Potassium hydroxide/dimethyl sulfoxide promoted intramolecular cyclization for the synthesis of benzimidazol-2-ones.

Science.gov (United States)

Beyer, Astrid; Reucher, Christine M M; Bolm, Carsten

2011-06-03

A new protocol for intramolecular N-arylations of ureas to form benzimidazol-2-ones has been developed. The cyclization reaction occurs in the presence of KOH and DMSO at close to ambient temperature. Under these conditions the yields are high and a wide range of functional groups are tolerated.

Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

Science.gov (United States)

Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

2014-12-08

A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methanetrisulfonic Acid: A Highly Efficient Strongly Acidic Catalyst for Wagner-Meerwein Rearrangement, Friedel-Crafts Alkylation and Acylation Reactions. Examples from Vitamin E Synthesis

Directory of Open Access Journals (Sweden)

Francesco Pace

2009-04-01

Full Text Available Methanetrisulfonic acid had been prepared for the first time over 140 years ago, but it was used only scarcely in chemical transformations. In the course of our activities dealing with key-steps of industrial syntheses of vitamins, e.g. economically important vitamin E (acetate, we found that methanetrisulfonic acid is an extremely effective catalyst in a variety of reactions. Examples of its applications are Wagner-Meerwein rearrangements, Friedel-Crafts alkylations and ring closures, as well as acylation reactions. Use of this catalyst in truly catalytic amounts (0.04-1.0 mol% resulted in highly selective transformations and yields over 95%. (Remark by the authors: We are describing only one example each for the various types of reactions. Therefore, it would be more appropriate to write (here and in the Introduction and in the Conclusion sections: “Wagner-Meerwein rearrangement, Friedel-Crafts alkylation and ring closure, as well as acylation reactions”

The synthesis of mono- and diacetyl-9H-fluorenes. Reactivity and selectivity in the Lewis acid catalyzed Friedel-Crafts acetylation of 9H-fluorene

DEFF Research Database (Denmark)

Titinchi, Salam J. J.; Kamounah, Fadhil S.; Abbo, Hanna S.

2008-01-01

Friedel-Crafts acetylation of 9H-fluorene is an effective route for the preparation of mono- and diacetyl-9H-fluorenes. Using acetylchloride as the reagent and aluminum chloride as the Lewis acid catalyst the effect of the solvent polarity, the temperature, the reaction time and the mode of addit......Friedel-Crafts acetylation of 9H-fluorene is an effective route for the preparation of mono- and diacetyl-9H-fluorenes. Using acetylchloride as the reagent and aluminum chloride as the Lewis acid catalyst the effect of the solvent polarity, the temperature, the reaction time and the mode......,7-diacetyl-9H-fluorene was obtained in 5-11 % yield when carbon disulfide was used as the solvent. Acetylation of 9H-fluorene in dichloroethane and carbon disulfide, using an excess of acetyl chloride and aluminum chloride at reflux temperature, gives 2,7-diacetyl-9H-fluorene exclusively in high yields (> 97...

NMR spectroscopic characterization and DFT calculations of zirconium(IV)-3,3'-Br2-BINOLate and related complexes used in an enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones.

Science.gov (United States)

Blay, Gonzalo; Cano, Joan; Cardona, Luz; Fernández, Isabel; Muñoz, M Carmen; Pedro, José R; Vila, Carlos

2012-12-07

Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br(2)-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti(IV) and a dimeric structure in the cases of Zr(IV) and Hf(IV). Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr(IV)(2)(μ-(R)-3,3'-Br(2)-BINOL)(2)] where each binaphthol ligand acts as bridge between the metal centers (Novak's model) is more stable than the dimeric structure with a doubly bridged motif [Zr(IV)(2)(μ-O(t)Bu)(2)] where the tert-butoxide groups act as bridging ligands (Kobayashi's model). The scope of the Friedel-Crafts alkylation with regard to the indole structure has been studied. Finally a plausible mechanism for the Friedel-Crafts reaction and a stereomodel for the mode of action of the catalyst that explain the observed stereochemistry of the reaction products have been proposed.

AlCl₃·6H₂O-Catalyzed Friedel-Crafts Alkylation of Indoles by the para-Quinone Methide Moiety of Celastrol.

Science.gov (United States)

Zhu, Yi; Chen, Ziwen; Huang, Zhenfei; Yan, Siwei; Li, Zhuoer; Zhou, Hu; Zhang, Xiaokun; Su, Ying; Zeng, Zhiping

2017-05-16

A classical Friedel-Crafts alkylation of different indoles catalyzed by AlCl₃·6H₂O has been developed for a well-known important natural product, celastrol, resulting in a series of derivatives for further biological evaluation. The catalyst loading was reduced to 5 mol %, the reaction proceeds at ambient temperature and reaction time is only 3 h. The product yields range from 20% to 99%. A reaction mechanism is also proposed, based on our experiment results.

Modification of an Amposta origin bitumen by using tlie Friedel and Crafts reaction with toluyiene-2,4-diisocyanate

Directory of Open Access Journals (Sweden)

Blanco, M.

1988-03-01

Full Text Available In this works, we have modified a bitumen from Amposta by using the Friedel and Crafts reaction with toluylene-2,4-diisocyanate in presence of aluminium trichloride, presenting as well as the characteristics of the original bitumen as the ones of the modification products. We have made technological test, aging of thin film, rheological test, thermical susceptibility and components analyses.

En el presente trabajo se ha modificado un betún procedente de Amposta por reacción de Friedei y Crafts con 4-metil-1,3-bencenodiisocianato, en presencia de tricloruro de aluminio. Se han determinado las características del betún original así como las de los productos obtenidos en la modificación. Se han llevado a cabo ensayos de tipo tecnológico, envejecimiento en película delgada, propiedades reológicas, susceptibilidad térmica y análisis de componentes.

A Large Scale Formal Synthesis of CoQ10: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

International Nuclear Information System (INIS)

Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik

2013-01-01

We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group

A Large Scale Formal Synthesis of CoQ{sub 10}: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

Energy Technology Data Exchange (ETDEWEB)

Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik [LG Life Sciences, Ltd., Daejeon (Korea, Republic of)

2013-04-15

We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group.

1-acetylvinyl acrylates: new captodative olefins bearing an internal probe for the evaluation of the relative reactivity of captodative against electron-deficient double bonds in Diels-Alder and Friedel-Crafts reactions

International Nuclear Information System (INIS)

Herrera, Rafael; Universidad Michoacana de San Nicolas de Hidalgo, Morelia, Mich.; Jimenez-Vazquez, Hugo A.; Delgado, Francisco; Tamariz, Joaquin; Soederberg, Bjoern C.G.

2005-01-01

The captodative olefins 1-acetylvinyl esters of methacrylic and trans-crotonic acids, 3a and 3b, have been prepared. The presence of a second double bond in the molecule, acting as an internal probe, allowed us to compare their relative reactivity in Diels-Alder and Friedel-Crafts reactions. The reactivity was evaluated with cyclopentadiene (6) as diene in Diels-Alder cycloadditions, and with furan (9) and thiophene (10) as heteroaromatic Friedel-Crafts substrates. In both processes, the captodative enone double bond proved to be more reactive than that in the acrylic moiety. FMO theory accounted for this chemo selectivity as a consequence of the major π contribution of the enone to the LUMO of these molecules. The slight exo stereoselectivity observed in the cycloaddition to 6 parallels the higher stability of the corresponding transition state, according to the results of B3LYP/6-311G(d,p) calculations. (author)

In situ activation of benzyl alcohols with XtalFluor-E: formation of 1,1-diarylmethanes and 1,1,1-triarylmethanes through Friedel-Crafts benzylation.

Science.gov (United States)

Desroches, Justine; Champagne, Pier Alexandre; Benhassine, Yasmine; Paquin, Jean-François

2015-02-28

The Friedel-Crafts benzylation of arenes using benzyl alcohols activated in situ with XtalFluor-E is described. A wide range of 1,1-diarylmethanes and 1,1,1-triarylmethanes were prepared under experimentally simple and mild conditions, without the need for a transition metal or a strong Lewis acid. Notably, the reactivity observed demonstrates the potential of XtalFluor-E to induce C-OH bond ionization and SN1 reactivity of benzylic alcohols.

Synthesis and Electronic Properties of Fluoreno[2,1-a]fluorenedione and Fluoreno[1,2-a]fluorenedione.

Science.gov (United States)

Hacker, Allison S; Pavano, Mauricio; Wood, James E; Immoos, Chad E; Hashimoto, Hannah; Genis, Sam P; Frantz, Derik K

2018-01-05

The [2,1-a]- and [1,2-a]-isomers of fluorenofluorenedione have been synthesized via intramolecular Friedel-Crafts acylations. DFT calculations indicate that the [1,2-a]-isomer adopts a twisted, helical C 2 -symmetric structure and that its protonated form is the thermodynamic product of the Friedel-Crafts acylation in hot sulfuric acid. Absorption spectroscopy and cyclic voltammetry measurements provide experimental estimations of frontier molecular orbital energy levels, which are reported and discussed.

4-Acyloxy-2,5-diphenyl-3-oxo-2,3-dihydrothiophene 1,1-dioxides as acylating agents in the Friedel-Crafts reaction

International Nuclear Information System (INIS)

Van Ree, T.

1989-01-01

The 'activated esters', 4-acyloxy-2,5-diphenyl-3-oxo-2,3-dihydrothiophene 1,1-dioxides, easily accessible from 4,6-diphenylthieno[3,4-d][1,3]dioxol-2-one 5,5-dioxide, have been found to be excellent acylating agents in the Friedel-Crafts reaction with olefins and activated aromatic compounds. In the case of the olefins, product mixtures containing β-chloroketones were treated with 1,8-diazabicyclo[5.4.0]undex-7-ene to afford the corresponding unsaturated ketones in 30 - 73% yields, whereas aromatic ketones were obtained in high yields. The activated esters react slightly faster than the corresponding alkanoyl chlorides, and form fewer by-products

Total Synthesis of Adunctin B.

Science.gov (United States)

Dethe, Dattatraya H; Dherange, Balu D

2018-03-16

Total synthesis of (±)-adunctin B, a natural product isolated from Piper aduncum (Piperaceae), has been achieved using two different strategies, in seven and three steps. The efficient approach features highly atom economical and diastereoselective Friedel-Crafts acylation, alkylation reaction and palladium catalyzed Wacker type oxidative cyclization.

Diversity-Oriented Synthesis of Coumarin-Linked Benzimidazoles via a One-Pot, Three-Step, Intramolecular Knoevenagel Cyclization.

Science.gov (United States)

Yao, Po-Hsin Eric; Kumar, Sunil; Liu, Yu-Li; Fang, Chiu-Ping; Liu, Chia-Chen; Sun, Chung-Ming

2017-04-10

Diversity-oriented synthesis of coumarin-linked benzimidazoles from N-(2-aminophenyl)-2-cyanoacetamide was achieved via a one-pot, three-step sequential reaction in excellent yields. In situ intramolecular cyclization of the cyanoacetamide afforded benzimidazoles which subsequently underwent a Knoevenagel condensation of the 2-cyanomethylbenzimidazoles with salicylaldehydes promoted by triethylamine to reach the target compounds. An important intermediate, 2-(2-imino-2H-chromen-3-yl)-1H-benzimidazole was characterized by X-ray analysis and further hydrolyzed to 2-(coumarin-3-yl)benzimidazole in acidic condition. Among the synthesized compounds, some were found to be promising inhibitors of porcine kidney d-amino acid oxidase (pkDAO).

Ready synthesis of free N-H 2-arylindoles via the copper-catalyzed amination of 2-bromo-arylacetylenes with aqueous ammonia and sequential intramolecular cyclization.

Science.gov (United States)

Wang, Huifeng; Li, Yaming; Jiang, Linlin; Zhang, Rong; Jin, Kun; Zhao, Defeng; Duan, Chunying

2011-07-07

A wide range of free N-H 2-arylindoles were synthesised via the copper(II)-catalyzed amination of 2-bromo-arylacetylenes with aqueous ammonia and sequential intramolecular cyclization. The convenience and atom economy of aqueous ammonia, and the low cost of the copper catalytic system make this protocol readily superior in practical application.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

Science.gov (United States)

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Cu(3)(BTC)(2) as a viable heterogeneous solid catalyst for Friedel-Crafts alkylation of indoles with nitroalkenes.

Science.gov (United States)

Nagaraj, Anbu; Amarajothi, Dhakshinamoorthy

2017-05-15

In the present work, Friedel-Crafts alkylation reaction of indole with β-nitrostyrene is examined using a readily available copper based metal-organic frameworks (MOFs) namely, Cu 3 (BTC) 2 (BTC: 1,3,5-benzenetricarboxylic acid) as solid catalyst under mild reaction conditions. Among the various catalysts screened for this reaction, Cu 3 (BTC) 2 exhibits higher activity under the optimized reaction conditions. Besides the absence of leaching of active sites, it is also observed that the catalyst can be reused for four cycles with a minimal decrease in its activity. Cu 3 (BTC) 2 is used as a catalyst to synthesise a series of heterocyclic compounds with different indole and β-nitrostyrene derivatives in moderate to high yields. The present catalytic system shows comparable activity against to recent reports but the advantage of Cu 3 (BTC) 2 is that it does not require any post-functionalization and above all it can be readily synthesised, thus contributing to the synthesis of heterocyclic compounds with high biological interest. Copyright © 2017 Elsevier Inc. All rights reserved.

A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

International Nuclear Information System (INIS)

Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu; Chou, Lingjun; Zhuo, Shuping

2017-01-01

Highlights: • A novel mesoporous ZrO_2/SO_4"2"− has been prepared via a facile one-pot EISA strategy. • The M-ZrO_2/SO_4"2"− exhibited excellent textural and acidic properties. • The introduced S species were homogeneously dispersed in mesoporous skeleton. • The M-ZrO_2/SO_4"2"− exhibited excellent catalytic performance and reusability. - Abstract: In this paper, a novel mesoporous sulfated zirconium (M-ZrO_2/SO_4"2"−) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N_2-physisorption and TEM characterization techniques indicated that M-ZrO_2/SO_4"2"− possessed distinct mesostructure with big specific surface area (133.5 m"2 g"−"1), large pore volume (0.18 cm"3 g"−"1) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N_2-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO_4"2"−, improved the textural properties of prepared materials. In addition, the NH_3-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO_2/SO_4"2"− even evacuated at 400 °C. Furthermore, the M-ZrO_2/SO_4"2"− was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

Synthesis of Cyclohexane-Fused Isocoumarins via Cationic Palladium(II)-Catalyzed Cascade Cyclization Reaction of Alkyne-Tethered Carbonyl Compounds Initiated by Intramolecular Oxypalladation of Ester-Substituted Aryl Alkynes.

Science.gov (United States)

Zhang, Jianbo; Han, Xiuling; Lu, Xiyan

2016-04-15

A cationic Pd(II)-catalyzed cascade cyclization reaction of alkyne-tethered carbonyl compounds was developed. This reaction is initiated by intramolecular oxypalladation of alkynes with an ester group followed by 1,2-addition of the formed C-Pd(II) bond to the carbonyl group, providing a highly efficient method for the synthesis of cyclohexane-fused isocoumarins.

A highly selective turn-on fluorescent probe for hypochlorous acid based on hypochlorous acid-induced oxidative intramolecular cyclization of boron dipyrromethene-hydrazone

International Nuclear Information System (INIS)

Chen, Wei-Chieh; Venkatesan, Parthiban; Wu, Shu-Pao

2015-01-01

Highlights: • A BODIPY-based fluorescent probe for sensing HOCl was developed. • The probe utilizes the HOCl-promoted cyclization in response to the amount of HOCl. • The probe might have application in the investigation of HOCl in biological systems. - Abstract: A BODIPY-based fluorescent probe, HBP, was developed for the detection of hypochlorous acid based on the specific hypochlorous acid-promoted oxidative intramolecular cyclization of heterocyclic hydrazone in response to the amount of HOCl. The reaction is accompanied by a 41-fold increase in the fluorescent quantum yield (from 0.004 to 0.164). The fluorescence intensity of the reaction between HOCl and HBP is linear in the HOCl concentration range of 1–8 μM with a detection limit of 2.4 nM (S/N = 3). Confocal fluorescence microscopy imaging using RAW264.7 cells showed that the new probe HBP could be used as an effective fluorescent probe for detecting HOCl in living cells

A highly selective turn-on fluorescent probe for hypochlorous acid based on hypochlorous acid-induced oxidative intramolecular cyclization of boron dipyrromethene-hydrazone

Energy Technology Data Exchange (ETDEWEB)

Chen, Wei-Chieh; Venkatesan, Parthiban; Wu, Shu-Pao, E-mail: spwu@mail.nctu.edu.tw

2015-07-02

Highlights: • A BODIPY-based fluorescent probe for sensing HOCl was developed. • The probe utilizes the HOCl-promoted cyclization in response to the amount of HOCl. • The probe might have application in the investigation of HOCl in biological systems. - Abstract: A BODIPY-based fluorescent probe, HBP, was developed for the detection of hypochlorous acid based on the specific hypochlorous acid-promoted oxidative intramolecular cyclization of heterocyclic hydrazone in response to the amount of HOCl. The reaction is accompanied by a 41-fold increase in the fluorescent quantum yield (from 0.004 to 0.164). The fluorescence intensity of the reaction between HOCl and HBP is linear in the HOCl concentration range of 1–8 μM with a detection limit of 2.4 nM (S/N = 3). Confocal fluorescence microscopy imaging using RAW264.7 cells showed that the new probe HBP could be used as an effective fluorescent probe for detecting HOCl in living cells.

A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

Energy Technology Data Exchange (ETDEWEB)

Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu [School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (China); Chou, Lingjun, E-mail: ljchou@licp.cas.cn [State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000 (China); Zhuo, Shuping, E-mail: zhuosp_academic@yahoo.com [School of Chemical Engineering, Shandong University of Technology, Zibo, 255049 (China)

2017-07-31

Highlights: • A novel mesoporous ZrO{sub 2}/SO{sub 4}{sup 2−} has been prepared via a facile one-pot EISA strategy. • The M-ZrO{sub 2}/SO{sub 4}{sup 2−} exhibited excellent textural and acidic properties. • The introduced S species were homogeneously dispersed in mesoporous skeleton. • The M-ZrO{sub 2}/SO{sub 4}{sup 2−} exhibited excellent catalytic performance and reusability. - Abstract: In this paper, a novel mesoporous sulfated zirconium (M-ZrO{sub 2}/SO{sub 4}{sup 2−}) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N{sub 2}-physisorption and TEM characterization techniques indicated that M-ZrO{sub 2}/SO{sub 4}{sup 2−} possessed distinct mesostructure with big specific surface area (133.5 m{sup 2} g{sup −1}), large pore volume (0.18 cm{sup 3} g{sup −1}) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N{sub 2}-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO{sub 4}{sup 2−}, improved the textural properties of prepared materials. In addition, the NH{sub 3}-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO{sub 2}/SO{sub 4}{sup 2−} even evacuated at 400 °C. Furthermore, the M-ZrO{sub 2}/SO{sub 4}{sup 2−} was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

Non-Conventional Methodologies in the Synthesis of 1-Indanones

Directory of Open Access Journals (Sweden)

Manuela Oliverio

2014-04-01

Full Text Available 1-Indanones have been successfully prepared by means of three different non-conventional techniques, namely microwaves, high-intensity ultrasound and a Q-tube™ reactor. A library of differently substituted 1-indanones has been prepared via one-pot intramolecular Friedel-Crafts acylation and their efficiency and “greenness” have been compared.

Mode selectivity in the intramolecular cyclization of ketenimines bearing N-acylimino units: a computational and experimental study.

Science.gov (United States)

Alajarín, Mateo; Sánchez-Andrada, Pilar; Vidal, Angel; Tovar, Fulgencio

2005-02-18

[reaction: see text] The mode selectivity in the intramolecular cyclization of a particular class of ketenimines bearing N-acylimino units has been studied by ab initio and DFT calculations. In the model compounds the carbonyl carbon atom and the keteniminic nitrogen atom are linked either by a vinylic or an o-phenylene tether. Two cyclization modes have been analyzed: the [2+2] cycloaddition furnishing compounds with an azeto[2,1-b]pyrimidinone moiety and a 6pi-electrocyclic ring closure leading to compounds enclosing a 1,3-oxazine ring. The [2+2] cycloaddition reaction takes place via a two-step process with formation of a zwitterionic intermediate, which has been characterized as a cross-conjugated mesomeric betaine. The 6pi-electrocyclic ring closure occurs via a transition state whose pseudopericyclic character has been established on the basis of its magnetic properties, geometry, and NBO analysis. The 6pi-electrocyclic ring closure is energetically favored over the [2+2] cycloaddition, although the [2+2] cycloadducts are the thermodynamically controlled products. A quantitative kinetic analysis predicts that 1,3-oxazines would be the kinetically controlled products, but they should transform rapidly and totally into the [2+2] cycloadducts at room temperature. In the experimental study, a number of N-acylimino-ketenimines, in which both reactive functions are supported on an o-phenylene scaffold, have been successfully synthesized in three steps starting from 2-azidobenzoyl chloride. These compounds rapidly convert into azeto[2,1-b]quinazolin-8-ones in moderate to good yields as a result of a formal [2+2] cycloaddition.

Intramolecular addition of benzylic radicals onto ketenimines. Synthesis of 2-alkylindoles.

Science.gov (United States)

Alajarín, Mateo; Vidal, Angel; Ortín, María-Mar

2003-12-07

The inter- and intramolecular addition of free radicals onto ketenimines is studied. All the attempts to add intermolecularly several silicon, oxygen or carbon centered radicals to N-(4-methylphenyl)-C,C-diphenyl ketenimine were unsuccessful. In contrast, the intramolecular addition of benzylic radicals, generated from xanthates, onto the central carbon of a ketenimine function with its N atom linked to the ortho position of the aromatic ring occurred under a variety of reaction conditions. These intramolecular cyclizations provide a novel radical-mediated synthesis of 2-alkylindoles.

A one-pot multistep cyclization yielding thiadiazoloimidazole derivatives

Directory of Open Access Journals (Sweden)

Debabrata Samanta

2014-12-01

Full Text Available A versatile synthetic procedure is described to prepare the benzimidazole-fused 1,2,4-thiadiazoles 2a–c via a methanesulfonyl chloride initiated multistep cyclization involving the intramolecular reaction of an in-situ generated carbodiimide with a thiourea unit. The structure of the intricate heterocycle 2a was confirmed by single-crystal X-ray analysis and its mechanism of formation supported by DFT computations.

Microwave-assisted facile and rapid Friedel-Crafts benzoylation of arenes catalysed by bismuth trifluoromethanesulfonate

DEFF Research Database (Denmark)

Tran, Phoung Hoang; Hansen, Poul Erik; Pham, Thuy Than

2014-01-01

The catalytic activity of metal triflates was investigated in Friedel–Crafts benzoylation under microwave irradiation. Friedel–Crafts benzoylation with benzoyl chloride of a variety of arenes containing electron-rich and electron-poor rings using bismuth triflate under microwave irradiation is de...

Synthesis and mechanism of formation of oxadeazaflavines by microwave thermal cyclization of ortho-halobenzylidene barbiturates

Energy Technology Data Exchange (ETDEWEB)

Figueroa-Villar, J. Daniel; Oliveira, Sandra C.G. de, E-mail: figueroa@ime.eb.br [Grupo de Quimica Medicinal, Departamento de Quimica, Instituto Militar de Engenharia, Rio de Janeiro, RJ (Brazil)

2011-09-15

The thermal cyclization reaction of o-halobenzylidene barbiturates was developed as an efficient and simple method for the preparation of oxadeazaflavines. The use of solid state reaction conditions with microwave irradiation afforded the products in 5 min with 47 to 98% yield. Experimental synthetic results and thermogravimetric reaction analyses agree with the molecular modeling mechanism simulation, indicating that this reaction occurs through an intramolecular hetero-Diels-Alder cyclization followed by fast re-aromatization. (author)

Friedel oscillations in graphene

DEFF Research Database (Denmark)

Lawlor, J. A.; Power, S. R.; Ferreira, M.S.

2013-01-01

Symmetry breaking perturbations in an electronically conducting medium are known to produce Friedel oscillations in various physical quantities of an otherwise pristine material. Here we show in a mathematically transparent fashion that Friedel oscillations in graphene have a strong sublattice...... asymmetry. As a result, the presence of impurities and/or defects may impact the distinct graphene sublattices very differently. Furthermore, such an asymmetry can be used to explain the recent observations that nitrogen atoms and dimers are not randomly distributed in graphene but prefer to occupy one...

Gold-Catalyzed Cyclization of Furan-Ynes bearing a Propargyl Carbonate Group: Intramolecular Diels-Alder Reaction with In Situ Generated Allenes.

Science.gov (United States)

Sun, Ning; Xie, Xin; Chen, Haoyi; Liu, Yuanhong

2016-09-26

Gold-catalyzed cyclization of various furan-ynes with a propargyl carbonate or ester moiety results in the formation of a series of polycyclic aromatic ring systems. The reactions can be rationalized through a tandem gold-catalyzed 3,3-rearrangement of the propargyl carboxylate moiety in furan-yne substrates to form an allenic intermediate, which is followed by an intramolecular Diels-Alder reaction of furan and subsequent ring-opening of the oxa-bridged cycloadduct. It was found that the steric and electronic properties of phosphine ligands on the gold catalyst had a significant impact on the reaction outcome. In the case of 1,5-furan-yne, the cleavage of the oxa-bridge in the cycloadduct with concomitant 1,2-migration of the R(1) group occurs to furnish anthracen-1(2H)-ones bearing a quaternary carbon center. For 1,4-furan-yne, a facile aromatization of the cycloadduct takes place to give 9-oxygenated anthracene derivatives. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrasonicated Synthesis of N-Benzyl-2,3-substituted Morpholines, via the Mitsunobu Diol Cyclisation

Directory of Open Access Journals (Sweden)

B. Jayachandra Reddy

2010-01-01

Full Text Available A facile five step synthesis of N-benzyl-2,3-substituted morpholines (i-iii was performed. The key steps were microwave assisted Friedel-crafts acylation and diol cyclization carried out via an ultra sonication of Mitsunobu reaction using DEAD (diethylazodicarboxylate, TPP in THF for 1 h. The morpholine products were generated as diasteriomers (ii andiii which has been separated by the column chromatography to good yield. The structure of compounds (i-iii has been characterized by the spectral and chemical studies.

Detecting Friedel oscillations in ultracold Fermi gases

Science.gov (United States)

Riechers, Keno; Hueck, Klaus; Luick, Niclas; Lompe, Thomas; Moritz, Henning

2017-09-01

Investigating Friedel oscillations in ultracold gases would complement the studies performed on solid state samples with scanning-tunneling microscopes. In atomic quantum gases interactions and external potentials can be tuned freely and the inherently slower dynamics allow to access non-equilibrium dynamics following a potential or interaction quench. Here, we examine how Friedel oscillations can be observed in current ultracold gas experiments under realistic conditions. To this aim we numerically calculate the amplitude of the Friedel oscillations which are induced by a potential barrier in a 1D Fermi gas and compare it to the expected atomic and photonic shot noise in a density measurement. We find that to detect Friedel oscillations the signal from several thousand one-dimensional systems has to be averaged. However, as up to 100 parallel one-dimensional systems can be prepared in a single run with present experiments, averaging over about 100 images is sufficient.

Formation of benzo[f]-1-indanone frameworks by regulable intramolecular annulations of gem-dialkylthio trienynes.

Science.gov (United States)

Fang, Zhongxue; Liu, Ying; Barry, Badru-Deen; Liao, Peiqiu; Bi, Xihe

2015-02-20

An atom-economic route to benzo[f]-1-indanone frameworks has been developed starting from the readily available gem-dialkylthio trienynes by intramolecular annulations. The chemoselectivity of the intramolecular cyclizations can be regulated by both the base and the type of gas atmosphere used in the reaction, thus allowing the divergent synthesis of the corresponding functionalized benzo[f]-1-indanones in good to excellent yields.

Tyrosine-lipid peroxide adducts from radical termination: para coupling and intramolecular Diels-Alder cyclization.

Science.gov (United States)

Shchepin, Roman; Möller, Matias N; Kim, Hye-young H; Hatch, Duane M; Bartesaghi, Silvina; Kalyanaraman, Balaraman; Radi, Rafael; Porter, Ned A

2010-12-15

Free radical co-oxidation of polyunsaturated lipids with tyrosine or phenolic analogues of tyrosine gave rise to lipid peroxide-tyrosine (phenol) adducts in both aqueous micellar and organic solutions. The novel adducts were isolated and characterized by 1D and 2D NMR spectroscopy as well as by mass spectrometry (MS). The spectral data suggest that the polyunsaturated lipid peroxyl radicals give stable peroxide coupling products exclusively at the para position of the tyrosyl (phenoxy) radicals. These adducts have characteristic (13)C chemical shifts at 185 ppm due to the cross-conjugated carbonyl of the phenol-derived cyclohexadienone. The primary peroxide adducts subsequently undergo intramolecular Diels-Alder (IMDA) cyclization, affording a number of diastereomeric tricyclic adducts that have characteristic carbonyl (13)C chemical shifts at ~198 ppm. All of the NMR HMBC and HSQC correlations support the structure assignments of the primary and Diels-Alder adducts, as does MS collision-induced dissociation data. Kinetic rate constants and activation parameters for the IMDA reaction were determined, and the primary adducts were reduced with cuprous ion to give a phenol-derived 4-hydroxycyclohexa-2,5-dienone. No products from adduction of peroxyls at the phenolic ortho position were found in either the primary or cuprous reduction product mixtures. These studies provide a framework for understanding the nature of lipid-protein adducts formed by peroxyl-tyrosyl radical-radical termination processes. Coupling of lipid peroxyl radicals with tyrosyl radicals leads to cyclohexenone and cyclohexadienone adducts, which are of interest in and of themselves since, as electrophiles, they are likely targets for protein nucleophiles. One consequence of lipid peroxyl reactions with tyrosyls may therefore be protein-protein cross-links via interprotein Michael adducts.

Heteropoly acid encapsulated into zeolite imidazolate framework (ZIF-67) cage as an efficient heterogeneous catalyst for Friedel–Crafts acylation

Energy Technology Data Exchange (ETDEWEB)

Ammar, Muhammad; Jiang, Sai; Ji, Shengfu, E-mail: jisf@mail.buct.edu.cn

2016-01-15

A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid (H{sub 3}PW{sub 12}O{sub 40} denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec) catalysts with different PTA content were prepared. The structure of the catalysts was characterized by XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that 14.6–31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic activity for Friedel-Crafts acylation. The conversion of anisole can reach ~100% and the selectivity of the production can reach ~94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of 120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%. - Graphical abstract: The PTA@ZIF-67 catalysts with different PTA content were prepared by encapsulating the PTA into ZIF-67 cage and the as-synthesized catalysts exhibited good catalytic activity for the Friedel–Craft acylation of anisole with benzoyl chloride.

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....

Synthesis of heterocyclic compounds through palladium-catalyzed C-H cyclization processes.

Science.gov (United States)

Inamoto, Kiyofumi

2013-01-01

Herein, we describe our development of synthetic methods for heterocyclic compounds based on the palladium-catalyzed carbon-hydrogen bond (C-H) functionalization/intramolecular carbon-heteroatom (nitrogen or sulfur) bond formation process. By this C-H cyclization method, we efficiently prepared various N-heterocycles, including indazoles, indoles, and 2-quinolinones, as well as S-heterocycles such as benzothiazoles and benzo[b]thiophenes. Yields are typically good to high and good functional-group tolerance is observed for each process, thereby indicating that the method provides a novel, highly applicable synthetic route to the abovementioned biologically important heterocyclic frameworks. As an application of this approach, an auto-tandem-type, one-pot process involving the oxidative Heck reaction and subsequent C-H cyclization using cinnamamides and arylboronic acids as starting materials in the presence of a palladium catalyst was also developed for the rapid construction of the 2-quinolinone nucleus.

Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

DEFF Research Database (Denmark)

Madec, David; Prestat, Guillaume; Martini, Elisabetta

2005-01-01

Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

Petasis/Diels-Alder/Cyclization Cascade Reactions for the Generation of Scaffolds with Multiple Stereogenic Centers and Orthogonal Handles for Library Production

DEFF Research Database (Denmark)

Flagstad, Thomas; Azevedo, Carlos M. G.; Min, Geanna

2018-01-01

A new effective strategy for the synthesis of sp3‐rich small molecules for library production is presented. The key steps to generate complexity highlight Petasis 3‐component reaction followed by an intramolecular Diels‐Alder and cyclization to generate a densely enriched tricyclic or tetracyclic...

Post-Ugi gold-catalyzed diastereoselective domino cyclization for the synthesis of diversely substituted spiroindolines

Directory of Open Access Journals (Sweden)

Amit Kumar

2013-10-01

Full Text Available An Ugi four-component reaction of propargylamine with 3-formylindole and various acids and isonitriles produces adducts which are subjected to a cationic gold-catalyzed diastereoselective domino cyclization to furnish diversely substituted spiroindolines. All the reactions run via an exo-dig attack in the hydroarylation step followed by an intramolecular diastereoselective trapping of the imminium ion. The whole sequence is atom economic and the application of a multicomponent reaction assures diversity.

p-TSA/Base-Promoted Propargylation/Cyclization of β-Ketothioamides for the Regioselective Synthesis of Highly Substituted (Hydro)thiophenes.

Science.gov (United States)

Nandi, Ganesh Chandra; Singh, Maya Shankar

2016-07-15

Metal-free, p-toluenesulfonic acid (p-TSA)-mediated, straightforward propargylation of β-ketothioamides with aryl propargyl alcohol has been achieved at room temperature. In addition, the reaction also provided thiazole rings as byproducts. Furthermore, the propargylated thioamides undergo intramolecular 1,5-cyclization to afford fully substituted (hydro)thiophenes in the presence of base. Notably, the approach is pot, atom, and step economical (PASE).

Synthesis of novel steroid-tetrahydroquinoline hybrid molecules and D-homosteroids by intramolecular cyclization reactions.

Science.gov (United States)

Magyar, Angéla; Wölfling, János; Kubas, Melanie; Cuesta Seijo, Jose Antonio; Sevvana, Madhumati; Herbst-Irmer, Regine; Forgó, Péter; Schneider, Gyula

2004-05-01

Steroidal aryliminium salts were prepared from D-seco-pregnene aldehyde 2b, and their BF3.OEt2-catalyzed reactions were studied. The nature of the substituent R1 in the anilines 3-6 essentially influenced the chemoselectivity. Using unsubstituted 3, 4-methoxy- (4) or 4-bromoaniline (5), different tetrahydroquinoline derivatives 7a-13a via intramolecular hetero Diels-Alder reaction were formed. In the case of 4-nitroaniline (6) the N-arylamino-D-homopregnane (14a) were also obtained. We assume, that an intramolecular Prins reaction led to this type of fluoro-D-homosteroid. The main products represent a new class of tetrahydroquinolino-androstenes.

Intramolecular cyclization in irradiated nucleic acids: correlation between high-performance liquid chromatography and an immunochemical assay for 8,5'-cycloadenosine in irradiated poly(A)

International Nuclear Information System (INIS)

Fuciarelli, A.F.; Shum, F.Y.; Raleigh, J.A.

1987-01-01

A correlation between high-performance liquid chromatography (HPLC) analysis and an in situ enzyme-linked immunosorbent assay (ELISA) for 8,5'-cycloadenosine formation in irradiated poly(A) has been established. The correlation shows that the ELISA precisely reflects changes in the combined yield of R- and S-8,5'-cycloadenosine but that a correction factor must be applied to the ELISA values for accuracy. The HPLC analysis reveals that the intramolecular cyclization proceeds stereoselectively in irradiated poly(A) to preferentially produce the R isomer at pH 7.0 which is similar to the result for irradiated adenosine but in contrast to the result for 5'-AMP where the S isomer predominates at neutral pH. The HPLC analysis shows that two events originating in hydroxyl radical attack at the sugar phosphate backbone in poly(A); that is, adenine release and 8,5'-cycloadenosine formation have somewhat different dose-yield responses. The formation of 8-hydroxyadenosine was detected in the HPLC chromatograms of poly(A) irradiated under N2O at neutral pH, and the yield of this compound was similar to the yield observed in 5'-AMP or adenosine irradiated under similar conditions

First examples of intramolecular addition of primary amidyl radicals to olefins

Energy Technology Data Exchange (ETDEWEB)

Gaudreault, P.; Drouin, C.; Lessard, J. [Sherbrooke Univ., PQ (Canada). Dept. de Chimie

2005-07-01

This paper presents the first examples of radical cyclization involving a primary amidyl radical and a pendant olefin. Amidyl radicals have attracted interest in terms of their structure, reactivity, and ways to generate them. The intramolecular addition of an amidyl radical on a pendant olefin appears to be a powerful synthetic tool for creating nitrogen-containing heterocycles. Although several examples of cyclization involving secondary amidyl radicals are cited in the the literature, there are no examples of a successful cyclization involving a primary amidyl radical. This is because all attempts to prepare the usual radical precursors have failed when applied to olefinic primary amides. This study reveals that N-(phenylthio) derivatives of olefinic primary amides can be easily prepared and that nitrogen heterocycles resulting from their radical cyclization can be obtained in good to very good yields. Four olefinic primary amides were chosen as models for radical cyclization of primary amidyl radicals. They were prepared from the corresponding carboxylic acids via the acid chlorides. Conversion of primary amides into suitable amidyl radical precursors was also examined. The study showed that N-(phenylthio) amides could be easily prepared by following a slightly modified protocol developed by Esker and Newcomb, by reacting the anion of the amide with phenylsulfenyl chloride. In particular, olefinic N-(phenylthio) amides were prepared and used as primary amidyl radical precursors in a reaction with a solution of 2,2'-azobis(isobutyronitrile) in catalytic quantities and tributyltin hydride in benzene. The resulting yields of cyclic products ranged from 63 to 85 per cent. The intent of the study was to demonstrate that it is no longer necessary to prepare an N-protected precursor and then remove the protecting group after cyclization. Further studies are currently underway. 10 refs., 1 tab.

Stabilization of chromium-bearing electroplating sludge with MSWI fly ash-based Friedel matrices.

Science.gov (United States)

Qian, Guangren; Yang, Xiaoyan; Dong, Shixiang; Zhou, Jizhi; Sun, Ying; Xu, Yunfeng; Liu, Qiang

2009-06-15

This work investigated the feasibility and effectiveness of MSWI fly ash-based Friedel matrices on stabilizing/solidifying industrial chromium-bearing electroplating sludge using MSWI fly ash as the main raw material with a small addition of active aluminum. The compressive strength, leaching behavior and chemical speciation of heavy metals and hydration phases of matrices were characterized by TCLP, XRD, FTIR and other experimental methods. The results revealed that MSWI fly ash-based Friedel matrices could effectively stabilize chromium-bearing electroplating sludge, the formed ettringite and Friedel phases played a significant role in the fixation of heavy metals in electroplating sludge. The co-disposal of chromium-bearing electroplating sludge and MSWI fly ash-based Friedel matrices with a small addition of active aluminum is promising to be an effective way of stabilizing chromium-bearing electroplating sludge.

Synthesis of Some New 2-(3-Aryl-1-phenyl-4-pyrazolyl-benzoxazoles Using Hypervalent Iodine Mediated Oxidative Cyclization of Schiff’s Bases

Directory of Open Access Journals (Sweden)

Ajay Kumar

2006-01-01

Full Text Available Ten new 2-(3-aryl-1-phenyl-4-pyrazolylbenzoxazoles have been synthesized by oxidative intramolecular cyclization of the corresponding Schiff’s bases using iodobenzene diacetate in methanol as an oxidant.

Competitive photocyclization/rearrangement of 4-aryl-1,1-dicyanobutenes controlled by intramolecular charge-transfer interaction. Effect of medium polarity, temperature, pressure, excitation wavelength, and confinement.

Science.gov (United States)

Ito, Tadashi; Nishiuchi, Emi; Fukuhara, Gaku; Inoue, Yoshihisa; Mori, Tadashi

2011-09-01

A series of 4-aryl-1,1-dicyanobutenes (1a-1f) with different substituents were synthesized to control the intramolecular donor-acceptor or charge-transfer (C-T) interactions in the ground state. Photoexcitation of these C-T substrates led to competitive cyclization and rearrangement, the ratio being critically controlled by various environmental factors, such as solvent polarity, temperature and static pressure, and also by excitation wavelength and supramolecular confinement (polyethylene voids). In non-polar solvents, the rearrangement was dominant (>10 : 1) for all examined substrates, while the cyclization was favoured in polar solvents, in particular at low temperatures. Selective excitation at the C-T band further enhanced the cyclization up to >50 : 1 ratios. More importantly, the cyclization/rearrangement ratio was revealed to be a linear function of the C-T transition energy. However, the substrates with a sterically demanding or highly electron-donating substituent failed to give the cyclization product.

The Relation between the Electric Conductance of Nanostructure Bridge and Friedel Sum Rule

International Nuclear Information System (INIS)

Kotani, Y; Shima, N; Makoshi, K

2012-01-01

We analyze the electric conductance through nanostructure bridges in terms of phase-shifts, which satisfy the Friedel sum rule. The phase-shifts are given by solving the eigenvalue equation obtained by extending the method applied to a single impurity problem in a metal. The local charge neutrality condition is introduced through the Friedel sum rule. It is analytically shown that the electric conductance can increase as the two electrodes separate with the condition in which the phase-shifts satisfy the Friedel sum rule. The increment of the distance between two electrodes is obtained by gradually separating interatomic distance.

Solvent and electronic effects on kinetics of cyclization of thermolabile aryllithium reagents. A comparison between 1-bromo-2-(2-bromoethylbenzene and 4,5-dimethoxy-1-bromo-2-(2-bromoethylbenzene

Directory of Open Access Journals (Sweden)

David A. Hunt

2009-05-01

Full Text Available A dramatic solvent effect on the stability and kinetics of intramolecular cyclization is described for the aryllithium species generated from 2-bromo-4,5-dimethoxy-(2-bromoethylbenzene. The aryllithium generated by the halogen-metal exchange reaction with n-butyllithium, is stable for > 1h when generated at -95 to -100 oC in diethyl ether/hexane and can be trapped with electrophiles. However, when the reaction is conducted in a THF/hexane mixture, the intermediate undergoes instantaneous intramolecular cyclization to afford 4,5-dimethoxybenzocyclobutene. By comparison, the corresponding 1-lithio-2-(2-bromoethyl-benzene intermediate is stable for >1h in either THF/hexane or diethyl ether/hexane at -95 to -100 oC. These results indicate that substituent effects as well as the nature of aggregation of these intermediates play key roles in determining the reaction pathway of functionalized aryllithium intermediates when quenched with electrophiles.

One-pot synthesis of spiropyrroloquinoline-isoindolinone and their aza-analogs via the Ugi-4CR/metal-free intramolecular bis-annulation process.

Science.gov (United States)

Ghandi, Mehdi; Zarezadeh, Nahid; Abbasi, Alireza

2015-08-14

This presentation discloses a one-pot synthesis of a series of spiropyrroloquinoline isoindolinone and spiropyrroloquinoline aza-isoindolinone scaffolds. The reaction proceeds by the combination of a Ugi four-component reaction (4CR) and two intramolecular cyclizations under metal-free conditions. The proof of the structures relies on analytical investigation and X-ray crystallography.

ELECTROPHILIC CYCLIZATION OF DITERPENOIDS

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Veaceslav Kulciţki

2006-06-01

Full Text Available A review of diterpenoid cyclization initiated by electrophilic reagents is provided. Conventional protonic and Lewis acids are examined along with superacids as initiators of cyclization cascade. An emphasis is placed on the use of cyclization reactions as a tool for the synthesis of compounds with potential practical utility. The review contains 74 references.

An Efficient Synthesis of Substituted Furans by Cupric Halide-Mediated Intramolecular Halocyclization of 2-(1-Alkynyl)-2-alken-1-ones

International Nuclear Information System (INIS)

Fu, Weijun; Guo, Wenbo; Zhu, Mei; Xu, Chen; Xu, Fengjuan

2013-01-01

An efficient synthesis of 3-halofurans by the intramolecular cyclization of 2-(1-alkynyl)-2-alken-1-ones with cupric halide has been developed. A broad range of 3-chloro- and 3-bromofuran derivatives could be obtained in the present method in moderate to good yields. The 3-halofuran derivatives are potential synthetic intermediates for amplification of molecular complexity

C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

OpenAIRE

Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

2012-01-01

We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexib...

Bioinspired intramolecular Diels-Alder reaction: a rapid access to the highly-strained cyclopropane-fused polycyclic skeleton.

Science.gov (United States)

Zhu, Shifa; Guo, Zhengjiang; Huang, Zhipeng; Jiang, Huanfeng

2014-02-24

A bioinsipred gold-catalyzed tandem Diels-Alder/Diels-Alder reaction of an enynal and a 1,3-diene, forming the highly-strained benzotricyclo[3.2.1.0(2,7) ]octane skeleton, was reported. In contrast, a Diels-Alder/Friedel-Crafts tandem reaction occurred instead when silver salts were used as the catalyst. Although both reactions experienced the similar Diels-Alder reaction of a pyrylium intermediate with a 1,3-diene, they have different reaction mechanisms. The former proceeded with a stepwise Diels-Alder reaction, while the latter one with a concerted one. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast and versatile microwave-assisted intramolecular Heck reaction in peptide macrocyclization using microwave energy.

Science.gov (United States)

Byk, Gerardo; Cohen-Ohana, Mirit; Raichman, Daniel

2006-01-01

We have revisited the intramolecular Heck reaction and investigated the microwave-assisted macrocyclization on preformed peptides using a model series of ring-varying peptides acryloyl-Gly-[Gly](n)-Phe(4-I)NHR; n = 0-4. The method was applied to both solution and solid supported cyclizations. We demonstrate that the intramolecular Heck reaction can be performed in peptides both in solution and solid support using a modified domestic microwave within 1 to 30 minutes in DMF under reflux with moderate yields ranging from 15 to 25% for a scale between 2-45 mg of linear precursors. The approach was applied to the synthesis of a constrained biologically relevant peptidomimetic bearing an Arg-Gly-Asp (RGD) sequence. These results make the microwave-assisted Heck reaction an attractive renovated approach for peptidomimetics. Copyright 2006 Wiley Periodicals, Inc.

Stereoselective synthesis of 1,3-disubstituted isoindolines via Rh(III)-catalyzed tandem oxidative olefination-cyclization of 4-aryl cyclic sulfamidates.

Science.gov (United States)

Son, Se-Mi; Seo, Yeon Ji; Lee, Hyeon-Kyu

2016-03-21

Rh(III)-catalyzed tandem ortho C-H olefination of cyclic 4-aryl sulfamidates (1) and subsequent intramolecular cyclization are described. This reaction serves as a method for the direct and stereoselective synthesis of 1,3-disubstituted isoindolines (3) starting with enantiomerically enriched 4-aryl cyclic sulfamidates. In this process, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained. In addition, the process generates trans-1,3-disubstituted isoindolines exclusively.

Friedel Transition in Layered Superconductors

International Nuclear Information System (INIS)

Dzierzawa, M.; Zamora, M.; Baeriswyl, D.; Bagnoud, X.

1996-01-01

Weakly coupled superconducting layers are described by the anisotropic 3D XY model. A low-temperature layer decoupling due to a proliferation of fluxons between planes, as proposed by Friedel, does not occur. The same is true for a periodic superlattice of high and low T c layers, although the interplane coherence can become extremely weak. On the other hand a true layer decoupling is found for a random stack. copyright 1996 The American Physical Society

Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

International Nuclear Information System (INIS)

Kim, Cheolwoong; Seo, Seung Woo; Lee, Yona; Kim, Sunggon

2014-01-01

We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used

Rapid examination of the kinetic process of intramolecular lactamization of gabapentin using DSC-FTIR

International Nuclear Information System (INIS)

Hsu, C.-H.; Lin, S.-Y.

2009-01-01

The thermal stability and thermodynamics of gabapentin (GBP) in the solid state were investigated by DSC and TG techniques, and FTIR microspectroscopy. The detailed intramolecular lactamization process of GBP to form gabapentin-lactam (GBP-L) was also determined by thermal FTIR microspectroscopy. GBP exhibited a DSC endothermic peak at 169 deg. C. The weight loss in TG curve of GBP suggested that the evaporation process of water liberated via intramolecular lactamization was simultaneously combined with the evaporation process of GBP-L having a DSC endothermic peak at 91 deg. C. A thermal FTIR microspectroscopy clearly evidenced the IR spectra at 3350 cm -1 for water liberated and at 1701 cm -1 for lactam structure formed due to the lactam formation of GBP. This study indicates that the activation energy for combined processes of intramolecular lactamization of GBP and evaporation of GBP-L was about 114.3 ± 23.3 kJ/mol, but for the evaporation of GBP-L alone was 76.2 ± 1.5 kJ/mol. A powerful simultaneous DSC-FTIR combined technique was easily used to quickly examine the detailed kinetic processes of intramolecular cyclization of GPB and evaporation of GBP-L in the solid state

Mesoporous ZSM-5 Zeolites in Acid Catalysis: Top-Down vs. Bottom-Up Approach

Directory of Open Access Journals (Sweden)

Pit Losch

2017-07-01

Full Text Available A top-down desilication of Al-rich ZSM-5 zeolites and a bottom-up mesopores creating method were evaluated in this study. Three liquid–solid and one gas–solid heterogeneously-catalysed reactions were chosen to establish relationships between zeolites textural properties and their catalytic behavior in acid-catalysed model reactions that are influenced by shape selectivity: Diels-Alder cyclization between isoprene and methylacrylate, Methanol-to-Olefins (MTO reaction, chlorination of iodobenzene with trichloroisocyanuric acid (TCCA, and Friedel-Crafts acylation of anisole by carboxylic acids with differing sizes. It is found amongst others that no optimal mesoporosity for all the different reactions can be easily obtained, but depending on the chosen application, a specific treatment has to be set to achieve high activity/selectivity and stability.

Indium triflate in 1-isobutyl-3-methylimidazolium dihydrogenphosphate: an efficient and green catalytic system for Friedel-Crafts acylation

DEFF Research Database (Denmark)

Tran, Phuong Hoang; Hoang, Huy Manh; Chau, Duy-Khiem Nguyen

2015-01-01

Indium triflate in the ionic liquid, 1-isobutyl-3-methylimidazolium dihydrogen phosphate ([i-BMIM]H2PO4), was found to show enhanced catalytic activity in the Friedel–Crafts acylation of various aromatic compounds with acid anhydrides. The catalytic system was easily recovered and reused without...

The meaning of craft: craft makers' descriptions of craft as an occupation.

Science.gov (United States)

Pöllänen, Sinikka

2013-05-01

The aim of this study is to examine how craft makers describe the meaning of craft as an activity in relation to their well-being. The study is based on an analysis of the written narratives of 92 textile craft makers aged 16 to 84. Based on the results, the well-being enhancing nature of craft as a meaningful occupation for those interested in crafting is evident. The significance of craft making as an occupation is described by the following three themes: (a) "the meaning and value of crafts", (b) "the feelings experienced during craft activity", and (c) "the holisticity and intentionality of craft-making". As an activity and a metaphor, craft making helped the participants to adjust to life situations. Elements of craft that enhance well-being can be traced to both the artefacts and the sense of achievement gained in producing them. The effects of craft include personal growth, development of physical and cognitive skills, control of one's body, thoughts, and feelings, as well as cultural and social awareness. The results indicate that the participants noticed the significance of craft as an agony- and stress-reducing and mind-calming activity. Holistic craft and ordinary craft played different roles in maintaining well-being.

Tandem Rh-Catalyzed Oxidative C-H Olefination and Cyclization of Enantiomerically Enriched Benzo-1,3-Sulfamidates: Stereoselective Synthesis of trans-1,3-Disubstituted Isoindolines.

Science.gov (United States)

Achary, Raghavendra; Jung, In-A; Lee, Hyeon-Kyu

2018-04-06

A tandem process, involving Rh(III)-catalyzed oxidative C-H olefination of enantiomerically enriched 4-aryl-benzo-1,3-sulfamidates and subsequent intramolecular aza-Michael cyclization has been developed. The reaction produces trans-benzosulfamidate-fused-1,3-disubstituted isoindolines as major products, in which the configurational integrity of the stereogenic center in the starting material is preserved. Further transformations of the benzosulfamidate-fused-1,3-disubstituted isoindolines are described.

Ternary iron(II) complex with an emissive imidazopyridine arm from Schiff base cyclizations and its oxidative DNA cleavage activity

OpenAIRE

Mukherjee, Arindam; Dhar, Shanta; Nethaji, Munirathinam; Chakravarty, Akhil R

2005-01-01

The ternary iron(II) complex [Fe(L')(L")] $(PF_6)_3(1)$ as a synthetic model for the bleomycins, where L' and L" are formed from metal-mediated cyclizations of N,N -(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine)(L), is synthesized and structurally characterized by X-ray crystallography. In the six-coordinate iron(II) complex, ligands L' and L" show tetradentate and bidentate chelating modes of bonding. Ligand L' is formed from an intramolecular attack of the alcoholic OH group of L to o...

Decomposition of cumyl peracetate on silica

International Nuclear Information System (INIS)

Barbas, J.T.; Leffler, J.E.

1985-01-01

When the Friedel-Crafts reaction was carried out with 1-1 13 C-2-Ph-d 5 and an excess of [ 2 H 6 ] benzene, the mass spectrum of the product, 1,2-diphenylethane again showed extensive hydrogen deuterium exchanges and the relative abundances for the various isotopomeric molecular ions for the product were given. The present results showed that because of exchanges, isotopes of hydrogen cannot be used in tracer studies on Friedel-Crafts alkylations with a high concentration of AlCl 3 as catalysts and with an excess of the arene being alkylated as solvents. The present work demonstrated that dynamic exchanges among both aromatic and side-chain H atoms do take place during Friedel-Crafts reactions, even though the occurrence of such dynamic process may not be apparent when the H atoms are not labeled. 1 table

The Cyclization of natural rubber

International Nuclear Information System (INIS)

Mirzataheri, M.

2000-01-01

The effect of solvent, temperature, time, weight percent of catalyst on the rate and mechanism of cyclization of natural rubber was studied in toluene and xylene solutions having tin tetra chloride catalyst (SnCl 4 ). Iodo metric titration show, with 8% SnCl 4 (based on polymer weight) cyclization occurs, leaving 27.4% of the total unsaturation. Infrared spectra of cyclized natural rubber show decreased absorption intensity at 840 and 780 cm -1 which are characteristic bands of the linear polymer and the appearance of absorption band at 890 cm -1 as cycles were formed. By using this chemical modification, natural rubber is transformed into a resinous thermoplastic, hard, non rubbery cyclized material with much less unsaturation than the original rubber, which could find commercial applications ad adhesives, printing inks, industrial and ship paints

Laccase-catalyzed oxidation and intramolecular cyclization of dopamine: A new method for selective determination of dopamine with laccase/carbon nanotube-based electrochemical biosensors

International Nuclear Information System (INIS)

Xiang, Ling; Lin, Yuqing; Yu, Ping; Su, Lei; Mao, Lanqun

2007-01-01

This study demonstrates a new electrochemical method for the selective determination of dopamine (DA) with the coexistence of ascorbic acid (AA) and 3,4-dihydroxyphenylacetic acid (DOPAC) with laccase/multi-walled carbon nanotube (MWNT)-based biosensors prepared by cross-linking laccase into MWNT layer confined onto glassy carbon electrodes. The method described here is essentially based on the chemical reaction properties of DA including oxidation, intramolecular cyclization and disproportionation reactions to finally give 5,6-dihydroxyindoline quinone and on the uses of the two-electron and two-proton reduction of the formed 5,6-dihydroxyindoline quinone to constitute a method for the selective determination of DA at a negative potential that is totally separated from those for the redox processes of AA and DOPAC. Instead of the ECE reactions of DA with the first oxidation of DA being driven electrochemically, laccase is used here as the biocatalyst to drive the first oxidation of DA into its quinone form and thus initialize the sequential reactions of DA finally into 5,6-dihydroxyindoline quinone. In addition, laccase also catalyzes the oxidation of AA and DOPAC into electroinactive species with the concomitant reduction of O 2 . As a consequence, a combinational exploitation of the chemical properties inherent in DA and the multifunctional catalytic properties of laccase as well as the excellent electrochemical properties of carbon nanotubes substantially enables the prepared laccase/MWNT-based biosensors to be well competent for the selective determination of DA with the coexistence of physiological levels of AA and DOPAC. This demonstration offers a new method for the selective determination of DA, which could be potentially employed for the determination of DA in biological systems

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

Science.gov (United States)

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

Aqueous Synthesis of 1-H-2-Substituted Benzimidazoles via Transition-Metal-Free Intramolecular Amination of Aryl Iodides

Directory of Open Access Journals (Sweden)

Chunxia Chen

2012-10-01

Full Text Available A straightforward method has been developed for the synthesis of the benzimidazole ring system through a carbon-nitrogen cross-coupling reaction. In the presence of 2.0 equiv. of K2CO3 in water at 100 °C for 30 h, the intramolecular cyclization of N-(2-iodoarylbenzamidine provides benzimidazole derivatives in moderate to high yields. Remarkably, the procedure occurs exclusively in water and doesn’t require the use of any additional reagent/catalyst, rendering the methodology highly valuable from both environmental and economical points of view.

Transformation Craft (T-Craft) Concept Study

National Research Council Canada - National Science Library

Marks, Cynthia; Phelps, Chance; Ryan, Justin; Sorensen, Paul

2007-01-01

The objective of the Transformation Craft (T-Craft) innovation team was to develop a conceptual craft that addresses the problem of transporting military vehicles at high speed from the Sea Base to troops inland...

Friedel's salt profiles from thermogravimetric analysis and thermodynamic modelling of Portland cement-based mortars exposed to sodium chloride solution

DEFF Research Database (Denmark)

Shi, Zhenguo; Geiker, Mette Rica; Lothenbach, Barbara

2017-01-01

Thermogravimetric analysis (TGA), powder X-ray diffraction (XRD) and thermodynamic modelling have been used to obtain Friedel's salt profiles for saturated mortar cylinders exposed to a 2.8 M NaCl solution. Comparison of the measured Friedel's salt profiles with the total chloride profiles...

The quantum-chemical investigation of N-cyclization reaction mechanism for epichlorohydrin aminolysis products

Directory of Open Access Journals (Sweden)

Andrey V. Tokar

2014-12-01

Full Text Available The mechanism of intramolecular cyclization for products of epichlorohydrin aminolysis by secondary amines has been investigated at ab initio level of theory. By comparative analysis of energetic characteristics, which obtained in vacuo as well as in acetonitrile solution with the trace quantities of water as an «active» solvation partner of reaction, it has been shown a decisive role of solvent, which occurs mainly at the expense of the polarizable effects for nonspecific solvation. Indeed, the addition to the substrate of one water molecule have decreased corresponding EACT values only 24.1 kJ/mol, while the appearance of acetonitrile surroundings have the same influence ~42.0 kJ/mol. The results of calculations are in good agreement with that data, which have been obtained for such type modeling previously.

Utilization of acidic α-amino acids as acyl donors: an effective stereo-controllable synthesis of aryl-keto α-amino acids and their derivatives.

Science.gov (United States)

Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Tachrim, Zetryana Puteri; Hashidoko, Yasuyuki; Hashimoto, Makoto

2014-05-16

Aryl-keto-containing α-amino acids are of great importance in organic chemistry and biochemistry. They are valuable intermediates for the construction of hydroxyl α-amino acids, nonproteinogenic α-amino acids, as well as other biofunctional components. Friedel-Crafts acylation is an effective method to prepare aryl-keto derivatives. In this review, we summarize the preparation of aryl-keto containing α-amino acids by Friedel-Crafts acylation using acidic α-amino acids as acyl-donors and Lewis acids or Brönsted acids as catalysts.

Dynamical Friedel oscillations of a Fermi sea

Science.gov (United States)

Zhang, J. M.; Liu, Y.

2018-02-01

We study the scenario of quenching an interaction-free Fermi sea on a one-dimensional lattice ring by suddenly changing the potential of a site. From the point-of-view of the conventional Friedel oscillation, which is a static or equilibrium problem, it is of interest what temporal and spatial oscillations the local sudden quench will induce. Numerically, the primary observation is that for a generic site, the local particle density switches between two plateaus periodically in time. Making use of the proximity of the realistic model to an exactly solvable model and employing the Abel regularization to assign a definite value to a divergent series, we obtain an analytical formula for the heights of the plateaus, which turns out to be very accurate for sites not too close to the quench site. The unexpect relevance and the incredible accuracy of the Abel regularization are yet to be understood. Eventually, when the contribution of the defect mode is also taken into account, the plateaus for those sites close to or on the quench site can also be accurately predicted. We have also studied the infinite lattice case. In this case, ensuing the quench, the out-going wave fronts leave behind a stable density oscillation pattern. Because of some interesting single-particle property, this dynamically generated Friedel oscillation differs from its conventional static counterpart only by the defect mode.

Contextualising Craft: Pedagogical Models for Craft Education

Science.gov (United States)

Pollanen, Sinikka

2009-01-01

Craft education in Finland is, in many aspects, in a state of change. This concerns the independent position of craft as a school subject, the content of the compulsory craft courses containing textiles and technical work, the implementation of the new concept of a holistic craft process in the National Core Curriculum and so on. This bears…

Nicholas reactions in the construction of cyclohepta[de]naphthalenes and cyclohepta[de]naphthalenones. The total synthesis of microstegiol.

Science.gov (United States)

Taj, Rafiq A; Green, James R

2010-12-03

The application of the Nicholas reaction chemistry of 2,7-dioxygenated naphthalenes in the synthesis of cyclohepta[de]napthalenes and in the synthesis of (±)-microstegiol (1) is presented. The substitution profile of Nicholas monosubstitution (predominantly C-1) and disubstitution reactions (predominantly 1,6-) on 2,7-dioxygenated napthalenes is reported. Application of a 1,8-dicondensation product and selected C-1 monocondensation products to the construction of cyclohepta[de]naphthalenes by way of ring closing metathesis and intramolecular Friedel-Crafts reactions, respectively, is described. Deprotection of the C-7 oxygen function to the corresponding naphthol allows tautomerization to cyclohepta[de]naphthalene-1-ones upon seven-membered-ring closure in most cases, and replacement of the C-2 oxygen function in the naphthalene by a methyl group ultimately allows the synthesis of (±)-microstegiol.

A general strategy for synthesis of cyclophane-braced peptide macrocycles via palladium-catalysed intramolecular sp3 C-H arylation

Science.gov (United States)

Zhang, Xuekai; Lu, Gang; Sun, Meng; Mahankali, Madhu; Ma, Yanfei; Zhang, Mingming; Hua, Wangde; Hu, Yuting; Wang, Qingbing; Chen, Jinghuo; He, Gang; Qi, Xiangbing; Shen, Weijun; Liu, Peng; Chen, Gong

2018-05-01

New methods capable of effecting cyclization, and forming novel three-dimensional structures while maintaining favourable physicochemical properties are needed to facilitate the development of cyclic peptide-based drugs that can engage challenging biological targets, such as protein-protein interactions. Here, we report a highly efficient and generally applicable strategy for constructing new types of peptide macrocycles using palladium-catalysed intramolecular C(sp3)-H arylation reactions. Easily accessible linear peptide precursors of simple and versatile design can be selectively cyclized at the side chains of either aromatic or modified non-aromatic amino acid units to form various cyclophane-braced peptide cycles. This strategy provides a powerful tool to address the long-standing challenge of size- and composition-dependence in peptide macrocyclization, and generates novel peptide macrocycles with uniquely buttressed backbones and distinct loop-type three-dimensional structures. Preliminary cell proliferation screening of the pilot library revealed a potent lead compound with selective cytotoxicity toward proliferative Myc-dependent cancer cell lines.

Anisotropic Friedel oscillations in a two-dimensional electron gas with a Rashba-Dresselhaus spin-orbit interaction

Science.gov (United States)

Kozlov, I. V.; Kolesnichenko, Yu. A.

2017-07-01

We present a theoretical study of the spatial distribution of the local density of states (LDOS) and the local magnetization density (LMD) in the vicinity of a magnetic point-defect in a degenerate two-dimensional electron gas with a mixed Rashba-Dresselhaus spin-orbit coupling interaction (SOI). The dependence of the Friedel oscillations, which arise under these conditions, on the ratio of the SOI constants is investigated. We obtain asymptotic expressions for the oscillatory parts of the LDOS and the LMD, that are accurate for large distances from the defect. It is shown, that the Friedel oscillations are significantly anisotropic and contain several harmonics for certain ratios of the SOI constants. Period of the oscillations for directions along the symmetry axes of the Fermi contours are determined. Finally, we introduce a method for determining the values of the two SOI constants by measuring the period of the Friedel oscillations of the LDOS and the LMD for different harmonics.

Engineering an Affinity-Enhanced Peptide through Optimization of Cyclization Chemistry.

Science.gov (United States)

Ngambenjawong, Chayanon; Pineda, Julio Marco B; Pun, Suzie H

2016-12-21

Peptide cyclization is a strategy used to improve stability and activity of peptides. The most commonly used cyclization method is disulfide bridge formation of cysteine-containing peptides, as is typically found in nature. Over the years, an increasing number of alternative chemistries for peptide cyclization with improved efficiency, kinetics, orthogonality, and stability have been reported. However, there has been less appreciation for the opportunity to fine-tune peptide activity via the diverse chemical entities introduced at the site of linkage by different cyclization strategies. Here, we demonstrate how cyclization optimization of an M2 "anti-inflammatory" macrophage-binding peptide (M2pep) resulted in a significant increase in binding affinity of the optimized analog to M2 macrophages while maintaining binding selectivity compared to M1 "pro-inflammatory" macrophages. In this study, we report synthesis and evaluation of four cyclic M2pep(RY) analogs with diverse cyclization strategies: (1) Asp-[amide]-Lys, (2) azido-Lys-[triazole(copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC))]-propargyl-Gly, (3) Cys-[decafluorobiphenyl (DFBP)]-Cys, and (4) Cys-[decafluorobiphenyl sulfone (DFS)]-Cys, whereby the chemical entity or linker at the linkage site is shown in the square bracket and is between the residues involved in cyclization. These peptides are compared to a disulfide-cyclized M2pep(RY) that we previously reported as a serum-stable, affinity-enhanced analog to the original linear M2pep. DFBP-cyclized M2pep(RY) exhibits the highest binding activity to M2 macrophages with apparent dissociation constant (K D ) about 2.03 μM compared to 36.3 μM for the original disulfide-cyclized M2pep(RY) and 220 μM for the original linear peptide. DFS-cyclized M2pep(RY) also binds more strongly than the original cyclized analog, whereas amide- and triazole-cyclized M2pep(RY) analogs bind less strongly. We verified that DFBP alone has negligible binding to M2

Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

Science.gov (United States)

Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

2017-12-01

The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

International Nuclear Information System (INIS)

Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F.

2013-01-01

Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

Energy Technology Data Exchange (ETDEWEB)

Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: luizfsjr@iq.usp.br [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental

2013-09-15

Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

The 5-Endo-trig Cyclization of D-Glucose Derived γ-Alkenylamines with Mercury (II Salts: Synthesis of 1-Deoxycastanospermine and its 8a-epi-Analogueâ€

Directory of Open Access Journals (Sweden)

S. Jachak

2005-08-01

Full Text Available The intramolecular aminomercuration of γ-alkenylamines 1a, 1b and 4 was shown to afford the 5-endo-trig cyclized product exclusively in good yield. The utility of pyrrolidine derivatives thus obtained from D-glucose derived γ-alkenylamines 1a and 1b was demonstrated in the synthesis of 1-deoxycastanospermine (3a and 1-deoxy-8a-epi- castanospermine (3b.

Study of cyclization of chelating compounds using electrospray ionization mass spectrometry

International Nuclear Information System (INIS)

Shi Ying; Campbell, J.A.

2000-01-01

Electrospray ionization mass spectrometry (ESI-MS) was used for the study of cyclization of organic chelating compounds (chelators). Four chelating compounds were studied: Symmetrical ethylenediaminediacetic acid (s-EDDA), Unsymmetrical ethylenediaminediacetic acid (u-EDDA), N-(2-hydroxyethyl) ethylenediaminetriacetic acid (HEDTA), and N-(2-hydroxyethyl)iminodiacetic acid (HEIDA). The chelators were cyclized with treatments of acids and heating. The open and cyclized form of the chelators were semi-quantified by both positive and negative ion modes ESI-MS. The kinetics of chelator cyclization was studied as a function of reaction temperature and the pH of the matrix. The cyclization of s-EDDA was found to be a pseudo-first order reaction in s-EDDA and overall second order. The cyclizations of HEIDA and HEDTA are reversible reactions. Higher temperature and lower pH favors cyclization. (author)

From Gender-segregated Subjects to Multi-material Craft: Craft Student Teachers’Views on the Future of the Craft Subject

Directory of Open Access Journals (Sweden)

Jaana Lepistö

2015-12-01

Full Text Available This paper describes the views of student teachers of craft about the future of craft as a school subject. The study was conducted at the University of Turku, Department of Teacher Education, in Rauma in 2014. The literature review revealed that the subject of craft in Finnish basic education is understood as a dialog between the maker and the materials. However, teaching and learning craft in schools and in teacher education has a strong gender-based tradition. The aim of this study is to investigate student teachers’ understanding of craft as a school subject in the future and their solutions to teaching craft in basic education. The data were collected from essays (N = 20 written by student teachers of craft. The essays were analyzed qualitatively using content analysis. The results showed that the student teachers of craft viewed holistic craft, reflective action readiness, entrepreneurial behaviour, multiple skills, the use of versatile materials, and craft as sources of pleasure and the main solutions for the future of craft as a subject.

In vitro structure-activity relationship of Re-cyclized octreotide analogues

Energy Technology Data Exchange (ETDEWEB)

Dannoon, Shorouk F. [Department of Chemistry, University of Missouri, Columbia, MO 65211 (United States); Bigott-Hennkens, Heather M. [Department of Veterinary Medicine and Surgery, University of Missouri, Columbia, MO 65211 (United States); Ma Lixin [Department of Radiology, University of Missouri, Columbia, MO 65211 (United States); International Institute of Nano and Molecular Medicine, University of Missouri, Columbia, MO 65211 (United States); Nuclear Science and Engineering Institute, University of Missouri, Columbia, MO 65211 (United States); Research Service, Harry S. Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States); Gallazzi, Fabio [Structural Biology Core, University of Missouri, Columbia, MO 65211 (United States); Lewis, Michael R., E-mail: lewismic@missouri.ed [Department of Veterinary Medicine and Surgery, University of Missouri, Columbia, MO 65211 (United States); Department of Radiology, University of Missouri, Columbia, MO 65211 (United States); Nuclear Science and Engineering Institute, University of Missouri, Columbia, MO 65211 (United States); Research Service, Harry S. Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States); Jurisson, Silvia S., E-mail: jurissons@missouri.ed [Department of Chemistry, University of Missouri, Columbia, MO 65211 (United States); Department of Radiology, University of Missouri, Columbia, MO 65211 (United States); Nuclear Science and Engineering Institute, University of Missouri, Columbia, MO 65211 (United States)

2010-07-15

Introduction: Development of radiolabeled octreotide analogues is of interest for targeting somatostatin receptor (SSTR)-positive tumors for diagnostic and therapeutic purposes. We are investigating a direct labeling approach for incorporation of a Re ion into octreotide analogues, where the peptide sequences are cyclized via coordination to Re rather than through a disulfide bridge. Methods: Various octreotide analogue sequences and coordination systems (e.g., S{sub 2}N{sub 2} and S{sub 3}N) were synthesized and cyclized with nonradioactive Re. In vitro competitive binding assays with {sup 111}In-DOTA-Tyr{sup 3}-octreotide in AR42J rat pancreatic tumor cells yielded IC{sub 50} values as a measure of SSTR affinity of the Re-cyclized analogues. Three-dimensional structures of Re-cyclized Tyr{sup 3}-octreotate and its disulfide-bridged analogue were calculated from two-dimensional NMR experiments to visualize the effect of metal cyclization on the analogue's pharmacophore. Results: Only two of the 11 Re-cyclized analogues investigated showed moderate in vitro binding affinity toward somatostatin subtype 2 receptors. Three-dimensional molecular structures of Re- and disulfide-cyclized Tyr{sup 3}-octreotate were calculated, and both of their pharmacophore turns appear to be very similar with minor differences due to metal coordination to the amide nitrogen of one of the pharmacophore amino acids. Conclusions: Various Re-cyclized analogues were developed and analogue 4 had moderate affinity toward somatostatin subtype 2 receptors. In vitro stable studies that are in progress showed stable radiometal cyclization of octreotide analogues via NS{sub 3} and N{sub 2}S{sub 2} coordination forming five- and six-membered chelate rings. In vivo biodistribution studies are underway of {sup 99m}Tc-cyclized analogue 4.

Cyclization of arylacetoacetates to indene and dihydronaphthalene derivatives in strong acids. Evidence for involvement of further protonation of O,O-diprotonated beta-ketoester, leading to enhancement of cyclization.

Science.gov (United States)

Kurouchi, Hiroaki; Sugimoto, Hiromichi; Otani, Yuko; Ohwada, Tomohiko

2010-01-20

The chemical features, such as substrate stability, product distribution, and substrate generality, and the reaction mechanism of Brønsted superacid-catalyzed cyclization reactions of aromatic ring-containing acetoacetates (beta-ketoesters) were examined in detail. While two types of carbonyl cyclization are possible, i.e., keto cyclization and ester cyclization, the former was found to take place exclusively. The reaction constitutes an efficient method to synthesize indene and 3,4-dihydronapthalene derivatives. Acid-base titration monitored with (13)C NMR spectroscopy showed that the acetoacetates are fully O(1),O(3)-diprotonated at H(0) = -11. While the five-membered ring cyclization of the arylacetoacetates proceeded slowly at H(0) = -11, a linear increase in the rate of the cyclization was found with increasing acidity in the high acidity region of H(0) = -11.8 to -13.3. Therefore, the O(1),O(3)-diprotonated acetoacetates exhibited some cyclizing reactivity, but they are not the reactive intermediates responsible for the acceleration of the cyclization in the high acidity region. The reactive cationic species might be formed by further protonation (or protosolvation) of the O(1),O(3)-diprotonated acetoacetates; i.e., they may be tricationic species. Thermochemical data on the acid-catalyzed cyclization of the arylacetoacetates showed that the activation energy is decreased significantly as compared with that of the related acid-catalyzed cyclization reaction of a compound bearing a single functional group, such as a ketone. These findings indicate that intervention of the trication contributes to the activation of the cyclization of arylacetoacetates in strong acid, and the electron-withdrawing nature of the O-protonated ester functionality significantly increases the electrophilicity of the ketone moiety.

DEVELOPMENT OF INTERACTIVE MULTIMEDIA COURSEWARE (E-CRAFT FOR CRAFT EDUCATION

Directory of Open Access Journals (Sweden)

Salyani OSMAN,

2012-08-01

Full Text Available The way of teaching and learning traditional crafts have always used traditional apprenticeship learning methods where the expert facilitates transfer of practice skill sets to novices. As a craft has been taught in conventional approach, the students and experts have been facing several problems especially when expert needs to teach a group of students. An appropriate mapping of craft education and Information and Communication Technologies using Multimedia technology for instance, has the potential in transforming traditional craft learning into more flexible environment. This paper reports on a research project on development of an interactive multimedia courseware package for teaching and learning traditional craft called e-CRAFT. The e-CRAFT is specially designed for songket weaving course taught to certificate and diploma students from Fakulti Seni Kraf Tenunan in their first year study at Institut Kraf Negara, Malaysia (National Craft Institute. The courseware was developed in a web-based environment and overall development process was based on the Dick and Carey's process model and conceptual Instructional Design framework. It is made up of eight learning modules: Introduction, Materials & Tools, Knowing Motifs, Learn How to Weave, Quizzes & Test, Online Discussion, Glossary and Help module. In order to test whether the courseware is suitable in terms of usability, pilot testing was done to a sample of 10 students. The results from pilot test received positive feedback which signifies the courseware is considered acceptable for effectiveness study and help for further improve of the e-CRAFT courseware.

In situ cyclization modification in polymerization of butadiene by rare earth coordination catalyst

International Nuclear Information System (INIS)

Wang Chaoyang

2005-01-01

Butadiene was polymerized to a certain extent in the presence of a rare earth coordination catalyst, neodymium compound of neodymium chloride and i-propyl alcohol and triethyl aluminum (NdCl 3 ·3i-PrOH-AlEt 3 ) in toluene and the allyl chloride was then added to the reactive solution in order to in situ cyclize the formed polybutadiene and cyclopolymerize the unreacted butadiene monomers. Effects of molar ratio of allylchloride to AlEt 3 (Cl/Al), cyclization reaction time and temperature, butadiene and NdCl 3 ·3i-PrOH concentrations on the cyclization reaction have been investigated. The cyclization reaction is very quick, only several minutes. The cyclization reaction temperature has few effects on the properties of the cyclized product. Cl/Al is a very important condition for this reaction system. Cyclized polybutadiene has a low value of intrinsic viscosity, free gelling and high yield at high Cl/Al. The microstructures and properties of the cyclized products have been characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy and gel permeation chromatography. The cyclization mechanism is put forward

Structural determinants of reductive terpene cyclization in iridoid biosynthesis

DEFF Research Database (Denmark)

Kries, Hajo; Caputi, Lorenzo; Stevenson, Clare E M

2016-01-01

The carbon skeleton of ecologically and pharmacologically important iridoid monoterpenes is formed in a reductive cyclization reaction unrelated to canonical terpene cyclization. Here we report the crystal structure of the recently discovered iridoid cyclase (from Catharanthus roseus) bound...

An excited-state intramolecular photon transfer fluorescence probe for localizable live cell imaging of cysteine

Science.gov (United States)

Liu, Wei; Chen, Wen; Liu, Si-Jia; Jiang, Jian-Hui

2017-03-01

Small molecule probes suitable for selective and specific fluorescence imaging of some important but low-concentration intracellular reactive sulfur species such as cysteine (Cys) pose a challenge in chemical biology. We present a readily available, fast-response fluorescence probe CHCQ-Ac, with 2-(5‧-chloro-2-hydroxyl-phenyl)-6-chloro-4(3 H)-quinazolinone (CHCQ) as the fluorophore and acrylate group as the functional moiety, that enables high-selectivity and high-sensitivity for detecting Cys in both solution and biological system. After specifically reacted with Cys, the probe undergoes a seven-membered intramolecular cyclization and released the fluorophore CHCQ with excited-state intramolecular photon transfer effect. A highly fluorescent, insoluble aggregate was then formed to facilitate high-sensitivity and high-resolution imaging. The results showed that probe CHCQ-Ac affords a remarkably large Stokes shift and can detect Cys under physiological pH condition with no interference from other analytes. Moreover, this probe was proved to have excellent chemical stability, low cytotoxicity and good cell permeability. Our design of this probe provides a novel potential tool to visualize and localize cysteine in bioimaging of live cells that would greatly help to explore various Cys-related physiological and pathological cellular processes in cell biology and diagnostics.

Human radiation studies: Remembering the early years: Oral history of radiologist Hymer L. Friedell, M.D., Ph.D., conducted January 28, 1995

International Nuclear Information System (INIS)

Fisher, D.; Melamed, E.

1995-07-01

NThis report is a transcript of an interview with Hymer L. Friedell by representatives of the US DOE Office of Human Radiation Experiments. Dr. Friedell was selected for this interview because of his participation in the early stages of the medical use of radioisotopes, his important role in the Manhattan Engineer District Medical Division, and his distinguished medical career and his involvement in the distribution of isotopes and the approval for their use in humans. After a brief biographical sketch Dr. Friedell discusses his remembrances on a wide range of subjects. Topics discussed include pre-war radiation therapy, information provided to patients, the Army Medical Corps and the Manhattan Project, his work at the Chicago Metallurgical Laboratory, inspection visits of Manhattan Project facilities and proposed sites, Plutonium injection studies, and actions of the AEC Isotope Distribution Committee

Friedel oscillations in one-dimensional metals: From Luttinger's theorem to the Luttinger liquid

International Nuclear Information System (INIS)

Vieira, Daniel; Freire, Henrique J.P.; Campo, V.L.; Capelle, K.

2008-01-01

Charge density and magnetization density profiles of one-dimensional metals are investigated by two complementary many-body methods: numerically exact (Lanczos) diagonalization, and the Bethe-Ansatz local-density approximation with and without a simple self-interaction correction. Depending on the magnetization of the system, local approximations reproduce different Fourier components of the exact Friedel oscillations

Crafting in context: Exploring when job crafting is dysfunctional for performance effectiveness.

Science.gov (United States)

Dierdorff, Erich C; Jensen, Jaclyn M

2018-05-01

Job crafting theory purports that the consequences of revising one's work role can be simultaneously beneficial and detrimental. Previous research, however, has almost exclusively emphasized the beneficial outcomes of job crafting. In the current study, we proposed dysfunctional consequences of crafting for performance-related outcomes in the form of a U-shaped relationship between job crafting and performance effectiveness (managerial ratings of job proficiency and peer ratings of citizenship behavior). We further predicted that elements of the task context (autonomy and ambiguity) and the social context (interdependence and social support) moderate these curvilinear relationships. Consistent with previous research, job crafting displayed positive and linear effects on work-related attitudes (job satisfaction and affective commitment). Consistent with our predictions, moderate levels of crafting were associated with dysfunctional performance-related outcomes and features of work context either exacerbated or dissipated these dysfunctional consequences of job crafting for individuals. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

From Gender-segregated Subjects to Multi-material Craft: Craft Student Teachers’Views on the Future of the Craft Subject

OpenAIRE

Jaana Lepistö; Eila Lindfors

2015-01-01

This paper describes the views of student teachers of craft about the future of craft as a school subject. The study was conducted at the University of Turku, Department of Teacher Education, in Rauma in 2014. The literature review revealed that the subject of craft in Finnish basic education is understood as a dialog between the maker and the materials. However, teaching and learning craft in schools and in teacher education has a strong gender-based tradition. The aim of this study is to in...

Learning craft skills. Exploring preschoolers' craft making process

Directory of Open Access Journals (Sweden)

Virpi Yliverronen

2016-06-01

Full Text Available The aim of this study was to explore a preschooler craft-making process in which 18 preschool novices cut pieces for fabric bags and designed and printed patterns to decorate the bags. Through the task, children were familiarised with a small-scale holistic craft process. The intention was to determine how preschoolers perceived, verbalised and interpreted the craft-making process and how children used bodily expressions when explaining a learned craft skill. The present study relies on the videographic method: two preschool groups’ stamp printing activities were recorded, and each child was interviewed individually. Children’s embodied expressions were particularly in focus in video analysis. The results reveal that all the children were able to sufficiently explain the making phase, however, some children compensated for missing words using bodily and facial expressions and gestures when talking about making. The results showed that children worked logically, and the skill learning phases of perceiving, making, and interpretation were revealed from their learning.

Knottin cyclization: impact on structure and dynamics

Directory of Open Access Journals (Sweden)

Gracy Jérôme

2008-12-01

Full Text Available Abstract Background Present in various species, the knottins (also referred to as inhibitor cystine knots constitute a group of extremely stable miniproteins with a plethora of biological activities. Owing to their small size and their high stability, knottins are considered as excellent leads or scaffolds in drug design. Two knottin families contain macrocyclic compounds, namely the cyclotides and the squash inhibitors. The cyclotide family nearly exclusively contains head-to-tail cyclized members. On the other hand, the squash family predominantly contains linear members. Head-to-tail cyclization is intuitively expected to improve bioactivities by increasing stability and lowering flexibility as well as sensitivity to proteolytic attack. Results In this paper, we report data on solution structure, thermal stability, and flexibility as inferred from NMR experiments and molecular dynamics simulations of a linear squash inhibitor EETI-II, a circular squash inhibitor MCoTI-II, and a linear analog lin-MCoTI. Strikingly, the head-to-tail linker in cyclic MCoTI-II is by far the most flexible region of all three compounds. Moreover, we show that cyclic and linear squash inhibitors do not display large differences in structure or flexibility in standard conditions, raising the question as to why few squash inhibitors have evolved into cyclic compounds. The simulations revealed however that the cyclization increases resistance to high temperatures by limiting structure unfolding. Conclusion In this work, we show that, in contrast to what could have been intuitively expected, cyclization of squash inhibitors does not provide clear stability or flexibility modification. Overall, our results suggest that, for squash inhibitors in standard conditions, the circularization impact might come from incorporation of an additional loop sequence, that can contribute to the miniprotein specificity and affinity, rather than from an increase in conformational rigidity

Mechanistic insights on the cycloisomerization of polyunsaturated precursors catalyzed by platinum and gold complexes.

Science.gov (United States)

Soriano, Elena; Marco-Contelles, José

2009-08-18

picture. The intramolecular nucleophilic attack of the double bond on the activated alkyne takes place by an endo-dig or exo-dig pathway to afford a cyclopropyl-metallocarbenoid. Through divergent routes, the cyclopropyl intermediate formed by exo-cyclopropanation could yield the metathesis adduct or bicyclic compounds. The endo-cyclization may be followed by a [1,2]-migration of the propargyl moiety to the internal acetylenic position to afford bicyclic [n.1.0] derivatives. This reaction mechanism is applicable for functional groups ranging from H to carboxylate propargyl substituents (Rautenstrauch reaction). In intramolecular reactions in which a shorter enyne bears a propargyl ester or in intermolecular reactions of an ester with an alkene, the ester preferentially attacks the activated alkyne because of enthalpic (ring strain) and entropic effects. Our calculations can predict the correct stereochemical outcome, which may aid the rational design of further stereoselective syntheses. The alkynes activated by electrophilic species can also react with other nucleophiles, such as aromatic rings. The calculations account for the high endo-selectivity observed and suggest that this transformation takes place through a Friedel-Crafts-type alkenylation mechanism, where the endo-dig cyclization promoted by PtCl(2) may involve a cyclopropylmetallacarbene as intermediate before the formation of the expected Wheland-type intermediate. These comparisons of the computational approach with experiment demonstrate the value of theory in the development of a solid mechanistic understanding of these reaction processes.

Self-Terminating, Oxidative Radical Cyclizations

Directory of Open Access Journals (Sweden)

Uta Wille

2004-05-01

Full Text Available The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described

32 CFR 700.406 - Naval Vessel Register, classification of naval craft, and status of ships and service craft.

Science.gov (United States)

2010-07-01

... craft, and status of ships and service craft. 700.406 Section 700.406 National Defense Department of... Register, classification of naval craft, and status of ships and service craft. (a) The Chief of Naval... craft and the designation of status for each ship and service craft. (b) Commissioned vessels and craft...

Aza-crown ether complex cation ionic liquids: preparation and applications in organic reactions.

Science.gov (United States)

Song, Yingying; Cheng, Chen; Jing, Huanwang

2014-09-26

Aza-crown ether complex cation ionic liquids (aCECILs) were devised, fabricated, and characterized by using NMR spectroscopy, MS, thermogravimetric differential thermal analysis (TG-DTA), elemental analysis and physical properties. These new and room-temperature ILs were utilized as catalysts in various organic reactions, such as the cycloaddition reaction of CO2 to epoxides, esterification of acetic acid and alcohols, the condensation reaction of aniline and propylene carbonate, and Friedel-Crafts alkylation of indole with aldehydes were investigated carefully. In these reactions, the ionic liquid exhibited cooperative catalytic activity between the anion and cation. In addition, the aza-[18-C-6HK][HSO4]2 was the best acidic catalyst in the reactions of esterification and Friedel-Crafts alkylation under mild reaction conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy profiles for ketene cyclizations. Interconversion of 1,3-oxazin-6-ones, mesoionic 1,3-oxazinium olates and acylketenes, imidoylketenes, oxoketenimines, and cyclization products.

Science.gov (United States)

Bornemann, Holger; Wentrup, Curt

2005-07-22

The energy surface connecting oxazinium olates 9, several possible conformers of ketenes 10 and 11, and the final cyclization products 12, 13 and 14, as well as the isomeric 1,3-oxazine-6-ones 15, ring opening of the latter to N-acylimidoylketenes 16, and subsequent rearrangement of 16 to oxoketenimines 17, azetinones 18, and the cyclization products 19 and 20 are evaluated computationally at the B3LYP/6-31G and B3LYP/6-311+G//B3LYP/6-31G levels. The cyclizations of ketenes to oxazinium olates 9 and oxazines 15 have the characteristics of pseudopericyclic reactions. Plots of the energy vs internal reaction coordinate for the cyclization of transoid acylketenes such as 10 to 9 (via TS1) and 16 to 15 (via TS7) feature two inflection points and indicate that the part of the energy surface above the lower inflection points describe internal rotation of the acyl function in the ketene moiety, and the part below this point describes the cyclization of the cisoid ketene to the planar mesoionic oxazinium olate 9 or oxazinone 15. The 1,3-shifts of the OR group that interconvert ketenes 16 and ketenimines 17 via four-membered cyclic transition states TS8 behave similarly, the first portion (from the ketenimine side) of the activation barrier being due largely to internal rotation of substituents, and the top part being due to the 1,3-shift proper.

Computational study of the rate constants and free energies of intramolecular radical addition to substituted anilines

Directory of Open Access Journals (Sweden)

Andreas Gansäuer

2013-08-01

Full Text Available The intramolecular radical addition to aniline derivatives was investigated by DFT calculations. The computational methods were benchmarked by comparing the calculated values of the rate constant for the 5-exo cyclization of the hexenyl radical with the experimental values. The dispersion-corrected PW6B95-D3 functional provided very good results with deviations for the free activation barrier compared to the experimental values of only about 0.5 kcal mol−1 and was therefore employed in further calculations. Corrections for intramolecular London dispersion and solvation effects in the quantum chemical treatment are essential to obtain consistent and accurate theoretical data. For the investigated radical addition reaction it turned out that the polarity of the molecules is important and that a combination of electrophilic radicals with preferably nucleophilic arenes results in the highest rate constants. This is opposite to the Minisci reaction where the radical acts as nucleophile and the arene as electrophile. The substitution at the N-atom of the aniline is crucial. Methyl substitution leads to slower addition than phenyl substitution. Carbamates as substituents are suitable only when the radical center is not too electrophilic. No correlations between free reaction barriers and energies (ΔG‡ and ΔGR are found. Addition reactions leading to indanes or dihydrobenzofurans are too slow to be useful synthetically.

Direct Lactamization of Azido Amides via Staudinger-Type Reductive Cyclization

Energy Technology Data Exchange (ETDEWEB)

Heo, In Jung; Lee, Su Jeong; Cho, Chang Woo [Kyungpook National University, Daegu (Korea, Republic of)

2012-01-15

The direct lactamization of 1,3- and 1,4-azido amides has been achieved using triphenylphosphine and water, affording various γ- and δ-lactams in good to excellent yields. The direct lactamization of the azido amides was performed via the Staudinger-type reductive cyclization in which the amide group acts as the electrophile for lactam synthesis. This lactamization provides a mild, functional group tolerant and efficient route for the synthesis of various γ- and δ-lactams found in natural products and pharmaceuticals. Further studies will be conducted to develop new synthetic routes for the synthesis of various lactams. The lactam ring system is one of the most ubiquitous structural motifs found in natural products and pharmaceuticals. Owing to the prevalence of lactams, their synthesis has attracted considerable attention. Lactams are usually prepared by the coupling of activated carboxylic acid derivatives with amines. Alternative routes include the Beckmann rearrangement of oximes, the Schmidt reaction of cyclic ketones and hydrazoic acid, the Kinugasa reaction of nitrones and terminal acetylenes, the Diels-Alder reaction of cyclopentadiene and chlorosulfonyl isocyanate, transition metal catalyzed lactamization of amino alcohols, and iodolactamization of amides and alkenes. In particular, the intramolecular Staudinger ligation of azides and activated carboxy acids, including esters, is well known as an environmentally friendly and mild protocol for lactam synthesis.

Direct Lactamization of Azido Amides via Staudinger-Type Reductive Cyclization

International Nuclear Information System (INIS)

Heo, In Jung; Lee, Su Jeong; Cho, Chang Woo

2012-01-01

The direct lactamization of 1,3- and 1,4-azido amides has been achieved using triphenylphosphine and water, affording various γ- and δ-lactams in good to excellent yields. The direct lactamization of the azido amides was performed via the Staudinger-type reductive cyclization in which the amide group acts as the electrophile for lactam synthesis. This lactamization provides a mild, functional group tolerant and efficient route for the synthesis of various γ- and δ-lactams found in natural products and pharmaceuticals. Further studies will be conducted to develop new synthetic routes for the synthesis of various lactams. The lactam ring system is one of the most ubiquitous structural motifs found in natural products and pharmaceuticals. Owing to the prevalence of lactams, their synthesis has attracted considerable attention. Lactams are usually prepared by the coupling of activated carboxylic acid derivatives with amines. Alternative routes include the Beckmann rearrangement of oximes, the Schmidt reaction of cyclic ketones and hydrazoic acid, the Kinugasa reaction of nitrones and terminal acetylenes, the Diels-Alder reaction of cyclopentadiene and chlorosulfonyl isocyanate, transition metal catalyzed lactamization of amino alcohols, and iodolactamization of amides and alkenes. In particular, the intramolecular Staudinger ligation of azides and activated carboxy acids, including esters, is well known as an environmentally friendly and mild protocol for lactam synthesis

Cyclization of the N-Terminal X-Asn-Gly Motif during Sample Preparation for Bottom-Up Proteomics

DEFF Research Database (Denmark)

Zhang, Xumin; Højrup, Peter

2010-01-01

We, herein, report a novel -17 Da peptide modification corresponding to an N-terminal cyclization of peptides possessing the N-terminal motif of X-Asn-Gly. The cyclization occurs spontaneously during sample preparation for bottom-up proteomics studies. Distinct from the two well-known N-terminal ......We, herein, report a novel -17 Da peptide modification corresponding to an N-terminal cyclization of peptides possessing the N-terminal motif of X-Asn-Gly. The cyclization occurs spontaneously during sample preparation for bottom-up proteomics studies. Distinct from the two well-known N......-terminal cyclizations, cyclization of N-terminal glutamine and S-carbamoylmethylcysteine, it is dependent on pH instead of [NH(4)(+)]. The data set from our recent study on large-scale N(α)-modified peptides revealed a sequence requirement for the cyclization event similar to the well-known deamidation of Asn to iso...

Computer Crafts for Kids.

Science.gov (United States)

Kuntz, Margy; Kuntz, Ann

This work presents a collection of craft projects that can be created by children. Necessary for completion of each craft is an IBM-compatible computer running Windows, "Word for Windows 6.0," with a mouse, a printer, and plain white printer paper. Simple craft supplies, including glue and scissors, also are needed. In each activity the child is…

Craft qualities translated from traditional crafts to smart textile services

NARCIS (Netherlands)

Kuusk, K.; Wensveen, S.A.G.; Tomico Plasencia, O.

2016-01-01

In this article we suggest craft and craftsmanship as an inspiration to design more sustainable smart textile services. We look into the opportunities that interactive properties and services bring into the textile and garment life cycle. We use traditional crafts as a source of inspiration for the

Supporting Craft Sense in Early Education

Directory of Open Access Journals (Sweden)

Kalle Virta

2013-10-01

Full Text Available The research task was to describe and construct theoretical background for Craft Sense in early education. Craft Sense represents a learner’s skill for obtaining Sloyd (Craft, Design & Technology related knowledge, skills and understanding. The development of Craft Sense is based on producing artefacts and evaluating the production process. In this research, the concept of Craft Sense is based on the integration of Sloyd and meta-cognitive regulation of learning activities. Based on theoretical information, an empirical research question was formulated: “What kind of Craft Sense do children have in early education Sloyd?” The method of study was assessing picture supported learning on a Sloyd course for young children. The data was analyzed by qualitative content analysis and Child Behaviour Rating Scale (CBRS. Findings indicate that the development of children’s Craft Sense can be supported with pictures. Furthermore, the CBRS can be used to evaluate and understand children’s Craft Sense. Keywords: Craft Sense, Sloyd, Sloyd Education, Meta-cognition

Employees’ Perceived Opportunities to Craft and In-Role Performance: The Mediating Role of Job Crafting and Work Engagement

Science.gov (United States)

van Wingerden, Jessica; Poell, Rob F.

2017-01-01

The present study was designed to gain knowledge of the relationship between employees’ perceived opportunities to craft, their actual job crafting behavior and, in line with JD-R theory, subsequently their work engagement and performance. Although scholars have suggested that employees’ perceived opportunities to craft their job may predict their actual job crafting behavior, which may have consequences for their well-being and performance, no study has examined the relationships between these variables. We collected data among a heterogeneous group of Dutch employees (N = 2090). Participants of the study reported their perceived opportunities to craft, job crafting behavior, work engagement and performance. Results indicated that individuals who experience a high level of opportunities to craft reported higher levels of job crafting behavior. In turn, perceived opportunities to craft and job crafting behavior related to higher levels of work engagement and subsequently performance. We discuss the implications of these findings for theory and practice. PMID:29118729

Employees' Perceived Opportunities to Craft and In-Role Performance: The Mediating Role of Job Crafting and Work Engagement.

Science.gov (United States)

van Wingerden, Jessica; Poell, Rob F

2017-01-01

The present study was designed to gain knowledge of the relationship between employees' perceived opportunities to craft, their actual job crafting behavior and, in line with JD-R theory, subsequently their work engagement and performance. Although scholars have suggested that employees' perceived opportunities to craft their job may predict their actual job crafting behavior, which may have consequences for their well-being and performance, no study has examined the relationships between these variables. We collected data among a heterogeneous group of Dutch employees ( N = 2090). Participants of the study reported their perceived opportunities to craft, job crafting behavior, work engagement and performance. Results indicated that individuals who experience a high level of opportunities to craft reported higher levels of job crafting behavior. In turn, perceived opportunities to craft and job crafting behavior related to higher levels of work engagement and subsequently performance. We discuss the implications of these findings for theory and practice.

Development of Interactive Multimedia Courseware (e-CRAFT) for Craft Education

Science.gov (United States)

Osman, Salyani; Sahari, Noraidah; Zin, Nor Azan Mat

2012-01-01

The way of teaching and learning traditional crafts have always used traditional apprenticeship learning methods where the expert facilitates transfer of practice skill sets to novices. As a craft has been taught in conventional approach, the students and experts have been facing several problems especially when expert needs to teach a group of…

SpyRing interrogation: analyzing how enzyme resilience can be achieved with phytase and distinct cyclization chemistries

Science.gov (United States)

Schoene, Christopher; Bennett, S. Paul; Howarth, Mark

2016-01-01

Enzymes catalyze reactions with exceptional selectivity and rate acceleration but are often limited by instability. Towards a generic route to thermo-resilience, we established the SpyRing approach, cyclizing enzymes by sandwiching between SpyTag and SpyCatcher (peptide and protein partners which lock together via a spontaneous isopeptide bond). Here we first investigated the basis for this resilience, comparing alternative reactive peptide/protein pairs we engineered from Gram-positive bacteria. Both SnoopRing and PilinRing cyclization gave dramatic enzyme resilience, but SpyRing cyclization was the best. Differential scanning calorimetry for each ring showed that cyclization did not inhibit unfolding of the inserted β-lactamase. Cyclization conferred resilience even at 100 °C, where the cyclizing domains themselves were unfolded. Phytases hydrolyze phytic acid and improve dietary absorption of phosphate and essential metal ions, important for agriculture and with potential against human malnutrition. SpyRing phytase (PhyC) resisted aggregation and retained catalytic activity even following heating at 100 °C. In addition, SpyRing cyclization made it possible to purify phytase simply by heating the cell lysate, to drive aggregation of non-cyclized proteins. Cyclization via domains forming spontaneous isopeptide bonds is a general strategy to generate resilient enzymes and may extend the range of conditions for isolation and application of enzymes. PMID:26861173

Polymeric molecular sieve membranes for gas separation

Science.gov (United States)

Dai, Sheng; Qiao, Zhenan; Chai, Songhai

2017-08-15

A porous polymer membrane useful in gas separation, the porous polymer membrane comprising a polymeric structure having crosslinked aromatic groups and a hierarchical porosity in which micropores having a pore size less than 2 nm are present at least in an outer layer of the porous polymer membrane, and macropores having a pore size of over 50 nm are present at least in an inner layer of the porous polymer membrane. Also described are methods for producing the porous polymer membrane in which a non-porous polymer membrane containing aromatic rings is subjected to a Friedel-Crafts crosslinking reaction in which a crosslinking molecule crosslinks the aromatic rings in the presence of a Friedel-Crafts catalyst and organic solvent under sufficiently elevated temperature, as well as methods for using the porous polymer membranes for gas or liquid separation, filtration, or purification.

Cyclization strategies of meditopes: affinity and diffraction studies of meditope–Fab complexes

International Nuclear Information System (INIS)

Bzymek, Krzysztof P.; Ma, Yuelong; Avery, Kendra A.; Horne, David A.; Williams, John C.

2016-01-01

An overview of cyclization strategies of a Fab-binding peptide to maximize affinity. Recently, a unique binding site for a cyclic 12-residue peptide was discovered within a cavity formed by the light and heavy chains of the cetuximab Fab domain. In order to better understand the interactions that drive this unique complex, a number of variants including the residues within the meditope peptide and the antibody, as well as the cyclization region of the meditope peptide, were created. Here, multiple crystal structures of meditope peptides incorporating different cyclization strategies bound to the central cavity of the cetuximab Fab domain are presented. The affinity of each cyclic derivative for the Fab was determined by surface plasmon resonance and correlated to structural differences. Overall, it was observed that the disulfide bond used to cyclize the peptide favorably packs against a hydrophobic ‘pocket’ and that amidation and acetylation of the original disulfide meditope increased the overall affinity ∼2.3-fold. Conversely, replacing the terminal cysteines with serines and thus creating a linear peptide reduced the affinity over 50-fold, with much of this difference being reflected in a decrease in the on-rate. Other cyclization methods, including the formation of a lactam, reduced the affinity but not to the extent of the linear peptide. Collectively, the structural and kinetic data presented here indicate that small perturbations introduced by different cyclization strategies can significantly affect the affinity of the meditope–Fab complex

Cyclization strategies of meditopes: affinity and diffraction studies of meditope–Fab complexes

Energy Technology Data Exchange (ETDEWEB)

Bzymek, Krzysztof P.; Ma, Yuelong; Avery, Kendra A.; Horne, David A.; Williams, John C., E-mail: jcwilliams@coh.org [Beckman Research Institute of City of Hope, 1710 Flower Street, Duarte, CA 91010 (United States)

2016-05-23

An overview of cyclization strategies of a Fab-binding peptide to maximize affinity. Recently, a unique binding site for a cyclic 12-residue peptide was discovered within a cavity formed by the light and heavy chains of the cetuximab Fab domain. In order to better understand the interactions that drive this unique complex, a number of variants including the residues within the meditope peptide and the antibody, as well as the cyclization region of the meditope peptide, were created. Here, multiple crystal structures of meditope peptides incorporating different cyclization strategies bound to the central cavity of the cetuximab Fab domain are presented. The affinity of each cyclic derivative for the Fab was determined by surface plasmon resonance and correlated to structural differences. Overall, it was observed that the disulfide bond used to cyclize the peptide favorably packs against a hydrophobic ‘pocket’ and that amidation and acetylation of the original disulfide meditope increased the overall affinity ∼2.3-fold. Conversely, replacing the terminal cysteines with serines and thus creating a linear peptide reduced the affinity over 50-fold, with much of this difference being reflected in a decrease in the on-rate. Other cyclization methods, including the formation of a lactam, reduced the affinity but not to the extent of the linear peptide. Collectively, the structural and kinetic data presented here indicate that small perturbations introduced by different cyclization strategies can significantly affect the affinity of the meditope–Fab complex.

Asymmetric, Stereodivergent Synthesis of (−)-Clusianone Utilizing a Biomimetic Cationic Cyclization **

Science.gov (United States)

Boyce, Jonathan H.

2014-01-01

We report a stereodivergent, asymmetric total synthesis of (−)-clusianone in six steps from commercial materials. We implement a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbons. Mechanistic studies point to the unique ability of formic acid to bring about successful cyclization to the clusianone framework. PMID:24916169

Research 2009-2011 - Digital Crafting

DEFF Research Database (Denmark)

Ramsgaard Thomsen, Mette; Tamke, Martin; Peder Pedersen, Claus

2012-01-01

The publication reports on the international research network 'Digital Crafting' organised in the period 2009-2011. The research network investigated profound changes in the design and building of architecture. Developing the term Digital Crafting, the network examined how the maturing of interfa......The publication reports on the international research network 'Digital Crafting' organised in the period 2009-2011. The research network investigated profound changes in the design and building of architecture. Developing the term Digital Crafting, the network examined how the maturing...

An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

International Nuclear Information System (INIS)

Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In

2013-01-01

The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones

An Efficient Synthesis of 1-Alkyl-2-phenyl-4-quinolones from 2-Halobenzoic Acids

Energy Technology Data Exchange (ETDEWEB)

Song, Yoon Ju; Choi, Jin Sun; Lee, Jae In [Duksung Women' s Univ., Seoul (Korea, Republic of)

2013-10-15

The present method offers an efficient synthesis of 1-alkyl-2-phenyl-4-quinolones from 2-haloben-zoic acids. It has the advantages with respect to (i) synthesis of 2 equiv of alkynones 5 from 1 equiv of 4,6-pyrimidyl di(2-halobenzoates) 3, (ii) synthesis of versatile 1-alkyl-2-phenyl-4-quinolones in high overall yields, and (iii) use of readily available and cheap starting materials. Therefore, this method could be utilized as a practical synthesis of 1-alkyl-2-phenyl-4-quinolones. Several methods have been developed to synthesize 1-alkyl-2-phenyl-4-quinolones from 2'-substituted acetophenones, anilines, and 2-halobenzoyl chlorides as starting materials. The reaction of N-methylisatoic anhydride with the lithium enolate of an 4'-methoxyacetophenone afforded the 1-methyl-2-phenyl-4-quinolone in a short sequence, but the yield was low. N-(2-Acetylphenyl)benzamides, prepared by Friedel-Crafts acylation of N-phenyl benzamides with acetyl chloride or benzoylation of 2'-aminoacetophenones with benzoyl chlorides,8 were cyclized with potassium t-butoxide to yield 2-aryl-4-quinolones, which were further alkylated with alkyl iodides to give 1-alkyl-2-aryl-4-quinolones.

Josiah Wedgwood, Manufacturing and Craft

DEFF Research Database (Denmark)

Holt, Robin; Popp, Andrew

2016-01-01

Craft and industrial manufacture are often seen as dichotomous, with craft being marginalized during the process of industrialization. We want to look beyond this position, searching for craft in places where it has gone unnoticed and where it might have bloomed anew in the interstices created...

Cross-Conjugated n-Dopable Aromatic Polyketone

NARCIS (Netherlands)

Voortman, Thomas P.; Bartesaghi, Davide; Koster, L. Jan Anton; Chiechi, Ryan C.

2015-01-01

This paper describes the synthesis and characterization of a high molecular weight cross-conjugated polyketone synthesized via scalable Friedel Crafts chemistry. Cross-conjugated polyketones are precursors to conjugated polyions; they become orders of magnitude more conductive after a two-electron

46 CFR 199.201 - Survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft. 199.201 Section 199.201 Shipping COAST... craft. (a) Each survival craft must be approved and equipped as follows: (1) Each lifeboat must be... addition to the survival craft required in paragraph (b)(1) of this section, additional liferafts must be...

Nazarov cyclization initiated by peracid oxidation: the total synthesis of (+/-)-rocaglamide.

Science.gov (United States)

Malona, John A; Cariou, Kevin; Frontier, Alison J

2009-06-10

The total syntheses of aglafolin, rocagloic acid, and rocaglamide using Nazarov cyclization are described. Generation of the necessary oxyallyl cation intermediate was accomplished via peracid oxidation of an allenol ether to generate an unusual oxycarbenium ion species that undergoes cyclization. The synthesis is efficient, highly diastereoselective, and strategically distinct from previous syntheses of rocaglamide.

Intramolecular Association within the SAFT Framework

DEFF Research Database (Denmark)

Avlund, Ane Søgaard; Kontogeorgis, Georgios; Chapman, Walter G.

2011-01-01

A general theory for modelling intramolecular association within the SAFT framework is proposed. Sear and Jackson [Phys. Rev. E. 50 (1), 386 (1994)] and Ghonasgi and Chapman [J. Chem. Phys. 102 (6), 2585 (1995)] have previously extended SAFT to include intramolecular association for chains with two...... the contribution to the Helmholtz free energy from association (inter- as well as intramolecularly) at equilibrium. Sear and Jackson rederived the contribution to the Helmholtz free energy from association from the theory by Wertheim [J. Stat. Phys. 42 (3–4), 459 (1986)] with inclusion of intramolecular...

Removal of arsenic from water by Friedel's salt (FS: 3CaO·Al2O3·CaCl2·10H2O).

Science.gov (United States)

Zhang, Danni; Jia, Yongfeng; Ma, Jiayu; Li, Zhibao

2011-11-15

Low levels of arsenic can be effectively removed from water by adsorption onto various materials and searching for low-cost, high-efficiency new adsorbents has been a hot topic in recent years. In the present study, the performance of Friedel's salt (FS: 3CaO·Al(2)O(3)·CaCl(2)·10H(2)O), a layered double hydroxide (LDHs), as an adsorbent for arsenic removal from aqueous solution was investigated. Friedel's salt was synthesized at lower temperature (50°C) compared to traditional autoclave methods by reaction of calcium chloride with sodium aluminate. Kinetic study revealed that adsorption of arsenate by Friedel's salt was fast in the first 12h and equilibrium was achieved within 48 h. The adsorption kinetics are well described by second-order Lageren equation. The adsorption capacity of the synthesized sorbent for arsenate at pH 4 and 7 calculated from Langmuir adsorption isotherms was 11.85 and 7.80 mg/g, respectively. Phosphate and silicate markedly decreased the removal of arsenate, especially at higher pH, but sulfate was found to suppress arsenate adsorption at lower pH and the adverse effect was disappeared at pH ≥ 6. Common metal cations (Ca(2+), Mg(2+)) enhanced arsenate adsorption. The results suggest that Friedel's salt is a potential cost-effective adsorbent for arsenate removal in water treatment. Copyright © 2011 Elsevier B.V. All rights reserved.

46 CFR 117.200 - Survival craft-general.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-general. 117.200 Section 117.200 Shipping... Number and Type of Survival Craft § 117.200 Survival craft—general. (a) Each survival craft required on a... craft they replace. (c) A summary of survival craft requirements is provided in Table 117.200(c). Table...

Oxidative cyclization of prodigiosin by an alkylglycerol monooxygenase-like enzyme

DEFF Research Database (Denmark)

de Rond, Tristan; Stow, Parker; Eigl, Ian

2017-01-01

Prodiginines, which are tripyrrole alkaloids displaying a wide array of bioactivities, occur as linear and cyclic congeners. Identification of an unclustered biosynthetic gene led to the discovery of the enzyme responsible for catalyzing the regiospecific C–H activation and cyclization of prodigi...... of prodigiosin to cycloprodigiosin in Pseudoalteromonas rubra. This enzyme is related to alkylglycerol monooxygenase and unrelated to RedG, the Rieske oxygenase that produces cyclized prodiginines in Streptomyces, implying convergent evolution....

Synthesis and properties of heterocyclic type I photoinitiators

International Nuclear Information System (INIS)

Liska, R.; Knaus, S.; Wendrinsky, J.

1999-01-01

The synthesis and properties of a series of new heterocyclic hydroxyalkylphenone-analogous photoinitiators (PIs) is described. The PIs are obtained by reaction of aromatic organolithium compounds with nitriles or by Friedel-Craft's-acylation. Preliminary photocalorimetric tests and UV absorption data are included

Synthesis and Reactions of Acenaphthenequinones-Part-2. The Reactions of Acenaphthenequinones

Directory of Open Access Journals (Sweden)

Mahmoud Shoukry

2002-02-01

Full Text Available The reactions of acenaphthenequinone and its derivatives with different nucleophiles, organic and inorganic reagents are reviewed. This survey also covers their oxidation and reduction reactions, in addition to many known reactions such as Friedel Crafts, Diels-Alder, bromination and thiolation.

SpyRings Declassified: A Blueprint for Using Isopeptide-Mediated Cyclization to Enhance Enzyme Thermal Resilience.

Science.gov (United States)

Schoene, C; Bennett, S P; Howarth, M

2016-01-01

Enzymes often have marginal stability, with unfolding typically leading to irreversible denaturation. This sensitivity is a major barrier, both for de novo enzyme development and for expanding enzyme impact beyond the laboratory. Seeking an approach to enhance resilience to denaturation that could be applied to a range of different enzymes, we developed SpyRing cyclization. SpyRings contain genetically encoded SpyTag (13 amino acids) on the N-terminus and SpyCatcher (12kDa) on the C-terminus of the enzyme, so that the Spy partners spontaneously react together through an irreversible isopeptide bond. SpyRing cyclization gave major increases in thermal resilience, including on a model for enzyme evolution, β-lactamase, and an industrially important enzyme in agriculture and nutrition, phytase. We outline the SpyRing rationale, including comparison of SpyRing cyclization to other cyclization strategies. The cloning strategy is presented for the simple insertion of enzyme genes for recombinant expression. We discuss structure-based approaches to select suitable enzyme cyclization targets. Approaches to evaluate the cyclization reaction and its effect on enzyme resilience are described. We also highlight the use of differential scanning calorimetry to understand how SpyRing cyclization promotes enzyme refolding. Efficiently searching sequence space will continue to be important for enzyme improvement, but the SpyRing platform may be a valuable rational adjunct for conferring resilience. © 2016 Elsevier Inc. All rights reserved.

A Robust Electroactive n-Dopable Aromatic Polyketone

NARCIS (Netherlands)

Chiechi, Ryan C.; Sonmez, Gursel; Wudl, Fred

2005-01-01

A new n-dopable polyketone, poly[(5-(2,5-dihexyl-4-(thiophen-2-yl)phenyl)thiophen-2-yl)(4-ketophenyl)methanone] (PTK), is synthesized via Friedel-Crafts acylation. Though insulating in the neutral state, PTK becomes conductive upon electrochemical reduction. The stable, two-electron, fully

Hydroquinone and quinone-grafted porous carbons for highly selective CO2 capture from flue gases and natural gas upgrading

NARCIS (Netherlands)

Wang, J.; Krishna, R.; Yang, J.; Deng, S.

2015-01-01

Hydroquinone and quinone functional groups were grafted onto a hierarchical porous carbon framework via the Friedel-Crafts reaction to develop more efficient adsorbents for the selective capture and removal of carbon dioxide from flue gases and natural gas. The oxygen-doped porous carbons were

46 CFR 180.175 - Survival craft equipment.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft equipment. 180.175 Section 180.175... TONS) LIFESAVING EQUIPMENT AND ARRANGEMENTS Survival Craft Arrangements and Equipment § 180.175 Survival craft equipment. (a) General. Each item of survival craft equipment must be of good quality, and...

46 CFR 117.175 - Survival craft equipment.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft equipment. 117.175 Section 117.175... AND ARRANGEMENTS Survival Craft Arrangements and Equipment § 117.175 Survival craft equipment. (a) General. Each item of survival craft equipment must be of good quality, and efficient for the purpose it...

46 CFR 133.105 - Survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft. 133.105 Section 133.105 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) OFFSHORE SUPPLY VESSELS LIFESAVING SYSTEMS Requirements for All OSVs § 133.105 Survival craft. (a) Each survival craft must be approved and equipped as...

Self-crafting vegetable snacks

NARCIS (Netherlands)

Raghoebar, Sanne; Kleef, van Ellen; Vet, de Emely

2017-01-01

Purpose: The purpose of this paper is to test whether the IKEA-effect (Norton et al., 2012) – better liking for self-crafted products than for identical products crafted by others – can be exploited to increase liking and consumption of vegetable snacks in children. Design/methodology/approach: A

Meaningful work and work engagement : The mediating role of perceived opportunity to craft and job crafting behavior

NARCIS (Netherlands)

Van Wingerden, Jessica; van der Stoep, Joost; Poell, R.F.

2018-01-01

This study examines the impact of meaningful work on employees’ level of work engagement as mediated by perceived opportunities to craft and job crafting. Based on the literature on meaningful work and job crafting, we hypothesize that meaningful work has a positive relationship with an employee’s

Three-dimensional grain mapping by x-ray diffraction contrast tomography and the use of Friedel pairs in diffraction data analysis

DEFF Research Database (Denmark)

Ludwig, W.; Reischig, P.; King, A.

2009-01-01

X-ray diffraction contrast tomography (DCT) is a technique for mapping grain shape and orientation in plastically undeformed polycrystals. In this paper, we describe a modified DCT data acquisition strategy which permits the incorporation of an innovative Friedel pair method for analyzing...

46 CFR 199.261 - Survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft. 199.261 Section 199.261 Shipping COAST... SYSTEMS FOR CERTAIN INSPECTED VESSELS Additional Requirements for Cargo Vessels § 199.261 Survival craft. (a) Each survival craft must be approved and equipped as follows: (1) Each lifeboat must be a totally...

46 CFR 28.120 - Survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Survival craft. 28.120 Section 28.120 Shipping COAST... VESSELS Requirements for All Vessels § 28.120 Survival craft. (a) Except as provided in paragraphs (b) through (h) of this section and 28.305, each vessel must carry the survival craft specified in Table 28...

Anodic Cyclization Reactions and the Mechanistic Strategies That Enable Optimization.

Science.gov (United States)

Feng, Ruozhu; Smith, Jake A; Moeller, Kevin D

2017-09-19

Oxidation reactions are powerful tools for synthesis because they allow us to reverse the polarity of electron-rich functional groups, generate highly reactive intermediates, and increase the functionality of molecules. For this reason, oxidation reactions have been and continue to be the subject of intense study. Central to these efforts is the development of mechanism-based strategies that allow us to think about the reactive intermediates that are frequently central to the success of the reactions and the mechanistic pathways that those intermediates trigger. For example, consider oxidative cyclization reactions that are triggered by the removal of an electron from an electron-rich olefin and lead to cyclic products that are functionalized for further elaboration. For these reactions to be successful, the radical cation intermediate must first be generated using conditions that limit its polymerization and then channeled down a productive desired pathway. Following the cyclization, a second oxidation step is necessary for product formation, after which the resulting cation must be quenched in a controlled fashion to avoid undesired elimination reactions. Problems can arise at any one or all of these steps, a fact that frequently complicates reaction optimization and can discourage the development of new transformations. Fortunately, anodic electrochemistry offers an outstanding opportunity to systematically probe the mechanism of oxidative cyclization reactions. The use of electrochemical methods allows for the generation of radical cations under neutral conditions in an environment that helps prevent polymerization of the intermediate. Once the intermediates have been generated, a series of "telltale indicators" can be used to diagnose which step in an oxidative cyclization is problematic for less successful transformation. A set of potential solutions to address each type of problem encountered has been developed. For example, problems with the initial

46 CFR 117.150 - Survival craft embarkation arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft embarkation arrangements. 117.150 Section... EQUIPMENT AND ARRANGEMENTS Survival Craft Arrangements and Equipment § 117.150 Survival craft embarkation... apparatus when either— (1) The embarkation station for the survival craft is on a deck more than 4.5 meters...

In Search of Craft

Science.gov (United States)

Schwalbe, Michael

2010-01-01

In the spring of 2009, this author asked the director of North Carolina State's Crafts Center to help him find people who might be willing to participate in a project about skill. Bill Wallace, an occasional teacher at the Crafts Center, was one of the people recommended to him. Bill Wallace is a man who can look at a tree and instinctively know…

Brane Craft

Science.gov (United States)

Janson, Siegfried

2017-01-01

A Brane Craft is a membrane spacecraft with solar cells, command and control electronics, communications systems, antennas, propulsion systems, attitude and proximity sensors, and shape control actuators as thin film structures manufactured on 10 micron thick plastic sheets. This revolutionary spacecraft design can have a thickness of tens of microns with a surface area of square meters to maximize area-to-mass ratios for exceptionally low-mass spacecraft. Communications satellites, solar power satellites, solar electric propulsion stages, and solar sails can benefit from Brane Craft design. It also enables new missions that require low-mass spacecraft with exceptionally high delta-V. Active removal of orbital debris from Earth orbit is the target application for this study.

46 CFR 117.130 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Stowage of survival craft. 117.130 Section 117.130... AND ARRANGEMENTS Survival Craft Arrangements and Equipment § 117.130 Stowage of survival craft. (a) Each survival craft must be: (1) Secured to the vessel by a painter with a float-free link permanently...

46 CFR 199.130 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Stowage of survival craft. 199.130 Section 199.130... craft. (a) General. Each survival craft must be stowed— (1) As close to the accommodation and service spaces as possible; (2) So that neither the survival craft nor its stowage arrangements will interfere...

46 CFR 180.130 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Stowage of survival craft. 180.130 Section 180.130... TONS) LIFESAVING EQUIPMENT AND ARRANGEMENTS Survival Craft Arrangements and Equipment § 180.130 Stowage of survival craft. (a) Each survival craft must be: (1) Secured to the vessel by a painter with a...

A simple, effective, green method for regioselective 3-acylation of unprotected indoles

DEFF Research Database (Denmark)

Tran, Phuong Huong; Tran, Hai N.; Hansen, Poul Erik

2015-01-01

A fast and green method is developed for regioselective acylation of indoles in the 3-position without the need for protection of the NH position. The method is based on Friedel-Crafts acylation using acid anhydrides. The method has been optimized, and Y(OTf)3 in catalytic amounts is found...

46 CFR 133.130 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Stowage of survival craft. 133.130 Section 133.130... SYSTEMS Requirements for All OSVs § 133.130 Stowage of survival craft. (a) General. Each survival craft must be stowed as follows: (1) Each survival craft must be as close to the accommodation and service...

Leading to Crafting: The Relation Between Leadership Perception and Nurses' Job Crafting.

Science.gov (United States)

Esteves, Tiago; Pereira Lopes, Miguel

2017-06-01

Whenever individuals adapt their jobs to make them closer of their personal preferences, they are performing job crafting. This study aims to investigate if the way nurses perceive their leaders' behaviors is related with job crafting development. To do so, a quantitative analysis was conducted among a group of 325 Portuguese nurses. Results indicate that the perception of an empowering leader was found to be strongly related with the increase of challenges in the work environment, and with the development of stronger relations with direct managers and co-workers, which are two job crafting dimensions. The perception of a directive leader was found to be positively related with the avoidance of performing hindering tasks. Strengthening relations with direct managers and co-workers was found to be particularly related to leadership perception. Theoretical and practical implications are discussed.

46 CFR 28.310 - Launching of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Launching of survival craft. 28.310 Section 28.310... Operate With More Than 16 Individuals on Board § 28.310 Launching of survival craft. A gate or other... each survival craft which weighs more than 110 pounds (489 Newtons), to allow the survival craft to be...

The meanings of craft to an occupational therapist.

Science.gov (United States)

Harris, Emma

2008-06-01

Craft was the first therapeutic occupation of occupational therapy. Since the early days of the profession, the value of craft in practice is a topic that has been discussed with fluctuating interest. Recent discussions by occupational therapists have reinforced that although craft is relevant to occupational therapy, there are uncertainties about its place in contemporary practice. Presently, scholars have identified that occupation is both the center of human experience and the core of our profession. Therefore, this study aimed to begin to clarify the meaning of craft to practice today by gaining a deep understanding of the meanings that one occupational therapist attributes to craft. Using narrative inquiry, data were gathered through a conversation held between the research participant and myself. A reflexive journal was also kept to support this data gathering process. Narrative analysis enabled intimate engagement with the data and the emergence of themes and sub-themes. The findings, in the form of an interpretive story, suggest first, that craft-making has therapeutic value; second, that reasoning about the therapeutic use of craft is similar to reasoning about other therapeutic activities; and third, that personal experience with craft-making can influence the selection of craft as therapeutic media. From this study, further research into the impact personal and professional experiences can have on choice of therapeutic media and an analysis of the sociopolitical context of the meanings that occupational therapists attribute to craft-making is suggested.

Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

Science.gov (United States)

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

33 CFR 401.58 - Pleasure craft scheduling.

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 3 2010-07-01 2010-07-01 false Pleasure craft scheduling. 401.58... OF TRANSPORTATION SEAWAY REGULATIONS AND RULES Regulations Seaway Navigation § 401.58 Pleasure craft scheduling. (a) The transit of pleasure craft shall be scheduled by the traffic controller or the officer in...

47 CFR 80.1095 - Survival craft equipment.

Science.gov (United States)

2010-10-01

... 47 Telecommunication 5 2010-10-01 2010-10-01 false Survival craft equipment. 80.1095 Section 80... for Ship Stations § 80.1095 Survival craft equipment. (a) At least three two-way VHF radiotelephone... they can be rapidly placed in any survival craft other than life rafts required by Regulation III/26.1...

Crafts and Craft Education as Expressions of Cultural Heritage: Individual Experiences and Collective Values among an International Group of Women University Students

Science.gov (United States)

Kokko, Sirpa; Dillon, Patrick

2011-01-01

This paper explores relationships between crafts, craft education and cultural heritage as reflected in the individual experiences and collective values of fifteen female university students of different nationalities. The students (all trainee teachers) were following a course in crafts and craft education as part of an International Study…

Synthesis of a new scintillator 2-phenyl-5(4-p-terphenylyl)Oxazole

International Nuclear Information System (INIS)

Dhane, D.L.; Gaiki, G.M.

1979-01-01

Friedel-Crafts reaction between hippuryl chloride and p-terphenyl gave benzoylaminomethyl-(4-p-terphenylyl) ketone (II) which on cyclodehydration gave hitherto unreported 2-phenyl-5-(4-p-terphenylyl) oxazole (I). IR, UV absorption and fluorescence spectra of I have been recorded. The performance of I as a scintillator solute has been tested. (auth.)

Simultaneous formation and detection of the reaction product of solid-state aspartame sweetener by FT-IR/DSC microscopic system.

Science.gov (United States)

Lin, S Y; Cheng, Y D

2000-10-01

The solid-state stability of aspartame hemihydrate (APM) sweetener during thermal treatment is important information for the food industry. The present study uses the novel technique of Fourier transform infrared microspectroscopy equipped with differential scanning calorimetry (FT-IR/DSC microscopic system) to accelerate and determine simultaneously the thermal-dependent impurity formation of solid-state APM. The results indicate a dramatic change in IR spectra from 50, 110 or 153 degrees C, which was respectively attributed to the onset temperature of water evaporation, dehydration and cyclization processes. It is suggested that the processes of dehydration and intramolecular cyclization occurred in the solid-state APM during the heating process. As an impurity, 3-carboxymethyl-6-benzyl-2,5-diketopiperazine (DKP) degraded from solid state APM via intramolecular cyclization and liberation of methanol. This was evidenced by this novel FT-IR/DSC microscopic system in a one-step procedure.

46 CFR 180.200 - Survival craft-general.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-general. 180.200 Section 180.200 Shipping...) LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 180.200 Survival craft—general. (a) Each survival craft required on a vessel by this part must meet one of the following: (1) For an...

46 CFR 28.130 - Survival craft equipment.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Survival craft equipment. 28.130 Section 28.130 Shipping... INDUSTRY VESSELS Requirements for All Vessels § 28.130 Survival craft equipment. (a) General. Each item of survival craft equipment must be of good quality, effective for the purpose it is intended to serve, and...

Ruthenium-catalyzed cyclization of N-carbamoyl indolines with alkynes: an efficient route to pyrroloquinolinones.

Science.gov (United States)

Manoharan, Ramasamy; Jeganmohan, Masilamani

2015-09-21

A regioselective synthesis of substituted pyrroloquinolinones via a ruthenium-catalyzed oxidative cyclization of substituted N-carbamoyl indolines with alkynes is described. The cyclization reaction was compatible with various symmetrical and unsymmetrical alkynes including substituted propiolates. Later, we performed the aromatization of pyrroloquinolinones into indole derivatives in the presence of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ).

Fungal decay of traditional fishing craft

Digital Repository Service at National Institute of Oceanography (India)

Gupta, R.

The artisanal fishermen land major portion of fish caught in India, employing traditional fishing craft and methods. These craft are built of indigenous wood and undergo rapid biodeterioration causing great economic loss. Soft-rot fungi...

New Palladium-Catalyzed Domino Reaction with Intramolecular Ring Closure of an N-(2-Chloro-3-heteroaryl) arylamide: First Synthesis of Oxazolo[4,5-b] pyrazines

DEFF Research Database (Denmark)

Demmer, Charles S.; Hansen, Jacob C.; Kehler, Jan

2014-01-01

The synthesis of novel planar heterocycles is at the heart of basic research as such scaffolds constitute key building blocks in important diverse areas of research: drug discovery, material sciences, and pesticides. The well-known benzoxazole is often contained in drug candidates but tweaking its...... lipophilicity and target interaction points are often desired. In this respect, the oxazolo[4,5-b]pyrazine is an attractive heterocyclic scaffold as it possesses increased water solubility as well as two additional hydrogen bonding acceptors. We here report a new Pd(II)-catalyzed domino reaction comprising...... the first Pd(II)-assisted intramolecular cyclization of an N-(2-chloro-3-heteroaryl)arylamide and validate its value by application to the first synthesis of 2-substituted oxazolo[4,5-b]pyrazines. We demonstrate that a bidentate phosphorus ligand as well as the presence of an aromatic nitrogen atom...

Tandem dinucleophilic cyclization of cyclohexane-1,3-diones with pyridinium salts

Directory of Open Access Journals (Sweden)

Mostafa Kiamehr

2013-06-01

Full Text Available The cyclization of cyclohexane-1,3-diones with various substituted pyridinium salts afforded functionalized 8-oxa-10-aza-tricyclo[7.3.1.02,7]trideca-2(7,11-dienes. The reaction proceeds by regioselective attack of the central carbon atom of the 1,3-dicarbonyl unit to 4-position of the pyridinium salt and subsequent cyclization by base-assisted proton migration and nucleophilic addition of the oxygen atom to the 2-position, as was elucidated by DFT computations. Fairly extensive screening of bases and additives revealed that the presence of potassium cations is essential for formation of the product.

33 CFR 84.24 - High-speed craft.

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false High-speed craft. 84.24 Section... RULES ANNEX I: POSITIONING AND TECHNICAL DETAILS OF LIGHTS AND SHAPES § 84.24 High-speed craft. (a) The masthead light of high-speed craft with a length to breadth ratio of less than 3.0 may be placed at a...

Proline-catalysed asymmetric ketol cyclizations: The template ...

Indian Academy of Sciences (India)

Unknown

Abstract. A modified template mechanism based on modelling studies of energy minimised complexes is presented for the asymmetric proline-catalysed cyclization of triketones 1, 2 and 3 to the 2S,3S-ketols. 1a, 2a and 3a respectively. The template model involves a three-point contact as favoured in enzyme– substrate ...

Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

KAUST Repository

Hu, Pan

2016-03-11

The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

Thermally Induced Denitrogenative Annulation for the Synthesis of Dihydroquinolinimines and Chroman-4-imines.

Science.gov (United States)

Chou, Chih-Hung; Chen, Ying-Yu; Rajagopal, Basker; Tu, Hsiu-Chung; Chen, Kuan-Lin; Wang, Sheng-Fu; Liang, Chien-Fu; Tyan, Yu-Chang; Lin, Po-Chiao

2016-03-04

A rapid growth in synthetic methods for the preparation of diverse organic molecules using N-sulfonyl-1,2,3-triazoles is of great interest in organic synthesis. Transition metals are generally used to activate the α-imino diazo intermediates. Metal-free methods have not been studied in detail, but can be a good complement to transition metal catalysis in the mild reaction conditions. We herein report a novel method for the preparation of 2,3-dihydroquinolin-4-imine and chroman-4-imine analogs from their corresponding N-sulfonyl-1,2,3-triazoles in the absence of metal catalysts. To achieve intramolecular annulation, the introduction of an electron-donating group is required at the meta position of N-sulfonyl-1,2,3-triazole methyl anilines. The inclusion of tailored substituents on the aniline moieties and nitrogen atoms enhances the nucleophilicity of the phenyl π-electrons, thus allowing them to undergo a Friedel-Crafts-type reaction with the highly electrophilic ketenimines. This metal-free method was carefully optimized to generate a variety of dihydroquinolin-4-imines and chroman-4-imines in moderate-to-good yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure

KAUST Repository

Hu, Pan; Lee, Sangsu; Park, Kyu Hyung; Das, Soumyajit; Herng, Tun Seng; Goncalves, Theo; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan

2016-01-01

The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl or pentafluorophenyl substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability under the ambient environment while OZI-M has high reactivity and can be easily oxidized to a dioxo-product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F and 15.

Chain elongation and cyclization in type III PKS DpgA.

Science.gov (United States)

Wu, Hai-Chen; Li, Yi-San; Liu, Yu-Chen; Lyu, Syue-Yi; Wu, Chang-Jer; Li, Tsung-Lin

2012-04-16

Chain elongation and cyclization of precursors of dihydroxyphenylacetyl-CoA (DPA-CoA) catalyzed by the bacterial type III polyketide synthase DpgA were studied. Two labile intermediates, di- and tri-ketidyl-CoA (DK- and TK-CoA), were proposed and chemically synthesized. In the presence of DpgABD, each of these with [(13)C(3)]malonyl-CoA (MA-CoA) was able to form partially (13)C-enriched DPA-CoA. By NMR and MS analysis, the distribution of (13)C atoms in the partially (13)C-enriched DPA-CoA shed light on how the polyketide chain elongates and cyclizes in the DpgA-catalyzed reaction. Polyketone intermediates elongate in a manner different from that which had been believed: two molecules of DK-CoA, or one DK-CoA plus one acetoacetyl-CoA (AA-CoA), but not two molecules of AA-CoA can form one molecule of DPA-CoA. As a result, polyketidyl-CoA serves as both the starter and extender, whereas polyketone-CoA without the terminal carboxyl group can only act as an extender. The terminal carboxyl group is crucial for the cyclization that likely takes place on CoA. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Excited state Intramolecular Proton Transfer in Anthralin

DEFF Research Database (Denmark)

Møller, Søren; Andersen, Kristine B.; Spanget-Larsen, Jens

1998-01-01

Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results in an unus......Quantum chemical calculations performed on anthralin (1,8-dihydroxy-9(10H)-anthracenone) predict the possibility of an excited-state intramolecular proton transfer process. Fluorescence excitation and emission spectra of the compound dissolved in n-hexane at ambient temperature results......, associated with an excited-state intramolecular proton transfer process....

Efficient Lewis Acid Ionic Liquid-Catalyzed Synthesis of the Key Intermediate of Coenzyme Q10 under Microwave Irradiation

Directory of Open Access Journals (Sweden)

Thomas Efferth

2010-12-01

Full Text Available An efficient synthesis of a valuable intermediate of coenzyme Q10 by microwave-assisted Lewis acidic ionic liquid (IL-catalyzed Friedel-Crafts alkylation is reported. The acidity of six [Etpy]BF4-based ionic liquids was characterized by means of the FT-IR technique using acetonitrile as a molecular probe. The catalytic activities of these ionic liquids were correlated with their Lewis acidity. With increasing Lewis acid strength of the ionic liquids, their catalytic activity in the Friedel-Crafts reaction increased, except for [Etpy]BF4-AlCl3. The effects of the reaction system, the molar fraction of Lewis acid in the Lewis acid ILs and heating techniques were also investigated. Among the six Lewis acid ionic liquids tested [Etpy]BF4-ZnCl2 showed the best catalytic activity, with a yield of 89% after a very short reaction time (150 seconds. This procedure has the advantages of higher efficiency, better reusability of ILs, energy conservation and eco-friendliness. The method has practical value for preparation of CoQ10 on an industrial scale.

Ternary iron(II) complex with an emissive imidazopyridine arm from Schiff base cyclizations and its oxidative DNA cleavage activity.

Science.gov (United States)

Mukherjee, Arindam; Dhar, Shanta; Nethaji, Munirathinam; Chakravarty, Akhil R

2005-01-21

The ternary iron(II) complex [Fe(L')(L")](PF6)3(1) as a synthetic model for the bleomycins, where L' and L" are formed from metal-mediated cyclizations of N,N'-(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine)(L), is synthesized and structurally characterized by X-ray crystallography. In the six-coordinate iron(ii) complex, ligands L' and L" show tetradentate and bidentate chelating modes of bonding. Ligand L' is formed from an intramolecular attack of the alcoholic OH group of L to one imine moiety leading to the formation of a stereochemically constrained five-membered ring. Ligand L" which is formed from an intermolecular reaction involving one imine moiety of L and pyridine-2-carbaldehyde has an emissive cationic imidazopyridine pendant arm. The complex binds to double-stranded DNA in the minor groove giving a Kapp value of 4.1 x 10(5) M(-1) and displays oxidative cleavage of supercoiled DNA in the presence of H2O2 following a hydroxyl radical pathway. The complex also shows photo-induced DNA cleavage activity on UV light exposure involving formation of singlet oxygen as the reactive species.

Bergman cyclization in polymer chemistry and material science.

Science.gov (United States)

Xiao, Yuli; Hu, Aiguo

2011-11-01

Bergman cyclization of enediynes, regarded as a promising strategy for anticancer drugs, now finds its own niche in the area of polymer chemistry and material science. The highly reactive aromatic diradicals generated from Bergman cyclization can undergo polymerization acting as either monomers or initiators of other vinyl monomers. The former, namely homopolymerization, leads to polyphenylenes and polynaphthalenes with excellent thermal stability, good solubility, and processability. The many remarkable properties of these aromatic polymers have further endowed them to be manufactured into carbon-rich materials, e.g., glassy carbons and carbon nanotubes. Whereas used as initiators, enediynes provide a novel resource for high molecular weight polymers with narrow polydispersities. The aromatic diradicals are also useful for introducing oligomers or polymers onto pristine carbonous nanomaterials, such as carbon nano-onions and carbon nanotubes, to improve their dispersibility in organic solvents and polymer solutions. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

46 CFR 180.150 - Survival craft embarkation arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft embarkation arrangements. 180.150 Section... (UNDER 100 GROSS TONS) LIFESAVING EQUIPMENT AND ARRANGEMENTS Survival Craft Arrangements and Equipment § 180.150 Survival craft embarkation arrangements. (a) A launching appliance approved under approval...

When Does Job Crafting Generalize To Home Crafting

DEFF Research Database (Denmark)

Demerouti, Evangelina; De Gieter, Sara; Haun, Verena

Purpose: Job crafting represents attempts to expand (seeking resources or challenges) or reduce (reducing demands) the scope of the job such that it fits better to one’s preferences. The spillover hypothesis suggests that individuals generalize behaviors at work also to the non-work domain...

Implementing digital crafting : developing

DEFF Research Database (Denmark)

Tamke, Martin; Ramsgaard Thomsen, Mette

2010 in the Danish Design Centre in Copenhagen. The exhibition presents 18 designers, architects and people from the crafts that have an innovative take on the future questions of sustainability, new materials and technology. Their products challenge traditional Danish Design and are yet interconnected...... in the countries traits and the way they design. Curated by the Danish Design Centre, The Danish Architectural Centre and the Danish Crafts Organisation groups of three from the different disciplines were identified in 6 scenarios with distinct expression....

46 CFR 185.518 - Inflatable survival craft placards.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Inflatable survival craft placards. 185.518 Section 185... 100 GROSS TONS) OPERATIONS Preparations for Emergencies § 185.518 Inflatable survival craft placards. (a) Every vessel equipped with an inflatable survival craft must have approved placards or other...

An improved approach to exchange non-rectangular departments in CRAFT algorithm

OpenAIRE

Esmaeili Aliabadi, Danial; Pourghannad, Behrooz

2012-01-01

In this Paper, an algorithm which improves CRAFT algorithm’s efficacy is developed. CRAFT is an algorithm widely used to solve facility layout problems. Our proposed method, named Plasma, can be used to improve CRAFT results. In this note, Plasma algorithm is tested in several sample problems. The comparison between Plasma and classic CRAFT and also Micro-CRAFT indicates that Plasma is successful in cost reduction in comparison with CRAFT and Micro-CRAFT.

47 CFR 97.215 - Telecommand of model craft.

Science.gov (United States)

2010-10-01

... 47 Telecommunication 5 2010-10-01 2010-10-01 false Telecommand of model craft. 97.215 Section 97... AMATEUR RADIO SERVICE Special Operations § 97.215 Telecommand of model craft. An amateur station transmitting signals to control a model craft may be operated as follows: (a) The station identification...

46 CFR 122.518 - Inflatable survival craft placards.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Inflatable survival craft placards. 122.518 Section 122... Preparations for Emergencies § 122.518 Inflatable survival craft placards. (a) Every vessel equipped with an inflatable survival craft must have approved placards or other cards containing instructions for launching...

46 CFR 108.530 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Stowage of survival craft. 108.530 Section 108.530... AND EQUIPMENT Lifesaving Equipment § 108.530 Stowage of survival craft. (a) General. Each survival craft required to be served by a launching appliance or marine evacuation system must be stowed as...

46 CFR 28.125 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Stowage of survival craft. 28.125 Section 28.125... FISHING INDUSTRY VESSELS Requirements for All Vessels § 28.125 Stowage of survival craft. (a) Each..., inflatable buoyant apparatus, and any auxiliary craft used in their place, must be kept readily accessible...

To craft or not to craft : The relationships between regulatory focus, job crafting and work outcomes

NARCIS (Netherlands)

Brenninkmeijer, Veerle; Hekkert-Koning, Marleen

2015-01-01

Purpose – The purpose of this paper is to examine relationships between regulatory focus, job crafting, work engagement and perceived employability. Regulatory focus theory distinguishes between promotion-focused individuals, who strive for growth and development, and preventionfocussed individuals,

Epimerization-free C-terminal peptide activation, elongation and cyclization

NARCIS (Netherlands)

Popović, S.

2015-01-01

C-terminal peptide activation and cyclization reactions are generally accompanied with epimerization (partial loss of C‐terminal stereointegrity). Therefore, the focus of this thesis was to develop epimerization-free methods for C-terminal peptide activation to enable C-terminal peptide elongation

The craft of intensive care medicine.

Science.gov (United States)

Carmel, Simon

2013-06-01

The practice of medicine is often represented as a dualism: is medicine a 'science' or an 'art'? This dualism has been long-lasting, with evident appeal for the medical profession. It also appears to have been rhetorically powerful, for example in enabling clinicians to resist the encroachment of 'scientific' evidence-based medicine into core areas of medical work such as individual clinical judgement. In this article I want to make the case for a more valid conceptualisation of medical practice: that it is a 'craft' activity. The case I make is founded on a theoretical synthesis of the concept of craft, combined with an analysis of ethnographic observations of routine medical practice in intensive care. For this context the craft aspects of medical work can be seen in how biomedical and other types of knowledge are used in practice, the embodied skills and practical judgement of practitioners and the technological and material environment. These aspects are brought together in two conceptual dimensions for 'craft': first, the application of knowledge; second, interaction with the material world. Some practical and political implications of a 'craft' metaphor for medical practice are noted. © 2013 The Author. Sociology of Health & Illness © 2013 Foundation for the Sociology of Health & Illness/John Wiley & Sons Ltd.

46 CFR 28.805 - Launching of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Launching of survival craft. 28.805 Section 28.805... FISHING INDUSTRY VESSELS Aleutian Trade Act Vessels § 28.805 Launching of survival craft. In addition to the survival craft requirements in subpart B, each vessel must have a gate or other opening in the...

46 CFR 199.230 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Stowage of survival craft. 199.230 Section 199.230... Stowage of survival craft. (a) To meet the requirements of § 199.130(b)(1), each lifeboat on a passenger... height of a survival craft must take into account the vessel's escape provisions, the vessel's size, and...

46 CFR 199.290 - Stowage of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Stowage of survival craft. 199.290 Section 199.290... of survival craft. (a) To meet the requirements of § 199.130(b)(1), each lifeboat— (1) On a cargo... required under § 199.261(e), no stowage position or muster and embarkation station for a survival craft on...

46 CFR 108.540 - Survival craft muster and embarkation arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft muster and embarkation arrangements. 108... OFFSHORE DRILLING UNITS DESIGN AND EQUIPMENT Lifesaving Equipment § 108.540 Survival craft muster and... craft muster station and embarkation station for a survival craft which is boarded before it is launched...

Job Crafting, Employee Well-being, and Quality of Care.

Science.gov (United States)

Yepes-Baldó, Montserrat; Romeo, Marina; Westerberg, Kristina; Nordin, Maria

2018-01-01

The main objective is to study the effects of job crafting activities of elder care and nursing home employees on their perceived well-being and quality of care in two European countries, Spain and Sweden. The Job Crafting, the General Health, and the Quality of Care questionnaires were administered to 530 employees. Correlations and hierarchical regression analyses were performed. Results confirm the effects of job crafting on quality of care ( r = .291, p employees' well-being ( r = .201, p well-being in Spain and Sweden and with quality of care in Spain. On the contrary, in Sweden, the relationship between job crafting and well-being was not linear. Job crafting contributes significantly to employees' and residents' well-being. Management should promote job crafting to co-create meaningful and productive work. Cultural effects are proposed to explain the differences found.

Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

Directory of Open Access Journals (Sweden)

Michael Gurry

2014-09-01

Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

47 CFR 80.223 - Special requirements for survival craft stations.

Science.gov (United States)

2010-10-01

... 47 Telecommunication 5 2010-10-01 2010-10-01 false Special requirements for survival craft... requirements for survival craft stations. (a) Survival craft stations capable of transmitting on: (1) 2182 kHz... operate with A3E or A3N emission. (b) Survival craft stations must be able to receive the frequency and...

Employees’ perceived opportunities to craft and in-role performance : The mediating role of job crafting and work engagement

NARCIS (Netherlands)

Van Wingerden, Jessica; Poell, R.F.

2017-01-01

The present study was designed to gain knowledge of the relationship between employees' perceived opportunities to craft, their actual job crafting behavior and, in line with JD-R theory, subsequently their work engagement and performance. Although scholars have suggested that employees' perceived

Microwave-assisted reductive cyclization: An easy entry to the indoloquinolines and spiro[2H-indole-2,30-oxindole].

Digital Repository Service at National Institute of Oceanography (India)

Parvatkar, P.T.; Majik, M.S.

and 15 can be synthesized from a common intermediate 16 via reductive cyclization reaction. The key intermediate 16 in turn can be obtained by Wittig reaction of (2-nitrobenzyl)triphenylphosphonium bromide with isatin. Hence compound 16 could... be considered as an advance intermediate for preparation of alkaloids in present work. N N 1 N H N 11 N H N 15NH O O2NN H O O + PPh3 NO2 + Br- 16 17 18 N N13 Wittig reaction reductive cyclization N-Methylation N-Methylation reductive cyclization Scheme 1...

Diverse orientations in craft education: Student teachers’ conceptions and perceptions

Directory of Open Access Journals (Sweden)

Tarja Kröger

2016-03-01

Full Text Available Craft education in Finland has been in a state of change. The concept of a holistic craft process was implemented in the National Core Curriculum in 2004 and the new Curriculum from 2014 strengthened it. Craft and holistic craft is not one unity but includes several orientations. This study aims to research student teachers’ conceptions and perceptions about diverse orientations and the necessity of craft education before they begin their studies in craft pedagogy. Given that the beliefs that student teachers bring to professional learning play a pivotal role in influencing what they can learn from teacher education, they are a subject worthy of investigation. The data consists of on‐line questionnaire answers by student teachers (N=113 at the University of Finland in teacher education in 2014. The on-line questionnaire was answered at the beginning of a basic course in textile craft education at an early stage of their teacher studies. Findings suggest that student teachers conceive of craft education primarily as model-oriented and skill-oriented rather than design-oriented and expression-oriented. Student teachers think that craft education is needed at school, but explanations are not very diverse. The findings of this study can be useful in the process of developing teacher education programmes.

Metal organic frameworks as heterogeneous catalysts for the production of fine chemicals

Czech Academy of Sciences Publication Activity Database

Dhakshinamoorthy, A.; Opanasenko, Maksym; Čejka, Jiří; Garcia, H.

2013-01-01

Roč. 3, č. 10 (2013), s. 2509-2540 ISSN 2044-4753 R&D Projects: GA ČR GBP106/12/G015 Grant - others:European Commission(XE) FP7/2007-2013, contract 228862 Institutional support: RVO:61388955 Keywords : FRIEDEL-CRAFTS ACYLATION * CALCIUM-CHANNEL BLOCKERS * LIQUID-PHASE OXIDATIONS Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.760, year: 2013

46 CFR 108.525 - Survival craft number and arrangement.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft number and arrangement. 108.525 Section... UNITS DESIGN AND EQUIPMENT Lifesaving Equipment § 108.525 Survival craft number and arrangement. (a... arrangement of survival craft: (1) Lifeboats with an aggregate capacity to accommodate the total number of...

Double reductive cyclization: A facile synthesis of the indoloquinoline alkaloid cryptotackieine

Digital Repository Service at National Institute of Oceanography (India)

Parvatkar, P.T.; Parameswaran, P.S.; Tilve, S.G.

A new synthesis of the indoloquinoline alkaloid cryptotackieine, isolated from Cryptolepis sanguinolenta, is described which involves a Perkin reaction, a tandem double reduction-double cyclization reaction followed by regioselective methylation...

75 FR 50773 - Invocation of Sunken Military Craft Act

Science.gov (United States)

2010-08-17

... Military Craft Act AGENCY: Coast Guard, DHS. ACTION: Notice. SUMMARY: The Coast Guard is announcing that a C-130 aircraft which crashed off the coast of California is a sunken military craft. It is therefore... is announcing that the wreckage of CG 1705 is a sunken military craft, and is therefore protected...

29 CFR 1202.8 - Hearings on craft or class.

Science.gov (United States)

2010-07-01

... 29 Labor 4 2010-07-01 2010-07-01 false Hearings on craft or class. 1202.8 Section 1202.8 Labor... craft or class. In the event the contesting parties or organizations are unable to agree on the..., specifying the craft or class of employees eligible to participate in the designation of representatives. ...

Modelling job crafting behaviours: Implications for work engagement

OpenAIRE

Bakker, Arnold B.; Rodríguez-Muñoz, Alfredo; Sanz Vergel, Ana Isabel

2016-01-01

In this study among 206 employees (103 dyads), we followed the job demands–resources approach of job crafting to investigate whether proactively changing one’s work environment influences employee’s (actor’s) own and colleague s (partner’s) work engagement. Using social cognitive theory, we hypothesized that employees would imitate each other’s job crafting behaviours, and therefore influence each other’s work engagement. Results showed that the crafting of social and structural job resources...

46 CFR 117.204 - Survival craft-vessels operating on coastwise routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-vessels operating on coastwise routes... PASSENGERS LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 117.204 Survival craft... allowed, the following survival craft requirements apply when not engaged in an overnight voyage: (1...

Salen- Zr(IV) complex grafted into amine-tagged MIL-101(Cr) as a robust multifunctional catalyst for biodiesel production and organic transformation reactions

Science.gov (United States)

Hassan, Hassan M. A.; Betiha, Mohamed A.; Mohamed, Shaimaa K.; El-Sharkawy, E. A.; Ahmed, Emad A.

2017-08-01

The synthesis of metal-organic frameworks (MOFs), porous coordination polymers with functional groups has received immense interest due to the functional groups can offer desirable properties and allow post-synthetic modification. Herein, for the first time, Zr(IV)-Sal Schiff base complex incorporated into amino-functionalized MIL-101(Cr) framework by salicylaldehyde condensing to amino group, and coordinating Zr(IV) ion have been successfully synthesized. The worthiness of the synthesized material as a catalyst has been examined for the esterification of oleic acid (free fatty acid) with methanol producing biodiesel (methyl oleate), Knoveonagel condensation reaction of aldehydes and Friedel-Crafts acylation of anisole. Our findings demonstrated that Salen-Zr(IV) grafted to framework of NH2-MIL-101(Cr) as a solid acid catalyst exhibited distinct catalytic performance for the production of biodiesel by esterification of oleic acid with methanol, Knoveonagel condensation and Friedel-Crafts acylation. These could be attributed to high surface area which allow high distribution of Zr(IV) species lead to a sufficient contact with the reactants species. Furthermore, the catalyst showed excellent recycling efficiency due to the strong interaction between the Zr(IV) ions and chelating groups in the NH2-MIL-101(Cr)-Sal.

32 CFR 700.872 - Ships and craft in drydock.

Science.gov (United States)

2010-07-01

... 32 National Defense 5 2010-07-01 2010-07-01 false Ships and craft in drydock. 700.872 Section 700... Special Circumstances/ships in Naval Stations and Shipyards § 700.872 Ships and craft in drydock. (a) The... ship or craft, not in commission, is in a naval drydock, the provisions of this article shall apply...

Labeling, stability and biodistribution studies of {sup 99m}Tc-cyclized Tyr{sup 3}-octreotate derivatives

Energy Technology Data Exchange (ETDEWEB)

Bigott-Hennkens, Heather M. [Department of Veterinary Medicine and Surgery, University of Missouri, Columbia, MO 65211 (United States); Dannoon, Shorouk F.; Noll, Samantha M. [Department of Chemistry, University of Missouri, Columbia, MO 65211 (United States); Ruthengael, Varyanna C. [Research Service, Harry S Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States); Jurisson, Silvia S., E-mail: JurissonS@missouri.ed [Department of Chemistry, University of Missouri, Columbia, MO 65211 (United States); Lewis, Michael R., E-mail: LewisMic@missouri.ed [Department of Veterinary Medicine and Surgery, University of Missouri, Columbia, MO 65211 (United States); Research Service, Harry S Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States)

2011-05-15

Introduction: To probe the interplay between radiotracer stability and somatostatin receptor affinity, Tyr{sup 3}-octreotate and six variations of its peptide sequence, for which the Re-cyclized products were previously reported, were radiolabeled with {sup 99m}Tc and investigated for their in vitro stability. Methods: Radiolabeling of the peptides was effected by ligand exchange from {sup 99m}Tc-glucoheptonate, and the desired products were purified by radio-RP-HPLC. The in vitro stability in phosphate buffered saline, mouse serum and cysteine solutions at physiological temperature and pH for all seven {sup 99m}Tc-cyclized peptides was determined by radio-RP-HPLC and radio-TLC. Normal CF-1 mouse biodistribution studies were performed for three of the {sup 99m}Tc-cyclized peptides. Results: Based on the fully characterized Re-cyclized peptide analogues, four {sup 99m}Tc-coordination motifs were proposed for the {sup 99m}Tc-cyclized peptides. Technetium-99m-cyclized Tyr{sup 3}-octreotate derivatives with N{sub 2}S{sub 2} metal coordination modes and large metal ring sizes were susceptible to oxidation and loss of {sup 99m}Tc in the form of {sup 99m}TcO{sub 4}{sup -}, as evidenced by their instability in the various solutions under physiological conditions (15-58% intact at 24 h). As anticipated, the addition of a third cysteine to the sequence stabilized the {sup 99m}Tc metal coordination, and peptides with NS{sub 3} coordination modes remained >85% intact out to 24 h. No significant differences were observed in the biodistribution studies performed with three peptides of varying stabilities. Conclusions: Improvements in stability were not sufficient to outweigh the low somatostatin receptor affinity for the peptides in this study. Further improvements in the peptide sequence and/or metal coordination are needed to result in a radiodiagnostic/radiotherapeutic pair for targeting the somatostatin receptor.

Photodecarboxylative Cyclizations of ω-Phthalimido-para-phenoxy Carboxylates

Energy Technology Data Exchange (ETDEWEB)

Kim, Ae Rhan; Lee, Younsik; Yoo, Dong Jin [Chonbuk National Univ., Jeonju (Korea, Republic of); Cho, Hyunseung [Seonam Univ., Namwon (Korea, Republic of)

2012-10-15

The chemistry of electronically-excited phthalimides is dictated by electron and/or hydrogen transfer reactions. The photochemistry of phthalimides has been intensively studied, and numerous synthetically useful transformations with high chemical and quantum yields have been developed. 3 Among the synthetic applications, intra- and intermolecular photodecarboxylation (PDC) of ω-phthalimidoalkyl carboxylates has been developed by Griesbeck and coworkers as a versatile pathway to medium- and large-ring heterocycles. Model reactions were further realized on macro- and micro-scales. We recently described PDC cyclizations of ω-phthalimidoalkynoates to produce macrocyclic alkynes with ring-sizes up to 17. In recent study, we expanded the portfolio of this reaction and investigated the photochemistry of related aryl-linked phthalimides in Scheme 1. Based on these approaches, we demonstrated that ω-phthalimido-ortho/meta-phenoxy carboxylates undergo efficient PDC cyclizations. While the yields of ω-phthalimido-ortho-phenoxy carboxylates steadily decreased with increasing chain-length and the maximum yield of the 6-membered product was obtained in 75%, the yields of meta-phenoxy carboxylates steadily increased with increasing chain-length and the extended 16-membered product was subsequently obtained in 48% yield.

CRAFT

DEFF Research Database (Denmark)

Gammelgaard Nielsen, Anders

2012-01-01

At the Aarhus School of Architecture, Associate Professor Anders Gammelgaard has erected a solid wood construction, based on traditional craftsmanship. The entire structure is made of heavy oak timber that is joined together using the old techniques of tongue and groove and dowels. The motivation......-air museums, as a performing art in front of an audience. In this article the author discusses the importance of craft and craftsmanship in contemporary architecture in relation to its users....

Reverse cope elimination of hydroxylamines and alkenes or alkynes: theoretical investigation of tether length and substituent effects.

Science.gov (United States)

Krenske, Elizabeth H; Davison, Edwin C; Forbes, Ian T; Warner, Jacqueline A; Smith, Adrian L; Holmes, Andrew B; Houk, K N

2012-02-01

Quantum mechanical calculations have been used to study the intramolecular additions of hydroxylamines to alkenes and alkynes ("reverse Cope eliminations"). In intermolecular reverse Cope eliminations, alkynes are more reactive than alkenes. However, competition experiments have shown that tethering the hydroxylamine to the alkene or alkyne can reverse the reactivity order from that normally observed. The exact outcome depends on the length of the tether. In agreement with experiment, a range of density functional theory methods and CBS-QB3 calculations predict that the activation energies for intramolecular reverse Cope eliminations follow the order 6-exo-dig hydroxylamine and alkyne. Cyclization onto an alkene in the 5-exo-trig fashion incurs slightly less tether strain than a 6-exo-dig alkyne cyclization, but its activation energy is higher because the hydroxylamine fragment must distort more before the TS is reached. If the alkene terminus is substituted with two methyl groups, the barrier becomes so much higher that it is also disfavored compared to the 5- and 7-exo-dig cyclizations. © 2012 American Chemical Society

The Reverse Cope Elimination of Hydroxylamines and Alkenes or Alkynes: Theoretical Investigation of Tether Length and Substituent Effects

Science.gov (United States)

Krenske, Elizabeth H.; Davison, Edwin C.; Forbes, Ian T.; Warner, Jacqueline A.; Smith, Adrian L.; Holmes, Andrew B.; Houk, K. N.

2012-01-01

Quantum mechanical calculations have been used to study the intramolecular additions of hydroxylamines to alkenes and alkynes (“reverse Cope eliminations”). In intermolecular reverse Cope eliminations, alkynes are more reactive than alkenes. However, competition experiments have shown that tethering the hydroxylamine to the alkene or alkyne can reverse the reactivity order from that normally observed. The exact outcome depends on the length of the tether. In agreement with experiment, a range of density functional theory methods and CBS-QB3 calculations predict that the activation energies for intramolecular reverse Cope eliminations follow the order 6-exo-dig hydroxylamine and alkyne. Cyclization onto an alkene in the 5-exo-trig fashion incurs slightly less tether strain than a 6-exo-dig alkyne cyclization, but its activation energy is higher because the hydroxylamine fragment must distort more before the TS is reached. If the alkene terminus is substituted with two methyl groups, the barrier becomes so much higher that it is also disfavored compared to the 5- and 7-exo-dig cyclizations. PMID:22280245

SOCl 2 catalyzed cyclization of chalcones: Synthesis and spectral ...

African Journals Online (AJOL)

Some aryl-aryl 1H pyrazoles have been synthesised by cyclization of aryl chalcones and hydrazine hydrate in the presence of SOCl2. The yields of the pyrazoles are more than 85%. These pyrazoles are characterized by their physical constants and spectral data. The infrared, NMR spectral group frequencies of these ...

Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes

International Nuclear Information System (INIS)

Croteau, R.; Gershenzon, J.; Wheeler, C.J.; Satterwhite, D.M.

1990-01-01

The conversion of geranyl pyrophosphate to (+)-bornyl pyrophosphate and (+)-camphene is considered to proceed by the initial isomerization of the substrate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this bound intermediate. In the case of (-)-bornyl pyrophosphate and (-)-camphene, isomerization of the substrate to the (+)-(3S)-linalyl intermediate precedes cyclization. The geranyl and linalyl precursors were shown to be mutually competitive substrates (inhibitors) of the relevant cyclization enzymes isolated from Salvia officinalis (sage) and Tanacetum vulgare (tansy) by the mixed substrate analysis method, demonstrating that isomerization and cyclization take place at the same active site. Incubation of partially purified enzyme preparations with (3R)-[1Z-3H]linalyl pyrophosphate plus [1-14C]geranyl pyrophosphate gave rise to double-labeled (+)-bornyl pyrophosphate and (+)-camphene, whereas incubation of enzyme preparations catalyzing the antipodal cyclizations with (3S)-[1Z-3H]-linalyl pyrophosphate plus [1-14C]geranyl pyrophosphate yielded double-labeled (-)-bornyl pyrophosphate and (-)-camphene. Each product was then transformed to the corresponding (+)- or (-)-camphor without change in the 3H:14C isotope ratio, and the location of the tritium label was deduced in each case by stereoselective, base-catalyzed exchange of the exo-alpha-hydrogen of the derived ketone. The finding that the 1Z-3H of the linalyl precursor was positioned at the endo-alpha-hydrogen of the corresponding camphor in all cases, coupled to the previously demonstrated retention of configuration at C1 of the geranyl substrate in these transformations, confirmed the syn-isomerization of geranyl pyrophosphate to linalyl pyrophosphate and the cyclization of the latter via the anti,endo- conformer

Space Craft

Science.gov (United States)

Demski, Jennifer

2009-01-01

This article discusses how craft innovative architecture is bringing form to the function of 21st-century learning. It describes the construction of New Tech High at Coppell, in Coppell, Texas, which produces an example of how workplace design principles can be coordinated with modern educational goals. The campus was built on the model of New…

Self-crafting vegetable snacks: testing the IKEA-effect in children.

Science.gov (United States)

Raghoebar, Sanne; van Kleef, Ellen; de Vet, Emely

2017-01-01

The purpose of this paper is to test whether the IKEA-effect (Norton et al. , 2012) - better liking for self-crafted products than for identical products crafted by others - can be exploited to increase liking and consumption of vegetable snacks in children. A between-subjects experiment was conducted at an after school care facility. In total, 86 children aged four to six either crafted a peacock with vegetables or with non-food objects following an example. After the task, children ate snack vegetables ad libitum, and rated their liking for the vegetables and pride in crafting the peacock. No significant main effect of the vegetable snack creation on consumption and liking was observed. Also, perceived pride did not mediate the effect of self-crafting vegetable snacks on consumption of and liking for vegetables. Vegetable consumption did not differ between children who were either simply exposed to vegetable snacks while crafting or those who were crafting the vegetable snacks themselves. The equal consumption might suggest that this is caused by simple exposure, but more research is needed comparing self-crafting and exposure to a condition where there is no initial exposure to vegetables. Although the IKEA-effect has been demonstrated in adults, this is one of the first studies evaluating the IKEA-effect in children and as a means to increase liking for a generally disliked product in this target group, i.e. vegetables. The IKEA-effect could not be replicated under these more stringent conditions, where the experimental set-up enabled disentangling exposure and crafting effects.

An Efficient, Mild and Solvent-Free Synthesis of Benzene Ring Acylated Harmalines

Directory of Open Access Journals (Sweden)

Sabira Begum

2009-12-01

Full Text Available A facile synthesis of a series of benzene ring acylated analogues of harmaline has been achieved by Friedel-Crafts acylation under solvent-free conditions at room temperature using acyl halides/acid anhydrides and AlCl3. The reaction afforded 10- and 12-acyl analogues of harmaline in good yield, along with minor quantities of N-acyl-tryptamines and 8-acyl analogues of N-acyltryptamines.

Constructing knowledge through perceptual processes in making craft-art

Directory of Open Access Journals (Sweden)

Milla Ojala

2013-10-01

Full Text Available The focus of the study is on the knowledge that is constructed through perceptual processes during craft making in the context of the Finnish Basic Education in the Arts (BEA system. Craft studies in the BEA are defined as craft-art. The research method used is the grounded theory. The data consists of seven interviews and participant observations. Participants in the study are adolescents who study craft-art in the BEA system in Visual Art School, Aimo in Hämeenlinna. The aim of the article is to present, define and reflect on the concepts, properties and dimensions concerning perceptual processes that are discovered in this stage of the study following grounded theory procedures. The perceptual processes are an essential means of constructing knowledge in craft-art. Consequently, one aim of the study is to discuss how these processes are connected to various types of knowledge. The perceptual processes are described by seven concepts: imitative, anticipative, evaluative, experimental, emotional, temporal and bodily perceptions. They indicate on a conceptual level the characteristic of knowledge constructed through perceptual processes in craft-art. Further, theconcepts have several properties that can vary dimensionally between two qualities. The properties are activity, function and position. The dimensions of the properties vary from active to passive, formal to informal and internal to external. In conclusion, the concepts can describe a large range of incidents in different situations. They also seem to describe well the practice of  craft-art and there are several connections with pre-existing concepts of knowledge.Keywords: Craft, Knowledge, Perceptual process, Basic Education in the Arts, Grounded Theory 

Utilizing redox-mediated Bergman cyclization toward the development of dual-action metalloenediyne therapeutics.

Science.gov (United States)

Lindahl, Sarah E; Park, Hyunsoo; Pink, Maren; Zaleski, Jeffrey M

2013-03-13

Reaction of 2 equiv of 1,2-bis((diphenylphosphino)ethynyl)benzene (dppeb, 1) with Pt(cod)Cl2 followed by treatment with N2H4 yields the reduced Pt(0) metalloenediyne, Pt(dppeb)2, 2. This complex is stable to both air oxidation and metal-mediated Bergman cyclization under ambient conditions due to the nearly idealized tetrahedral geometry. Reaction of 2 with 1 equiv of I2 in the presence of excess 1,4-cyclohexadiene (1,4-CHD) radical trap rapidly and near-quantitatively generates the cis-Bergman-cyclized, diiodo product 3 ((31)P: δ = 41 ppm, J(Pt-P) = 3346 Hz) with concomitant loss of 1 equiv of uncyclized phosphine chelate ((31)P: δ = -33 ppm). In contrast, addition of 2 equiv of I2 in the absence of additional radical trap instantaneously forms a metastable Pt(dppeb)2(2+) intermediate species, 4, that is characterized by δ = 51 ppm in the (31)P NMR (J(Pt-P) = 3171 Hz) and ν(C≡C) = 2169 cm(-1) in the Raman profile, indicating that it is an uncyclized, bis-ligated complex. Over 24 h, 4 undergoes ligand exchange to form a neutral, square planar complex that spontaneously Bergman cyclizes at ambient temperature to give the crystalline product Pt(dppnap-I2)I2 (dppnap-I2 = (1,4-diiodonaphthalene-2,3-diyl)bis(diphenylphosphine)), 5, in 52% isolated yield. Computational analysis of the oxidation reaction proposes two plausible flattened tetrahedral structures for intermediate 4: one where the phosphine core has migrated to a trans-spanning chelate geometry, and a second, higher energy structure (3.3 kcal/mol) with two cis-chelating phosphine ligands (41° dihedral angle) via a restricted alkyne-terminal starting point. While the energies are disparate, the common theme in both structures is the elongated Pt-P bond lengths (>2.4 Å), indicating that nucleophilic ligand substitution by I(-) is on the reaction trajectory to the cyclized product 5. The efficiency of the redox-mediated Bergman cyclization reaction of this stable Pt(0) metalloenediyne prodrug and

Intramolecular hydrogen bonding in malonaldehyde and its radical analogues.

Science.gov (United States)

Lin, Chen; Kumar, Manoj; Finney, Brian A; Francisco, Joseph S

2017-09-28

High level Brueckner doubles with triples correction method-based ab initio calculations have been used to investigate the nature of intramolecular hydrogen bonding and intramolecular hydrogen atom transfer in cis-malonaldehyde (MA) and its radical analogues. The radicals considered here are the ones that correspond to the homolytic cleavage of C-H bonds in cis-MA. The results suggest that cis-MA and its radical analogues, cis-MA RS , and cis-MA RA , both exist in planar geometry. The calculated intramolecular O-H⋯O=C bond in cis-MA is shorter than that in the radical analogues. The intramolecular hydrogen bond in cis-MA is stronger than in its radicals by at least 3.0 kcal/mol. The stability of a cis-malonaldehyde radical correlates with the extent of electron spin delocalization; cis-MA RA , in which the radical spin is more delocalized, is the most stable MA radical, whereas cis-MA RS , in which the radical spin is strongly localized, is the least stable radical. The natural bond orbital analysis indicates that the intramolecular hydrogen bonding (O⋯H⋯O) in cis-malonaldehyde radicals is stabilized by the interaction between the lone pair orbitals of donor oxygen and the σ * orbital of acceptor O-H bond (n → σ * OH ). The calculated barriers indicate that the intramolecular proton transfer in cis-MA involves 2.2 kcal/mol lower barrier than that in cis-MA RS .

46 CFR 133.110 - Survival craft muster and embarkation arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft muster and embarkation arrangements. 133... VESSELS LIFESAVING SYSTEMS Requirements for All OSVs § 133.110 Survival craft muster and embarkation... lighting supplied from the emergency source of electrical power. (e) Each davit-launched survival craft...

1,7-Cyclization of 1-diazo-2,4-pentadiene and its heteroanalogues: DFT study

Science.gov (United States)

Subbotina, Julia O.; Bakulev, V. A.; Herges, R.; Fabian, W. M. F.

1,7-Dipolar cyclizations of 1-diazo-2,4-pentadiene 1a and its heteroanalogues 1b,c and 4c were studied using density functional theory (DFT). Although the heteroanalogue 1c has an appropriate electronic structure to allow for pseudopericyclic cyclization, natural bond order (NBO) analysis has provided evidence for the electrocyclic ring closure. Magnetic criteria (anisotropy of the induced current density [ACID], nucleus-independent chemical shifts [NICS]) confirmed the pericyclic character of the located transition states 2a,c and 5c. The activation barriers for the cyclization of 1-diazo-2,4-pentadiene 1a and its aza analogues 1c, 4c are 3.3, 8.2, and 12.3 kcal/mol at the B3LYP/6-31G(d) level, respectively. The higher barrier of the 1c?3c and 4c?3c reactions compared with 1a?3a is in line with the Hammond postulate. The out-of-plane distorted geometry of the cyclic product is an additional factor arguing against a pseudopericyclic mechanism.

Parallel and four-step synthesis of natural-product-inspired scaffolds through modular assembly and divergent cyclization

Directory of Open Access Journals (Sweden)

Hiroki Oguri

2012-06-01

Full Text Available By emulating the universal biosynthetic strategy, which employs modular assembly and divergent cyclizations, we have developed a four-step synthetic process to yield a collection of natural-product-inspired scaffolds. Modular assembly of building blocks onto a piperidine-based manifold 6, having a carboxylic acid group, was achieved through Ugi condensation, N-acetoacetylation and diazotransfer, leading to cyclization precursors. The rhodium-catalyzed tandem cyclization and divergent cycloaddition gave rise to tetracyclic and hexacyclic scaffolds by the appropriate choice of dipolarophiles installed at modules 3 and 4. A different piperidine-based manifold 15 bearing an amino group was successfully applied to demonstrate the flexibility and scope of the unified four-step process for the generation of structural diversity in the fused scaffolds. Evaluation of in vitro antitrypanosomal activities of the collections and preliminary structure–activity relationship (SAR studies were also undertaken.

46 CFR 199.110 - Survival craft muster and embarkation arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft muster and embarkation arrangements. 199... § 199.110 Survival craft muster and embarkation arrangements. (a) Each muster station must have... emergency source of electrical power. (e) Each davit-launched and free-fall survival craft muster station...

46 CFR 199.245 - Survival craft embarkation and launching arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft embarkation and launching arrangements... Passenger Vessels § 199.245 Survival craft embarkation and launching arrangements. (a) Each davit-launched liferaft must be arranged to be rapidly boarded by its full complement of persons. (b) All survival craft...

46 CFR 199.280 - Survival craft embarkation and launching arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft embarkation and launching arrangements... Cargo Vessels § 199.280 Survival craft embarkation and launching arrangements. (a) Each lifeboat must be.... (d) All survival craft required for abandonment by the total number of persons on board must be...

Formation of polycyclic aromatic hydrocarbons by ionizing radiations

International Nuclear Information System (INIS)

Perez, G.; Lilia, E.; Cristalli, A.

1986-01-01

Gaseous 0-terphenyl, 1-phenylnaphthalene, and 9-phenylanthracene were submitted to gamma rays. The yields of cyclization products, polycyclic aromatic hydrocarbons, show that at least one twentieth of the intermediates formed undergo intramolecular reaction. (author)

Smooth isoindolinone formation from isopropyl carbamates via Bischler-Napieralski-type cyclization.

Science.gov (United States)

Adachi, Satoshi; Onozuka, Masao; Yoshida, Yuko; Ide, Mitsuaki; Saikawa, Yoko; Nakata, Masaya

2014-01-17

Isopropyl carbamates derived from benzylamines provide isoindolinones by treatment with phosphorus pentoxide at room temperature. Utility of this Bischler-Napieralski-type cyclization and a new mechanism involving a carbamoyl cation for rationalization of this smooth conversion are discussed.

46 CFR 199.175 - Survival craft and rescue boat equipment.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft and rescue boat equipment. 199.175....175 Survival craft and rescue boat equipment. (a) All lifeboat and rescue boat equipment— (1) Must be... craft or rescue boat; or (iii) Overload the launching appliance. (b) Each lifeboat, rigid liferaft, and...

46 CFR 199.100 - Manning of survival craft and supervision.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Manning of survival craft and supervision. 199.100....100 Manning of survival craft and supervision. (a) There must be a sufficient number of trained... craft and launching arrangements required for abandonment by the total number of persons on board. (c...

Direct Synthesis of Medium-Bridged Twisted Amides via a Transannular Cyclization Strategy

Science.gov (United States)

Szostak, Michal; Aubé, Jeffrey

2009-01-01

The sequential RCM to construct a challenging medium-sized ring followed by a transannular cyclization across a medium-sized ring delivers previously unattainable twisted amides from simple acyclic precursors. PMID:19708701

Job crafting: Towards a new model of individual job redesign

Directory of Open Access Journals (Sweden)

Maria Tims

2010-12-01

Research purpose: The purpose of the study was to fit job crafting in job design theory. Motivation for the study: The study was an attempt to shed more light on the types of proactive behaviours of individual employees at work. Moreover, we explored the concept of job crafting and its antecedents and consequences. Research design, approach and method: A literature study was conducted in which the focus was first on proactive behaviour of the employee and then on job crafting. Main findings: Job crafting can be seen as a specific form of proactive behaviour in which the employee initiates changes in the level of job demands and job resources. Job crafting may be facilitated by job and individual characteristics and may enable employees to fit their jobs to their personal knowledge, skills and abilities on the one hand and to their preferences and needs on the other hand. Practical/managerial implications: Job crafting may be a good way for employees to improve their work motivation and other positive work outcomes. Employees could be encouraged to exert more influence on their job characteristics. Contribution/value-add: This article describes a relatively new perspective on active job redesign by the individual, called job crafting, which has important implications for job design theories.

46 CFR 109.323 - Manning of survival craft and supervision.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Manning of survival craft and supervision. 109.323... DRILLING UNITS OPERATIONS Operation and Stowage of Safety Equipment § 109.323 Manning of survival craft and supervision. (a) There must be a sufficient number of trained persons on board the survival craft for...

Highly fluorescent benzofuran derivatives of the GFP chromophore

DEFF Research Database (Denmark)

Christensen, Mikkel Andreas; Jennum, Karsten Stein; Abrahamsen, Peter Bæch

2012-01-01

Intramolecular cyclization reactions of Green Fluorescent Protein chromophores (GFPc) containing an arylethynyl ortho-substituent at the phenol ring provide new aryl-substituted benzofuran derivatives of the GFPc. Some of these heteroaromatic compounds exhibit significantly enhanced fluorescence...

46 CFR 111.75-16 - Lighting of survival craft and rescue boats.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Lighting of survival craft and rescue boats. 111.75-16... craft and rescue boats. (a) During preparation, launching, and recovery, each survival craft and rescue... of circuits must be such that the lighting for adjacent launching stations for survival craft or...

46 CFR 117.206 - Survival craft-vessels operating on Great Lakes routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-vessels operating on Great Lakes routes... PASSENGERS LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 117.206 Survival craft... vessel certificated to operate on a Great Lakes route must be provided with the survival craft required...

33 CFR 149.313 - How must survival craft be arranged?

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false How must survival craft be... Equipment Manned Deepwater Port Requirements § 149.313 How must survival craft be arranged? The operator must arrange survival craft so that they meet the requirements of 46 CFR 108.525 (a) and § 108.530 and...

46 CFR 117.205 - Survival craft-vessels operating on limited coastwise routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-vessels operating on limited coastwise... PASSENGERS LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 117.205 Survival craft... the survival craft required by §§ 117.204 (a) through (d) of this part, as applicable. (b) Each vessel...

Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer.

Science.gov (United States)

Bovino, Michael T; Chemler, Sherry R

2012-04-16

Problem solved: the title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines. Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modern electrical installation for craft students

CERN Document Server

Scaddan, Brian

2013-01-01

Modern Electrical Installation for Craft Students, Volume 2, Third Edition discusses several topics concerning electrical installations. The book is comprised of eight chapters that deal with craft theory, associated subjects, and electrical industries. Chapter 1 covers inductors and inductance, while Chapter 2 tackles capacitors and capacitance. Chapter 3 deals with inductance and capacitance in installation work. The book also discusses cells, batteries, and transformers. The electrical industries, control and earthing, and testing are also dealt with. The last chapter discusses the basic el

Reactions of adducts of phosphorus pentachloride and 1-alkenes with arsenic trifluoride

International Nuclear Information System (INIS)

Fridland, S.V.; Miftakhov, M.N.; Dmitrieva, N.V.

1986-01-01

As a result of NMR investigations of models of σ and π nu complexes of 1-heptene (or 1-hexene) and phosphorus pentachloride in reactions with arsenic trifluoride it was shown that the formation of the phosphorus-containing arylated product by the Friedel-Crafts scheme is possible only with the participation of the σ complex, but in the case of the π nu complex the arylation of the olefin occurs

A new hypercrosslinked supermicroporous polymer, with scope for sulfonation, and its catalytic potential for the efficient synthesis of biodiesel at room temperature.

Science.gov (United States)

Bhunia, Subhajit; Banerjee, Biplab; Bhaumik, Asim

2015-03-25

We have designed a new hypercrosslinked supermicroporous polymer (HMP-1) with a BET surface area of 913 m(2) g(-1) by FeCl3 via a catalyzed Friedel-Crafts alkylation reaction between carbazole and α,α'-dibromo-p-xylene. Upon sulfonation HMP-1 yielded a very efficient solid acid catalyst for the production of biodiesels via esterification/transesterification of free fatty acids (FFA)/esters at room temperature.

Monodisperse microbeads of hypercrosslinked polystyrene for liquid and supercritical fluid chromatography

Science.gov (United States)

Tsyurupa, M. P.; Blinnikova, Z. K.; Il'in, M. M.; Davankov, V. A.; Parenago, O. O.; Pokrovskii, O. I.; Usovich, O. I.

2015-11-01

Monodisperse styrene-divinylbenzene (1 wt %) copolymer microbeads are obtained via the elaborate method of high-productivity precipitation polymerization. The crosslinking of this copolymer with chloromethyl methyl ether in the presence of Friedel-Crafts catalyst yields porous hypercrosslinked polymers with degrees of crosslinking that range from 200 to 500%. Microbead sorbents are shown to be suited for selective stationary phases for high-performance liquid chromatography and supercritical fluid chromatography.

46 CFR 199.220 - Survival craft and rescue boat embarkation arrangements.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft and rescue boat embarkation arrangements... APPLIANCES AND ARRANGEMENTS LIFESAVING SYSTEMS FOR CERTAIN INSPECTED VESSELS Additional Requirements for Passenger Vessels § 199.220 Survival craft and rescue boat embarkation arrangements. (a) Survival craft...

Minimum Plate Thickness in High-Speed Craft

DEFF Research Database (Denmark)

Pedersen, Preben Terndrup; Zhang, Shengming

1998-01-01

The minimum plate thickness requirements specified by the classification societies for high-speed craft are supposed to ensure adequate resistance to impact loads such as collision with floating objects and objects falling on the deck. The paper presents analytical methods of describing such impact...... phenomena and proposes performance requirements instead of thickness requirements for hull panels in high-speed craft made of different building materials....

46 CFR 108.550 - Survival craft launching and recovery arrangements: General.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft launching and recovery arrangements...-MOBILE OFFSHORE DRILLING UNITS DESIGN AND EQUIPMENT Lifesaving Equipment § 108.550 Survival craft.... (c) Each survival craft must be arranged to clear each leg, column, footing, brace, mat, and each...

46 CFR 199.150 - Survival craft launching and recovery arrangements; general.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft launching and recovery arrangements... Vessels § 199.150 Survival craft launching and recovery arrangements; general. (a)(1) Each launching...) Unless expressly provided otherwise in this part, each survival craft must be provided with a launching...

46 CFR 133.150 - Survival craft launching and recovery arrangements: General.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft launching and recovery arrangements...) OFFSHORE SUPPLY VESSELS LIFESAVING SYSTEMS Requirements for All OSVs § 133.150 Survival craft launching and recovery arrangements: General. (a) All survival craft required for abandonment by the total number of...

33 CFR 146.120 - Manning of survival craft.

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false Manning of survival craft. 146.120 Section 146.120 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY... craft. The owner, the owner's agent, or the person in charge shall assign a person to each life float...

46 CFR 117.202 - Survival craft-vessels operating on oceans routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-vessels operating on oceans routes. 117... LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 117.202 Survival craft—vessels... number of overnight persons allowed, the survival craft requirements contained in paragraph (e) of this...

Diversity Oriented Synthesis of Natural 2-Arylbenzofuran, Moracin F

International Nuclear Information System (INIS)

Yun, So-Ra; Jun, Jong-Gab

2016-01-01

Diversity oriented synthesis of natural 2-arylbenzofuran, moracin F (1) has been carried out from the commercially available starting materials using Sonogashira coupling, Suzuki coupling, neutral Al 2 O 3 mediated cyclization, and intramolecular Wittig reaction as key steps.

Craft vs. industrial: Habits, attitudes and motivations towards beer consumption in Mexico.

Science.gov (United States)

Gómez-Corona, Carlos; Escalona-Buendía, Héctor B; García, Mauricio; Chollet, Sylvie; Valentin, Dominique

2016-01-01

Food choices tend to be stable over time; they do not change fast, since consumers tend to act like creatures of habits. However, food habits can evolve, like currently the craft beer category. A change of habits involves a change of perception towards a product. Therefore, what is changing in the perception of beer? Two studies were conducted to address this question. First study was preliminary and aimed at exploring beer consumption habits in Mexico and a better understanding of craft beer representation among beer users. A questionnaire was administrated to 207 consumers in Mexico City during a beer festival. Results showed that respondents could be classified in: industrial beer (41.1%), occasional industrial (24.1%), and craft beer (34.8%) consumers. Craft cluster included mostly 25-35 years old men with high-income level. Among the craft beers cited by respondents from this cluster some are industrial, suggesting that the concept of craft beer might not be well defined, or defined in ideological terms. The second and main study was conducted using consumer ethnographies to understand the motivations and benefits of craft beer consumption. Opposite to industrial, craft beer emerges as an experience-based and symbolic product rather than a utilitarian one. The main motivation for drinking craft beer seems to be the quest of authenticity. Respondents' motivations to drink craft beer are generated by three important factors: desire for more knowledge, new taste experiences, and move away from the mainstream beer consumption. Craft consumers do not drink the product for its functional attributes, they consume it for what it means and as a consequence they build an identity, perceived as more authentic and unique, in comparison to the mainstream industrial beer consumption in Mexico. Copyright © 2015 Elsevier Ltd. All rights reserved.

New stereoselective intramolecular

Science.gov (United States)

Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

2000-11-03

Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

46 CFR 108.520 - Type of survival craft.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Type of survival craft. 108.520 Section 108.520 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) A-MOBILE OFFSHORE DRILLING UNITS DESIGN AND EQUIPMENT Lifesaving Equipment § 108.520 Type of survival craft. (a) Each lifeboat must be a fire-protected...

The comparative risk assessment framework and tools (CRAFT)

Science.gov (United States)

Southern Research Station. USDA Forest Service

2010-01-01

To help address these challenges, the USDA Forest Service’s Eastern Forest Environmental Threat Assessment Center (EFETAC) and the University of North Carolina Asheville’s National Environmental Modeling and Analysis Center (NEMAC) designed a planning framework, called the Comparative Risk Assessment Framework and Tools (CRAFT). CRAFT is...

Empowering leadership and job crafting: The role of employee optimism.

Science.gov (United States)

Thun, Sylvi; Bakker, Arnold B

2018-06-08

The objective of this study was to test the relationship between empowering leadership and job crafting and to examine the moderating role of optimism as a personal resource. We hypothesized that the association between empowering leadership and job crafting would be stronger for employees with high (vs. low) levels of optimism. A total of 331 Norwegian workers from a variety of occupations participated in our study. Results of structural equation modelling analysis generally supported our hypotheses. Empowering leadership was positively related to 3 of the 4 job crafting strategies investigated (increasing structural job resources, increasing social job resources, and increasing challenging job demands; but not reducing hindrance job demands). Moreover, as hypothesized, optimism strengthened the empowering leadership-job crafting relationship for increasing structural resources and increasing challenging demands. The results suggest that empowering leadership is an important antecedent of job crafting strategies, except for reducing hindrance demands. The implications of these findings are discussed. Copyright © 2018 John Wiley & Sons, Ltd.

The synthesis of [U-{sup 14}C phenyl] LS 840606, an agricultural fungicide

Energy Technology Data Exchange (ETDEWEB)

Madegard, G.; Mestre, P.; Raimond, P.; Noel, J.-P. [CEA Centre d`Etudes de Saclay, 91 - Gif-sur-Yvette (France)

1995-12-01

2,2`,4`-Trichloro-[ring U-{sup 14}C]acetophenone was the key intermediate of this synthesis patterned after the industrial route. An unexpected poor yield was observed during the preparation by the Friedel-Crafts reaction of chloroacetyl chloride with 1,3-dichloro-[U-{sup 14}C]benzene, possibly the result of an isotope effect although this poor yield might be explained by other factors. Two routes were checked for the preparation of 1,3-dichloro-[U-{sup 14} C]benzene. The action of CCl{sub 4} with 1,3-dinitro-[U-{sup 14} C]benzene at 280{sup o}C was entailed with explosions. A safer route started from [U-{sup 14}C]aniline via 2,4-dichloro-[ring U-{sup 14}C]acetanilide. Friedel-Crafts reaction with acetyl chloride gave rise in 52% yield to 2`,4`-dichloro-[ring U-{sup 14}C]acetophenone which was brominated to 2-bromo-2`,4`-dichloro-[ring U-{sup 14}C]acetophenone; was condensed with 2,2-(ethylenedioxy)etylmagnesium bromide to compound, was condensed with 1,2,4-triazole then successively treated with HCl:water:dioxane and 2,2,2-trifluoroethanol/HCl. Separation of the two diastereomers by medium pressure liquid chromatography. 7% overall radioactivity yield from [U-{sup 14}C]aniline. Radiochemical purity 99%. (author).

The synthesis of [U-14C phenyl] LS 840606, an agricultural fungicide

International Nuclear Information System (INIS)

Madegard, G.; Mestre, P.; Raimond, P.; Noel, J.-P.

1995-01-01

2,2',4'-Trichloro-[ring U- 14 C]acetophenone was the key intermediate of this synthesis patterned after the industrial route. An unexpected poor yield was observed during the preparation by the Friedel-Crafts reaction of chloroacetyl chloride with 1,3-dichloro-[U- 14 C]benzene, possibly the result of an isotope effect although this poor yield might be explained by other factors. Two routes were checked for the preparation of 1,3-dichloro-[U- 14 C]benzene. The action of CCl 4 with 1,3-dinitro-[U- 14 C]benzene at 280 o C was entailed with explosions. A safer route started from [U- 14 C]aniline via 2,4-dichloro-[ring U- 14 C]acetanilide. Friedel-Crafts reaction with acetyl chloride gave rise in 52% yield to 2',4'-dichloro-[ring U- 14 C]acetophenone which was brominated to 2-bromo-2',4'-dichloro-[ring U- 14 C]acetophenone; was condensed with 2,2-ethylenedioxy)etylmagnesium bromide to compound, was condensed with 1,2,4-triazole then successively treated with HCl:water:dioxane and 2,2,2-trifluoroethanol/HCl. Separation of the two diastereomers by medium pressure liquid chromatography. 7% overall radioactivity yield from [U- 14 C]aniline. Radiochemical purity 99%. (author)

46 CFR 117.208 - Survival craft-vessels operating on rivers routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-vessels operating on rivers routes. 117... LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 117.208 Survival craft—vessels... vessel certificated to operate on a rivers route in warm water is not required to carry survival craft...

Alternative synthesis of 9-{3-[(diisopropoxyphosphoryl)-methoxy]-2-hydroxypropyl}adenine and its free phosphonates substituted at the C-8 position of purine base

Czech Academy of Sciences Publication Activity Database

Janeba, Zlatko; Masojídková, Milena; Holý, Antonín

2010-01-01

Roč. 75, č. 3 (2010), s. 371-381 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40550506 Keywords : acyclic nucleoside phosphonates * HPMPA * nucleophilic substitution * intramolecular cyclization Subject RIV: CC - Organic Chemistry Impact factor: 0.853, year: 2010

Theoretical Study of Gold-Catalyzed Cyclization of 2-Alkynyl-N-propargylanilines and Rationalization of Kinetic Experimental Phenomena.

Science.gov (United States)

Duan, Yeqing; Liu, Yuxia; Bi, Siwei; Ling, Baoping; Jiang, Yuan-Ye; Liu, Peng

2016-10-07

Gold-catalyzed cyclization of 2-alkynyl-N-propargylanilines provides a step-economic method for the construction of three-dimensional indolines. In this article, the M06 functional of density functional theory was employed to gain deeper insights into the reaction mechanism and the associated intriguing experimental observations. The reaction was found to first undergo Au(I)-induced cyclization to form an indole intermediate, 1,3-propargyl migration, and substitution with the substrate 2-alkynyl-N-propargylaniline (R1) to generate the intermediate product P1, an allene species. Subsequently, Au(I)-catalyzed conversion of P1 into the final product P2, an indoline compound, occurs first through direct cyclization rather than via the previously proposed four-membered carbocycle intermediate. Thereafter, water-assisted oxygen heterocycle formation and proton transfer generate the final product. The calculated activation free energies indicate that P1 formation is 5.9 times slower than P2 formation, in accordance with the fact that P1 formation is rate-limiting. Futhermore, the intriguing experimental phenomenon that P2 can be accessed only after almost all the substrate R1 converts to P1 although P1 formation is rate-limiting was rationalized by employing an energetic span model. We found the initial facile cyclization to form a highly stable indole intermediate in the formation of P1 is the key to the intriguing experimental phenomenon.

47 CFR 80.271 - Technical requirements for portable survival craft radiotelephone transceivers.

Science.gov (United States)

2010-10-01

... craft radiotelephone transceivers. 80.271 Section 80.271 Telecommunication FEDERAL COMMUNICATIONS... Authorization for Compulsory Ships § 80.271 Technical requirements for portable survival craft radiotelephone transceivers. (a) Portable survival craft radiotelephone transceivers must comply with the following: (1) The...

Creating Chicago History: Making Outreach Craft Activities Meaningful

Science.gov (United States)

Karp, Madeline

2012-01-01

When it comes to having a traveling outreach activity for a museum, a craft can seem like the perfect solution. It can seemingly be all things at once--educational, quick and fun. But, if poorly constructed, crafts can also have serious fallbacks. Using the Chicago History Museum and the Millennium Park Family Fun Festival as a case study, this…

Craft Lessons: Teaching Writing K-8. Second Edition

Science.gov (United States)

Fletcher, Ralph; Portalupi, JoAnn

2007-01-01

Since its publication in 1998 Craft Lessons has become a mainstay of writing teachers, both new and experienced. Practical lessons--each printed on one page--and the instructional language geared to three grade-level groupings: K-2, 3-4, and 5-8 are contained in this book. In the decade since Craft Lessons' publication the world has changed in…

Cyclization of lapachol induced by thallium salts

International Nuclear Information System (INIS)

Ribeiro, Carlos Magno R.; Souza, Pablo P. de; Ferreira, Leticia L.D.M.; Pinto, Lia A.; Almeida, Leonardo S. de; Jesus, Janaina G. de

2008-01-01

This work describes the cyclization of lapachol (1) induced by thallium triacetate (TTA) and thallium trinitrate (TTN) in several solvents using magnetic stirring and under microwave irradiation. α-Xyloidone (2) - dehydro-a-lapachone - was obtained as the main product in these reactions in 20 - 75% yield. However, rhinacanthin-A (4) was isolated as main product in a 40% yield, using TTA and acetic anhydride:water (1:1) as solvent, and dehydroiso- a-lapachone (3) in 21% yield, using TTA and dichloromethane as solvent. The reaction time decreased drastically under microwave conditions, but the yields of these reactions were not the expected. (author)

Scaffold Diversity from N-Acyliminium Ions

DEFF Research Database (Denmark)

Wu, Peng; Nielsen, Thomas E

2017-01-01

N-Acyliminium ions are powerful reactive species for the formation of carbon-carbon and carbon-heteroatom bonds. Strategies relying on intramolecular reactions of N-acyliminium intermediates, also referred to as N-acyliminium ion cyclization reactions, have been employed for the construction...... of structurally diverse scaffolds, ranging from simple bicyclic skeletons to complex polycyclic systems and natural-product-like compounds. This review aims to provide an overview of cyclization reactions of N-acyliminium ions derived from various precursors for the assembly of structurally diverse scaffolds...

Formation control of marine surface craft: a Lagrangian approach

DEFF Research Database (Denmark)

Ihle, Ivar-Andre F.; Jouffroy, Jerome; Fossen, Thor I.

2006-01-01

This paper presents a method for formation control of marine surface craft inspired by Lagrangian mechanics. The desired formation configuration and response of the marine surface craft are given as a set of constraints in analytical mechanics. Thus, constraints forces arise and feedback from...

Legal and economic implications of the German Craft Code Amendment 2004

Directory of Open Access Journals (Sweden)

Wolfgang Benzel

2012-01-01

Full Text Available As the main reason for initiating an amendment of the Trade and Crafts Code in 2004 was the decrease in the number of companies in general and the number of skilled crafts enterprises in particular and was also due to the fact that the number of employees in the skilled crafts sector had constantly fallen and many companies were not able to find a successor, it was the declared aim of the amendment to counter this structural crisis as well as reducing illegal employment and removing native discrimination. This would then ensure a higher level of employment especially through new company formations and takeovers of existing companies.In addition to providing an important contribution towards the assessment of the basic success of the 2004 Trade and Crafts Code amendment, the results can therefore be used at an international level for discussions on skilled crafts legislation outside Germany. As German skilled crafts legislation developed in a completely different manner from skilled crafts legislation in most other European countries, this aspect is particularly significant and it is conceivable that the results will be useful beyond the borders of the Federal Republic of Germany. The research findings will also be important in determining the limits of deregulation and when it can be considered counterproductive from an economic point of view.

One-pot cascade michael.cyclization reactions of ο-hydroxycinnamaldehydes: Synthesis of functionalized 2,3-dihydrobenzofuranes

Energy Technology Data Exchange (ETDEWEB)

Gwon, Sung Hyuk; Kim, Sunggon [Kyonggi Univ., Suwon (Korea, Republic of)

2012-04-15

We described the cascade Michael.cyclization reaction of o-hydroxycinnamaldehydes with diethyl α-bromomalonate promoted by potassium carbonate. The reactions provided functionalized 2,3-dihydrobenzofurans in good yields for a variety of o-hydroxyaromatic α,β-unsaturated aldehydes. Current work focuses on expanding the scope of this reaction to other substrates such as sulfur yields, and on developing an efficient catalytic asymmetric variant. 2,3-Dihydrobenzofurans are found in numerous biologically active natural products and synthetic compounds. These are an attractive type of oxygenated compound because their basic core skeleton is present in neolignans, pterocarpans, and synthetic drugs used in the treatment of pulmonary hypertension, atherosclerotic peripheral arterial disease, and central nervous system trauma and ischemia. Owing to the importance of their structures, numerous synthetic methods for 2,3-dihydrobenzofurans have been developed, primarily: radical cyclizations, Lewis acid promoted reactions, anionic cyclizations, and transition-metal catalyzed processes. However, these methods cannot be generalized as much as is desirable, and they yielded poor chemo- and/or stereoselectivities. Hence, the development of an efficient enantioselective synthetic method for obtaining 2,3-dihydrobenzofuran scaffolds attracted our attention.

One-pot cascade michael.cyclization reactions of ο-hydroxycinnamaldehydes: Synthesis of functionalized 2,3-dihydrobenzofuranes

International Nuclear Information System (INIS)

Gwon, Sung Hyuk; Kim, Sunggon

2012-01-01

We described the cascade Michael.cyclization reaction of o-hydroxycinnamaldehydes with diethyl α-bromomalonate promoted by potassium carbonate. The reactions provided functionalized 2,3-dihydrobenzofurans in good yields for a variety of o-hydroxyaromatic α,β-unsaturated aldehydes. Current work focuses on expanding the scope of this reaction to other substrates such as sulfur yields, and on developing an efficient catalytic asymmetric variant. 2,3-Dihydrobenzofurans are found in numerous biologically active natural products and synthetic compounds. These are an attractive type of oxygenated compound because their basic core skeleton is present in neolignans, pterocarpans, and synthetic drugs used in the treatment of pulmonary hypertension, atherosclerotic peripheral arterial disease, and central nervous system trauma and ischemia. Owing to the importance of their structures, numerous synthetic methods for 2,3-dihydrobenzofurans have been developed, primarily: radical cyclizations, Lewis acid promoted reactions, anionic cyclizations, and transition-metal catalyzed processes. However, these methods cannot be generalized as much as is desirable, and they yielded poor chemo- and/or stereoselectivities. Hence, the development of an efficient enantioselective synthetic method for obtaining 2,3-dihydrobenzofuran scaffolds attracted our attention

Craft-Art as a Basis for Human Activity

Science.gov (United States)

Karppinen, Seija

2008-01-01

This article based on my doctoral thesis examines the Basic Arts Education system in Finland, focusing on Basic Crafts Education and its description through action concepts. The main task of the study was to create a concept model. In the first part of the study a concept map was created from the practice of Basic Crafts Education. The aim of the…

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

An efficient synthesis of (-)-wodeshiol 1 is described. The key reactions include highly stereoselective aldol condensation of piperonal with the dianion of chiral oxazolidinone, subsequent intramolecular ring cyclization of the aldol product 8 and a diastereocontrolled oxygenation of dilactone 7 in good yield.

Preparation of Spirocyclic β-Proline Esters

DEFF Research Database (Denmark)

Fjelbye, Kasper; Marigo, Mauro; Clausen, Rasmus Prætorius

2017-01-01

A series of novel N-Bn-protected spirocyclic β-proline esters were prepared using [3+2] cycloaddition and subsequently converted into their corresponding aldehydes. In addition, two novel N-Cbz-protected spirocyclic β-proline esters were prepared using intramolecular cyclization starting from...

Synthesis of a criss-cross overlapped tetrathiafulvalenophane and a topologically new [2]catenane

DEFF Research Database (Denmark)

Nielsen, Mogens Brønsted; Thorup, Niels; Becher, Jan

1998-01-01

Using stepwise cyclization reactions followed by an intramolecular coupling., a criss-cross overlapped tetrathiafulvalenophane was prepared. The structure of the cis,cis isomer was elucidated by X-ray crystallography which revealed a host-guest complex with chloroform. This electron donor was use...

Job crafting among health care professionals: The role of work engagement.

Science.gov (United States)

Bakker, Arnold B

2018-04-01

The aim of this study was to examine the impact of job crafting on the quality of the work environment of health care professionals. Job crafting refers to proactive behavior aimed at optimizing the fit between person and job. Using job demands-resources theory, we hypothesized that job crafting would be positively related to job resources and person-organisation fit, and negatively to hindrance demands. Furthermore, we hypothesized that these relationships would be qualified by work engagement. A total of 5,272 health care professionals from one of 35 different organisations filled out an electronic questionnaire (response is 55%). Regression analyses were used to test hypotheses. Consistent with hypotheses, job crafting in the form of increasing job resources was positively related to opportunities for development, performance feedback and P-O fit; and negatively related to hindrance job demands - particularly when work engagement was high. The combination of job crafting and work engagement is important for the realization of a resourceful work environment and fit between person and organisation. Interventions aimed at fostering job crafting should be tailored to the motivation of health care professionals. © 2017 John Wiley & Sons Ltd.

Intramolecular and nonlinear dynamics

Energy Technology Data Exchange (ETDEWEB)

Davis, M.J. [Argonne National Laboratory, IL (United States)

1993-12-01

Research in this program focuses on three interconnected areas. The first involves the study of intramolecular dynamics, particularly of highly excited systems. The second area involves the use of nonlinear dynamics as a tool for the study of molecular dynamics and complex kinetics. The third area is the study of the classical/quantum correspondence for highly excited systems, particularly systems exhibiting classical chaos.

Craft Training in Russia: Theory and Practice of Development

Science.gov (United States)

Romantsev, Gennadij M.; Efanov, Andrei V.; Moiseev, Andrei V.; Bychkova, Ekaterina Yu.; Karpova, Natalia P.; Tidemann, Bruno

2016-01-01

The relevance of the research topic is substantiated by the social commitment to the establishment of a system of craft training focused on training personnel for craft enterprises. The purpose of the article is to provide theoretical and methodological substantiation of the necessity to provide organizational and pedagogical foundations for the…

Tandem Michael addition/radical cyclizations for the construction of highly functionalized cyclopentanes

Czech Academy of Sciences Publication Activity Database

Holan, Martin; Pohl, Radek; Císarová, I.; Jahn, Ullrich

2012-01-01

Roč. 106, - (2012), s1298-s1298 ISSN 0009-2770. [EuCheMS Chemistry Congress /4./. 26.08.2012-30.08.2012, Prague] Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclization * diastereoselectivity * Michael addiction * radical reactions * domino reactions Subject RIV: CC - Organic Chemistry

Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions

Czech Academy of Sciences Publication Activity Database

Holan, Martin; Pohl, Radek; Císařová, I.; Klepetářová, Blanka; Jones, P. G.; Jahn, Ullrich

2015-01-01

Roč. 21, č. 27 (2015), s. 9877-9888 ISSN 0947-6539 R&D Projects: GA ČR GA13-40188S Institutional support: RVO:61388963 Keywords : cyclization * domino reactions * electron transfer * Michael addition * radical reactions Subject RIV: CC - Organic Chemistry Impact factor: 5.771, year: 2015

Malleable Thought: The Role of Craft Thinking in Practice-Led Graphic Design

Science.gov (United States)

Ings, Welby

2015-01-01

This article considers the potential of craft processes as creative engagements in graphic design research. It initially discusses the uneasy history of craft within the discipline, then draws upon case studies undertaken by three established designers who, in their postgraduate theses, engaged with craft as a process of thinking. In doing so, the…

46 CFR 180.206 - Survival craft-vessels operating on Great Lakes routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-vessels operating on Great Lakes routes... Craft § 180.206 Survival craft—vessels operating on Great Lakes routes. (a) Except as allowed by... with the survival craft required by § 180.205 (a) through (e), as appropriate. (b) Each vessel...

46 CFR 180.205 - Survival craft-vessels operating on limited coastwise routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-vessels operating on limited coastwise... Craft § 180.205 Survival craft—vessels operating on limited coastwise routes. (a) Except as allowed by... survival craft required by § 180.204(d). (e) Each vessel certificated to operate on a limited coastwise...

Automatic Construction by Contour Crafting Technology

Directory of Open Access Journals (Sweden)

Mohammad Reza Khorramshahi

2017-07-01

Full Text Available Contour Crafting is a novel technology in construction industry based on 3D printing that uses robotics to construct free form building structures by repeatedly laying down layers of material such as concrete. It is actually an approach to scale up automatic fabrication from building small industrial parts to constructing buildings. However, there are little information about contour crafting (CC in current use; present paper aims to describe the operational steps of creating a whole building by the machine reviewing relevant literature. Furthermore, it will represent the advantages of CC usage compared to traditional construction methods, as well as its applicability in construction industry.

A discussion of the necessity of craft education in the 21st century

Directory of Open Access Journals (Sweden)

Eva Veeber

2015-02-01

Full Text Available Craft education has held a permanent place in Estonian and Finnish schools, although its value and appreciation have changed over time. The aim of the article is to discuss the necessity of craft education in today’s world and its possible impact on the development of children and adolescents. The discussion seeks an interdisciplinary explanation using three perspectives that complement each other. The first describes the challenges of modern society with respect to individual development and schooling. The second deals with Aaron Antonovsky's theory of generalized resistance resources and an individual's possibility to manage in a stressful society. The third addresses the individual as a developing neurological being, along with the effect of learning and practicing motor skills on the human brain. We conclude that crafts is a multidisciplinary phenomenon, and that learning and practicing crafts promotes the comprehension of diversity and challenges in life. Additionally, educational crafts enriches the learning environment, offering opportunities to develop transferable skills that human beings constantly need in society. In addition, crafts provides a balanced way to come to understand the world and one’s role in it, by simultaneously promoting motor and cognitive development and making unique demands on one’s being.Keywords: crafts, craft education, making, sense of coherence, education, embodiment

The impact of job crafting on job demands, job resources, and well-being.

Science.gov (United States)

Tims, Maria; Bakker, Arnold B; Derks, Daantje

2013-04-01

This longitudinal study examined whether employees can impact their own well-being by crafting their job demands and resources. Based on the job demands-resources model, we hypothesized that employee job crafting would have an impact on work engagement, job satisfaction, and burnout through changes in job demands and job resources. Data was collected in a chemical plant at three time points with one month in between the measurement waves (N = 288). The results of structural equation modeling showed that employees who crafted their job resources in the first month of the study showed an increase in their structural and social resources over the course of the study (2 months). This increase in job resources was positively related to employee well-being (increased engagement and job satisfaction, and decreased burnout). Crafting job demands did not result in a change in job demands, but results revealed direct effects of crafting challenging demands on increases in well-being. We conclude that employee job crafting has a positive impact on well-being and that employees therefore should be offered opportunities to craft their own jobs.

Intramolecular and Transannular Diels-Alder Reactions

DEFF Research Database (Denmark)

Tanner, David Ackland; Ascic, Erhad

2014-01-01

Few reactions can compete with the Diels-Alder (DA) [4+2] cycloaddition for the rapid and efficient generation of molecular complexity. The DA reaction is atom-economic and stereospecific, as well as diastereo- and regioselective. The intramolecular version (IMDA) of the DA cycloaddition and its...... and dienophile, methods for acceleration of IMDA reactions (such as use of high pressure) and catalysis (using oxophilic or carbophilic metal complexes, Brønsted acids, and enzymes). The use of furans as diene components (IMDAF), intramolecular hetero-DA (IMHDA) and IMDA reactions with inverse electron demand...... are also covered. Applications of IMDA to asymmetric synthesis (from substrate control through to enantioselective catalysis, including organocatalysis) are presented, along with tandem sequences involving IMDA cycloaddition. A theme pervading the whole chapter is the use of IMDA reactions for the total...

Guides crafting meaning and identity in a flexible working life

DEFF Research Database (Denmark)

Meged, Jane Widtfeldt

2017-01-01

and adding a critical perspective, we understand the guides’ agency, and how they craft scope, tasks and relations in order to sustain a positive self-image and a meaningful working life. Comparing certified guides’ job-crafting practices, we learn that guides are alike across the three countries......Certified guides are exemplary, well-educated, self-employed, casual labourers in a liberal and competitive job market. Applying grounded theory, this exploratory study builds on in-depth qualitative interviews with Danish, Italian and French certified guides. Informed by the theory of job crafting...

Recent Advances in Substrate-Controlled Asymmetric Cyclization for Natural Product Synthesis

Directory of Open Access Journals (Sweden)

Jeyun Jo

2017-06-01

Full Text Available Asymmetric synthesis of naturally occurring diverse ring systems is an ongoing and challenging research topic. A large variety of remarkable reactions utilizing chiral substrates, auxiliaries, reagents, and catalysts have been intensively investigated. This review specifically describes recent advances in successful asymmetric cyclization reactions to generate cyclic architectures of various natural products in a substrate-controlled manner.

Modular Three-Component Synthesis of 4-Aminoquinolines via an Imidoylative Sonogashira/Cyclization Cascade

NARCIS (Netherlands)

Collet, Jurriën W.; Ackermans, Kelly; Lambregts, Jeffrey; Maes, Bert U.W.; Orru, Romano V.A.; Ruijter, Eelco

2018-01-01

We developed a one-pot, two-stage synthetic route to substituted 4-aminoquinolines involving an imidoylative Sonogashira coupling followed by acid-mediated cyclization. This three-component reaction affords pharmaceutically valuable 4-aminoquinolines in a one-pot procedure from readily available

Deaminated zeolite, ITQ-6 as heterogeneous catalyst for Friedel crafts alkylation

International Nuclear Information System (INIS)

Zainab Ramli; Noor Ashikin Mohd Yusoff; Halimaton Hamdan

2007-01-01

The ability of ITQ-6, a kind of meso porous zeolitic material to replace microporous zeolite as catalyst has attracted particular attention. In this study, modification of a precursor of microporous ferrierite, PREFER to meso porous material, ITQ-6 was carried out by delamination technique. The XRD results show that the crystalline phase of PREFER diminished for the sample after delamination. Porosity study of the ITQ-6 sample shows formation of homogeneous meso pores in the size between 3.5-4.0 nm. The acidity study indicates that ITQ-6 still contains appreciable amounts of Bronsted and Lewis acidities. Catalytic evaluation of the resulting material, ITQ-6 was carried out in the alkylation of resorcinol with methyl tert-butyl ether which gave 4-tert-butyl resorcinol and 4, 6-di-tert-butyl resorcinol as main products. The conversion of resorcinol when using ITQ-6 was ten times higher than ferrierite, FER with similar selectivity of disubstituted product. It shows that the meso porosity of ITQ-6 was responsible for the higher activity of the catalyst in the reaction. (author)

Intramolekulare Friedel-Crafts-Acylierung von N-Phthaloyl-substituierten Aryl- und Homophenylalanylchloriden

OpenAIRE

Effenberger, Franz; Steegmüller, Dieter; Null, Volker; Ziegler, Thomas

1988-01-01

Die intramolekulare Acylierung von N-Phthaloyl-geschützten Aryl- und Homophenylalanychloriden 5 mit zweifach molaren Mengen AlCl3 oder katalytischen Mengen FeCl3 führt zu 2-Phthal-imido-l-indanonen 6 bzw. -1-tetralon (6d). Während die Cyclo-acylierung zum Tetralon 6d mit AlCl3 und mit FeCl3 racemisierungsfrei mit sehr guten Ausbeuten abläuft, erfolgt die Bildung des Indanons 6a mit FeCl3 unter Racemisierung. N-Phthaloyl-geschützte α-Aminosäurechloride bilden mit Silber-trifluormethansulf...

The craft of screenwriting

NARCIS (Netherlands)

Weijers, G.W.M.

2014-01-01

Isn't it ironic? Screenwriting is not something you learn from a book, or a talent that just falls into your lap. Nevertheless, without talent you will never become a great scriptwriter. Above all scriptwriting is a craft that you learn to master by writing, reflecting, and rewriting time after

Synthesis, Antibacterial and Antitubercular Activities of Some 5H-Thiazolo[3,2-a]pyrimidin-5-ones and Sulfonic Acid Derivatives

Directory of Open Access Journals (Sweden)

Dong Cai

2015-09-01

Full Text Available A series of 5H-thiazolo[3,2-a]pyrimidin-5-ones were synthesized by the cyclization reactions of S-alkylated derivatives in concentrated H2SO4. Upon treatment of S-alkylated derivatives at different temperatures, intramolecular cyclization to 7-(substituted phenylamino-5H-thiazolo[3,2-a]pyrimidin-5-ones or sulfonation of cyclized products to sulfonic acid derivatives occurred. The structures of the target compounds were confirmed by IR, 1H-NMR, 13C-NMR and HRMS studies. The compounds were evaluated for their preliminary in vitro antibacterial activity against some Gram-positive and Gram-negative bacteria and screened for antitubercular activity against Mycobacterium tuberculosis by the broth dilution assay method. Some compounds showed good antibacterial and antitubercular activities.

Taking control: Is job crafting related to the intention to leave surgical training?

Science.gov (United States)

Dominguez, Luis Carlos; Stassen, Laurents; de Grave, Willem; Sanabria, Alvaro; Alfonso, Edgar; Dolmans, Diana

2018-01-01

The intention to leave surgical training, hereinafter referred as proxy of "attrition," is associated with poor well-being in the workplace. Attrition is suggested to diminish when residents possess job-crafting skills, that is, the ability to redefine their job in meaningful ways and maximize well-being at work by increasing structural and social resources and challenges and decreasing hindering demands. However, the evidence supporting this relationship is scant. This study sought to: 1) investigate to what extent residents possess job-crafting skills and compare residents' levels of job-crafting skills across years of residency training; 2) investigate the relationship between job crafting, well-being as measured by burnout and work-engagement rates, and the intention to leave; and 3) compare the levels of job-crafting skills and well-being between residents with and without serious intentions to leave. This cross sectional study was conducted in fifteen residency programs in Colombia. Surgical residents completed different questionnaires including the Dutch Job Crafting Scale (DJCS), MBI-Human Services Survey (MBI-HSS), Utrecht Work Engagement Scale (UWES-17) and an adapted version of the Nurse Turnover Intention Scale (NTIS). The objectives were addressed by independent analyses of variance (ANOVA), structural equation modeling techniques (SEM) and independent t-tests, respectively. A total of 202 residents participated. Residents generally scored high on their job-crafting skills to increase structural and social resources as well as challenging demands, but were less positive about their skills to reduce hindering demands. No differences across years of training were found. Job crafting correlated positively with work-engagement, which was inversely related to the intention to leave. Conversely, job crafting correlated negatively with burnout, which bore a positive relationship to the intention to leave. Residents with serious intentions to leave exhibited

Productive and counterproductive job crafting: A daily diary study.

Science.gov (United States)

Demerouti, Evangelia; Bakker, Arnold B; Halbesleben, Jonathon R B

2015-10-01

The present study aims to uncover the way daily job crafting influences daily job performance (i.e., task performance, altruism, and counterproductive work behavior). Job crafting was conceptualized as "seeking resources," "seeking challenges," and "reducing demands" and viewed as strategies individuals use to optimize their job characteristics. We hypothesized that daily job crafting relates to daily job demands and resources (work pressure and autonomy), which consequently relate to daily work engagement and exhaustion and ultimately to job performance. A sample of 95 employees filled in a quantitative diary for 5 consecutive working days (n occasions = 475). We predicted and found that daily seeking resources was positively associated with daily task performance because daily autonomy and work engagement increased. In contrast, daily reducing demands was detrimental for daily task performance and altruism, because employees lower their daily workload and consequently their engagement and exhaustion, respectively. Only daily seeking challenges was positively (rather than negatively) associated with daily counterproductive behavior. We conclude that employee job crafting can have both beneficial and detrimental effects on job performance. (c) 2015 APA, all rights reserved).

Crafting by concepts fiber arts and mathematics

CERN Document Server

Belcastro, Sarah-Marie

2016-01-01

From the editors of the popular Making Mathematics with Needlework, this book presents projects that highlight the relationship between types of needlework and mathematics. Chapters start with accessible overviews presenting the interplay between mathematical concepts and craft expressions. Following sections explain the mathematics in more detail, and provide suggestions for classroom activities. Each chapter ends with specific crafting instructions. Types of needlework included are knitting, crochet, needlepoint, cross-stitch, quilting, temari balls, beading, tatting, and string art. Instructions are written as ordinary patterns, so the formatting and language will be familiar to crafters.

Strong Quantum Size Effects in Pb(111) Thin Films Mediated by Anomalous Friedel Oscillations

Science.gov (United States)

Jia, Yu; Wu, Biao; Li, Chong; Einstein, T. L.; Weitering, H. H.; Zhang, Zhenyu

2010-08-01

Using first-principles calculations within density functional theory, we study Friedel oscillations (FOs) in the electron density at different metal surfaces and their influence on the lattice relaxation and stability of ultrathin metal films. We show that the FOs at the Pb(111) surface decay as 1/x with the distance x from the surface, different from the conventional 1/x2 power law at other metal surfaces. The underlying physical reason for this striking difference is tied to the strong nesting of the two different Fermi sheets along the Pb(111) direction. The interference of the strong FOs emanating from the two surfaces of a Pb(111) film, in turn, not only results in superoscillatory interlayer relaxations around the center of the film, but also determines its stability in the quantum regime. As a simple and generic picture, the present findings also explain why quantum size effects are exceptionally robust in Pb(111) films.

When craft and science collide: Improving therapeutic practices through evidence-based innovations.

Science.gov (United States)

Justice, Laura M

2010-04-01

Evidence-based practice (EBP) is a model of clinical decision-making that is increasingly being advocated for use in the field of speech-language pathology. With the increased emphasis on scientific evidence as a form of knowledge important to EBP, clinicians may wonder whether their craft-based knowledge (i.e., knowledge derived from theory and practice), remains a legitimate form of knowledge for use in clinician decisions. This article describes forms of knowledge that may be used to address clinical questions, to include both craft and science. Additionally, the steps used when engaging in EBP are described so that clinicians understand when and how craft comes into play. The major premise addressed within this article is that craft is a legitimate form of knowledge and that engagement in EBP requires one to employ craft-based knowledge.

Hydroxyl-substituted ladder polyethers via selective tandem epoxidation/cyclization sequence.

Science.gov (United States)

Czabaniuk, Lara C; Jamison, Timothy F

2015-02-20

A new and highly selective method for the synthesis of hydroxyl-substituted tetrahydropyrans is described. This method utilizes titanium(IV) isopropoxide and diethyl tartrate to perform a diastereoselective epoxidation followed by in situ epoxide activation and highly selective endo-cyclization to form the desired tetrahydropyran ring. The HIJ ring fragment of the marine ladder polyether yessotoxin was synthesized using this two-stage tactic that proceeds with high efficiency and excellent regioselectivity.

Searching the Soul: Veterans and Their Arts and Crafts

Science.gov (United States)

Hasio, Cindy

2011-01-01

For military veterans suffering from the long-term trauma of warfare, arts and crafts become much more than the fabrication of relics; they can literally save the spirit. Dialogue and interaction between the veterans, volunteers, and staff are crucial to the success of veterans' arts and crafts program. The purpose of this research was threefold.…

Major factors influencing craft productivity in nuclear power plant construction

International Nuclear Information System (INIS)

Borcherding, J.D.; Sebastian, S.J.

1980-01-01

This paper reports on a research study whose objective was to determine the most influential factors adversely affecting craft productivity in nuclear power plant construction from the perspective of the tradesmen employed at the sites. Data were collected through the use of a questionnaire survey and group interview sessions, predominantly with workmen, at six nuclear power plant construction projects. Craftsmen were chosen as the major data base because of their awareness of how their time would actually be spent on the project. Topics considered include the factors influencing craft productivity, material availability, redoing work, crew interfacing, overcrowded work areas, instruction time, inspection delays, craft turnover, craft absenteeism, foreman changes, foreman incompetence, engineering design lead time, comprehensive scheduling of the design function, the responsibility of the utility, value engineering, plant standardization, the effective utilization of the planning and scheduling system, and the labor-management committee

Concept annotation in the CRAFT corpus.

Science.gov (United States)

Bada, Michael; Eckert, Miriam; Evans, Donald; Garcia, Kristin; Shipley, Krista; Sitnikov, Dmitry; Baumgartner, William A; Cohen, K Bretonnel; Verspoor, Karin; Blake, Judith A; Hunter, Lawrence E

2012-07-09

Manually annotated corpora are critical for the training and evaluation of automated methods to identify concepts in biomedical text. This paper presents the concept annotations of the Colorado Richly Annotated Full-Text (CRAFT) Corpus, a collection of 97 full-length, open-access biomedical journal articles that have been annotated both semantically and syntactically to serve as a research resource for the biomedical natural-language-processing (NLP) community. CRAFT identifies all mentions of nearly all concepts from nine prominent biomedical ontologies and terminologies: the Cell Type Ontology, the Chemical Entities of Biological Interest ontology, the NCBI Taxonomy, the Protein Ontology, the Sequence Ontology, the entries of the Entrez Gene database, and the three subontologies of the Gene Ontology. The first public release includes the annotations for 67 of the 97 articles, reserving two sets of 15 articles for future text-mining competitions (after which these too will be released). Concept annotations were created based on a single set of guidelines, which has enabled us to achieve consistently high interannotator agreement. As the initial 67-article release contains more than 560,000 tokens (and the full set more than 790,000 tokens), our corpus is among the largest gold-standard annotated biomedical corpora. Unlike most others, the journal articles that comprise the corpus are drawn from diverse biomedical disciplines and are marked up in their entirety. Additionally, with a concept-annotation count of nearly 100,000 in the 67-article subset (and more than 140,000 in the full collection), the scale of conceptual markup is also among the largest of comparable corpora. The concept annotations of the CRAFT Corpus have the potential to significantly advance biomedical text mining by providing a high-quality gold standard for NLP systems. The corpus, annotation guidelines, and other associated resources are freely available at http://bionlp-corpora.sourceforge.net/CRAFT/index.shtml.

Highly efficient induction of chirality in intramolecular

Science.gov (United States)

Cossio; Arrieta; Lecea; Alajarin; Vidal; Tovar

2000-06-16

Highly stereocontrolled, intramolecular [2 + 2] cycloadditions between ketenimines and imines leading to 1,2-dihydroazeto[2, 1-b]quinazolines have been achieved. The source of stereocontrol is a chiral carbon atom adjacent either to the iminic carbon or nitrogen atom. In the first case, the stereocontrol stems from the preference for the axial conformer in the first transition structure. In the second case, the origin of the stereocontrol lies on the two-electron stabilizing interaction between the C-C bond being formed and the sigma orbital corresponding to the polar C-X bond, X being an electronegative atom. These models can be extended to other related systems for predicting the stereochemical outcome in this intramolecular reaction.

Automatic Generation of the Planning Tunnel High Speed Craft Hull Form

Institute of Scientific and Technical Information of China (English)

Morteza Ghassabzadeh; Hassan Ghassemi

2012-01-01

The creation of geometric model of a ship to determine the characteristics of hydrostatic and hydrodynamic,and also for structural design and equipments arrangement are so important in the ship design process.Planning tunnel high speed craft is one of the crafts in which,achievement to their top speed is more important.These crafts with the use of tunnel have the aero-hydrodynamics properties to diminish the resistance,good sea-keeping behavior,reduce slamming and avoid porpoising.Because of the existence of the tunnel,the hull form generation of these crafts is more complex and difficult.In this paper,it has attempted to provide a method based on geometry creation guidelines and with an entry of the least control and hull form adjustment parameters,to generate automatically the hull form of planning tunnel craft.At first,the equations of mathematical model are described and subsequent,three different models generated based on present method are compared and analyzed.Obviously,the generated model has more application in the early stages of design.

Crafting qualities in designing QR-coded embroidery and bedtime stories

NARCIS (Netherlands)

Kuusk, K.; Wensveen, S.A.G.; Tomico, O.

2014-01-01

There is a renewed interest into crafts and what it can mean when integrating new technologies into textiles. This paper proposes to embed craft qualities and sustainable values into designing smart textile projects. Our design iterations QR-Coded Embroidery and Bedtime Stories combine textiles,

Valuing Craftsmanship: In particular the crafting of Chinese porcelain and Dutch Delft Blue

NARCIS (Netherlands)

L. Jiang (Lili)

2018-01-01

markdownabstract“How important are crafts for a society?” When a conventional economist gets the question, the answer is most likely about the prices of craft products, the income of craftspeople, and the contribution that the crafts sector makes to GDP. This thesis gives another answer. Applying

A green and efficient method for the synthesis of homodimeric (β ...

African Journals Online (AJOL)

... derivatives by intramolecular cyclization in various yields. Of particular interest is the use of the water as solvent of reaction and in absence of catalyst. Also these operating conditions protect the environment and economic points of view. Keywords: aqueous synthesis; bioactivity; dihydropyridine; dimedone; green method; ...

Enzyme-Like Catalysis of the Nazarov Cyclization by Supramolecular Encapsulation

Energy Technology Data Exchange (ETDEWEB)

Hastings, Courtney; Pluth, Michael; Bergman, Robert; Raymond, Kenneth

2010-03-29

A primary goal in the design and synthesis of molecular hosts has been the selective recognition and binding of a variety of guests using non-covalent interactions. Supramolecular catalysis, which is the application of such hosts towards catalysis, has much in common with many enzymatic reactions, chiefly the use of both spatially appropriate binding pockets and precisely oriented functional groups to recognize and activate specific substrate molecules. Although there are now many examples which demonstrate how selective encapsulation in a host cavity can enhance the reactivity of a bound guest, all have failed to reach the degree of increased reactivity typical of enzymes. We now report the catalysis of the Nazarov cyclization by a self-assembled coordination cage, a carbon-carbon bond-forming reaction which proceeds under mild, aqueous conditions. The acceleration in this system is over a million-fold, and represents the first example of supramolecular catalysis that achieves the level of rate enhancement comparable to that observed in several enzymes. We explain the unprecedented degree of rate increase as due to the combination of (a) preorganization of the encapsulated substrate molecule, (b) stabilization of the transition state of the cyclization by constrictive binding, and (c) increase in the basicity of the complexed alcohol functionality.

33 CFR 149.310 - What are the muster and embarkation requirements for survival craft?

Science.gov (United States)

2010-07-01

... embarkation requirements for survival craft? 149.310 Section 149.310 Navigation and Navigable Waters COAST... and embarkation requirements for survival craft? Muster and embarkation arrangements for survival craft must comply with 46 CFR 108.540. ...

Craft's brand equity in CZ, focusing on canoeing

OpenAIRE

Šťastný, Šimon

2013-01-01

Title: Craft's brand equity in CZ, focusing on flat water canoeing. Objectives: The objective of this dissertation is to find out what is the Craft's brand equity and to suggest how to improve it on the Czech market. That would be based on marketing research and supplementary interview. I will be using marketing research and supplementary interview. Methods: In this dissertation the method of electronic questioning was used. The questionnaires were sent by email address after first contact on...

Construction and Validation of the Perceived Opportunity to Craft Scale.

Science.gov (United States)

van Wingerden, Jessica; Niks, Irene M W

2017-01-01

We developed and validated a scale to measure employees' perceived opportunity to craft (POC) in two separate studies conducted in the Netherlands (total N = 2329). POC is defined as employees' perception of their opportunity to craft their job. In Study 1, the perceived opportunity to craft scale (POCS) was developed and tested for its factor structure and reliability in an explorative way. Study 2 consisted of confirmatory analyses of the factor structure and reliability of the scale as well as examination of the discriminant and criterion-related validity of the POCS. The results indicated that the scale consists of one dimension and could be reliably measured with five items. Evidence was found for the discriminant validity of the POCS. The scale also showed criterion-related validity when correlated with job crafting (+), job resources (autonomy +; opportunities for professional development +), work engagement (+), and the inactive construct cynicism (-). We discuss the implications of these findings for theory and practice.

Photoswitchable Intramolecular H-Stacking of Perylenebisimide

NARCIS (Netherlands)

Wang, Jiaobing; Kulago, Artem; Browne, Wesley R.; Feringa, Ben L.

2010-01-01

Dynamic control over the formation of H- or J-type aggregates of chromophores is of fundamental importance for developing responsive organic optoelectronic materials. In this study, the first example of photoswitching between a nonstacked and an intramolecularly H-stacked arrangement of

Rhodium Catalyzed Intramolecular C-H Insertion of α-Aryl-α-diazo Ketones

Science.gov (United States)

Taber, Douglass F.; Tian, Weiwei

2011-01-01

Direct diazo transfer proceeds smoothly with α-aryl ketones. The derived α-aryl-α-diazo ketones cyclize efficiently with Rh catalysis to give the corresponding α-aryl cyclopentanones. PMID:17385917

Digitizing Craft: Creative Writing Studies and New Media--A Proposal

Science.gov (United States)

Koehler, Adam

2013-01-01

This article identifies and examines a digital arm of creative writing studies and organizes that proposal into four categories through which to theorize the "craft" of creative production, each borrowed from Tim Mayers's "(Re)Writing Craft: Composition, Creative Writing, and the Future of English Studies": process, genre, author, and…

Hydroxyl Radical-Mediated Novel Modification of Peptides: N-Terminal Cyclization through the Formation of α-Ketoamide.

Science.gov (United States)

Lee, Seon Hwa; Kyung, Hyunsook; Yokota, Ryo; Goto, Takaaki; Oe, Tomoyuki

2015-01-20

The hydroxyl radical-mediated oxidation of peptides and proteins constitutes a large group of post-translational modifications that can result in structural and functional changes. These oxidations can lead to hydroxylation, sulfoxidation, or carbonylation of certain amino acid residues and cleavage of peptide bonds. In addition, hydroxyl radicals can convert the N-terminus of peptides to an α-ketoamide via abstraction of the N-terminal α-hydrogen and hydrolysis of the ketimine intermediate. In the present study, we identified N-terminal cyclization as a novel modification mediated by a hydroxyl radical. The reaction of angiotensin (Ang) II (DRVYIHPF) and the hydroxyl radical generated by the Cu(II)/ascorbic acid (AA) system or UV/hydrogen peroxide system produced N-terminal cyclized-Ang II (Ang C) and pyruvamide-Ang II (Ang P, CH3COCONH-RVYIHPF). The structure of Ang C was confirmed by mass spectrometry and comparison to an authentic standard. The subsequent incubation of isolated Ang P in the presence of Cu(II)/AA revealed that Ang P was the direct precursor of Ang C. The proposed mechanism involves the formation of a nitrogen-centered (aminyl) radical, which cyclizes to form a five-membered ring containing the alkoxy radical. The subsequent β-scission reaction of the alkoxyl radical results in the cleavage of the terminal CH3CO group. The initial aminyl radical can be stabilized by chelation to the Cu(II) ions. The affinity of Ang C toward the Ang II type 1 receptor was significantly lower than that of Ang II or Ang P. Ang C was not further metabolized by aminopeptidase A, which converts Ang II to Ang III. Hydroxyl radical-mediated N-terminal cyclization was also observed in other Ang peptides containing N-terminal alanine, arginine, valine, and amyloid β 1-11 (DAEFRHDSGYE).

33 CFR 149.305 - What are the survival craft requirements for temporary personnel?

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false What are the survival craft... EQUIPMENT Lifesaving Equipment Manned Deepwater Port Requirements § 149.305 What are the survival craft... complement exceeds the capacity of the survival craft required under § 149.304 of this subpart, the port must...

A systematic first-principles study of surface energies, surface relaxation and Friedel oscillation of magnesium surfaces

International Nuclear Information System (INIS)

Tang, Jia-Jun; Yang, Xiao-Bao; Zhao, Yu-Jun; OuYang, LiuZhang; Zhu, Min

2014-01-01

We systematically study the surface energies and surface relaxations of various low-index and high-index Mg surfaces. It is found that low-index surfaces are not necessarily stable as Mg(1 0  1-bar  0) is the most unstable surface in the series of Mg(1 0  1-bar  n) (n = 0–9). A surface-energy predicting model based on the bond cutting is proposed to explain the relative surface stabilities. The local relaxations of the low-index surfaces could be explained by the Friedel oscillation. For the high-index surfaces, the combination of charge smoothing effect and dramatic charge depletion influences the relaxations, which show a big difference from the low-index ones. Our findings provide theoretical data for considerable insights into the surface energies of hexagonal close-packed metals. (paper)

76 FR 38153 - California State Nonroad Engine Pollution Control Standards; Commercial Harbor Craft Regulations...

Science.gov (United States)

2011-06-29

... Standards; Commercial Harbor Craft Regulations; Opportunity for Public Hearing and Comment AGENCY... engines on commercial harbor craft. CARB has requested that EPA issue a new authorization under [email protected] . SUPPLEMENTARY INFORMATION: I. California's Commercial Harbor Craft Regulations In a...

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

Gold-Catalyzed Cyclizations of Alkynol-Based Compounds: Synthesis of Natural Products and Derivatives

Directory of Open Access Journals (Sweden)

Pedro Almendros

2011-09-01

Full Text Available The last decade has witnessed dramatic growth in the number of reactions catalyzed by gold complexes because of their powerful soft Lewis acid nature. In particular, the gold-catalyzed activation of propargylic compounds has progressively emerged in recent years. Some of these gold-catalyzed reactions in alkynes have been optimized and show significant utility in organic synthesis. Thus, apart from significant methodology work, in the meantime gold-catalyzed cyclizations in alkynol derivatives have become an efficient tool in total synthesis. However, there is a lack of specific review articles covering the joined importance of both gold salts and alkynol-based compounds for the synthesis of natural products and derivatives. The aim of this Review is to survey the chemistry of alkynol derivatives under gold-catalyzed cyclization conditions and its utility in total synthesis, concentrating on the advances that have been made in the last decade, and in particular in the last quinquennium.

Practical synthesis of methyl 7-(3-hydroxy-5-oxocyclopent-1-en-1-yl-heptanoate

Directory of Open Access Journals (Sweden)

Xinpeng Jiang

2017-07-01

Full Text Available The key intermediate of misoprostol, methyl 7-(3-hydroxy-5-oxocyclopent-1-en-1-yl-heptanoate was prepared from commercially available suberic acid in 40% yield over five steps. The key step involved a ZnCl2 catalyzed Friedel-Crafts reaction between furan and 2,9-oxonanedione. Sulfuric acid catalyzed methylation of 8-(furan-2-yl-8-oxooctanoic acid followed by sequential reduction and ZnCl2 catalyzed Piancatelli rearrangement resulted in the formation of the key intermediate of misoprostol.

A Concise Synthesis and the Antibacterial Activity of 5,6-Dimethoxynaphthalene-2-carboxylic Acid

OpenAIRE

GÖKSU, Süleyman; UĞUZ, Metin Tansu

2014-01-01

5,6-Dimethoxynaphthalene-2-carboxylic acid was synthesized in 7 steps and with an overall yield of 46%. Bromination of 2-naphthol, and methylation with dimethyl sulfate followed by Friedel-Crafts acylation with AcCl gave 2-acetyl-5-bromo-6-methoxynaphthalene. 2-Acetyl-5-bromo-6-methoxynaphthalene was converted to 5-bromo-6- methoxynaphthalene-2-carboxylic acid by a haloform reaction. The esterification of the acid with methanol, methoxylation with NaOCH3 in the presence of CuI and s...

Conductance and activation energy for electron transport in series and parallel intramolecular circuits.

Science.gov (United States)

Hsu, Liang-Yan; Wu, Ning; Rabitz, Herschel

2016-11-30

We investigate electron transport through series and parallel intramolecular circuits in the framework of the multi-level Redfield theory. Based on the assumption of weak monomer-bath couplings, the simulations depict the length and temperature dependence in six types of intramolecular circuits. In the tunneling regime, we find that the intramolecular circuit rule is only valid in the weak monomer coupling limit. In the thermally activated hopping regime, for circuits based on two different molecular units M a and M b with distinct activation energies E act,a > E act,b , the activation energies of M a and M b in series are nearly the same as E act,a while those in parallel are nearly the same as E act,b . This study gives a comprehensive description of electron transport through intramolecular circuits from tunneling to thermally activated hopping. We hope that this work can motivate additional studies to design intramolecular circuits based on different types of building blocks, and to explore the corresponding circuit laws and the length and temperature dependence of conductance.

Job crafting, work engagement, and psychological distress among Japanese employees: a cross-sectional study

OpenAIRE

Sakuraya, Asuka; Shimazu, Akihito; Eguchi, Hisashi; Kamiyama, Kimika; Hara, Yujiro; Namba, Katsuyuki; Kawakami, Norito

2017-01-01

Background Job crafting, an employee-initiated job design/redesign, has become important for employees? well-being. However, most studies on the relationship between job crafting and employees? well-being have been conducted in western countries; thus, it is unclear whether job crafting can be effectively applied to Asian cultures, such as Japan, which emphasizes group harmony. The aim of this study was to examine the cross-sectional associations of self-reported job crafting with work engage...

Synthesis of fused azole-piperidionoses: A free radical cyclization approach

Energy Technology Data Exchange (ETDEWEB)

Marco-Contelles, Jose; Alhambra Jimenez, Carolina [Instituto de Quimica Organica General (CSIC), Madrid (Spain)

1999-08-01

A new strategy has been reported for the synthesis of fused azole-piperidinoses featuring and unprecedented and very efficient 6-exo-trig free radical cyclization onto heterocyclic sugar templates. These compounds are key intermediates for the synthesis of known or analogues of azole-glycosidase inhibitors. In this communication we describe our recent and successful results on the synthesis of fused triazole-piperidinoses. Radical precursors have been prepared by standard methodologies from 1, 2:5, 6-bis-O-isopropylidene-{alpha}-D-glucofuranose (4) via triazoles linked at C3 with {beta}-orientation, readily obtained by 1, 3-dipolar cycloaddition of azide 5 with diethyl acetylenedicarboxylate or methyl propiolate, and by S{sub N}2 displacement of the tosylate at C3 with 1, 2, 4-triazole in compound 20. The key 6-exp-trig free radical cyclizations proceeded in the usual conditions [tributyltin hydride or tris(trimethylsily)silane, AIBN, toluene] yielding the azaannulated sugars 9, 11, 19 and 23 in good or excellent yields. A mechanism for these cyclizations has been proposed. [Spanish] Se ha informado una nueva estrategia para la sintesis azol-piperidinosas fusionadas mediante una ciclizacion 6-exo-trig muy eficiente y sin precedentes, sobre plantillas de azucares heterociclicos. Estos compuestos son intermediarios claves para la sintesis de inhibidores de azol-glicosidasa conocidos analogos de ellos. En esta comunicacion describimos nuestros resultados recientes y exitosos sobre la sintesis de triazol-piperidinosas. Los precursores de radicales fueron preparados por la metodologia usual a partir de 1, 2:5, 6-bis-O-isopropiliden-{alpha}-D-glucofuranosa (4) via triazoles unidos en C3, con orientacion {beta}, los cuales se obtienen facilmente por cicloadicion 1, 3-dipolar de la azida 5 con acetilendicarboxilato de dietilo o propiolato de metilo y por desplazamiento S{sub N}2 del tosilato en C3 con 1, 2, 4-triazol en el compuesto 20. Las ciclizaciones 6-exo

Side Chain Cyclized Aromatic Amino Acids

DEFF Research Database (Denmark)

Van der Poorten, Olivier; Knuhtsen, Astrid; Sejer Pedersen, Daniel

2016-01-01

Constraining the conformation of flexible peptides is a proven strategy to increase potency, selectivity, and metabolic stability. The focus has mostly been on constraining the backbone dihedral angles; however, the correct orientation of the amino acid side chains (χ-space) that constitute...... the peptide pharmacophore is equally important. Control of χ-space utilizes conformationally constrained amino acids that favor, disfavor, or exclude the gauche (-), the gauche (+), or the trans conformation. In this review we focus on cyclic aromatic amino acids in which the side chain is connected...... to the peptide backbone to provide control of χ(1)- and χ(2)-space. The manifold applications for cyclized analogues of the aromatic amino acids Phe, Tyr, Trp, and His within peptide medicinal chemistry are showcased herein with examples of enzyme inhibitors and ligands for G protein-coupled receptors....

A study of the breakdown of Friedel's law in electron backscatter Kikuchi diffraction patterns: Application to zincblende-type structures

International Nuclear Information System (INIS)

Baba-Kishi, K.Z.

1991-01-01

The breakdown of Friedel's law has been observed in backscatter Kikuchi diffraction patterns (BKDP) obtained in the scanning electron microscope (SEM) from a series of zincblende structures including GaAs, InP, GaSb, CdHgTe and the minerals sphalerite (ZnS), chalcopyrite (CuFeS 2 ) and tetrahedrite (Cu 12 Sb 4 S 13 ). Differences in intensities were observed between the reflections 11anti 1 and 5anti 1anti 1 in InP, GaSb, CdHgTe and sphalerite, thus allowing the non-centrosymmetric point group anti 43 m to be determined. In GaAs, differences in intensities were noted between anti 511 and anti 5anti 11. In chalcopyrite and tetrahedrite, non-equivalent intensities were observed between anti 215 and 2anti 1anti 5 and between 3anti 1anti 2 and 31anti 2, respectively. In addition, BKDPs obtained from chalcopyrite revealed a small displacement at the point where the pair of equivalent reflections anti 406 and 460 intersect within the Kikuchi band 02anti 2. The presence of this displacement together with observation of the breakdown of Friedel's law confirmed the tetragonal point group anti 42m for chalcopyrite. Although the point groups of GaAs, chalcopyrite and tetrahedrite were derived successfully using BKDPs, determination of their space groups proved unsuccessful. The superstructure reflections were invisible because the structure factors are very small. The behaviour of the invisible 200 reflection in GaAs is investigated using many-beam dynamical intensity profiles calculated across the h00 systematic row of reflections. Dynamical intensity profiles calculated across the h00 systematic rows of reflections for Ge, InP and sphalerite are also discussed. (orig.)

New amidines from intramolecular cyclization in triflic acid of ...

Indian Academy of Sciences (India)

TECS

2007-05-22

May 22, 2007 ... various heterocyclic compounds. 5. In particular, aromatic amidines have been shown to function as excellent arginine side-chain mimetic due to their favorable spatial and electrostatic properties. 6. Some N-Aryl substituted derivatives show insecti- cidal activity against the housefly, muska domestica,.

Students' Attitudes towards Craft and Technology in Iceland and Finland

Science.gov (United States)

Thorsteinsson, Gísli; Ólafsson, Brynjar; Autio, Ossi

2012-01-01

Craft education in both Finland and Iceland originated over 140 years ago and was influenced by the Scandinavian Sloyd pedagogy. Since then, the subject has moved away from craft and towards technology, with the aim being to increase students' technological abilities. In the beginning, the subject largely focused on the students copying artefacts,…

Two-craft Coulomb formation study about circular orbits and libration points

Science.gov (United States)

Inampudi, Ravi Kishore

This dissertation investigates the dynamics and control of a two-craft Coulomb formation in circular orbits and at libration points; it addresses relative equilibria, stability and optimal reconfigurations of such formations. The relative equilibria of a two-craft tether formation connected by line-of-sight elastic forces moving in circular orbits and at libration points are investigated. In circular Earth orbits and Earth-Moon libration points, the radial, along-track, and orbit normal great circle equilibria conditions are found. An example of modeling the tether force using Coulomb force is discussed. Furthermore, the non-great-circle equilibria conditions for a two-spacecraft tether structure in circular Earth orbit and at collinear libration points are developed. Then the linearized dynamics and stability analysis of a 2-craft Coulomb formation at Earth-Moon libration points are studied. For orbit-radial equilibrium, Coulomb forces control the relative distance between the two satellites. The gravity gradient torques on the formation due to the two planets help stabilize the formation. Similar analysis is performed for along-track and orbit-normal relative equilibrium configurations. Where necessary, the craft use a hybrid thrusting-electrostatic actuation system. The two-craft dynamics at the libration points provide a general framework with circular Earth orbit dynamics forming a special case. In the presence of differential solar drag perturbations, a Lyapunov feedback controller is designed to stabilize a radial equilibrium, two-craft Coulomb formation at collinear libration points. The second part of the thesis investigates optimal reconfigurations of two-craft Coulomb formations in circular Earth orbits by applying nonlinear optimal control techniques. The objective of these reconfigurations is to maneuver the two-craft formation between two charged equilibria configurations. The reconfiguration of spacecraft is posed as an optimization problem using the

The effects of job crafting on subjective well-being amongst South African high school teachers

Directory of Open Access Journals (Sweden)

Sergio Peral

2016-09-01

Full Text Available Orientation: Job crafting can result in a number of positive outcomes for teachers, such as increased meaningfulness and engagement at work. Increased work engagement and psychological meaningfulness may yield positive benefits for the practice of teaching, thus highlighting the pivotal role of job crafting. Research purpose: The study’s aim was to investigate the relationship between job crafting and subjective well-being amongst South African high school teachers. Subjective well-being comprises psychological meaningfulness and work engagement. The potential mediating effect that psychological meaningfulness had on this relationship was further explored. Motivation for the study: Being in a highly stressful occupation, teachers need to continuously find ways to craft their working practices in order to deal effectively with their job demands and to capitalise on their available job resources. Furthermore, South Africa’s current education system calls for serious proactive measures to be taken to improve and rectify the current status, such as job crafting. Research approach, design and method: A quantitative, cross-sectional survey design was used and administered to a sample of South African high school teachers situated in Gauteng, South Africa (N = 251. Main findings: A positive relationship was found between job crafting (increasing structural resources and challenging job demands and work engagement. Furthermore, psychological meaningfulness mediated the relationship between job crafting and work engagement amongst the sampled high school teachers. Practical/managerial implications: Teachers who craft their work to better suit their preferences and needs will obtain greater meaning in their work and experience increased levels of work engagement. Training programmes and/or group-based interventions targeted around job crafting techniques may be particularly useful in the South African teaching context. Contribution/value-add: This

Cooking and Hammering: Primary School Pupils' Concepts of their Craft Skills

Directory of Open Access Journals (Sweden)

Mare MÜÜRSEPP

2014-07-01

Full Text Available The aim of the study is to clear the significance of craft skills for the pupils in age nine and twelve years. More than 200 pupils were asked to define, what are the most important skills for the pupils of their age. The results bring out that category of the skills related to craft subject is of the most presented categories in pupils' self description. Thus the primary school pupils essentially defined themselves by the activities they could do practically (building, cooking, repairing of things. The most undefined relation to craft activities is reflected in the answer of smaller boys in our study. A suspicion arisen from the analysis of pupils' sayings, that the craft lessons in the 1st school stage tend to be organized kind of poorly was asserted by the teachers who pointed out the need for special rooms and materials to implement different techniques.

Learning Practices of Femininity through Gendered Craft Education in Finland

Science.gov (United States)

Kokko, Sirpa

2009-01-01

This paper discusses the processes and practices that link crafts and gender in the upbringing and education of girls. The paper is based on a study conducted among female primary school trainee teachers in Finland. The data are comprised of their experiences with crafts as schoolgirls. The methods of the study were memory work and writing of…

Primary student teachers’ perceptions of their prior experiences with craft-making in light of Hannah Arendt’s human condition

Directory of Open Access Journals (Sweden)

Seija Karppinen

2013-09-01

Full Text Available This article presents the results of a study about student teachers’ feelings toward craft-making and teaching crafts. As a teacher educator in teacher training, my interest lies first in student teachers’ prior craft experiences and in their prejudices about themselves as craft-makers in relation to the human condition as set forth by philosopher Hannah Arendt (1958/2002. Second, I am interested in how students’ experiences and their image of crafts affect their attitude to crafts and teaching crafts. The study uses qualitative content analysis (e.g. Cohen, Manion & Morrison, 2007, concept clarification (e.g. Kramer, 1993; Burkin, 2011 and thought experiments (Zalta, 2011; Cohnitz, 2006; Sorensen, 1992 to identify and categorise student teachers’ emotional experiences. The data consist of essays (craft biographies, N=144 by first-year student teachers which were written in 2008 and 2009 during a basic course in crafts as part of teacher education at the University of Helsinki. Arendt (1958/2002 labelled the elements of the human condition as labour, work and action. In this study I discuss how, for instance, Arendtian concepts could be explained in relation to crafts, craft-making and education. Arendt categorises craft, defined as things made by hand, as part of the concept of work. In this study, I consider whether crafts and craft-making could be part of other Arendtian terms as well and how these terms fit various educational situations. As a result, there is a need for additional terms alongside Arendtian terms to describe multifaceted craft-making and primary student teachers’ perceptions of themselves as craft-makers. In relation to student teachers’ memories on primary school crafts, I have labelled Arendtian concept labour as students’ credit-orientated activity, the concept of work as making-orientated activity and the concept of action as interaction-orientated activity. These three orientations of craft frame student

Experimental Investigation of a Wing-in-Ground Effect Craft

Directory of Open Access Journals (Sweden)

M. Mobassher Tofa

2014-01-01

Full Text Available The aerodynamic characteristics of the wing-in-ground effect (WIG craft model that has a noble configuration of a compound wing was experimentally investigated and Universiti Teknologi Malaysia (UTM wind tunnel with and without endplates. Lift and drag forces, pitching moment coefficients, and the centre of pressure were measured with respect to the ground clearance and the wing angle of attack. The ground effect and the existence of the endplates increase the wing lift-to-drag ratio at low ground clearance. The results of this research work show new proposed design of the WIG craft with compound wing and endplates, which can clearly increase the aerodynamic efficiency without compromising the longitudinal stability. The use of WIG craft is representing an ambitious technology that will help in reducing time, effort, and money of the conventional marine transportation in the future.

Experimental investigation of a wing-in-ground effect craft.

Science.gov (United States)

Tofa, M Mobassher; Maimun, Adi; Ahmed, Yasser M; Jamei, Saeed; Priyanto, Agoes; Rahimuddin

2014-01-01

The aerodynamic characteristics of the wing-in-ground effect (WIG) craft model that has a noble configuration of a compound wing was experimentally investigated and Universiti Teknologi Malaysia (UTM) wind tunnel with and without endplates. Lift and drag forces, pitching moment coefficients, and the centre of pressure were measured with respect to the ground clearance and the wing angle of attack. The ground effect and the existence of the endplates increase the wing lift-to-drag ratio at low ground clearance. The results of this research work show new proposed design of the WIG craft with compound wing and endplates, which can clearly increase the aerodynamic efficiency without compromising the longitudinal stability. The use of WIG craft is representing an ambitious technology that will help in reducing time, effort, and money of the conventional marine transportation in the future.

Gold(I-catalyzed domino cyclization for the synthesis of polyaromatic heterocycles

Directory of Open Access Journals (Sweden)

Mathieu Morin

2013-11-01

Full Text Available Gold(I complexes have emerged as powerful and useful catalysts for the formation of new C–C, C–O and C–N bonds. Taking advantage of the specificity of [IPrAuNCMe][SbF6] complexes to favor the 5-exo-dig cyclization over the 6-endo-dig pathway, we report a high yielding and efficient method to generate substituted polyaromatic heterocycles under remarkably mild reaction conditions.

Analyzing components of Community Reinforcement and Family Training (CRAFT): Is treatment entry training sufficient?

Science.gov (United States)

Kirby, Kimberly C; Benishek, Lois A; Kerwin, MaryLouise E; Dugosh, Karen L; Carpenedo, Carolyn M; Bresani, Elena; Haugh, James A; Washio, Yukiko; Meyers, Robert J

2017-11-01

Community Reinforcement and Family Training (CRAFT) assists family members with a treatment-resistant loved one. The most consistent outcome of CRAFT is increased treatment entry of the identified treatment-resistant person (IP). This led us to question whether all 6 components of CRAFT are necessary. In a randomized clinical trial, 115 concerned significant others (CSOs) of an IP received 12-14 sessions of the full CRAFT intervention, 4-6 sessions focused on Treatment Entry Training (TEnT), or 12-14 sessions of Al-Anon/Nar-Anon Facilitation (ANF). We monitored treatment entry, attendance, and substance use of the IP and the CSO's mood and functioning. Data were collected at baseline and 4, 6, and 9 months after the baseline. We found significant reductions in time to treatment entry (χ(2)2 = 8.89, p = .01) and greater treatment entry rates for CRAFT (62%; odds ratio [OR] = 2.7, 95% confidence interval [CI] = 1.1-6.9) and TEnT (63%; OR = 2.9, 95% CI = 1.2-7.5) compared with ANF (37%), but CRAFT and TEnT did not differ significantly from each other (OR = 1.1, 95% CI = 0.4-2.7). No between-group differences in IP drug use were reported by CSOs, but days of drug use decreased over time for all groups (F(3, 277) = 13.47, p CRAFT produces greater treatment entry rates than ANF and found similar treatment entry rates for CRAFT and TEnT. This suggests that treatment entry training is sufficient for producing the best established outcome of CRAFT. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

High Job Demands, Still Engaged and Not Burned Out? The Role of Job Crafting.

Science.gov (United States)

Hakanen, Jari J; Seppälä, Piia; Peeters, Maria C W

2017-08-01

Traditionally, employee well-being has been considered as resulting from decent working conditions arranged by the organization. Much less is known about whether employees themselves can make self-initiated changes to their work, i.e., craft their jobs, in order to stay well, even in highly demanding work situations. The aim of this study was to use the job demands-resources (JD-R model) to investigate whether job crafting buffers the negative impacts of four types of job demands (workload, emotional dissonance, work contents, and physical demands) on burnout and work engagement. A questionnaire study was designed to examine the buffering role of job crafting among 470 Finnish dentists. All in all, 11 out of 16 possible interaction effects of job demands and job crafting on employee well-being were significant. Job crafting particularly buffered the negative effects of job demands on burnout (7/8 significant interactions) and to a somewhat lesser extent also on work engagement (4/8 significant interactions). Applying job crafting techniques appeared to be particularly effective in mitigating the negative effects of quantitative workload (4/4 significant interactions). By demonstrating that job crafting can also buffer the negative impacts of high job demands on employee well-being, this study contributed to the JD-R model as it suggests that job crafting may even be possible under high work demands, and not only in resourceful jobs, as most previous studies have indicated. In addition to the top-down initiatives for improving employee well-being, bottom-up approaches such as job crafting may also be efficient in preventing burnout and enhancing work engagement.

Secondary School Design: Workshop Crafts.

Science.gov (United States)

Department of Education and Science, London (England).

Design features are described for school shop facilities. Some general requirements common to most workshops are discussed; and specific design information is provided for general woodwork, general metalwork, and combined wood and metalwork facilities. The grouping of the workshop crafts and their relation to other parts of the school are also…

Solvent control of intramolecular proton transfer

DEFF Research Database (Denmark)

Manolova, Y.; Marciniak, Heinz; Tschierlei, S.

2017-01-01

of molecules in the enol and zwitterionic proton transfer (PT) form exists in the ground state. However, the zwitterion is the energetically favored one in the electronically excited state. Optical excitation of the enol form results in intramolecular proton transfer and formation of the PT form within 1.4 ps...

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

Directory of Open Access Journals (Sweden)

Peter I. Nagy

2014-10-01

Full Text Available A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011 or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic in acid-base complexes have been surveyed.

Synthesis, Characterization, and In Vitro Evaluation of New (99m)Tc/Re(V)-Cyclized Octreotide Analogues: An Experimental and Computational Approach.

Science.gov (United States)

Li, Yawen; Ma, Lixin; Gaddam, Vikram; Gallazzi, Fabio; Hennkens, Heather M; Harmata, Michael; Lewis, Michael R; Deakyne, Carol A; Jurisson, Silvia S

2016-02-01

Radiolabeled proteolytic degradation-resistant somatostatin analogues have been of long-standing interest as cancer imaging and radiotherapy agents for targeting somatostatin receptor-positive tumors. Our interest in developing (186)Re- and (188)Re-based therapeutic radiopharmaceuticals led to investigation of a new Re(V)-cyclized octreotide analogue, Re(V)-cyclized, thiolated-DPhe(1)-Cys(2)-Tyr(3)-DTrp(4)-Lys(5)-Thr(6)-Cys(7)-Thr(OH)(8) (Re-SDPhe-TATE) using both experimental and quantum chemical methods. The metal is directly coordinated to SDPhe-TATE through cyclization of the peptide around the [ReO](3+) core. Upon complexation, four isomers were observed; the isolated/semi-isolated isomers exhibited different somatostatin receptor (sstr) binding affinities, 0.13 to 1.5 μM, in rat pancreatic tumor cells. Two-dimensional NMR experiments and electronic structure calculations were employed to elucidate the structural differences among the different isomers. According to NMR studies, the metal is coordinated to three thiolates and the backbone amide of Cys(2) in isomers 1 and 4, whereas the metal is coordinated to three thiolates and the backbone amide of Tyr(3) in isomer 2. Quantum chemical methods clarified the stereochemistry of Re-SDPhe-TATE and the possible peptide arrangements around the [ReO](3+) core. The re-cyclization reaction was translated to the (99m)Tc radiotracer level with four isomers observed on complexation with comparable HPLC retention times as the Re-SDPhe-TATE isomers. About 85% total (99m)Tc labeling yield was achieved by ligand exchange from (99m)Tc-glucoheptonate at 60 °C for an hour. About 100% and 51% of (99m)Tc(V)-cyclized SDPhe-TATE remained intact in phosphate buffered saline and 1 mM cysteine solution under physiological conditions at 6 h, respectively.

46 CFR 180.204 - Survival craft-vessels operating on coastwise routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-vessels operating on coastwise routes. 180.204 Section 180.204 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) SMALL... Craft § 180.204 Survival craft—vessels operating on coastwise routes. (a) Except as allowed by paragraph...

46 CFR 180.207 - Survival craft-vessels operating on lakes, bays, and sounds routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-vessels operating on lakes, bays, and... Survival Craft § 180.207 Survival craft—vessels operating on lakes, bays, and sounds routes. (a) Except as... warm water is not required to carry survival craft. (d) A vessel certificated to operate on lakes, bays...

Leader–member exchange fosters work engagement: The mediating role of job crafting

Directory of Open Access Journals (Sweden)

Mirjam Radstaak

2017-09-01

Full Text Available Orientation: The right balance between job demands and job resources are essential for employees to bring energy and enthusiasm to work. Employees who experience high-quality relationships with their supervisors may actively craft their job demands and job resources and feel more engaged. Research purpose: The current study examined the associations between leader–member exchange (LMX, job crafting and work engagement. Motivation: This study attempts to gain more insight in the associations between LMX, job crafting and work engagement. It was hypothesised that high-quality relationships with supervisors fosters work engagement because it stimulates employees to craft their jobs by increasing social and structural job resources and challenging job demands and by decreasing hindering job demands. Research approach, design and methodology: Participants (N = 402 working for a leading mail and parcels company in the Netherlands completed questionnaires measuring LMX, work engagement and job crafting. Structural equation modelling was used to examine the hypotheses. Main findings: Increasing social job resources (β = 0.01, SE = 0.00, p < 0.001 and increasing challenging job demands (β = 0.08, SE = 0.04, p < 0.05 were significant mediators in the association between LMX and work engagement. Increasing structural job resources (β = 0.00, SE = 0.00, p = 0.92 and decreasing hindering job demands (β = -0.00, SE 0.00, p = 0.09 were not significant mediators. Practical and managerial implications: Supervisors who are capable of building high-quality relationships with their employees based on trust, respect and loyalty will foster a positive, fulfilling work-related state of mind among employees because they are more willing to proactively craft a challenging and resourceful work environment. Contribution or value-add: The findings of this study showed the importance of high-quality relationships with supervisors and were unique in examining the

46 CFR 180.202 - Survival craft-vessels operating on oceans routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-vessels operating on oceans routes. 180... VESSELS (UNDER 100 GROSS TONS) LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 180.202 Survival craft—vessels operating on oceans routes. (a) Each vessel certificated to operate on...

46 CFR 180.208 - Survival craft-vessels operating on rivers routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Survival craft-vessels operating on rivers routes. 180... VESSELS (UNDER 100 GROSS TONS) LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 180.208 Survival craft—vessels operating on rivers routes. (a) Except as allowed by paragraphs (c), (d...

Which employees craft their jobs and how? Basic dimensions of personality and employees' job crafting behaviour

NARCIS (Netherlands)

Bipp, T.; Demerouti, E.

2015-01-01

The aim of the current research was to examine to what degree basic personality dimensions serve as determinants of job crafting behaviour and to investigate how this behaviour can be influenced via behavioural intentions. In Study 1, we investigated the relationship of approach and avoidance

Intramolecularly Hydrogen-Bonded Polypyrroles as Electro-Optical Sensors

National Research Council Canada - National Science Library

Nicholson, Jesse

2001-01-01

We have developed a new class of polypyrroles bearing both hydrogen-bond acceptor and hydrogen-donor groups such that the intramolecular hydrogen bonding holds the system planar enhancing conjugation...

Transformational leadership, adaptability, and job crafting : the moderating role of organizational identification.

NARCIS (Netherlands)

Wang, H.; Demerouti, E.; Le Blanc, P.M.

In this study, we aim to explore the link between transformational leadership and job crafting. We predict that transformational leadership will stimulate employee job crafting (seeking resources, seeking challenges, and reducing demands) by increasing their adaptability; but that transformational

INTRAMOLECULAR ISOTOPE EFFECTS IN HYDROCARBON MASS SPECTRA

Energy Technology Data Exchange (ETDEWEB)

Stevenson, D. P.; Schachtschneider, J. H.

1963-07-15

Approximate calculations based on the quasi-equilibrium rate theory of the origin of mass spectra are shown to lead to an approximately correct magnitude for the intramolecular ( pi /sup -/) isotope effect on C--H bond dissociation probabilities of various deuterohydrocarbons. (auth)

Crafting digital media

CERN Document Server

James, Daniel

2010-01-01

Open source software, also known as free software, now offers a creative platform with world-class programs. Just ask the people who have completed high-quality projects or developed popular web 2.0 sites using open source desktop applications. This phenomenon is no longer underground or restricted to techies - there have been more than 61 million downloads of the Audacity audio editor and more than 60 million downloads of the GIMP for Windows photographic tool from SourceForge.net alone. Crafting Digital Media is your foundation course in photographic manipulation, illustration, animation, 3D

Green chemistry: solvent- and metal-free Prins cyclization. Application to sequential reactions.

Science.gov (United States)

Clarisse, Damien; Pelotier, Béatrice; Piva, Olivier; Fache, Fabienne

2012-01-04

Prins cyclization between a homoallylic alcohol and an aldehyde, promoted by trimethylsilyl halide, afforded 4-halo-tetrahydropyrans with good to excellent yields. Thanks to the absence of the solvent and metal, the THP thus obtained have been implicated without purification in several other reactions, in a sequential way, affording in particular new indole derivatives. This journal is © The Royal Society of Chemistry 2012

The Validity of the School Assessment in the Craft Subject

Directory of Open Access Journals (Sweden)

Antti Hilmola

2016-06-01

Full Text Available In this research project, the validity of the school assessment is examined in the craft subject in Finland’s basic education. The criteria for the school assessment are based on the Finnish Na-tional Core Curriculum (FNCC in which the idea of the Entire Craft (EC is highlighted. How-ever, the discussion as to whether or not the school practice is based on the idea of EC, or whether the teachers are still focused on the technical details of products in reflecting on the pupils’ tool-handling skills, is still an ongoing debate. Learner-centred learning is implicated in EC since the pupils are expected to set goals for the implementation of their own ideating, plan-ning and constructing. And, finally, in such a process, the self-reflection of the implemented out-comes against the goals will take place.  Altogether 73 craft teachers from 59 upper level schools participated in this research project. The pupils’ (N = 982 success was assessed during an EC period using the indicator validated by the previous nation-wide evaluation by the Finn-ish National Board of Education (FNBE. Since the valid school assessment was expected to reflect the success in the Entire Craft Assessment Period (ECAP, the outcomes were assessed against the criteria of the FNCC and compared to the pupils’ school scores. The data was ana-lysed using the Linear Regression Analysis (Enter Method. The central observation was that the pupils’ success in the criteria of the EC do not reflect the 7th grade school scores, in all re-spects. Moreover, the pupils’ success does not reflect the 6th grade school scores. The instruc-tions and supplementary education of the FNCC criteria are needed for craft teachers, especial-ly for class teachers at the lower level. In Finland, also the craft subject is taught by the class teachers at the lower level while, at the upper level, the subject teachers take their place. Ac-cording to the new FNCC, the number of class lessons will be

Marian Roberts, Developing the Craft of Mediation: Reflections on Theory and Practice

Directory of Open Access Journals (Sweden)

Ghislaine M. Lanteigne

2008-10-01

Full Text Available In Developing the Craft of Mediation, Marian Roberts proposes that mediation is akin to a craft with its focus on learning from experience and from others working in the field to develop and master knowledge and skills.

33 CFR 100.916 - Chris Craft Silver Cup Races, Algonac, MI.

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 1 2010-07-01 2010-07-01 false Chris Craft Silver Cup Races, Algonac, MI. 100.916 Section 100.916 Navigation and Navigable Waters COAST GUARD, DEPARTMENT OF HOMELAND SECURITY REGATTAS AND MARINE PARADES SAFETY OF LIFE ON NAVIGABLE WATERS § 100.916 Chris Craft Silver Cup...

Antecedents of daily team job crafting

NARCIS (Netherlands)

Mäkikangas, Anne; Bakker, Arnold B.; Schaufeli, Wilmar B.

2017-01-01

This study investigated potential antecedents of team job crafting defined as the extent to which team members engage together in increasing (social and structural) job resources and challenges, and decreasing hindering job demands. Mindful of the teamwork literature, we hypothesized that individual

Classification of Intact Stability Standards for Dynamically Supported Craft.

Science.gov (United States)

1979-10-01

introduced (by the U.S. Navy) in the late 1950’s. Both military and commercial applications of this type have since proved very successful . From the... successful and safe planing craft have been built for military, commercial and private use. The stability of planing craft, however, is an extremely...forlces. Broaching- [ n I, 111, I ikeA LL) tOCCUr in suvvre following seas, when the Cr aft runs do L tht ! act of ort wav docd slope- ts bovw Ma’ thes

Pd(II)-Catalyzed Hydroxyl-Directed C–H Olefination Enabled by Mono-Protected Amino Acid Ligands

Science.gov (United States)

Lu, Yi; Wang, Dong-Hui; Engle, Keary M.

2010-01-01

A novel Pd(II)-catalyzed ortho-C–H olefination protocol has been developed using spatially remote, unprotected tertiary, secondary, and primary alcohols as the directing groups. Mono-N-protected amino acid ligands were found to promote the reaction, and an array of olefin coupling partners could be used. When electron-deficient alkenes were used, the resulting olefinated intermediates underwent subsequent Pd(II)-catalyzed oxidative intramolecular cyclization to give the corresponding pyran products, which could be converted into ortho-alkylated alcohols under hydrogenolysis conditions. The mechanistic details of the oxidative cyclization step are discussed and situated in the context of the overall catalytic cycle. PMID:20359184

Studies using 27Al MAS NMR of AFm and AFt phases and the formation of Friedel's salt

International Nuclear Information System (INIS)

Jones, M.R.; Macphee, D.E.; Chudek, J.A.; Hunter, G.; Lannegrand, R.; Talero, R.; Scrimgeour, S.N.

2003-01-01

This paper describes the application of the magic angle spinning (MAS) NMR spectroscopy to study the chemical environment of 27 Al-bearing phases in Portland cement-based concrete. A specific methodology is described that allows reliable spectra to be determined for combinations of different types of cements and fillers (in this case, Portland cement, fly ash, slag, silica fume, metakaolin and limestone filler). As well as the study of 'molecular structure' of cement matrix, the paper reviews the mechanism of Friedel's salt formation in cement systems. Mechanisms based on ion exchange of chloride for hydroxide in hydroxy-AF m and on chloride absorption on formation are discussed. Finally, the nature of the chloride/hydrate binding phenomena are described to provide a reasonable robust and fundamental picture of the role different cements can play in the provision of overall concrete durability to chloride ingress from a chemical perspective

26 CFR 1.861-16 - Income from certain craft first leased after December 28, 1980.

Science.gov (United States)

2010-04-01

... 26 Internal Revenue 9 2010-04-01 2010-04-01 false Income from certain craft first leased after... the United States § 1.861-16 Income from certain craft first leased after December 28, 1980. (a) General rule. If a taxpayer— (1) Owns a qualified craft (as defined in paragraph (b) of this section). (2...

46 CFR 24.15-5 - Canadian pleasure craft temporarily using navigable waters of the United States.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Canadian pleasure craft temporarily using navigable... SECURITY UNINSPECTED VESSELS GENERAL PROVISIONS Equivalents § 24.15-5 Canadian pleasure craft temporarily using navigable waters of the United States. Uninspected Canadian pleasure craft (uninspected vessels...

Facile synthesis of benzofurans via copper-catalyzed aerobic oxidative cyclization of phenols and alkynes.

Science.gov (United States)

Zeng, Wei; Wu, Wanqing; Jiang, Huanfeng; Huang, Liangbin; Sun, Yadong; Chen, Zhengwang; Li, Xianwei

2013-07-28

Regioselective synthesis of polysubstituted benzofurans using a copper catalyst and molecular oxygen from phenols and alkynes in a one-pot procedure has been reported. The transformation consists of a sequential nucleophilic addition of phenols to alkynes and oxidative cyclization. A wide variety of phenols and alkynes can be used in the same manner.

Formation control of surface marine craft using Lagrange multipliers

DEFF Research Database (Denmark)

Ihle, Ivar-Andre F.; Jouffroy, Jerome; Fossen, Thor I.

We propose a method for constructing control laws for formation control of marine craft using classical tools from analytical mechanics. The control law is based on applying inter-vessel constraint functions which again impose forces on the individual vessels that maintain the given constraints...... on the total system. In this way, a formation can be assembled and stay together when exposed to external forces. A brief comparison with other control designs for a group of marine craft is done. Further, control laws for formation assembling (with dynamic positioning), and formation keeping during...

Silica Gel-Mediated Organic Reactions under Organic Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Satoaki Onitsuka

2012-09-01

Full Text Available Silica gel was found to be an excellent medium for some useful organic transformations under organic solvent-free conditions, such as (1 the Friedel-Crafts-type nitration of arenes using commercial aqueous 69% nitric acid alone at room temperature, (2 one-pot Wittig-type olefination of aldehydes with activated organic halides in the presence of tributyl- or triphenylphosphine and Hunig’s base, and (3 the Morita-Baylis-Hillman reaction of aldehydes with methyl acrylate. After the reactions, the desired products were easily obtained in good to excellent yields through simple manipulation.

Catalytic property of an indium-deposited powder-type material containing silicon and its dependence on the dose of indium nano-particles irradiated by a pulse arc plasma process

Directory of Open Access Journals (Sweden)

Satoru Yoshimura

2017-06-01

Full Text Available Indium nano-particle irradiations onto zeolite powders were carried out using a pulse arc plasma source system. X-ray photoelectron spectroscopic and scanning electron microscopic studies of an indium irradiated zeolite sample revealed that indium nano-particles were successfully deposited on the sample. Besides, the sample was found to be capable of catalyzing an organic chemical reaction (i.e., Friedel-Crafts alkylation. Then, we examined whether or not the catalytic ability depends on the irradiated indium dose, having established the optimal indium dose for inducing the catalytic effect.

Nuevas rutas más respetuosas con el medio ambiente para la síntesi de 2-feniletanol y óxido de estireno

OpenAIRE

Kirm, Ilham

2005-01-01

El 2-feniletanol es uno de los principales componentes del aceite de rosas. Éste posee innumerables propiedades que le hacen apto para su utilización en perfumería, en cosmética, en detergentes, en medicina, etc., así como en alimentación.Industrialmente, este compuesto suele ser sintetizado mediante una tecnología tradicional como es la alquilación de Friedel-Crafts empleando benceno y óxido de etileno como reactivos y cantidades estequiométricas de AlCl3 como catalizador. No obstante, la ut...

Dipolar Quinoidal Acene Analogues as Stable Isoelectronic Structures of Pentacene and Nonacene

KAUST Repository

Shi, Xueliang

2015-10-08

Quinoidal thia-acene analogues, as the respective isoelectronic structures of pentacene and nonacene, were synthesized and an unusual 1,2-sulfur migration was observed during the Friedel-Crafts alkylation reaction. The analogues display a closed-shell quinoidal structure in the ground state with a distinctive dipolar character. In contrast to their acene isoelectronic structures, both compounds are stable because of the existence of more aromatic sextet rings, a dipolar character, and kinetic blocking. They exhibit unique packing in single crystals resulting from balanced dipole-dipole and [C-H⋯π]/[C-H⋯S] interactions.

Difference in Reactivity during Alkylation of 2-(2-Hydroxyaryl)-1,3-indanedione and N-(2-Hydroxyphenyl)phthalimide

Energy Technology Data Exchange (ETDEWEB)

Song, Hyun Nam; Kim, Hyoung Shik; Kim, Jae Nyoung [Chonnam National University, Gwangju (Korea, Republic of)

1999-06-15

Friedel-Crafts type reactions of ninhydrin (1,2,3-indantrione) have been examined by us and other groups. Besides the common arene compounds phenolic compounds could be used to prepare the corresponding 2-(2-hydroxyaryl)-2- hydroxy-1,3-indanedione derivatives such as 1. Recently, we have reported on the unusual formation of benzo[b]indeno[2,1-d]furanone ring system 3 as well as the normally expected 2 during alkylation of 2-(2-hydroxyaryl)- 2-hydroxy-1,3-indanedione derivative 1 as shown in Scheme 1

Legal status of crew members on pleasure craft and vessels used in nautical tourism

Directory of Open Access Journals (Sweden)

Giovanni Marchiafava

2018-02-01

Full Text Available The paper aims at examining the issues related to the legal status of crew members of pleasure craft and vessels used in nautical tourism from an Italian perspective. Firstly, the definition of crew and its composition on pleasure craft and vessels is examined. Additionally, the legal regime of crew members together with the crew on-board documentation, is discussed. Furthermore, the main similarities and dissimilarities of the crew regime according to the type of pleasure craft and vessel and their use, as well as, the on-board services, is dealt with. Finally, the issue related to the legal classification of ‘’guests’’, undertaking complementary on-board services of pleasure craft and vessels is considered.

Effects of acid concentration on intramolecular charge transfer ...

Indian Academy of Sciences (India)

rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results. Keywords. Intramolecular charge transfer; absorption and fluorescence; time resolved fluorescence measurements; acid concentration dependence; time-dependent density functional theory.

Job crafting, work engagement, and psychological distress among Japanese employees: a cross-sectional study.

Science.gov (United States)

Sakuraya, Asuka; Shimazu, Akihito; Eguchi, Hisashi; Kamiyama, Kimika; Hara, Yujiro; Namba, Katsuyuki; Kawakami, Norito

2017-01-01

Job crafting, an employee-initiated job design/redesign, has become important for employees' well-being. However, most studies on the relationship between job crafting and employees' well-being have been conducted in western countries; thus, it is unclear whether job crafting can be effectively applied to Asian cultures, such as Japan, which emphasizes group harmony. The aim of this study was to examine the cross-sectional associations of self-reported job crafting with work engagement and psychological distress among employees in Japan. A questionnaire survey through the internet was conducted among all employees of a manufacturing company in Japan. We analyzed the data from 894 respondents, all employees with regular employment. Job crafting, work engagement, and psychological distress were assessed using the Japanese version of the Job Crafting Questionnaire, the Japanese version of the Utrecht Work Engagement Scale (UWES), and the Brief Job Stress Questionnaire (BJSQ), respectively. Hierarchical multiple regression showed that increasing structural job resources, social job resources, and challenging job demands was significantly and positively associated with work engagement ( β  = 0.31, p  engagement and lower psychological distress. In addition, increasing social job resources and challenging job demands are also associated with higher work engagement.

Base-catalyzed bicyclization of dialkyl glutaconates with cinnamoylacetamides: a synthetic strategy for isoquinolinedione derivatives.

Science.gov (United States)

Li, Lei; Zhao, Yu-Long; Wang, He; Li, Yi-Jin; Xu, Xianxiu; Liu, Qun

2014-06-21

We report here that polysubstituted dihydroisoquinolones and isoquinolones can be constructed by the one-pot reaction of the readily available acyclic α,β-unsaturated carbonyl precursors and dialkyl glutaconates under mild basic conditions (1-45 min for the former vs. 1-6 h for the latter) via the domino process involving [3+3] annulation/intramolecular aza-cyclization.

Biosynthesis of cyclic 2,3-diphosphoglycerate. Isolation and characterization of 2-phosphoglycerate kinase and cyclic 2,3-diphosphoglycerate synthetase from Methanothermus fervidus.

Science.gov (United States)

Lehmacher, A; Vogt, A B; Hensel, R

1990-10-15

Starting from 2-phosphoglycerate the biosynthesis of cDPG comprises two steps: (i) the phosphorylation of 2-phosphoglycerate to 2,3-diphosphoglycerate and (ii) the intramolecular cyclization to cyclic 2,3-diphosphoglycerate. The involved enzymes, 2-phosphoglycerate kinase and cyclic 2,3-diphosphoglycerate synthetase, were purified form Methanothermus fervidus. Their molecular and catalytic properties were characterized.

Alternative theoretical and methodological approaches for exploring higher education in Art and Crafts

Directory of Open Access Journals (Sweden)

Marte Sørebø Gulliksen

2009-12-01

Full Text Available This article presents and discusses approaches for exploring higher education in Art and Crafts. The concepts exploring versus research and the different foci in an insider perspective versus an outsider perspective introduces the theme. An insider perspective is said to be a useful starting point for inquiry, referring to Frayling’s trichotomy research into, research on and research through from 1993. The field of higher education in Art and Crafts education is shortly presented as comprising two main areas of knowledge: knowledge of education, and knowledge about the different subject areas within Art and Crafts. Both theory and practice are a part of these areas of knowledge. As higher education in Art and Crafts is a making profession, the most prominent challenge when exploring this today is thus said to be to develop research based knowledge on Education in Art and Crafts as a making discipline.  Two keywords are deemed to be useful in approaching this theme: Mode 2 knowledge production and transdisciplinarity. The article concludes with describing specific ways of doing this today from within the context of application. Two examples of large research projects in Scandinavia are presented as examples of such projects.

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

Computer Technology-Integrated Projects Should Not Supplant Craft Projects in Science Education

Science.gov (United States)

Klopp, Tabatha J.; Rule, Audrey C.; Schneider, Jean Suchsland; Boody, Robert M.

2014-01-01

The current emphasis on computer technology integration and narrowing of the curriculum has displaced arts and crafts. However, the hands-on, concrete nature of craft work in science modeling enables students to understand difficult concepts and to be engaged and motivated while learning spatial, logical, and sequential thinking skills. Analogy…

“Making our job hospitable” – Assessment of job-crafting behavior among dental academic faculty in South India

Directory of Open Access Journals (Sweden)

V Siva Kalyan

2018-01-01

Full Text Available Introduction: Employees are regularly offered opportunities to make their work more appealing and rewarding. These opportunities might be as simple as making fine changes to their daily tasks to boost happiness and to connect with more people at vocation. Hence, an attempt is made to assess job-crafting behavior among the dental academic faculty. Materials and Methods: A cross-sectional study was conducted among dental academic faculty from five dental colleges. Job Crafting Questionnaire (JCQ was used to assess the job-crafting behavior. Mean scores were calculated for different domains of JCQ. Gender differences were analyzed using Student's “t-” test and one-way ANOVA to test the difference between different academic positions of the faculty members. Results: A total of 228 dental faculty members with a mean age of 34.43 ± 6.13 years participated in the study. The mean value of job-crafting behavior was found to be highest among female faculty (60.07 ± 8.38 and professors (61.35 ± 8.30. Male faculty scored higher in task-crafting domain and female faculty scored higher in both cognitive- and relational-crafting domains. The professors scored highest in all the three domains of job-crafting behavior as compared to that of senior lecturers and readers. Conclusion: Job crafting is an effectual workplace intervention, where employees assume an active role in shaping their work experience to enhance their job satisfaction and well-being. The overall score of job-crafting behavior was found to be highest among both professors and female faculty members. Male faculty members scored higher in task-crafting domain. With regard to individual domains, the participants scored highest in cognitive crafting followed by task and relational crafting.

Intramolecular Hydrogen Bonding and Conformational Preferences of Arzanol—An Antioxidant Acylphloroglucinol

Directory of Open Access Journals (Sweden)

Liliana Mammino

2017-08-01

Full Text Available Arzanol is a naturally-occurring prenylated acylphloroglucinol isolated from Helichrysum italicum and exhibiting anti-oxidant, antibiotic and antiviral activities. The molecule contains an α-pyrone moiety attached to the phloroglucinol moiety through a methylene bridge. The presence of several hydrogen bond donor or acceptor sites makes intramolecular hydrogen bonding patterns the dominant stabilising factor. Conformers with all the possible different hydrogen bonding patterns were calculated at the HF/6-31G(d,p and DFT/B3LYP/6-31+G(d,p levels with fully relaxed geometry in vacuo and in three solvents—chloroform, acetonitrile and water (these levels being chosen to enable comparisons with previous studies on acylphloroglucinols. Calculations in solution were performed with the Polarisable Continuum Model. The results show that the lowest energy conformers have the highest number of stronger intramolecular hydrogen bonds. The influence of intramolecular hydrogen bonding patterns on the other molecular properties is also analysed.

Cooking and Hammering: Primary School Pupils' Concepts of Their Craft Skills

Science.gov (United States)

Müürsepp, Mare; Kikkull, Andry

2014-01-01

The aim of the study is to clear the significance of craft skills for the pupils in age nine and twelve years. More than 200 pupils were asked to define, what are the most important skills for the pupils of their age. The results bring out that category of the skills related to craft subject is of the most presented categories in pupils' self…

Application of CRAFT in two-dimensional NMR data processing.

Science.gov (United States)

Krishnamurthy, Krish; Sefler, Andrea M; Russell, David J

2017-03-01

Two-dimensional (2D) data are typically truncated in both dimensions, but invariably and severely so in the indirect dimension. These truncated FIDs and/or interferograms are extensively zero filled, and Fourier transformation of such zero-filled data is always preceded by a rapidly decaying apodization function. Hence, the frequency line width in the spectrum (at least parallel to the evolution dimension) is almost always dominated by the apodization function. Such apodization-driven line broadening in the indirect (t 1 ) dimension leads to the lack of clear resolution of cross peaks in the 2D spectrum. Time-domain analysis (i.e. extraction of frequency, amplitudes, line width, and phase parameters directly from the FID, in this case via Bayesian modeling into a tabular format) of NMR data is another approach for spectral resonance characterization and quantification. The recently published complete reduction to amplitude frequency table (CRAFT) technique converts the raw FID data (i.e. time-domain data) into a table of frequencies, amplitudes, decay rate constants, and phases. CRAFT analyses of time-domain data require minimal or no apodization prior to extraction of the four parameters. We used the CRAFT processing approach for the decimation of the interferograms and compared the results from a variety of 2D spectra against conventional processing with and without linear prediction. The results show that use of the CRAFT technique to decimate the t 1 interferograms yields much narrower spectral line width of the resonances, circumventing the loss of resolution due to apodization. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Dissociation of protonated N-(3-phenyl-2H-chromen-2-ylidene)-benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer.

Science.gov (United States)

Wang, Shanshan; Dong, Cheng; Yu, Lian; Guo, Cheng; Jiang, Kezhi

2016-01-15

In the tandem mass spectrometry of protonated N-(3-phenyl-2H-chromen-2-ylidene)benzenesulfonamides, the precursor ions have been observed to undergo gas-phase dissociation via two competing channels: (a) the predominant channel involves migration of the sulfonyl cation to the phenyl C atom and the subsequent loss of benzenesulfinic acid along with cyclization reaction, and (b) the minor one involves dissociation of the precursor ion to give an ion/neutral complex of [sulfonyl cation/imine], followed by decomposition to afford sulfonyl cation or the INC-mediated electron transfer to give an imine radical cation. The proposed reaction channels have been supported by theoretical calculations and D-labeling experiments. The gas-phase cyclization reaction originating from the N- to C-sulfonyl cation transfer has been first reported to the best of our knowledge. For the substituted sulfonamides, the presence of electron-donating groups (R(2) -) at the C-ring effectively facilitates the reaction channel of cyclization reaction, whereas that of electron-withdrawing groups inhibits this pathway. Copyright © 2015 John Wiley & Sons, Ltd.

Electrooxidative Tandem Cyclization of Activated Alkynes with Sulfinic Acids To Access Sulfonated Indenones

Energy Technology Data Exchange (ETDEWEB)

Wen, Jiangwei [The; Center; Shi, Wenyan [The; Zhang, Fan [The; Liu, Dong [The; Tang, Shan [The; Wang, Huamin [The; Lin, Xiao-Min [Center; Lei, Aiwen [The

2017-05-25

An,electrooxidative direct arylsulfonlylation of yones sulfintc acids via a radical tandem cyclization strategy has been developed for the construction of sulfonated ilicIenones:under oxidant, free conditions. This method provides a simple and efficient approach to prepare various sulfonylindenones in good to,excellent:Tyidds,, demonstrating the tremendous prospect of utilizing electrocatalysis in oxidative coupling, Notably, this reaction could Be easily scaled up with good, efficiency.

The nature of creativity in craft

DEFF Research Database (Denmark)

Glaveanu, Vlad Petre

2012-01-01

The present article explores the nature of creativity in craft and does so with the help of a case study of traditional Easter egg decoration. It starts by positioning the domain of folk art in relation to fine art and within a larger category of everyday life forms of creative expression...

33 CFR 150.503 - What are the time interval requirements for maintenance on survival craft falls?

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false What are the time interval requirements for maintenance on survival craft falls? 150.503 Section 150.503 Navigation and Navigable Waters... maintenance on survival craft falls? (a) Each fall used in a launching device for survival craft or rescue...

Vinylcyclopropylacyl and polyeneacyl radicals. Intramolecular ketene alkyl radical additions in ring synthesis.

Science.gov (United States)

De Boeck, Benoit; Herbert, Nicola M A; Harrington-Frost, Nicole M; Pattenden, Gerald

2005-01-21

Treatment of a variety of substituted vinylcyclopropyl selenyl esters, e.g. 11, with Bu(3)SnH-AIBN in refluxing benzene leads to the corresponding acyl radical intermediates, which undergo rearrangement and intramolecular cyclisations via their ketene alkyl radical equivalents producing cyclohexenones in 50-60% yield. By contrast, treatment of conjugated triene selenyl esters, e.g. 32, with Bu(3)SnH-AIBN produces substituted 2-cyclopentenones via intramolecular cyclisations of their ketene alkyl radical intermediates. Under the same radical-initiating conditions the selenyl esters derived from o-vinylbenzoic acid and o-vinylcinnamic acid undergo intramolecular cyclisations producing 1-indanone and 5,6-dihydrobenzocyclohepten-7-one respectively in 60-70% yields. A tandem radical cyclisation from the alpha,beta,gamma,delta-diene selenyl ester 31 provides an expeditious synthesis of the diquinane 35 in 69% yield.

Sustainable Innovation of Glass Design and Craft

DEFF Research Database (Denmark)

Sparre-Petersen, Maria

2014-01-01

Barely any research has been made into the implementation of sustainable principles in glass design and craft. A common tendency among students and practitioners is to consider it problematic if not impossible to develop a “truly sustainable practice”. Generally glass crafts people and glass...... designers aim to explore new aesthetic possibilities for the material and see sustainability as a hindrance for aesthetic freedom. On the contrary the field of design has strong and growing emphasis on sustainable development. Fry (2009) argues that what he defines as sustain-ability is not an end goal...... but an ongoing process of re-directing the way we design our world and thereby our future. This approach along with further research into sustainable development within the field of design and combined with material specific methodologies may reveal new possibilities for sustainable as well as aesthetic...

Craft Arts and Tourism in Ceramic Art Village of Kasongan in Yogyakarta

Directory of Open Access Journals (Sweden)

sp gustami

2014-03-01

Full Text Available Yogyakarta is one of Indonesia’s major tourist destinations. This is due to its nature, interesting, unique and fantastic ancient cultural and art sites. Creative industries and the ceramic crafts play an important role in the development of tourism in Yogyakarta. In this paper, ethnographic approach is used to describe the creative process and the ceramic crafts industry in the village of Kasongan, Yogyakarta. Based on the results of the field research, the authors conclude that the ceramic crafts tourist village of Kasongan is moving toward greater commoditization whereby the ceramics centre is now more oriented towards meeting the needs of tourist industry in Yogyakarta. Due to extensive interaction and the positive response from the general public, ceramic crafts practitioners of Kasongan experience unique and characteristic creative period. The crafters manage to negotiate between the old and the new values, in the village one can find both traditional pottery and new, creative and innovative ceramic products of export quality. Today, Kasongan is a trade mark ceramic tourism village that is entering the global era.

Tandem electrophilic cyclization-[3+2] cycloaddition-rearrangement reactions of 2-alkynylbenzaldoxime, DMAD, and Br2.

Science.gov (United States)

Ding, Qiuping; Wang, Zhiyong; Wu, Jie

2009-01-16

Tandem electrophilic cyclization-[3+2] cycloaddition-rearrangement reactions of 2-alkynylbenzaldoximes, DMAD, and bromine are described, which afford the unexpected isoquinoline-based azomethine ylides in good to excellent yields. The products could be further elaborated via palladium-catalyzed cross-coupling reactions to generate highly functionalized isoquinoline-based stable azomethine ylides.

Different types of employee well-being across time and their relationships with job crafting.

Science.gov (United States)

Hakanen, Jari J; Peeters, Maria C W; Schaufeli, Wilmar B

2018-04-01

We used and integrated the circumplex model of affect (Russell, 1980) and the conservation of resources theory (Hobfoll, 1998) to hypothesize how various types of employee well-being, which can be differentiated on theoretical grounds (i.e., work engagement, job satisfaction, burnout, and workaholism), may differently predict various job crafting behaviors (i.e., increasing structural and social resources and challenging demands, and decreasing hindering demands) and each other over time. At Time 1, we measured employee well-being, and 4 years later at Time 2, job crafting and well-being, using a large sample of Finnish dentists (N = 1,877). The results of structural equation modeling showed that (a) work engagement positively predicted both types of increasing resources and challenging demands and negatively predicted decreasing hindering demands; (b) workaholism positively predicted increasing structural resources and challenging demands; (c) burnout positively predicted decreasing hindering demands and negatively predicted increasing structural resources, whereas (d) job satisfaction did not relate to job crafting over time; and (e) work engagement positively influenced job satisfaction and negatively influenced burnout, whereas (f) workaholism predicted burnout after controlling for baseline levels. Thus, work engagement was a stronger predictor of future job crafting and other types of employee well-being than job satisfaction. Although workaholism was positively associated with job crafting, it also predicted burnout. We conclude that the relationship between job crafting and employee well-being may be more complex than assumed, because the way in which employees will craft their jobs in the future seems to depend on how they currently feel. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Integrated Design of Semi-Displacement Patrol Crafts

National Research Council Canada - National Science Library

Gillespy, Andrew J

2008-01-01

... of any one change on the entire system. The initial design of smaller patrol craft is especially difficult due to the lack of design tools able to deal with ships of small size operating in the semi-planing region...

The impact of job crafting on job demands, job resources, and well-being

NARCIS (Netherlands)

Tims, M.; Bakker, A.B.; Derks, D.

2013-01-01

This longitudinal study examined whether employees can impact their own well-being by crafting their job demands and resources. Based on the Job Demands-Resources model, we hypothesized that employee job crafting would have an impact on work engagement, job satisfaction, and burnout through changes

Pd-Catalyzed C-H activation/oxidative cyclization of acetanilide with norbornene: concise access to functionalized indolines.

Science.gov (United States)

Gao, Yang; Huang, Yubing; Wu, Wanqing; Huang, Kefan; Jiang, Huanfeng

2014-08-07

An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C-H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C-H activation of acetanilides is supposed to be a key intermediate in this transformation.

Structure and Intramolecular Proton Transfer of Alanine Radical Cations

International Nuclear Information System (INIS)

Lee, Gab Yong

2012-01-01

The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the NH 2 group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [NH 3 + -CHCH 3 -COO·], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol

A crafting of potentials

DEFF Research Database (Denmark)

Kilbourn, Kyle

In the movement from understanding the past towards creating the future design anthropology, as a discipline, will turn from one with archival qualities to one endowed with potentials for change. One challenge facing design anthropology is how to show relevance for theory generation while also in......-as is complemented by designing for as design anthropologists stage design workshops, span knowledge traditions, and make design moves. Reflecting on my own research process, I trace a few research tools that underline the craft of design anthropology....

Locked and proteolysis-based transcription activator-like effector (TALE) regulation.

Science.gov (United States)

Lonzarić, Jan; Lebar, Tina; Majerle, Andreja; Manček-Keber, Mateja; Jerala, Roman

2016-02-18

Development of orthogonal, designable and adjustable transcriptional regulators is an important goal of synthetic biology. Their activity has been typically modulated through stimulus-induced oligomerization or interaction between the DNA-binding and activation/repression domain. We exploited a feature of the designable Transcription activator-like effector (TALE) DNA-binding domain that it winds around the DNA which allows to topologically prevent it from binding by intramolecular cyclization. This new approach was investigated through noncovalent ligand-induced cyclization or through a covalent split intein cyclization strategy, where the topological inhibition of DNA binding by cyclization and its restoration by a proteolytic release of the topologic constraint was expected. We show that locked TALEs indeed have diminished DNA binding and regain full transcriptional activity by stimulation with the rapamycin ligand or site-specific proteolysis of the peptide linker, with much higher level of activation than rapamycin-induced heterodimerization. Additionally, we demonstrated reversibility, activation of genomic targets and implemented logic gates based on combinations of protein cyclization, proteolytic cleavage and ligand-induced dimerization, where the strongest fold induction was achieved by the proteolytic cleavage of a repression domain from a linear TALE. © The Author(s) 2016. Published by Oxford University Press on behalf of Nucleic Acids Research.

33 CFR 150.515 - What are the requirements for weight testing of newly installed or relocated craft?

Science.gov (United States)

2010-07-01

... weight testing of newly installed or relocated craft? 150.515 Section 150.515 Navigation and Navigable... testing of newly installed or relocated craft? (a) The operator must perform installation weight testing... (a) of this section, when survival crafts are relocated to another deepwater port. ...

Catalytic stereoselective synthesis of highly substituted indanones via tandem Nazarov cyclization and electrophilic fluorination trapping.

Science.gov (United States)

Nie, Jing; Zhu, Hong-Wei; Cui, Han-Feng; Hua, Ming-Qing; Ma, Jun-An

2007-08-02

A new catalytic stereoselective tandem transformation via Nazarov cyclization/electrophilic fluorination has been accomplished. This sequence is efficiently catalyzed by a Cu(II) complex to afford fluorine-containing 1-indanone derivatives with two new stereocenters with high diastereoselectivity (trans/cis up to 49/1). Three examples of catalytic enantioselective tandem transformation are presented.

Intramolecular electron transfer in single-site-mutated azurins

DEFF Research Database (Denmark)

Farver, O; Skov, L K; Pascher, T

1993-01-01

. Natl. Acad. Sci. U.S.A. 86, 6968-6972]. The RSSR- radical produced in the above reaction was reoxidized in a slower intramolecular electron-transfer process (30-70 s-1 at 298 K) concomitant with a further reduction of the Cu(II) ion. The temperature dependence of the latter rates was determined......, lambda = 135 kJ mol-1 for the reorganization energy was derived. When Trp48, situated midway between the donor and the acceptor, was replaced by Leu or Met, only a small change in the rate of intramolecular electron transfer was observed, indicating that the aromatic residue in this position...... is apparently only marginally involved in electron transfer in wild-type azurin. Pathway calculations also suggest that a longer, through-backbone path is more efficient than the shorter one involving Trp48. The former pathway yields an exponential decay factor, beta, of 6.6 nm-1. Another mutation, raising...

Investigations of Thickness Requirement in DNV Rules for High-Speed Craft

DEFF Research Database (Denmark)

Pedersen, Preben Terndrup; Zhang, Shengming

1997-01-01

Simple formulas for determining impact strength of high-speed craft collisions with floating objects are given in this note. Thereby the minimum mass of a floating object that just ruptures the shell plating is predicted. The minimum thickness requirements of DNV rules for aluminiumcrafts and GRP...... single skin crafts can be converted to critical impact energy and minimum object mass. Some comparisons show an acceptable agreement between present method and DNV test results....

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

Directory of Open Access Journals (Sweden)

Jakub Saadi

2016-06-01

Full Text Available Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II back to palladium(0 which is apparently achieved by the present triethylamine.

Synthesis, structure, and glutathione peroxidase-like activity of amino acid containing ebselen analogues and diaryl diselenides.

Science.gov (United States)

Selvakumar, Karuthapandi; Shah, Poonam; Singh, Harkesh B; Butcher, Ray J

2011-11-04

The synthesis of some ebselen analogues and diaryl diselenides, which have amino acid functions as an intramolecularly coordinating group (Se···O) has been achieved by the DCC coupling procedure. The reaction of 2,2'-diselanediylbis(5-tert-butylisophthalic acid) or the activated ester tetrakis(2,5-dioxopyrrolidin-1-yl) 2,2'-diselanediylbis(5-tert-butylisophthalate) with different C-protected amino acids (Gly, L-Phe, L-Ala, and L-Trp) afforded the corresponding ebselen analogues. The used precursor diselenides have been found to undergo facile intramolecular cyclization during the amide bond formation reaction. In contrast, the DCC coupling of 2,2'-diselanediyldibenzoic acid with C-protected amino acids (Gly, L/D-Ala and L-Phe) affords the corresponding amide derivatives and not the ebselen analogues. Some of the representative compounds have been structurally characterized by single-crystal X-ray crystallography. The glutathione peroxidase (GPx)-like activities of the ebselen analogues and the diaryl diselenides have been evaluated by using the coupled reductase assay method. Intramolecularly stabilized ebselen analogues show slightly higher maximal velocity (V(max)) than ebselen. However, they do not show any GPx-like activity at low GSH concentrations at which ebselen and related diselenides are active. This could be attributed to the peroxide-mediated intramolecular cyclization of the corresponding selenenyl sulfide and diaryl diselenide intermediates generated during the catalytic cycle. Interestingly, the diaryl diselenides with alanine (L,L or D,D) amide moieties showed excellent catalytic efficiency (k(cat)/K(M)) with low K(M) values in comparison to the other compounds. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

Energy Technology Data Exchange (ETDEWEB)

Scorzo, Cecilia M.; Fascio, Mirta L.; D' Accorso, Norma B. [Universidad de Buenos Aires, Buenos Aires (Argentina). Facultad de Ciencias Exactas y Naturales. Dept. de Quimica Organica; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo [Universidad de Talca (Chile). Inst. de Quimica de Productos Naturales. Lab. de Sintesis Organica

2010-07-01

We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by {sup 1}H and {sup 13}C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

Synthesis and antiacetylcholinesterase activity of new D-glyceraldehyde heterocyclic derivatives

International Nuclear Information System (INIS)

Scorzo, Cecilia M.; Fascio, Mirta L.; D'Accorso, Norma B.; Cabrera, Margarita Gutierrez; Saavedra, Luis Astudillo

2010-01-01

We report herein the convenient procedures for the syntheses of different heterocyclic compounds from 2,3-O-isopropylidene-D-glyceraldehyde using intramolecular cyclization, 1,3-dipolar cycloaddition or bimolecular coupling reactions. The products were characterized by 1 H and 13 C NMR spectroscopy and elemental analysis. The new heterocycles and their derivatives were evaluated as inhibitors of acetylcholinesterase enzyme. (author)

Use your eyes - metallographic versus superficial traces of the crafting of Bronze Age ornaments

DEFF Research Database (Denmark)

Nørgaard, Heide Wrobel

and superficial archaeological examinations can be used to understand prehistoric craft. Furthermore, it will show that with an intensive knowledge about previous scientific investigations the superficial traces preserved can reveal a great amount of information and could talk for themselves. Taking as an example...... the early and middle Bronze Age bronze ornaments from North Germany, superficial traces of the metal crafting process, visible with the naked eye, will be compared with metallographic images. The aim of this presentation is to give an overview over the crafting traces everybody could see (with a bit...

Tracking Porters: Learning the Craft of Techno-Anthropology.

Science.gov (United States)

Bruun, Maja Hojer; Krause-Jensen, Jakob; Saltofte, Margit

2015-01-01

Anthropology attempts to gain insight into people's experiential life-worlds through long-term fieldwork. The quality of anthropological knowledge production, however, does not depend solely on the duration of the stay in the field, but also on a particular way of seeing social situations. The anthropological perspective is grounded in socio-cultural theory and forged by a distinct relativist or contextualist epistemological stance. The point is to understand events, concepts and phenomena from the insiders' point of view and to show how this view relates to the particular social and cultural context. In this chapter, we argue that although anthropology has its specific methodology - including a myriad of ethnographic data-gathering tools, techniques, analytical approaches and theories - it must first and foremost be understood as a craft. Anthropology as craft requires a specific 'anthropological sensibility' that differs from the standardized procedures of normal science. To establish our points we use an example of problem-based project work conducted by a group of Techno-Anthropology students at Aalborg University, we focus on key aspects of this craft and how the students began to learn it: For two weeks the students followed the work of a group of porters. Drawing on anthropological concepts and research strategies the students gained crucial insights about the potential effects of using tracking technologies in the hospital.

The Art and Craft of Science

Science.gov (United States)

Root-Bernstein, Robert; Root-Bernstein, Michele

2013-01-01

Walter Alvarez, a doctor and physiologist of some renown, decided to send his scientifically talented son, Luis, to an arts and crafts school where Luis took industrial drawing and woodworking instead of calculus. Luis Alvarez won the Nobel Prize in physics in 1968. Einstein was certainly not a standout in his mathematics and physics classes. Yet…

Crafted - meisterdatud / Mihkel Tüür

Index Scriptorium Estoniae

Tüür, Mihkel, 1976-

2012-01-01

12. Alvar Aalto sümpoosion Jyväskyläs 10.-12. augustil 2012 teemal "Crafted". Kuraator Pekka Heikkinen. Pikemalt Mohsen Mostafavi ettekandest "Arhitektuur on materiaalne" ja Jürg Conzetti ettekandest "Strukturaalse tava jätkamine". Autori sõnul jäi kõlama mõte, et meisterlikult ehitatud maja saab olla ainus arhitektuuri tegelik mõõde

Job crafting in changing organizations: Antecedents and implications for exhaustion and performance.

Science.gov (United States)

Petrou, Paraskevas; Demerouti, Evangelia; Schaufeli, Wilmar B

2015-10-01

The present study addressed employee job crafting behaviors (i.e., seeking resources, seeking challenges, and reducing demands) in the context of organizational change. We examined predictors of job crafting both at the organizational level (i.e., perceived impact of the implemented changes on the working life of employees) and the individual level (i.e., employee willingness to follow the changes). Job crafting behaviors were expected to predict task performance and exhaustion. Two-wave longitudinal data from 580 police officers undergoing organizational changes were analyzed with structural equation modeling. Findings showed that the degree to which changes influence employees' daily work was linked to reducing demands and exhaustion, whereas employee willingness to change was linked to seeking resources and seeking challenges. Furthermore, while seeking resources and seeking challenges were associated with high task performance and low exhaustion respectively, reducing demands seemed to predict exhaustion positively. Our findings suggest that job crafting can act as a strategy of employees to respond to organizational change. While seeking resources and seeking challenges enhance employee adjustment and should be encouraged by managers, reducing demands seems to have unfavorable implications for employees. (c) 2015 APA, all rights reserved).

Rationalizing Cooperation: Moroccan Craft, Politics, and Education

Science.gov (United States)

Nicholas, Claire

2018-01-01

State attempts to rationalize Moroccan craft education reflect the ambivalent status of traditional knowledge in a modern economy. Female artisans, recently organized as a cooperative, navigate this ambivalence in a weaving "theory" class and in their "occupation" of the cooperative structure itself. During performances of…

Synthesis of benzimidazoles by potassium tert-butoxide-promoted intermolecular cyclization reaction of 2-iodoanilines with nitriles.

Science.gov (United States)

Xiang, Shi-Kai; Tan, Wen; Zhang, Dong-Xue; Tian, Xian-Li; Feng, Chun; Wang, Bi-Qin; Zhao, Ke-Qing; Hu, Ping; Yang, Hua

2013-11-14

The synthesis of benzimidazoles by intermolecular cyclization reaction of 2-iodoanilines with nitriles has been developed. These reactions proceeded without the aid of any transition metals or ligands and just using KOBu(t) as the base. A variety of substituted benzimidazole derivatives can be synthesized by the approach.

Symmetry of intramolecular quantum dynamics

CERN Document Server

Burenin, Alexander V

2012-01-01

The main goal of this book is to give a systematic description of intramolecular quantum dynamics on the basis of only the symmetry principles. In this respect, the book has no analogs in the world literature. The obtained models lead to a simple, purely algebraic, scheme of calculation and are rigorous in the sense that their correctness is limited only to the correct choice of symmetry of the internal dynamics. The book is basically intended for scientists working in the field of molecular spectroscopy, quantum and structural chemistry.

Design and Craft Education in Iceland, Pedagogical Background and Development: A Literature Review

Science.gov (United States)

Olafsson, Brynjar; Thorsteinsson, Gisli

2009-01-01

Sloyd pedagogy was introduced towards the close of the 18th century to Icelandic educators. Subsequently craft was established as a specific subject aimed at general education. In the beginning craft was called "school industry," to distinguish it from "home industry" whose aim was to help homes to be self-sufficient for…

Preservation of Cultural Heritage Embodied in Traditional Crafts in the Developing Countries. A Case Study of Pakistani Handicraft Industry

Directory of Open Access Journals (Sweden)

Yongzhong Yang

2018-04-01

Full Text Available Cultural heritage embodied in traditional crafts is an integral part of any nation which reflects the culture and tradition of a particular region. Although the importance of handicraft has been widely recognized, the literature regarding preservation of traditional craft is scarce. The present paper aimed to explore and identify issues faced by traditional craftsmanship in developing countries and to address those issues in order to contribute to the sustainability of traditional craft heritage and ensure continuous transmission of craft skills and knowledge from generation to generation. Our study identified several key issues which poses substantial challenges to the preservation of traditional craft heritage in developing countries. In order to add empirical evidence, we examined the case of Pakistani handicraft industry that provided further understanding of highlighted issues which traditional craft heritage face. We have suggested some policies to promote, develop and preserve the traditional craft heritage. The significance of these policy suggestions is underlined with the case study of Pakistan.

A Hierarchically Porous Hypercrosslinked and Novel Quinone based Stable Organic Polymer Electrode for Lithium-Ion Batteries

International Nuclear Information System (INIS)

Ahmad, Aziz; Meng, Qinghai; Melhi, Saad; Mao, Lijuan; Zhang, Miao; Han, Bao-Hang; Lu, Kun; Wei, Zhixiang

2017-01-01

Highlights: •A novel hypercrosslinked Poly-Pillar[5]quinone (Poly-P5Q) polymer has been prepared and applied as electrode material in Li-ion batteries. •The novel synthetic route of Poly-P5Q was introduced by the oxidation of Poly-Dimethoxypillar[5]arene. •A Friedel-Crafts reaction was employed to prepare a novel Poly-P5Q as organic cathode material for lithium-ion batteries. -- Abstract: In the recent years, organic electrode materials have attracted tremendous attention and becoming promising electrode candidates for the green and sustainable lithium-ion batteries. A novel hypercrosslinked Poly-Pillar[5]quinone (Poly-P5Q) polymer was prepared and applied as electrode material in Li-ion batteries. Poly-P5Q is the oxidized form of Poly-Dimethoxypillar[5]arene (Poly-DMP5A) which was obtained from the condensation of dimethoxypillar[5]arene and formaldehyde dimethyl acetal using Friedel-Crafts reaction. The prepared materials were characterized by 13 C solid state NMR, FTIR, SEM, EDX and TGA analysis. The Poly-P5Q cathode showed an initial discharge capacity up to 105 mAh g −1 whereas it retained 82.3% of its initial discharge capacity after 100 charge-discharge cycles at a current speed of 100 mA g −1 in the potential window between 1.75 to 3.25 V. In future, research in this direction will provide great insight for the development of novel polymers from various small organic molecules as a stable and high performance electrode materials for green lithium-ion batteries.

Job crafting at the team and individual level: Implications for work engagement and performance

NARCIS (Netherlands)

Tims, M.; Bakker, A.B.; Derks, D.; Rhenen, van W.

2013-01-01

Previous research suggests that employee job crafting is positively related to job performance through employee work engagement. The present study expands this individual-level perspective to the team level by hypothesizing that team job crafting relates positively to team performance through team

Ascorbic Acid-Initiated Tandem Radical Cyclization of N-Arylacrylamides to Give 3,3-Disubstituted Oxindoles

Directory of Open Access Journals (Sweden)

Sheng Liu

2015-08-01

Full Text Available An ascorbic acid-promoted and metal-free tandem room temperature cyclization of N-arylacrylamides with 4-nitrobenzenediazonium generated in situ was developed. This reaction proceeds smoothly through a radical mechanism and provides an environmentally friendly alternative approach to biologically active 3-alkyl-3-benzyloxindoles, avoiding the use of excess oxidants and light irradiation.

Analysis on online word-of-mouth of customer satisfaction in cultural and creative industries of Taiwan: using crafts as an example

Science.gov (United States)

Tsai, Li-Fen; Shaw, Jing-Chi; Wang, Pei-Wen; Shih, Meng-Long; Yang, Min-Chieh

2011-10-01

This study aims to analyze customers' online word-of-mouth for crafts in Cultural and Creative Industries of Taiwan, and extracts articles from Yahoo and Wretch Blogs by the online writing mining technique. The research scope is from Jan. 1, 2008 to Dec. 31, 2010. The subjects include 2457 valid articles on customers' online word-of-mouth regarding the craft industry of Taiwan. Findings demonstrate that, regarding online word-of-mouth, the most important word-of-mouth items of ceramics, stone craft, wood craft manufacturing, and metal craft is decoration and display of surroundings; while brand is valued in glass craft; and the most important item for consumers of paper craft is cultural characteristics of handicrafts.

Job crafting in schools for special education: A qualitative analysis [Job crafting in het speciaal onderwijs: Een kwalitatieve analyse

NARCIS (Netherlands)

Wingerden, J. van; Derks, D.; Bakker, A.B.; Dorenbosch, L.

2013-01-01

In this article we discuss the design and qualitative (process) evaluation of a job crafting intervention among employees at three Dutch schools for special education. In a period of 1.5 months, fifty employees participated in a group-based training intervention that addressed individual's job

Development of the Vinylogous Pictet-Spengler Cyclization and Total Synthesis of (±)-Lundurine A.

Science.gov (United States)

Nash, Aaron; Qi, Xiangbing; Maity, Pradip; Owens, Kyle; Tambar, Uttam K

2018-04-16

A novel vinylogous Pictet-Spengler cyclization has been developed for the generation of indole-annulated medium-sized rings. The method enables the synthesis of tetrahydroazocinoindoles with a fully substituted carbon center, a prevalent structural motif in many biologically active alkaloids. The strategy has been applied to the total synthesis of (±)-lundurine A. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

25 CFR 309.24 - How will statements about Indian origin of art or craft products be interpreted?

Science.gov (United States)

2010-04-01

... 25 Indians 2 2010-04-01 2010-04-01 false How will statements about Indian origin of art or craft products be interpreted? 309.24 Section 309.24 Indians INDIAN ARTS AND CRAFTS BOARD, DEPARTMENT OF THE INTERIOR PROTECTION OF INDIAN ARTS AND CRAFTS PRODUCTS § 309.24 How will statements about Indian origin of...

Emotions in Risk Assessment and Decision Making Processes During Craft Practice

Directory of Open Access Journals (Sweden)

Camilla Groth

2015-12-01

Full Text Available Traditionally subjective experiences and emotions have been overlooked in the practice of scientific research. In the field of design and craft research too, feelings and emotions have been considered as interfering with the rigour of research. However, as a result of findings in neuroscience, a new understanding has emerged, providing emotions a central role in risk assessment and decision making processes. This has implications also for how we understand craft practice. In this practice-led research, a craft practitioner analysed five video-recordings of herself while throwing clay blindfolded. The researcher-practitioner specifically studied critical incidents in the throwing process and made a detailed analysis of how sensory experiences and emotions guided her in risk assessment, decision making, and problem solving during the clay-throwing sessions. She found that her tactile experience gave her important clues on the condition of the material and its consequent possibilities at different stages. These experiences in turn affected her emotions in either positive or negative ways, affecting her risk assessment, decision making, and problem solving activities. This research has shown that sensory experiences and emotions influence the craft making process and are thus important elements in the expertise of the craftsperson. The role of such emotions remains to be studied further in the expertise of researchers in general.

Arts and Crafts Classes in Years I–III, Based on Methods Featuring Pupils’ Practical Activities

OpenAIRE

Piwowarska, Ewa

2016-01-01

The issue to be analysed here concerns teachers’ planning of arts and crafts classes in Years I–III, with specific reference to methods featuring pupils’ practical activities. A theoretical part briefly presents the concepts involved in teaching a subject that was initially defined as drawing, then as arts and crafts education, and finally as arts and crafts classes. It points out the factors that influence the process of stimulating pupils’ artistic activities. The technique used in the cour...

The Development of Indian and Eskimo Art and Crafts in the Far North.

Science.gov (United States)

Phillips, R. A. J.; And Others

The focus of the conference, "The Development of Indian and Eskimo Art and Crafts in the Far North," was the creation of a market for reputable Indian and Eskimo art work on an economically sound basis which would benefit both the native artists and the Canadian economy. Two governmental reports, "Northern Arts and Crafts" and…

D Digital Simulation of Minnan Temple Architecture CAISSON'S Craft Techniques

Science.gov (United States)

Lin, Y. C.; Wu, T. C.; Hsu, M. F.

2013-07-01

Caisson is one of the important representations of the Minnan (southern Fujian) temple architecture craft techniques and decorative aesthetics. The special component design and group building method present the architectural thinking and personal characteristics of great carpenters of Minnan temple architecture. In late Qing Dynasty, the appearance and style of caissons of famous temples in Taiwan apparently presented the building techniques of the great carpenters. However, as the years went by, the caisson design and craft techniques were not fully inherited, which has been a great loss of cultural assets. Accordingly, with the caisson of Fulong temple, a work by the well-known great carpenter in Tainan as an example, this study obtained the thinking principles of the original design and the design method at initial period of construction through interview records and the step of redrawing the "Tng-Ko" (traditional design, stakeout and construction tool). We obtained the 3D point cloud model of the caisson of Fulong temple using 3D laser scanning technology, and established the 3D digital model of each component of the caisson. Based on the caisson component procedure obtained from interview records, this study conducted the digital simulation of the caisson component to completely recode and present the caisson design, construction and completion procedure. This model of preserving the craft techniques for Minnan temple caisson by using digital technology makes specific contribution to the heritage of the craft techniques while providing an important reference for the digital preservation of human cultural assets.

Synthesis of 1-(2-Ethynyl-6-methylphenyl)- and 1-(2-Ethynyl-6-methoxyphenyl)-Naphthalene and Their Cyclization

Czech Academy of Sciences Publication Activity Database

Storch, Jan; Čermák, Jan; Karban, Jindřich

2007-01-01

Roč. 48, č. 38 (2007), s. 6814-6816 ISSN 0040-4039 R&D Projects: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40720504 Keywords : aromate * cyclization * cycloizomerization Subject RIV: CC - Organic Chemistry Impact factor: 2.615, year: 2007

33 CFR 125.15 - Access to waterfront facilities, and port and harbor areas, including vessels and harbor craft...

Science.gov (United States)

2010-07-01

..., and port and harbor areas, including vessels and harbor craft therein. 125.15 Section 125.15....15 Access to waterfront facilities, and port and harbor areas, including vessels and harbor craft....09 to those waterfront facilities, and port and harbor areas, including vessels and harbor craft...

How Valuable is a Well-Crafted Design and Name Brand?

DEFF Research Database (Denmark)

Kristensen, Tore; Gabrielsen, Gorm; Zaichkowsky, Judith

2012-01-01

Preferences for similarly designed consumer products, evaluated blind and branded and also with and without prices, were tested in a consumer setting. The consumer's perceptual experience led to preference of the well-crafted high-priced option. This preference was enhanced by priming consumers w...... of choices using measures of inherent design acumen, prior experience, and purchasing behavior were largely unsuccessful.......Preferences for similarly designed consumer products, evaluated blind and branded and also with and without prices, were tested in a consumer setting. The consumer's perceptual experience led to preference of the well-crafted high-priced option. This preference was enhanced by priming consumers...

Mycotoxin profiling of 1000 beer samples with a special focus on craft beer.

Directory of Open Access Journals (Sweden)

Jeroen Peters

Full Text Available Currently beer is booming, mainly due to the steady rise of craft breweries worldwide. Previous surveys for occurrence of mycotoxins in beer, were mainly focussed on industrial produced beer. The present survey reports the presence of mycotoxins in craft beer and how this compares to industrial produced beer. More than 1000 beers were collected from 47 countries, of which 60% were craft beers. A selection of 1000 samples were screened for the presence of aflatoxin B1, ochratoxin A (OTA, zearalenone (ZEN, fumonisins (FBs, T-2 and HT-2 toxins (T-2 and HT-2 and deoxynivalenol (DON using a mycotoxin 6-plex immunoassay. For confirmatory analysis, a liquid chromatography tandem mass spectrometry (LC-MS/MS method was developed and applied. The 6-plex screening showed discrepancies with the LC-MS/MS analysis, possibly due to matrix interference and/or the presence of unknown mycotoxin metabolites. The major mycotoxins detected were DON and its plant metabolite deoxynivalenol-3-β-D-glucopyranoside (D3G. The 6-plex immunoassay reported the sum of DON and D3G (DON+D3G contaminations ranging from 10 to 475 μg/L in 406 beers, of which 73% were craft beers. The popular craft beer style imperial stout, had the highest percentage of samples suspected positive (83% with 29% of all imperial stout beers having DON+D3G contaminations above 100 μg/L. LC-MS/MS analysis showed that industrial pale lagers from Italy and Spain, predominantly contained FBs (3-69 μg/L. Besides FBs, African traditional beers also contained aflatoxins (0.1-1.2 μg/L. The presence of OTA, T-2, HT-2, ZEN, β-zearalenol, 3/15-acetyl-DON, nivalenol and the conjugated mycotoxin zearalenone 14-sulfate were confirmed in some beers. This study shows that in 27 craft beers, DON+D3G concentrations occurred above (or at the Tolerable Daily Intake (TDI. Exceeding the TDI, may have a health impact. A better control of brewing malts for craft beer, should be put in place to circumvent this potential

Mycotoxin profiling of 1000 beer samples with a special focus on craft beer.

Science.gov (United States)

Peters, Jeroen; van Dam, Ruud; van Doorn, Ronald; Katerere, David; Berthiller, Franz; Haasnoot, Willem; Nielen, Michel W F

2017-01-01

Currently beer is booming, mainly due to the steady rise of craft breweries worldwide. Previous surveys for occurrence of mycotoxins in beer, were mainly focussed on industrial produced beer. The present survey reports the presence of mycotoxins in craft beer and how this compares to industrial produced beer. More than 1000 beers were collected from 47 countries, of which 60% were craft beers. A selection of 1000 samples were screened for the presence of aflatoxin B1, ochratoxin A (OTA), zearalenone (ZEN), fumonisins (FBs), T-2 and HT-2 toxins (T-2 and HT-2) and deoxynivalenol (DON) using a mycotoxin 6-plex immunoassay. For confirmatory analysis, a liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed and applied. The 6-plex screening showed discrepancies with the LC-MS/MS analysis, possibly due to matrix interference and/or the presence of unknown mycotoxin metabolites. The major mycotoxins detected were DON and its plant metabolite deoxynivalenol-3-β-D-glucopyranoside (D3G). The 6-plex immunoassay reported the sum of DON and D3G (DON+D3G) contaminations ranging from 10 to 475 μg/L in 406 beers, of which 73% were craft beers. The popular craft beer style imperial stout, had the highest percentage of samples suspected positive (83%) with 29% of all imperial stout beers having DON+D3G contaminations above 100 μg/L. LC-MS/MS analysis showed that industrial pale lagers from Italy and Spain, predominantly contained FBs (3-69 μg/L). Besides FBs, African traditional beers also contained aflatoxins (0.1-1.2 μg/L). The presence of OTA, T-2, HT-2, ZEN, β-zearalenol, 3/15-acetyl-DON, nivalenol and the conjugated mycotoxin zearalenone 14-sulfate were confirmed in some beers. This study shows that in 27 craft beers, DON+D3G concentrations occurred above (or at) the Tolerable Daily Intake (TDI). Exceeding the TDI, may have a health impact. A better control of brewing malts for craft beer, should be put in place to circumvent this potential problem.

SUSTAINABLE WASTE MANAGEMENT OF TRADITIONAL CRAFT INDUSTRY IN LOPATI TOURISM VILLAGE, YOGYAKARTA

OpenAIRE

VITASURYA Vincentia Reni; PUDIANTI Anna

2016-01-01

Ecotourism has been growing in Yogyakarta that can be seen through the development of rural tourism. The development of rural tourism has positive impact to improve local community’s welfare nevertheless, it has also negative impact onto environmental carrying capacity. Lopati tourism village is located in Bantul, Yogyakarta, relying on traditional craft industry as tourism attraction. Traditional crafts are livelihood of local residents, so that environmental management efforts become part o...

"Just as the Structural Formula Does": Names, Diagrams, and the Structure of Organic Chemistry at the 1892 Geneva Nomenclature Congress.

Science.gov (United States)

Hepler-Smith, Evan

2015-02-01

At the Geneva Nomenclature Congress of 1892, some of the foremost organic chemists of the late nineteenth century crafted a novel relationship between chemical substances, chemical diagrams, and chemical names that has shaped practices of chemical representation ever since. During the 1880s, the French chemist Charles Friedel organised the nomenclature reform effort that culminated in the Geneva Congress; in the disorderly nomenclature of German synthetic chemistry, Friedel saw an opportunity to advance French national interests and his own pedagogical goals. Friedel and a group of close colleagues reconceived nomenclature as a unified field, in which all chemical names ought to relate clearly to one another and to the structure of the compounds they represented. The German chemist Adolf von Baeyer went a step farther, arguing for names that precisely and uniquely corresponded to the structural formula of each compound, tailored for use in chemical dictionaries and handbooks. Baeyer's vision prevailed at the Geneva Congress, which consequently codified rules for rigorously mapping structural formulas into names, resulting in names that faithfully represented the features of these diagrams but not always the chemical behaviour of the compounds themselves. This approach ultimately limited both the number of chemical compounds that the Geneva rules were able to encompass and the breadth of their application. However, the relationship between diagram and name established at the Geneva Congress became the foundation not only of subsequent systems of chemical nomenclature but of methods of organising information that have supported the modern chemical sciences.

Combining Organometallic Catalysis and Organocatalysis for the Synthesis of Heterocyclic Scaffolds

DEFF Research Database (Denmark)

Hansen, Casper Lykke

The main work presented in this thesis describes the development of efficient and novel methodologies for the synthesis of pharmaceutically interesting indolecontaining alkaloids, i.e., the 1,2,3,4-tetrahydro-β-carboline and the 1,2,3,4-tetrahydrocarbazole scaffolds. The synthesis of 1...... to the nitrogen in the allylic system proved to be highly important for the enantioselectivity. Enantiomeric excesses up to 57% was obtained. The synthesis of 1,2,3,4-tetrahydrocarbazole relied on novel Brønsted acidcatalyzed Friedel-Crafts-type reactions. Three different kinds of 1,2,3,4-tetrahydrocarbazole...

Transition state structures in solution

International Nuclear Information System (INIS)

Bertran, J.; Lluch, J. M.; Gonzalez-Lafont, A.; Dillet, V.; Perez, V.

1995-01-01

In the present paper the location of transition state structures for reactions in solution has been studied. Continuum model calculations have been carried out on the Friedel-Crafts alkylation reaction and a proton transfer through a water molecule between two oxygen atoms in formic acid. In this model the separation between the chemical system and the solvent has been introduced. On the other hand, the discrete Monte Carlo methodology has also been used to simulate the solvent effect on dissociative electron transfer processes. In this model, the hypothesis of separability is not assumed. Finally, the validity of both approaches is discussed

Kinetic evidence for the formation of discrete 1,4-dehydrobenzene intermediates. Trapping by inter- and intramolecular hydrogen atom transfer and observation of high-temperature CIDNP

Energy Technology Data Exchange (ETDEWEB)

Lockhart, Thomas P. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States); Comita, Paul B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States); Bergman, Robert G. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)

1981-07-01

Upon heating, alkyl-substituted cis-1,2-diethynyl olefins undergo cyclization to yield reactive 1,4-dehydrobenzenes; the products isolated may be derived from either unimolecular or bimolecular reactions of the intermediate. (Z)-4,5-Diethynyl-4-octene (4) undergoes rearrangement to yield 2,3-di-n-propyl-1,4-dehydrobenzene (17). Solution pyrolysis of 4 in inert aromatic solvents produces three unimolecular products, (Z)-dodeca-4,8-diyn-6-ene (7), benzocyclooctene (9), and o-allyl-n-propylbenzene (10), in high yield. When 1,4-cyclohexadiene is added to the pyrolysis solution as a trapping agent, high yields of the reduced product o-di-n-propylbenzene (12) are obtained. The kinetics of solution pyrolysis of 4 in the presence and absence of trapping agent establish that 2,3-di-n-propyl-1,4-dehydrobenzene is a discrete intermediate on the pathway leading to products. When the reaction was run in the heated probe of an NMR spectrometer, CIDNP was observed in 10. This observation, along with kinetic and chemical trapping evidence, indicates the presence of two additional intermediates, formed from 17 by sequential intramolecular [1,5] hydrogen transfer, on the pathway to products. The observation of CIDNP, coupled with the reactivity exhibited by 17 and the other two intermediates, implicate a biradical description of these molecules. Biradical 17 has been estimated to have a lifetime of about 10^-9 s at 200°C and to lie in a well of about 5 kcal/mol with respect to the lowest energy unimolecular pathway ([1,5] hydrogen transfer). Ring opening (expected to be the lowest energy process for 1,4-dehydrobenzenes in which intramolecular hydrogen transfer is unlikely) to the isomeric diethynyl olefin 7 appears to have an activation enthalpy of about 10 kcal/moL Upon thermal reaction in the gas phase (400°C) or in solution in inert solvents (Z)-hexa-2,3-diethyl-1,5-diyn-3-ene (5) rearranges in good yield to the isomeric diethynyl olefin (Z)-deca-3,7-diyn-5-ene (8

ARKTOS amphibious oil spill response craft for mixed ice/water conditions

Energy Technology Data Exchange (ETDEWEB)

Seligman, Bruce H.J.W. [ARKTOS International S.A., Tavannes (Switzerland)], email: bruce.seligman@arktoscraft.com; Hall, T.A. [Hall Marine Design Ltd., Vancouver B.C. (Canada)], email: thallhmd@telus.net

2010-07-01

The oil spill which occurred recently in the Gulf of Mexico highlighted the lack of efficient oil spill clean-up equipment for an offshore environment. With the increase in industrial operations in the Arctic Seas it is of high importance to develop an efficient oil spill response as the absence of reliable oil spill contingency plans will not be tolerated in such environmentally sensitive areas. The aim of this paper is to present the use of the ARKTOS amphibious craft for cleaning up an oil spill in the Arctic. This craft is usually used for logistical services and evacuation purposes; its use for clean-up purposes has been under study since 2000. This study showed that the ARKTOS craft could be an efficient means for oil spill clean-up in the Arctic because of its proven ice capable amphibious platforms and its hydraulic power; however oil collection trials should be performed to validate it.

ARKTOS amphibious oil spill response craft for mixed ice/water conditions

International Nuclear Information System (INIS)

Seligman, Bruce H.J.W.; Hall, T.A.

2010-01-01

The oil spill which occurred recently in the Gulf of Mexico highlighted the lack of efficient oil spill clean-up equipment for an offshore environment. With the increase in industrial operations in the Arctic Seas it is of high importance to develop an efficient oil spill response as the absence of reliable oil spill contingency plans will not be tolerated in such environmentally sensitive areas. The aim of this paper is to present the use of the ARKTOS amphibious craft for cleaning up an oil spill in the Arctic. This craft is usually used for logistical services and evacuation purposes; its use for clean-up purposes has been under study since 2000. This study showed that the ARKTOS craft could be an efficient means for oil spill clean-up in the Arctic because of its proven ice capable amphibious platforms and its hydraulic power; however oil collection trials should be performed to validate it.

25 CFR 309.9 - When can non-Indians make and sell products in the style of Indian arts and crafts?

Science.gov (United States)

2010-04-01

... of Indian arts and crafts? 309.9 Section 309.9 Indians INDIAN ARTS AND CRAFTS BOARD, DEPARTMENT OF THE INTERIOR PROTECTION OF INDIAN ARTS AND CRAFTS PRODUCTS § 309.9 When can non-Indians make and sell products in the style of Indian arts and crafts? A non-Indian can make and sell products in the style of...

The job crafting intervention: effects on job resources, self-efficacy, and affective well-being

NARCIS (Netherlands)

van den Heuvel, M.; Demerouti, E.; Peeters, M.C.W.

2015-01-01

This quasi-experimental field study examines the effects of an intervention designed to boost job resources, affective well-being, and self-efficacy via job crafting behaviour. Employees (n = 39) in a Dutch police district received a 1-day training, after which they worked towards self-set crafting

The job crafting intervention : Effects on job resources, self-efficacy, and affective well-being

NARCIS (Netherlands)

van den Heuvel, Machteld; Demerouti, Evangelia; Peeters, Maria|info:eu-repo/dai/nl/07487893X

2015-01-01

This quasi-experimental field study examines the effects of an intervention designed to boost job resources, affective well-being, and self-efficacy via job crafting behaviour. Employees (n = 39) in a Dutch police district received a 1-day training, after which they worked towards self-set crafting

Benzothiazole-Based AIEgen with Tunable Excited-State Intramolecular Proton Transfer and Restricted Intramolecular Rotation Processes for Highly Sensitive Physiological pH Sensing.

Science.gov (United States)

Li, Kai; Feng, Qi; Niu, Guangle; Zhang, Weijie; Li, Yuanyuan; Kang, Miaomiao; Xu, Kui; He, Juan; Hou, Hongwei; Tang, Ben Zhong

2018-04-23

In this work, a benzothiazole-based aggregation-induced emission luminogen (AIEgen) of 2-(5-(4-carboxyphenyl)-2-hydroxyphenyl)benzothiazole (3) was designed and synthesized, which exhibited multifluorescence emissions in different dispersed or aggregated states based on tunable excited-state intramolecular proton transfer (ESIPT) and restricted intramolecular rotation (RIR) processes. 3 was successfully used as a ratiometric fluorescent chemosensor for the detection of pH, which exhibited reversible acid/base-switched yellow/cyan emission transition. More importantly, the pH jump of 3 was very precipitous from 7.0 to 8.0 with a midpoint of 7.5, which was well matched with the physiological pH. This feature makes 3 very suitable for the highly sensitive detection of pH fluctuation in biosamples and neutral water samples. 3 was also successfully used as a ratiometric fluorescence chemosensor for the detection of acidic and basic organic vapors in test papers.

46 CFR 25.25-17 - Survival craft requirements for uninspected passenger vessels of at least 100 gross tons.

Science.gov (United States)

2010-10-01

... 46 Shipping 1 2010-10-01 2010-10-01 false Survival craft requirements for uninspected passenger... Survival craft requirements for uninspected passenger vessels of at least 100 gross tons. (a) Each uninspected passenger vessel of at least 100 gross tons must have adequate survival craft with enough capacity...

Expedient pyrrolizidine synthesis by propargylsilane addition to N-acyliminium ions followed by gold-catalyzed α-allenyl amide cyclization

NARCIS (Netherlands)

Breman, A.C.; Dijkink, J.; van Maarseveen, J.H.; Kinderman, S.S.; Hiemstra, H.

2009-01-01

A reaction sequence, involving the addition of (substituted) propargylsilanes to lactate-derived N-acyliminium ions followed by gold-catalyzed cyclization of the resulting alpha-allenyl amide, is applied in expedient syntheses of pyrrolizidine alkaloids heliotridine and ent-retronecine in five steps

Preparation of CN /Carbon Nanotube Intramolecular Junctions by ...

African Journals Online (AJOL)

NICO

intramolecular junctions composed of CNx with a bamboo-like structure and empty hollow carbon nanotubes were observed, ... and excellent thermal and mechanical properties.1,2 In recent .... tion of hexane, and the other segment with a curved compart- ... by an arrow lies at the interface of the junction between 'b' and.

Sarawak Bamboo Craft: Symbolism and Phenomenon

Directory of Open Access Journals (Sweden)

Arshad Mohd Zaihidee

2014-04-01

Full Text Available The relationship between human beings and their environment has stirred reactions between nature and the development of mind and actions that can be discussed using interdisciplinary approaches such as psychology, sociology, anthropology and history, in understanding human thinking and behavior. A psychological approach is intended to evaluate the individual choices and needs in society. A sociological approach details the various patterns in the social organization. An anthropological approach is tied with culture and belief to fulfil human needs which are based on their habitat, while a historical approach looks at the development which is related to the past. Dimensions of experiences, order and logic, selective elaboration and expressions are used to analyze the bamboo craft of Iban, Melanau and Bidayuh societies in Sarawak long-houses. The existence of constitutive, moral, expressive and cognitive symbols has been interpreted based on a theoretical framework that has been developed by Langer Art Theory, Parsons Social Theory and Kaplan Culture Theory. The values and meaning formed are interpreted to understand matters related to the lives of villagers and the finding suggests that bamboo craft expresses the multi-ethnic mind and character in the socio-culture of long- houses in Sarawak.

Regulation of interleukin-4 signaling by extracellular reduction of intramolecular disulfides

International Nuclear Information System (INIS)

Curbo, Sophie; Gaudin, Raphael; Carlsten, Mattias; Malmberg, Karl-Johan; Troye-Blomberg, Marita; Ahlborg, Niklas; Karlsson, Anna; Johansson, Magnus; Lundberg, Mathias

2009-01-01

Interleukin-4 (IL-4) contains three structurally important intramolecular disulfides that are required for the bioactivity of the cytokine. We show that the cell surface of HeLa cells and endotoxin-activated monocytes can reduce IL-4 intramolecular disulfides in the extracellular space and inhibit binding of IL-4 to the IL-4Rα receptor. IL-4 disulfides were in vitro reduced by thioredoxin 1 (Trx1) and protein disulfide isomerase (PDI). Reduction of IL-4 disulfides by the cell surface of HeLa cells was inhibited by auranofin, an inhibitor of thioredoxin reductase that is an electron donor to both Trx1 and PDI. Both Trx1 and PDI have been shown to be located at the cell surface and our data suggests that these enzymes are involved in catalyzing reduction of IL-4 disulfides. The pro-drug N-acetylcysteine (NAC) that promotes T-helper type 1 responses was also shown to mediate the reduction of IL-4 disulfides. Our data provides evidence for a novel redox dependent pathway for regulation of cytokine activity by extracellular reduction of intramolecular disulfides at the cell surface by members of the thioredoxin enzyme family.

Intramolecular BSSE and dispersion affect the structure of a dipeptide conformer

Science.gov (United States)

Hameed, Rabia; Khan, Afsar; van Mourik, Tanja

2018-05-01

B3LYP and MP2 calculations with the commonly-used 6-31+G(d) basis set predict qualitatively different structures for the Tyr-Gly conformer book1, which is the most stable conformer identified in a previous study. The structures differ mainly in the ψtyr Ramachandran angle (138° in the B3LYP structure and 120° in the MP2 structure). The causes for the discrepant structures are attributed to missing dispersion in the B3LYP calculations and large intramolecular BSSE in the MP2 calculations. The correct ψtyr value is estimated to be 130°. The MP2/6-31+G(d) profile identified an additional conformer, not present on the B3LYP surface, with a ψtyr value of 96° and a more folded structure. This minimum is, however, likely an artefact of large intramolecular BSSE values. We recommend the use of basis sets of at least quadruple-zeta quality in density functional theory (DFT), DFTaugmented with an empirical dispersion term (DFT-D) and second-order Møller-Plesset perturbation theory (MP2 ) calculations in cases where intramolecular BSSE is expected to be large.

Purpose and pleasure in late life: Conceptualising older women's participation in art and craft activities.

Science.gov (United States)

Liddle, Jeannine L M; Parkinson, Lynne; Sibbritt, David W

2013-12-01

The fourth age, as the last stage of life, represents a final challenge to find personal meaning in the face of changing capacities, illness and disability. Participation in valued activities is important for sustaining interest in life and has been associated with enhanced health and well-being. Art and craft activities are a popular form of participation amongst women in late life with growing international interest in the potential for these types of activities to maintain health and well-being and address problems of social isolation. Drawing on open text comments from 114 women enrolled in the Australian Longitudinal Study on Women's Health and in-depth interviews with 23 women all aged in their eighties, this paper explores the nature of older women's participation in art and craft activities and conceptualises links between participation in these activities and health and well-being in late life. Participation in art and craft activities is complex and dynamic, comprising cognitive and physical processes infused with emotion and occurs in the context of social relationships, physical spaces, physical ailments and beliefs about the value of the activities. By participating in art and craft activities, older women find purpose in their lives, contributing to their subjective well-being whilst helping and being appreciated by others. They develop a self view as enabled and as such take on new art and craft challenges, continue to learn and develop as art and craft makers and remain open to new possibilities. © 2013.

Job crafting and its impact on work engagement and job satisfaction in mining and manufacturing

Directory of Open Access Journals (Sweden)

Leon T de Beer

2016-09-01

Full Text Available The purpose of this study was to investigate job crafting and its relationship with work engagement and job satisfaction within the South African context. This research is important as job crafting has been shown to have a positive influence on employee motivation. A cross-sectional survey design was used to collect primary data from organisations in the mining and manufacturing industries of South Africa (N = 470. The results of multi-group structural equation modelling showed that the original four-factor structure of the job crafting scale was supported by the data, but that a three-factor structure was necessary due to a discriminant validity concern regarding two job crafting dimensions. Regression results revealed that increasing structural job resources with challenging job demands, and increasing social job resources were significant predictors of work engagement in both groups. Contrary to expectations decreasing hindering job demands was a negative predictor of job satisfaction in the mining group. Furthermore, increasing social job resources was also a significant predictor of job satisfaction in both groups. This study indicates the importance of job crafting for work engagement and job satisfaction in organisations.

46 CFR 117.207 - Survival craft-vessels operating on lakes, bays, and sounds routes.

Science.gov (United States)

2010-10-01

... 46 Shipping 4 2010-10-01 2010-10-01 false Survival craft-vessels operating on lakes, bays, and... 49 PASSENGERS LIFESAVING EQUIPMENT AND ARRANGEMENTS Number and Type of Survival Craft § 117.207 Survival craft—vessels operating on lakes, bays, and sounds routes. (a) Each vessel with overnight...

Shifting Values: The Promotional Policies of Craft and Industrial Design in Flanders (1980-2001)

NARCIS (Netherlands)

Gimeno Martinez, J.C.

2014-01-01

This article looks at the shifts in cultural promotion of craft as a result of a particular political conjuncture in the region of Flanders (Belgium). In 1991, as a consequence of Belgian federalization, the promotion policies for craft in Flanders passed from being answerable to the Belgian state

77 FR 32985 - Notice of Inventory Completion: U.S. Department of the Interior, Indian Arts and Crafts Board...

Science.gov (United States)

2012-06-04

... Inventory Completion: U.S. Department of the Interior, Indian Arts and Crafts Board, Museum of the Plains... Plains Indian, Indian Arts and Crafts Board, has completed an inventory of human remains, in consultation..., Indian Arts and Crafts Board. Disposition of the human remains to the Indian tribes stated below may...

Bottom Raking Damage to High-Speed Craft

DEFF Research Database (Denmark)

Simonsen, Bo Cerup

1998-01-01

This paper presents a comparative study of the raking damage to high speed craft (HSC) and conventional ships. The analysis is based on a detailed theoretical model for the raking resistance of an assembled ship bottom structure and on the idea that the impact conditions for various ship types have...

Sky-blue emitting bridged diiridium complexes: beneficial effects of intramolecular π-π stacking.

Science.gov (United States)

Congrave, Daniel G; Hsu, Yu-Ting; Batsanov, Andrei S; Beeby, Andrew; Bryce, Martin R

2018-02-06

The potential of intramolecular π-π interactions to influence the photophysical properties of diiridium complexes is an unexplored topic, and provides the motivation for the present study. A series of diarylhydrazide-bridged diiridium complexes functionalised with phenylpyridine (ppy)-based cyclometalating ligands is reported. It is shown by NMR studies in solution and single crystal X-ray analysis that intramolecular π-π interactions between the bridging and cyclometalating ligands rigidify the complexes leading to high luminescence quantum efficiencies in solution and in doped films. Fluorine substituents on the phenyl rings of the bridge promote the intramolecular π-π interactions. Notably, these non-covalent interactions are harnessed in the rational design and synthesis of the first examples of highly emissive sky-blue diiridium complexes featuring conjugated bridging ligands, for which they play a vital role in the structural and photophysical properties. Experimental results are supported by computational studies.

Enantio- and Stereoselective Construction of Atisane Scaffold via Organocatalytic Intramolecular Michael Reaction and Diels-Alder Reaction.

Science.gov (United States)

Sekita, Hiroko; Adachi, Kyohei; Kobayashi, Ippei; Sato, Yusuke; Nakada, Masahisa

2017-05-05

An enantio- and stereoselective construction of the atisane scaffold via organocatalytic intramolecular Michael reaction and Diels-Alder reaction is described. The organocatalytic intramolecular Michael reaction has been found to stereoselectively generate a trans-stereodiad comprising an all-carbon quaternary and a tertiary stereogenic centers. Use of the chiral secondary amine bearing thiourea with benzoic acid as additive is the key to obtaining the desired product with excellent ee in synthetically acceptable yield. The prepared chiral building block has been successfully converted to the compound including the atisane scaffold via the highly stereoselective intramolecular Diels-Alder reaction.

Total Syntheses of Polycyclic Polyprenylated Acylphloroglucinol Natural Products and Analogs Utilizing Alkylative Dearomatizations and Cationic Cyclizations

Science.gov (United States)

Boyce, Jonathan H.

Polycyclic polyprenylated acylphloroglucinols (PPAPs) are structurally complex natural products with promising biological activities. These compounds have interesting anticancer and anti-HIV properties as well as other biological activities making them highly attractive synthetic targets. We report a stereodivergent, asymmetric total synthesis of (-)-clusianone in six steps from commercial materials. We have implemented a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework. We also present a biosynthesis-inspired, diversity-oriented synthesis approach for rapid construction of PPAP analogs via palladium-catalyzed dearomative conjunctive allylic alkylation (DCAA). These efficient palladium-catalyzed protocols construct the [3.3.1]-bicyclic PPAP core in a single step from their stable aromatic precursors. The first syntheses of 13,14-didehydroxyisogarcinol and garcimultiflorone A stereoisomers are reported in six steps from a commercially available phloroglucinol. Lewis acid-controlled, diastereoselective cationic oxycyclizations enabled asymmetric syntheses of (-)-6-epi-13,14-didehydroxyisogarcinol and (+)-30-epi-13,14-didehydroxyisogarcinol. A similar strategy enabled production of the meso-derived isomers (+/-)-6,30- epi-13,14-didehydroxyisogarcinol and (+/-)-6,30-epi -garcmultiflorone A. A convenient strategy for gram scale synthesis of these stereoisomers was developed utilizing diastereomer separation at a later stage in the synthesis that minimized the number of necessary synthetic operations to access all possible stereoisomers. Finally, we report cationic rearrangements of dearomatized acylphloroglucinols leading to the formation of unprecedented PPAP scaffolds. A novel type A [3.3.1]-bicyclic PPAP was produced as a major product and the structure confirmed by X-ray crystallographic

N,2,3,4-Tetrasubstituted Pyrrolidines through Tandem Lithium Amide Conjugate Addition/Radical Cyclization/Oxygenation Reactions

Czech Academy of Sciences Publication Activity Database

Kafka, František; Pohl, Radek; Císařová, I.; Mackman, R.; Bahador, G.; Jahn, Ullrich

2016-01-01

Roč. 2016, č. 22 (2016), s. 3862-3871 ISSN 1434-193X R&D Projects: GA ČR GA13-40188S Grant - others:COST(XE) CM1201 Institutional support: RVO:61388963 Keywords : tandem reactions * nitrogen heterocycles * Michael addition * radical reactions * cyclization * enolates Subject RIV: CC - Organic Chemistry Impact factor: 2.834, 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.

The Influence of Future Time Perspective on Worker Outcomes: The Role of Job Crafting

NARCIS (Netherlands)

Kooij, T.A.M.; Tims, M.; Akkermans, J.

2017-01-01

This two-wave study aimed to examine future time perspective (FTP) as an antecedent of job crafting, and in turn job crafting as a mediator in associations between FTP and work outcomes. Based on the lifespan socio-emotional selectivity theory, we expected that open-ended and limited FTP would evoke

Classification of radiolarian images with hand-crafted and deep features

Science.gov (United States)

Keçeli, Ali Seydi; Kaya, Aydın; Keçeli, Seda Uzunçimen

2017-12-01

Radiolarians are planktonic protozoa and are important biostratigraphic and paleoenvironmental indicators for paleogeographic reconstructions. Radiolarian paleontology still remains as a low cost and the one of the most convenient way to obtain dating of deep ocean sediments. Traditional methods for identifying radiolarians are time-consuming and cannot scale to the granularity or scope necessary for large-scale studies. Automated image classification will allow making these analyses promptly. In this study, a method for automatic radiolarian image classification is proposed on Scanning Electron Microscope (SEM) images of radiolarians to ease species identification of fossilized radiolarians. The proposed method uses both hand-crafted features like invariant moments, wavelet moments, Gabor features, basic morphological features and deep features obtained from a pre-trained Convolutional Neural Network (CNN). Feature selection is applied over deep features to reduce high dimensionality. Classification outcomes are analyzed to compare hand-crafted features, deep features, and their combinations. Results show that the deep features obtained from a pre-trained CNN are more discriminative comparing to hand-crafted ones. Additionally, feature selection utilizes to the computational cost of classification algorithms and have no negative effect on classification accuracy.

33 CFR 149.303 - What survival craft and rescue boats may be used on a manned deepwater port?

Science.gov (United States)

2010-07-01

... 33 Navigation and Navigable Waters 2 2010-07-01 2010-07-01 false What survival craft and rescue boats may be used on a manned deepwater port? 149.303 Section 149.303 Navigation and Navigable Waters... craft and rescue boats may be used on a manned deepwater port? (a) Each survival craft on a manned...

"Miss! I'm Done!" Finishing Craft Assignments as a Situated Activity System in Preschool

Science.gov (United States)

Deunk, Marjolein; Berenst, Jan; de Glopper, Kees

2010-01-01

We describe the Situated Activity System of finishing craft assignments in preschool: the specific, routinized way that child and teacher jointly close the child's craft assignment, employing a specific discourse pattern. We analyzed the interactions of 14 Dutch children between 2.1 and 3.10 years old while they were finishing their craft…

Improving the stability of alpha-conotoxin AuIB through N-to-C cyclization

DEFF Research Database (Denmark)

Armishaw, Christopher J; Jensen, Anders A; Balle, Lena D

2011-01-01

Modification of alpha-conotoxin frameworks through cyclization via an oligopeptide linker has previously been shown as an effective strategy for improving in vivo stability. We have extended this strategy by investigating cyclic analogs of alpha-conotoxin AuIB, a selective alpha3beta4 nicotinic a......-AuIB. As such, the cAuIB-2 globular isomer could constitute a useful probe for studying the role of the alpha3beta4 nicotinic acetylcholine receptor in a range of in vivo experimental paradigms....

NATURAL BASES AND ARTISTIC MEANS OF MODERN ARTS AND CRAFTS OF DAGESTAN

Directory of Open Access Journals (Sweden)

G. G. Gazimagomedov

2015-01-01

Full Text Available The aim is to carry out a generalized analysis of the history of formation of a new artistic language in contemporary arts and crafts of Dagestan. An innovative search for applied artist has gained further development in a series of works of the leading masters of folk arts and crafts of Dagestan. Discussion. For millennia, arts and crafts of Dagestan have been organically linked with the life of people and their everyday way of life and daily activities, with their worldview and understanding of beauty. In the middle of the 1st millennium BC in the mountainous Dagestan, art of bronze casting has reached a high degree of perfection, most vividly represented by statues of different wild and domestic animals. Images of animals are interpreted generically, without study of small details, but with the characteristic features of the exterior. Paired images of birds are often found in the arts and crafts of the medieval Dagestan. This heraldic composition, two-part or in conjunction with the sacred tree - a three-part, presented in metal-plastic and carved stone and wood, was one of the most popular and enduring decorative items that was common during the Middle Ages and has survived to the present day. This also has been further developed and improved and inherited by craftsmen of Dagestan.Conclusion. When creating works of arts and crafts craftsmen use diverse traditional arts and engineering techniques, the ancient but substantially revised and reinterpreted iconic scenes and ornamental motifs. In art, folk craftsmen emphasize the unity of man and nature. Most ornamental motifs common in Dagestan, go back to the very specific nature prototypes. Compositional structure, as the artistic analysis shows, is often borrowed from nature. This feeling becomes a condition for cultural and biological development, acting as a factor of co-evolution of man and nature.

25 CFR 309.1 - How do the regulations in this part carry out the Indian Arts and Crafts Act of 1990?

Science.gov (United States)

2010-04-01

... Arts and Crafts Act of 1990? 309.1 Section 309.1 Indians INDIAN ARTS AND CRAFTS BOARD, DEPARTMENT OF THE INTERIOR PROTECTION OF INDIAN ARTS AND CRAFTS PRODUCTS § 309.1 How do the regulations in this part carry out the Indian Arts and Crafts Act of 1990? These regulations define the nature and Indian origin...

Dataset on Investigating the role of onsite learning in the optimisation of craft gang's productivity in the construction industry.

Science.gov (United States)

Ugulu, Rex Asibuodu; Allen, Stephen

2017-12-01

The data presented in this article is an original data on "Investigating the role of onsite learning in the optimisation of craft gang's productivity in the construction industry". This article describes the constraints influencing craft gang's productivity and the influence of onsite learning on the blockwork craft gang's productivity. It also presented the method of data collection, using a semi-structured interview and an observation method to collect data from construction organisations. We provided statistics on the top most important constraints affecting the craft gang's productivity using 3-D Bar charts. In addition, we computed the correlation coefficients and the regression model on the influence of onsite learning on craft gang's productivity using the man-hour as the dependent variable. The relationship between blockwork inputs and cycle numbers was determined at 5% significance level. Finally, we presented data information on the application of the learning curve theory using the unit straight-line model equations and computed the learning rate of the observed craft gang's blockwork repetitive work.

Synthesis of phenanthridines via palladium-catalyzed picolinamide-directed sequential C–H functionalization

Directory of Open Access Journals (Sweden)

Ryan Pearson

2013-05-01

Full Text Available We report a new synthesis of phenanthridines based on palladium-catalyzed picolinamide-directed sequential C–H functionalization reactions starting from readily available benzylamine and aryl iodide precursors. Under the catalysis of Pd(OAc2, the ortho-C–H bond of benzylpicolinamides is first arylated with an aryl iodide. The resulting biaryl compound is then subjected to palladium-catalyzed picolinamide-directed intramolecular dehydrogenative C–H amination with PhI(OAc2 oxidant to form the corresponding cyclized dihydrophenanthridines. The benzylic position of these dihydrophenanthridines could be further oxidized with Cu(OAc2, removing the picolinamide group and providing phenathridine products. The cyclization and oxidation could be carried out in a single step and afford phenathridines in moderate to good yields.

Craft Knowledge: Of Disciplinarity in Writing Studies

Science.gov (United States)

Johnson, Robert R.

2010-01-01

This article argues that craft knowledge can provide a disciplinary rationale for writing studies. It draws from the ancient concepts of teche, phronesis, and the four causes of making and makes the case for a definition of disciplinary knowledge fitting for writing studies. The article concludes with a conceptual framework that can serve as a…

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides.

Science.gov (United States)

Liang, Zhongwei; Xu, Song; Tian, Wenyan; Zhang, Ronghua

2015-01-01

A novel and simple strategy for the efficient synthesis of the corresponding tetrahydroquinolines from N,N-dimethylanilines and maleimides using visible light in an air atmosphere in the presence of Eosin Y as a photocatalyst has been developed. The metal-free protocol involves aerobic oxidative cyclization via sp(3) C-H bond functionalization process to afford good yields in a one-pot procedure under mild conditions.

Intramolecular inverse electron demand Diels-Alder reactions of pyrimidines

NARCIS (Netherlands)

Frissen, A.E.

1990-01-01

This thesis deals with the intramolecular inverse electron demand Diels-Alder reaction of pyrimidines. The main objective of the study was to investigate the synthetic applicability of this reaction and to get more insight in the electronic and steric effects which determine the reactivity

Intramolecular 13C analysis of tree rings provides multiple plant ecophysiology signals covering decades.

Science.gov (United States)

Wieloch, Thomas; Ehlers, Ina; Yu, Jun; Frank, David; Grabner, Michael; Gessler, Arthur; Schleucher, Jürgen

2018-03-22

Measurements of carbon isotope contents of plant organic matter provide important information in diverse fields such as plant breeding, ecophysiology, biogeochemistry and paleoclimatology. They are currently based on 13 C/ 12 C ratios of specific, whole metabolites, but we show here that intramolecular ratios provide higher resolution information. In the glucose units of tree-ring cellulose of 12 tree species, we detected large differences in 13 C/ 12 C ratios (>10‰) among carbon atoms, which provide isotopically distinct inputs to major global C pools, including wood and soil organic matter. Thus, considering position-specific differences can improve characterisation of soil-to-atmosphere carbon fluxes and soil metabolism. In a Pinus nigra tree-ring archive formed from 1961 to 1995, we found novel 13 C signals, and show that intramolecular analysis enables more comprehensive and precise signal extraction from tree rings, and thus higher resolution reconstruction of plants' responses to climate change. Moreover, we propose an ecophysiological mechanism for the introduction of a 13 C signal, which links an environmental shift to the triggered metabolic shift and its intramolecular 13 C signature. In conclusion, intramolecular 13 C analyses can provide valuable new information about long-term metabolic dynamics for numerous applications.

Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond

Indian Academy of Sciences (India)

Ultrafast Dynamics of Chemical Reactions in Condensed Phase: Intramolecular Energy Transfer, Charge Transfer & Hydrogen Bond · PowerPoint Presentation · Slide 3 · Slide 4 · Slide 5 · Slide 6 · Slide 7 · Slide 8 · Slide 9 · Slide 10 · Slide 11 · Slide 12 · Slide 13 · Slide 14 · Slide 15 · Slide 16 · Slide 17 · Slide 18 · Slide 19.

Conceptualizing responsible innovation in craft villages in Vietnam

NARCIS (Netherlands)

Voeten, J.; de Haan, J.A.C.; Roome, N.; de Groot, G.A.; Nguyen Thi, Huong; van den Hoven, J.; Doorn, N.; Swierstra, T.; Koops, B.-J.; Romijn, H.

2014-01-01

Previous research by the authors has explored small-scale innovations in poor craft producers’ clusters in villages in the Red River Delta in northern Vietnam. Although these innovations resulted in value creation and increased incomes, they also often gave rise to negative environmental or social

Effects of a job crafting intervention program on work engagement among Japanese employees: a pretest-posttest study

OpenAIRE

Sakuraya, Asuka; Shimazu, Akihito; Imamura, Kotaro; Namba, Katsuyuki; Kawakami, Norito

2016-01-01

Abstract Background Job crafting, an employee-initiated job design/redesign, has become important for employees’ well-being such as work engagement. This study examined the effectiveness of a newly developed job crafting intervention program on work engagement (as primary outcome), as well as job crafting and psychological distress (as secondary outcomes), using a pretest-posttest study design among Japanese employees. Methods Participants were managers of a private company and a private psyc...

Job crafting and its impact on work engagement and job satisfaction in mining and manufacturing

NARCIS (Netherlands)

De Beer, L.T. (Leon T.); M. Tims (Maria); A.B. Bakker (Arnold)

2016-01-01

textabstractThe purpose of this study was to investigate job crafting and its relationship with work engagement and job satisfaction within the South African context. This research is important as job crafting has been shown to have a positive influence on employee motivation. A cross-sectional

Workaholism versus work engagement and job crafting : What is the role of self-management strategies?

NARCIS (Netherlands)

Zeijen, Marijntje E.L.; Peeters, Maria C.W.; Hakanen, Jari J.

2018-01-01

Job crafting refers to the proactive actions employees take to redesign their jobs in order to get a better fit with their competencies, expectations, and wishes. So far, little is known about job crafting's underlying mechanisms. In this study, we examine how two different states of affective

Workaholism versus work engagement and job crafting : What is the role of self-management strategies?

NARCIS (Netherlands)

Zeijen, M.; Peeters, M.C.W.; Hakanen, J.

Job crafting refers to the proactive actions employees take to redesign their jobs in order to get a better fit with their competencies, expectations, and wishes. So far, little is known about job crafting's underlying mechanisms. In this study, we examine how two different states of affective

3D DIGITAL SIMULATION OF MINNAN TEMPLE ARCHITECTURE CAISSON'S CRAFT TECHNIQUES

Directory of Open Access Journals (Sweden)

Y. C. Lin

2013-07-01

Full Text Available Caisson is one of the important representations of the Minnan (southern Fujian temple architecture craft techniques and decorative aesthetics. The special component design and group building method present the architectural thinking and personal characteristics of great carpenters of Minnan temple architecture. In late Qing Dynasty, the appearance and style of caissons of famous temples in Taiwan apparently presented the building techniques of the great carpenters. However, as the years went by, the caisson design and craft techniques were not fully inherited, which has been a great loss of cultural assets. Accordingly, with the caisson of Fulong temple, a work by the well-known great carpenter in Tainan as an example, this study obtained the thinking principles of the original design and the design method at initial period of construction through interview records and the step of redrawing the "Tng-Ko" (traditional design, stakeout and construction tool. We obtained the 3D point cloud model of the caisson of Fulong temple using 3D laser scanning technology, and established the 3D digital model of each component of the caisson. Based on the caisson component procedure obtained from interview records, this study conducted the digital simulation of the caisson component to completely recode and present the caisson design, construction and completion procedure. This model of preserving the craft techniques for Minnan temple caisson by using digital technology makes specific contribution to the heritage of the craft techniques while providing an important reference for the digital preservation of human cultural assets.

Evidence of Validity of the Job Crafting Behaviors Scale

Directory of Open Access Journals (Sweden)

Renata Silva de Carvalho Chinelato

2015-12-01

Full Text Available AbstractJob crafting behavior refers to the changes made by workers in their job context for adjusting their activities to their preferences. We sought to adapt and collect validity evidences of the Job Crafting Behaviors Scale for the Brazilian context, in a sample of 491 workers, with a mean age of 26.7 years. Factor analysis revealed that the final instrument consisted of three dimensions (increasing structural job resources, increasing social job resources, increasing challenging job demands, which showed good internal consistency indexes. These dimensions showed low or moderate correlations with work engagement, positive psychological capital, positive job affect, and in-role performance. The scale showed evidence of validity, the use of which is recommended for future research on the changes that people make in their jobs.