bluuebunny/crossref_metadata_2025 huggingface dataset:
Derivatives of 3‐(2‐hydroxyethyl)2‐benzothiazolinone and related compounds
Authors: D'Amico John J. , Bellinger Frederic G.
Published: April 2009

The reaction of the appropriate 2‐benzothiazolinone with 2‐chloroethanol or 3‐chloropropanol under basic conditions afforded 3‐(2‐hydroxyethyl or 3‐hydroxypropyl)‐2‐benzothiazolinone and related compounds 1–7. The reaction of the alcohols 1,4, 5 or 7 with potassium hydroxide and excess carbon disulfide furnished the potassium salts of xanthic acid 8–11 which upon oxidation gave the disulfides 12–15. Esters of xanthic acid 16–23 were prepared by the reaction of 8 or 11 with various halogen compounds. Esters of acetic acid 24–28 were prepared by the reaction of the appropriate 2‐benzothiazolinone with 2‐bromoethyl acetate under basic conditions. Esterification of 1 with various acids afforded the esters 25, 29–32.
β‐Carbolines derived from β‐methyltryptophan and a stereoselective synthesis of (2RS,3SR)‐β‐methyltryptophan methyl ester
Authors: Behforouz Mohammad , Zarrinmayeh Hamideh , Ogle Mark E. , Riehle Tammy J. , Bell Frank W.
Published: April 2009

The methyl ester of isomer A of β‐methyltryptophan (2SR,3RS; 2A) was stereoselectively prepared by an efficient modified method through the reaction of a‐methyl‐N‐(1‐Methylethyl)‐1H‐indole‐3‐methanamine (3) with methyl nitroacetate to give the desired nitro compound as a mixture of two racemates 5A, and 5B. During the recrystallization process epimerization occurred and only racemate 5A crystallized out. Catalytic hydrogenation of 5A in the presence of acid stereoselectively yielded the desired amino acid ester 2A. Pictet‐Spengler condensation of 2A with aldehydes under aprotic conditions followed by dehydrogenation gave excellent yields of β‐carbolines 7a‐i, (R = methyl, ethyl, acetyl, phenyl, pyridine‐2‐yl, furan‐2‐yl, quinoline‐2‐yl, styryl, phenethyl). Also β‐carbolines 7a,b,i were synthesized by the Pictet‐Spengler condensation of (3‐meth‐yltryptophan under acidic aqueous conditions followed by esterification and dehydrogenation.
Conformational behaviour of non‐fused biheterocycles. Part XV. Isomeric phenylisoxazoles
Authors: Russo Nino , Toscano Marirosa , Barone Vincenzo
Published: April 2009

The conformational behaviour of isomeric phenylisoxazoles has been investigated at the STO‐3G level optimizing the most significant geometrical parameters. The energy minima of the two isomers having an heteroatom in an ortho position correspond to planar structures, whereas the 4‐isomer has a twisted equilibrium conformation. This confirms that HH non‐bonded repulsions are stronger than (lone‐pair)‐H ones. The similar conformational behaviour of corresponding phenylfurans and phenylisoxazoles shows that the second heteroatom has a negligible effect and that the conformational behaviour of non‐fused biheterocycles is dictated by the nature of the ortho substituents.
Studies on pyrazines. 17.. An efficient synthesis of pteridine‐6‐carboxylic acids
Authors: Sato Nobuhiro , Saito Noriko
Published: April 2009

2,4‐Diaminopteridine‐6‐carboxylic acid (1) and pterin‐6‐carboxylic acid (2) were prepared by permanganate oxidation of the corresponding 6‐(2‐furyl)‐substituted pteridines under much milder conditions. Several attempts to cleave the furan ring with other oxidizing agents are also described.
Synthesis of 2,3‐quinolinedicarboxylic acid
Authors: Maulding Donald R.
Published: April 2009

A new procedure for making 2,3‐quinolinedicarboxylic acid (6), starting with aniline and maleic anhydride has been developed. Evidence for the formation of 2‐anilino‐3‐formyl‐N‐phenylmaleimide (7) in the cyclization of S‐phenylimino‐4‐dimethylaminomethylene‐N‐phenylsuccinimide (4a) to N‐phenylacridinimide (5a) is presented.
Large‐ring, chromogenic benzocrown compounds
Authors: Czech Anna , Czech Bronislaw P. , Bartsch Richard A.
Published: April 2009

Eight novel, large‐ring chromogenic benzocrown compounds have been synthesized. Two incorporate 19‐and 20‐membered crown units with six ring oxygens. Six others contain large rings ranging from 21‐crown‐7 to 30‐crown‐10. For all six benzocrown compounds, the 4′‐(2″,4″‐dinitro‐6″‐trifluoromethylphenyl)amino group was employed as the chromogenic unit. In addition, 4′‐picrylamino and 4′‐(2″,6″‐dinitro‐4″‐trifluoromethylphenyl)amino groups were also attached to benzo‐21‐crown‐7.
1,2,3‐thiadiazoles. I. Synthesis of sodium (or potassium) 1,2,3‐thiadiazole‐4‐thiolates via thiocarbazonate esters and N‐acylthiohydrazonate esters
Authors: Lee Ving J. , Curran William V. , Fields Thomas F. , Learn Keith
Published: April 2009

A general synthesis of 1,2,3‐thiadiazole‐4‐thiolates 1 and their derivatives 2–3 by an extension of the Hurd‐Mori 1,2,3‐thiadiazole synthesis is described. Treatment of methyl (or ethyl) [1‐(alkylthio)alkylidene]hydrazinocarboxylates 11 (thiocarbazonate esters) or other N‐acylthiohydrazonate esters [Y = ureido (12) or arenesulfonyl (13)] with thionyl chloride affords 2–3 efficiently. Intermediates 11–13 are readily obtained from the N2‐thioacylcarbazates 8, N3‐thioacylsemicarbazides 9, or N2‐thioacyl‐N1‐(p‐toluenesulfonyl)hydrazides 10, respectively, by S‐alkylation. Physicochemical properties of the 1,2,3‐thiadiazoles 1–3 and N‐acylthiohydrazonate esters 11–13 are also described.
Functionalization and cyclization reactions of 4‐benzoyl‐1,5‐diphenyl‐ 1H‐pyrazole‐3‐carboxylic acid
Authors: Akcamur Yunus , Sener Ahmet , Ipekoglu Alemdar Mustafa , Kollenz Gert
Published: April 2009

The 1H‐pyrazole‐3‐carboxylic acid 2 or its remarkably stable acid chloride 3 can easily be converted into the corresponding ester or amide derivatives 4 or 5, respectively, from reaction with alcohols or N‐nucleophiles. Pyrazolo[3,4‐d]pyridazines 6a,b are obtained from cyclocondensation reactions of the pyrazoles 2 and 3, respectively, with phenylhydrazine or hydrazine hydrate, while 6c is formed in an one‐pot procedure from the furan‐2,3‐dione 1 and hydrazine hydrate.
Aminoacids in the synthesis of heterocyclic systems. The synthesis of methyl 2‐acetylamino‐3‐dimethylaminopropenoate and 2‐(N‐methyl‐N‐trifluoroacetyl)amino‐3‐dimethylaminopropenoate and their application in the synthesis of heterocyclic compounds
Authors: Kralj Lucija , Hvala Aleš , Svete Jurij , Golič Ljubo , Stanovnik Branko
Published: April 2009

Methyl (Z)‐2‐acetylamino‐3‐dimethylaminopropenoate (3) was prepared from N‐acetylglycine (1), which was converted with N,N‐dimethylformamide and phosphorus oxychloride into 4‐dimethylaminomethylene‐2‐methyl‐5(4H)‐oxazolone (2), followed by treatment with methanol in the presence of potassium carbonate, into 3. The compound 3 was shown to be a versatile reagent in the synthesis of various heterocyclic systems. With N‐nucleophiles, such as heterocyclic amines 4, either methyl 2‐acetylamino‐3‐heteroarylaminopropenoates 5 or fused pyrimidinoncs 6 were formed, dependent on the reaction conditions and/or heterocyclic substituents: C‐nuclcophiles with an active or potentially active methylene group, such as 1,3‐dicarbonyl compounds 7, 8 and 9, substituted phenols 10a,b, naphthols 11, 12a‐c, and substituted coumarin 13a, afforded substituted pyranones 20 and 22, and fused pyranones 21, 23–26. The nitrogen containing heterocycles 14–19 produced pyranoazines 27–31 and pyranoazole 32. In all of these systems the acetylamino group is attached at position 3 of the newly formed pyranone ring. The orientation around the double bond for methyl (Z)‐2‐(N‐methyl‐N‐trifluo‐roacetyl)‐3‐dimethylaminopropenoate (36) was established by X‐ray analysis.
Positive ions and negative ions fab (fast atom bombardment) mass spectrometry of some bisazolium salts
Authors: Cabildo Pilar , Claramunt Rosa , Lavandera José Luis , Sanz Dionisia , Elguero Jose , Enjalbal Christine , Aubagnac Jean‐Louis
Published: April 2009

Significant information on the structure of various bisazolium salts of the type CA2 (C++ 2A−) were revealed by the study of the FAB spectra of their positive and negative ions. Thus only one spectrum, whatever it consists of the positive or of the negative ions spectrum, enables the identification of the cation C++ and of the anion A−. Moreover, the same information are collected from the CAD spectrum of the adduct ion CA+ allowing the identification of such a compound in a mixture.
Ethyl (4‐N‐acylaminopyridin‐3‐yl)glyoxylate and 5‐azaisatin as new synthons for a route to various new polyheterocycles
Authors: Rivalle Christian , Bisagni Emile
Published: April 2009

From 4‐N‐protected‐aminopyridines which were functionalized at their 3‐position, 5‐azaisatin and equivalent synthons where obtained. Via the use of the Pfitzinger reaction, these compounds provided an easy route to new and various polyheterocyclic compounds.
The reaction of 3,5‐dichloro‐2,4,6‐trimethylbenzonitrile oxide with chiral fluoro‐substituted allyl sulfoxides
Authors: Bravo Pierfrancesco , Bruché Luca , Seresini Paolo , Zanda Matteo , Arnone Alberto
Published: April 2009

The title reaction allowed the synthesis, with total regio‐ and moderate stereo‐selectivity, of chiral fluorosubstituted 4,5‐dihydroisoxazoles.
Kinetic study on the synthesis of some benzo[g]quinoxalin‐2(1H)‐one derivatives
Authors: Rodrigo Gabriela A. , Renou Sergio G. , Bekerman Diana G. , Abasolo M. Inés , Fernández Beatriz M.
Published: April 2009

Some novel 3‐substituted benzoquinoxalinones [R = H, CH3, C6H5, (CH2)2COOH] were synthesized by the Hinsberg reaction between 2,3‐diaminonaphthalene and several α‐dicarbonyl compounds. The course of the reactions was followed by the second uv/visible Derivative Spectroscopy Method at different pH values (‐0.89 to 9.0) and also in organic solvents at 25°. The compound non‐substituted at C‐3 was the only one that could be obtained in every media in good yields (80%), having pseudo first‐order anelation rate constants of relative high values (1 × 10−1 — 1 × 10−2 min−1). On the other hand, only methanol could be used as the organic solvent for the synthesis of all of the other compounds; aqueous media always provided better results. In the 3‐methyl derivative, as well as in the 3‐phenyl derivative the change of the reaction pH medium modified the stoichiometry of the anelation, turning a non‐quantitative reaction into a quantitative one. This is explained by a change in the mechanism of the reaction on going to lower hydrogen concentrations, a fact that was supported by complementary quantitative hptlc experiments. In general, pseudo first‐order rate constants for the anelation were one or two logarithmic units lower than those of the non‐substituted compound (RC‐3 = H), but yields were above 60% in every case. A reaction scheme is presented which includes a probable mechanism.
Use of sulfur derivatives as an ortho directing group for the metalation of diazines. Metalation of diazines. XVIII
Authors: Turck Alain , Plé Nelly , Pollet Paméla , Mojovic Ljubica , Duflos Jack , Quéguiner Guy
Published: April 2009

The metalation of thioethers, methyl and phenyl sulfoxides and sulfones of pyrazine and pyridazine has been performed. Methyl sulfoxides and sulfones were first metalated on the methyl group. The ortho directing effect of thioethers, sulfoxides and sulfones have been compared with the methoxy group. The sulfoxides were shown to be very good ortho directing groups.
Molecular structure and electronic spectrum of ellagic acid: Semiempirical molecular orbital calculations
Authors: Sato Tsuguo , Kataoka Masahiro
Published: April 2009

The molecular structure of ellagic acid has been optimized by using PM3 semiempirical MO method. Ellagic acid has been calculated to be planar with the molecular symmetry of C2h. The lactone carbonyl groups are not tilted from the molecular plane. CNDO/S MO method has been used to interpret the experimental uv‐vis spectroscopic data. The results of the PM3 and CNDO/S calculations have been in good agreement with the experimental data.
Synthesis of some piperazinylpyrazolo[3,4‐b]pyridines as selective serotonin re‐uptake inhibitors
Authors: Shutske Gregory M. , Roehr Joachim E.
Published: April 2009

A number of 3‐substituted 6‐piperazinylpyrazolo[3,4‐b]pyridines were synthesized from 2,6‐difluoropyridine by directed ortho metallation and sequential intra‐ and intermolecular displacement of fluorine. Three derivatives with a cyano group in the 3‐position showed activity as selective serotonin re‐uptake inhibitors.
Furopyridines. XXIV. Nitration, chlorination, acetoxylation and cyanation of 2,3‐dihydrofuro[2,3‐b]‐, ‐[3,2‐b]‐, ‐[2,3‐c]‐ and ‐[3,2‐c]pyridine N‐Oxides
Authors: Shiotani Shunsaku , Kurosaki Masahide , Taniguchi Katsunori , Moriyama Miwa
Published: April 2009

Nitration of 2,3‐dihydrofuro[3,2‐b]‐ N‐oxide 3b and ‐[2,3‐c]pyridine N‐oxide 3c afforded the nitropyridine compounds 4b, 5b and 6 from 3b and 4c, 5c, 5′c and 7 from 3c, while ‐[2,3‐b]‐ N‐oxide 3a and ‐[3,2‐c]pyridine N‐oxide 3d did not give the nitro compound. Chlorination of 3b and 3c with phosphorus oxychloride yielded mainly the chloropyridine derivatives 15b, 15′b from 3b and 15c and 15′c from 3c, whereas 3a and 3d gave pyridine derivatives formed through fission of the 1–2 ether bond of the furo‐pyridines 13a, 14 and 13d. Acetoxylation of 3b and 3c gave 3‐acetoxy derivatives 18b and 18c and the parent compound 1b and 1c. Acetoxylation of 3a yielded compounds formed through fission of the 1–2 bond 16 and 17 and 3d gave furopyridones 19 and 19′. Cyanation of 3b and 3c yielded mainly the cyanopyridine compounds 20b, 20c and 20′c. Cyanation of 3a and 3d gave the cyanopyridine compounds 20a, 20d and 20′d accompanying formation of the pyridine derivatives 21a, 21d and 21′d.
Synthesis of substituted 1‐benzyl‐2,4,6‐triphenyl‐2,3‐dihydro‐pyrazolo [3,4‐b] [1,4]diazepines
Authors: Insuasty Braulio , Rodriguez Ricaurte , Quiroga Jairo , Martinez Roberto , Angeles Enrique
Published: April 2009

The acid catalyzed condensation of 4,5‐diaminopyrazoles and chalcones gave the hitherto unknown 1‐benzyl‐2,4,6‐triphenyl‐2,3‐dihydropyrazolo[3,4‐b][1,4]diazepines derivatives. The structure of all products was supported by ir, 1H and 13C‐nmr and mass spectra.
Synthesis of 6‐phenyl‐atevirdine
Authors: Troschütz Reinhard , Karger Alexander
Published: April 2009

The synthesis of 6‐phenyl‐atevirdine (17), a lipophilic derivative of the potent HIV‐1 reverse transcriptase inhibitor atevirdine (1), is described. The title compound was prepared from dithioacetale 2 via keteneaminal 4 and the nitropyridine derivative 10. Unexpectedly, no anti HIV activity was observed for the novel atevirdine derivative 17. The key intermediates 6, 8 and 10 could also be prepared from keteneaminal 18 via chloropyridines 22–24.
Preparation and NMR spectra of substituted 2‐phenyl‐5,5‐dialkylimidazolinones
Authors: Sedlák Miloš , Halama Aleš , Mitaš Petr , Kaválek Jaromír , Macháček Vladimír
Published: April 2009

Eighteen substituted 2‐phenyl‐5,5‐dialkylimidazolinones 2 have been prepared by cyclizations of substituted 2‐(N‐benzoylamino)alkanamides 1. The cyclization of methylamides 1 proceeds at room temperature whereas primary amides are cyclized on boiling. The 1H and 13C nmr spectra of the imidazolinones are presented and the changes in their spectra connected with their protonation in hexadeuteriodimethyl sulfoxide‐trifluoroacetic acid mixtures are discussed.
Isopropenyldihydrofuran derivatives. Preparation and reactions of some isopropenyldihydrofurandicarboxylates
Authors: Yamaguchi Seiji , Sugioka Yosbihiko , Ishida Miwa , Yokoyama Hajime , Hirai Yoshiro
Published: April 2009

Diethyl 5‐isopropenyl‐4,5‐dihydrofuran‐2,3‐dicarboxylate 1a and methyl 5‐isopropenyl‐3‐methoxy‐carbonyl‐4,5‐dihydrofuran‐2‐acetate 2a were prepared by cylization of diethyl 2‐oxosuccinate or dimethyl 3‐oxoglutarate with (E)‐1,4‐dibromo‐2‐methyl‐2‐butene. Their chemical properties were studied.
A convenient synthesis of 8‐substituted indolizines as precursors to 5‐substituted cycl{3.2.2}azine derivatives
Authors: Smith Jonathan O. , Mandal Braja K.
Published: April 2009

The synthesis of 8‐substituted indolizines is described via a two step process in which a 1,4‐diketone, containing a rerf‐butyl group, is cyclocondensed with a trialkylsilyl protected pyrrole to provide 5,8‐disubstituted indolizines in higher yields than the identical reaction with unprotected pyrrole. Cleavage of the tert‐butyl group from the indolizine 5‐position, by treatment with 85% phosphoric acid, provides 8‐substituted indolizines in good yields. Treatment of 8‐substituted indolizines with dimethyl acetylenedicarboxylate, in the presence of palladium‐on‐carbon, provides novel 5‐substituted cycl{3.2.2) derivatives.
The synthesis and transformation of ethyl 2‐(2‐acetyl‐2‐benzoyl‐1‐ethenyl)amino‐3‐dimethylaminopropenoate. A new synthesis of 2,3,4‐trisubstituted pyrroles
Authors: Malešič Mateja , Krbavčič Aleš , Golobič Amalija , Golič Ljubo , Stanovnik Branko
Published: April 2009

The synthesis of ethyl 2‐(2‐acetyl‐2‐benzoyl‐1‐ethenyl)amino‐3‐dimethylarninopropenoate (4) from benzoylacetone (1) via 3‐dimethylarninomethylenebenzoylacetone (2) and ethyl N‐(2‐acetyl‐2‐benzoyl‐1‐ethenyl)glycinate (3) and its transformation into 4‐benzoyl‐2‐ethoxycarbonyl‐3‐methylpyrrole (9) is described. Cyclization of 4 into 9 represents a new synthesis of polysubstituted pyrroles.
Synthesis of the novel thieno[4,3,2‐ef][1,4]benzoxazepine ring system: 4,5‐Dihydro‐3‐(4‐pyridinyl)thieno[4,3,2‐ef][1,4]benzox‐azepine maleate
Authors: Tomer John D. , Shutske Gregory M. , Friedrich Dirk
Published: April 2009

4,5‐Dihydro‐3‐(4‐pyridinyl)‐thieno[4,3,2‐ef][1,4]benzoxazepine maleate 2 has been synthesized from 3‐amino‐4‐fluorobenzo[fc]thiophene by employing an intramolecular nucleophilic aromatic fluoride displacement. In the presence of strong base and heat, 2 rearranges to form the isomeric hemiaminal, 3,4‐dihydro‐4‐methyl‐3‐(4‐pyridinyl)thieno[4,3,2‐ef][1,3]benzoxazine 10. A proposed mechanism for this rearrangement is discussed.
Synthesis of dendritic polypyridines using divergent methodology
Authors: Chessa Gavino , Scrivanti Alberto
Published: April 2009

The synthesis of dendritic polypyridines is described. The dendrimers were prepared by a divergent approach using diethl 4‐hydroxypyridine‐2,6‐dicarboxylate 1 and 4‐hydroxy‐2,6‐bis(acetoxymethyl)pyridine 6 as building blocks. The transformation of the surface functionalities of the second generation dendrimer led to imperfections which did not allow us to further increase the size of the macromolecule.
A back‐trajectory and air mass climatology for the Northern Shenandoah Valley, USA
Authors: Hondula David M. , Sitka Luke , Davis Robert E. , Knight David B. , Gawtry Stephen D. , Deaton Michael L. , Lee Temple R. , Normile Caroline P. , Stenger Philip J.
Published: April 2009

Synoptic‐scale air quality climatologies can often be categorized into trajectory methods based on air parcel movement or air mass approaches that are primarily dictated by thermal and moisture conditions. Here, we examine the relationship between these two essentially independent methods of synoptic‐scale climate classification: 72‐h Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model back‐trajectories and the Spatial Synoptic Classification (SSC) of air masses for Martinsburg, West Virginia, located at the northern end of the Shenandoah Valley, from 1997 to 2006. Statistically significant differences exist between trajectory groups across the six SSC air mass types within each season and between seasons within each air mass type.

Further examination of the trajectory distributions reveals a high degree of overlap between trajectories associated with different air mass types. In some cases, up to 50% of one air mass's trajectories are statistically closer to the trajectories of a different air mass type. Accordingly, air mass alone cannot be used to identify specific source regions of pollutants. This suggests that, while an air mass classification system can be used to identify general flow patterns, the integration of both thermodynamic and air‐flow variables in a synoptic classification should provide information that is not discernible from either method independently. The inclusion of both back‐trajectory and air mass information represents the suite of environmental conditions that may enhance or suppress pollutant concentrations in the Shenandoah Valley better than using either measure independently. Copyright © 2009 Royal Meteorological Society
IgE‐mediated fungal allergy in allergic fungal sinusitis
Authors: Pant Harshita , Schembri Mark A. , Wormald Peter J. , Macardle Peter J.
Published: April 2009

This review will address the current knowledge of the pathogenic mechanisms in allergic fungal sinusitis (AFS) and the basis for the current classification of a subgroup of chronic rhinosinusitis patients. Special attention is directed to the role of immunoglobulin E (IgE)‐mediated fungal allergy in the pathogenesis of AFS. Concepts relating to the mucosal inflammatory response are introduced, as a knowledge of the reactions of the sinus mucosal cells can lead to a better understanding of the mechanisms perpetuating and maintaining the chronic inflammation. Laryngoscope, 2009
Office‐based sclerotherapy for benign parotid lymphoepithelial cysts in the HIV‐positive patient
Authors: Berg Eric E. , Moore Charles E.
Published: April 2009

Objective:

To determine the efficacy of sodium morrhuate injection therapy in the control of benign lymphoepithelial cysts of the parotid gland.

Study Design:

Retrospective review.

Methods:

The medical records of human immunodeficiency virus (HIV)‐positive patients who presented to an indigent care hospital for the evaluation and management of benign lymphoepithelial cysts of the parotid gland are reviewed. Cyst laterality, aspiration and injection volumes, and noted complications were recorded. When applicable, elapsed time between recurrent interventions was recorded.

Results:

Medical records were available for a total of nine patients who underwent aspiration and injection of 34 cysts. Five of the nine patients required therapy for additional cyst formation an average of 11.8 months after initial intervention. There have been no known instances of facial nerve or parotid gland injury, and the only recorded postprocedure complaints were pain and mild edema.

Conclusions:

While multiple cysts may arise and serial intervention may be required, we believe that in association with broader clinical experience, the data presented here support aspiration and sodium morrhuate injection as a safe, minimally invasive, and efficacious technique in the treatment of benign lymphoepithelial cysts of the parotid gland in the HIV‐positive population. Laryngoscope, 2009
Does vocal cord fixation preclude nonsurgical management of laryngeal cancer?
Authors: Solares C. Arturo , Wood Benjamin , Rodriguez Cristina P. , Lorenz Robert R. , Scharpf Joseph , Saxton Jerrold , Rybicki Lisa A. , Strome Marshall , Esclamado Ramon , Lavertu Pierre , Adelstein David J.
Published: April 2009

Objectives/Hypothesis:

To determine whether vocal cord fixation precludes nonsurgical management of T3/T4 laryngeal carcinoma.

Study Design:

A retrospective chart review.

Methods:

Between 1989 and 2005 patient records with T3/T4 squamous cell carcinoma of the larynx with vocal cord fixation at presentation were reviewed. All were treated with a concomitant cisplatin‐based chemoradiotherapy protocol and were part of the institutional head and neck cancer chemoradiotherapy registry. Only patients with adequate pre‐ and post‐treatment fiberoptic evaluations were included. Charts were reviewed for demographics and tumor characteristics; return of vocal cord function; local, regional, or distant recurrence after treatment; and need for salvage surgery. The Kaplan‐Meier method was used to estimate outcomes, and the log‐rank test was used to compare those patients whose vocal cords remained fixed to those with recovery of function.

Results:

Twenty‐three patients met the inclusion criteria, 19 males and 4 females. The median age was 59 years (range, 39–73). Fourteen patients had T3 and nine had T4 tumors. Twelve patients recovered full range of mobility, three had partial recovery, and eight did not recover motion. The median follow‐up was 68 months (range, 34–191). Comparing patients with post‐treatment partial or fully mobile cords to those with persistent fixation revealed the following: A projected five‐year overall survival of 100% versus 25%, (P < .001), freedom from recurrence of 86.7 versus 25% (P < .001), local control without surgery of 86.7% versus 30% (P = .003), and survival with functional larynx of 86.7% versus 25% (P = .008), respectively.

Conclusions:

Nonsurgical therapy in patients with pretreatment vocal cord fixation is feasible. However, persistence of vocal cord fixation after definitive chemoradiotherapy is a poor prognostic sign and early surgical intervention should be considered. Laryngoscope, 2009
Systematic review and meta‐analysis of the adverse effects of thyroidectomy combined with central neck dissection as compared with thyroidectomy alone
Authors: Chisholm Edward J. , Kulinskaya Elena , Tolley Neil S.
Published: April 2009

Objectives/Hypothesis:

Meta‐analysis to assess the increased morbidity of performing a central neck dissection with thyroidectomy to thyroidectomy alone.

Study Design:

Systematic review and meta‐analysis.

Methods:

Published articles were searched for using PubMed. Suitability was assessed by using predefined inclusion/exclusion criteria. Meta‐analysis on the data was performed using the Mantel‐Haenszel method and a risk difference calculated.

Results:

Five studies with a total of 1,132 patients were included. For every 7.7 central neck dissections performed with thyroidectomy, there was one extra case of temporary hypocalcemia when compared to thyroidectomy alone. There was no significant increased risk of permanent hypocalcemia or temporary or permanent vocal cord palsy when a central neck dissection was performed in addition to a thyroidectomy.

Conclusions:

The benefits of prophylactic central neck dissection in differentiated thyroid carcinoma may be debated but there is no increased permanent morbidity by performing the procedure at the same time as thyroidectomy. Laryngoscope, 2009
Nanocomposites of Size‐Tunable ZnO‐Nanoparticles and Amphiphilic Hyperbranched Polymers
Authors: Richter Thomas V. , Schüler Fabian , Thomann Ralf , Mülhaupt Rolf , Ludwigs Sabine
Published: April 2009

Highly dispersed ZnO nanoparticles with variable particle sizes were successfully prepared within an amphiphilic hyperbranched polyetherpolyol matrix via decomposition of an organometallic precursor in the presence of air leading to stable nanocomposites. The high degree of stabilization during and after the synthesis by the polymer permits control over the nanoparticle size and therefore, due to the quantum‐size‐effect, the particle properties. Furthermore, these polymer‐inorganic nanocomposites can easily be dispersed in apolar solvents to yield highly transparent, stable solutions.

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Validation of cerebral blood perfusion imaging as a modality for quantitative pharmacological MRI in rats
Authors: Bruns Andreas , Künnecke Basil , Risterucci Céline , Moreau Jean‐Luc , von Kienlin Markus
Published: April 2009

The aim of this study was to validate continuous arterial spin labeling (CASL) as a quantitative imaging modality for pharmacological MRI (phMRI) based on local cerebral blood perfusion. Specifically, the capability of CASL to assess brain‐activity signatures of pharmacological interventions in animal models was evaluated with respect to drug discovery in diseases of the central nervous system (CNS). Perfusion as a surrogate for neuronal activity was measured in various brain areas of the rat. The validation approach was threefold. First, perfusion was shown to reliably reflect differential effects of anesthesia on striatal activation. Different baseline levels and different temporal response profiles after amphetamine challenges under isoflurane, propofol, ketamine, and α‐chloralose anesthesia were consistent with known properties of these anesthetics. Second, remarkable consistency of multi‐area baseline perfusion patterns between independent groups of animals confirmed the notion that CASL is highly reproducible and thus particularly suitable for long‐term longitudinal studies. Third, administration of the well‐characterized psychotomimetic compounds amphetamine and phencyclidine (PCP) elicited dose‐dependent activation patterns that were related to the drugs' particular interactions with the dopaminergic and glutamatergic systems, respectively. In conclusion, perfusion‐based phMRI is a robust, reliable and valid quantitative technique suitable for evaluating brain‐activation patterns in animal models of CNS diseases. Magn Reson Med, 2009. © 2009 Wiley‐Liss, Inc.
Water saturation shift referencing (WASSR) for chemical exchange saturation transfer (CEST) experiments
Authors: Kim Mina , Gillen Joseph , Landman Bennett A. , Zhou Jinyuan , van Zijl Peter C.M.
Published: April 2009

Chemical exchange saturation transfer (CEST) is a contrast mechanism that exploits exchange‐based magnetization transfer (MT) between solute and water protons. CEST effects compete with direct water saturation and conventional MT processes, and generally can only be quantified through an asymmetry analysis of the water saturation spectrum (Z‐spectrum) with respect to the water frequency, a process that is exquisitely sensitive to magnetic field inhomogeneities. Here it is shown that direct water saturation imaging allows measurement of the absolute water frequency in each voxel, allowing proper centering of Z‐spectra on a voxel‐by‐voxel basis independently of spatial B0 field variations. Optimal acquisition parameters for this “water saturation shift referencing” (WASSR) approach were estimated using Monte Carlo simulations and later confirmed experimentally. The optimal ratio of the WASSR sweep width to the linewidth of the direct saturation curve was found to be 3.3–4.0, requiring a sampling of 16–32 points. The frequency error was smaller than 1 Hz at signal‐to‐noise ratios of 40 or higher. The WASSR method was applied to study glycogen, where the chemical shift difference between the hydroxyl (OH) protons and bulk water protons at 3T is so small (0.75–1.25 ppm) that the CEST spectrum is inconclusive without proper referencing. Magn Reson Med, 2008. © 2009 Wiley‐Liss, Inc.
Preparation and properties of PU/MCMMT nanocomposites
Authors: Qiao Min , Wu Shishan , Ran Qianping , Shen Jian
Published: April 2009

The cetyltrimethyl ammonium bromide (CTAB) was used as a swelling agent to be intercalated into the galleries of the montmorillonite (MMT) platelets to get the organic MMT (CMMT). Then 4,4′‐diphenylmethane diisocyanate (MDI) were grafted on CMMT by the reaction between hydroxyls in organic MMT platelets and MDI to synthesize the MDI modified CMMT (MCMMT). Polyurethane (PU)/MCMMT composites were prepared by situ polymerization. The MCMMT platelets dispersed in a PU matrix in nanometer scale. The dispersion and intercalation degree of the MCMMT platelets decreased with increase in the content of MCMMT. Under the same content of fillers, the tensile strength and tear strength of PU/MCMMT nanocomposites were higher than those of PU/organic MMT nanocomposites. The reinforcing effect of the MCMMT platelets to the PU was better than that of the organic MMT platelets. With increase in the content of MCMMT, the tensile strength and tear strength of the PU/MCMMT nanocomposites were increased, while the extent of the increase slowed down. Compared with those of PU, the thermal stability of PU/MCMMT nanocomposites was increased. Copyright © 2009 John Wiley & Sons, Ltd.
Dissatisfaction with hospital care for children with sickle cell disease not due only to race and chronic disease
Authors: Brousseau David C. , Mukonje Terence , Brandow Amanda M. , Nimmer Mark , Panepinto Julie A.
Published: April 2009

Background

A previous study reported increased dissatisfaction with hospital care for children with sickle cell disease (SCD); however, its small size excluded determining whether race and chronic disease explained the difference.

Procedure

At hospital discharge, parents of children with SCD completed a survey assessing satisfaction with their child's hospital care. Results were compared to three years of satisfaction surveys for children with asthma or admitted to a general pediatrician's service collected as quality improvement for the hospital. The primary outcome was parent reported dissatisfaction with care. A chi‐square was used to compare dissatisfaction between SCD and each comparison group.

Results

Parents of 639 children were included, 34 children with SCD, 124 with asthma, and 481 general pediatric patients. Parents of children with SCD were more often dissatisfied with their child's care compared to children with asthma (32.4% vs. 16.9%, P < 0.05) and general pediatric patients (32.4% vs. 14.6%, P < 0.05). Among all children, dissatisfaction was higher in families with minority children (21.1% vs. 12.6%); this difference did not exist among children with asthma. Among African‐American children, a higher proportion of parents of children with SCD believed their child was treated differently because of race than children with asthma (45.5% vs. 2.8%, P < 0.01) or general pediatric patients (45.5% vs. 8.3%, P < 0.01).

Conclusion

Parents of children with SCD report increased dissatisfaction with care. While dissatisfaction was higher in minority families, the high rate of parental concern about race as a reason for families of children with SCD is not seen in African‐American families of children with asthma. Pediatr Blood Cancer 2009;53:174–178. © 2009 Wiley‐Liss, Inc.
Changes in breast cancer patients after psychosocial intervention as indicated in drawings
Authors: Ho R. T. H. , Potash J. S. , Fu Wai , Wong K. P. L. , Chan C. L. W.
Published: April 2009

Objective: The present study attempts to understand the experience of breast cancer patients who had participated in an Eastern‐based body–mind–spirit (BMS) psychosocial intervention program by observing changes in the images made by the patients.

Methods: Pre‐ and post‐intervention drawings on the theme of ‘my cancer’ were collected from 67 primary breast cancer patients. Two creative art therapists compared the drawings according to the structural and formal art elements (body), the symbols used (mind), and the emotions and feelings presented in the drawings (spirit). Numbers of pre‐ and post‐intervention drawings, showing the presence of each element in these three dimensions, were also counted and compared.

Results: There were several changes noted between pre‐ and post‐intervention drawings. The use of color, space, and multiplicity increased from 12 to 17%. Images of breasts decreased from 13 to 0%. Representations of cancer decreased from 15 to 7%. There was a slight increase in symbolic representations of natural, landscapes, and social support in post‐drawings (3–6%). The portrayal of negative emotions was greatly reduced from 52 to 3%, while positive emotions increased from 28 to 93% in post‐drawings.

Conclusions: The comparison of pre‐ and post‐intervention drawings revealed changes in subject matter and accompanying emotions. Overall, there was a trend in changes toward a more peaceful and hopeful attitude. Through the use of realistic and symbolic images, participants depicted a range of emotions. Limitations and recommendations for using art–making, as an assessment tool and intervention, are addressed. Copyright © 2009 John Wiley & Sons, Ltd.
Identification of melanoma‐specific serological markers using proteomic analyses
Authors: Takikawa Masako , Akiyama Yasuto , Ashizawa Tadashi , Yamamoto Akifumi , Yamazaki Naoya , Kiyohara Yoshio , Oku Naoto , Yamaguchi Ken
Published: April 2009

The discovery of novel melanoma markers for not only early detection but also monitoring disease status is promising to improve the clinical outcome of patients. In the present study, we performed proteomic comparative analysis of plasma proteins between healthy volunteers and melanoma patients using NanoLC and MALDI‐TOF‐MS. As a result, we were successful in identifying nine proteins that were specifically expressed in melanoma plasma compared with healthy plasma, most of which had not previously been identified as plasma markers of melanoma. The mRNA expression levels of four proteins [pro‐platelet basic protein precursor (PPBP), serum amyloid A2 (SAA2), complement factor H‐related protein 1 precursor (FHR1), inter‐alpha‐trypsin inhibitor heavy chain H4 precursor (IAIH4)] were prominently up‐regulated in several melanoma cell lines compared with melanocytes. Moreover, two proteins (PPBP, SAA) were shown to be expressed in tumor specimens from melanoma patients. In the survival time analysis regarding melanoma patients, the semi‐quantified plasma PPBP levels were statistically negatively correlated with the survival time. Most interestingly, the significant survival benefit was seen in low PBPP level group (< index 20) versus high level (≥ index 20) group. The results suggest that PPBP might be a novel promising serological marker and a prognostic factor specific to melanomas.
Generalization of Schrödinger invariance. Applications to Bose‐Einstein condensation
Authors: Stoimenov S.
Published: April 2009

The symmetries of non‐linear Schrödinger equations with power‐law non‐linearities are investigated. It is shown that Galilei invariance can be extended to Schrödinger invariance if the coupling constant(s) in non‐linearity is treated as dimensionful quantity. This is used to find a new non‐stationary solutions from given stationary ones.
Supersymmetric gauge theories in three dimensions
Authors: Bergshoeff E. , Hohm O.
Published: April 2009

We show how superconformal gaugings in three dimensions can be systematically constructed using the embedding tensor technique. These gaugings have been argued to describe the worldvolume theory of multiple M2‐branes. Applying our technique we construct the most general superconformal gaugings with 𝒩 = 5, 6 and 8 supersymmetry. In the case of 𝒩 = 5 supersymmetry we find three exceptional gaugings. We briefly discuss new developments concerning the massive deformations of the superconformal gauge theories.
Cremmer‐Gervais quantum Lie algebra
Authors: Ogievetsky O. , Popov T.
Published: April 2009

We describe a quantum Lie algebra based on the Cremmer‐Gervais R‐matrix. The algebra arises upon a restriction of an infinite‐dimensional quantum Lie algebra.
Formulation affecting alachlor efficacy and persistence in sandy soils
Authors: Sopeña Fátima , Maqueda Celia , Morillo Esmeralda
Published: April 2009

BACKGROUND: The development of controlled‐release formulations of alachlor to extend the period of weed control was studied. This extended duration reduces the need for high herbicide application rates that could lead to environmental contamination. For this purpose, the influence of formulation, as well as the influence of soil characteristics, on alachlor efficacy and persistence in soil of a commercial formulation (CF) and different ethylcellulose microencapsulated formulations (MEFs) was evaluated.

RESULTS: Higher alachlor rates yielded an enhanced initial herbicidal activity. The prolonged release of alachlor provided by the MEFs resulted in a higher herbicidal efficacy and a longer period of weed control compared with the effects of CF in the two soils tested (at 40 days after treatment, oat growth inhibition for CF and MEFs was 1.96% and 93.5% respectively). Soil characteristics strongly influenced alachlor efficacy and weed control by MEFs. The highest alachlor efficacy and persistence were observed in the soil with lowest microbial activity and clay and organic matter content.

CONCLUSIONS: The use of MEFs can be advantageous because they permit the maintenance of the desired concentration of the herbicide in the soil for longer periods of weed control. Copyright © 2009 Society of Chemical Industry
Observation of non‐radiative de‐excitation processes in silicon nanocrystals
Authors: Knights A. P. , Milgram J. N. , Wojcik J. , Mascher P. , Crowe I. , Sherliker B. , Halsall M. P. , Gwilliam R. M.
Published: April 2009

We describe the impact of non‐radiative de‐excitation mechanisms on the optical emission from silicon nanocrystals formed in SiO2. Auger excitation via free carriers deliberately introduced through phosphorus ion implantation, shows a monotonic increase with increasing phosphorus concentration which can be modelled adequately using a simple statistical approach. We also report a reduction in nanocrystal luminescence intensity with increasing exposure to UV radiation and suggest this phenomenon results from the introduction of non‐radiative defects in the Si/SiO2 network. The effect of UV radiation varies significantly depending on the sample preparation. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Tuning block copolymer structural information by adjusting salt concentration in liquid chromatography at critical conditions coupled with electrospray tandem mass spectrometry
Authors: Girod Marion , Phan Trang N. T. , Charles Laurence
Published: April 2009

Different cationic adducts of poly(ethylene oxide)/polystyrene block co‐oligomers could be produced by adjusting the salt concentration in the mobile phase using a coupling between liquid chromatography at critical conditions and electrospray ionization mass spectrometry. Formation of doubly lithiated adducts was observed at high LiCl concentration (1 mM) while lowering the salt concentration down to 0.1 mM allowed co‐oligomers to be ionized with both a proton and a lithium. The fragmentation pathways observed to occur upon collision‐induced dissociation of ionized copolymers were shown to be highly dependent on the nature of the cationic adducts. As a result, complementary structural information could be reached by performing MS/MS experiments on different ionic forms of the same co‐oligomer molecule. On one hand, release of the nitroxide end‐group as a radical from [M+2Li]2+was followed by a complete depolymerization of the polystyrene block, allowing both this end‐group and the polystyrene segment size to be determined. On the other hand, [M+H+Li]2+precursor ions mainly dissociated via reactions involving bond cleavages within the nitroxide moiety, yielding useful structural information on this end‐group. Copyright © 2009 John Wiley & Sons, Ltd.
In situ detection of the intermediates in the biosynthesis of surfactin, a lipoheptapeptide from Bacillus subtilis OKB 105, by whole‐cell cell matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry in combination with mutant analysis
Authors: Vater Joachim , Wilde Christopher , Kell Henny
Published: April 2009

An innovative technique to investigate the intermediates involved in the biosynthesis of the lipoheptapeptide surfactin from Bacillus subtilis OKB105 combining whole‐cell matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) with targeted generation of knock‐out mutants was demonstrated. This method allows efficient, sensitive detection of biosynthetic intermediates in a minimum of time directly at the outer surface of microbial cells picked from agar plates or in surface extracts prepared thereof. Biosynthesis of surfactin is encoded by the srf‐operon which is organized into four open reading frames which have been attributed to three multifunctional NRPS enzymes (SrfA‐C) and a thioesterase/acyltransferase enzyme SrfD. For the wild‐type strain OKB 105 only the end product surfactin was found mass spectrometrically. For the detection of lipopeptide intermediates three plasmid‐ and transposon‐insertion mutants were generated interrupting the surfactin assembly line at defined positions. Strain LAB 327 was mutated in the spacer region between enzymes SrfA and B. Here only SrfA was active with the lipotripeptide β‐OH‐acyl‐L‐Glu‐L‐Leu‐D‐Leu as the end product. Mutant OKB 120 bears a transposon mutation in SrfB between the first and second amino acid activating modules SrfB1 and SrfB2. It showed all intermediates from the lipodi‐ until to the lipotetrapeptide β‐OH‐acyl‐L‐Glu‐L‐Leu‐D‐Leu‐L‐Val. In LAB 223 SrfC was knocked out by a transposon mutation. It produced the lipohexapeptide β‐OH‐acyl‐L‐Glu‐L‐Leu‐D‐Leu‐L‐Val‐L‐Asp‐D‐Leu. Our work highlights the applicability and the potential of whole‐cell MALDI‐TOFMS as an innovative efficient tool for the analysis of intermediate steps of biosynthetic pathways. Copyright © 2009 John Wiley & Sons, Ltd.
Erste Erfahrungen bei der Realisierung der Tragstrukturen von Offshore‐Windenergieanlagen in der deutschen ausschließlichen Wirtschaftszone
Authors: Baeßler Matthias , Dahlke Christian , Eißfeldt Fritz , Lüddecke Falk , Rücker Werner , Vierfuß Ulrich , Zeiler Manfred
Published: April 2009

Zukünftig soll durch die Installation von Windparks in der ausschließlichen Wirtschaftszone und deren Betrieb ein wesentlicher Anteil des Strombedarfs in Deutschland gedeckt werden. Für die zugehörige Realisierung der Windenergieanlagen hat die zuständige Behörde, das Bundesamt für Seeschifffahrt und Hydrographie, Standards veröffentlicht, über deren Inhalte im Hinblick auf die zu errichtenden Stahlkonstruktionen von Windenergieanlagen berichtet wird. Über die zu absolvierenden Freigabephasen und deren Bestandteile sowie über die Anforderungen, die die Genehmigungsbehörde an die Art und den Umfang der zu erbringenden Nachweise für die Tragstrukturen stellt, wird im Rahmen des Aufsatzes berichtet. Bei der zuständigen Genehmigungsbehörde durchlaufen derzeit die ersten Anträge das Genehmigungsverfahren. Über die hierbei gesammelten Erfahrungen wird aus Sicht der zuständigen Behörde und deren Fachgutachtern berichtet. Speziell hierbei auftretende Diskussionspunkte werden benannt und Hinweise gegeben.
One‐Pot Assembly of a New Mixed‐Valent Aggregate Based on Inorganic Polyoxometalate Ligands
Authors: Chen Weilin , Li Yangguang , Wang Yonghui , Wang Enbo , Zhang Zhiming
Published: April 2009

Employing a “one‐pot” synthesis strategy, the reaction of Na2WO4·2H2O, Na2HAsO4·7H2O, FeCl3·6H2O, various Ln3+ ions, and hexamethylenetetramine (HMTA) in aqueous solutions with pH values ranging from 5.5 to 6.5 results in the isolation of polytungstoarsenate‐based iron aggregates, ‐K8Na14[HMTA]4[(FeIII3FeII0.25(OH)3)(AsO4)(AsW9O34)]4·24H2O (1) (HMTA = hexamethylenetetraamine). The polyoxoanion of 1 contains a mixed‐valent {FeIII12FeII(μ3‐OH)12(μ4‐AsO4)4} cluster surrounded by four [B‐α‐AsW9O34]9− units. It is the first polytungstatoarsenate‐based mixed‐valent {FeIII12FeII} aggregate and the largest iron cluster based on [AsW9O34]9− ligands. The compound was characterized by elemental analyses, IR, UV/Vis absorption, and diffuse‐reflectance UV/Vis spectroscopy, TG analyses, XRPD, XPS and gel‐filtration chromatography. The electrochemical and electrocatalytical properties were also investigated. Crystal data for 1, orthorhombic, Fddd, a = 28.156(6) Å, b = 36.003(7) Å, c = 42.126(8) Å, α = 90°, β = 90°, γ = 90°, Z = 8.
Tetrachlorophenyl‐λ5‐arsane and Tetramethoxyphenyl‐λ5‐arsane: Crystal Structures, NMR Spectra and Bonding Situation
Authors: Betz Richard , Reichvilser Moritz M. , Schumi Emanuel , Miller Christian , Klüfers Peter
Published: April 2009

Two phenyl‐substituted λ5‐arsanes were prepared from phenylarsonic acid in two‐step procedures. Their molecular structures were determined by single‐crystal X‐ray diffraction. NBO analyses for the title compounds were conducted.
The First Ruthenium Complex of a Heteroleptic Organostannylene: [4‐tBu‐2,6‐{P(O)(O‐iPr)2}2C6H2]Sn(Cl)Ru(C6H6)Cl2
Authors: Deaáky Vajk , Schürmann Markus , Jurkschat Klaus
Published: April 2009

The synthesis of the intramolecularly coordinated organostannylene ruthenium complex [4‐tBu‐2,6‐{P(O)(O‐iPr)2}2‐C6H2]Sn(Cl)Ru(C6H6)Cl2, 1, is reported. It is characterized by elemental analysis, 1H, 13C, 31P, 119Sn NMR spectroscopy, and, as its toluene solvate 1·C7H8, by single‐crystal X‐ray diffraction analysis. In compound 1·C7H8 the tin atom is five‐coordinate and shows a strongly distorted trigonal‐bipyramidal configuration. The intramolecular O–Sn distances are 2.291(3) and 2.394(3) Å. The Sn–Ru distance is 2.5856 Å.