethers: Implications for the design of heavy metal chelators

Energy Technology Data Exchange (ETDEWEB)

Desper, J.M.; Powell, D.R.; Gellman, S.H. (Univ. of Wisconsin, Madison (USA))

1990-05-23

The crystal structures of the 1,9-bis(p-tolyl)-2,5,8-trithianonane (1) and 1,12-bis(p-tolyl)-2,5,8,11-tetrathiadodecane (2) are reported. Previous studies of macrocyclic polythioethers have revealed a pronounced tendency for backbone CS-CC bonds to adopt gauche torsion angles. The same tendency is observed in the homologous acyclic polythioethers 1 and 2, demonstrating that the gauche preference is not simply the result of a macrocyclic constraint. Because of this gauche preference of CS-CC torsion units and the well-established anti preference of SC-CS torsion units, polythioethers constructed from ethylene sulfide subunits are generally far from preorganized for metal ion chelation.

Polystyrene-Supported Acyclic Diaminocarbene Palladium Complexes in Sonogashira Cross-Coupling: Stability vs. Catalytic Activity

Directory of Open Access Journals (Sweden)

Vladimir N. Mikhaylov

2018-04-01

Full Text Available Two types of immobilized on the amino-functionalized polystyrene-supported acyclic diaminocarbene palladium complexes (ADC-PdII are investigated under Sonogashira cross-coupling conditions. Depending on substituents in the diaminocarbene fragment immobilized ADC-PdII, systems are found to have different catalytic activity and stability regarding Pd-leaching. PdII-diaminocarbenes possessing protons at both nitrogen atoms smoothly decompose into Pd0-containing species providing a catalytic “cocktail system” with high activity and ability to reuse within nine runs. Polymer-supported palladium (II complex bearing NBn–Ccarbene–NH-moiety exhibits greater stability while noticeably lower activity under Sonogashira cross-coupling. Four molecular ADC-PdII complexes are also synthesized and investigated with the aim of confirming proposed base-promoted pathway of ADC-PdII conversion through carbodiimide into an active Pd0 forms.

Surface characterisation of ethylene-propylene-diene rubber upon exposure to aqueous acidic solution

DEFF Research Database (Denmark)

Mitra, S.; Ghanbari-Siahkali, Afshin; Kingshott, P.

2006-01-01

but significantly different with respect to molar mass and the presence of long chain branching. Both rubbers contained 5-ethylidene-2-norbomene (ENB) as diene. Solution cast films of pure EPDM samples were exposed in two different acidic solutions, viz. chromosulphuric (Cr (VI)/H2SO4) and sulphuric acid (H2SO4....... Furthermore, 20% Cr (VI)/H2SO4 also attacked the allylic carbon-hydrogen (C-H) bonds of ENB resulting in more oxygenated species on the surface compared to 20% H2SO4 under identical conditions. Cr (VI) in the 20% Cr (VI)/H2SO4 was found to play an important role in alteration of surface chemistry. Studies...

Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

Energy Technology Data Exchange (ETDEWEB)

Vatansever, Fatma, E-mail: vatansever.fatma@mgh.harvard.edu; Hamblin, Michael R., E-mail: hamblin@helix.mgh.harvard.edu [Massachusetts General Hospital, Wellman Center for Photomedicine (United States)

2016-10-15

Core–shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original tri-octylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48–53 nm.

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

KAUST Repository

Żukowska, Karolina; Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi; Slugovc, Christian

2015-01-01

Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

KAUST Repository

Żukowska, Karolina

2015-08-20

Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes.

Study of ethylene/2-butene cross-metathesis over W-H/Al2O 3 for propylene production: Effect of the temperature and reactant ratios on the productivity and deactivation

KAUST Repository

Mazoyer, Etienne

2013-05-01

A highly active and selective catalyst based on supported tungsten hydride for the cross-metathesis between ethylene and 2-butenes yielding propylene has been investigated at low pressure with various temperatures and feed ratios. At low temperature (120 °C), the catalyst deactivates notably with time on stream. This phenomenon was extensively examined by DRIFTS, TGA, DSC, and solid-state NMR techniques. It was found that a large amount of carbonaceous species were formed due to a side-reaction such as olefin polymerization which took place simultaneously with the metathesis reaction. However, at 150 °C, the catalyst was stable with time and thereby gave a high productivity in propylene. Importantly, the slight increase in temperature clearly disfavored the side reaction. The ratio of ethylene to trans-2-butene was also studied, and surprisingly, the W-H/Al2O3 catalyst is stable and highly selective to propylene even at substoichiometric ethylene ratios. © 2013 Elsevier Inc. All rights reserved.

Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

KAUST Repository

Mazoyer, Etienne; Merle, Nicolas; Mallmann, Aimery De; Basset, Jean-Marie; Berrier, Elise; Delevoye, Laurent; Paul, Jean Franois; Nicholas, Christopher P.; Gauvin, Ré gis M.; Taoufik, Mostafa

2010-01-01

A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts. © 2010 The Royal Society of Chemistry.

Conformational analysis of an acyclic tetrapeptide: ab-initio structure determination from X-ray powder diffraction, Hirshfeld surface analysis and electronic structure.

Science.gov (United States)

Das, Uday; Naskar, Jishu; Mukherjee, Alok Kumar

2015-12-01

A terminally protected acyclic tetrapeptide has been synthesized, and the crystal structure of its hydrated form, Boc-Tyr-Aib-Tyr-Ile-OMe·2H2O (1), has been determined directly from powder X-ray diffraction data. The backbone conformation of tetrapeptide (1) exhibiting two consecutive β-turns is stabilized by two 4 → 1 intramolecular N-H · · · O hydrogen bonds. In the crystalline state, the tetrapeptide molecules are assembled through water-mediated O-H · · · O hydrogen bonds to form two-dimensional molecular sheets, which are further linked by intermolecular C-H · · · O hydrogen bonds into a three-dimensional supramolecular framework. The molecular electrostatic potential (MEP) surface of (1) has been used to supplement the crystallographic observations. The nature of intermolecular interactions in (1) has been analyzed quantitatively through the Hirshfeld surface and two-dimensional fingerprint plot. The DFT optimized molecular geometry of (1) agrees closely with that obtained from the X-ray structure analysis. The present structure analysis of Boc-Tyr-Aib-Tyr-Ile-OMe·2H2 O (1) represents a case where ab-initio crystal structure of an acyclic tetrapeptide with considerable molecular flexibility has been accomplished from laboratory X-ray powder diffraction data. Copyright © 2015 European Peptide Society and John Wiley & Sons, Ltd.

Moving from Classical Ru-NHC to Neutral or Charged Rh-NHC Based Catalysts in Olefin Metathesis

Directory of Open Access Journals (Sweden)

Albert Poater

2016-01-01

Full Text Available Considering the versatility of oxidation states of rhodium together with the successful background of ruthenium-N-heterocyclic carbene based catalysts in olefin metathesis, it is envisaged the exchange of the ruthenium of the latter catalysts by rhodium, bearing an open-shell neutral rhodium center, or a +1 charged one. In the framework of in silico experiments, density functional theory (DFT calculations have been used to plot the first catalytic cycle that as a first step includes the release of the phosphine. DFT is, in this case, the tool that allows the discovery of the less endergonic reaction profile from the precatalytic species for the neutral catalyst with respect to the corresponding ruthenium one; increasing the endergonic character when dealing with the charged system.

Poisoning Experiments Aimed at Discriminating Active and Less-Active Sites of Silica-Supported Tantalum Hydride for Alkane Metathesis

KAUST Repository

Saggio, Guillaume

2010-10-04

Only 50% of the silica-supported tantalum hydride sites are active in the metathesis of propane. Indeed, more than 45% of the tantalum hydride can be eliminated by a selective oxygen poisoning of inactive sites with no significant decrease in the global turnover. Conversely, cyclopentane induces no such selective poisoning. Hence, the active tantalum hydride sites that show greater resistance to oxygen poisoning correspond to the νTa-H bands of higher wavenumbers, particularly that at 1860cm-1. These active tantalum hydride sites should correspond to tris- or monohydride species relatively far from silica surface oxygen atoms. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ludwig, un roi sur la lune : l’histoire d’un roi fou jouée par des comédien.ne.s en situation de handicap mental

Directory of Open Access Journals (Sweden)

Marie Astier

2017-12-01

Full Text Available Ludwig, un roi sur la lune, spectacle mis en scène par Madeleine Louarn avec les comédien.ne.s professionnels en situation de handicap mental de l’Atelier Catalyse et présenté lors de la dernière édition du Festival d’Avignon n’est pas une reconstitution historique de la vie de Louis II de Bavière, roi du XIXe siècle diagnostiqué paranoïaque et destitué pour être interné, mais une tentative de transcrire théâtralement la perception du monde d’un homme amoureux de l’Art, de la nature et des hommes, mais qui devait être Roi. Ce n’est ni un personnage ni des comédien.ne.s « handicapé.e.s » que nous sommes invités à voir, mais les visions de Ludwig incarnées par des comédien.ne.s qui se trouvent être en situation de handicap mental. Dans ce spectacle, la « folie » devenue plus tard « handicap mental » apparaît sous les traits de la non-conformité bien plus que sous ceux de la pathologie.

Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

Directory of Open Access Journals (Sweden)

Shawna L. Balof

2015-10-01

Full Text Available Three new ruthenium alkylidene complexes (PCy3Cl2(H2ITapRu=CHSPh (9, (DMAP2Cl2(H2ITapRu=CHPh (11 and (DMAP2Cl2(H2ITapRu=CHSPh (12 have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl-4,5-dihydroimidazol-2-ylidene. Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP and ring closing metathesis (RCM reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA, however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD and mixtures of DCPD with cyclooctene (COE in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes.

Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

Science.gov (United States)

Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

2015-09-23

Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

Directed acyclic graphs (DAGs): an aid to assess confounding in dental research.

Science.gov (United States)

Merchant, Anwar T; Pitiphat, Waranuch

2002-12-01

Confounding, a special type of bias, occurs when an extraneous factor is associated with the exposure and independently affects the outcome. In order to get an unbiased estimate of the exposure-outcome relationship, we need to identify potential confounders, collect information on them, design appropriate studies, and adjust for confounding in data analysis. However, it is not always clear which variables to collect information on and adjust for in the analyses. Inappropriate adjustment for confounding can even introduce bias where none existed. Directed acyclic graphs (DAGs) provide a method to select potential confounders and minimize bias in the design and analysis of epidemiological studies. DAGs have been used extensively in expert systems and robotics. Robins (1987) introduced the application of DAGs in epidemiology to overcome shortcomings of traditional methods to control for confounding, especially as they related to unmeasured confounding. DAGs provide a quick and visual way to assess confounding without making parametric assumptions. We introduce DAGs, starting with definitions and rules for basic manipulation, stressing more on applications than theory. We then demonstrate their application in the control of confounding through examples of observational and cross-sectional epidemiological studies.

Bifurcatriol, a New Antiprotozoal Acyclic Diterpene from the Brown Alga Bifurcaria bifurcata

Directory of Open Access Journals (Sweden)

Vangelis Smyrniotopoulos

2017-08-01

Full Text Available Linear diterpenes that are commonly found in brown algae are of high chemotaxonomic and ecological importance. This study reports bifurcatriol (1, a new linear diterpene featuring two stereogenic centers isolated from the Irish brown alga Bifurcaria bifurcata. The gross structure of this new natural product was elucidated based on its spectroscopic data (IR, 1D and 2D-NMR, HRMS. Its absolute configuration was identified by experimental and computational vibrational circular dichroism (VCD spectroscopy, combined with the calculation of 13C-NMR chemical shielding constants. Bifurcatriol (1 was tested for in vitro antiprotozoal activity towards a small panel of parasites (Plasmodium falciparum, Trypanosoma brucei rhodesiense, T. cruzi, and Leishmania donovani and cytotoxicity against mammalian primary cells. The highest activity was exerted against the malaria parasite P. falciparum (IC50 value 0.65 μg/mL with low cytotoxicity (IC50 value 56.6 μg/mL. To our knowledge, this is the first successful application of VCD and DP4 probability analysis of the calculated 13C-NMR chemical shifts for the simultaneous assignment of the absolute configuration of multiple stereogenic centers in a long-chain acyclic natural product.

Synthesis of modified cyclic and acyclic dextrins and comparison of their complexation ability

Directory of Open Access Journals (Sweden)

Kata Tuza

2014-12-01

Full Text Available We compared the complex forming ability of α-, β- and γ-cyclodextrins (α-CD, β-CD and γ-CD with their open ring analogs. In addition to the native cyclodextrins also modified cyclodextrins and the corresponding maltooligomers, functionalized with neutral 2-hydroxypropyl moieties, were synthesized. A new synthetic route was worked out via bromination, benzylation, deacetylation and debenzylation to obtain the 2-hydroxypropyl maltooligomer counterparts. The complexation properties of non-modified and modified cyclic and acyclic dextrins were studied and compared by photon correlation spectroscopy (PCS and capillary electrophoresis (CE using model guest compounds. In some cases cyclodextrins and their open-ring analogs (acyclodextrins show similar complexation abilities, while with other guests considerably different behavior was observed depending on the molecular dimensions and chemical characteristics of the guests. This was explained by the enhanced flexibility of the non-closed rings. Even the signs of enantiorecognition were observed for the chloropheniramine/hydroxypropyl maltohexaose system. Further studies are planned to help the deeper understanding of the interactions.

The Effect of Nitrogen Surface Ligands on Propane Metathesis: Design and Characterizations of N-modified SBA15-Supported Schrock-type Tungsten Alkylidyne

KAUST Repository

Eid, Ahmed A.

2014-04-01

Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science[1]. Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis[1]. The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts[2]. The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands: -\\tOne with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and, -\\tAnother\\tone\\twith\\tvicinal\\tbis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15[3]. The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis. The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials[4]. A fairly good

Structural determination of ethylene-propylene-diene rubber (EPDM) containing high degree of controlled long-chain branching

DEFF Research Database (Denmark)

Mitra, Susanta; Jørgensen, Mikkel; Pedersen, Walther Batsberg

2009-01-01

findings and the available theories, an attempt was made to identify the chemical nature and degree of LCB. This study reveals the possibility of detailed characterization of molecular architecture of EPDM containing LCB by comparing with an essentially linear EPDM in light of an existing theory. © 2009...... mass and the presence of LCB. Both rubbers contained 5-ethylidene-2-norbornene (ENB) as diene. Solution cast films of pure EPDM samples were used for different characterization techniques. 1H-NMR, and 13C-NMR were used for assessing the comonomer ratios and LCB. Size exclusion chromatography (SEC...

A Modular Approach to Aryl-C-ribonucleosides via the Allylic Substitution and Ring-Closing Metathesis Sequence. A Stereocontrolled Synthesis of All Four alpha-/beta- and D-/L-C-Nucleoside Stereoisomers

Czech Academy of Sciences Publication Activity Database

Štambaský, J.; Kapras, V.; Štefko, Martin; Kysilka, O.; Hocek, Michal; Malkov, A. V.; Kočovský, P.

2011-01-01

Roč. 76, č. 19 (2011), s. 7781-7803 ISSN 0022-3263 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550902 Institutional research plan: CEZ:AV0Z40550506 Keywords : C-nucleosides * allylic substitution * metathesis * dihydroxylation Subject RIV: CC - Organic Chemistry Impact factor: 4.450, year: 2011

Diethylenetriamine/diamines/copper (II complexes [Cu(dien(NN]Br2: Synthesis, solvatochromism, thermal, electrochemistry, single crystal, Hirshfeld surface analysis and antibacterial activity

Directory of Open Access Journals (Sweden)

Fatima Abu Saleemh

2017-09-01

Full Text Available Two dicationic water soluble mixed triamine/diamine copper (II complexes, of general formula [Cu(dienNN]Br2 (1–2 [dien = diethelenetriamine and NN is en = ethylenediamine or Me4en = N,N′,N,N′-tetramethylethylenediamine] were prepared under ultrasonic mode with a relatively high yield. These complexes were characterized by elemental microanalysis, UV visible IR spectroscopy, and thermal and electrochemical techniques. In addition, complex 2 structure was solved by X-ray single crystal and Hirshfeld surface analysis. The complex exhibits a distorted square pyramidal coordination environment around Cu(II centre. The solvatochromism of the desired complexes was investigated in water and other suitable organic solvents. The results show that the Guttmann’s DN parameter values of the solvents have mainly contributed to the shift of the d–d absorption band towards the linear increase in the wavelength of the absorption maxima of the complexes. The complex 1 showed higher antibacterial activity against the studied microorganisms compared to complex 2. Both complexes revealed promising antibacterial activities.

Spectral, Electrochemical, Fluorescence, Kinetic and Anti-microbial Studies of Acyclic Schiff-base Gadolinium(III) Complexes

International Nuclear Information System (INIS)

Vijayaraj, A.; Prabu, R.; Suresh, R.; Narayanan, V.; Sangeetha Kumari, R.; Kaviyarasan, V.

2012-01-01

A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V. The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity

Spectral, Electrochemical, Fluorescence, Kinetic and Anti-microbial Studies of Acyclic Schiff-base Gadolinium(III) Complexes

Energy Technology Data Exchange (ETDEWEB)

Vijayaraj, A.; Prabu, R.; Suresh, R.; Narayanan, V.; Sangeetha Kumari, R.; Kaviyarasan, V. [Univ. of Madras, Madras (India)

2012-11-15

A new series of acyclic mononuclear gadolinium(III) complexes have been prepared by Schiff-base condensation derived from 5-methylsalicylaldehyde, diethylenetriamine, tris(2-aminoethyl) amine, triethylenetetramine, N,N-bis(3-aminopropyl)ethylene diamine, N,N-bis(aminopropyl) piperazine, and gadolinium nitrate. All the complexes were characterized by elemental and spectral analyses. Electronic spectra of the complexes show azomethine (CH=N) within the range of 410-420 nm. The fluorescence efficiency of Gd(III) ion in the cavity was completely quenched by the higher chain length ligands. Electrochemical studies of the complexes show irreversible one electron reduction process around -2.15 to -1.60 V. The reduction potential of gadolinium(III) complexes shifts towards anodic directions respectively upon increasing the chain length. The catalytic activity of the gadolinium(III) complexes on the hydrolysis of 4-nitrophenylphosphate was determined. All gadolinium(III) complexes were screened for antibacterial activity.

Abcès thyroïdien révélant un basedow: à propos d'un cas et revue ...

African Journals Online (AJOL)

Une radiographie thoracique a été demandée montrant un foyer alvéolaire pulmonaire apical droit. L'étude cytobactériologique des crachats ont isolé le bacille de koch. Le bilan biologique thyroïdien était en faveur d'un Basedow. La prise en charge était médicale comprenait une tri-antibiothérapie par voie parentérale, ...

Structure aggregation of carbon black in ethylene-propylene diene polymer

Directory of Open Access Journals (Sweden)

2009-03-01

Full Text Available The modulus of filled and unfilled Ethylene-propylene diene rubber (EPDM vulcanizates was used to predict the shape-factor of carbon black aggregation in the polymer. Four types of carbon black that vary in particle size and structure were used in this study. Quadratic curves relating the carbon black volume concentration and the modulus ratio of filled and unfilled rubber vulcanizates were used to adopt the shape factor of certain carbon black type. The shape factor of MT, HAF, SRF and Lampblack were 3, 3.75, 4 and 4.25 respectively. X-ray diffraction technique (XRD was also used to evaluate the relative size of crystallite on the filler surface to that of the rubber and correlating it to the shape factor of carbon black aggregation in the polymer. Effect of the pH values and structure of carbon blacks used on the shape factor of filler aggregates were also studied. It was found that the shape factor is independent on the particle size while it is dependent on the pH value and structure of carbon black. Also the crystallites size of the filler is proportional to the shape factor.

Evaluation of Novel Acyclic Nucleoside Phosphonates against Human and Animal Gammaherpesviruses Revealed an Altered Metabolism of Cyclic Prodrugs upon Epstein-Barr Virus Reactivation in P3HR-1 Cells

Czech Academy of Sciences Publication Activity Database

Coen, N.; Duraffour, S.; Naesens, L.; Krečmerová, Marcela; Van Den Oord, J.; Snoeck, R.; Andrei, G.

2013-01-01

Roč. 87, č. 22 (2013), s. 12422-12432 ISSN 0022-538X R&D Projects: GA MPO FR-TI4/625 Institutional support: RVO:61388963 Keywords : acyclic nucleoside phosphonate * gammaherpesvirus * Epstein-Barr virus * Kaposi's sarcoma * HPMP-5-azaC * cidofovir Subject RIV: EE - Microbiology, Virology Impact factor: 4.648, year: 2013

Synthesis of densely functionalized enantiopure indolizidines by ring-closing metathesis (RCM of hydroxylamines from carbohydrate-derived nitrones

Directory of Open Access Journals (Sweden)

Goti Andrea

2007-12-01

Full Text Available Abstract Background Indolizidine alkaloids widely occur in nature and display interesting biological activity. This is the reason for which their total synthesis as well as the synthesis of non-natural analogues still attracts the attention of many research groups. To establish new straightforward accesses to these molecules is therefore highly desirable. Results The ring closing metathesis (RCM of enantiopure hydroxylamines bearing suitable unsaturated groups cleanly afforded piperidine derivatives in good yields. Further cyclization and deprotection of the hydroxy groups gave novel highly functionalized indolizidines. The synthesis of a pyrroloazepine analogue is also described. Conclusion We have developed a new straightforward methodology for the synthesis of densely functionalized indolizidines and pyrroloazepine analogues in 6 steps and 30–60% overall yields from enantiopure hydroxylamines obtained straightforwardly from carbohydrate-derived nitrones.

Rapid synthesis of graphitic carbon nitride powders by metathesis reaction between CaCN2 and C2Cl6

International Nuclear Information System (INIS)

Pang Linlin; Bi Jianqiang; Bai Yujun; Qi Yongxin; Zhu Huiling; Wang Chengguo; Wu Jiwei; Lu Chengwei

2008-01-01

Carbon nitride powders were rapidly synthesized at low temperature via the chemical metathesis reaction between CaCN 2 and C 2 Cl 6 . X-ray diffraction results confirm the formation of crystalline graphitic carbon nitride. Besides the dominant morphology of nanoparticles, flakes, nanorods, hollow and solid spheres can be observed by transmission electron microscopy. The absorption peaks of C-N, C=N and s-triazine rings, as well as the absence of C≡N peak in the infrared spectra, further verify the formation of graphite-like sp 2 -bonded structure with planar networks. Elemental analysis gives an atomic ratio of N/C around 0.3. X-ray photoelectron spectra exhibit the existence of chemical bonding between C and N

An investigation on changes in chemical properties of pure ethylene-propylene-diene rubber in aqueous acidic environments

DEFF Research Database (Denmark)

Mitra, S.; Ghanbari-Siahkali, Afshin; Kingshott, Peter

2006-01-01

The influence of two aqueous acidic environments on two types of pure ethylene-propylene-diene (EPDM) rubber (i.e., elastomer) thin films is studied. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) results revealed the formation of several oxygenated species...... formation on the surface of EPDM rubbers compared to 20% H2SO4 under identical conditions. Complex formation on the surface of EPDM samples exposed to 20% Cr(VI)/H2SO4 through reactions of carboxylic groups (generated due to EPDM degradation) with Cr(III) (formed due to reduction of Cr(VI)) was also evident...

Synthesis and Crystal Structure Determination of a Nickel(II Complex of an Acyclic Pentadentate (N5 Mono Schiff Base Ligand

Directory of Open Access Journals (Sweden)

R. V. Parish

2001-10-01

Full Text Available The asymmetrical tripodal tetraamine ligand N[(CH23NH2]2[(CH22NH2] (ppe was condensed with 2-acetylpyridine in the presence of nickel(II ion. In ethanolwater solution the reaction stops after the first stage of condensation, and a new nickel(II complex of an acyclic pentadentate (N5 mono Schiff base ligand was obtained. X-ray structure analysis of the resulting complex, [Ni(ppe-py(H2O](ClO42, indicates that condensation with 2-acetylpyridine is at the propylene chain of ppe. The geometry around the nickel ion is distorted octahedral in which the sixth co-ordination group is a solvent molecule.

Combining the [2,3] Sigmatropic Rearrangement and Ring-Closing Metathesis Strategies for the Synthesis of Spirocyclic Alkaloids. A Short and Efficient Route to (+/-)-Perhydrohistrionicotoxin

DEFF Research Database (Denmark)

Tanner, David Ackland; Hagberg, Lars; Poulsen, Anders

1999-01-01

This paper describes the use of selenium-based [2,3] sigmatropic rearrangement in combination with ruthenium-catalyzed ring-closing metathesis (RCM) for the synthesis of azaspiro ring systems, as exemplified by the reactions of model substrates 5 and 6. The methodology has been applied to a short...... is potentially enantioselective, and key steps were the [2,3] sigmatropic rearrangement of 11 to 12 via the corresponding allylic selenide (86% yield) and ruthenium-catalyzed RCM of 13 to 14 (80%). (C) 1999 Elsevier Science Ltd. All rights reserved....

Synthesis and characterization of a homogeneous and silica supported homoleptic cationic tungsten(vi) methyl complex: application in olefin metathesis

KAUST Repository

Dey, Raju

2016-08-19

A method for the synthesis of a homogeneous cationic tungsten(VI)penta-methyl complex [(WMe5)(+)(C6F5)(3)BMe-] from neutral tungstenhexamethyl (WMe6) and a silica supported cationic tungstentetramethyl complex [( Si-O-)WMe4+ (C6F5)(3)BMe-] from a neutral silica supported tungstenpentamethyl complex [( Si-O-)WMe5] is described. In both cases a direct demethylation using the B(C6F5)(3) reagent was used. The aforesaid complexes were characterized by liquid or solid state NMR spectroscopy. Interestingly, the homogeneous cationic complex [(WMe5)(+)(C6F5)(3)BMe-] shows moderate activity whereas the supported cationic complex [( Si-O-)WMe4+(C6F5)(3)BMe-] exhibits good activity in olefin metathesis reactions.

Synthesis and characterization of a homogeneous and silica supported homoleptic cationic tungsten(vi) methyl complex: application in olefin metathesis

KAUST Repository

Dey, Raju; Samantaray, Manoja; Poater, Albert; Hamieh, Ali Imad Ali; Kavitake, Santosh Giridhar; Abou-Hamad, Edy; Callens, Emmanuel; Emwas, Abdul-Hamid M.; Cavallo, Luigi; Basset, Jean-Marie

2016-01-01

A method for the synthesis of a homogeneous cationic tungsten(VI)penta-methyl complex [(WMe5)(+)(C6F5)(3)BMe-] from neutral tungstenhexamethyl (WMe6) and a silica supported cationic tungstentetramethyl complex [( Si-O-)WMe4+ (C6F5)(3)BMe-] from a neutral silica supported tungstenpentamethyl complex [( Si-O-)WMe5] is described. In both cases a direct demethylation using the B(C6F5)(3) reagent was used. The aforesaid complexes were characterized by liquid or solid state NMR spectroscopy. Interestingly, the homogeneous cationic complex [(WMe5)(+)(C6F5)(3)BMe-] shows moderate activity whereas the supported cationic complex [( Si-O-)WMe4+(C6F5)(3)BMe-] exhibits good activity in olefin metathesis reactions.

Novel UTP derivative with diene-containing spacer arm for Diels-Alder reaction: potential tool for radioactive or fluorescent detection upon its incorporation into ribonucleic acid

Czech Academy of Sciences Publication Activity Database

Točík, Zdeněk; Krásný, Libor; Kovačková, Soňa; Rejman, Dominik; Rosenberg, Ivan

2007-01-01

Roč. 6, č. 5 (2007), s. 357 ISSN 1535-3508. [International Conference of the European Society for Molecular Imaging /2./. 14.06.2007-15.06.2007, Naples] Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50520701 Keywords : UTP derivative * Diels - Alder reaction * diene * spacer arm Subject RIV: CC - Organic Chemistry

Crystal structure of chloridobis[(1,2,5,6-η-cycloocta-1,5-diene]iridium(I

Directory of Open Access Journals (Sweden)

A. K. Fazlur Rahman

2017-02-01

Full Text Available The title complex, [IrCl(C8H122], was synthesized directly from the reaction of IrCl3·3H2O with a large excess of cod (cod = cycloocta-1,5-diene in alcoholic solvent. Large yellow needles were obtained by the slow cooling of a hot solution. Based on the positions of the chloride ligand and the mid-points of the four C=C bonds, the molecule adopts a five-coordinate geometry that is midway between square pyramidal and trigonal bipyramidal. The material crystallizes in the orthorhombic space group Pbca with one molecule per asymmetric unit in a general position and shows no significant intermolecular interactions. Individual molecules are aligned along [010], and these rows form a pseudo-hexagonal packing arrangement.

Function-oriented synthesis: biological evaluation of laulimalide analogues derived from a last step cross metathesis diversification strategy.

Science.gov (United States)

Mooberry, Susan L; Hilinski, Michael K; Clark, Erin A; Wender, Paul A

2008-01-01

Laulimalide is a potent microtubule stabilizing agent and a promising anticancer therapeutic lead. The identification of stable, efficacious and accessible analogues is critical to clinically exploiting this novel lead. To determine which structural features of laulimalide are required for beneficial function and thus for accessing superior clinical candidates, a series of side chain analogues were prepared through a last step cross metathesis diversification strategy and their biological activities were evaluated. Five analogues, differing in potency from 233 nM to 7.9 muM, effectively inhibit cancer cell proliferation. Like laulimalide, they retain activity against multidrug resistant cells, stabilize microtubules and cause the formation of aberrant mitotic spindles, mitotic accumulation, Bcl-2 phosphorylation and initiation of apoptosis. Structural modifications in the C 23-C 27 dihydropyran side chain can be made without changing the overall mechanism of action, but it is clear that this subunit has more than a bystander role.

A novel 13 residue acyclic peptide from the marine snail, Conus monile, targets potassium channels.

Science.gov (United States)

Sudarslal, Sadasivannair; Singaravadivelan, Govindaswamy; Ramasamy, Palanisamy; Ananda, Kuppanna; Sarma, Siddhartha P; Sikdar, Sujit K; Krishnan, K S; Balaram, Padmanabhan

2004-05-07

A novel 13-residue peptide Mo1659 has been isolated from the venom of a vermivorous cone snail, Conus monile. HPLC fractions of the venom extract yielded an intense UV absorbing fraction with a mass of 1659Da. De novo sequencing using both matrix assisted laser desorption and ionization and electrospray MS/MS methods together with analysis of proteolytic fragments successfully yielded the amino acid sequence, FHGGSWYRFPWGY-NH(2). This was further confirmed by comparison with the chemically synthesized peptide and by conventional Edman sequencing. Mo1659 has an unusual sequence with a preponderance of aromatic residues and the absence of apolar, aliphatic residues like Ala, Val, Leu, and Ile. Mo1659 has no disulfide bridges distinguishing it from the conotoxins and bears no sequence similarity with any of the acyclic peptides isolated thus far from the venom of cone snails. Electrophysiological studies on the effect of Mo1659 on measured currents in dorsal root ganglion neurons suggest that the peptide targets non-inactivating voltage-dependent potassium channels.

Stereo-controlled synthesis of polyheterocycles via the diene-transmissive hetero-Diels-Alder reaction of β,γ-unsaturated α-keto esters.

Science.gov (United States)

Otani, Takashi; Tamai, Yumiko; Seki, Kazunori; Kikuchi, Tomohiro; Miyazawa, Taiichiro; Saito, Takao

2015-06-07

We describe the stereoselective synthesis of polyring-fused heterocyclic compounds based on diene-transmissive hetero-Diels-Alder reactions utilizing β,γ-unsaturated α-keto esters. This protocol involves the initial endo- or exo-selective Diels-Alder (DA) reactions with electron-rich dienophiles, methylenation of the ester carbonyl groups with the Tebbe reagent, and a stereoselective second DA reaction with electron-deficient dienophiles. The use of enantioselective DA reactions in the initial reaction enables access to chiral polyring-fused heterocyclic compounds with multiple chiral centres.

Absolute rate constants for the reaction of NO₃ radicals with a series of dienes at 295 K

DEFF Research Database (Denmark)

Ellermann, T.; Nielsen, O.J.; Skov, H.

1992-01-01

The rate constants for the reaction of NO3 radicals with a series of 7 dienes, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, trans-1,3-pentadiene, cis-1,3-pentadiene, trans,trans-2,4-hexadiene, and 1,3-cyclohexadiene, were measured at 295 K and at a total pressure of 1 atm. The rate consta...... were obtained using the absolute technique of pulse radiolysis combined with kinetic UV-VIS spectroscopy. The results are discussed in terms of reactivity trends and previous literature data....

Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

KAUST Repository

Pump, Eva; Poater, Albert; Zirngast, Michaela; Torvisco, Ana; Fischer, Roland C.; Cavallo, Luigi; Slugovc, Christian

2014-01-01

A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity

KAUST Repository

Pump, Eva

2014-06-09

A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.

Accuracy of a new ring-opening metathesis elastomeric dental impression material with spray and immersion disinfection.

Science.gov (United States)

Kronström, Mats H; Johnson, Glen H; Hompesch, Richard W

2010-01-01

A new elastomeric impression material has been formulated with a ring-opening metathesis chemistry. In addition to other properties of clinical significance, the impression accuracy must be confirmed. The purpose of this study was to compare the accuracy of the new elastomeric impression material with vinyl polysiloxane and polyether following both spray and immersion disinfection. Impressions of a modified dentoform with a stainless steel crown preparation in the lower right quadrant were made, and type IV gypsum working casts and dies were formed. Anteroposterior (AP), cross-arch (CA), buccolingual (BL), mesiodistal (MD), occlusogingivobuccal (OGB), and occlusogingivolingual (OGL) dimensions were measured using a microscope. Working cast and die dimensions were compared to those of the master model. The impression materials were a newly formulated, ring-opening metathesis-polymerization impression material (ROMP Cartridge Tray and ROMP Volume Wash), vinyl polysiloxane (VPS, Aquasil Ultra Monophase/LV), and a polyether (PE, Impregum Penta Soft/Permadyne Garant L). Fifteen impressions with each material were made, of which 5 were disinfected by spray for 10 minutes (CaviCide), 5 were disinfected by immersion for 90 minutes (ProCide D), and 5 were not disinfected. There were significant cross-product interactions with a 2-way ANOVA, so a 1-way ANOVA and Dunnett's T3 multiple comparison test were used to compare the dimensional changes of the 3 impression materials, by disinfection status and for each location (alpha=.05). For ROMP, there were no significant differences from the master, for any dimension, when comparing the control and 2 disinfectant conditions. No significant differences were detected among the 3 impression materials for CA, BL, and MD. The working die dimensions of OGB and OGL for VPS with immersion disinfection were significantly shorter than with PE and ROMP (P<.05). Overall, the AP dimension was more accurate than CA, and the BL of working dies

Synthesis and Characterization of Pyridino(1,4-Η-cyclohexa-1,3-dieneDerivatives of Iron Tricarbonyl Complexes

Directory of Open Access Journals (Sweden)

T. I. Odiaka

2011-01-01

Full Text Available In this synthesis, we have been able to show that, the addition of x- substituted pyridines, (X = H, 2- Me, 3- Me 4- Me, 4-NH2 and 4-N(CH32 to the dienyl ring of the organometallic cation, [(Fe(CO3 (1-5- η-2-Me0C3H6]BF4 and [(Fe(CO3(1-5-η-C6H7]BF4 gives ionic substituted diene products, (X C5H4-C6H6Y (Fe(CO3] BF4,Y=H or 2-MeO. The reaction takes place at ordinary room temperature. The resulting products were isolated and characterized.

Olefin Metathesis with Ru-Based Catalysts Exchanging the Typical N-Heterocyclic Carbenes by a Phosphine–Phosphonium Ylide

Directory of Open Access Journals (Sweden)

Laia Arnedo

2017-03-01

Full Text Available Density functional theory (DFT calculations have been used to describe the first turnover of an olefin metathesis reaction calling for a new in silico family of homogenous Ru-based catalysts bearing a phosphine–phosphonium ylide ligand, with ethylene as a substrate. Equal to conventional Ru-based catalysts bearing an N-heterocyclic carbene (NHC ligand, the activation of these congeners occurs through a dissociative mechanism, with a more exothermic first phosphine dissociation step. In spite of a stronger electron-donating ability of a phosphonium ylide C-ligand with respect to a diaminocarbene analogue, upper energy barriers were calculated to be on average ca. 5 kcal/mol higher than those of Ru–NHC standards. Overall, the study also highlights advantages of bidentate ligands over classical monodentate NHC and phosphine ligands, with a particular preference for the cis attack of the olefin. The new generation of catalysts is constituted by cationic complexes potentially soluble in water, to be compared with the typical neutral Ru–NHC ones.

How does the addition of steric hindrance to a typical N-heterocyclic carbene ligand affect catalytic activity in olefin metathesis?

KAUST Repository

Poater, Albert; Falivene, Laura; Urbina-Blanco, Cé sar A.; Manzini, Simone; Nolan, Steven P.; Cavallo, Luigi

2013-01-01

Density functional theory (DFT) calculations were used to predict and rationalize the effect of the modification of the structure of the prototype 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) N-heterocyclic carbene (NHC) ligand. The modification consists in the substitution of the methyl groups of ortho isopropyl substituent with phenyl groups, and here we plan to describe how such significant changes affect the metal environment and therefore the related catalytic behaviour. Bearing in mind that there is a significant structural difference between both ligands in different olefin metathesis reactions, here by means of DFT we characterize where the NHC ligand plays a more active role and where it is a simple spectator, or at least its modification does not significantly change its catalytic role/performance. © 2013 The Royal Society of Chemistry.

Olefins metathesis, synthesis and properties of homogeneous models of the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst; Methathese des olefines, synthese et proprietes des modeles homogenes du catalyseur Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3}

Energy Technology Data Exchange (ETDEWEB)

Doledec, G.

1999-10-05

The aim of this work was to synthesize and to study homogeneous models of the rhenium oxide on alumina catalyst in order to better understand the influence of the alumina environment over the activity in olefin metathesis. A series of aluminium complexes (ArO){sub 2}Al-Y have been synthesised, where ArO is a 4-substituted-2,6-di-tert-butyl-phenoxy, or (ArO){sub 2} is a CH{sub 2{sup -}} or S-ortho bridged-4,4'-di-tert-butyl-di-phenoxy, and Y is an alkyl or chlorine ligand. The reaction of (ArO){sub 2}Al-Cl with AgReO{sub 4} led to new complexes (ArO){sub 2}Al-OReO{sub 3} (A). These complexes exhibit a low to moderate activity in metathesis of 2-pentene (TOF = 0,5 min{sup -1} at 25 deg. C in a toluene solution). Complexes (ArO){sub 2}Al-R (R = iBu, Et) react with Re{sub 2}O{sub 7} in THF or dioxane giving type B complexes including oligomeric linkages like O{sub 3}Re-[Al(OAr)-O){sub 2}-ReO{sub 3}. They show a fairly high activity in the metathesis of 2-pentene, with TOF values as high as 100 min{sup -1}. As far as we know, these are the most active rhenium-based homogeneous metathesis catalysts. Complexes type A may be converted into type B complexes upon reaction with (ArO){sub 2}Al-R in an ether solvent. The high activity of B complexes is tentatively related to the Al-O-Al linkages that are molecular in the homogeneous models or present at the surface of the alumina in the heterogeneous catalyst. These results bear out again the role of the Lewis acidity in these catalysts. We used (ArO){sub 2}Al-R complexes to modify the heterogenous catalyst. It appears that it is an excellent way to reduce the rhenium loading without any loss of activity. (author)

Maximizing survivability of acyclic transmission networks with multi-state retransmitters and vulnerable nodes

International Nuclear Information System (INIS)

Levitin, Gregory

2002-01-01

In this paper, an algorithm for optimal allocation of multi-state elements (MEs) in acyclic transmission networks (ATNs) with vulnerable nodes is suggested. The ATNs consist of a number of positions (nodes) in which MEs capable of receiving and sending a signal are allocated. Each network has a root position where the signal source is located, a number of leaf positions that can only receive a signal, and a number of intermediate positions containing MEs capable of transmitting the received signal to some other nodes. Each ME that is located in a nonleaf node can have different states determined by a set of nodes receiving the signal directly from this ME. The probability of each state is assumed to be known for each ME. Each ATN node with all the MEs allocated at this node can be destroyed by external impact (common cause failure) with a given probability. The ATN survivability is defined as the probability that a signal from the root node is transmitted to each leaf node. The optimal distribution of MEs with different characteristics among ATN positions provides the greatest possible ATN survivability. It is shown that the node vulnerability index affects the optimal distribution. The suggested algorithm is based on using a universal generating function technique for network survivability evaluation. A genetic algorithm is used as the optimization tool. Illustrative examples are presented

Crystal structure of 4,4-dibromo-1-(3,4-dimethoxyphenyl-2-azabuta-1,3-diene-1-carbonitrile

Directory of Open Access Journals (Sweden)

Marwa Chaabene

2016-08-01

Full Text Available The title compound, C12H10Br2N2O2, represents an example of a planar π-conjugated 2-azabutadiene molecule, which is both an interesting starting material for further organic transformations and a potential ligand in organometallic coordination chemistry. Its metric molecular parameters are typical for the family of 2-azabuta-1,3-dienes not substituted at the (CH 3-position. In the crystal, the almost planar (r.m.s. deviation = 0.0658 Å azadiene molecules form one-dimensional double-wide ribbons through intermolecular halogen bonds (C—Br...O and C—Br...Br—C, which then stack in a slipped manner through weak C—H...Br and π–π interactions to generate a three-dimensional network.

Six years of experience in connection with the performance of ethylene-propylene-diene terpolymer Rubber (EPDM) geo membranes used in waterproofing reservoirs; Sesis anos de experiencia en el empleo de geomembranas de etileno-propileno-monomero dienico (EPDM) en la impermeabilizacion de balsas

Energy Technology Data Exchange (ETDEWEB)

Blanco, M.; Aguiar, E.; Cea, J. C. de; Soriano, J.; Castillo, F.; Garcia, F.; Crespo, M. A.

2008-07-01

This paper provides to show the performance of synthetic geo membranes based on ethylene-propylene-diene terpolymer rubber (EPDM). Results after six years one applied are presented. The samples of geo membranes came from eight Spanish reservoirs: Bigastro, Bullas, La Casa de las Chumberas, el Boqueron, El Golfo, Los Dos Pinos, Los Pozos (La Torrecilla) and El Saltadero (experimental field). Characteristics of ethylene-propylene-diene terpolymer rubber were evaluated: tensile properties, impact resistance, static perforation, low temperature folding, joint strength (shear and peeling test), optic microscopy and electron microscopy scanner. (Author) 13 refs.

Diels-Alder cyclo-addition as an efficient tool for linking π-donors onto fullerene C60

International Nuclear Information System (INIS)

Hudhomme, P.

2006-01-01

Diels-Alder reaction of endo-cyclic, acyclic 1,3-dienes or (hetero) o-quinodimethanes with the dienophilic fullerene C 60 is presented as an efficient tool for linking electro-active units giving rise to systems where both the donor and C 60 partners take up well defined volumes and orientations with respect to one another. While porphyrin is the most frequently used electron donor in artificial photosynthetic models, C 60 -based tetrathiafulvalene (TTF) or p-conjugated oligomer adducts remain interesting candidates for the preparation of photovoltaic devices. In this account, we focus on the use of the Diels-Alder cyclo-addition and its use in the synthesis of TTF-C 60 dyads, (TTF) n -C 60 polyads and C 60 -TTF-C 60 dumbbells as part of ongoing research into materials which display efficient photo-induced electron transfer. (author)

Rapid synthesis of graphitic carbon nitride powders by metathesis reaction between CaCN{sub 2} and C{sub 2}Cl{sub 6}

Energy Technology Data Exchange (ETDEWEB)

Pang Linlin [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Bi Jianqiang [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Bai Yujun [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China) and Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China)], E-mail: byj97@126.com; Qi Yongxin [Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Zhu Huiling [Key Laboratory of Liquid Structure and Heredity of Materials, Ministry of Education, Shandong University, Jinan, 250061 (China); Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Wang Chengguo; Wu Jiwei [Carbon Fiber Engineering Research Center of Shandong Province, Shandong University, Jinan 250061 (China); Lu Chengwei [Department of Equipment, Shandong University of Science and Technology, Jinan 250031 (China)

2008-12-20

Carbon nitride powders were rapidly synthesized at low temperature via the chemical metathesis reaction between CaCN{sub 2} and C{sub 2}Cl{sub 6}. X-ray diffraction results confirm the formation of crystalline graphitic carbon nitride. Besides the dominant morphology of nanoparticles, flakes, nanorods, hollow and solid spheres can be observed by transmission electron microscopy. The absorption peaks of C-N, C=N and s-triazine rings, as well as the absence of C{identical_to}N peak in the infrared spectra, further verify the formation of graphite-like sp{sup 2}-bonded structure with planar networks. Elemental analysis gives an atomic ratio of N/C around 0.3. X-ray photoelectron spectra exhibit the existence of chemical bonding between C and N.

Design and Synthesis of Novel Antimicrobial Acyclic and Heterocyclic Dyes and Their Precursors for Dyeing and/or Textile Finishing Based on 2-N-Acylamino-4,5,6,7-tetrahydro-benzo[b]thiophene Systems

Directory of Open Access Journals (Sweden)

Rafat Milad Mohareb

2011-07-01

Full Text Available A series of novel polyfunctionalized acyclic and heterocyclic dye precursors and their respective azo (hydrazone counterpart dyes and dye precursors based on conjugate enaminones and/or enaminonitrile moieties were synthesized. The dyes and their precursors are based on 2-cyano-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl-acetamide, 2-ethoxycarbonyl-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl-acetamide or 2-phenylcarbamoyl-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl-acetamide systems as precursors. The latter compounds were used to synthesize polyfunctional thiophene-, thiazole-, pyrazole, pyridine-, pyrimidine-, oxazine-, as well as acyclic moieties. The dyes and dye precursors were characterized by elemental analysis and spectral methods. All dyes and their precursors were screened in vitro and evaluated for both their antibacterial and antifungal activities. MIC data of the novel dye systems and their respective precursors showed significant antimicrobial activity against most tested organisms. Some compounds exhibited comparable or even higher efficiency than selected standards. Dyes were applied at 5% depth for disperse dyeing of nylon, acetate and polyester fabrics. Their spectral characteristics and fastness properties were measured and evaluated.

An integrated QSAR-PBK/D modelling approach for predicting detoxification and DNA adduct formation of 18 acyclic food-borne α,β-unsaturated aldehydes

Energy Technology Data Exchange (ETDEWEB)

Kiwamoto, R., E-mail: reiko.kiwamoto@wur.nl; Spenkelink, A.; Rietjens, I.M.C.M.; Punt, A.

2015-01-01

Acyclic α,β-unsaturated aldehydes present in food raise a concern because the α,β-unsaturated aldehyde moiety is considered a structural alert for genotoxicity. However, controversy remains on whether in vivo at realistic dietary exposure DNA adduct formation is significant. The aim of the present study was to develop physiologically based kinetic/dynamic (PBK/D) models to examine dose-dependent detoxification and DNA adduct formation of a group of 18 food-borne acyclic α,β-unsaturated aldehydes without 2- or 3-alkylation, and with no more than one conjugated double bond. Parameters for the PBK/D models were obtained using quantitative structure–activity relationships (QSARs) defined with a training set of six selected aldehydes. Using the QSARs, PBK/D models for the other 12 aldehydes were defined. Results revealed that DNA adduct formation in the liver increases with decreasing bulkiness of the molecule especially due to less efficient detoxification. 2-Propenal (acrolein) was identified to induce the highest DNA adduct levels. At realistic dietary intake, the predicted DNA adduct levels for all aldehydes were two orders of magnitude lower than endogenous background levels observed in disease free human liver, suggesting that for all 18 aldehydes DNA adduct formation is negligible at the relevant levels of dietary intake. The present study provides a proof of principle for the use of QSAR-based PBK/D modelling to facilitate group evaluations and read-across in risk assessment. - Highlights: • Physiologically based in silico models were made for 18 α,β-unsaturated aldehydes. • Kinetic parameters were determined by in vitro incubations and a QSAR approach. • DNA adduct formation was negligible at levels relevant for dietary intake. • The use of QSAR-based PBK/D modelling facilitates group evaluations and read-across.

New catalysts for selective hydrogenation of diene and acetylene hydrocarbons into olefins

Energy Technology Data Exchange (ETDEWEB)

Frolov, V.M.; Parenago, O.P.; Shuikina, L.P.

1978-12-01

New catalysts for selective hydrogenation of diene and acetylene hydrocarbons into olefins were obtained by reacting aqueous palladium, rhodium, or nickel chloride (0.005-0.05 mole/l.) at 50/sup 0/C, in an argon atmosphere with chelating nitrogen compounds, i.e., o-phenanthroline, ..cap alpha..,..cap alpha..'-dipyridyl, sodium ethylenediaminetetracetate, morpholine, branched polyethylene imines, or amino acids such as glycine, ..cap alpha..-alanine, ..beta..-phenyl-..cap alpha..-alanine, tyrosine, or histidine, and treating the complexes so obtained with sodium borohydride at 1:1-1:5 NaBH/sub 4/-metal ratios, in an aqueous medium. Palladium-based complexes showed the highest activities (20-98Vertical Bar3< conversion) and selectivities (98-100Vertical Bar3<) in heterogeneous hydrogenation of cyclopentadiene, butadiene, 1-hexyne, 1,3-cyclohexadiene, or 1,3-cyclooctadiene at 20/sup 0/-60/sup 0/C and 0.5-15 atm hydrogen, carried out in a kinetic circulation reactor or a metallic autoclave. Thus, a catalytic system based on PdCl/sub 2/ and ..beta..-phenyl-..cap alpha..-alanine converted 98Vertical Bar3< of cyclopentadiene to cyclopentene with 99Vertical Bar3< selectivity. The palladium-based catalyst did not deactivate on the contact with air.

Response of ethylene propylene diene monomer rubber (EPDM) to simulant Hanford tank waste

Energy Technology Data Exchange (ETDEWEB)

NIGREY,PAUL J.

2000-02-01

This report presents the findings of the Chemical Compatibility Program developed to evaluate plastic packaging components that may be incorporated in packaging mixed-waste forms for transportation. Consistent with the methodology outlined in this report, the author performed the second phase of this experimental program to determine the effects of simulant Hanford tank mixed wastes on packaging seal materials. That effort involved the comprehensive testing of five plastic liner materials in an aqueous mixed-waste simulant. The testing protocol involved exposing the materials to {approximately}143, 286, 571, and 3,670 krad of gamma radiation and was followed by 7-, 14-, 28-, 180-day exposures to the waste simulant at 18, 50, and 60 C. Ethylene propylene diene monomer (EPDM) rubber samples subjected to the same protocol were then evaluated by measuring seven material properties: specific gravity, dimensional changes, mass changes, hardness, compression set, vapor transport rates, and tensile properties. The author has determined that EPDM rubber has excellent resistance to radiation, this simulant, and a combination of these factors. These results suggest that EPDM is an excellent seal material to withstand aqueous mixed wastes having similar composition to the one used in this study.

Rhodium/chiral diene-catalyzed asymmetric 1,4-addition of arylboronic acids to chromones: a highly enantioselective pathway for accessing chiral flavanones.

Science.gov (United States)

He, Qijie; So, Chau Ming; Bian, Zhaoxiang; Hayashi, Tamio; Wang, Jun

2015-03-01

Chromone has been noted to be one of the most challenging substrates in the asymmetric 1,4-addition of α,β-unsaturated carbonyl compounds. By employing the rhodium complex associated with a chiral diene ligand, (R,R)-Ph-bod*, the 1,4-addition of a variety of arylboronic acids was realized to give high yields of the corresponding flavanones with excellent enantioselectivities (≥97% ee, 99% ee for most substrates). Ring-opening side products, which would lead to erosion of product enantioselectivity, were not observed under the stated reaction conditions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxytocin promotes bone formation during the alveolar healing process in old acyclic female rats.

Science.gov (United States)

Colli, Vilma Clemi; Okamoto, Roberta; Spritzer, Poli Mara; Dornelles, Rita Cássia Menegati

2012-09-01

OT was reported to be a direct regulator of bone mass in young rodents, and this anabolic effect on bone is a peripheral action of OT. The goal of this study was to investigate the peripheral action of oxytocin (OT) in the alveolar healing process in old female rats. Females Wistar rats (24-month-old) in permanent diestrus phase, received two ip (12h apart) injections of saline (NaCl 0.15M - control group) or OT (45μg/rat - treated group). Seven days later, the right maxillary incisor was extracted and analyses were performed up to 28 days of the alveolar healing process (35 days after saline or OT administration). Calcium and phosphorus plasma concentrations did not differ between the groups. The plasma biochemical bone formations markers, alkaline phosphatase (ALP) and osteocalcin were significantly higher in the treated group. Histomorphometric analyses confirmed bone formation as the treated group presented the highest mean value of post-extraction bone formation. Tartrate-resistant acid phosphatase (TRAP) was significantly reduced in the treated group indicating an anti-resorptive effect of OT. Immunohistochemistry reactions performed in order to identify the presence of osteocalcin and TRAP in the bone cells of the dental socket confirmed these outcomes. OT was found to promote bone formation and to inhibit bone resorption in old acyclic female rats during the alveolar healing process. Published by Elsevier Ltd.

Executive Summary of Ares V: Lunar Capabilities Concept Review Through Phase A-Cycle 3

Science.gov (United States)

Holladay, J. B.; Baggett, K. E.; Feldman, S. M.

2011-01-01

This Technical Memorandum (TM) was generated as an overall Ares V summary from the Lunar Capabilities Concept Review (LCCR) through Phase A-Cycle 3 (PA-C3) with the intent that it may be coupled with separately published appendices for a more detailed, integrated narrative. The Ares V has evolved from the initial point of departure (POD) 51.00.48 LCCR configuration to the current candidate POD, PA-C3D, and the family of vehicles concept that contains vehicles PA-C3A through H. The logical progression from concept to POD vehicles is summarized in this TM and captures the trade space and performance of each. The family-of-vehicles concept was assessed during PA-C3 and offered flexibility in the path forward with the ability to add options deemed appropriate. A description of each trade space is given in addition to a summary of each Ares V element. The Ares V contributions to a Mars campaign are also highlighted with the goal of introducing Ares V capabilities within the trade space. The assessment of the Ares V vehicle as it pertains to Mars missions remained locked to the architecture presented in Mars Design Reference Authorization 5.0 using the PA-C3D vehicle configuration to assess Mars transfer vehicle options, in-space EDS capabilities, docking adaptor and propellant transfer assessments, and lunar and Mars synergistic potential.

All-Polymer Photovoltaic Devices of Poly(3-(4- n -octyl)-phenylthiophene) from Grignard Metathesis (GRIM) Polymerization

KAUST Repository

Holcombe, Thomas W.

2009-10-14

(Graph Presented) The synthesis of poly[3-(4-n-octyl)-phenylthiophene] (POPT) from Grignard Metathesis (GRIM) is reported. GRIM POPT is found to have favorable electronic, optical, and processing properties for organic photovoltaics (OPVs). Space-charge limited current and field effect transistor measurements for POPT yielded hole mobilities of 1 × 10-4 cm2/(V s) and 0.05 cm2/(V s), respectively. Spincasting GRIM POPT from chlorobenzene yields a thin film with a 1.8 eV band gap, and PC61BM:POPT bulk heterojection devices provide a peak performance of 3.1%. Additionally, an efficiency of 2.0% is achieved in an all-polymer, bilayer OPV using poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyanovinylene) phenylene] (CNPPV) as an acceptor. This state-of-the-art all-polymer device is analyzed in comparison to the analogous poly(3-hexylthiophene) (P3HT)/CNPPV device. Counter to expectations based on more favorable energy level alignment, greater active layer light absorption, and similar hole mobility, P3HT/CNPPV devices perform less well than POPT/CNPPV devices with a peak efficiency of 0.93%. © 2009 American Chemical Society.

All-Polymer Photovoltaic Devices of Poly(3-(4- n -octyl)-phenylthiophene) from Grignard Metathesis (GRIM) Polymerization

KAUST Repository

Holcombe, Thomas W.; Woo, Claire H.; Kavulak, David F.J.; Thompson, Barry C.; Fréchet, Jean M. J.

2009-01-01

(Graph Presented) The synthesis of poly[3-(4-n-octyl)-phenylthiophene] (POPT) from Grignard Metathesis (GRIM) is reported. GRIM POPT is found to have favorable electronic, optical, and processing properties for organic photovoltaics (OPVs). Space-charge limited current and field effect transistor measurements for POPT yielded hole mobilities of 1 × 10-4 cm2/(V s) and 0.05 cm2/(V s), respectively. Spincasting GRIM POPT from chlorobenzene yields a thin film with a 1.8 eV band gap, and PC61BM:POPT bulk heterojection devices provide a peak performance of 3.1%. Additionally, an efficiency of 2.0% is achieved in an all-polymer, bilayer OPV using poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-(1-cyanovinylene) phenylene] (CNPPV) as an acceptor. This state-of-the-art all-polymer device is analyzed in comparison to the analogous poly(3-hexylthiophene) (P3HT)/CNPPV device. Counter to expectations based on more favorable energy level alignment, greater active layer light absorption, and similar hole mobility, P3HT/CNPPV devices perform less well than POPT/CNPPV devices with a peak efficiency of 0.93%. © 2009 American Chemical Society.

The divergent synthesis of nitrogen heterocycles by rhodium(II)-catalyzed cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes.

Science.gov (United States)

Shang, Hai; Wang, Yuanhao; Tian, Yu; Feng, Juan; Tang, Yefeng

2014-05-26

The first rhodium(II)-catalyzed aza-[4+3] cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes have been developed, and enable the efficient synthesis of highly functionalized 2,5-dihydroazepines from readily available precursors. In some cases, the reaction pathway could divert to formal aza-[3+2] cycloadditions, thus leading to 2,3-dihydropyrroles. In this context, the titled reaction represents a capable tool for the divergent synthesis of two types of synthetically valuable aza-heterocycles from common rhodium(II) iminocarbene intermediates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acyclic cucurbit[n]uril-type molecular containers: influence of glycoluril oligomer length on their function as solubilizing agents.

Science.gov (United States)

Gilberg, Laura; Zhang, Ben; Zavalij, Peter Y; Sindelar, Vladimir; Isaacs, Lyle

2015-04-07

We present the synthesis of a series of six new glycoluril derived molecular clips and acyclic CB[n]-type molecular containers (1–3) that all feature SO3(−) solubilizing groups but differ in the number of glycoluril rings between the two terminal dialkoxyaromatic sidewalls. We report the X-ray crystal structure of 3b which shows that its dialkoxynaphthalene sidewalls actively define a hydrophobic cavity with high potential to engage in π–π interactions with insoluble aromatic guests. Compounds 1–3 possess very good solubility characteristics (≥38 mM) and undergo only very weak self-association (Ks containers 3a and 3b which feature three glycoluril rings between the terminal dialkoxy-o-xylylene and dialkoxynaphthalene sidewalls are less efficient solubilizing agents than 4a and 4b because of their smaller hydrophobic cavities. Containers 1 and 2 behave as molecular clip type receptors and therefore possess the ability to bind to and thereby solubilize aromatic drugs like camptothecin, ziprasidone, and PBS-1086.

WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

KAUST Repository

Samantaray, Manoja

2014-01-22

The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

WMe6 tamed by silica: Si-O-WMe5 as an efficient, well-defined species for alkane metathesis, leading to the observation of a supported W-methyl/methylidyne species

KAUST Repository

Samantaray, Manoja; Callens, Emmanuel; Abou-Hamad, Edy; Rossini, Aaron J.; Widdifield, Cory M.; Dey, Raju; Emsley, Lyndon; Basset, Jean-Marie

2014-01-01

The synthesis and full characterization of a well-defined silica-supported ≡Si-O-W(Me)5 species is reported. Under an inert atmosphere, it is a stable material at moderate temperature, whereas the homoleptic parent complex decomposes above -20 °C, demonstrating the stabilizing effect of immobilization of the molecular complex. Above 70 °C the grafted complex converts into the two methylidyne surface complexes [(≡SiO-)W(≡CH) Me2] and [(≡SiO-)2W(≡CH)Me]. All of these silica-supported complexes are active precursors for propane metathesis reactions. © 2013 American Chemical Society.

60Co-labeling in 59Co(n,γ)60Co reaction and γ-ray irradiation of [Co(dien)2]3+ and [Co(en)3]3+ in crystals and/or in polyvinyl alcohol

International Nuclear Information System (INIS)

Sasaki, K.; Iiyoshi, N.; Watanabe, J.; Yamatera, H.

1982-01-01

Three isomers (sym-fac, unsym-fac, and mer forms) of [Co(dien) 2 ]Cl 3 were irradiated in a reactor in the form of crystals and in amorphous solids, where the ions were dissolved in polyvinyl alcohol (PVA) or adsorbed on an SP-Sephadex ion exchanger. The distribution of produced 60 Co among the isomers of the Co(III) complex and the Co(II) species was determined. The preferential labeling on the parent isomer was observed in crystals but not in PVA. In the Sephadex, no marked labeling occurred. For comparison with reactor-irradiated samples, mixed solutions of [Co(dien) 2 ]Cl 3 and 60 Co-labeled cobalt (II) chloride dissolved in PVA films ([Co(III)]/[Co(II)] = 2 - 3) were irradiated by γ-rays. Significant labeling was observed after the irradiation. Comparison of the results from the above experiments showed that the labeling was enhanced by radiation chemical reactions, and that the preferential labeling on the parent isomer of crystal samples resulted from the stiffness of the crystal matrix. (orig.)

5-Methyl-3,8-di-(2-amino-4-bromophenyl-4,9-dioxa-1,2,6,7-tetraaza-5λ5-phosphaspiro[4.4]nona-2,7-diene

Directory of Open Access Journals (Sweden)

Sławomir Kasperowicz

2018-01-01

Full Text Available 5-Methyl-3,8-di-(2-amino-4-bromophenyl-4,9-dioxa-1,2,6,7-tetraaza-5λ5-phosphaspiro[4.4]nona-2,7-diene was obtained by condensation of 2-amino-5-bromobenzohydrazide and methylphosphonyl dichloride in the presence of triethylamine. An initial biological screening was performed for the resulting product. The synthesized compound showed relatively strong cytotoxic activity, which was, however, similar for cancer and non-cancer cell lines.

Preparation of Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization (ROP) and Ring-Opening Metathesis Polymerization (ROMP) Grafting-Through Strategy.

Science.gov (United States)

Radzinski, Scott C; Foster, Jeffrey C; Matson, John B

2016-04-01

Bottlebrush polymers are synthesized using a tandem ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) strategy. For the first time, ROP and ROMP are conducted sequentially in the same pot to yield well-defined bottlebrush polymers with molecular weights in excess of 10(6) Da. The first step of this process involves the synthesis of a polylactide macromonomer (MM) via ROP of d,l-lactide initiated by an alcohol-functionalized norbornene. ROMP grafting-through is then carried out in the same pot to produce the bottlebrush polymer. The applicability of this methodology is evaluated for different MM molecular weights and bottlebrush backbone degrees of polymerization. Size-exclusion chromatographic and (1)H NMR spectroscopic analyses confirm excellent control over both polymerization steps. In addition, bottlebrush polymers are imaged using atomic force microscopy and stain-free transmission electron microscopy on graphene oxide. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Limitations of using Raman microscopy for the analysis of high-content-carbon-filled ethylene propylene diene monomer rubber

DEFF Research Database (Denmark)

Ghanbari-Siahkali, A.; Almdal, K.; Kingshott, P.

2003-01-01

The effects of laser irradiation on changes to the surface chemistry and structure of a commercially available ethylene propylene diene monomer (EPDM) rubber sample after Raman microscopy analysis was investigated. The Raman measurements were carried out with different levels of laser power...... on the sample, ranging from 4.55 mW to 0.09 mW. The surface of the EPDM was analyzed before and after laser exposure using X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The techniques have surface probe depths of approximately less...... than or equal to10 nm and 1 mum, respectively. Both sets of analysis show that ingredients of the blended EPDM rubber "bloom" to the surface as a result of local heating that takes place due to the absorption of laser by carbon black during the Raman analysis. Scanning electron microscopy (SEM...

Synthesis of [14α, 15α-3H]-17α-cyanomethyl-17β-hydroxyestra-4.9-diene-3-one - a specifically tritium labelled gestagen

International Nuclear Information System (INIS)

Roemer, J.; Wagner, H.

1978-05-01

Synthesis of [14α, 15α- 3 H 2 ]-17α-cyanomethyl-17β-hydroxyestra-4.9-diene-3-one from quantitativly tritiated [14α, 15α- 3 H 2 ]-3-methoxyestra-1,3,5(10),8-tetraene-17β-ol is described. The determination of the radiochemical purity and chemical yield was carried out by thin-layer chromatography. Preparative thin-layer chromatography was used for purifying the final product. By-products formed in the course of synthesis could be detected by determining and comparing specific activities of the intermediate products. Radiolytic investigations revealed the instability of the tritium labelled dienone system. (author)

Surface modification of argon/oxygen plasma treated vulcanized ethylene propylene diene polymethylene surfaces for improved adhesion with natural rubber

International Nuclear Information System (INIS)

Basak, Ganesh C.; Bandyopadhyay, Abhijit; Neogi, Sudarsan; Bhowmick, Anil K.

2011-01-01

Vulcanized ethylene propylene diene polymethylene (EPDM) rubber surface was treated in a radio frequency capacitatively coupled low pressure argon/oxygen plasma to improve adhesion with compounded natural rubber (NR) during co-vulcanization. The plasma modified surfaces were analyzed by means of contact angle measurement, surface energy, attenuated total reflection-infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive X-ray sulfur mapping and atomic force microscopy. Several experimental variables such as plasma power, length of exposure time and composition of the argon-oxygen gas mixture were considered. It was delineated that plasma treatment changed both surface composition and roughness, and consequently increased peel strength. The change in surface composition was mainly ascribed to the formation of C-O and -C=O functional groups on the vulcanized surfaces. A maximum of 98% improvement in peel strength was observed after plasma treatment.

Surface modification of argon/oxygen plasma treated vulcanized ethylene propylene diene polymethylene surfaces for improved adhesion with natural rubber

Energy Technology Data Exchange (ETDEWEB)

Basak, Ganesh C. [Rubber Technology Centre, Indian Institute of Technology, Kharagpur 721302 (India); Bandyopadhyay, Abhijit [Department of Polymer Science and Technology, University of Calcutta, Calcutta 700 009 (India); Neogi, Sudarsan [Department of Chemical Engineering, Indian Institute of Technology, Kharagpur 721302 (India); Bhowmick, Anil K., E-mail: anilkb@rtc.iitkgp.ernet.in [Rubber Technology Centre, Indian Institute of Technology, Kharagpur 721302 (India)

2011-01-15

Vulcanized ethylene propylene diene polymethylene (EPDM) rubber surface was treated in a radio frequency capacitatively coupled low pressure argon/oxygen plasma to improve adhesion with compounded natural rubber (NR) during co-vulcanization. The plasma modified surfaces were analyzed by means of contact angle measurement, surface energy, attenuated total reflection-infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive X-ray sulfur mapping and atomic force microscopy. Several experimental variables such as plasma power, length of exposure time and composition of the argon-oxygen gas mixture were considered. It was delineated that plasma treatment changed both surface composition and roughness, and consequently increased peel strength. The change in surface composition was mainly ascribed to the formation of C-O and -C=O functional groups on the vulcanized surfaces. A maximum of 98% improvement in peel strength was observed after plasma treatment.

Peretinoin, an Acyclic Retinoid, Inhibits Hepatitis B Virus Replication by Suppressing Sphingosine Metabolic Pathway In Vitro

Directory of Open Access Journals (Sweden)

Kazuhisa Murai

2018-01-01

Full Text Available Hepatocellular carcinoma (HCC frequently develops from hepatitis C virus (HCV and hepatitis B virus (HBV infection. We previously reported that peretinoin, an acyclic retinoid, inhibits HCV replication. This study aimed to examine the influence of peretinoin on the HBV lifecycle. HBV-DNA and covalently closed circular DNA (cccDNA were evaluated by a qPCR method in HepG2.2.15 cells. Peretinoin significantly reduced the levels of intracellular HBV-DNA, nuclear cccDNA, and HBV transcript at a concentration that did not induce cytotoxicity. Conversely, other retinoids, such as 9-cis, 13-cis retinoic acid (RA, and all-trans-retinoic acid (ATRA, had no effect or rather increased HBV replication. Mechanistically, although peretinoin increased the expression of HBV-related transcription factors, as observed for other retinoids, peretinoin enhanced the binding of histone deacetylase 1 (HDAC1 to cccDNA in the nucleus and negatively regulated HBV transcription. Moreover, peretinoin significantly inhibited the expression of SPHK1, a potential inhibitor of HDAC activity, and might be involved in hepatic inflammation, fibrosis, and HCC. SPHK1 overexpression in cells cancelled the inhibition of HBV replication induced by peretinoin. This indicates that peretinoin activates HDAC1 and thereby suppresses HBV replication by inhibiting the sphingosine metabolic pathway. Therefore, peretinoin may be a novel therapeutic agent for HBV replication and chemoprevention against HCC.

Product Distribution from Precursor Bite Angle Variation in Multitopic Alkyne Metathesis: Evidence for a Putative Kinetic Bottleneck.

Science.gov (United States)

Moneypenny, Timothy P; Yang, Anna; Walter, Nathan P; Woods, Toby J; Gray, Danielle L; Zhang, Yang; Moore, Jeffrey S

2018-05-02

In the dynamic synthesis of covalent organic frameworks and molecular cages, the typical synthetic approach involves heuristic methods of discovery. While this approach has yielded many remarkable products, the ability to predict the structural outcome of subjecting a multitopic precursor to dynamic covalent chemistry (DCC) remains a challenge in the field. The synthesis of covalent organic cages is a prime example of this phenomenon, where precursors designed with the intention of affording a specific product may deviate dramatically when the DCC synthesis is attempted. As such, rational design principles are needed to accelerate discovery in cage synthesis using DCC. Herein, we test the hypothesis that precursor bite angle contributes significantly to the energy landscape and product distribution in multitopic alkyne metathesis (AM). By subjecting a series of precursors with varying bite angles to AM, we experimentally demonstrate that the product distribution, and convergence toward product formation, is strongly dependent on this geometric attribute. Surprisingly, we discovered that precursors with the ideal bite angle (60°) do not afford the most efficient pathway to the product. The systematic study reported here illustrates how seemingly minor adjustments in precursor geometry greatly affect the outcome of DCC systems. This research illustrates the importance of fine-tuning precursor geometric parameters in order to successfully realize desirable targets.

Wavelet entropy and directed acyclic graph support vector machine for detection of patients with unilateral hearing loss in MRI scanning

Directory of Open Access Journals (Sweden)

Shuihua Wang

2016-10-01

Full Text Available (Aim Sensorineural hearing loss (SNHL is correlated to many neurodegenerative disease. Now more and more computer vision based methods are using to detect it in an automatic way. (Materials We have in total 49 subjects, scanned by 3.0T MRI (Siemens Medical Solutions, Erlangen, Germany. The subjects contain 14 patients with right-sided hearing loss (RHL, 15 patients with left-sided hearing loss (LHL, and 20 healthy controls (HC. (Method We treat this as a three-class classification problem: RHL, LHL, and HC. Wavelet entropy (WE was selected from the magnetic resonance images of each subjects, and then submitted to a directed acyclic graph support vector machine (DAG-SVM. (Results The 10 repetition results of 10-fold cross validation shows 3-level decomposition will yield an overall accuracy of 95.10% for this three-class classification problem, higher than feedforward neural network, decision tree, and naive Bayesian classifier. (Conclusions This computer-aided diagnosis system is promising. We hope this study can attract more computer vision method for detecting hearing loss.

General patterns in the photochemistry of pregna-1,4-dien-3,20-diones.

Science.gov (United States)

Ricci, Andrea; Fasani, Elisa; Mella, Mariella; Albini, Angelo

2003-05-30

The photochemistry of six pregna-1,4-dien-3,20-diones has been compared and found to involve both the cyclohexadienone moiety in ring A and the isolated ketone at C-20. The two reactions take place proportionally to the fraction of light absorbed by each chromophore. The cross-conjugated ketone absorbs predominantly or exclusively at both 254 and 366 nm and undergoes the "lumi" rearrangement to bicyclo[3.1.0]hex-3-en-2-one. The quantum yield of the reaction diminished somewhat with increasing lambda(exc), e.g., for prednisolone Phi(254) (nm) = 0.42, Phi(366) (nm) = 0.3. A much stronger lowering is caused by halogen substitution in position 9 (by a factor of 3 for F, >50 for Cl), apparently due to a shortened triplet lifetime caused by heavy atom effect. At 310 nm, both chromophores absorb to a comparable degree and both may react. The reaction at C(20) ketone involves either quite efficient alpha-cleavage (C(17)-C(20)) for compounds bearing an acetal or hydroxyl function at C(17) or less effective (by a factor of ca. 10) hydrogen abstraction from the 18-methyl group in the other cases (finally resulting in Norrish II fragmentation or Yang cyclization). The results allow generalizing how the substitution pattern surrounding each chromophore affects the photoreactivity at that site and the competition between the two modes, allowing predicting the photochemistry of this family of antiinflammatory drugs.

Production of diesel fuels from vegetable oils by means of homogenous catalysed metathesis of methyl oleate; Gewinnung von dieselartigen Kraftstoffen aus Pflanzenoelen mittels homogen katalysierter Metathese von Methyloleat

Energy Technology Data Exchange (ETDEWEB)

Erben, Friedrich; Paetzold, Eckhard [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse; Schuemann, Ulrike; Wichmann, Volker; Fluegge, Evelyn; Berndt, Silvia; Harndorf, Horst [Rostock Univ. (Germany). Lehrstuhl fuer Kolbenmaschinen und Verbrennungsmotoren; Kragl, Udo [Rostock Univ. (Germany). Leibniz-Institut fuer Katalyse; Rostock Univ. (Germany). Inst. fuer Chemie

2013-10-01

Due to the increasing shortage of fossil combustibles renewable resources like oils and fats have great potential for the production of diesel-like fuels. A key step in adapting the properties of biogenic fuels to those from fossil sources is cracking or isomerisation of linear hydrocarbon chains. This is necessary for optimal cold flow properties and a continuously rising boiling curve. The present work describes the potential of metathesis for this purpose. By formal exchange of parts of molecules of a small number of starting materials a variety of products is formed which exhibit a fuel-like composition. Ethenolysis as well as hexenolysis is examined, whereat hexenolysis owns the greater potential for production of diesel-like fuels out of unsaturated fatty acid esters. (orig.)

The resolution of acyclic P-stereogenic phosphine oxides via the formation of diastereomeric complexes: A case study on ethyl-(2-methylphenyl)-phenylphosphine oxide.

Science.gov (United States)

Bagi, Péter; Varga, Bence; Szilágyi, András; Karaghiosoff, Konstantin; Czugler, Mátyás; Fogassy, Elemér; Keglevich, György

2018-04-01

As an example of acyclic P-chiral phosphine oxides, the resolution of ethyl-(2-methylphenyl)-phenylphosphine oxide was elaborated with TADDOL derivatives, or with calcium salts of the tartaric acid derivatives. Besides the study on the resolving agents, several purification methods were developed in order to prepare enantiopure ethyl-(2-methylphenyl)-phenylphosphine oxide. It was found that the title phosphine oxide is a racemic crystal-forming compound, and the recrystallization of the enantiomeric mixtures could be used for the preparation of pure enantiomers. According to our best method, the (R)-ethyl-(2-methylphenyl)-phenylphosphine oxide could be obtained with an enantiomeric excess of 99% and in a yield of 47%. Complete racemization of the enantiomerically enriched phosphine oxide could be accomplished via the formation of a chlorophosphonium salt. Characterization of the crystal structures of the enantiopure phosphine oxide was complemented with that of the diastereomeric intermediate. X-ray analysis revealed the main nonbonding interactions responsible for enantiomeric recognition. © 2018 Wiley Periodicals, Inc.

Isolation and Characterization of an Acyclic Isoprenoid from Semecarpus anacardium Linn. and its Antibacterial Potential in vitro - Antimicrobial Activity of Semecarpus anacardium Linn. Seeds -

Directory of Open Access Journals (Sweden)

Ayyakkannu Purushothaman

2017-06-01

Full Text Available Objectives: Semecarpus anacardium Linn. is a plant well-known for its antimicrobial, antidiabetic and anti-arthritic properties in the Ayurvedic and Siddha system of medicine. This has prompted the screening of this plant for antibacterial activity. The main aims of this study were to isolate compounds from the plant’s seeds and to evaluate their antibacterial effects on clinical bacterial test strains. Methods: The n-butanolic concentrate of the seed extract was subjected to thin layer chromatography (TLC and repeated silica gel column chromatography followed by elution with various solvents. The compound was identified based on observed spectral (IR, 1H NMR, 13C NMR and high-resolution mass spectrometry data. The well diffusion method was employed to evaluate the antibacterial activities of the isolated acyclic isoprenoid compound (final concentration: 5 - 15 μg/mL on four test bacterial strains, namely, Staphylococcus aureus (MTCC 96, Bacillus cereus

Process for Biotransformation of Androsta-4-ene-3, 17-Dione (4-AD) to Androsta-1,4-Diene-3,17-Dione (ADD).

Science.gov (United States)

Prakash, Surya; Bajaj, Abhay

2017-01-01

Androsta-1,4-diene-3,17-dione (androstadienedione, ADD) is key intermediate for the organic synthesis of a variety of female sex hormones such as estrone, estradiol, estriol and other related derivatives. De novo synthesis of this molecule is not yet reported in any form of living system, i.e., microbial, plant, and animal. The structural complexities due to presence of several chiral carbon centers create significant hurdles in chemical synthesis of such molecules. Microbe-mediated biotransformation offer a highly reliable, cost-effective, and relatively non hazardous way for commercial manufacturing of steroidal key intermediates. Currently microbial biotransformations are extensively being exploited for large-scale production of basic intermediates such as androstenedione (AD), ADD, and several types of hydroxylated derivatives of androstane compounds. In this chapter several aspects of microbial biotransformation process of AD to ADD are discussed.

Increased Yield of Biotransformation of Androsta-1, 4-Dien-3, 17-Dione from Β-Sitosterol by Using Sulfobutyl Ether-Β-Cyclodextrin Complexation Technique

Directory of Open Access Journals (Sweden)

Wang Jingwen

2016-01-01

Full Text Available Substrate solubility in steroid biotransformation is critical for enhancing the biotransformation of hydrophobic compounds. In this study, the sulfobutyl ether-β-cyclodextrin (SBE-β-CD complexation technique was used for the biotransformation of β-sitosterol to androsta-1, 4-diene-3, 17-dione with Mycobacterium ATCC25795. The production yield was increased by 26.72%, and the biotransformation course was shortened by 24h using β-sitosterol/SBE-β-CD inclusion complexes as substrates (1.0 g/L. Fourier transform infrared spectroscopy and differential scanning calorimetry indicated that an inclusion complex was formed between SBE-β-CD and β-sitosterol. The complex significantly increased the solubility of β-sitosterol and improved the biotransformation efficiency of the substrate.

Calorimetric study of alternating copolymer of bicyclo[2,2,1]-hepta-2,5-diene and carbon monoxide in the range from T->0 to 510K

International Nuclear Information System (INIS)

Smirnova, N.N.; Nikishchenkova, L.V.; Bykova, T.A.; Kulagina, T.G.; Belov, G.P.; Novikova, E.V.

2006-01-01

By adiabatic vacuum and dynamic calorimetry, the temperature dependence of heat capacity for alternating copolymer of bicyclo[2,2,1]-hepta-2,5-diene and carbon monoxide has been determined over the 6-510K range with an uncertainty of 0.2-0.5% between 6 and 350K and 0.5-1.5% from 330 to 510K. In the above temperature ranges, the physical transformations of the copolymer have been detected and their thermodynamic characteristics have been estimated. In a calorimeter with a static bomb and an isothermal shield, the energy of combustion of the copolymer has been measured at 298.15K. Based on the experimental data, the thermodynamic functions of the copolymer, namely, the heat capacity C p - bar (T), enthalpy H o (T)-H o (0), entropy S o (T)-S o (0) and Gibbs function G o (T)-H o (0) have been determined for the range from T->0 to 400K. The enthalpy of combustion Δ c H o and the thermodynamic parameters Δ f H o , Δ f S o , Δ f G o and lnK f - bar of reaction of formation of the copolymer from simple substances at T=298.15K and p=0.1MPa have been calculated. The data cited in the present work and literature data were used to calculate the thermodynamic characteristics of the alternating copolymerization in bulk of bicyclo[2,2,1]-hepta-2,5-diene and CO in the 0-340K range at standard pressure as well as to compare them with the thermodynamic characteristics of the synthesis of isomeric polyketone

Radiation processed polychloroprene-co-ethylene-propene diene terpolymer blends: Effect of radiation vulcanization on solvent transport kinetics

Energy Technology Data Exchange (ETDEWEB)

Dubey, K.A. [Radiation Technology Development Section, Bhabha Atomic Research Centre, Room No. S-1, HIRUP Building, Trombay, Mumbai 400 085 (India); Bhardwaj, Y.K. [Radiation Technology Development Section, Bhabha Atomic Research Centre, Room No. S-1, HIRUP Building, Trombay, Mumbai 400 085 (India)], E-mail: ykbhard@barc.gov.in; Chaudhari, C.V.; Kumar, Virendra; Goel, N.K.; Sabharwal, S. [Radiation Technology Development Section, Bhabha Atomic Research Centre, Room No. S-1, HIRUP Building, Trombay, Mumbai 400 085 (India)

2009-03-15

Blends of polychloroprene rubber (PCR) and ethylene propylene diene terpolymer rubber (EPDM) of different compositions were made and exposed to different gamma radiation doses. The radiation sensitivity and radiation vulcanization efficiency of blends was estimated by gel-content analysis, Charlesby-Pinner parameter determination and crosslinking density measurements. Gamma radiation induced crosslinking was most efficient for EPDM (p{sub 0}/q{sub 0} {approx} 0.08), whereas it was the lowest for blends containing 40% PCR (p{sub 0}/q{sub 0} {approx} 0.34). The vulcanized blends were characterized for solvent diffusion characteristics by following the swelling dynamics. Blends with higher PCR content showed anomalous swelling. The sorption and permeability of the solvent were not strictly in accordance with each other and the extent of variation in two parameters was found to be a function of blend composition. The {delta}G values for solvent diffusion were in the range -2.97 to -9.58 kJ/mol and indicated thermodynamically favorable sorption for all blends. These results were corroborated by dynamic swelling, experimental as well as simulated profiles and have been explained on the basis of correlation between crosslinking density, diffusion kinetics, thermodynamic parameters and polymer-polymer interaction parameter.

Non-aqueous metathesis as a general approach to prepare nanodispersed materials: Case study of scheelites

International Nuclear Information System (INIS)

Afanasiev, Pavel

2015-01-01

A general approach to the preparation of inorganic nanoparticles is proposed, using metathesis of precursor salts in non-aqueous liquids. Nanoparticles of scheelites AMO 4 (A=Ba, Sr, Ca; M=Mo, W), were obtained with a quantitative yield. Precipitations in formamide, N-methylformamide, propylene carbonate, DMSO and polyols often provide narrow particle size distributions. Advantageous morphology was explained by strong ionic association in non-aqueous solvents, leading to slow nucleation and negligible Ostwald ripening. Mean particle size below 10 nm and high specific surface areas were obtained for several Ca(Sr)Mo(W)O 4 materials, making them promising for applications as adsorbents or catalysts. Zeta-potential of scheelites in aqueous suspensions showed negative values in a wide range of pH. Systematic study of optical properties demonstrated variation of optical gap in the sequences W>Mo and Ba>Sr>Ca. The observed trends were reproduced by DFT calculations. No quantum confinement effect was observed for small particles, though the surface states induce low-energy features in the optical spectra. - Graphical abstract: Scheelites AMO 4 (A=Ca, Sr, Ba; M=Mo, W) were prepared in various non-aqueous liquids with high specific surface areas and narrow size distributions. The optical gap of scheelites changes in the series Ca

Enhancing the thermal stability of natural rubber/recycled ethylene–propylene–diene rubber blends by means of introducing pre-vulcanised ethylene–propylene–diene rubber and electron beam irradiation

International Nuclear Information System (INIS)

Nabil, H.; Ismail, H.

2014-01-01

Highlights: • New route of processing was introduced to optimise the thermal stability of NR/R-EPDM blends. • Pre-vulcanised EPDM and EB irradiation were introduced into NR/R-EPDM blends. • Thermal stability is obviously enhanced by applying these two techniques. • Applying new route of processing methods is clearly successful to NR/R-EPDM blends. - Abstract: Most rubber materials are subjected to oxidation. The rate of oxidation depends on the type of rubber, processing method, and end-use conditions. The oxidation of rubber can result in the loss of physical properties, such as tensile strength, elongation, and flexibility. Hence, the service life is determined by oxidation stability. Thermal properties are relevant to the potential use of polymeric materials in many consumer oriented applications. Thermo-oxidative ageing and thermogravimetric analysis (TGA) have been proven to be successful techniques in determining the thermal stability of polymers and polymer blends. In this article, preparation of a series of natural rubber/recycled ethylene–propylene–diene rubber (NR/R-EPDM) blends is described. Processing of the blends, by means of introducing pre-vulcanised EPDM and electron beam (EB) irradiation, was carried out. Two thermal analysis methods, namely thermo-oxidative ageing and thermogravimetric analysis, were conducted. The results indicated that pre-vulcanising EPDM for 1.45 min (ts − 2) is sufficient to gain the optimum retained tensile and elongation at break. It was simultaneously observed that the introduction of pre-vulcanised EPDM increased decomposition temperature and activation energy by showing optimum values at a pre-vulcanising time of 3.45 min (ts). In the latter study, the retained properties increased after EB irradiation. The results can be verified by the thermal decomposition temperature and their activation energy. The obtained TG profiles and the calculated kinetic parameters indicated that introducing EB irradiation

Enhanced Production of Androst-1,4-Diene-3,17-Dione by Mycobacterium neoaurum JC-12 Using Three-Stage Fermentation Strategy

Science.gov (United States)

Shao, Minglong; Zhang, Xian; Rao, Zhiming; Xu, Meijuan; Yang, Taowei; Li, Hui; Xu, Zhenghong

2015-01-01

To improve the androst-1,4-diene-3,17-dione (ADD) production from phytosterol by Mycobacterium neoaurum JC-12, fructose was firstly found favorable as the initial carbon source to increase the biomass and eliminate the lag phase of M. neoaurum JC-12 in the phytosterol transformation process. Based on this phenomenon, two-stage fermentation by using fructose as the initial carbon source and feeding glucose to maintain strain metabolism was designed. By applying this strategy, the fermentation duration was decreased from 168 h to 120 h with the ADD productivity increased from 0.071 g/(L·h) to 0.108 g/(L·h). Further, three-stage fermentation by adding phytosterol to improve ADD production at the end of the two-stage fermentation was carried out and the final ADD production reached 18.6 g/L, which is the highest reported ADD production using phytosterol as substrate. Thus, this strategy provides a possible way in enhancing the ADD production in pharmaceutical industry. PMID:26352898

Enhanced Production of Androst-1,4-Diene-3,17-Dione by Mycobacterium neoaurum JC-12 Using Three-Stage Fermentation Strategy.

Directory of Open Access Journals (Sweden)

Minglong Shao

Full Text Available To improve the androst-1,4-diene-3,17-dione (ADD production from phytosterol by Mycobacterium neoaurum JC-12, fructose was firstly found favorable as the initial carbon source to increase the biomass and eliminate the lag phase of M. neoaurum JC-12 in the phytosterol transformation process. Based on this phenomenon, two-stage fermentation by using fructose as the initial carbon source and feeding glucose to maintain strain metabolism was designed. By applying this strategy, the fermentation duration was decreased from 168 h to 120 h with the ADD productivity increased from 0.071 g/(L·h to 0.108 g/(L·h. Further, three-stage fermentation by adding phytosterol to improve ADD production at the end of the two-stage fermentation was carried out and the final ADD production reached 18.6 g/L, which is the highest reported ADD production using phytosterol as substrate. Thus, this strategy provides a possible way in enhancing the ADD production in pharmaceutical industry.

An intermolecular Diels-Alder cycloaddition under various condition between 1,3-cyclohexadiene and 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate

Directory of Open Access Journals (Sweden)

Özgür Yılmaz

2017-10-01

Full Text Available The reaction between 1,3-cyclohexadiene and dimethyl 7-oxabicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylate both without a catalyst and with different catalysts, in both atmospheric and at high pressure, over 20 days were studied. At the end of the reactions, different products (retro Diels-Alder addition product 5 and Diels-Alder addition product 6 were obtained in different yields. When we look at the percentage of the addition product, it is observed that the yield of reaction at high pressure in water is the highest. All structures of these products were characterized by 1H-NMR, 13C-NMR, MS, and IR spectroscopy.

Influence of the acid and basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis; Influence des proprietes acido-basiques de l`oxyde de rhenium supporte sur les performances catalytiques en metathese des olefines

Energy Technology Data Exchange (ETDEWEB)

Nahama, F.

1996-11-30

The aim of this work is to study the influence of the acid-basic properties of rhenium oxide supported on alumina catalyst on the catalytic performance in olefin metathesis. The literature data indicate that the environment of the active site does possess acid properties. However, the nature of the acid sites is still matter of debate. Concerning the Re O{sub x} - Al{sub 2}O{sub 3} interactions, we have shown that perrhenate ions are electrostatically absorbed on alumina. The uptake of rhenium is favoured at acidic pH (below 4), and the absorbed rhenium is in equilibrium with rhenium in solution. The results of rhenium extraction by water strongly suggest that the surface compounds of the calcined Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} materials is aluminium perrhenate. Characterization of surface acidity of the catalyst by infrared spectroscopy reveals that the initiation of the metathesis reaction is governed essentially by Lewis acidity. This strongly supports the role of Lewis acidity, which is exalted by the increase of the rhenium content and the calcination temperature. Finally, we point out by ammonia adsorption-thermodesorption a band at 1320 cm{sup -1} characteristic of the Lewis acidity of aluminium perrhenate. This result is a second indication of the presence of aluminium perrhenate on the Re{sub 2}O{sub 7}/Al{sub 2}O{sub 3} catalyst surface. (author)

Calorimetric study of alternating copolymer of bicyclo[2,2,1]-hepta-2,5-diene and carbon monoxide in the range from T->0 to 510K

Energy Technology Data Exchange (ETDEWEB)

Smirnova, N.N. [Research Institute of Chemistry, Nizhny Novgorod University, Gagarin Prospekt 23/5, 603950 Nizhny Novgorod (Russian Federation)]. E-mail: smirnova@ichem.unn.runnet.ru; Nikishchenkova, L.V. [Research Institute of Chemistry, Nizhny Novgorod University, Gagarin Prospekt 23/5, 603950 Nizhny Novgorod (Russian Federation); Bykova, T.A. [Research Institute of Chemistry, Nizhny Novgorod University, Gagarin Prospekt 23/5, 603950 Nizhny Novgorod (Russian Federation); Kulagina, T.G. [Research Institute of Chemistry, Nizhny Novgorod University, Gagarin Prospekt 23/5, 603950 Nizhny Novgorod (Russian Federation); Belov, G.P. [Institute of Problems of Chemical Physics of Russian Academy Sciences, 142432 Chernogolovka, Moscow Region (Russian Federation); Novikova, E.V. [Institute of Problems of Chemical Physics of Russian Academy Sciences, 142432 Chernogolovka, Moscow Region (Russian Federation)

2006-12-01

By adiabatic vacuum and dynamic calorimetry, the temperature dependence of heat capacity for alternating copolymer of bicyclo[2,2,1]-hepta-2,5-diene and carbon monoxide has been determined over the 6-510K range with an uncertainty of 0.2-0.5% between 6 and 350K and 0.5-1.5% from 330 to 510K. In the above temperature ranges, the physical transformations of the copolymer have been detected and their thermodynamic characteristics have been estimated. In a calorimeter with a static bomb and an isothermal shield, the energy of combustion of the copolymer has been measured at 298.15K. Based on the experimental data, the thermodynamic functions of the copolymer, namely, the heat capacity C{sub p}{sup -}bar (T), enthalpy H{sup o}(T)-H{sup o}(0), entropy S{sup o}(T)-S{sup o}(0) and Gibbs function G{sup o}(T)-H{sup o}(0) have been determined for the range from T->0 to 400K. The enthalpy of combustion {delta}{sub c}H{sup o} and the thermodynamic parameters {delta}{sub f}H{sup o}, {delta}{sub f}S{sup o}, {delta}{sub f}G{sup o} and lnK{sub f}{sup -}bar of reaction of formation of the copolymer from simple substances at T=298.15K and p=0.1MPa have been calculated. The data cited in the present work and literature data were used to calculate the thermodynamic characteristics of the alternating copolymerization in bulk of bicyclo[2,2,1]-hepta-2,5-diene and CO in the 0-340K range at standard pressure as well as to compare them with the thermodynamic characteristics of the synthesis of isomeric polyketone.

Synthesis and Characterization of Acyclic and Cyclic Azabridged Ligands Incorporating 2,2'-Bipyridine Subunits and Their Complexes With Copper(II, Cobalt(II, and Nickel(II

Directory of Open Access Journals (Sweden)

Andrea Pappalardo

2003-07-01

Full Text Available The synthesis of a series of N,N'-disubstituted acyclic (AL and cyclic (CL aza-bridged ligands incorporating 2,2-pipryidine subunits is described. 1H-NMR and IR spectral data support the proposed ligand structures. Dynamic 1H-NMR studies on diurea and diamide derivatives point to the presence of slowly interconverting conformers on the 1H-NMR time-scale, owing to N−H···N hydrogen bonding and/or a restricted rotation around the amide bonds. The ligands synthesized form 1:1 complexes with divalent transition metal ions. Upon complexation, bis-ester derivatives AL5 and CL5 undergo a metal-induced hydrolysis of the ester groups to carboxyl functions, which act as additional binding sites for the metal ion, as well as hydrogen-bonding donor-acceptor binding site to produce dimeric complexes.

In situ crosslinking of surface-initiated ring opening metathesis polymerization of polynorbornene for improved stability.

Science.gov (United States)

Fursule, Ishan A; Abtahi, Ashkan; Watkins, Charles B; Graham, Kenneth R; Berron, Brad J

2018-01-15

In situ crosslinking is expected to increase the solvent stability of coatings formed by surface-initiated ring opening metathesis polymerization (SI ROMP). Solvent-associated degradation limits the utility of SI ROMP coatings. SI ROMP coatings have a unique capacity for post-functionalization through reaction of the unsaturated site on the polymer backbone. Any post-reaction scheme which requires a liquid solvent has the potential to degrade the coating and lower the thickness of the resulting film. We designed a macromolecular crosslinking group based on PEG dinorbornene. The PEG length is tailored to the expected mean chain to chain distance during surface-initiated polymerization. This crosslinking macromer is randomly copolymerized with norbornene through SI ROMP on a gold coated substrate. The solvent stability of polynorbornene coatings with and without PEG dinorbornene is quantitatively determined, and the mechanism of degradation is further supported through XPS and AFM analyses. The addition of the 0.25mol% PEG dinorbornene significantly increases the solvent stability of the SI ROMP coatings. The crosslinker presence in the more stable films is supported with observable PEG absorbances by FTIR and an increase in contact angle hysteresis when compared to non-crosslinked coatings. The oxidation of the SI ROMP coatings is supported by the observation of carbonyl oxygen in the polynorbornene coatings. The rapid loss of the non-crosslinked SI ROMP coating corresponds to nanoscale pitting across the surface and micron-scale regions of widespread film loss. The crosslinked coatings have uniform nanoscale pitting, but the crosslinked films show no evidence of micron-scale film damage. In all, the incorporation of minimal crosslinking content is a simple strategy for improving the solvent stability of SI ROMP coatings. Copyright © 2017 Elsevier Inc. All rights reserved.

Reversible Twisting of Primary Amides via Ground State N-C(O) Destabilization: Highly Twisted Rotationally Inverted Acyclic Amides.

Science.gov (United States)

Meng, Guangrong; Shi, Shicheng; Lalancette, Roger; Szostak, Roman; Szostak, Michal

2018-01-17

Since the seminal studies by Pauling in 1930s, planarity has become the defining characteristic of the amide bond. Planarity of amides has central implications for the reactivity and chemical properties of amides of relevance to a range of chemical disciplines. While the vast majority of amides are planar, nonplanarity has a profound effect on the properties of the amide bond, with the most common method to restrict the amide bond relying on the incorporation of the amide function into a rigid cyclic ring system. In a major departure from this concept, here, we report the first class of acyclic twisted amides that can be prepared, reversibly, from common primary amides in a single, operationally trivial step. Di-tert-butoxycarbonylation of the amide nitrogen atom yields twisted amides in which the amide bond exhibits nearly perpendicular twist. Full structural characterization of a range of electronically diverse compounds from this new class of twisted amides is reported. Through reactivity studies we demonstrate unusual properties of the amide bond, wherein selective cleavage of the amide bond can be achieved by a judicious choice of the reaction conditions. Through computational studies we evaluate structural and energetic details pertaining to the amide bond deformation. The ability to selectively twist common primary amides, in a reversible manner, has important implications for the design and application of the amide bond nonplanarity in structural chemistry, biochemistry and organic synthesis.

Acyclic retinoid in chemoprevention of hepatocellular carcinoma: Targeting phosphorylated retinoid X receptor-α for prevention of liver carcinogenesis

Directory of Open Access Journals (Sweden)

Masahito Shimizu

2012-01-01

Full Text Available One of the key features of hepatocellular carcinoma (HCC is the high rate of intrahepatic recurrence that correlates with poor prognosis. Therefore, in order to improve the clinical outcome for patients with HCC, development of a chemopreventive agent that can decrease or delay the incidence of recurrence is a critical issue for urgent investigation. Acyclic retinoid (ACR, a synthetic retinoid, successfully improves HCC patient survival by preventing recurrence and the formation of secondary tumors. A malfunction of the retinoid X receptor-α (RXRα due to phosphorylation by the Ras-MAPK signaling pathway plays a critical role in liver carcinogenesis, and ACR exerts chemopreventive effects on HCC development by inhibiting RXRα phosphorylation. Here, we review the relationship between retinoid signaling abnormalities and liver disease, the mechanisms of how RXRα phosphorylation contributes to liver carcinogenesis, and the detailed effects of ACR on preventing HCC development, especially based on the results of our basic and clinical research. We also outline the concept of "clonal deletion and inhibition" therapy, which is defined as the removal and inhibition of latent malignant clones from the liver before they expand into clinically detectable HCC, because ACR prevents the development of HCC by implementing this concept. Looking toward the future, we discuss "combination chemoprevention" using ACR as a key drug since it can generate a synergistic effect, and may thus be an effective new strategy for the prevention of HCC.

MORPHOPHONOLOGICAL PROCESSES OF THE C'LELA NOUN

African Journals Online (AJOL)

M A ALIERO

The indeterminacy/attestation model of metathesis. Language 80.2. Hume, Elizabeth, 2007. The interaction of internal and external factors in metathesis and deletion. Conference on Precedence Relations, CUNY Phonology Forum 9. Hume, Elizabeth and Jeff Mielke, 2001. Consequences of word recognition for metathesis.

{2-[Bis(2,4-di-tert-butylphenoxyphosphanyloxy-κP]-3,5-di-tert-butylphenyl-κC1}[(1,2,5,6-η-cycloocta-1,5-diene]rhodium(I toluene monosolvate

Directory of Open Access Journals (Sweden)

Detlef Selent

2012-02-01

Full Text Available The reaction of (η3-allyl[(1,2,5,6-η-cycloocta-1,5-diene]rhodium(I with tris(2,4-di-tert-butylphenylphosphite in toluene produces the title compound, [Rh(C42H62O3P(C8H12]·C7H8, by spontaneous metallation at one of the nonsubstituted phenyl ortho-C atoms of the phosphite molecule. The coordination geometry at the RhI ion is distorted square-planar. The toluene solvent molecule is disordered over two different orientations, with site-occupation factors of 0.810 (2 and 0.190 (2.

Ethylene–propylene–diene terpolymer/hexa fluoropropylene–vinylidinefluoride dipolymer rubber blends: Thermal and mechanical properties

International Nuclear Information System (INIS)

Balachandran Nair, Ajalesh; Kurian, Philip; Joseph, Rani

2012-01-01

Highlights: ► The EPDM/MA-g-EPDM/FKM blends show good mechanical properties. ► In compatibilized blends, better thermal and swelling resistance was obtained. ► Random nucleation mechanism is the rate controlling process in degradation. ► Good phase morphology is obtained in the case of compatibilized blends. -- Abstract: Hexa fluoropropylene–vinylidinefluoride dipolymer, fluoroelastomer (FKM) and ethylene propylene diene rubber (EPDM) blends with and without compatibilizer (MA-g-EPDM) were prepared by two-roll mill mixing. The effects of blend ratio and amount of compatibilizer on mechanical properties and thermal stability were investigated. The cure characteristics and mechanical properties of EPDM, FKM and their blends of varying compositions were studied for unaged and aged samples. The 50:50 (w/w) FKM/EPDM showed highest mechanical properties. The tensile properties of all the composites, especially those with higher proportion of FKM increased with aging. Swelling of the blends was reduced after aging. The thermal stability of FKM/EPDM rubber blends was studied using thermogravimetric analysis (TGA). The incorporation of FKM rubber improved the thermal stability of EPDM rubber. The apparent degradation activation energy (E) of EPDM/FKM reactive blends was calculated by the Coats–Redfern method. The results showed that the EPDM/FKM reactive blends had higher thermal stability but lower E than FKM. The thermal degradation process of both EPDM/FKM reactive blends and FKM were determined by nucleation and growth mechanism. The differential scanning calorimetry (DSC) results suggest that glass transition temperature (T g ) peak for EPDM region is shifted to FKM phase, due to improved compatibility on addition of compatibilizer. The morphology of blends was investigated using scanning electron microscopy (SEM).

Combination of in situ metathesis reaction with a novel "magnetic effervescent tablet-assisted ionic liquid dispersive microextraction" for the determination of endogenous steroids in human fluids.

Science.gov (United States)

Wu, Jia; Xu, Zilin; Pan, Yixuan; Shi, Yi; Bao, Xiujie; Li, Jun; Tong, Yu; Tang, Han; Ma, Shuyan; Wang, Xuedong; Lyu, Jianxin

2018-05-01

Herein, a novel magnetic effervescence tablet-assisted microextraction coupled to in situ metathesis reaction of ionic liquid (IS-META-ILDM) is presented for the determination of four endogenous steroids in human urine, pregnant women's blood, and fetal umbilical cord blood. The magnetic effervescent tablets, which were composed of Fe 3 O 4 nanoparticles, sodium carbonate (alkaline source), and tartaric acid (acidic source), were used to disperse the extractant and for convenient magnetic separation. After the effervescent reaction, in situ reaction between NH 4 PF 6 and [C 6 MIM]BF 4 was adopted to change hydrophilic ionic liquid to hydrophobic liquid, which could be separated from the aqueous phase. The newly developed method has three obvious advantages: (1) combination of effervescent dispersion and magnetic nanoparticles' retrieval is cost-effective and the dispersion and collection of the extractant can be completed almost simultaneously; (2) as compared to temperature-controlled ionic liquid dispersive microextraction and cold-induced solidified microextraction, this method avoids a heating and cooling process which significantly reduces the extraction time and energy cost; and (3) the combination of adsorption by magnetic nanoparticles with extraction by in situ metathesis reaction easily produces high recoveries for target analytes. The optimized composition of effervescent tablet and experimental parameters are as follows: 0.64 g mixture of sodium carbonate and tartaric acid, 7 mg of Fe 3 O 4 (20 nm) as magnetic sorbents, 40 μL of [C 6 MIM]BF 4 as the extraction solvent, 0.15 g NH 4 PF 6 , and 300 μL of elution solvent. Under the optimized conditions, the newly developed method provided high extraction recoveries (90.0-118.5%) and low LODs (0.14-0.17 μg L -1 ) in urine and blood samples. In total, this IS-META-ILDM method provided high extraction efficiency, fast and convenient separation, and underutilization of any organic solvent, and thus

Evaluasi terhadap Pelaksanaan Komunikasi Pemasaran Sosial Non-Goverment Organization (NGO) untuk Isu-Isu Anti Kekerasan terhadap Perempuan (Studi Kasus Kampanye Anti Kekerasan Terhadap Perempuan Cut Nyak Dien Yogyakarta dan Solidaritas Perempuan untuk Ha

OpenAIRE

Tri Hastuti Nur R

2013-01-01

Abstract: This paper explains how social marketing communication used by Cut Nyak Dien, Yogyakarta and Spekham, Surakarta–those are non goverment organization (NGO)– to sosialize issues about anti-violences to women. The result of research show evaluation fase in the social marekting fases were not done. They were not evaluate the messages were received or not;and they were not identify the level of target audiens’ behaviour changes. The media that they used were variatives. Having soci...

Evaluasi Terhadap Pelaksanaan Komunikasi Pemasaran Sosial Non-Goverment Organization (NGO) Untuk Isu-Isu Anti Kekerasan Terhadap Perempuan (Studi Kasus Kampanye Anti Kekerasan Terhadap Perempuan Cut Nyak Dien YOGYAKARTA Dan Solidaritas Perempuan Untuk Ha

OpenAIRE

Nur R, Tri Hastuti

2006-01-01

This paper explains how social marketing communication used by Cut Nyak Dien, Yogyakarta and Spekham, Surakarta–those are non goverment organization (NGO)– to sosialize issues about anti-violences to women. The result of research show evaluation fase in the social marekting fases were not done. They were not evaluate the messages were received or not;and they were not identify the level of target audiens’ behaviour changes. The media that they used were variatives. Having social marketi...

Reactions of Fischer carbene complexes with Electron-deficient olefins: Scope and limitations of this route to donor-acceptor-substituted cyclopropanes

Energy Technology Data Exchange (ETDEWEB)

Wienand, A.; Reissig, H.U. (Inst. fuer Organische Chemie der Technischen Hochschule Darmstadt (West Germany))

1990-12-01

The Fischer carbene complex ((CO){sub 5}Cr{double bond}C(OMe)Ph) (1) is able to transfer its carbene ligand to a variety of electron-deficient olefins and provides donor-acceptor-substituted cyclopropanes in good yields. Apt activating groups with respect to the alkene are ester, amide, nitrile, sulfone, and dialkyl phosphonate functions. Methyl vinyl ketone (19) affords products in low yield that may arise from an intermediate cyclopropane derivative. Phenyl vinyl sulfoxide (24) mainly acts as an oxidizing agent, transforming 1 into methyl benzoate. for olefin 24 and {alpha}-(N-methylanilino)acrylonitrile the authors found products that should be formed on an olefin metathesis pathway. The methyl-substituted carbene complex 48 also affords the expected donor-acceptor-substituted cyclopropanes; however, acyclic isomers are formed in higher amounts. The molybdenum and tungsten complexes 55 and 56, respectively, also furnish cyclopropane derivatives, but the yields are lower than with the chromium compound 1. Disubstituted olefins and complex 1 still give the cyclopropanes in moderate yields, while all trisubstituted and most of the difunctionalized alkenes do not react with this Fischer carbene complex. The cyclopropanes synthesized can be deprotonated and alkylated or transformed into ring-opened products. These model reactions demonstrate the synthetic potentials of donor-acceptor-substituted cyclopropanes prepared via Fischer carbene complexes.

Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

KAUST Repository

Hamieh, Ali Imad Ali

2016-07-28

An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

Investigation of Surface Alkylation Strategy in SOMC: In Situ Generation of a Silica-Supported Tungsten Methyl Catalyst for Cyclooctane Metathesis

KAUST Repository

Hamieh, Ali Imad Ali; Dey, Raju; Samantaray, Manoja; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Chen, Yin; Pelletier, Jeremie; Cavallo, Luigi; Basset, Jean-Marie

2016-01-01

An efficient and potentially scalable method is described for the synthesis of the silica-supported complexes [(≡Si-O-)WMe5] and [(≡Si-O-)WMe2(≡CH)] obtained by in situ alkylation of the surface-grafted tungsten chloride [(≡Si-O-)WCl5] (1). [(≡Si-O-)WCl5] can be readily prepared by the reaction of commercially available and stable tungsten hexachloride WCl6 with partially dehydroxylated silica at 700 °C (SiO2-700). Further reaction with ZnMe2 at room temperature rapidly forms a mixture of surface-alkylated tungsten complexes. They were fully characterized by microanalysis, FTIR, mass balance, and solid-state NMR (1H, 13C, 1H-13C HETCOR, 1H-1H double quantum and triple quantum) and identified as [(≡Si-O-)WMe5] and another product, [(≡Si-O-)WMe2(≡CH)]. The latter might have been generated by partial decomposition of the tungsten methyl chloride compound, which is formed during the stepwise alkylation of [(≡Si-O-)WCl5]. DFT calculations were carried out to check the relative stability of the tungsten methyl chloride intermediates and the feasibility of the reaction and corroborate the experimental results. This tungsten complex and its derivative were found to be active catalysts for the metathesis of cyclooctane. © 2016 American Chemical Society.

Synthetic incorporation of Nile Blue into DNA using 2′-deoxyriboside substitutes: Representative comparison of (R- and (S-aminopropanediol as an acyclic linker

Directory of Open Access Journals (Sweden)

Daniel Lachmann

2010-02-01

Full Text Available The Nile Blue chromophore was incorporated into oligonucleotides using “click” chemistry for the postsynthetic modification of oligonucleotides. These were synthesized using DNA building block 3 bearing an alkyne group and reacted with the azide 4. (R-3-amino-1,2-propanediol was applied as the linker between the phosphodiester bridges. Two sets of DNA duplexes were prepared. One set carried the chromophore in an A-T environment, the second set in a G-C environment. Both were characterized by optical spectroscopy. Sequence-dependent fluorescence quenching was applied as a sensitive tool to compare the stacking interactions with respect to the chirality of the acyclic linker attachment. The results were compared to recent results from duplexes that carried the Nile Blue label in a sequentially and structurally identical context, except for the opposite chirality of the linker ((S-3-amino-1,2-propandiol. Only minor, negligible differences were observed. Melting temperatures, UV–vis absorption spectra together with fluorescence quenching data indicate that Nile Blue stacks perfectly between the adjacent base pairs regardless of whether it has been attached via an S- or R-configured linker. This result was supported by geometrically optimized DNA models.

Effects of carbon blacks with various structures on vulcanization and reinforcement of filled ethylene-propylene-diene rubber

Directory of Open Access Journals (Sweden)

2008-10-01

Full Text Available The effects of carbon blacks on vulcanization and mechanical properties of filled ethylene-propylene-diene rubber (EPDM are investigated, by comparing with five types of rubber-grade carbon blacks. Curing kinetics is studied by rheometer and the results indicate that the curing characteristics are influenced by combination of surface area of carbon black and sulphur content on the filler surface, because the former one enhances the physical cross-linking and the latter one introduces the additional chemical cross-linking. Both the degree of cross-linking and cure rate increase with increasing surface area and sulphur content, whereas the optimum cure time and scorch time decrease. The reinforcing nature of the carbon black is assessed from mechanical measurements. It is suggested that the surface area of carbon blacks strongly affects the physical properties of EPDM/carbon black composites. Conductive carbon black (N472 can be used as desirable reinforcing filler due to the higher degree of cross-linking of EPDM with N472 than other EPDM/carbon black composites. The morphology and distribution of particles are studied by using scanning electron microscope. The sound reinforcing ability of N472 is also supported by scanning electron microscope due to the notable dispersibility of N472 within EPDM matrix. N472 ensures the EPDM/N472 composite the most conductive sample among the five composites.

Effect of material and processing parameters on mechanical properties of Polypropylene/Ethylene-Propylene-Diene-Monomer/clay nanocomposites

International Nuclear Information System (INIS)

Hejazi, Iman; Sharif, Farhad; Garmabi, Hamid

2011-01-01

Highlights: → Improved mechanical properties over a broad range of processing conditions. → Moderate levels of clay and processing parameters lead to higher toughness of TPO. → Significant improvement of tensile strength and modulus of TPO materials. -- Abstract: Polypropylene/Ethylene-Propylene-Diene-Monomer (PP/EPDM) blends are well known for having a combination of favourable mechanical properties. In this paper, addition of organoclay to PP/EPDM to make PP/EPDM nanocomposites with enhanced mechanical properties is studied. PP/EPDM/organoclay nanocomposites were prepared using a lab scale twin-screw extruder. Maleic anhydride grafted polypropylene (PP-g-MA) was used to enhance the intercalation/exfoliation process and to create good adhesion at the polymer/polymer and polymer/filler interfaces. Taguchi method was employed to deign the experiments and optimize material and processing parameters for optimized mechanical properties. Organoclay (NC) and compatibilizer content were selected as material parameters and the main processing variables were feeding rate and average shear rate (RPM). X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) were used to study the microstructure of the nanocomposites samples. It was observed that NC content and shear rate in extruder improved the tensile strength and modulus. Another important result was the insignificant effect of NC content on impact strength while increasing shear rate first increased and then decreased the impact strength.

Comparison of Current Chemical and Stereochemical Tests for the Identification and Differentiation of Pelargonium graveolens L'Hér. (Geraniaceae Essential Oils: Analytical Data for (--(1S, 4R, 5S-Guaia-6,9-diene and (--(7R,10S-10-epi-γ-Eudesmol

Directory of Open Access Journals (Sweden)

Mei Wang

2014-07-01

Full Text Available Commercial geranium oil samples, steam-distilled oils of authenticated plant samples, and a reference sample were investigated by GC/MS to determine the validity and applicability of a series of chemical and stereochemical tests that have been proposed in the literature to identify the country of origin, phytochemical identity or authenticity of geranium oils. The chemical tests evaluated include the ratio of the concentrations of geraniol to citronellol and the presence or absence of certain sesquiterpenes, viz., (-- guaia-6,9-diene and (--10-epi-γ-eudesmol. The stereochemical tests include the stereochemical distribution of i citronellol, ii menthone and isomenthone, and iii rose oxides. The most reliable chemical test was the presence or absence of the sesquiterpene probes. The stereochemical tests proved to be less reliable. Most of the tests could be used to classify geranium oils into general types; however, none of the tests provided a foolproof method to distinguish cultivars or country of origin. During this study, the ambiguity in the absolute stereochemistry of (--10-epi-γ-eudesmol and (--guaia-6,9-diene was addressed, and these two sesquiterpenes could serve as effective markers for the authentication of P. graveolens essential oils.

Optimal Hydrophobicity in Ring-Opening Metathesis Polymerization-Based Protein Mimics Required for siRNA Internalization.

Science.gov (United States)

deRonde, Brittany M; Posey, Nicholas D; Otter, Ronja; Caffrey, Leah M; Minter, Lisa M; Tew, Gregory N

2016-06-13

Exploring the role of polymer structure for the internalization of biologically relevant cargo, specifically siRNA, is of critical importance to the development of improved delivery reagents. Herein, we report guanidinium-rich protein transduction domain mimics (PTDMs) based on a ring-opening metathesis polymerization scaffold containing tunable hydrophobic moieties that promote siRNA internalization. Structure-activity relationships using Jurkat T cells and HeLa cells were explored to determine how the length of the hydrophobic block and the hydrophobic side chain compositions of these PTDMs impacted siRNA internalization. To explore the hydrophobic block length, two different series of diblock copolymers were synthesized: one series with symmetric block lengths and one with asymmetric block lengths. At similar cationic block lengths, asymmetric and symmetric PTDMs promoted siRNA internalization in the same percentages of the cell population regardless of the hydrophobic block length; however, with 20 repeat units of cationic charge, the asymmetric block length had greater siRNA internalization, highlighting the nontrivial relationships between hydrophobicity and overall cationic charge. To further probe how the hydrophobic side chains impacted siRNA internalization, an additional series of asymmetric PTDMs was synthesized that featured a fixed hydrophobic block length of five repeat units that contained either dimethyl (dMe), methyl phenyl (MePh), or diphenyl (dPh) side chains and varied cationic block lengths. This series was further expanded to incorporate hydrophobic blocks consisting of diethyl (dEt), diisobutyl (diBu), and dicyclohexyl (dCy) based repeat units to better define the hydrophobic window for which our PTDMs had optimal activity. High-performance liquid chromatography retention times quantified the relative hydrophobicities of the noncationic building blocks. PTDMs containing the MePh, diBu, and dPh hydrophobic blocks were shown to have superior

Effect of cork loading on mechanical and thermal properties of silica-Ethylene-propylene-diene monomer composite

International Nuclear Information System (INIS)

Gul, J.; Mirza, S.

2011-01-01

Ethylene-propylene diene ter-monomer (EPDM) filled with asbestos are widely used as thermal insulation in space vehicles because of its low specific gravity, low temperature flexibility, high ozone and oxygen resistant, superior thermal and ablation characteristics. However, asbestos has been banned worldwide because of its carcinogenic nature. This study was aimed to replace asbestos by environmental friendly and low specific gravity filler, cork in thermal insulation for space vehicles. Various batches of cork filled EPDM were obtained by compounding 0, 10, 20, 40, 50, 60, 70 and 100 Phr (parts per hundred parts of rubber) of cork powder with EPDM in Two-roll-mill in presence of other necessary compounding ingredients. The resulted vulcanizates were characterized for mechanical, thermal and ablation performances. It was observed that cork loadings significantly enhanced tensile strength and hardness of EPDM. However, elongation at break of EPDM decreased with the increase of cork concentration. Moreover, no significant reduction in density of EPDM was obtained instead of compounding with lower specific gravity cork powder. Temperatures cures in Thermo-gravimetric analysis shifted to lower temperature with increasing of cork percentage in the formulation. Furthermore, char formation of the EPDM composites decreased with the increase of cork Phr in the composition which was the indication of degrading thermal stability of EPDM by cork powders. It can be concluded that on the basis of mechanical properties asbestos can be replaced by cork powder however, cork filled EPDM exhibited inferior thermal properties as compared to asbestos filled EPDM. (author)

Evaluasi terhadap Pelaksanaan Komunikasi Pemasaran Sosial Non-Goverment Organization (NGO untuk Isu-Isu Anti Kekerasan terhadap Perempuan (Studi Kasus Kampanye Anti Kekerasan Terhadap Perempuan Cut Nyak Dien Yogyakarta dan Solidaritas Perempuan untuk Ha

Directory of Open Access Journals (Sweden)

Tri Hastuti Nur R

2013-12-01

Full Text Available Abstract: This paper explains how social marketing communication used by Cut Nyak Dien, Yogyakarta and Spekham, Surakarta–those are non goverment organization (NGO– to sosialize issues about anti-violences to women. The result of research show evaluation fase in the social marekting fases were not done. They were not evaluate the messages were received or not;and they were not identify the level of target audiens’ behaviour changes. The media that they used were variatives. Having social marketing communication, they always do with advocacy activities.

The effect of acyclic retinoid on the metabolomic profiles of hepatocytes and hepatocellular carcinoma cells.

Directory of Open Access Journals (Sweden)

Xian-Yang Qin

Full Text Available BACKGROUND/PURPOSE: Acyclic retinoid (ACR is a promising chemopreventive agent for hepatocellular carcinoma (HCC that selectively inhibits the growth of HCC cells (JHH7 but not normal hepatic cells (Hc. To better understand the molecular basis of the selective anti-cancer effect of ACR, we performed nuclear magnetic resonance (NMR-based and capillary electrophoresis time-of-flight mass spectrometry (CE-TOFMS-based metabolome analyses in JHH7 and Hc cells after treatment with ACR. METHODOLOGY/PRINCIPAL FINDINGS: NMR-based metabolomics revealed a distinct metabolomic profile of JHH7 cells at 18 h after ACR treatment but not at 4 h after ACR treatment. CE-TOFMS analysis identified 88 principal metabolites in JHH7 and Hc cells after 24 h of treatment with ethanol (EtOH or ACR. The abundance of 71 of these metabolites was significantly different between EtOH-treated control JHH7 and Hc cells, and 49 of these metabolites were significantly down-regulated in the ACR-treated JHH7 cells compared to the EtOH-treated JHH7 cells. Of particular interest, the increase in adenosine-5'-triphosphate (ATP, the main cellular energy source, that was observed in the EtOH-treated control JHH7 cells was almost completely suppressed in the ACR-treated JHH7 cells; treatment with ACR restored ATP to the basal levels observed in both EtOH-control and ACR-treated Hc cells (0.72-fold compared to the EtOH control-treated JHH7 cells. Moreover, real-time PCR analyses revealed that ACR significantly increased the expression of pyruvate dehydrogenase kinases 4 (PDK4, a key regulator of ATP production, in JHH7 cells but not in Hc cells (3.06-fold and 1.20-fold compared to the EtOH control, respectively. CONCLUSIONS/SIGNIFICANCE: The results of the present study suggest that ACR may suppress the enhanced energy metabolism of JHH7 cells but not Hc cells; this occurs at least in part via the cancer-selective enhancement of PDK4 expression. The cancer-selective metabolic pathways

Methods of refining natural oils, and methods of producing fuel compositions

Science.gov (United States)

Firth, Bruce E.; Kirk, Sharon E.

2015-10-27

A method of refining a natural oil includes: (a) providing a feedstock that includes a natural oil; (b) reacting the feedstock in the presence of a metathesis catalyst to form a metathesized product that includes olefins and esters; (c) passivating residual metathesis catalyst with an agent that comprises nitric acid; (d) separating the olefins in the metathesized product from the esters in the metathesized product; and (e) transesterifying the esters in the presence of an alcohol to form a transesterified product and/or hydrogenating the olefins to form a fully or partially saturated hydrogenated product. Methods for suppressing isomerization of olefin metathesis products produced in a metathesis reaction, and methods of producing fuel compositions are described.

Peretinoin, an acyclic retinoid, improves the hepatic gene signature of chronic hepatitis C following curative therapy of hepatocellular carcinoma

International Nuclear Information System (INIS)

Honda, Masao; Yamashita, Taro; Yamashita, Tatsuya; Arai, Kuniaki; Sakai, Yoshio; Sakai, Akito; Nakamura, Mikiko; Mizukoshi, Eishiro; Kaneko, Shuichi

2013-01-01

The acyclic retinoid, peretinoin, has been shown to be effective for suppressing hepatocellular carcinoma (HCC) recurrence after definitive treatment in a small-scale randomized clinical trial. However, little has been documented about the mechanism by which peretinoin exerts its inhibitory effects against recurrent HCC in humans in vivo. Twelve hepatitis C virus-positive patients whose HCC had been eradicated through curative resection or ablation underwent liver biopsy at baseline and week 8 of treatment with either a daily dose of 300 or 600 mg peretinoin. RNA isolated from biopsy samples was subjected to gene expression profile analysis. Peretinoin treatment elevated the expression levels of IGFBP6, RBP1, PRB4, CEBPA, G0S2, TGM2, GPRC5A, CYP26B1, and many other retinoid target genes. Elevated expression was also observed for interferon-, Wnt-, and tumor suppressor-related genes. By contrast, decreased expression levels were found for mTOR- and tumor progression-related genes. Interestingly, gene expression profiles for week 8 of peretinoin treatment could be classified into two groups of recurrence and non-recurrence with a prediction accuracy rate of 79.6% (P<0.05). In the liver of patients with non-recurrence, expression of PDGFC and other angiogenesis genes, cancer stem cell marker genes, and genes related to tumor progression was down-regulated, while expression of genes related to hepatocyte differentiation, tumor suppression genes, and other genes related to apoptosis induction was up-regulated. Gene expression profiling at week 8 of peretinoin treatment could successfully predict HCC recurrence within 2 years. This study is the first to show the effect of peretinoin in suppressing HCC recurrence in vivo based on gene expression profiles and provides a molecular basis for understanding the efficacy of peretinoin

Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

Directory of Open Access Journals (Sweden)

Thibault E. Schmid

2015-09-01

Full Text Available A silver-free methodology was developed for the synthesis of unprecedented N-heterocyclic carbene ruthenium indenylidene complexes bearing a bidentate picolinate ligand. The highly stable (SIPr(picolinateRuCl(indenylidene complex 4a (SIPr = 1,3-bis(2-6-diisopropylphenylimidazolidin-2-ylidene demonstrated excellent latent behaviour in ring closing metathesis (RCM reaction and could be activated in the presence of a Brønsted acid. The versatility of the catalyst 4a was subsequently demonstrated in RCM, cross-metathesis (CM and enyne metathesis reactions.

Metátese na linguagem infantil: “porfessora” é bom, “professora” é melhor

Directory of Open Access Journals (Sweden)

Rosa M. Lima

2013-12-01

Full Text Available A leitura e a escrita são ensinadas a crianças cuja linguagem oral contém ainda, muitas vezes, desvios subtis. A metátese é um desses desvios, consistindo na troca da ordem de fonemas na palavra, tal como acontece em “corcodilo”. Analisámos a presença da metátese na linguagem infantil. Num primeiro estudo, investigámos a aquisição da linguagem oral dos 3 aos 7 anos de idade. A metátese mostrou um peso crescente ao longo da idade. Num segundo estudo, analisámos o desempenho de crianças do 4º ano na deteção auditiva e visual da metátese, e na escrita de palavras passíveis de induzir a metátese. A deteção visual da metátese foi inferior ao nível do acaso. Na escrita de palavras, a metátese deu conta de 69% a 75% dos erros observados. Os resultados sugerem que a metátese constitui um processo indicador de domínio da linguagem oral, revelando formas de gestão de estruturas silábicas complexas. Contudo, essas formas de gestão podem cristalizar-se durante o primeiro ciclo, afetando negativamente a aquisição da linguagem escrita. Children often learn to read and write when their oral language is still marked by subtle errors. Metathesis is one such error. It is a phonological process whereby the order of phonemes is interchanged in the word, such as “corcodilo” instead of “crocodilo”. We investigated metathesis in child language. In a first study, we investigated spoken language acquisition from 3 to7 and half years of age. Metathesis increased with age. In a second study, we analysed the performance of children attending the 4th grade, in auditory and visual detection of metathesis, as well as in spelling words prone to metathesis. Performance in the visual detection of metathesis was significantly below chance. In word spelling tasks, metathesis accounted for 69% to 75% of errors. Results suggest that metathesis indexes some mastery of spoken language, and that it reveals the ability to deal with complex

Flexible Acyclic Polyol-Chloride Anion Complexes and Their Characterization by Photoelectron Spectroscopy and Variable Temperature Binding Constant Determinations

Energy Technology Data Exchange (ETDEWEB)

Shokri, Alireza; Wang, Xue B.; Wang, Yangping; O' Doherty, George A.; Kass, Steven R.

2016-03-17

Flexible acyclic alcohols with 1–5 hydroxyl groups were bound to chloride anion and these complexes were interrogated by negative ion photoelectron spectroscopy and companion density functional theory computations. The resulting vertical detachment energies are reproduced on average to 0.10 eV by M06-2X/aug-cc-pVTZ predictions and range from 4.45 – 5.96 eV. These values are 0.84 – 2.35 eV larger than the adiabatic detachment energy of Cl– as a result of the larger hydrogen bond networks in the bigger polyols. Adiabatic detachment energies of the alcohol–Cl– clusters are more difficult to determine both experimentally and computationally. This is due to the large geometry changes that occur upon photodetachment and the large bond dissociation energy of H–Cl which enables the resulting chlorine atom to abstract a hydrogen from any of the methylene (CH2) or methine (CH) positions. Both ionic and non-ionic hydrogen bonds (i.e., OH•••Cl– and OH•••OH•••Cl–) form in the larger polyols complexes, and are found to be energetically comparable. Subtle structural differences, consequently can lead to the formation of different types of hydrogen bonds and maximizing the ionic ones is not always preferred. Solution equilibrium binding constants between the alcohols and tetrrabuylammonium chloride (TBACl) in acetonitrile at -24.2, 22.0, and 53.6 °C were also determined. The free energies of association are nearly identical for all of the substrates (i.e., ΔG° = -2.8 ± 0.7 kcal mol–1). Compensating enthalpy and entropy values reveal, contrary to expectation and the intrinsic gas-phase preferences, that the bigger systems with more hydroxyl groups are entropically favored and enthalpically disfavored relative to the smaller species. This suggests that more solvent molecules are released upon binding TBACl to alcohols with more hydroxyl groups and is consistent with the measured negative heat capacities. These quantities increase with

Exceptionally Stable and Efficient Solid Supported Hoveyda-Type Catalyst

Czech Academy of Sciences Publication Activity Database

Skowerski, K.; Pastva, J.; Czarnocki, S. J.; Janošcová, Jana

2015-01-01

Roč. 19, č. 7 (2015), s. 872-877 ISSN 1083-6160 Institutional support: RVO:61388955 Keywords : OLEFIN-METATHESIS CATALYSTS * RING-CLOSING METATHESIS * N-HETEROCYCLIC CARBENES Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.922, year: 2015

Rhodium(I) catalysis in olefin photoreactions

International Nuclear Information System (INIS)

Salomon, R.G.; El Sanadi, N.

1975-01-01

The photorearrangement (254 nm) of 1,5-cyclooctadiene (1) in the presence of rhodium(I) chloride to give 1,4-cyclooctadiene (4) was found by deuterium labeling to involve an intramolecular [1,3] shift of hydrogen. A rate-determining cleavage of an allylic C--H bond is indicated by a deuterium isotope effect, k/sub H//k/sub D/ = 1.55 +- 0.03 for the 1 → 4 rearrangement. The acyclic 1,5-diene, 3,3-dimethyl-1,5-hexadiene (8), rearranges in the presence of rhodium(I) chloride upon uv irradiation (254 nm) to give cis-3,3-dimethyl-1,4-hexadiene (10) and the trans isomer 11 in a 1:4 ratio, respectively. This observation supports a mechanism for the photorearrangement of olefins catalyzed by rhodium(I) involving an initial photodissociation of one of two rhodium(I) coordinated carbon-carbon double bonds. This results in an increase in the coordinative unsaturation of rhodium(I) and enhances the proclivity of this d/sub s/ metal atom toward oxidative addition of an allylic C--H bond. A eta 3 -allylrhodium hydride intermediate then gives rearranged olefin by reductive elimination. Lastly, a novel photochemical, rhodium(I) catalyzed hydrogen transfer is reported which gives cyclooctene (7) from cyclooctadienes under unprecedentedly mild conditions. (auth)

Highly toughened polypropylene/ethylene–propylene-diene monomer/zinc dimethacrylate ternary blends prepared via peroxide-induced dynamic vulcanization

Energy Technology Data Exchange (ETDEWEB)

Chen, Yukun, E-mail: cyk@scut.edu.cn [The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou 510640 (China); School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510640 (China); Xu, Chuanhui [College of Material Science and Engineering, South China University of Technology, Guangzhou 510640 (China); Cao, Liming [The Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of Technology, Guangzhou 510640 (China); School of Mechanical and Automotive Engineering, South China University of Technology, Guangzhou 510640 (China); Cao, Xiaodong [College of Material Science and Engineering, South China University of Technology, Guangzhou 510640 (China)

2013-02-15

Polypropylene (PP)/ethylene–propylene-diene monomer (EPDM)/zinc dimethacrylate (ZDMA) blends with remarkable toughness and extensibility were successfully prepared via peroxide dynamical vulcanization. A unique structure with the EPDM particles surrounded by a transition zone containing numerous polymerized ZDMA (PZDMA) nano-particles was observed for the first time by using transmission electron microscopy (TEM) examination, which contributed to the dramatically increase of Izod impact strength. Dynamic mechanical analysis (DMA) confirmed that the possible PZDMA graft products resulted from peroxide dynamical vulcanization improved the compatibility between EPDM and PP phases. The specific morphology of the PP/EPDM/ZDMA blends indicated that ZDMA can lead to size reduction and good distribution uniformity of the crosslinked rubber particles and the increase of adhesion between PP matrix and EPDM phases during deformation. The synergic effect of the increase in the effective volume of the EPDM phase, the improved compatibility and adhesion between EPDM and PP phases and the deformation of those fine rubber particles is believed to result in the remarkable high toughness and extensibility of the PP/EPDM/ZDMA blends. Particularly for the PP/EPDM ratio of 70/30, the PP/EPDM/ZDMA (70/30/9, w/w/w) ternary blends with the Izod impact strength nearly 2 times higher than PP/EPDM (70/30, w/w) binary blends and 15–20 times higher than PP are achieved; besides, the elongation at break of PP/EPDM/ZDMA ternary blends is 4–5 times higher than that of PP/EPDM binary blends. - Highlights: ► ZDMA largely toughen peroxide dynamically vulcanized PP/EPDM blend. ► PZDMA graft products improved the compatibility and adhesion between EPDM and PP. ► Size reduction and good distribution uniformity of crosslinked rubber particles.

Highly toughened polypropylene/ethylene–propylene-diene monomer/zinc dimethacrylate ternary blends prepared via peroxide-induced dynamic vulcanization

International Nuclear Information System (INIS)

Chen, Yukun; Xu, Chuanhui; Cao, Liming; Cao, Xiaodong

2013-01-01

Polypropylene (PP)/ethylene–propylene-diene monomer (EPDM)/zinc dimethacrylate (ZDMA) blends with remarkable toughness and extensibility were successfully prepared via peroxide dynamical vulcanization. A unique structure with the EPDM particles surrounded by a transition zone containing numerous polymerized ZDMA (PZDMA) nano-particles was observed for the first time by using transmission electron microscopy (TEM) examination, which contributed to the dramatically increase of Izod impact strength. Dynamic mechanical analysis (DMA) confirmed that the possible PZDMA graft products resulted from peroxide dynamical vulcanization improved the compatibility between EPDM and PP phases. The specific morphology of the PP/EPDM/ZDMA blends indicated that ZDMA can lead to size reduction and good distribution uniformity of the crosslinked rubber particles and the increase of adhesion between PP matrix and EPDM phases during deformation. The synergic effect of the increase in the effective volume of the EPDM phase, the improved compatibility and adhesion between EPDM and PP phases and the deformation of those fine rubber particles is believed to result in the remarkable high toughness and extensibility of the PP/EPDM/ZDMA blends. Particularly for the PP/EPDM ratio of 70/30, the PP/EPDM/ZDMA (70/30/9, w/w/w) ternary blends with the Izod impact strength nearly 2 times higher than PP/EPDM (70/30, w/w) binary blends and 15–20 times higher than PP are achieved; besides, the elongation at break of PP/EPDM/ZDMA ternary blends is 4–5 times higher than that of PP/EPDM binary blends. - Highlights: ► ZDMA largely toughen peroxide dynamically vulcanized PP/EPDM blend. ► PZDMA graft products improved the compatibility and adhesion between EPDM and PP. ► Size reduction and good distribution uniformity of crosslinked rubber particles

Polymeric membrane neodymium(III)-selective electrode based on 11,13-diaza-4,7,12-trioxo-2(3),8(9)-dibenzoyl- cyclotetridecane-1,11-diene

Energy Technology Data Exchange (ETDEWEB)

Chandra, Sulekh [Department of Chemistry, Zakir Husain College, University of Delhi, J.L.N. Marg, New Delhi, 110002 (India)], E-mail: schandra_00@yahoo.com; Singh, Dev Raj [Department of Chemistry, Zakir Husain College, University of Delhi, J.L.N. Marg, New Delhi, 110002 (India)

2009-02-25

We found that 11, 13-diaza-4, 7, 12-trioxo-2(3), 8(9)-dibenzoyl-cyclotetridecane-1, 11-diene (DATODBCT) can be used as an excellent ionophore in the construction of a novel neodymium(III) poly(vinylchloride) (PVC)-based membrane sensor. A membrane composition of 29% poly(vinylchloride), 59% dibutylphthalate (DBP), 9% DATODBCT and 3% sodiumtetrakis (p-chlorophenyl) borate (NaTpClPB), led to the optimum results. The Nd(III)-selectivity of the sensor, is relatively better as compared to a large number of lanthanide metal ions, such as lanthanum, gadolinium, samarium, dysprosium, praseodymium and ytterbium ions. The sensor response is Nernstian (with slope of 19.4 {+-} 0.3 mV per decade for the triply charged ion) over a wide concentration range (1.0 x 10{sup -8} to 1.0 x 10{sup -1} mol L{sup -1}) with a detection limit of 8.0 x 10{sup -7} mol L{sup -1}, a relatively fast response time, in the whole concentration range (<15 s), and a considerable life time at least for seven weeks in the pH range of 3.0-7.0.

Polymeric membrane neodymium(III)-selective electrode based on 11,13-diaza-4,7,12-trioxo-2(3),8(9)-dibenzoyl- cyclotetridecane-1,11-diene

International Nuclear Information System (INIS)

Chandra, Sulekh; Singh, Dev Raj

2009-01-01

We found that 11, 13-diaza-4, 7, 12-trioxo-2(3), 8(9)-dibenzoyl-cyclotetridecane-1, 11-diene (DATODBCT) can be used as an excellent ionophore in the construction of a novel neodymium(III) poly(vinylchloride) (PVC)-based membrane sensor. A membrane composition of 29% poly(vinylchloride), 59% dibutylphthalate (DBP), 9% DATODBCT and 3% sodiumtetrakis (p-chlorophenyl) borate (NaTpClPB), led to the optimum results. The Nd(III)-selectivity of the sensor, is relatively better as compared to a large number of lanthanide metal ions, such as lanthanum, gadolinium, samarium, dysprosium, praseodymium and ytterbium ions. The sensor response is Nernstian (with slope of 19.4 ± 0.3 mV per decade for the triply charged ion) over a wide concentration range (1.0 x 10 -8 to 1.0 x 10 -1 mol L -1 ) with a detection limit of 8.0 x 10 -7 mol L -1 , a relatively fast response time, in the whole concentration range (<15 s), and a considerable life time at least for seven weeks in the pH range of 3.0-7.0

The Labdane Ent-3-Acetoxy-Labda-8(17), 13-Dien-15-Oic Decreases Blood Pressure In Hypertensive Rats

Energy Technology Data Exchange (ETDEWEB)

Simplicio, Janaina A. [Programa de Pós-Graduação em Farmacologia - Faculdade de Medicina de Ribeirão Preto, Universidade de São Paulo (USP), Ribeirão Preto, SP (Brazil); Departamento de Enfermagem Psiquiátrica e Ciências Humanas - Laboratório de Farmacologia - Escola de Enfermagem de Ribeirão Preto (USP), Ribeirão Preto, SP (Brazil); Simão, Marilia R.; Ambrosio, Sergio R. [Núcleo de Pesquisa em Ciências e Tecnologia - Universidade de Franca (UNIFRAN), Franca, SP (Brazil); Tirapelli, Carlos R., E-mail: crtirapelli@eerp.usp.br [Departamento de Enfermagem Psiquiátrica e Ciências Humanas - Laboratório de Farmacologia - Escola de Enfermagem de Ribeirão Preto (USP), Ribeirão Preto, SP (Brazil)

2016-06-15

Labdane-type diterpenes induce lower blood pressure via relaxation of vascular smooth muscle; however, there are no studies describing the effects of labdanes in hypertensive rats. The present study was designed to investigate the cardiovascular actions of the labdane-type diterpene ent-3-acetoxy-labda-8(17), 13-dien-15-oic acid (labda-15-oic acid) in two-kidney 1 clip (2K-1C) renal hypertension. Vascular reactivity experiments were performed in aortic rings isolated from 2K-1C and normotensive (2K) male Wistar rats. Nitrate/nitrite (NOx) measurement was performed in aortas by colorimetric assay. Blood pressure measurements were performed in conscious rats. Labda-15-oic acid (0.1-300 µmol/l) and forskolin (0.1 nmol/l - 1 µmol/l) relaxed endothelium-intact and endothelium-denuded aortas from both 2K-1C and 2K rats. Labda-15-oic acid was more effective at inducing relaxation in endothelium-intact aortas from 2K pre-contracted with phenylephrine when compared to the endothelium-denuded ones. Forskolin was more potent than labda-15-oic acid at inducing vascular relaxation in arteries from both 2K and 2K-1C rats. Labda-15-oic acid-induced increase in NOx levels was lower in arteries from 2K-1C rats when compared to 2K rats. Intravenous administration of labda-15-oic acid (0.3-3 mg/kg) or forskolin (0.1-1 mg/kg) induced hypotension in conscious 2K-1C and 2K rats. The present findings show that labda-15-oic acid induces vascular relaxation and hypotension in hypertensive rats.

Structure-Activity Relationships for Some Diamine, Triamine and Schiff Base Derivatives and Their Copper(II) Complexes

OpenAIRE

Bolos, C. A.; Nikolov, G. St.; Ekateriniadou, L.; Kortsaris, A.; Kyriakidis, D. A.

1998-01-01

Ethylenediamine (en), putrescine (pu), diethylenetriamine (dien), dipropylenetriamine (dpta), spermidine (spmd) and their CuII compounds as well as the Schiff bases with 2-furaldehyde (dienOO), 2- thiophenecarboxaldehyde (dienSS) and pyrrole-2-carboxaldehyde (dienNN) of dien and that of dpta with 2- thiophenecarboxaldehyde (dptaSS), were prepared and characterised. They were tested against Bacillus substilis, Bacillus cereus, Staphylococcus aureus, Escherichia coli, Proteus vulgaris and Xanth...

and 8-Membered Oxygen-containing Benzo-fused Rings using ...

African Journals Online (AJOL)

NJD

A number of benzo-fused oxygen-containing heterocycles were synthesized from allyl-3-isopropoxy-4-methoxybenzaldehyde using metathesis or an alkene isomerization-metathesis sequence as key synthetic steps. Benzo-fused compounds thus formed included a 3,6-dihydro-1H-2-benzoxocine, ...

Computational Investigation of the Competition between the Concerted Diels-Alder Reaction and Formation of Diradicals in Reactions of Acrylonitrile with Non-Polar Dienes

Science.gov (United States)

James, Natalie C.; Um, Joann M.; Padias, Anne B.; Hall, H. K.; Houk, K. N.

2013-01-01

The energetics of the Diels-Alder cycloaddition reactions of several 1,3-dienes with acrylonitrile, and the energetics of formation of diradicals, were investigated with density functional theory (B3LYP and M06-2X) and compared to experimental data. For the reaction of 2,3-dimethyl-1,3-butadiene with acrylonitrile, the concerted reaction is favored over the diradical pathway by 2.5 kcal/mol using B3LYP/6-31G(d); experimentally this reaction gives both cycloadduct and copolymer. The concerted cycloaddition of cyclopentadiene with acrylonitrile is preferred computationally over the stepwise pathway by 5.9 kcal/mol; experimentally, only the Diels-Alder adduct is formed. For the reactions of (E)-1,3-pentadiene and acrylonitrile, both cycloaddition and copolymerization were observed experimentally; these trends were mimicked by the computational results, which showed only a 1.2 kcal/mol preference for the concerted pathway. For the reactions of (Z)-1,3-pentadiene and acrylonitrile, the stepwise pathway is preferred by 3.9 kcal/mol, in agreement with previous experimental findings that only polymerization occurs. M06-2X is known to give more accurate activation and reaction energetics but the energies of diradicals are too high. PMID:23758325

Ring opening metathesis polymerization-derived block copolymers bearing chelating ligands: synthesis, metal immobilization and use in hydroformylation under micellar conditions

Directory of Open Access Journals (Sweden)

Gajanan M. Pawar

2010-03-01

Full Text Available Norborn-5-ene-(N,N-dipyrid-2-ylcarbamide (M1 was copolymerized with exo,exo-[2-(3-ethoxycarbonyl-7-oxabicyclo[2.2.1]hept-5-en-2-carbonyloxyethyl]trimethylammonium iodide (M2 using the Schrock catalyst Mo(N-2,6-Me2-C6H3(CHCMe2Ph(OCMe(CF322 [Mo] to yield poly(M1-b-M2. In water, poly(M1-b-M2 forms micelles with a critical micelle-forming concentration (cmc of 2.8 × 10−6 mol L−1; Reaction of poly(M1-b-M2 with [Rh(CODCl]2 (COD = cycloocta-1,5-diene yields the Rh(I-loaded block copolymer poly(M1-b-M2-Rh containing 18 mg of Rh(I/g of block copolymer with a cmc of 2.2 × 10−6 mol L−1. The Rh-loaded polymer was used for the hydroformylation of 1-octene under micellar conditions. The data obtained were compared to those obtained with a monomeric analogue, i.e. CH3CON(Py2RhCl(COD (C1, Py = 2-pyridyl. Using the polymer-supported catalyst under micellar conditions, a significant increase in selectivity, i.e. an increase in the n:iso ratio was accomplished, which could be further enhanced by the addition of excess ligand, e.g., triphenylphosphite. Special features of the micellar catalytic set up are discussed.

Quantum chemical investigations on the molecular structure, FTIR, UV-Vis and HOMO-LUMO analysis of 15-16-epoxy-7b, 9a dihydroxylabdane 13(16), 14-dien-6-one

Science.gov (United States)

Uppal, Anshul; Pathania, Kamni; Khajuria, Yugal

2018-05-01

The structural, spectroscopic (Fourier Transform Infrared (FT-IR), Ultra-Violet Visible (UV-VIS)) and thermodynamic properties of 15, 16-epoxy-7b, 9a dihydroxylabdane-13(16), 14-dien-6-one were studied by using both experimental techniques and theoretical methods. The FTIR spectrum of the title compound was recorded in the spectral range 4000-400 cm-1. The UV-VIS spectrum was measured in the spectral range 190-800 nm. The quantum chemistry calculations have been performed to compute optimized geometry, molecular parameters, vibrational frequencies along with intensities using Hartree Fock (HF) theory and Density Functional Theory (DFT) with 6-31G basis set. The calculated HOMO-LUMO energies show that the charge transfer occurs within the molecule. The temperature dependence of the thermodynamic properties like heat capacity, entropy and enthalpy of the optimized structure were obtained. Finally, a comparison between the experimental data and the calculated results presented a good agreement.

The Presence of Amorpha-4, 11-Diene Synthase, a Key Enzyme in Artemisinin Production in Ten Artemisia Species

Directory of Open Access Journals (Sweden)

GA. Garoosi

2011-12-01

Full Text Available Background and the purpose of the study: Artemisinin is one of the most effective medicine against malaria, which is produced naturally by Artemisia annua in low yield. It is produced in a metabolic pathway, in which several genes and gene products are involved. One of the key genes in this pathway is am1, which encodes amorpha-4, 11-diene synthase (ADS, a key enzyme in artemisinin biosynthesis pathway. The aim of this study was to determine the presence of this gene in ten Artemisia species in order to increase the yield of production of Artemisinin. Methods : The experiments were carried out using PCR. Specific primers were designed based on the published am1 gene sequence obtained from A. annua (NCBI, accession number AF327527. Results: The amplification of this gene by the specific primers was considered as a positive sign for the potentiality of artemisinin production. Since the entire am1 gene was not amplified in any of the 10 species used, four parts of the gene, essential in ADS enzyme function, corresponding to a pair site of Arg10-Pro12 in the first 100 amino acids, b aspartate rich motif (DDXXD, c active site final lid and d active site including farnesyl diphosphate (FDP ionization sites and catalytic site in the ADS enzyme, were investigated. Major conclusion: The sequence corresponding to ADS active site was amplified only in A. annua, A. aucheri and A. chamaemelifolia. The negative results obtained with other species could be due to some sequence alteration, such as point mutations or INDELs. We propose A. aucheri and A. chamaemelifolia as two potential candidate species for further characterization, breeding and transferring am1 gene for artemisinin overproduction.

Molecular and Silica-Supported Molybdenum Alkyne Metathesis Catalysts: Influence of Electronics and Dynamics on Activity Revealed by Kinetics, Solid-State NMR, and Chemical Shift Analysis.

Science.gov (United States)

Estes, Deven P; Gordon, Christopher P; Fedorov, Alexey; Liao, Wei-Chih; Ehrhorn, Henrike; Bittner, Celine; Zier, Manuel Luca; Bockfeld, Dirk; Chan, Ka Wing; Eisenstein, Odile; Raynaud, Christophe; Tamm, Matthias; Copéret, Christophe

2017-12-06

Molybdenum-based molecular alkylidyne complexes of the type [MesC≡Mo{OC(CH 3 ) 3-x (CF 3 ) x } 3 ] (MoF 0 , x = 0; MoF 3 , x = 1; MoF 6 , x = 2; MoF 9 , x = 3; Mes = 2,4,6-trimethylphenyl) and their silica-supported analogues are prepared and characterized at the molecular level, in particular by solid-state NMR, and their alkyne metathesis catalytic activity is evaluated. The 13 C NMR chemical shift of the alkylidyne carbon increases with increasing number of fluorine atoms on the alkoxide ligands for both molecular and supported catalysts but with more shielded values for the supported complexes. The activity of these catalysts increases in the order MoF 0 molecular and supported species. Detailed solid-state NMR analysis of molecular and silica-supported metal alkylidyne catalysts coupled with DFT/ZORA calculations rationalize the NMR spectroscopic signatures and discernible activity trends at the frontier orbital level: (1) increasing the number of fluorine atoms lowers the energy of the π*(M≡C) orbital, explaining the more deshielded chemical shift values; it also leads to an increased electrophilicity and higher reactivity for catalysts up to MoF 6 , prior to a sharp decrease in reactivity for MoF 9 due to the formation of stable metallacyclobutadiene intermediates; (2) the silica-supported catalysts are less active than their molecular analogues because they are less electrophilic and dynamic, as revealed by their 13 C NMR chemical shift tensors.

New ROMP Synthesis of Ferrocenyl Dendronized Polymers.

Science.gov (United States)

Liu, Xiong; Ling, Qiangjun; Zhao, Li; Qiu, Guirong; Wang, Yinghong; Song, Lianxiang; Zhang, Ying; Ruiz, Jaime; Astruc, Didier; Gu, Haibin

2017-10-01

First- and second-generation Percec-type dendronized ferrocenyl norbornene macromonomers containing, respectively, three and nine ferrocenyl termini are synthesized and polymerized by ring-opening metathesis polymerization using Grubbs' third-generation olefin metathesis catalyst with several monomer/catalyst feed ratios between 10 and 50. The rate of polymerization is highly dependent on the generation of the dendronized macromonomers, but all these ring-opening metathesis polymerization reactions are controlled, and near-quantitative monomer conversions are achieved. The numbers of ferrocenyl groups obtained are in agreement with the theoretical ones according to the cyclic voltammetry studies as determined using the Bard-Anson method. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Variation of the Sterical Properties of the N-Heterocyclic Carbene Coligand in Thermally Triggerable Ruthenium-Based Olefin Metathesis Precatalysts/Initiators

KAUST Repository

Pump, Eva

2015-11-09

A series of ruthenium complexes based on the κ(C,N)-(2-(benzo[h]quinolin-10-yl)methylidene ruthenium dichloride fragment featuring different neutral coligands L (L = 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydroimidazol-2-ylidene (SIPr), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIMes), 1,3-bis(2,4-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene (SIXyl), and 1,3-bis(2-methylphenyl)-4,5-dihydroimidazol-2-ylidene (SITol)) was prepared, characterized, and tested in the thermally induced ring-opening metathesis polymerization of dicyclopentadiene. In addition, the corresponding tricyclohexylphosphine derivative was investigated for comparison. All compounds were isolated as their trans-dichloro isomers. NMR spectroscopic features as well as structural features are, particularly within the NHC-bearing complexes, very similar, but their polymerization activity at elevated temperatures is distinctly different. While the SIMes derivative shows the desired properties, i.e., latency at room temperature and pronounced polymerization activity at elevated temperature, all other preinitiators do not. The preinitiator featuring the SIPr coligand is the most latent one, needing temperatures > 140 °C to show moderate activity in the polymerization of dicyclopentadiene. Compounds bearing the smaller N-heterocyclic carbene congeners are stable and latent at room temperature, but decompose upon heating, diminishing the polymerization activity at elevated temperatures. Density functional calculations show that the SIMes derivative is the easiest to activate and yields the most stable 14-electron intermediate. Finally calculations reveal a distinct influence of the nature of the N-heterocyclic carbene ligand on the position of the equilibrium of cis- and trans-dichloro isomers of the complexes. While the SIPr and the SIMes derivatives prefer the cis-configuration, all other derivatives favor, at least in solvents with low dielectric constants, the trans

Triterpenos da resina de Protium heptaphyllum March (B0urseraceae: caracterização em misturas binárias

Directory of Open Access Journals (Sweden)

Maia Robinson Magalhães

2000-01-01

Full Text Available Eight triterpenes, maniladiol, breine, ursa-9(11:12-dien-3beta-ol, oleana-9(11:12-dien-3beta-ol, 3alpha-hydroxy-tirucalla-8,24-dien-21-oic acid, 3alpha-hydroxy-tirucalla-7,24-dien-21-oic, alpha and beta amyrines were isolated as binary mixtures obtained from the chloroform extract of the oil-resin of Protium heptaphyllum March. The identification of the compounds was based mainly in 13C NMR data and mass spectra. The diene and the tetracyclic acid triterpenes were not reported before in the literature as constituents of the studied resin.

Structure-Activity Relationships for Some Diamine, Triamine and Schiff Base Derivatives and Their Copper(II) Complexes.

Science.gov (United States)

Bolos, C A; Nikolov, G S; Ekateriniadou, L; Kortsaris, A; Kyriakidis, D A

1998-01-01

Ethylenediamine (en), putrescine (pu), diethylenetriamine (dien), dipropylenetriamine (dpta), spermidine (spmd) and their Cu(II) compounds as well as the Schiff bases with 2-furaldehyde (dienOO), 2- thiophenecarboxaldehyde (dienSS) and pyrrole-2-carboxaldehyde (dienNN) of dien and that of dpta with 2- thiophenecarboxaldehyde (dptaSS), were prepared and characterised. They were tested against Bacillus substilis, Bacillus cereus, Staphylococcus aureus, Escherichia coli, Proteus vulgaris and Xanthomonas campestris as antibacterial reagents, the highest activity being exhibited by Cu(dptaSS)(NO(3))(2) complex, which acts as antibiotic. In the antiproliferative tests (vs. T(47)D,L(929) and BHK(21/c13) cell lines) the best results were obtained with Cu(dptaSS)(2+) and Cu(dienSS)(2+). Electronic structure calculations gave for dptaSS and dienSS the higher negative charges on the N atoms. The counter-ions (Br(-), NO(3) (-) and SO(4) (2-)) play an important role by modulating the reagent's selectivity versus the bacteria [Gram(+) or Gram(-)], but they have no effect on the antiproliferative activity.

Antifungal isopimaranes from Hypoestes serpens.

Science.gov (United States)

Rasoamiaranjanahary, L; Guilet, D; Marston, A; Randimbivololona, F; Hostettmann, K

2003-09-01

Five isopimarane diterpenes (7beta-hydroxyisopimara-8,15-dien-14-one, 14alpha-hydroxyisopimara-7,15-dien-1-one, 1beta,14alpha-dihydroxyisopimara-7,15-diene, 7beta-hydroxyisopimara-8(14),15-dien-1-one and 7beta-acetoxyisopimara-8(14),15-dien-1-one) have been isolated from the leaves of Hypoestes serpens (Acanthaceae). All compounds exhibited antifungal activity against both the plant pathogenic fungus Cladosporium cucumerinum and the yeast Candida albicans; two of them also displayed an acetylcholinesterase inhibition. The structures of the compounds were determined by means of spectrometric methods, including 1D and 2D NMR experiments and MS analysis.

Optimisation of accelerators and vulcanising systems on thermal stability of natural rubber/recycled ethylene–propylene–diene-monomer blends

International Nuclear Information System (INIS)

Nabil, H.; Ismail, H.; Azura, A.R.

2014-01-01

Highlights: • Accelerator types and vulcanising systems were optimised in NR/R-EPDM blends. • Two methods of thermal analysis namely thermal ageing and TGA were employed. • EV and peroxide provided superior thermal stability due to stable –S–S and –C–C– linkages. • Crosslinking of the blends is a major concern on the retained properties of the blends. • A CBS-vulcanised using EV system is highly recommended for NR/R-EPDM blends. - Abstract: The present paper concerns the thermal stability of natural rubber/recycled ethylene–propylene–diene-monomer (NR/R-EPDM) blends. The blends were prepared using various accelerators and vulcanising systems. Four types of accelerators were selected, i.e., N-tert-butyl-2-benzothiazyl-sulphonamide (TBBS), N-cyclohexyl-benzothiazyl-sulphenamide (CBS), tetramethylthiuram disulphide (TMTD) and 2-mercaptobenzothiazol (MBT). Subsequently, semi-efficient vulcanisation (semi-EV), efficient vulcanisation (EV), peroxide and mixed sulphur/peroxide vulcanising systems (semi-EV/Peroxide and EV/Peroxide) were observed in the latter study. Two methods of thermal analysis namely, thermo-oxidative ageing and thermogravimetric analysis were conducted. The results indicated that TMTD and MBT-vulcanised blends showed slightly higher thermal stability than that of CBS and TBBS vulcanised blends however, CBS-vulcanised blends exhibited satisfactory overall mechanical and thermal stability in comparison to the other accelerators used. In the case of optimisation of vulcanising systems, semi-EV showed the highest un-aged tensile strength when compared against semi-EV/Peroxide, EV, EV/Peroxide and peroxide vulcanising systems, respectively. However, EV, EV/Peroxide and peroxide vulcanising systems provided slightly higher thermal stability, due to the blends consisted of more stable monosulphidic and carbon–carbon linkages in the vulcanised network. The activation energies of degradation of the blends were determined by applying

Acyclic Cucurbit[n]uril-Type Molecular Container Enables Systemic Delivery of Effective Doses of Albendazole for Treatment of SK-OV-3 Xenograft Tumors.

Science.gov (United States)

Hettiarachchi, Gaya; Samanta, Soumen K; Falcinelli, Shane; Zhang, Ben; Moncelet, Damien; Isaacs, Lyle; Briken, Volker

2016-03-07

Approximately, 40-70% of active pharmaceutical ingredients (API) are severely limited by their extremely poor aqueous solubility, and consequently, there is a high demand for excipients that can be used to formulate clinically relevant doses of these drug candidates. Here, proof-of-concept studies demonstrate the potential of our recently discovered acyclic cucurbit[n]uril-type molecular container Motor1 (M1) as a solubilizing agent for insoluble drugs. M1 did not induce significant rates of mutations in various Salmonella typhimurium test strains during the Ames test, suggesting low genotoxicity. M1 also has low risk of causing cardiac toxicity in humans since it did not inhibit the human Ether-à-go-go-Related Gene channel as tested on transfected CHO cell lines via patch clamp analysis. Albendazole (ABZ) is a widely used antihelminthic agent but that has also shown promising efficacy against cancerous cells in vitro. However, due to its low aqueous solubility (2.7 μM) and poor pharmacokinetics, ABZ is clinically limited as an anticancer agent. Here we investigated the potential of M1 as a solubilizing excipient for ABZ formulation. A pharmacokinetic study indicated that ABZ escapes the peritoneal cavity resulting in 78% absolute bioavailability, while its active intermediate metabolite, albendazole sulfoxide, achieved 43% absolute bioavailability. The daily dosing of 681 mg/kg M1 complexed with 3.2 mg/kg of ABZ for 14 days did not result in significant weight loss or pathology in Swiss Webster mice. In vivo efficacy studies using this M1·ABZ inclusion complex showed significant decreases in tumor growth rates and increases in survival of mice bearing SK-OV-3 xenograft tumors. In conclusion, we provide substantial new evidence demonstrating that M1 is a safe and efficient excipient that enables in vivo parenteral delivery of poorly water-soluble APIs.

Assessment of the Thermodynamic Properties of DL-p-Mentha-1,8-diene, 4-Isopropyl-1-Methylcyclohexene (DL-limonene) by Inverse Gas Chromatography (IGC).

Science.gov (United States)

Farshchi, Negin; Abbasian, Ali; Larijani, Kambiz

2018-05-10

Limonene is a colorless liquid hydrocarbon and had been investigated as a plasticizer for many plastics. Prediction of solubility between different materials is an advantage in many ways, one of the most convenient ways to know the compatibility of materials is to determine the degree of solubility of them in each other. The concept of "solubility parameter" can help practitioners in this way.In this study, inverse gas chromatography (IGC) method at infinite dilution was used for determination of the thermodynamic properties of DL-p-mentha-1,8-diene, 4-Isopropyl-1-methylcyclohexene (DL-limonene). The interaction between DL-limonene and 13 solvents were examined in the temperature range of 63-123°C through the assessment of the thermodynamic sorption parameters, the parameters of mixing at infinite dilution, the weight fraction activity coefficient and the Flory-Huggins interaction parameters. Additionally, the solubility parameter for DL-limonene and the temperature dependence of these parameters was investigated as well.Results show that there is a temperature dependence in solubility parameter, which increases by decreasing temperature. However, there were no specific dependence between interaction parameters and temperature, but chemical structure appeared to have a significant effect on them as well as on the type and strength of intermolecular interactions between DL-limonene and investigated solvents. The solubility parameter δ2 of DL-limonene determined to be 19.20 (J/cm3)0.5 at 25°C.

Efficient androst-1,4-diene-3,17-dione production by co-expressing 3-ketosteroid-Δ1 -dehydrogenase and catalase in Bacillus subtilis.

Science.gov (United States)

Shao, M; Sha, Z; Zhang, X; Rao, Z; Xu, M; Yang, T; Xu, Z; Yang, S

2017-01-01

3-ketosteroid-Δ 1 -dehydrogenase (KSDD), a flavin adenine dinucleotide (FAD)-dependent enzyme involved in sterol metabolism, specifically catalyses the conversion of androst-4-ene-3,17-dione (AD) to androst-1,4-diene-3,17-dione (ADD). However, the low KSDD activity and the toxic effects of hydrogen peroxide (H 2 O 2 ) generated during the biotransformation of AD to ADD with FAD regeneration hinder its application on AD conversion. The aim of this work was to improve KSDD activity and eliminate the toxic effects of the generated H 2 O 2 to enhance ADD production. The ksdd gene obtained from Mycobacterium neoaurum JC-12 was codon-optimized to increase its expression level in Bacillus subtilis, and the KSDD activity reached 12·3 U mg -1 , which was sevenfold of that of codon-unoptimized gene. To improve AD conversion, catalase was co-expressed with KSDD in B. subtilis 168/pMA5-ksdd opt -katA to eliminate the toxic effects of H 2 O 2 generated during AD conversion. Finally, under optimized bioconversion conditions, fed-batch strategy was carried out and the ADD yield improved to 8·76 g l -1 . This work demonstrates the potential to improve enzyme activity by codon-optimization and eliminate the toxic effects of H 2 O 2 by co-expressing catalase. This study showed the highest ADD productivity ever reported and provides a promising strain for efficient ADD production in the pharmaceutical industry. © 2016 The Society for Applied Microbiology.

Metal-metal bonded compounds. V. Compounds with Ir (Rh)-Hg bonds containing a bridging and a chelating triazenido group which interconvert intramolecularly

NARCIS (Netherlands)

Koten, G. van; Vliet, P.I. van; Kokkes, M.; Vrieze, K.

1980-01-01

The compounds [(Diene)(RN{3}R'){2}MHgCl]{2} (M = Ir; Diene = COD; R = CH{3}, C{2}H{5}; R' = p-CH{3}C{6}H{4} and M = Rh; Diene = COD, NOR; R = CH{3}, C{2}H{5}, p-CH{3}-C{6}H{4}; R' = p-CH{3}C{6}H{4} have been prepared by reaction of [(Diene)MCl]{2} with [Hg(RN{3}R'){2}] and by reaction of

Six new ergostane-type steroids from king trumpet mushroom (Pleurotus eryngii) and their inhibitory effects on nitric oxide production.

Science.gov (United States)

Kikuchi, Takashi; Maekawa, Yukina; Tomio, Arisa; Masumoto, Yuki; Yamamoto, Taishi; In, Yasuko; Yamada, Takeshi; Tanaka, Reiko

2016-11-01

Six new ergostane-type steroids; (22E)-3β,5α,6α,11-tetrahydroxy-9(11)-seco-ergosta-7,22-dien-9-one (1), (22E)-8,14-epoxyergosta-6,22-diene-3β,5α,9α-triol (2), (22E)-4α,5α-epoxyergosta-7,22-diene-3β,6β-diol (3), (22E)-3β,4β,5α-trihydroxyergosta-7,22-dien-6-one (4), (22E)-ergosta-7,22-diene-3β,5β,6α-triol (5), and (22E)-6β-methoxyergosta-7,22-diene-3β,5α-diol 3-O-β-d-glucopyranoside (6) were isolated from the fruiting bodies of king trumpet mushroom (Pleurotus eryngii), along with fourteen known compounds (7-20). All isolated compounds were evaluated for their inhibitory effects on macrophage activation using a nitric oxide production inhibition assay. Copyright © 2016. Published by Elsevier Inc.

Synthesis of porphyryl boronates with (un)saturated side-chains

OpenAIRE

SENGE, MATHIAS; SERGEEVA, NATALIA

2008-01-01

PUBLISHED Porphyrins with (un)saturated side?chains containing boron residues were developed as synthons for porphyrin functionalization. Porphyrins with mono and bis-substituted unsaturated boronyl residues were prepared in good yields (52?66 %) using a cross?metathesis approach in the presence of Grubbs I-generation catalysts. In all cases complete E?stereoselectivity (100 %) was observed. Furthermore, formal cross?metathesis products with ?,??unsaturated chains smoothly underwent additi...

Design and synthesis of new hybrids from 2-cyano-3,12-dioxooleana- 9-dien-28-oic acid and O2-(2,4-dinitrophenyl) diazeniumdiolate for intervention of drug-resistant lung cancer.

Science.gov (United States)

Kang, Fenghua; Ai, Yong; Zhang, Yihua; Huang, Zhangjian

2018-04-10

To search for new drugs for intervention of drug-resistant lung cancer, a series of hybrids 4-15 from 2-cyano-3,12-dioxooleana-9-dien-28-oic acid (CDDO) and O 2 -(2,4-dinitrophenyl) diazeniumdiolate were designed, synthesized and biologically evaluated. The most active compound 7 produced relatively high levels of nitric oxide (NO) and reactive oxygen species (ROS) in drug-resistant lung cancer A549/Taxol cells which over-express glutathione S-transferase π (GSTπ), and significantly inhibited the cells' proliferation (IC 50  = 0.349 ± 0.051 μM), superior to the positive controls CDDO-Me, JS-K and Taxol. The inhibitory activity of 7 could be attenuated by an NO scavenger, ROS scavenger or GSTπ inhibitor. In addition, 7 suppressed the Lon protease expression as well as induced cell apoptosis and cycle arrest in A549/Taxol cells more strongly than CDDO-Me or JS-K. Together, our findings suggest that 7 may be worth studying further for intervention of drug-resistant lung cancer. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Functionalized linear and cyclic polyolefins

Energy Technology Data Exchange (ETDEWEB)

Tuba, Robert; Grubbs, Robert H.

2018-02-13

This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

Improved direct production of 2,3-dimethylbutenes and 3,3-dimethylbutene from 2-methylpropene on tungsten hydride based catalysts

KAUST Repository

Garron, Anthony; Stoffelbach, Franç ois; Merle, Nicolas; Szeto, Kaï Chung; Thivolle-Cazat, Jean; Basset, Jean-Marie; Norsic, Sé bastien; Taoufik, Mostafa

2012-01-01

2-Methylpropene in the presence of W-H/Ni 1%-Al 2O 3-(500) is transformed in high selectivity into a mixture of 2,3-dimethylbutenes (2,3-DMBs = DMB-1 and DMB-2) and neohexene. 2,3-DMBs arise from the unfavoured 2-methylpropene self-metathesis reaction whereas the neohexene originates from a cascade reaction: 2-methylpropene dimerisation followed by cross metathesis. © 2012 The Royal Society of Chemistry.

Antitenascin antibody 81C6 armed with {sup 177}Lu: in vivo comparison of macrocyclic and acyclic ligands

Energy Technology Data Exchange (ETDEWEB)

Yordanov, Alexander T. [Department of Radiology, Duke University Medical Center Durham, NC 27710 (United States); Hens, Marc [Department of Radiology, Duke University Medical Center Durham, NC 27710 (United States); Pegram, Charles [Department of Pathology, Duke University Medical Center Durham, NC 27710 (United States); Bigner, Darell D. [Department of Pathology, Duke University Medical Center Durham, NC 27710 (United States); Zalutsky, Michael R. [Department of Radiology, Duke University Medical Center Durham, NC 27710 (United States)]. E-mail: zalut001@mc.duke.edu

2007-02-15

Introduction: When labeled with iodine-131, the antitenascin monoclonal antibody (mAb) 81C6 has shown promise as a targeted radiotherapeutic in patients with brain tumors. Because of its more favorable {gamma}-ray properties, lutetium-177 might be a better low-energy {beta}-emitter for this type of therapy. Materials and Methods: Chimeric 81C6 (ch81C6) was labeled with {sup 177}Lu using the acyclic 1B4M ligand and the macrocyclic ligands NHS-DOTA and MeO-DOTA and evaluated for binding to tenascin. Three paired-label tissue distribution experiments were performed in normal mice receiving one of the {sup 177}Lu-labeled immunoconjugates plus {sup 125}I-labeled ch81C6 labeled using Iodogen. Paired-label experiments in athymic mice bearing subcutaneous D54 MG human glioma xenografts were done to directly compare the biodistribution of ch81C6-1B4M-{sup 177}Lu and {sup 125}I-labeled ch81C6, and ch81C6-MeO-DOTA-{sup 177}Lu and {sup 125}I-labeled ch81C6. Similar comparisons were done using murine (mu) instead of ch81C6. The primary parameter utilized for evaluation was the {sup 177}Lu/{sup 125}I uptake ratio in each tissue. Results: In the studies performed in normal mice, the NHS-DOTA ligand yielded the highest {sup 177}Lu/{sup 125}I uptake ratios in tissues indicative of loss of label from the chelate; for this reason, only 1B4M and MeO-DOTA were evaluated further. The {sup 177}Lu/{sup 125}I ratio in bone increased gradually with time for the chimeric conjugates; however, there were no significant differences between ch81C6-1B4M-DTPA-{sup 177}Lu and ch81C6-MeO-DOTA-{sup 177}Lu. In contrast, mu81C6-1B4M-DTPA-{sup 177}Lu and mu81C6-MeO-DOTA-{sup 177}Lu showed a more dramatic increase in the {sup 177}Lu/{sup 125}I ratio in bone - from 2.4{+-}0.3 and 1.7{+-}0.2 at Day 1 to 8.5{+-}1.1 and 4.2{+-}0.5 at Day 7, respectively. Conclusion: With these antitenascin constructs, the nature of the mAb had a profound influence on the relative degree of loss of {sup 177}Lu from these

CO2/N2 Gas Separation Using Nanocomposite Membranes Comprised of Ethylene-Propylene-Diene Monomer/Multi-Walled Carbon Nanotube (EPDM/MWCNT

Directory of Open Access Journals (Sweden)

Zeinab Rajabi

2015-07-01

Full Text Available Nanocomposite membranes of ethylene-propylene-diene monomer/multiwalled carbon nanotubes (EPDM/MWCNT were prepared by solution casting, solvent evaporation and cross-link technique to be applied in CO2/N2 gas separation. Both simple and functionalized MWCNTs have been used. The effect of incorporated different amounts multiwalled carbon nanotubes (0-4 wt%, of both simple and functionalized types, on the performance of nanocomposite membranes was studied. Fourier transform infrared (FTIR spectroscopy and field emission scanning electron microscopy (FESEM were used to evaluate the structural/morphological observations of nanocomposite membranes. Comparing the FTIR results of pure and functionalized nanotubes confirmed the presence of carboxylic groups on the functional carbon nanotubes. The FESEM images indicated that at low concentrations, carbon nanotube particles were dispersed well in the EPDM matrix, but they formed agglomerates at concentrations beyond 1 wt%. By incorporation of MWCNTs, the mechanicalproperties of nanocomposite membranes including tensile strength, Young's modulus and elongation-at-break considerably were improved. By increasing carbon nanotube loading up to 0.75 wt%, the permeability of both CO2 and N2 and the CO2/N2 selectivity increased. Further loading led to higher permeability of CO2/N2, while the selectivity ofthe system decreased that could be attributed to further agglomeration of carbon nanotube particles. Furthermore, functionalization of carbon nanotubes improved their dispersion and the mechanical properties and gas separation performance of nanocomposite membranes. Through functionalizing of MWCNTs, both the CO2 permeability and CO2/N2 selectivity of the optimum membrane (0.75 wt% MWCNTs increased from 37.95 and 18.03 Barrer to 57.57 and 23.43 Barrer, respectively. At ambient temperature, by the increase in feed pressure a slight increase in the permeability of both CO2 and N2 gases was observed, while the CO2

Probabilistic Networks

DEFF Research Database (Denmark)

Jensen, Finn Verner; Lauritzen, Steffen Lilholt

2001-01-01

This article describes the basic ideas and algorithms behind specification and inference in probabilistic networks based on directed acyclic graphs, undirected graphs, and chain graphs.......This article describes the basic ideas and algorithms behind specification and inference in probabilistic networks based on directed acyclic graphs, undirected graphs, and chain graphs....

Build/Couple/Pair and Multifunctional Catalysis Strategies for the Synthesis of Heterocycles from Simple Starting Materials

DEFF Research Database (Denmark)

Ascic, Erhad

. Multifunctional Catalysis: Synthesis of Heterocycles from Simple Starting Materials A multifunctional catalysis approach, involving a ruthenium-catalyzed tandem ringclosing metathesis/isomerization/N-acyliminium cyclization sequence, is described. Double bonds created during ring-closing metathesis isomerize......, a series of interesting indolizidinones are formed in good yields with excellent diastereoselectivities, including a formal total synthesis of the antiparasitic natural product harmicine and the first total synthesis of mescalotam. Furthermore, preliminary asymmetric variants of the tandem process have...

VOLUME 8 (2003) Sada and J. Guthrie ABSTRACT

African Journals Online (AJOL)

denise

Conjugated dienes tend to form 1:1 Diels. Alder adducts instead of copolymerizing while non - conjugated dienes can react to form 1:1 or 1:2 copolymers with vinyl groups which are cyclic15. A more extensive description of the current knowledge on the kinetics of copolymerization of maleic anhydride with dienes is found in ...

Volatile constituents of Trichothecium roseum.

Science.gov (United States)

Vanhaelen, M; Vanhaelen-Fastre, R; Geeraerts, J

1978-06-01

In the course of investigation of Trichothecium roseum (Fungi Imperfecti) for its attractancy against Tyrophagus putrescentiae (cheese mite), the twenty following volatile compounds produced at a very low concentration by the microfungus were identified by gc, gc/ms, gc/c.i.ms and tlc: 3-methyl-1-butanol, 3-octanone, 1-octen-3-one, 3-octanol, octa-1,5-dien-3 one, 1-octen-3-ol, 6-methyl-5-hepten-2-ol, octa-1,5-dien-3 ol, furfural, linalool, linalyl acetate, terpineol (alpha and beta) citronellyl acetate, nerol, citronellol, phenylacetaldehyde, benzyl alcohol geranyl acetate, 1-phenyl ethanol and nerolidol. Octa-1,5-dien-3-ol and octa-1,5-dien-3-one have not been previously isolated from fungi; octa-1,5-dien-3-ol is the most potent attractant amount the volatile compounds detected by gc.

Plasma-polymerized perfluoro(methylcyclohexane) coating on ethylene propylene diene elastomer surface: Effect of plasma processing condition on the deposition kinetics, morphology and surface energy of the film

International Nuclear Information System (INIS)

Tran, N.D.; Dutta, N.K.; Choudhury, N. Roy

2005-01-01

Plasma polymerization of perfluoro (methylcyclohexane) was carried out under cold plasma process operated at 13.56 MHz to deposit pore-free, uniform, ultra-thin film on an ethylene propylene diene terpolymer (EPDM) substrate in a view to modify the surface characteristics. The plasma fluoropolymeric films were formed at different plasma treatment times (from 20 s to 16 min), applied powers (20 to 100 W) and precursor flow rates to produce high quality films in a controllable yet tunable fashion. Scanning electron microscopy was employed successfully to characterize the evolution of the morphological feature in the film and also to determine the thickness of the coating. The surface energy of the film was determined by sessile drop method using different solvents as probe liquids. It is observed that a pore-free homogeneous plasma polymer thin film is formed within 20 s of treatment time, however, the morphology of the film depends on the plasma processing conditions, such as plasma power, precursor flow rate and deposition time. With increased time and power at a constant flow rate, the morphology of the film progressively changes from flat smooth to globular and rough. The kinetics and activation energy of the plasma polymer film deposition process were also estimated. The surface energy of the EPDM substrate decreased dramatically with plasma coating, however, it appears to be independent of the treatment time

Saturated versus unsaturated hydrocarbon interactions with carbon nanostructures

Directory of Open Access Journals (Sweden)

Deivasigamani eUmadevi

2014-09-01

Full Text Available The interactions of various acyclic and cyclic hydrocarbons in both saturated and unsaturated forms with the carbon nanostructures (CNSs have been explored by using density functional theory (DFT calculations. Model systems representing armchair and zigzag carbon nanotubes (CNTs and graphene have been considered to investigate the effect of chirality and curvature of the CNSs towards these interactions. Results of this study reveal contrasting binding nature of the acyclic and cyclic hydrocarbons towards CNSs. While the saturated molecules show stronger binding affinity in acyclic hydrocarbons; the unsaturated molecules exhibit higher binding affinity in cyclic hydrocarbons. In addition, acyclic hydrocarbons exhibit stronger binding affinity towards the CNSs when compared to their corresponding cyclic counterparts. The computed results excellently corroborate the experimental observations. The interaction of hydrocarbons with graphene is more favourable when compared with CNTs. Bader’s theory of atoms in molecules has been invoked to characterize the noncovalent interactions of saturated and unsaturated hydrocarbons. Our results are expected to provide useful insights towards the development of rational strategies for designing complexes with desired noncovalent interaction involving CNSs.

Process for compound transformation

KAUST Repository

Basset, Jean-Marie

2016-12-29

Embodiments of the present disclosure provide for methods of using a catalytic system to chemically transform a compound (e.g., a hydrocarbon). In an embodiment, the method does not employ grafting the catalyst prior to catalysis. In particular, embodiments of the present disclosure provide for a process of hydrocarbon (e.g., C1 to C20 hydrocarbon) metathesis (e.g., alkane, olefin, or alkyne metathesis) transformation, where the process can be conducted without employing grafting prior to catalysis.

A Concise Synthesis of Castanospermine by the Use of a Transannular Cyclization

DEFF Research Database (Denmark)

Jensen, Thomas; Mikkelsen, Mette; Lauritsen, Anne

2009-01-01

A nine-step synthesis of (+)-castanospermine has been accomplished in 22% overall yield from methyl alpha-D-glucopyranoside. The key transformations involve a zinc-mediated fragmentation of benzyl-protected methyl 6-iodoglucopyranoside, ring-closing olefin metathesis, and strain-release transannu......A nine-step synthesis of (+)-castanospermine has been accomplished in 22% overall yield from methyl alpha-D-glucopyranoside. The key transformations involve a zinc-mediated fragmentation of benzyl-protected methyl 6-iodoglucopyranoside, ring-closing olefin metathesis, and strain...

A comparison between the effects of gamma radiation and sulfur cure system on the microstructure and crosslink network of (styrene butadiene rubber/ethylene propylene diene monomer) blends in presence of nanoclay

Science.gov (United States)

Shoushtari Zadeh Naseri, Aida; Jalali-Arani, Azam

2015-10-01

Rubber blends based on (styrene-butadiene rubber (SBR)/ethylene-propylene-diene monomer (EPDM)) with and without organoclay (OC) were prepared through a melt mixing process. The concentration ratio of the rubber phases (EPDM/SBR; 50/50 wt%) and the amount of the OC were kept constant. The samples were then vulcanized by means of gamma radiation using a Co-60 gamma source as well as sulfur cure system. The effect of absorbed dose on the formation of the crosslinks was confirmed by the Fourier transform infrared spectroscopy (FTIR). The effects of absorbed dose, sulfur cure system and OC on the gel content, and crosslink density were evaluated by the chemical tests. Applying the Charlesby-Pinner equation to estimate the radiation chemical yield, revealed that the use of OC in the blend caused 20% reduction in the degradation/crosslinking ratio. Employing the swelling test data, some thermodynamic parameters were determined. Using field emission scanning electron microscopy (FE-SEM) to investigate microstructure of the samples revealed a more homogeneous structure and also an increase in compatibility of the blend components in the sample cured by the irradiation in comparison to that cured by the sulfur curing system.

Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

Science.gov (United States)

Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.

2015-01-01

The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

A Combinatorial Formula for Certain Elements of Upper Cluster Algebras

Science.gov (United States)

Lee, Kyungyong; Li, Li; Mills, Matthew R.

2015-06-01

We develop an elementary formula for certain non-trivial elements of upper cluster algebras. These elements have positive coefficients. We show that when the cluster algebra is acyclic these elements form a basis. Using this formula, we show that each non-acyclic skew-symmetric cluster algebra of rank 3 is properly contained in its upper cluster algebra.

Radiation Vulcanization of Polymeric Blends Based on Ethylene Propylene Diene Monomer Rubber/ Waste Materials in Presence of Different Additives

International Nuclear Information System (INIS)

MOHAMED, R.M.

2015-01-01

In this investigation, the mechanical blending technique was applied for preparation of elastomeric blend of ethylene propylene diene monomer rubber (EPDM)and nitrile butadiene rubber (NBR) having a fixed ratio of (50/50) by weight. The prepared blend of EPDM/NBR (50/50) was used as a rubber matrix to be loaded with waste materials, namely rice husk (RH) as a natural waste filler and then with ground tire rubber (GTR) as an artificial one. The degree of loading varied from 5 p hr to 20 p hr. Ionizing radiation, namely ,gamma rays were applied for inducing vulcanization of prepared and loaded rubber blends, in the range from 5 kGy to 250 kGy. Different properties of prepared composites were followed up as a function of degree of loading with the waste material and dose of irradiation. The mechanical properties, namely tensile strength and elongation at break percent of the composites slightly decreased as the filler loading increased over the whole range of irradiation .Tensile modulus and hardness, on the other hand, showed an opposite trend, i.e. the increased. Other properties, namely physical, thermal and morphological confirmed the mechanical ones. Obtained results were affiliated with lack of interface adhesion between the waste materials and the rubber matrix elastomers. The lack of interface adhesion was improved by filling the composite with a limited content, up to 7 p hr, of the compatibilizer, namely, maleic anhydride (MAH). Measurements of different properties was carried out for composite loaded with 10 p hr of waste material. It has been found that the tensile properties were significantly improved with addition of the compatibilizing agent Further and significant improvement was attained in properties of prepared later composite by its loading with 40 p hr of either HAF- carbon black or Hisil as reinforcing fillers that participates in chemical as well as physical bonding. Similarly and lastly 8 p hr of N, N- methylene di acrylamide (MDA) were loaded

Ionizable polyethers as specific metal ion carriers in liquid-liquid extraction and liquid membrane separations

International Nuclear Information System (INIS)

Walkowiak, W.; Charewicz, W.A.; Bartsch, R.A.; Ndip, G.M.

1988-01-01

Consideration is given to results of investigations into competitive extraction and penetration through a liquid membrane of alkali and alkaline earth cations from aqueous solutions by a series of lipophilic and ionizable acyclic polyethers of various molecular structure. It is shown that specificity and selectiviy of cation carriers in liquid-liquid extraction and liquid membrane separation depend on molecular structure of acyclic polyethers

Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene

KAUST Repository

Hamieh, Ali Imad Ali

2015-04-03

The silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.

Well-Defined Surface Species [(≡Si - O -)W(=O)Me3] Prepared by Direct Methylation of [(≡Si - O -)W(=O)Cl3], a Catalyst for Cycloalkane Metathesis and Transformation of Ethylene to Propylene

KAUST Repository

Hamieh, Ali Imad Ali; Chen, Yin; Abdel-Azeim, Safwat; Abou-Hamad, Edy; Goh, Li Min Serena; Samantaray, Manoja; Dey, Raju; Cavallo, Luigi; Basset, Jean-Marie

2015-01-01

The silica-supported tungsten oxo-trimethyl complex [(≡Si - O -)W(=O)Me3] was synthesized using a novel SOMC synthetic approach. By grafting the inexpensive stable compound WOCl4 on the surface of silica, partially dehydroxylated at 700 °C (SiO2-700), a well-defined monopodal surface complex [(≡Si - O -)W(=O)Cl3] was produced. The supported complex directly methylated with ZnMe2 and transformed into [(≡Si - O -)W(=O)Me3], which we fully characterized by microanalysis, IR, mass balance and SS NMR (1H, 13C, 1H-13C HETCOR, 1H-1H DQ and TQ). [(≡Si - O)W(=O)Me3] has two conformational isomers on the surface at room temperature. The conversion of one to the other was observed at 318 K by variable-temperature 13C CP/MAS and 1H spin echo MAS solid-state NMR; this was also confirmed by NMR and DFT calculations. [(≡Si - O)W(=O)Me3] was found to be active in cyclooctane metathesis and to have a wide distribution range in ring-contracted and ring-expanded products. In addition, [(≡Si - O)W(=O)Me3] proved to be highly active for selective transformation of ethylene to propylene compared to other silica-supported organometallic complexes. (Chemical Equation Presented). © 2015 American Chemical Society.

Synthesis and characterization of PTP/[Fe(CN)_3(dien)]·H_2O nanocomposite; study of electrical, thermal and photocatalytic properties

International Nuclear Information System (INIS)

Moosvi, Syed Kazim; Majid, Kowsar; Ara, Tabassum

2016-01-01

Highlights: • Synthesis of PTP nanocomposite with photoadduct via in-situ chemical polymerisation. • Photoadduct and its nanocomposite are characterized by UV–Vis, FTIR, XRD, and SEM characterisation techniques. • Enhanced thermal stability of nanocomposite as compared to pure PTP. • Nanocomposite exhibit non-linear I–V behaviour. • Improved electrical properties and photocatalytic activity of nanocomposite as compared to pure PTP. - Abstract: Polythiophene/[Fe(CN)_3(dien)]·H_2O nanocomposite was synthesised by oxidative chemical polymerisation method. Photoadduct was synthesised by irradiating an equimolar mixture of potassium ferricyanide and diethylenetriamine which was then reduced to nanosize by high energy ball mill. The reduction of photoadduct to nanosize was confirmed from XRD. Nanocomposite of PTP with photoadduct was then prepared by oxidative chemical polymerisation using FeCl_3 as oxidant. The successful synthesis of nanocomposite was confirmed from FTIR, XRD and SEM. TGA revealed higher thermal stability of nanocomposite as compared to pure PTP. I–V characteristics plotted on a log–log scale showed two distinct power law regions in case of nanocomposite. At lower voltages, the transport mechanism follows Ohm’s law. At higher voltages, the mechanism is consistent with space charge-limited emission. Furthermore, nanocomposite shows enhanced conductivity as compared to pure PTP. From dielectric studies, an appreciable high value of dielectric constant (4.4 × 10"6 at 100 Hz) and ac conductivity (2.1 × 10"9 S/m at 300 kHz) of nanocomposite was obtained. This indicates the possible application of this nanocomposite in charge storage devices. The photocatalytic activity of the materials was studied against the methyl orange (MO) dye under UV–Vis light and 76% degradation of MO dye was achieved in presence of nanocomposite in just 2 h, hence indicating its better photocatalytic efficiency. Results thus obtained indicate the

The antidiabetic compound 2-dodecyl-6-methoxycyclohexa-2,5-diene-1,4-dione, isolated from Averrhoa carambola L., demonstrates significant antitumor potential against human breast cancer cells.

Science.gov (United States)

Gao, Ying; Huang, Renbin; Gong, Yixuan; Park, Hyo Sim; Wen, Qingwei; Almosnid, Nadin Marwan; Chippada-Venkata, Uma D; Hosain, Najlaa Abdulrhman; Vick, Eric; Farone, Anthony; Altman, Elliot

2015-09-15

2-Dodecyl-6-methoxycyclohexa-2,5-diene-1,4-dione (DMDD) is a cyclohexanedione found in the roots of Averrhoa carambola L., commonly known as starfruit. Researchers have shown that DMDD has significant therapeutic potential for the treatment of diabetes; however, the effects of DMDD on human cancers have never been reported. We investigated the cytotoxic effects of DMDD against human breast, lung and bone cancer cells in vitro and further examined the molecular mechanisms of DMDD-induced apoptosis in human breast cancer cells. DMDD suppressed the growth of breast carcinoma cells, but not normal mammary epithelial cells, via induction of G1 phase cell cycle arrest, oxidative stress and apoptosis. DMDD increased the level of intracellular reactive oxygen species (ROS) and DMDD-induced ROS generation was found to be associated with the mitochondrial activity. The cytotoxicity that was induced by DMDD was attenuated by co-treatment with the antioxidant N-acetyl-L-cysteine (NAC). DMDD-induced cell apoptosis involved the activation of both the intrinsic mitochondrial pathway and the extrinsic receptor pathway. In addition, DMDD inhibited the canonical NF-κB signaling pathway at all steps, including TNF-α production, phosphorylation of NF-κB p65 and IκBα, as well as TNF-α activated NF-κB p65 nuclear translocation.Collectively, our studies indicate that DMDD has significant potential as a safe and efficient therapeutic agent for the treatment of breast cancer.

Chemical constituents from the stem of Brosimum potabile (Moraceae Constituintes químicos do cerne de Brosimum potabile (Moraceae

Directory of Open Access Journals (Sweden)

Viviane Gomes da Costa Abreu

2010-12-01

Full Text Available Three coumarins, 5-methoxypsoralene, xanthyletin, and (--marmesin, have been isolated from the ethanolic extract of the stem of the Amazonian plant Brosimum potabile. The structures were determined on the basis of NMR analyses and by comparison with spectroscopic data in the literature. The analysis of the hexane fractions by GC-MS in EIMS mode suggested the presence of (1-methylpentyl-benzene; α,α-dimethyl-4-(1-methylethyl-benzenemethanol; 1-methyl-3,5-bis(1-methylethyl-benzene; urs-12-ene; chola-5,22-dien-3β-ol; cholesta-4,6-dien-3β-ol; sitosteryl 9(Z-octadecenoate; cholesta-5,22-dien-3β-ol; cholesta-4,6,22-trien-3-one; and cholesta-4,22-dien-3-one. NMR data of other hexane fractions indicated the presence of 3β-acetoxy-lup-12,20(29-diene; 3β-acetoxy-olean-12-ene; 3β-acetoxy-urs-12-ene; and adian-5-ene. All these compounds are first described in B. potabile.Três cumarinas, 5-metoxipsoraleno, xantiletina e (--marmesina, foram isoladas no extrato etanólico do cerne da planta amazônica Brosimum potabile. Suas estruturas foram determinadas a partir das análises por RMN e por comparação com dados espectroscópicos da literatura. As análises das frações hexânicas por CG/EM sugeriram a presença de (1-metilpentil-benzeno; α,α-dimetil-4-(1-metiletil-benzenometanol; 1-metil-3,5-bis(1-metiletil-benzeno; urs-12-eno; cola-5,22-dien-3β-ol; colesta-4,6-dien-3β-ol; (9Z-octadecenoato de sitosterila; colesta-5,22-dien-3β-ol; colesta-4,6,22-trien-3-ona e colesta-4,22-dien-3-ona. Dados de RMN de outras frações hexânicas indicaram a presença de 3β-acetóxi-lup-12,20(29-dieno; 3β-acetóxi-olean-12-eno; 3β-acetóxi-urs-12-eno e adian-5-eno. Todos esses compostos foram identificados pela primeira vez em B. potabile.

Short syntheses of enantiopure calystegine B-2, B-3, and B-4

DEFF Research Database (Denmark)

Skaanderup, Philip Robert; Madsen, Robert

2001-01-01

Calystegine B-2 B-3, and B-4 have been prepared in 5 steps from the benzyl protected methyl 6-iodoglycopyranosides of glucose, galactose and mannose, respectively, by using a zinc-mediated domino reaction followed by ring-closing olefin metathesis as the key steps.......Calystegine B-2 B-3, and B-4 have been prepared in 5 steps from the benzyl protected methyl 6-iodoglycopyranosides of glucose, galactose and mannose, respectively, by using a zinc-mediated domino reaction followed by ring-closing olefin metathesis as the key steps....

Protection of HepG2 cells against acrolein toxicity by 2-cyano-3,12-dioxooleana-1,9-dien-28-imidazolide via glutathione-mediated mechanism.

Science.gov (United States)

Shah, Halley; Speen, Adam M; Saunders, Christina; Brooke, Elizabeth A S; Nallasamy, Palanisamy; Zhu, Hong; Li, Y Robert; Jia, Zhenquan

2015-10-01

Acrolein is an environmental toxicant, mainly found in smoke released from incomplete combustion of organic matter. Several studies showed that exposure to acrolein can lead to liver damage. The mechanisms involved in acrolein-induced hepatocellular toxicity, however, are not completely understood. This study examined the cytotoxic mechanisms of acrolein on HepG2 cells. Acrolein at pathophysiological concentrations was shown to cause apoptotic cell death and an increase in levels of protein carbonyl and thiobarbituric acid reactive acid substances. Acrolein also rapidly depleted intracellular glutathione (GSH), GSH-linked glutathione-S-transferases, and aldose reductase, three critical cellular defenses that detoxify reactive aldehydes. Results further showed that depletion of cellular GSH by acrolein preceded the loss of cell viability. To further determine the role of cellular GSH in acrolein-mediated cytotoxicity, buthionine sulfoximine (BSO) was used to inhibit cellular GSH biosynthesis. It was observed that depletion of cellular GSH by BSO led to a marked potentiation of acrolein-mediated cytotoxicity in HepG2 cells. To further assess the contribution of these events to acrolein-induced cytotoxicity, triterpenoid compound 2-cyano-3,12-dioxooleana-1,9-dien-28-imidazolide (CDDO-Im) was used for induction of GSH. Induction of GSH by CDDO-Im afforded cytoprotection against acrolein toxicity in HepG2 cells. Furthermore, BSO significantly inhibited CDDO-Im-mediated induction in cellular GSH levels and also reversed cytoprotective effects of CDDO-Im in HepG2 cells. These results suggest that GSH is a predominant mechanism underlying acrolein-induced cytotoxicity as well as CDDO-Im-mediated cytoprotection. This study may provide understanding on the molecular action of acrolein which may be important to develop novel strategies for the prevention of acrolein-mediated toxicity. © 2014 by the Society for Experimental Biology and Medicine.

Crystal Structure and Magnetic Behavior of Two New Dinuclear Carbonato-Bridged Copper(II) Compounds. Superexchange Pathway for the Different Coordination Modes of the Carbonato Bridge in Polynuclear Copper(II) Compounds.

Science.gov (United States)

Escuer, Albert; Mautner, Franz A.; Peñalba, Evaristo; Vicente, Ramon

1998-08-24

Four new &mgr;-CO(3)(2-) copper(II) complexes with different coordination modes for the carbonato bridge have been obtained by fixation of atmospheric CO(2): {(&mgr;(3)-CO(3))[Cu(3)(ClO(4))(3)(Et(3)dien)(3)]}(ClO(4)) (1), Et(3)dien = N,N',N"-triethylbis(2-aminoethane)amine; {(&mgr;-CO(3))[Cu(2)(H(2)O)(Et(4)dien)(2)]}(ClO(4))(2).H(2)O (2), Et(4)dien = N,N,N",N"-tetraethyl-bis(2-aminoethane)amine; {(&mgr;-CO(3))[Cu(2)(H(2)O)(2)(EtMe(4)dien)(2)]} (ClO(4))(2).2H(2)O (3), EtMe(4)dien = N'-ethyl-N,N,N",N"-tetramethylbis(2-aminoethane)amine; and {(&mgr;-CO(3))[Cu(2)(H(2)O)(Me(5)dien)(2)]}(ClO(4))(2).H(2)O (4), Me(5)dien = N,N,N',N",N"-pentamethylbis(2-aminoethane)amine. The crystal structures have been solved for 2, monoclinic system, space group P2(1)/n, formula [C(25)H(62)Cl(2)Cu(2)N(6)O(13)] with a = 12.763(6) Å, b = 25.125(8) Å, c = 13.261(4) Å, beta = 111.85(3) degrees, Z = 4, and for 3, triclinic system, space group P&onemacr;, formula [C(21)H(58)Cl(2)Cu(2)N(6)O(15)] with a = 8.412(3) Å, b = 14.667(4) Å, c = 16.555(5) Å, alpha = 99.66(2) degrees, beta = 102.14(2) degrees, gamma = 104.72(2) degrees, Z = 2. Susceptibility measurements show ferromagnetic behavior (J = +6.7(6) cm(-)(1)) for the trinuclear compound 1 whereas 2-4 are antiferromagnetically coupled with J = -17.8(8), -125.5(9), and -21.2(3) cm(-)(1) respectively. Certain synthetic aspects that may be related to the nuclearity of the copper(II) &mgr;-CO(3)(2-) compounds and the superexchange pathway for the different coordination modes of the carbonato bridge are discussed.

On the Dehydrocoupling of Alkenylacetylenes Mediated by Various Samarocene Complexes: A Charming Story of Metal Cooperativity Revealing a Novel Dual Metal σ-Bond Metathesis Type of Mechanism (DM|σ-BM

Directory of Open Access Journals (Sweden)

Christos E. Kefalidis

2015-12-01

Full Text Available The prevailing reductive chemistry of Sm(II has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds, as well as peculiar transformations of unsaturated substrates (e.g., C–C couplings. Among other important C–C coupling reactions, the reaction of phenylacetylene with different mono- or bimetallic samarocene complexes affords trienediyl complexes of the type {[(C5Me52Sm]2(µ-η2:η2-PhC4Ph}. In contrast, when t-butylacetylene is used, uncoupled monomers of the type (C5Me52Sm(C≡C–tBu were obtained. Although this type of reactivity may appear to be simple, the mechanism underlying these transformations is complex. This conclusion is drawn from the density functional theory (DFT mechanistic studies presented herein. The operating mechanistic paths consist of: (i the oxidation of each samarium center and the concomitant double reduction of the alkyne to afford a binuclear intermediate; (ii the C–H scission of the acetylinic bond that lies in between the two metals; (iii a dual metal σ-bond metathesis (DM|σ-SBM process that releases H2; and eventually (iv the C–C coupling of the two bridged μ-alkynides to give the final bimetallic trienediyl complexes. For the latter mechanistic route, the experimentally used phenylacetylene was considered first as well as the aliphatic hex-1-yne. More interestingly, we shed light into the formation of the mono(alkynide complex, being the final experimental product of the reaction with t-butylacetylene.

(1R,6R,13R,18R-(Z,Z-1,18-Bis[(4R-2,2-dimethyl-1,3-dioxolan-4-yl]-3,16-dimethylene-8,20-diazadispiro[5.6.5.6]tetracosa-7,19-diene

Directory of Open Access Journals (Sweden)

Stéphanie M. Guéret

2010-07-01

Full Text Available The crystal structure of the title compound, C34H54N2O4, has been solved in order to prove the relative and absolute chirality of the newly-formed stereocentres which were established using an asymmetric Diels–Alder reaction at an earlier stage in the synthesis. This unprecedented stable dialdimine contains a 14-membered ring and was obtained as the minor diastereoisomer in the Diels–Alder reaction. The absolute stereochemistry of the stereocentres of the acetal functionality was known to be R based on the use of a chiral (R-trisubstituted dienophile derived from enantiopure (S-glyceraldehyde. The assignment of the configuration in the dienophile and the title di-aldimine differs from (S-glyceraldehyde due to a change in the priority order of the substituents. The crystal structure establishes the presence of six stereocentres all attributed to be R. The 14-membered ring contains two aldimine bonds [C—N = 1.258 (2 and 1.259 (2 Å]. It adopts a similar conformation to that proposed for trans–trans-cyclotetradeca-1,8-dienes.

Cucurbitane-type triterpenoids from the fruit pulp of Momordica charantia.

Science.gov (United States)

Liao, Yun-Wen; Chen, Chiy-Rong; Kuo, Yueh-Hsiung; Hsu, Jue-Liang; Shih, Wen-Ling; Cheng, Hsueh-Ling; Huang, Tzou-Chi; Chang, Chi-I

2012-12-01

Three new cucurbitane-type triterpenoids, 5beta,19-epoxy-23(R)-methoxycucurbita-6,24-dien-3beta-ol (1), 5beta,19-epoxy-23(S)-methoxycucurbita-6,24-dien-3beta-ol (2), and 3beta-hydroxy-23(R)-methoxycucurbita-6,24-dien-5beta,19-olide (3), were isolated from the fruit pulp of Momordica charantia. Their structures were established on the basis of extensive NMR (1H, 13C, COSY, HMQC, HMBC, and NOESY) and EI-MS studies. Compound 1 exhibited cytotoxic activity against the SK-Hep 1 cell line.

Caraterização composicional do AES - um copolímero de enxertia de poli(estireno-co-acrilonitrila em poli(etileno-co-propileno-co-dieno Compositional characterization of AES a graft copolymer based on poly(styrene-co-acrylonitrile and poly(etyhlene-co-propylene-co-diene

Directory of Open Access Journals (Sweden)

Renato Turchet

2006-06-01

Full Text Available O objetivo deste trabalho é a caracterização do AES, um copolímero de enxertia de poli(estireno-co-acrilonitrila, SAN, em poli(etileno-co-propileno-co-dieno, EPDM. Para tanto, o AES foi submetido à extração seletiva de seus componentes: o SAN livre, o EDPM livre, e o copolímero de enxertia EPDM-g-SAN. O AES e suas frações foram caracterizados por espectroscopia de infravermelho, análise elementar, calorimetria diferencial de varredura e ressonância magnética nuclear, RMN¹H e RMN13C. O AES analisado apresenta a seguinte composição em massa: 65% de EPDM-g-SAN, 13% de EPDM livre e 22% de SAN livre. O EPDM apresenta 69,8% em massa de etileno, 26,5% em massa de propileno e 4,6% em massa do dieno, 2-etilideno-5-norboneno, ENB. O SAN apresenta razão em massa acrilonitrila/estireno de 28/72 e distribuição randômica de comonômeros de estireno e acrilonitrila. Estes resultados são concordantes com a composição do AES fornecida pelo fabricante, indicando que a metodologia proposta é adequada.This work aims the characterization of AES, a graft copolymer based on poly(styrene-co-acrylonitrile, SAN, and poly(etyhlene-co-propylene-co-diene, EPDM. AES was submitted to selective extraction of its components: free SAN, EPDM chains and the graft copolymer EPDM-g-SAN. AES and its fractions were characterized by infrared spectroscopy, elemental analysis, differential scanning calorimetry, 13C and ¹H nuclear magnetic resonance. The AES has 65 wt % of EPDM-g-SAN, 13 wt % of free EPDM and 22 wt % of free SAN. EPDM has 69.8 wt % of ethylene, 26.5 wt % of propylene and 4.6 wt % of diene, 2-ethylidene-5-norbonene ENB. SAN presents acrylonitrile/styrene mass ratio of 28/72 and a random distribution of acrylonitrile and styrene comonomers. These results are in agreement with the composition reported by the AES supplier, indicating that the proposed methodology is adequate.

Synthesis and characterization of PTP/[Fe(CN){sub 3}(dien)]·H{sub 2}O nanocomposite; study of electrical, thermal and photocatalytic properties

Energy Technology Data Exchange (ETDEWEB)

Moosvi, Syed Kazim; Majid, Kowsar, E-mail: kowsarmajid@rediffmail.com; Ara, Tabassum

2016-10-20

Highlights: • Synthesis of PTP nanocomposite with photoadduct via in-situ chemical polymerisation. • Photoadduct and its nanocomposite are characterized by UV–Vis, FTIR, XRD, and SEM characterisation techniques. • Enhanced thermal stability of nanocomposite as compared to pure PTP. • Nanocomposite exhibit non-linear I–V behaviour. • Improved electrical properties and photocatalytic activity of nanocomposite as compared to pure PTP. - Abstract: Polythiophene/[Fe(CN){sub 3}(dien)]·H{sub 2}O nanocomposite was synthesised by oxidative chemical polymerisation method. Photoadduct was synthesised by irradiating an equimolar mixture of potassium ferricyanide and diethylenetriamine which was then reduced to nanosize by high energy ball mill. The reduction of photoadduct to nanosize was confirmed from XRD. Nanocomposite of PTP with photoadduct was then prepared by oxidative chemical polymerisation using FeCl{sub 3} as oxidant. The successful synthesis of nanocomposite was confirmed from FTIR, XRD and SEM. TGA revealed higher thermal stability of nanocomposite as compared to pure PTP. I–V characteristics plotted on a log–log scale showed two distinct power law regions in case of nanocomposite. At lower voltages, the transport mechanism follows Ohm’s law. At higher voltages, the mechanism is consistent with space charge-limited emission. Furthermore, nanocomposite shows enhanced conductivity as compared to pure PTP. From dielectric studies, an appreciable high value of dielectric constant (4.4 × 10{sup 6} at 100 Hz) and ac conductivity (2.1 × 10{sup 9} S/m at 300 kHz) of nanocomposite was obtained. This indicates the possible application of this nanocomposite in charge storage devices. The photocatalytic activity of the materials was studied against the methyl orange (MO) dye under UV–Vis light and 76% degradation of MO dye was achieved in presence of nanocomposite in just 2 h, hence indicating its better photocatalytic efficiency. Results thus

Zinc mediated domino elimination-alkylation of methyl 5-iodopentofuranosides

DEFF Research Database (Denmark)

Hyldtoft, Lene; Poulsen, Carina Storm; Madsen, Robert

1999-01-01

5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions.......5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions....

Sequential Diels–Alder/[3,3]-sigmatropic rearrangement reactions of β-nitrostyrene with 3-methyl-1,3-pentadiene

Directory of Open Access Journals (Sweden)

Peter A. Wade

2013-10-01

Full Text Available The tin(IV-catalyzed reaction of β-nitrostyrene with (E-3-methyl-1,3-pentadiene in toluene afforded two major nitronic ester cycloadducts in 27% and 29% yield that arise from the reaction at the less substituted diene double bond. Also present were four cycloadducts from the reaction at the higher substituted diene double bond, two of which were the formal cycloadducts of (Z-3-methyl-1,3-pentadiene. A Friedel–Crafts alkylation product from the reaction of the diene, β-nitrostyrene, and toluene was also obtained in 10% yield. The tin(IV-catalyzed reaction of β-nitrostyrene with (Z-3-methyl-1,3-pentadiene in dichloromethane afforded four nitronic ester cycloadducts all derived from the reaction at the higher substituted double bond. One cycloadduct was isolated in 45% yield and two others are formal adducts of the E-isomer of the diene. The product formation in these reactions is consistent with a stepwise mechanism involving a zwitterionic intermediate. The initially isolated nitronic ester cycloadducts underwent tin(IV-catalyzed interconversion, presumably via zwitterion intermediates. Cycloadducts derived from the reaction at the less substituted double bond of (E-3-methyl-1,3-pentadiene underwent a [3,3]-sigmatropic rearrangement on heating to afford 4-nitrocyclohexenes. Cycloadducts derived from the reaction at the higher substituted diene double bond of either diene failed to undergo a thermal rearrangement. Rates and success of the rearrangement are consistent with a concerted mechanism possessing a dipolar transition state. An initial assessment of substituent effects on the rearrangement process is presented.

Morphologies of precise polyethylene-based acid copolymers and ionomers

Science.gov (United States)

Buitrago, C. Francisco

Acid copolymers and ionomers are polymers that contain a small fraction of covalently bound acidic or ionic groups, respectively. For the specific case of polyethylene (PE), acid and ionic pendants enhance many of the physical properties such as toughness, adhesion and rheological properties. These improved properties result from microphase separated aggregates of the polar pendants in the non-polar PE matrix. Despite the widespread industrial use of these materials, rigorous chemical structure---morphology---property relationships remain elusive due to the inevitable structural heterogeneities in the historically-available acid copolymers and ionomers. Recently, precise acid copolymers and ionomers were successfully synthesized by acyclic diene metathesis (ADMET) polymerization. These precise materials are linear, high molecular weight PEs with pendant acid or ionic functional groups separated by a precisely controlled number of carbon atoms. The morphologies of nine precise acid copolymers and eleven precise ionomers were investigated by X-ray scattering, solid-state 13C nuclear magnetic resonance (NMR) and differential scanning calorimetry (DSC). For comparison, the morphologies of linear PEs with pseudo-random placement of the pendant groups were also studied. Previous studies of precise copolymers with acrylic acid (AA) found that the microstructural precision produces a new morphology in which PE crystals drive the acid aggregates into layers perpendicular to the chain axes and presumably at the interface between crystalline and amorphous phases. In this dissertation, a second new morphology for acid copolymers is identified in which the aggregates arrange on cubic lattices. The fist report of a cubic morphology was observed at room and elevated temperatures for a copolymer functionalized with two phosphonic acid (PA) groups on every 21st carbon atom. The cubic lattice has been identified as face-centered cubic (FCC). Overall, three morphology types have been

13C Kinetic isotopic effect of polymerization on monomers with multiple bond

International Nuclear Information System (INIS)

Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

1988-01-01

13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

Kinetic investigation of uranyl-uranophile complexation. 1. Macrocyclic kinetic effect and macrocyclic protection effect

International Nuclear Information System (INIS)

Tabushi, I.; Yoshizawa, A.

1986-01-01

Equilibria and rates of ligand-exchange reactions between uranyl tricarbonate and dithiocarbamates and between uranyl tris-(dithiocarbamates) and carbonate were studied under a variety of conditions. The dithiocarbamates used were acyclic diethyl-dithiocarbamate and macrocyclic tris(dithiocarbamate). The acyclic ligand showed a triphasic (successive three-step) equilibrium with three different equilibrium constants while the macrocyclic ligand showed a clear monophasic (one-step) equilibrium with a much larger stability constant for the dithiocarbamate-uranyl complex. The macrocyclic ligand showed the S/sub N/2-type ligand-exchange rate in the forward as well as reverse process, while the first step of the acyclic ligand-exchange reaction proceeded via the S/sub N/1-type mechanism. This kinetic macrocyclic effect on molecularity is interpreted as the result of a unique topological requirement of uranyl complexation. The macrocyclic ligand also exhibited a clear protection effect, leading to the large stability constant. 19 references, 10 figures, 2 tables

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.; Stewart, Ian C.; Seashore-Ludlow, Brinton A.; Grubbs, Robert H.; Stoltz, Brian M.

2010-01-01

Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

Novel microwave initiated synthesis of Zn{sub 2}SiO{sub 4} and MCrO{sub 4} (M = Ca, Sr, Ba, Pb)

Energy Technology Data Exchange (ETDEWEB)

Parhi, Purnendu [Department of Mechanical Engineering, Colorado State University, Fort Collins 80523 (United States); Manivannan, V. [Department of Mechanical Engineering, Colorado State University, Fort Collins 80523 (United States)], E-mail: mani@engr.colostate.edu

2009-02-05

A novel microwave initiated solid-state metathesis synthesis of metal chromates and zinc silicate has been investigated. The high lattice energy of NaCl drives the solid-state metathesis reaction (CaCl{sub 2}.2H{sub 2}O + Na{sub 2}CrO{sub 4}.4H{sub 2}O {yields} NaCl + CaCrO{sub 4} + 6H{sub 2}O{up_arrow}) in the forward direction to obtain the products. The structural, optical, and chemical properties of synthesized compounds are determined by powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and diffused reflectance spectroscopy in the UV-vis range.

A general enantioselective route to the chamigrene natural product family

KAUST Repository

White, David E.

2010-06-01

Described in this report is an enantioselective route toward the chamigrene natural product family. The key disconnections in our synthetic approach include sequential enantioselective decarboxylative allylation and ring-closing olefin metathesis to form the all-carbon quaternary stereocenter and spirocyclic core present in all members of this class of compounds. The generality of this strategy is demonstrated by the first total syntheses of elatol and the proposed structure of laurencenone B, as well as the first enantioselective total syntheses of laurencenone C and α-chamigrene. A brief exploration of the substrate scope of the enantioselective decarboxylative allylation/ring-closing metathesis sequence with fully substituted vinyl chlorides is also presented.

Sterol composition from inflorescences of Hieracium pilosella L.

Directory of Open Access Journals (Sweden)

Tadeusz Krzaczek

2011-01-01

Full Text Available The fraction of sterol acetates from the inflorescences of Hieracium pilosella has been isolated in the typical way from petroleum ether extract. By means of the weight method the total amount of sterols was determined (0.2659%. The mixtures of sterol acetates and free sterols were investigated using GC-MS techniques. The occurrence of about 18 sterols has been observed. Cholesterol, cholest-8(14-en-3b-ol, cholesta-5.7-dien-3b-ol, cholest-7-en-3b-ol, ergosta-5.24-dien-3b-ol, campesterol, stigmasterol, b-sitosterol, fucosterol, 5a-stigmast-7-en-3a-ol were identified. The probable structures of lophenol, isofucosterol, 5a-stigmasta-7.24-dien-3b-ol, lanosta-9(11.24-dien-3b-ol and 24-ethylidene lophenol were stated on the basis of literature data. The last 4 sterols occur in a vestigial quantity, which made its identification impossible. Sitos erol and cholesterol are remarkably dominating sterols in the fraction.

Sterols from the Lakshadweep sponge, Ircinia ramosa (Killer)

Digital Repository Service at National Institute of Oceanography (India)

Parameswaran, P.S.; Naik, C.G.; Das, B.; Kamat, S.Y.

Four monohydroxy sterols, viz, (22E,24S)-24-methylcholest-5,22-dien-3(beta)-ol (3), cholesterol (4), 24(Xi)-ethylcholesterol (8) and the corresponding Delta super(4)-3 ketones, viz. (22E,24S)-24-methylcholest-4,22-dien-3-one (1), cholest-4-en-3-one...

Labdane diterpenoids from Curcuma amada rhizomes collected in Myanmar and their antiproliferative activities.

Science.gov (United States)

Win, Nwet Nwet; Ito, Takuya; Ngwe, Hla; Win, Yi Yi; Prema; Okamoto, Yasuko; Tanaka, Masami; Asakawa, Yoshinori; Abe, Ikuro; Morita, Hiroyuki

2017-10-01

Four new labdane diterpenoids, 12β-hydroxy-15-norlabda-8(17),13(14)-dien-16-oic acid (1), (E)-15-ethoxy-15-methoxylabda-8(17),12-dien-16-al (2), (E)-15α-ethoxy-14α-hydroxylabda-8(17),12-dien-16-olide (3), and 15-ethoxy-12β-hydroxylabda-8(17),13(14)-dien-16,15-olide (4) were isolated from the methanol extract of Curcuma amada rhizomes collected in Myanmar, together with 13 known analogs. Their structures were elucidated by extensive spectroscopic techniques. All of the isolates were evaluated for their antiproliferative activities against a small panel of five different human cancer cell lines (A549, human lung cancer; HeLa, human cervical cancer; MCF7, human breast cancer; PANC-1 and PSN-1, human pancreatic cancer). Among the isolates, compounds 2-4, 7, 8, 12, and 17 showed mild antiproliferative activities with IC 50 values ranging from 19.7 to 96.1μM. (E)-14-Hydroxy-15-norlabda-8(17),12-dien-16-al (11) exhibited strong antiproliferative activities selectively against HeLa, PANC-1, and PSN-1 cells, with IC 50 values of 5.88, 1.00, and 3.98μM, respectively. These potencies were comparable to those of the positive control, 5-fluorouracil. Copyright © 2017 Elsevier B.V. All rights reserved.

New α-Glucosidase Inhibitory Triterpenic Acid from Marine Macro Green Alga Codium dwarkense Boergs

Directory of Open Access Journals (Sweden)

Liaqat Ali

2015-07-01

Full Text Available The marine ecosystem has been a key resource for secondary metabolites with promising biological roles. In the current study, bioassay-guided phytochemical investigations were carried out to assess the presence of enzyme inhibitory chemical constituents from the methanolic extract of marine green alga—Codium dwarkense. The bioactive fractions were further subjected to chromatographic separations, which resulted in the isolation of a new triterpenic acid; dwarkenoic acid (1 and the known sterols; androst-5-en-3β-ol (2, stigmasta-5,25-dien-3β,7α-diol (3, ergosta-5,25-dien-3β-ol (4, 7-hydroxystigmasta-4,25-dien-3-one-7-O-β-d-fucopyranoside (5, 7-hydroxystigmasta-4,25-dien-3-one (6, and stigmasta-5,25-dien-3β-ol (7. The structure elucidation of the new compound was carried out by combined mass spectrometry and 1D (1H and 13C and 2D (HSQC, HMBC, COSY, and NOESY NMR spectroscopic data. The sub-fractions and pure constituents were assayed for enzymatic inhibition of alpha-glucosidase. Compound 1 showed significant inhibition at all concentrations. Compounds 2, 3, 5, and 7 exhibited a dose-dependent response, whereas compounds 4–6 showed moderate inhibition. Utilizing such marine-derived biological resources could lead to drug discoveries related to anti-diabetics.

Low-temperature synthesis, phonon and luminescence properties of Eu doped Y{sub 3}Al{sub 5}O{sub 12} (YAG) nanopowders

Energy Technology Data Exchange (ETDEWEB)

Mączka, M., E-mail: m.maczka@int.pan.wroc.pl [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2 (Poland); Bednarkiewicz, A. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2 (Poland); Mendoza-Mendoza, E.; Fuentes, A.F. [Cinvestav Unidad Saltillo, Apartado Postal 663, 25000 Saltillo, Coahuila (Mexico); Kępiński, L. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, P.O. Box 1410, 50-950 Wrocław 2 (Poland)

2014-02-14

This contribution presents two simple and cost-effective routes for the low-temperature and large-scale production of pure and Eu-doped Y{sub 3}Al{sub 5}O{sub 12} (yttrium aluminum garnet YAG) nanopowders. The proposed methodologies combine a mechanically assisted metathesis reaction or coprecipitation from solution followed by crystallization of the obtained precursors from molten sodium nitrate/nitrite. Both procedures allow obtaining pure and/or doped YAG nanopowders at remarkably low temperatures, i.e. already at 350 °C although firing at 500 °C is needed in order to get single phase and fully crystalline materials. As-obtained samples were characterized by XRD, TEM, Raman, IR and luminescence methods. These methods showed that the mean crystallite size is near 23–31 and 51 nm, when crystallization is performed from the amorphous precursor obtained by a mechanically assisted metathesis reaction and coprecipitation, respectively. Raman and IR spectra indicated better crystallinity of the powders prepared at 500 °C. The emission study showed that the intensity ratio between hypersensitive {sup 5}D{sub 0} → {sup 7}F{sub 2} and magnetic-dipole {sup 5}D{sub 0} → {sup 7}F{sub 1} transitions of Eu{sup 3+} is significantly larger than expected for well-crystallized YAG. Origin of this behavior is discussed. - Highlights: • Nanoparticles of Y{sub 3}Al{sub 5}O{sub 12} (YAG) and YAG:Eu{sup 3+} have been prepared at remarkable 350 °C. • Metathesis/molten salts and coprecipitation/molten salts methods were used. • Metathesis/molten salts method is suitable for preparation of rare-earth doped YAG. • Emission properties of YAG:Eu{sup 3+} are significantly different from bulk YAG.

On the problem of finding disjoint cycles and dicycles in a digraph

DEFF Research Database (Denmark)

Bang-Jensen, Jørgen; Kriesell, M.

2011-01-01

.e. the smallest cardinality of a set T of vertices in D such that D-T is acyclic: If tau (D)a parts per thousand yen3 then we employ McCuaig's framework on intercyclic digraphs to (always) find these cycles. If tau (D) = 2 then we can characterize the digraphs for which the answer is "yes" by using topological...... methods relying on Thomassen's theorem on 2-linkages in acyclic digraphs. For the case tau (D)a parts per thousand currency sign1 we provide an algorithm independent from any earlier work....

Investigation of the ROMP catalysis mechanism of norbornene using methods of density functional; Investigacao do mecanismo de catalise ROMP do norborneno utilizando metodos de funcional de densidade

Energy Technology Data Exchange (ETDEWEB)

Silva, Carlos Pereira da, E-mail: carlosps1985@gmail.co [Institutor Federal de Educacao, Ciencia e Tecnologia do Piaui, Teresina, PI (Brazil); Lima, Francisco das Chagas Alves [Universidade Estadual do Piaui, Teresina, PI (Brazil). Coordenacao de Quimica; Leal, Regis Casimiro; Moita Neto, Jose Machado [Universidade Federal do Piaui (UFPI), Teresina, PI (Brazil)

2010-07-01

This work presents a density functional theory study of the norbornene ROMP metathesis reactions. The energies have been calculated in a Grubbs catalyst model Cl{sub 2}(PH{sub 3}){sub 2}Ru=CH{sub 2}. The geometries and energy profile are similar to the Grubbs methylidene (Cl{sub 2}(PCy{sub 3}){sub 2}Ru=CH{sub 2} real model. It was found that the metathesis reaction proceeds via associative mechanism (catalyst-norbornene) followed by dissociative substitution of a phosphine ligand with norbornene, giving a monophosphine complex. The results are in reasonable agreement with the available experimental data. The dissociation energy of the phosphines is predicted to be 23.2 kcal mol{sup -1}. (author)

Triterpene Esters: Natural Products from Dorstenia arifolia (Moraceae

Directory of Open Access Journals (Sweden)

Maria Auxiliadora C. Kaplan

2013-04-01

Full Text Available The phytochemical study of Dorstenia arifolia Lam. (Moraceae has led to the identification of 18 triterpenes esterified by fatty acids, five triterpenes without esterification, 12 triterpenes esterified by acetic acid, together with a known furanocoumarin: α-amyrin (1, β-amyrin (2 α-amyrin acetate (3 β-amyrin acetate (4, α-amyrin octanoate (5, β-amyrin octanoate (6, α-amyrin decanoate (7, β-amyrin decanoate (8, α-amyrin dodecanoate (9, β-amyrin dodecanoate (10, α-amyrin tetradecanoate (11, β-amyrin tetradecanoate (12, α-amyrin hexadecanoate (13, β-amyrin hexadecanoate (14, glutinol (15, glutinyl acetate (16, 11-oxo-α-amyrin (17, 11-oxo-β-amyrin (18, 11-oxo-α-amyrin acetate (19, 11-oxo-β-amyrin acetate (20 11-oxo-α-amyrin octanoate (21 11-oxo-β-amyrin octanoate (22, 11-oxo-α-amyrin decanoate (23, 11-oxo-β-amyrin decanoate (24 11-oxo-α-amyrin dodecanoate (25 11-oxo-β-amyrin dodecanoate (26, ursa-9(11,12-dien-3-yl acetate (27, oleana-9(11,12-dien-3-yl acetate (28, ursa-9(11,12-dien-3-yl decanoate (29, oleana-9(11,12-dien-3-yl decanoate (30, 12,13-epoxyolean-3-yl acetate (31, 12,13-epoxyolean-9(11en-3-yl acetate (32, taraxeryl acetate (33, lupenyl acetate (34, lanosta-8,24-dien-3-yl acetate (35 and psoralen (36. The identification of the triterpene compounds isolated as isomeric mixtures obtained from the hexane extract was based mainly in mass spectra and 13C-NMR data. The long-chain alkanoic acid esters of the triterpenes α- and β-amyrin; 11-oxo-α- and 11-oxo-β-amyrin; ursa- and olean-9(11,12-dien-3-yl; have not been reported before in the literature as constituents of the Dorstenia genus.

Triterpenoids from Arctium lappa.

Science.gov (United States)

Jeelani, S; Khuroo, M A

2012-01-01

Phytochemical investigation of the leaves of Arctium lappa led to the isolation of two triterpenoids, characterised by NMR, IR and MS as 3α-hydroxylanosta-5,15-diene and 3α-acetoxy-hop-22(29)-ene. 3α-hydroxylanosta-5,15-diene is a new triterpenoid and is isolated for the first time from this genus.

Presidential Green Chemistry Challenge: 2012 Small Business Award

Science.gov (United States)

Presidential Green Chemistry Challenge 2012 award winner, Elevance Renewable Sciences, used Nobel-prize-winning metathesis catalysis to produce high-value difunctional chemicals from renewable feedstocks including natural oils.

Effect of 2-dodecyl-6-methoxycyclohexa-2,5-diene-1,4-dione, isolated from Averrhoa carambola L. (Oxalidaceae) roots, on advanced glycation end-product-mediated renal injury in type 2 diabetic KKAy mice.

Science.gov (United States)

Zheng, Ni; Lin, Xing; Wen, Qingwei; Kintoko; Zhang, Shijun; Huang, Jianchun; Xu, Xiaohui; Huang, Renbin

2013-05-10

The roots of Averrhoa carambola L. (Oxalidaceae) have a long history of medical use in traditional Chinese medicine for treating diabetes and diabetic nephropathy. 2-Dodecyl-6-methoxycyclohexa-2,5-diene-1,4-dione (DMDD) was isolated from the tuberous roots of A. carambola L. The purpose of this study was to investigate the beneficial effect of DMDD on the advanced glycation end-product-mediated renal injury in type 2 diabetic KKAy mice with regard to prove its efficacy by local traditional practitioners in the treatment of kidney frailties in diabetics. KKAy mice were orally administrated DMDD (12.5, 25, 50mg/kg body weight/d) or aminoguanidine (200mg/kg body weight/d) for 8 weeks. Hyperglycemia, renal AGE formation, and the expression of related proteins, such as the AGE receptor, nuclear factor-κB, transforming growth factor-β1, and N(ε)-(carboxymethyl)lysine, were markedly decreased by DMDD. Diabetes-dependent alterations in proteinuria, serum creatinine, creatinine clearance, and serum urea-N and glomerular mesangial matrix expansion were attenuated after treatment with DMDD for 8 weeks. The activities of superoxide dismutase and glutathione peroxidase, which are reduced in the kidneys of KKAy mice, were enhanced by DMDD. These findings suggest that DMDD may inhibit the progression of diabetic nephropathy and may be a therapeutic agent for regulating several pharmacological targets to treat or prevent of diabetic nephropathy. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

In diens van die Kompanjie

African Journals Online (AJOL)

was ook siektes WQl Jit onvoldoende of ondoel- treffende voeding, eentonige kos en ontoerei- kende geneesmiddels voortgespruit het, terwyl behoorlike versorging dikwels ontbreek he!. Doodsoorsake tydens die seereis het voartge- vloei uit ongelukke aan boord, beperkte ruimte vir die bemanning en geringe vars lug, ...

Uranyl(VI) and lanthanum(III) complexes with functionalized macrocyclic and macroacyclic Schiff bases

International Nuclear Information System (INIS)

Aguiari, A.; Brianese, N.; Tamburini, S.; Vigato, P.A.

1995-01-01

Acyclic Schiff bases have been prepared by [2 + 1] condensation of 2,6-diformyl-4-chlorophenol and H 2 NCH 2 [CH 2 XCH 2 ] n CH 2 NH 2 (n =3D 0 H 2 -I; X =3D NH, S, O n =3D 1 H 2 -II...H 2 -IV; X =3D 0 n =3D 2 H 2 -V; X =3D 0 n =3D 3 H 2 -VI). The related uranlyl(VI) and lanthanum (III) complexes have bee synthesized by reaction by reaction of the preformed ligands with the appropriate salt or by the template procedure, in the presence of base. No base was employed in the preparation of lanthanum (III) complexes, La(H 2 -II)(NO 3 ) 3 , La(H 2 -IV)(NO 3 ) 3 where the Schiff bases coordinate as neutral chelate ligands. These acyclic complexes have been used for further condensation, and symmetric and asymmetric cyclic complexes have been obtained by their reaction with the polyamines H 2 NCH 2 [CH 2 XCH 2 ]nCH 2 NH 2 or with 4,4'-diaminodibenzo -18-crown-6. By reaction with 4-aminobenzo-15-crown-5 or 2-amino-methyl-15-crown-5, the same acyclic complexes give rise to functionalized complexes bearing crown-ether moieties. Analogously, the acyclic ligand H 3 -IXX, prepared by condensation of 2,6 diformyl-4-chlorophenol and tris(aminoethyl)amine, forms mono and homodinuclear lanthanum (III) complexes, which may undergo further condensation when reacted with primary functionalized amines. (authors). 42 refs., 2 figs., 2 schemes, 1 tab

Generalising tree traversals and tree transformations to DAGs

DEFF Research Database (Denmark)

Bahr, Patrick; Axelsson, Emil

2017-01-01

We present a recursion scheme based on attribute grammars that can be transparently applied to trees and acyclic graphs. Our recursion scheme allows the programmer to implement a tree traversal or a tree transformation and then apply it to compact graph representations of trees instead. The resul......We present a recursion scheme based on attribute grammars that can be transparently applied to trees and acyclic graphs. Our recursion scheme allows the programmer to implement a tree traversal or a tree transformation and then apply it to compact graph representations of trees instead...... as the complementing theory with a number of examples....

Independencies Induced from a Graphical Markov Model After Marginalization and Conditioning: The R Package ggm

Directory of Open Access Journals (Sweden)

Giovanni M. Marchetti

2006-02-01

Full Text Available We describe some functions in the R package ggm to derive from a given Markov model, represented by a directed acyclic graph, different types of graphs induced after marginalizing over and conditioning on some of the variables. The package has a few basic functions that find the essential graph, the induced concentration and covariance graphs, and several types of chain graphs implied by the directed acyclic graph (DAG after grouping and reordering the variables. These functions can be useful to explore the impact of latent variables or of selection effects on a chosen data generating model.

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

KAUST Repository

Maity, Niladri; Barman, Samir; Callens, Emmanuel; Samantaray, Manoja K.; Abou-Hamad, Edy; Minenkov, Yury; D'Elia, Valerio; Hoffman, Adam S.; Widdifield, Cory M.; Cavallo, Luigi; Gates, Bruce C.; Basset, Jean-Marie

2015-01-01

The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

KAUST Repository

Maity, Niladri

2015-11-30

The well-defined single-site silica-supported tungsten complex [([triple bond, length as m-dash]Si–O–)W(Me)5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at −78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [([triple bond, length as m-dash]Si–O–)WH3(Me)2], as the predominant species at −78 °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between −78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [([triple bond, length as m-dash]Si–O–)WH3([double bond, length as m-dash]CH2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.

A comparison between the effects of gamma radiation and sulfur cure system on the microstructure and crosslink network of (styrene butadiene rubber/ethylene propylene diene monomer) blends in presence of nanoclay

International Nuclear Information System (INIS)

Shoushtari Zadeh Naseri, Aida; Jalali-Arani, Azam

2015-01-01

Rubber blends based on (styrene–butadiene rubber (SBR)/ethylene–propylene-diene monomer (EPDM)) with and without organoclay (OC) were prepared through a melt mixing process. The concentration ratio of the rubber phases (EPDM/SBR; 50/50 wt%) and the amount of the OC were kept constant. The samples were then vulcanized by means of gamma radiation using a Co-60 gamma source as well as sulfur cure system. The effect of absorbed dose on the formation of the crosslinks was confirmed by the Fourier transform infrared spectroscopy (FTIR). The effects of absorbed dose, sulfur cure system and OC on the gel content, and crosslink density were evaluated by the chemical tests. Applying the Charlesby–Pinner equation to estimate the radiation chemical yield, revealed that the use of OC in the blend caused 20% reduction in the degradation/crosslinking ratio. Employing the swelling test data, some thermodynamic parameters were determined. Using field emission scanning electron microscopy (FE-SEM) to investigate microstructure of the samples revealed a more homogeneous structure and also an increase in compatibility of the blend components in the sample cured by the irradiation in comparison to that cured by the sulfur curing system. - Highlights: • SBR/EPDM and SBR/EPDM/OC samples were prepared and irradiated by gamma radiation. • Increasing the absorbed dose and using OC enhanced gel content and crosslink density. • The increase in the absorbed dose resulted in an increase in ΔS and decrease in ΔG. • The use of OC in the blend caused 20% reduction in the degradation/crosslinking ratio. • In compare to sulfur cure sample the irradiated one showed more homogeneous structure

On acyclicity of games with cycles

DEFF Research Database (Denmark)

Andersson, Klas Olof Daniel; Hansen, Thomas Dueholm; Gurvich, Vladimir

2010-01-01

We study restricted improvement cycles (ri-cycles) in finite positional n-person games with perfect information modeled by directed graphs (di-graphs) that may contain directed cycles (di-cycles). We assume that all these di-cycles form one outcome c, for example, a draw. We obtain criteria...

Influence of alkene substituent in dictating the reaction course to ...

Indian Academy of Sciences (India)

RITABRATA DATTA

2017-11-06

Nov 6, 2017 ... form carbocycles or oxacycles during ring closing metathesis of ... Electronic supplementary material: The online version of this article (https:// doi.org/ ...... tific and Industrial Research for a Senior Research Fellowship.

Silica-supported tungsten carbynes (≡SiO)xW(≡CH)(Me)y (x = 1, y = 2; X = 2, y = 1): New efficient catalysts for alkyne cyclotrimerization

KAUST Repository

Riache, Nassima; Dé ry, Alexandre; Callens, Emmanuel; Poater, Albert; Samantaray, Manoja; Dey, Raju; Hong, Jinhua; Li, Kun; Cavallo, Luigi; Basset, Jean-Marie

2015-01-01

demonstrate that this catalyst species is active for alkyne cyclotrimerization without the formation of significant alkyne metathesis products. Additional DFT calculations highlight the importance of the W coordination sphere in supporting this experimental

Free Sterols of the red alga Chondria armata (Kutz.) Okamura

Digital Repository Service at National Institute of Oceanography (India)

Govenkar, M.B.; Wahidullah, S.

. Results and Discussion The analysis of the sterol fraction by 1 H and 13 C NMR indicated it to be a mixture of four major D 5 3b-hydroxy sterols 2 cholest 5-en-3b-ol (choles- terol), 24j-methyl cholest-5,22-diene-3b-ol, 24j-ethyl cholest-5,22-diene-3b-ol....388 9 % 400 23j-Methyl 5a-cholestan-3b-ol C 28 H 50 O 30.759 6.7 % 402 24b-Ethyl cholest-5,22-diene-3b-ol C 29 H 48 O 31.21 4 % 412 24b-Ethyl cholest-5-en-3b-ol C 29 H 50 O 31.790 18.02 % 414 Table II. Mass spectroscopic characteristic of sterol acetates...

Ni(II

African Journals Online (AJOL)

Preferred Customer

analytical chemistry, catalysis, electrochemistry, ring-opening metathesis ... Ethanol was dried over anhydrous copper(II) sulfate and distilled over metallic sodium. ... All bacteria were inoculated into Nutrient Broth (Difco) and incubated for 24 h ...

Hydrazones as substrates for cycloaddition reactions

International Nuclear Information System (INIS)

Belskaya, N P; Eliseeva, A I; Bakulev, V A

2015-01-01

The [2+2]-, [4+2]- and [3+2]-cycloaddition reactions of hydrazones and 1,2-diazabuta-1,3-dienes, azomethine imines, nitrile imines and azomethine ylides formed upon hydrazone transformations with dienophiles, dipolarophiles and dienes are considered. The principal issues of structure and reactivity of active substrates and the influence of the reaction conditions and catalysts on the reaction regioselectivity and efficiency are discussed. The bibliography includes 288 references

Kyste arachnoidien intra et supra sellaire: apport de l'IRM | Badaoui ...

African Journals Online (AJOL)

Les kystes arachnoïdiens intrasellaires sont rares et souvent étendus en suprasellaire. Leur diagnostic doit être évoqué devant toute formation de nature kystique dont le signal est identique à celui du liquide cérébro-spinal. Nous rapportons le cas d'un kyste arachnoïdien de siège intra et suprasellaire révélé par une ...

(2E,2′E-3-(4-{[4-(4-Hydroxy-3-methoxyphenylbut-2-en-1-yl]oxy}phenyl-1-(2-hydroxy-4-methoxyphenylprop-2-en-1-one

Directory of Open Access Journals (Sweden)

Muhamad S. Fareza

2016-12-01

Full Text Available A hybrid of eugenol and a chalcone has been synthesized in good yield via cross olefin metathesis. The title compound (3 was characterized by spectroscopic data including NMR, infrared, and ESI-MS.

Thermoplastic vulcanizate nanocomposites based on polypropylene/ethylene propylene diene terpolymer (PP/EPDM) prepared by reactive extrusion

Science.gov (United States)

Mirzadeh, Amin

using the solvent extraction and gravimetry technique. Additionally, the effect of continuity on rheological behaviour of TPE nanocomposites was investigated. The ultimate goal in this field is to maximize the rubber like behaviour by controlling the blend morphology and the level of crosslinking. Therefore, this study also covers the effects of nanoclay presence and its dispersion level on the crosslinking reaction of thermoplastic vulcanizate nanocomposites prepared by reactive extrusion. Here, the rubber phase was dynamically vulcanized using dimethylol phenolic resin or octylphenol-formaldehyde resin along with stannous chloride dihydrate as the catalyst. In the present study, the dynamic vulcanization of the prepared TPVs and corresponding nanocomposites are characterized using different criteria, such as gel content, viscosity and normalized storage modulus in the time sweep tests, nuclear magnetic resonance (NMR) signal line width, bound curative content and residual diene concentration. The combination of the above parameters appears to be sufficient to provide a clear description of the systems. The last part of the present study is devoted to find how the dispersion level of nanoclay and consequently the extent of crosslinking change the rubber like behaviour and the morphology of the prepared TPVs. Therefore, recently developed method named temperature scanning stress relaxation (TSSR) was used to estimate the rubber indices of TPVs and TPV nanocomposites. The mentioned method also successfully provided information about the extent of crosslinking reaction. It is shown that the rubber like behaviour of the blends containing 50wt% and 60wt% of EPDM in which morphological studies suggest the presence of the rubber droplets in vicinity of irregular shape rubber particles with a low level of interconnectivity, correlates with the rubber droplet size. Therefore, the nanoclay presence affects the rubber index values mainly through its effect on the size of the

SYNTHESIS AND PHARMACOLOGICAL EFFECTS OF BUTADIENE AND CYCLOPENTADIENE ADDUCTS OF METHANDROSTENOLONE IN RATS

Directory of Open Access Journals (Sweden)

FAZEL SHAMSA

2006-06-01

Full Text Available In this study the reactivity of methandrostenolone or [(17b-17-hydroxy-17-methylandrosta-1, 4-diene-3-one], as a dienophil in a Diels-Alder type cycloaddition reaction was investigated. The purpose of this approach was to investigate whether the 1-dehydro position of methandrostenolone 1 undergoes a cycloaddition reaction with dienes, such as 1, 3 butadiene or cyclopentadiene, and to investigate the biological behavior of the reaction adducts, i.e, compound 3 {(17b-17-hydroxy-17-methyl androsta [1a, 2a] cyclohex 3’, 4-diene-3-one} and compound 4 {(17b-17-hydroxy-17-methyl androsta [1a, 2a] cyclohex (2’,5’ methylene 3’, 4-diene-3-one}, relative to compound 1. The results indicated that thedDiels-Alder reactionddid notpproceed under the usual circumstances of high pressure and temperature, but could proceed in the presence of a Lewis acid (AlCl3. The structures of compounds 3 and 4 were confirmed by spectroscopic methods. The androgenic behavior of compounds 3 and 4 in comparison to compound 1 in the apomorphine test indicated that both compounds were almost devoid of androgenic activity, but prevented apomorphine mediated penile erection in male rats in a similar manner as cyproterone acetate.

Growth-arresting Activity of Acmella Essential Oil and its Isolated Component D-Limonene (1, 8 P-Mentha Diene) against Trichophyton rubrum (Microbial Type Culture Collection 296).

Science.gov (United States)

Padhan, Diptikanta; Pattnaik, Smaranika; Behera, Ajaya Kumar

2017-10-01

Spilanthes acmella is used as a remedy in toothache complaints by the tribal people of Western part of Odisha, India. The objective of this study was to study the growth-arresting activity of an indigenous Acmella essential oil (EO) ( S. acmella Murr, Asteraceae ) and its isolated component, d-limonene against Trichophyton rubrum (microbial type culture collection 296). The EO was extracted from flowers of indigenous S. acmella using Clevenger's apparatus and analyzed by gas chromatography-mass spectrometry (GC-MS). High pressure liquid chromatography (HPLC) was carried out to isolate the major constituent. The isolated fraction was subjected to fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). The antidermatophytic activity was screened for using "disc diffusion" and "slant dilution" method followed by optical, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) studies. The molecular dockings were made between d-limonene with cell wall synthesis-related key enzymes (14 methyl deaminase and monooxygenase). The GC-MS analysis EO had inferred the presence of 7 number of major (≥2%) components. The component with highest peak area (%) was found to be 41.02. The HPLC-isolated fraction was identified as d-limonene (1,8 p-Mentha-diene) by FTIR and NMR. Qualitative and quantitative assays had suggested the growth inhibitory activity of Acmella EO and its component. Shrinkage, evacuation, cell wall puncture, and leakage of cellular constituents by the activity of Acmella oil and d-limonene were evidenced from optical, SEM, and TEM studies. The computer simulation had predicted the binding strengths of d-limonene and fluconazole with dermatophyte cell wall enzymes. There could have been synergistic action of all or some of compounds present in indigenous Acmella EO. There was presence of seven number of (d-limonene, ocimene, β-myrcene, cyclohexene, 3-(1, 5-dimethyl-4-hexenyl)-6-methylene, �