bluuebunny/crossref_metadata_2025 huggingface dataset:
Asymmetric borane reduction of ketones catalyzed by N‐hydroxyalkyl‐l‐menthopyrazoles
Authors: Kashima Choji , Tsukamoto Yoshihiro , Higashide Kohei , Nakazono Hiroyuki
Published: March 2009

The equimolar mixture of N‐(hydroxyalkyl)pyrazoles and borane formed boric ester complex, in which the remaining borane was stabilized by the adjacent nitrogen of thr pyrazole ring. The borane complex derived from the chiral pyrazoles such as 3‐phenyl‐l‐menthopyrazole reduced p‐methylacetophenone (21) enantioselectively. When (2′S)‐2‐(2′‐phenyl‐2′‐hydroxyethyl)‐3‐phenyl‐l‐menthopyrazole ((2′S)‐10b) was used, 21 was reduced into (S)‐p‐methylphenyl‐1‐ethanol (22) in moderate chemical and optical yields. Due to the inconvenience of the preparation and the lower optical yield, the use of N‐(α‐hydroxyalkyl)pyrazoles was unpromising for the enantioselective reduction of ketones by borane.
Synthesis of 5,6‐dihydro‐2‐trifluoromethyl‐1,4‐dioxin‐3‐carboxanilides through polymer‐bound activated ester: Construction of dihydro‐1,4‐dioxin
Authors: Mah Heduck , Chang Kee Hyuk , Nam Kee Dal , Hahn Hoh‐Gyu , Bae Su Yeoul
Published: March 2009

A new construction of dihydro‐1,4‐dioxin and a synthesis of 5,6‐dihydro‐2‐trifluoromethyl‐1,4‐dioxin‐3‐carboxanilides 22 through polymer‐bound activated ester are described. An intermediate β‐hydroxy ether 18 was prepared from the substitution reaction of α‐thio‐α‐chloro compound 8 with ethylene glycol followed by treatment with Raney Ni. Replacement of hydroxy by chlorine and then dehydrochlorination afforded trifluoromethyl dihydro‐1,4‐dioxin ester 15. The polymer‐bound trifluoromethyl dihydro‐1,4‐dioxin‐3‐carboxylic acid, 4‐hydroxy‐3‐nitrobenzophenone ester (21) was prepared through the reaction of polystyrene‐bound 4‐hydroxy‐3‐nitrobenzophenone (19) with the trifluoromethyl dihydro‐1,4‐dioxin‐3‐carbonyl chloride (20). Refluxing of 21 with substituted aniline in acetonitrile gave the corresponding carboxanilide 22. The reaction rate depended on the nucleophilicity of nitrogen of the aniline.
Syntheses of 2‐alkylthio‐1‐[4‐(N‐α‐ethoxycarbonylbenzyl)‐aminobenzyl]‐5‐hydroxymethylimidazoles
Authors: Shafiee A. , Hadizadeh F. , Noori S. B.
Published: March 2009

Starting from the readily available p‐nitrobenzylamine a series of 2‐Alkylthio‐1‐[4‐(N‐α‐ethoxycarbonylbenzyl)aminobenzyl]‐5‐hydroxymethylirnidazoles were prepared.
Synthesis of 3‐imidazolylazole derivatives from a new nitrile oxide
Authors: Foti Francesco , Grassi Giovanni , Risitano Francesco , La Rosa Salvatore
Published: March 2009

The synthesis of a series of 3‐Imidazolylazole derivatives using cycloaddition reactions of a useful new nitrile oxide is described.
Synthesis of new methylated thieno[2,3‐a] and [3,2‐b]carbazoles by reductive cyclization of 6‐(2′‐Nitrophenyl)benzo[b]thiophenes obtained by palladium‐catalyzed cross‐coupling isabel
Authors: Ferreira C. F. R. , Queiroz Maria‐João R. P. , Kirsch Gilbert
Published: March 2009

The synthesis of new methylated thieno[2,3‐a] and [3,2‐b]carbazoles (5) (R=H) was achieved by a palladium‐catalyzed cross‐coupling, intramolecular reductive cyclization sequence of reactions. The cyclization precursors 6‐(2′‐nitrophenyl)benzo[b]thiophenes (3) were obtained by Suzuki cross‐coupling of 6‐boronated methylbenzo[b]thiophenes intermediates (2) with 2‐bromo or iodonitrobenzene. The boronated intermediates (2) were prepared via bromine‐lithium exchange followed by boron transmetalation and coupled in situ using Pd(OAc)2 giving thus a “one‐pot” three steps reaction from the 6‐bromobenzo[b]thio‐phenes (1) to the cyclization precursors (3). In the reductive cyclization step, N‐ethylthienocarbazoles (5) (R=Et) were also obtained. Several experiments have been made varying the amount of triethylphosphite and the time of reaction, to avoid their formation.
Kinetic and thermodynamic control in the cyclization via thiiranium ions. Stereoselective synthesis of a 2,3,5‐trisubstituted tetrahydropyran ring
Authors: Gruttadauria Michelangelo , Noto Renato
Published: March 2009

The stereoselective rearrangement of tetrahydrofuran or tetrahydropyran rings having a phenylsulfanyl group in an exo position, via the intermediate thiiranium ions, is reported. The 5‐ or 6‐exo‐tet cyclization of hydroxy sulfides gave the kinetic products while the 6‐endo‐tet or 5‐endo‐tet gave the thermodynamic products. The rearrangement of the 5‐exo product to the 6‐endo‐ one is an interesting way for the stereoselective synthesis of substituted tetrahydropyrans.
A short synthesis of the parp inhibitor 2‐(4‐trifluoro‐methylphenyl)benzimidazole‐4‐carboxamide (NU1077)
Authors: Austen Steven C. , Kane John M.
Published: March 2009

A four‐step synthesis of the PARP inhibitor 2‐(4‐trifluoromethylphenyl)benzimidazole‐4‐carboxamide (1, NU1077) is presented. Condensation of 2,3‐diaminotoluene and 4‐trifluoromethylbenzaldehyde afforded 4‐methyl‐2‐(4‐trifluoromethylphenyl)benzimidazole. Oxidation of the methyl group with potassium permanganate in warm t‐butanol afforded the carboxylic acid that was converted to the corresponding carboxamide via,/ the acid chloride.
Sythesis of methylthiomaleimides for the preparation of pyridazines and related comopounds
Authors: Tominaga Yoshionori , Shigemitsu Yasuhiro , Sasaki Kejni
Published: March 2009

New functionalized maleimides (3‐methylthio‐2,5‐dioxo‐1H‐pyrroles) were obtained by the reaction of ketene dithioacetals with nitromethane or the reaction of nitro ketene dithioacetal with active methylene compounds in the presence of the appropriate base in dimethyl sulfoxide followed by treatment with methanol.

These nakeunudes reacted with various nucleophilic reagents such as election‐rich aromatic and heteroaromatic compounds like dialkylanilines, aminophenols, indoles, indolizines, and cyalazines to give the corresponding 3‐aryl‐ or heteroaryl‐ 1H‐pyrole‐2,5‐diones. Styryl and merocyanie dyes, and polycyclic pyridazine‐diones as chemiluminophors and succinimides were also obtained from these maleimides with good results.
Thermolytic ring closure reactions of 4‐azido‐3‐phenylsulfanyl‐and 4‐azido‐3‐phenylsulfonyl‐2‐quinolones to 12H‐quinolino‐[3,4‐b][1,4]benzothiazin‐6(5H)‐ones
Authors: Täubl Anna E. , Langhans Klaus , Kappe Thomas , Stadlbauer Wolfgang
Published: March 2009

4‐Hydroxy‐3‐phenylsulfanyl‐2‐quinolones 2 and 4‐hydroxy‐3‐sulfonyl‐2‐quinolones 7, which are readily accessible from 4‐hydroxy‐2‐quinolones 1 and diphenyldisulfide or thiophenol, can be converted to 4‐azido‐3‐phenylsulfanyl‐2‐quinolones 10 or 4‐azido‐3‐phenylsulfonyl‐2‐quinolones 12 via 4‐chloro‐3‐phenylsul‐fanyl‐2‐quinolones 5 or 4‐chloro‐3‐phenylsulfonyl‐2‐quinolones 9, respectively. Thermolysis of the azides 10 and 12 results in a cyclization reaction to give quinolino[3,4‐b][1,4]benzothiazinone 11 and quino‐lino[3,4‐b][1,4]benzothiazinone dioxides 13, respectively. The conditions for thermolysis have been studied by differential scanning calorimetry (DSC).
A one‐pot synthesis of 2‐aryl‐2,3‐dihydro‐4(lH)‐quinazolinones by use of samarium iodide
Authors: Cai Guoping , Xu Xiaoliang , Li Zhifang , Lu Ping , Weber William P.
Published: March 2009

2‐Aryl‐2,3‐dihydro‐4(lH)‐quinazolines have been prepared in a one‐pot synthesis by samarium idoide (SmI2) promoted reaction of o‐nitrobenzamide and aldehydes.
Synthesis and spectral properties of 2‐methylthio‐3H‐7‐[(o‐; m‐ and p‐substituted)phenoxy]‐4‐(p‐substituted‐phenyl)‐[1,5]benzodiazepines
Authors: Cortés Eduardo Cortés , Romero Cristina A. Cortés , Mellado Olivia García
Published: March 2009

A series of eleven new 2‐methylthio‐3H‐7‐[(o‐; m‐ and p‐substituted) phenoxy]‐4‐(p‐substituted‐phenyl)‐[1,5]benzodiazepines, which have potentially useful pharmacological activities, has been synthesized by condensing the 4‐[(o‐; m‐ and p‐R1)phenoxy]‐1,2‐phenylendiamines with 3,3‐dimercapto‐1‐(p‐R2‐phenyl)‐2‐propen‐1‐one. Afterward the lH‐[1,5]benzodiazepine‐2‐thiones obtained were treated with sodium hydride and methyl iodide. The structure of all products was corroborated by ir, 1H nmr, 13C nmr and ms.
Synthesis of 3‐aroyl‐4‐(3‐chromonyl)‐2‐pyrazolines
Authors: Lévai Albert , Jekö József
Published: March 2009

New 3‐aroyl‐4‐(3‐chromonyl)‐2‐pyrazolines have been synthesized by the reaction of 3‐(3‐aryl‐3‐oxo‐propenyl)chromen‐4‐ones and diazomethane. Some of these 2‐pyrazolines have also been N‐acylated with a mixture of anhydrous pyridine and acetic anhydride or propionic anhydride. Structures of all new compounds have been elucidated by elemental analyses, mass spectrometry, ir and nmr spectroscopic measurements.
Application of the randomly optimized RDSQC experiment for the elucidation of an unknown compound
Authors: Hadden Chad E.
Published: March 2009

The application of the randomly optimized RDSQC (Randomly optimized Direct correlation Single Quantum Coherence) experiment for the detection of direct correlations facilitated the characterization of an unknown compound. The expected structure consisted of purely aliphatic moieties. The actual, identified compound contained the desired structure plus an adenosine functionality with two protons whose direct proton‐carbon couplings were over 200 Hz. Application of a 130 Hz optimized direct heteronuclear GHSQC experiment afforded no correlations for the adenine responses. The RDSQC experiment allowed for the simultaneous optimization of multiple couplings in a range of 130 to 220 Hz producing a direct correlation spectrum with all the expected responses.
Studies towards the synthesis of the benzodiazepine alkaloid auranthine
Authors: Witt Anette , Gustavsson Annika , Bergan Jan
Published: March 2009

Different approaches towards the synthesis of auranthine have been investigated. A completed synthesis of 3‐[2‐(4‐oxo‐3,4‐dihydro‐quinazolin‐2‐yl)‐3,4‐dihydro‐1H‐benzo[e][1,4]‐diazepine‐2,5‐dione, an auranthine precursor, which after dehydration with 50% propylphophonic acid anhydride solution in ethl acetate and DMA gave a C‐acetyl derivative of aurnathine. Additionally studies towards the synthesis of fused quinazolinones yielded the C‐acetylated pyrido[2,1‐b]quinazolinones or butyric acid derivatives.
Synthesis of dihydrofuran rings using α‐substituted β‐ketoamides
Authors: Stefani Héalio A. , Silva Diogo O. , Costa Iguatemi M. , Petragnani Nicola
Published: March 2009

In this paper is described an unreported method employing α‐alkenyl β‐ketoamides as starting material to give 2,3‐dihydrofurans, precursors of substituted furans.
Cyclization of thiohydrazonate esters and azo‐hydrazone tautomerism of 2‐arylhydrazono‐3‐oxo‐1,4‐benzothiazines
Authors: Shawali Ahmad S. , Elsheikh Said , Párkányi Cyril
Published: March 2009

Reaction of ethyl arylhydrazonochloroacetates (1) with 2‐aminothiophenol (2) in ethanol in the presence of triethylamine yielded the respective ethyl thiohydrazonate esters (3). Similarly, methyl arylhydrazonochloroacetates (6) gave the corresponding methyl thiohydrazonate esters (7). Treatment of both 3 and 7 with hydrogen chloride in ethanol afforded the respective 1,4‐benzothiazine derivatives 4. Identical products (4) were obtained by refluxing 1 or 6 in ethanol in the presence of triethylamine. The structure of 4 was confirmed by their alternate synthesis starting with diethyl chloromalonate in ethanol in the presence of triethylamine which yielded the intermediate 1,4‐benzothiazine derivatives 8. The subsequent coupling of 8 with diazotized anilines in ethanol in the presence of potassium hydroxide afforded 4.
Decarboxylation in the synthesis of 4‐alkyl‐, 4‐alkenyl‐ and 4‐acylpyrimidines
Authors: Herstad Gunnar , Benneche Tore
Published: March 2009

Decarboxylation of allylic esters of 4‐carboxypyrimidines in toluene at 111 °C in the presence of a Pd(0) catalyst, gives a mixture of a 4‐alkenylpyrimidine and a pyrimidine unsubstituted in the 4‐position. If the decarboxylation is carried out in the presence of benzaldehyde, then benzaldehyde is added to the 4‐position. Decarboxylation of 4‐carboxypyrimidines in the presence of different electrophiles, results in incorporation of the electrophile into the 4‐position together with a pyrimidine unsubstituted in the 4‐position. Use of microwave irradiation enhances the rate of the decarboxylations.
Enaminones as building blocks in organic synthesis: A novel route to polyfunctionally substituted benzonitriles, pyridines, eneylbenzotriazoles and diazepines
Authors: Hassanien Abu Zeid A. , Ghozlan Said A. S. , Elnagdi Mohamed H.
Published: March 2009

An efficient synthesis of enaminones 1a‐c is reported. Compounds 1a‐c reacted with diefhyl‐3‐amino‐2‐cyanopenten‐1,5‐dicarboxylate (3) to yield the benzonitriles 6. On the other hand, the reaction of la‐c with 3‐amino‐2‐cyano‐2‐pentene dinitrile (7) afforded a mixture of benzonitriles 10 and pyridines 9. The reaction of la‐c with 3‐aminocrotononitrile 11 has afforded the 4‐substituted‐3‐cyano‐2‐methylpyridines 15a‐c. The reaction of ethylene diamine with la‐c afforded 5‐substituted‐2,3‐dihydro‐lH‐[1,4]diazepines 18a‐c. On the other hand, la‐c reacted with o‐phenylenediamine to yield the 4‐(2‐aminopheynlamino)‐substituted enaminones 21. Compounds 21 could be converted into the benzotriazolylenones 22 on treatment with sodium nitrite in acetic acid solution.
Synthesis and biological effects of new derivatives of azines incorporating coumarin
Authors: Al‐Omran Fatima , Elassar Abdel‐Zaher A. , El‐Khair Adel Abou
Published: March 2009

New synthetic routes for triazolopyridine, pyridopyrimidine, pyridotriazine, imidazopyridine and pyri‐dazine derivatives incorporating a coumarin moiety with interesting biological activities are reported. Reactions of the 2‐oxo‐4‐(2‐dimethylaminoethenyl)‐2H‐chromene‐3‐carbonitrile (4) and 2‐amino‐4‐(2‐dimethylaminoethenyl)quinoline‐3‐carbonitrile (5) with benzotriazol‐1‐yl‐acetic acid hydrazide (6) affords the substituted [1,2,4]triazolo[1,5‐a]pyrido[3,4‐c]coumarines 9 and quinoline 12, respectively. Treatment of 4 with 2‐amino‐pyridine, glycine, urea, 3‐aminocrotononitrile or cyanothioacetamide affords 14–18, respectively. Treatment of 3‐amino‐3,4‐dihydro‐4‐imino‐chromeno[3,4‐c]pyridin‐5‐one (10) with α‐chloro‐acetylacetone affords pyridotriazine derivative 21. Compound 4 was also coupled with benzenediazonium chloride to afford 2‐oxo‐4‐[2‐oxo‐1‐(phenyl‐hydrazono)‐ethyl]‐2H‐chromene‐3‐carbonitrile 25. Treatment of the latter product with malononitrile afforded the 1‐phenyl‐3‐(3′‐Cyano‐2′‐oxo‐coumarin‐4′‐yl)‐6‐oxo‐pyridazine‐5‐carbonitrile (27). The structures of the newly synthesized compounds have been established on the basis of analytical and spectral data.
Synthesis of novel benzo[h] [1,6]naphthyridines via a rearrangement of hexahydro‐5H‐pyrrolo [2,1 ‐c] [1,4]benzodiazepines
Authors: Hinschberger Antoine , Fabis Frédéric , Santos Jana Sopkova‐De Oliveira , Rault Sylvain
Published: March 2009

Heating of hexahydro‐5H‐pyrrolo[2,1‐c][1,4]benzodiazepine‐2,5,11‐trione in boiling phosphoryl chloride led to a rearranged product like 3,5‐dichlorobenzo[h][1,6]naphthyridine. This structure was established from X‐ray diffraction analysis.
Efficient synthesis of bromocyclopenta[b] indoles via a bromination ‐ reduction sequence
Authors: Lachance Nicolas , Chan Wing Yan
Published: March 2009

Substituted cyclopenta[b]indoles are selectively brominated in good yields with excess pyridine ‐ Br2 charge‐transfer complex (PyBr2) in a one‐pot reaction to provide 5 and/or 7‐bromoindoles. The mechanism involves the formation of an adduct (addition of bromine on the central double bond) which is subsequently reduced in situ with Zn and AcOH. A variety of functional groups in the cyclopentyl and the benzenoid rings are tolerated.
Synthesis anti‐fungal and anti‐bacterial screening of 3‐phenyl‐1,4,5‐trihydro‐pyrazol and 2, 4‐dihydro[ 1,2,4]‐triazol‐3‐one derivatives of 4‐hydroxy‐2‐oxo‐2H‐1‐benzopyran
Authors: Mulwad V. V. , Shirodkar Jyoti M.
Published: March 2009

4‐Hydroxy‐2‐oxo‐2H‐1‐benzopyran‐3‐carboxaldehydes 2a‐d are prepared from 4‐hydroxy‐2‐oxo‐2H‐1‐benzopyrans 1a‐d via the Vielsmeyer Haack reaction. The 4‐hydroxy‐2‐oxo‐3‐(3′oxo‐3′‐phenylprop‐1′‐enyl)‐2H‐1‐benzopyrans 3a‐d are obtained from 2a‐d via the Claisen reaction. Refluxing compounds 3a‐d with hydrazine hydrate gave the 3‐phenyl‐5‐(4‐hydroxy‐2‐oxo‐2H‐1‐benzopyran‐3‐yl)‐1,4,5‐trihydropyra‐zols 4a‐d. Stirring compounds 2a‐d with semicarbazide hydrochloride in acidic medium gave the 4‐hydroxy‐2‐oxo‐2H‐1‐benzopyran‐3‐aldehyde‐semicarbazone 5a‐d, which on cyclisation with ferric chloride hexahydrate gave the 5‐(4‐hydroxy‐2‐oxo‐2H‐1‐benzopyran‐3‐yl)‐2,4‐dihydro[1,2,4]triazol‐3‐ones 6a‐d. All these compounds show significant antibacterial activities.
Synthesis of azomethylene derivatives of 4‐chloro‐5H‐1,2,3‐dithiazole
Authors: Yarovenko Vladimir N. , Es'kov Andrey A. , Zatonsky George V. , Zavarzin Igor V. , Krayushkin Mikhail M. , Averkiev Boris B. , Antipin Mikhail yu.
Published: March 2009

Previously unknown azomethylene derivatives of 4‐chloro‐5H‐1,2,3‐dithiazole 5–7 were synthesized by the reaction of the Appel salt 1 with N‐monosubstituted hydrazones 2–4. It was shown that they could be transformed into heterocyclic compounds 8–10.
Synthesis and stereochemistry of indano[1,2‐d][1,3]oxazines and thiazines, new ring systems
Authors: Palkó Märta , Hetényi Anasztäzia , Fülöp Ferenc
Published: March 2009

A set of structurally varied indano[1,2‐d][1,3]oxazines and thiazines, which are new ring systems, were prepared by ring‐closure reactions of amino alcohols 4–6. The reactions of cis‐ and trans‐1‐amino‐ and cis‐ 1‐benzylamino‐2‐hydroxymethylindane (4–6) with 1 equivalent of an aromatic aldehyde in methanol at room temperature resulted in three‐component equilibria (15a‐g), or a Schiff base (16), or a ring‐closure product alone (17a‐c), respectively, depending on the substitution or configuration of the starting amino alcohol. The ring‐chain tautomeric equilibria can be described by an equation of Hammett type.
One‐pot synthesis of the indole derivative 4‐chloro‐3‐sulphamoyl‐N‐(2,3‐dihydro‐2‐methyl‐1H‐indol‐1‐yl)benzamide (indapamide)
Authors: Ziobro Barbara , Sienkiewicz Barbara , Kowalski Piotr
Published: March 2009

New methods for the synthesis the indole derivative, Indapamide (1), using mixed anhydrides of the general formula R1COOCOOR2 (2) or DCC (N,N'‐dicyclohexylcarbodiimide) (3), are described.
β‐Carboline alkaloids 9 [1]. Total synthesis of the β‐carboline alkaloids arenarine A and (±)arenarine B
Authors: Bracher Franz , Puzik Andreas
Published: March 2009

The first total synthesis of the β‐carboline alkaloids arenarine A (1) and arenarine B (2) is described. Methanolysis of the α‐bromoketone 9 gives 1 in good yield. Alternatively 1 can be obtained from the diazoketone 11 with boron trifluoride/methanol in poor yield. Reduction of 1 with sodium borohydride gives racemic arenarine B (2). Regioselective homolytic methylation of norharmane (4) with tert‐butyl hydroperoxide/ferrous sulfate gives the alkaloid harmane (6).
Efficient synthesis and spectral determination of 11‐[(o‐ m‐ and p‐substituted)‐phenyl]‐8‐chloro‐3,3‐dimethyl‐2,3,4,5,10,11‐hexahydro‐1H‐dibenzo[b,e][1,4]diazepin‐1‐ones
Authors: Cortéas Eduardo Cortés , Baños Miryan Adaya , De Cortés Olivia García‐Mellado
Published: March 2009

A new synthesis to obtain eleven novel derivatives of 11‐[(o‐ m‐ and p‐substituted)‐phenyl]‐8‐chloro‐3,3‐dimethyl‐2,3,4,5,10,11‐hexahydro‐1H‐dibenzo[b,e][1,4]diazepin‐1‐ones with possible pharmacological activity in the central nervous system in two efficient steps has been developed. The final products were obtained by condensation and cyclization between 3‐[4‐chloro‐1,2‐phenylenediamine]‐5,5‐dimethyl‐2‐cyclohexenone with (o‐ m‐ and p‐substituted)benzaldehyde. The structure of all products was corroborated by ir, 1H‐nmr, 13C‐nmr and high resolution in ms.
An aminoisoflavone — salicyloylindole ring transformation
Authors: Löwe Werner , Witzel Sonja , Tappmeyer Silvia , Albuschat Rica
Published: March 2009

A series of 2′‐nitroisoflavones 8–10, 15, 22, 27 and 28 was prepared via the (2‐nitro‐phenyl)‐acetic acids 1, 13, 19 and 25. In order to obtain the corresponding 2′‐aminoisoflavones the reduction of 8–10, 15, 22, 27 and 28 was undertaken. Surprisingly, new 3‐salicyloylindoles instead of the expected 2′‐aminoisoflavones were the main reduction products. In the following paper the preparation of the 2′‐nitroisoflavones 8–10, 15, 22, 27 and 28 as well as the reduction experiments obtaining the 2′‐aminoisoflavones 33 and 35 and the 3‐salicyloylindoles 29–32, 34 and 36 will be described. Furthermore, a possible mechanism responsible for the formation of the 3‐salicyloylindoles from 2′‐nitroisoflavones under reductive conditions will be discussed.
Synthesis of new isoxazoles derivatives attached to sugar moieties
Authors: Pinheiro Jorge M. , Ismael M. Isabel , Figueiredo J. Albertino , Silva Artur M. S.
Published: March 2009

This work reports the synthesis of isoxazoles linked to sugar derivatives in different positions of furanosidic rings, by intramolecular oxidative cyclization of α,β‐unsaturated oximes with iodine, potassium iodide and sodium hydrogen carbonate. These oximes were obtained from aldehyde‐sugar derivatives.
2,4,6‐Trifluoropyrimidine. Reactions with nitrogen nucleophiles
Authors: Delia Thomas J. , Anderson Dennis P. , Schomaker Jennifer M.
Published: March 2009

In a continuation of our studies involving the nucleophilic displacement of one of the chlorines from 2,4,6‐trichloropyrimidine, we now report the initial displacement of one of the fluorine atoms from 2,4,6‐trifluoropyrimidine using both aliphatic and aromatic amines. The monosubstitution products favor 2‐substitution with ammonia and ethanolamine while aniline gave the 4‐substituted derivative as the preferred product.
Fast extraction of resonant vibrational response from CARS spectra with arbitrary nonresonant background
Authors: Liu Yuexin , Lee Young Jong , Cicerone Marcus T.
Published: March 2009

We describe a new, robust method of numerically extracting equivalent Raman spectra from coherent anti‐Stokes Raman scattering (CARS) spectra. The extraction procedure requires no a priori information regarding the vibrational resonances or the shape of the nonresonant background (NRB). The method we present here is robust to situations where the NRB is not spectrally flat, and is accurate over a wide range of signal‐to‐background ratios. This simple and quick computation method, which relies primarily on a small number of fast Fourier transforms, could reasonably be used in conjunction with spectral imaging, where millions of spectra must be analyzed. Published 2009 by John Wiley & Sons, Ltd.
Evaluation of temperature and concentration in H2N2 dual‐pump CARS spectra using the Keilson and Storer three‐dimensional model for H2 Q‐branch
Authors: Gao Yi , Weikl Markus C. , Seeger Thomas , Leipertz Alfred , Joubert Pierre , Bonamy Jeanine
Published: March 2009

Coherent anti‐Stokes Raman scattering (CARS) is a widely accepted standard for thermometry in combustion environments. Accurate lineshape models are of crucial importance for the computation of CARS spectra used for temperature and concentration evaluations. Therefore, a new lineshape model for the H2 molecule is developed and tested for ambient pressure applications. Measurements were taken in a heated cell and in a partially premixed flame with dual‐pump CARS techniques, respectively. Line broadening coefficients for H2N2 mixture are calculated using the new speed memory effects model. The experimental vibrational‐CARS (VCARS) spectra were evaluated with this new lineshape model and the temperature and relative H2 concentration results were compared with an already existing model. Copyright © 2009 John Wiley & Sons, Ltd.
Effect of bovine colostrum on the growth inhibition and differentiation of human leukemic U937 cells
Authors: Ma Chia‐Yu , Kung Hua‐Ting , Chen Jian‐Nan , Chang Chi‐Yue , Chang Huang‐Min , Wu James Swi‐Bea
Published: March 2009

BACKGROUND: Colostrum is the breast milk of female mammals produced within in a short time after giving birth. It is thought to protect neonates from infection as well as to facilitate immune system maturation. In this study the effect of bovine colostrum on the proliferation and differentiation of human leukemic U937 cells was investigated to understand more about its immunomodulatory activity.

RESULTS: Human mononuclear cells (MNCs) were stimulated with bovine colostrum (CS) and then filtered to obtain a conditioned medium (CM) (CS‐MNC‐CM). CS‐MNC‐CMs prepared with day 1 to day 4 colostrums inhibited U937 cells by 39.4–64.4%. The expressions of surface markers CD11b and CD14 on U937 cells in the treated groups were 30.6–33.5% and 40.0–42.6% respectively. High levels of cytokines IL‐1β, IFN‐γ and TNF‐α were detected in CS‐MNC‐CMs.

CONCLUSION: Evidence indicates that colostrums stimulate human MNCs to secrete cytokines IL‐1β, IFN‐γ and TNF‐α which subsequently inhibit the growth of U937 cells and induce their differentiation into mature monocytes and macrophages. There is a possibility for bovine colostrum to be processed into an anti‐leukemia ingredient for use in health foods. Copyright © 2009 Society of Chemical Industry
New piperazine‐based polymerizable monoquaternary cationic surfactants: Synthesis, polymerization, and swelling characteristics of gels
Authors: Deen G. Roshan , Gan L. H.
Published: March 2009

Monoquaternary cationic polymerizable surfactants of type N‐acryloyl‐N′‐methyl‐N′‐alkyl piperazinium bromide based on piperazine heterocycle was synthesized by reacting N‐acryloyl‐N′methyl piperazine with the corresponding n‐alkyl bromide (decyl, dodecyl, tetradecyl, and hexadecyl) in anhydrous acetone at room temperature. The resulting surfactants were deliquescent to display any sharp melting points. The surface activity was studied by surface tension measurements. Due to the complex head group geometry of these surfactants, the critical micelle concentration value was high in comparison to the analogous alkyltrimethyl ammonium bromides of similar alkyl chain length. The surfactants were polymerized by micellar (in water) and isotropic (in benzene) conditions and the resulting polymers were characterized by solubility and viscosity studies. The polymers prepared in water showed higher viscosity than the ones prepared in benzene as a result of micellar aggregation in water. The reduced viscosity of the polymers in polar solvents such as methanol and dimethyl formamide (DMF) showed polyelectrolyte‐like behavior, whereas nonelectrolyte behavior was observed in chloroform. pH‐responsive hydrogels were prepared by polymerizing the surfactants in the bicontinuous phase of a microemulsion. The resulting polymers did not exhibit any definite micro/nanostructure due to cross‐polymerization of the hydrophilic oil in the bicontinuous network structure. The gels were highly responsive to changes in pH of the medium and showed high‐swelling degree in acidic media owing to the protonation of the tertiary nitrogen of the piperazine ring. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2059–2072, 2009
Poly(styrene‐b‐tetrahydrofuran)/clay nanocomposites by mechanistic transformation
Authors: Yenice Zuleyha , Tasdelen M. Atilla , Oral Ayhan , Guler Cetin , Yagci Yusuf
Published: March 2009

Synthesis of poly(styrene‐block‐tetrahydrofuran) (PSt‐b‐PTHF) block copolymer on the surfaces of intercalated and exfoliated silicate (clay) layers by mechanistic transformation was described. First, the polystyrene/montmorillonite (PSt/MMT) nanocomposite was synthesized by in situ atom transfer radical polymerization (ATRP) from initiator moieties immobilized within the silicate galleries of the clay particles. Transmission electron microscopy (TEM) analysis showed the existence of both intercalated and exfoliated structures in the nanocomposite. Then, the PSt‐b‐PTHF/MMT nanocomposite was prepared by mechanistic transformation from ATRP to cationic ring opening polymerization (CROP). The TGA thermogram of the PSt‐b‐PTHF/MMT nanocomposite has two decomposition stages corresponding to PTHF and PSt segments. All nanocomposites exhibit enhanced thermal stabilities compared with the virgin polymer segments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2190–2197, 2009
Becoming a member of a school community while working toward science education reform: Teacher induction from a cultural historical activity theory (CHAT) perspective
Authors: Saka Yavuz , Southerland Sherry A. , Brooks Jeffrey S.
Published: March 2009

The first years of teaching can be demanding, as the novice works to gain familiarity with many aspects of professional work. Often, what they have been prepared to do in teacher education programs is not aligned with what is expected at them in schools. As a consequence, many teachers leave the profession or move away from the reform‐minded practice emphasized in their preparation as they accept the norms of their new community of practice. Using cultural historical activity theory, this comparative case study explored two beginning science teachers' transition into the teaching profession and the roles a community of practice played in this transition. Findings suggest that these science teachers were influenced by the social and professional structures at their schools and by the level of institutional and interpersonal support they received from peer teachers and administrators. The extent to which these teachers became involved in the community of practices at their schools greatly influenced their instructional practice. Implications suggest that science teacher preparation and induction programs must go beyond simply emphasizing teaching and learning—they must also address strategies young teachers can use to access the support they need to be able to consistently enact reform‐based practices. © 2009 Wiley Periodicals, Inc. Sci Ed 93:996–1025, 2009
Optimization of Enzymatic Hydrolysis of Chicken Fat in Emulsion by Response Surface Methodology
Authors: Teng Dike , Le Rensi , Yuan Fang , Yang Jia , He Li , Gao Yanxiang
Published: March 2009

Chicken fat in an emulsion prepared with mechanical shearing and high pressure homogenization (HPH) was hydrolyzed using Candida cylindracea lipase. A homogenization pressure of 50 MPa, which can generate smaller droplets and higher hydrolysis efficiency than mechanical shearing, was fixed to prepare the emulsion for hydrolysis optimization. Response surface methodology (RSM) was applied to study the effect of temperature, enzyme loading, shaking rate and reaction time on the hydrolysis process. The results showed that all three‐second‐order polynomial models adequately fitted the experimental data. Additionally, hydrolysis parameters for the optimal yields of free oleic and linoleic acids were also obtained using the desirability function: a temperature of 38 °C, an enzyme loading of 0.48% (g/g fat basis), a shaking rate of 100 rpm and a reaction time of 80 min. Under the optimal conditions, the yields of free oleic and linoleic acids were predicted as being 0.470 and 0.118 g/g fat with recoveries of 94.6 and 93.7%, respectively. During the hydrolysis process, the particle size increased with concomitant boosting of the degree of hydrolysis and the stability of the emulsion system was gradually undermined by this reaction process.
Psychiatric Survivors and Experiential Rights
Authors: Cresswell Mark
Published: March 2009

Human rights may be categorised as belonging to ‘three generations’: political, social and ‘solidarity’ rights. This paper considers this schema theoretically, deploying the example of the ‘psychiatric survivor’ movement in Britain in support of its central claims. Psychiatric survivors comprise groups of psychiatric patients who have campaigned both for political and social rights in addition to a singular form of ‘right’, which is referred to here as ‘experiential’. The paper clarifies the meaning of the ‘experiential right’ and, drawing upon aspects of social theory, considers how it is to be understood in the context of the ‘three generations’ schema.
Acute-phase responsiveness of mannose-binding lectin in community-acquired pneumonia is highly dependent uponMBL2genotypes
Authors: Herpers B L , Endeman H , De Jong B A W , De Jongh B M , Grutters J C , Biesma D H , Van Velzen-Blad H
Published: March 2009

Mannose-binding lectin (MBL) is a pattern recognition receptor of the complement system and plays an important role in innate immunity. Whether or not MBL acts as an acute-phase response protein in infection has been an issue of extensive debate, because MBL responses have shown a high degree of heterogeneity. Single nucleotide polymorphisms (SNPs) in the promoter (wild-type Y versus X) and exon 1 (A versus 0) of the MBL2 gene can lead to MBL deficiency. This study investigated the influence of SNPs in the promoter and exon 1 of the MBL2 gene on the acute-phase responsiveness of MBL in 143 patients with community-acquired pneumonia. Acute-phase reactivity was observed only in MBL-sufficient genotypes (YA/YA, XA/YA, XA/XA and YA/0). In patients with wild-type exon 1 genotype A/A, positive acute-phase responses were associated with the presence of the YA haplotype and negative responses with its absence. Genotypes YA/0 and XA/XA produced equal levels of MBL in convalescence. In the acute phase, however, patients with genotype XA/XA displayed negative acute-phase responses more often than those with genotype YA/0. Correlation of MBL and C-reactive protein levels in the acute phase of pneumonia also depended upon the MBL2 genotype. In conclusion, acute-phase responsiveness of MBL was highly dependent upon the MBL2 genotype. These data suggest that heterogeneity in protein responses in the acute phase of disease should always be viewed in the light of possible influences of genetic differences in both structural and regulatory parts of the gene.
Tryptophan aspartate-containing coat protein (CORO1A) suppresses Toll-like receptor signalling in Mycobacterium leprae infection
Authors: Tanigawa K , Suzuki K , Kimura H , Takeshita F , Wu H , Akama T , Kawashima A , Ishii N
Published: March 2009

Mycobacterium leprae is an intracellular pathogen that survives within the phagosome of host macrophages. Several host factors are involved in producing tolerance, while others are responsible for killing the mycobacterium. Tryptophan aspartate-containing coat protein (TACO; also known as CORO1A or coronin-1) inhibits the phagosome maturation that allows intracellular parasitization. In addition, the Toll-like receptor (TLR) activates the innate immune response. Both CORO1A and TLR-2 co-localize on the phagosomal membrane in the dermal lesions of patients with lepromatous leprosy. Therefore, we hypothesized that CORO1A and TLR-2 might interact functionally. This hypothesis was tested by investigating the effect of CORO1A in TLR-2-mediated signalling and, inversely, the effect of TLR-2-mediated signalling on CORO1A expression. We found that CORO1A suppresses TLR-mediated signal activation in human macrophages, and that TLR2-mediated activation of the innate immune response resulted in suppression of CORO1A expression. However, M. leprae infection inhibited the TLR-2-mediated CORO1A suppression and nuclear factor-κB activation. These results suggest that the balance between TLR-2-mediated signalling and CORO1A expression will be key in determining the fate of M. leprae following infection.
Seed weevils living on the edge: pressures and conflicts over body size in the endoparasitic Curculio larvae
Authors: BONAL RAÚL , MUÑOZ ALBERTO
Published: March 2009

Abstract 1. Body size in parasitic insects can be subjected to contrasting selective pressures, especially if they complete their development within a single host. On the one hand, a larger body size is associated with a higher fitness. On the other hand, the host offers a discrete amount of resources, thus constraining the evolution of a disproportionate body size.

2. The present study used the weevil Curculio elephas as a study model. Larvae develop within a single acorn, feeding on its cotyledons, and larval body size is strongly related to individual fitness.

3. The relationship between larval and acorn size was negatively exponential. Larval growth was constrained in small acorns, which did not provide enough food for the weevils to attain their potential size. Larval size increased and levelled off in acorns over a certain size (inflexion point), in which cotyledons were rarely depleted. When there were more than one larva per acorn, a larger acorn was necessary to avoid food depletion.

4. The results show that C. elephas larvae are sometimes endoparasitic, living on the edge of host holding capacity. If they were smaller they could avoid food depletion more easily, but the fitness benefits linked to a larger size have probably promoted body size increase. The strong negative effects of conspecific competition may have possibly influenced female strategy of laying a single egg per seed.

5. Being larger and fitter, but always within the limits of the available host sizes, may be one main evolutionary dilemma in endoparasites.
Morphological correlates of bite force and diet in the skull and mandible of phyllostomid bats
Authors: Nogueira Marcelo R. , Peracchi Adriano L. , Monteiro Leandro R.
Published: March 2009

Bite force is an important performance measure for vertebrate and is related to a variety of ecological challenges. Phyllostomid bats present highly diversified feeding habits associated with extensive cranial shape divergence. Biomechanical models predict that the cranial shape changes are linked to dietary variation through bite force. However, the relationship of cranial shape, diet and bite force had not been explicitly tested before.

Here we use a combination of geometric morphometric techniques and comparative methods to test for morphological correlates of bite force and diet in 14 phyllostomid bat species. Skull and mandible shape variation were assessed by vectors, derived from a two‐block partial least squares analysis of geometric shape and size‐independent bite forces. The relationship between bite force, skull shape and diet was assessed by phylogenetic generalized least square regressions.

Most variation in the bite force data examined here (approximately 74%) was explained by size variation alone, but the shape vectors for both skull and mandible explained a significant part of the residual variation in bite force (83% and 56%, respectively), as did the dietary differences (56%). Although the first principal component of diet variation is associated with a negative correlation between insectivory and frugivory, residual bite force and cranial shape are not associated with this diet contrast. Shape and residual bite force variation in the sample were strongly associated with the second diet component, depicting an increase in nectarivory.

Species with stronger bites (insectivorous and frugivorous) than expected for their sizes presented a shorter rostrum and mandible, higher skulls, and more developed muscle attachment areas. On the other hand, the characteristic cranial elongation of nectarivorous species (supporting the long tongue) is a trade‐off with bite force. These morphological correlates of bite force are similar to those observed in carnivores and non‐herbivorous marsupials, and can be related to morphological characters used in biomechanical models for bite force prediction.

Our results reinforce the effectiveness of statistically integrating geometric shape variables to bite force and diet information in the investigation of patterns of cranial shape change and trophic radiation in ecologically diverse vertebrate groups.
Methylene blue‐assisted lymph node dissection in combination with ex vivo sentinel lymph node mapping in gastric cancer
Authors: Märkl Bruno , Wünsch Katharina , Hebick Kai‐Uwe , Anthuber Matthias , Probst Andreas , Arnholdt Hans Martin , Spatz Hanno
Published: March 2009

Aims:  Lymph node (LN) stage is still the strongest prognostic marker in potentially curable gastric cancer. Accuracy of histopathological lymph node assessment depends on the number of investigated LNs and detection rate of metastases and micrometastases. The aim was to perform a feasibility study employing intra‐arterial methylene blue injection – a novel method to improve LN harvest – and ex vivo sentinel LN mapping.

Methods and results:  A total of 33 cases were enrolled, including 14 retrospective cases that served as a control group. The methylene group showed a highly significant improved mean LN harvest compared with unstained cases, with 38 ± 14 versus 21 ± 10 LNs (P < 0.001), respectively. The detection rate of ex vivo sentinel mapping was 88%. No skip metastases occurred.

Conclusion:  Both techniques have the potential to improve the accuracy of histopathological LN staging and can be combined successfully.
Effectiveness of gerontologically informed nursing assessment and referral interventions for older persons attending the emergency department: systematic review
Authors: Fealy Gerard , McCarron Mary , O’Neill Desmond , McCallion Philip , Clarke Mike , Small Valerie , O’Driscoll Anne , Cullen Audrey
Published: March 2009

Title.  Effectiveness of gerontologically informed nursing assessment and referral interventions for older persons attending the emergency department: systematic review

Aim.  This paper is a report of a literature review conducted to analyse data from published studies reporting nursing interventions targeted at older attendees of emergency departments (EDs), and to provide a critical appraisal of the evidence concerning their effectiveness.

Background.  Attendance at hospital EDs by older persons presents opportunities for targeted interventions to address actual and potential problems associated with or in addition to the presenting problem. The evidence concerning the effectiveness of such interventions is mixed.

Data sources.  Studies were retrieved from a systematic search of published works indexed in CINAHL, MEDLINE (PubMed), Science Direct and the Cochrane Central Register of Controlled Trials (CENTRAL).

Methods.  A systematic review of effectiveness was conducted using the Cochrane Effective Practice and Organisation of Care guidelines and a narrative synthesis approach for data handling and presentation. The review period was 1992 to 31 August 2008.

Results.  Nursing assessment and referral interventions have demonstrated effectiveness in reducing service use and improving physical function, but have failed to demonstrate statistically significant effects on predicted patient and/or health systems outcomes.

Conclusion.  The evidence of the effectiveness of gerontologically informed nursing assessment and referral interventions in EDs must be accepted with caution, as not all studies demonstrated effectiveness in predicted patient and/or health systems outcomes, and the testing of complex social interventions in randomized clinical trials is inherently problematic. Further evidence of the effectiveness of nursing interventions is required, and such evidence might be usefully demonstrated using pragmatic, as opposed to explanatory, trials.
Temporal variation in the genetic structure of a drone congregation area: an insight into the population dynamics of wild African honeybees (Apis mellifera scutellata)
Authors: JAFFÉ R. , DIETEMANN V. , CREWE R. M. , MORITZ R. F. A.
Published: March 2009

The mating system of the honeybee (Apis mellifera) has been regarded as one of the most panmictic in the animal kingdom, with thousands of males aggregating in drone congregation areas (DCAs) that virgin queens visit to mate with tens of partners. Although males from many colonies gather at such congregations, the temporal changes in the colonies contributing drones remain unknown. Yet, changes in the DCAs’ genetic structure will ultimately determine population gene flow and effective population size. By repeatedly sampling drones from an African DCA over a period of 3 years, we studied the temporal changes in the genetic structure of a wild honeybee population. Using three sets of tightly linked microsatellite markers, we were able to reconstruct individual queen genotypes with a high accuracy, follow them through time and estimate their rate of replacement. The number of queens contributing drones to the DCA varied from 12 to 72 and was correlated with temperature and rainfall. We found that more than 80% of these queens were replaced by mostly unrelated ones in successive eight months sampling intervals, which resulted in a clear temporal genetic differentiation of the DCA. Our results suggest that the frequent long‐range migration of colonies without nest‐site fidelity is the main driver of this high queen turnover. DCAs of African honeybees should thus be regarded as extremely dynamic systems which together with migration boost the effective population size and maintain a high genetic diversity in the population.
ATHB4, a regulator of shade avoidance, modulates hormone response in Arabidopsis seedlings
Authors: Sorin Céline , Salla‐Martret Mercè , Bou‐Torrent Jordi , Roig‐Villanova Irma , Martínez‐García Jaime F
Published: March 2009

Plants sense the presence of competing neighboring vegetation as a change in light quality: i.e. they sense the reduced ratio of red light to far‐red light. The responses to shade are generally referred to as the shade avoidance syndrome (SAS), and involve various developmental changes intended to outgrow or outcompete the neighboring plants. Here, we analyze the function of ATHB4, a gene encoding a homeodomain‐leucine zipper (HD‐Zip) class‐II transcription factor from Arabidopsis thaliana, the expression of which is rapidly and directly upregulated after proximity perception by the phytochrome photoreceptors. ATHB4 acts redundantly with other members of the HD‐Zip class‐II transcription factors. The expression of these genes is regulated by other members of the same class, forming a small transcriptional network of factors in which homeostasis is mutually controlled. Our results suggest that some members of this small gene subfamily can modulate SAS responses by controlling auxin, brassinosteroid and gibberellin molecular and/or physiological responsiveness. In particular, we propose ATHB4 as a new shade signaling component that participates in integrating shade perception and hormone‐mediated growth.
Role of Phenylalanine Ammonia Lyase and Polyphenol Oxidase in Host Resistance to Bacterial Wilt of Tomato
Authors: Vanitha Shyanadrahalli Chandrashekaraiah , Niranjana Siddapura Ramachandrappa , Umesha Sharanaiah
Published: March 2009

Plants respond to bacterial pathogen attack by activating various defence responses, which are associated with the accumulation of several factors like defence‐related enzymes and inhibitors which serve to prevent pathogen infection. The present study focused on the role of the defence‐related enzymes phenylalanine ammonia lyase (PAL) and polyphenol oxidase (PPO) in imparting resistance to tomato against bacterial wilt pathogen Ralstonia solanacearum. The temporal pattern of induction of these enzymes showed maximum activity at 12 h and 15 h for PAL and PPO, respectively, after the pathogen inoculation (hpi) in resistant cultivars. Twenty different tomato cultivars were analyzed for PAL, PPO and total phenol content following pathogen inoculation. The enzyme activities and total phenol content increased significantly (P < 0.05) in resistant cultivars upon pathogen inoculation. The increase in enzyme activities and total phenol content were not significant in susceptible and highly susceptible cultivars. The role of PAL and PPO in imparting resistance to tomato against bacterial wilt disease is discussed.