bluuebunny/crossref_metadata_2025 huggingface dataset:
Hei and heii spectra of 3‐halopyridines
Authors: Xue Jing , Hughes Jason M. , Von Nagy‐Felsobuki Ellak I.
Published: March 2009

The ultraviolet photoelectron spectra (UPS) of 3‐fluoro‐, 3‐ chloro‐, 3‐bromo‐ and 3‐ iodopyridine were recorded and interpreted using a composite‐molecule model. The sequence of the four lowest ionization energies for 3‐fluoro‐ and 3‐chloropyridine is: π3 (1a2) < nN (11a1)ππ2 (2b1)π∼pyr (7b2), whereas for 3‐bromo‐ and 3‐iodopyridine the assignment is: π3 (1a2) ‐ πxπnN (11a1)πσx π2 (2b1) (where X represents a bromine or iodine lone‐pair). Comparison of the HeI and HeII band intensities and correlations with the UPS assignment of the 2‐halopyridines confirm this sequence. However, ab initio calculations using the STO‐3G*//STO‐3G* and 6–31G**//STO‐3G* models do not agree with either the composite‐molecule model, simple UPS correlations and HeI/HeII cross‐section ratios. For 3‐fluoropyridine, the HAM/3 model was in agreement with the proposed assignment.
Interactions of porphyrinyl‐nucleosides with DNA using the example of porphyrinyl‐thymidine
Authors: Trumble William R. , Wandrekar Vinay , Czuchajowski Leszek
Published: March 2009

meso‐Tri(N‐memyl‐4‐pyridinium)porphyrinyl‐p‐phenylene‐5′‐O‐thymidine, interacting with plasmid ds DNA showed an 8 nm red‐shift of the Soret band. The observed Soret band shift was 4 run less than the shift of the respective meso‐tetra(N‐methyl‐4‐pyridinium)porphyrin, which is usually assumed to indicate intercalation. Experimental spectra and the MMX‐ and AM‐1 calculations of a series of model structures further suggest that the investigated porphyrinyl‐thymidine also interacts with adenine due to its nucleobase. The possibility of intercalation was also viewed based on interaction of immobilized porphyrin with ds DNA. Theoretical considerations suggested that there are no steric limitations to the formation of a system in which the porphyrinyl‐thymidine in question interacts with a molecule of porphyrinyl‐adenosine, via A‐T base pairing, to join two ds DNA molecules.
Synthesis of 3,6‐disubstituted pyridazine derivatives
Authors: Mernari Bouchaib , Lagrenée Michel
Published: March 2009

The synthesis of pyridazine functionalized with dioximes side chains are described. Several 3,6‐disubsti‐tuted pyridazine derivatives were prepared and their structures determined by spectroscopic methods (nmr, ir and ms).
Diastereoselective synthesis of cis‐3‐ and 3,5‐alkylpyrrolizidines
Authors: Provot Olivier , Célérier Jean‐Pierre , Lhommet GÉRard
Published: March 2009

Cis‐3 and 3,5‐substituted pyrrolizidines can be prepared from β‐enaminolactones. Substituted pyrrolidinoketones lead to these compounds by an amino reductive annelation with a low diastereomeric excess, but a best access to these azabicycles consists in preparing cis‐2,5‐disubstituted pyrrolidines which are then transformed into the expected heterocycles.
Synthesis of 4H‐1,3,4‐oxadiazino[5,6‐b]quinoxalines from 2‐substituted quinoxaline 4‐oxides
Authors: Kim Ho Sik , Kim Eun Ah , Jeong Geuk , Park Yong Tae , Hong Young Seuk , Okamoto Yoshihisa , Kurasawa Yoshihisa
Published: March 2009

The reaction of 6‐chloro‐2‐(1‐methylhydrazino)quinoxaline 4‐oxide 8 with acetic anhydride resulted in the intramolecular cyclization to give 8‐chloro‐2,4‐dimethyl‐4H‐1,3,4‐oxadiazino[5,6‐b]quinoxaline 7a, while the reaction of compound 8 with acetic anhydride/pyridine or acetic anhydride/acetic acid afforded 3‐(2,2‐diacetyl‐1‐memymydrazmo)‐7‐chloro‐2‐oxo‐1,2‐dihydroquinoxaline 9, effecting no intramolecular cyclization. The reaction of 2‐(2‐acetyl‐1‐methylhydrazino)‐6‐chloroquinoxaline 4‐oxide 10a or 6‐chloro‐2‐(1‐methyl‐2‐trifluoroacetylhydrazino)quinoxaline 4‐oxide 10b with phosphoryl chloride provided compound 7a or 8‐chloro‐4‐memyl‐2‐trifluoromethyl‐4H‐1,3,4‐oxadiazino[5,6‐b]quinoxaline 7b, respectively. The reaction of compound 7b with phosphorus pentasulfide gave 7‐chloro‐3‐(1‐methyl‐2‐trifluoroacetylhydrazino)‐2‐thioxo‐1,2‐dihydroquinoxaline 11, whose dehydration with sulfuric acid in acetic acid afforded 8‐chloro‐4‐methyl‐2‐trifluoromemyl‐4H‐1,3,4‐thiadiazino[5,6‐b]quinoxaline 12.
A novel synthesis of quinolinium salts via benzotriazole methodology
Authors: Katritzky Alan R. , Semenzin Delphine , Yang Baozhen , Pleynet David P. M.
Published: March 2009

A novel method for the synthesis of 1,4‐ and 1,3,4‐substituted quinolinium salts and 1,2,4‐ and 1,2,3,4‐substituted‐1,2‐dibydroquinolines from N‐substituted‐N(benzotriazol‐1‐ylmethyl)aniline derivatives is reported.
Preparation of (R)‐11‐hydroxyaporphine directly from (R)‐10,11‐dihydroxyaporphine ((R)‐apomorphine)
Authors: Kim Jack C. , Bae Sang‐Duk , Kim Ji‐A , Choi Soon‐Kyu
Published: March 2009

A Regioselective synthesis of (R)‐11‐hydroxyaporphine 2 directly from (R)‐10,11‐dihydroxyaporphine ((R)‐apomorphine, 1) is described for the first time. The isopropylidene ketal ring of 10,11‐(isopropyl‐idenyldioxy)aporphine 5 obtained by the isopropylidenation of apomorphine was regioselectively opened by ten equivalents of trimethylaluminum to give (R)‐10‐hydroxy‐11‐tert‐butyloxyaporphine 6. The free 10‐hydioxyl position of 6 was triflated with N‐pbenyltrifluoromethanesulfonimide and potassium carbonate under reflux to give (R)‐10‐[(trifluoromethyl)sulfonyloxy]‐11‐tert‐butyloxyaporphine 7. The reduced product, 11‐tert‐butyloxyaporphine 8 was prepared from 7 by a palladium‐catalyzed hydrogenolysis. The ether cleavage of (R)‐11‐tert‐butyloxyaporphine with 48% hydrobromic acid afforded the desired (R)‐11‐hydroxyaporphine 2 in good yield.
Studies on the chemical transformations of rotenoids. 5. Synthesis and cytotoxicity of 1,3‐diazepino[5,6‐b]benzofuran and pyridazino[4,5‐b]benzofurans fused with thiazole, imidazole and pyrimidine
Authors: Nagai Shin‐ichi , Ueda Taisei , Sakakibara Hiroyuki , Nagatsu Akito , Murakami Nobutoshi , Sakakibara Jinsaku
Published: March 2009

Novel benzofuro[2,3‐d]pyridazinium chlorides fused with thiazole 5a, imidazole 5b‐c and pyrimidine 5d‐f were prepared starting from 4‐chloropyridazino[4,5‐b]benzofuran 3a. Treatment of 5b, 5d and 5e with 10% potassium carbonate solution provided the corresponding free bases 6a‐c. Ring closure of methyl rotenononate 1b with amidines proceeded in the presence of sodium methoxide to give 1,3‐diazepino[5,6‐b]benzofuran‐5‐ones 7a‐c. Compound 5d showed cytotoxicity against P388 and L1210 leukemia cells.
v‐Triazolines. XXXIX. 1,2,4‐Triaryl‐3‐aminopyrroles. Unusual Reaction Products in the Pyrolysis of 5‐Amino‐v‐triazolines and the Crystal Structure of 2‐(3‐Morpholin‐4‐yl‐2,4‐pyrrol‐1‐yl)benzonitrile
Authors: Pocar Donato , Trimarco Pasqualina , Bombieri Gabriella
Published: March 2009

Pyrolysis of 4‐aryl‐5‐amino‐v‐triazolines affords, generally, amidines and/or benzanilides. Pyrolysis of 4‐aryl‐5‐morpholino‐v‐triazolines 6, together with the expected amidines 7 and/or aryanilides 8, produced the morpholinopyrroles 9. The reaction mechanism of this unusual transformation is discussed. Influence of solvent dipole moment in pyrrole formation is suggested. Pyrrole 9a [i.e. 2‐(3‐morpholin‐4‐yl‐2,4‐pyrrol‐1‐yl)‐benzonitrile] has been fully characterized and its molecular structure has been determined by X‐ray diffraction analysis.
A simple one‐pot synthesis of [1]benzotelluro[3,2‐b][1]‐benzotellurophenes and its selenium and sulfur analogues from 2,2′‐dibromodiphenylacetylene
Authors: Sashida Haruki , Yasuike Syuji
Published: March 2009

Treatment of 2, 2′‐dibromodiphenylacetylene 7 with tert‐butyllithium followed by tellurium insertion resulted in intramolecular ring closure to afford [1]benzotelluro[3,2‐b][1]benzotellurophene 8a. Similarly, [1]benzoseleno‐[3,2‐b][1]benzoselenophene 8b and [1]benzothieno[3,2‐b][1]benzothiophene 8c were also obtained.
Synthesis of 4‐oxopyrimidinium and 4‐oxo‐1,4‐dihydropyrimidines
Authors: Vedernikova Irina V. , Haemers Achiel , Ryabukhin Yuryi I.
Published: March 2009

The synthesis of N1‐substituted 4‐pyrimidones is described. These compounds were prepared from their corresponding 4‐oxopyrimidinium perchlorates or from a reaction of a primary amine with a N‐acyl‐β‐ketoamide.
Synthesis and anticonvulsant activities of 5‐(2‐Chlorophenyl)‐7H‐pyrido[4,3‐f][1,2,4]triazolo[4,3‐a][1,4]diazepines
Authors: Fiakpui Charles Y. , Phillips Oludotun A. , Murthy K. S. Keshava , Knaus Edward E.
Published: March 2009

A group of 5‐(2‐chlorophenyl)‐10‐(substituted)‐7H‐pyrido[4,3‐f][1,2,4]triazolo[4,3‐a][1,4]diazepines 7a‐c were synthesized by the acid catalyzed reaction of 5‐(2‐chlorophenyl)‐2‐hydrazino‐3H‐pyrido[3,4‐e]‐[1,4]diazepine (6) with either trimethyl orthoformate, triethyl orthoacetate or triethyl orthobenzoate, respectively. 5‐(2‐Chlorophenyl)‐7H‐pyrido[4,3‐f][1,2,4]triazolo[4,3‐a][1,4]diazepine (7a) and 5‐(2‐chlo‐rophenyl)‐10‐methyl‐7H‐pyrido[4,3‐f][1,2,4]triazolo[4,3‐a][1,4]diazepine (7b) exhibited good anticonvulsant activity in the subcutaneous metrazol anticonvulsant screen which serves as a model for absence (petit mal) epilepsy.
New 2‐substituted 4‐hydroxy‐2H‐1,2‐benzothiazine‐3‐carboxamide 1,1‐dioxides: Spectral and pharmacological properties
Authors: Maso Monica Dal , Perillo Isabel A. , Schapira Celia B. , Gorzalczany Susana , Acevedo María C. , Sicardi Susana M.
Published: March 2009

A series of 4‐hydroxy‐2H‐1,2‐benzothiazme‐3‐carboxamide 1,1‐dioxides substituted on the sulfonamide nitrogen with ethoxycarbonylalkyl, cyanoalkyl and dialkylaminoalkyl groups was synthesized. Spectroscopic properties of the obtained products were analyzed. Findings from the pharmacological study of some of the compounds as antiinflammatory and analgesic agents are reported.
Bringing the outside in: Can “external” workers experience insider status?
Authors: Lapalme Marie‐Ève , Stamper Christina L. , Simard Gilles , Tremblay Michel
Published: March 2009

The current study examines the possibility that agency workers can experience perceived insider status despite their assumed “outsider” category. One hundred ninety‐one agency workers from Canadian financial firms completed surveys assessing agency worker perceptions regarding the level of support from both their supervisors and the client firms' permanent workers, as well as the agency workers' level of perceived insider status and affective commitment toward the client firm. Agency worker supervisors (within the client firm) assessed the agency workers' level of interpersonal facilitation. Results indicate that: (1) Agency workers can experience perceived insider status, regardless of their objective classification as outsiders; (2) perceived support from supervisors and the client firms' permanent workers contribute to agency worker perceptions of insider status; and (3) perceptions of insider status are associated with higher levels of both affective commitment and interpersonal facilitation, even in workers that are considered marginally tied to the organization. Copyright © 2009 John Wiley & Sons, Ltd.
Effect of nitrogen fertilization on quality markers of strawberry (Fragaria × ananassa Duch. cv. Aromas)
Authors: Ojeda‐Real Laura A , Lobit Philippe , Cárdenas‐Navarro Raúl , Grageda‐Cabrera Oscar , Farías‐Rodríguez Rodolfo , Valencia‐Cantero Eduardo , Macías‐Rodríguez Lourdes
Published: March 2009

BACKGROUND: Nitrogen is an indispensable element for fruit metabolism and low or excessive N levels can affect the accumulation of the most important components that contribute to the flavour and aroma of the fruit. Among them, sugars, acids and volatile compounds can be considered quality markers. The objective of this study was to evaluate the effect of N fertilization on these quality markers of the fruit at two harvest dates.

RESULTS: Strawberry plants were grown in a hydroponic system and N was applied as Ca(NO3)2 at concentrations of 0.3, 3 and 6 mmol L−1 in the nutrient solution. Total soluble solids, soluble carbohydrates, amino acids and organic acids and volatile compounds of the fruit were analyzed. The fruits produced at 3 and 6 mmol L−1 N had higher contents of esters, soluble carbohydrates and amino acids. The hexanal content increased with the 6 mmol L−1 dose. The effect of fertilization was more marked at the second harvest date.

CONCLUSION: The availability of N in strawberry plants affected the accumulation of quality markers. The fruits expected to have the best flavour and aroma, with both high levels of soluble carbohydrate and esters and low levels of hexanal, were obtained with 3 mmol L−1 nitrate in the solution. Copyright © 2009 Society of Chemical Industry
Bioeffects of chromium(III) on the growth of Spirulina platensis and its biotransformation
Authors: Wang Ying , Xu Wentao , Luo Yunbo , Ma Liyan , Li Yuansa , Yang Shuran , Huang Kunlun
Published: March 2009

BACKGROUND: In this study the bioeffects of chromium(III) (Cr(III)) on the growth of Spirulina platensis and its biotransformation were investigated. Spirulina platensis was batch cultured in Zarrouk medium containing different concentrations of CrCl3 · 6H2O. Total and organic Cr contents in S. platensis were determined by inductively coupled plasma mass spectrometry (ICP‐MS), and Cr speciation was assayed by high‐performance liquid chromatography/ICP‐MS.

RESULTS: Results based on the dry weight, growth curve, chlorophyll yield and morphology change of S. platensis indicated that the growth of S. platensis was facilitated by Cr(III) below 4.51 mol L−1 and inhibited by a higher concentration of Cr(III). It was found that Cr(III) could be accumulated efficiently in S. platensis, with a highest Cr yield of 173.17 g kg−1 and a highest organic Cr proportion of 50.19 g kg−1 (96.04% of the total concentration of Cr). No evidence of oxidation of Cr(III) to Cr(VI) in S. platensis cells was found.

CONCLUSION: The results of this study suggest that S. platensis could potentially be used as a safe food carrier to accumulate Cr(III) through some metabolic process. Copyright © 2009 Society of Chemical Industry
Rationale and methods for compiling an atlas of desertification in Italy
Authors: Costantini E. A. C. , Urbano F. , Aramini G. , Barbetti R. , Bellino F. , Bocci M. , Bonati G. , Fais A. , L'Abate G. , Loj G. , Magini S. , Napoli R. , Nino P. , Paolanti M. , Perciabosco M. , Tascone F.
Published: March 2009

This study presents the main results and the methodology used in the creation of the atlas of the risk of desertification in Italy. A desertified area was defined as an unproductive area for agricultural or forestry use, due to soil degradation processes. An area at risk of desertification was a tract of the earth's surface which is vulnerable or sensitive to the processes of desertification. In a vulnerable land, environmental characteristics are close to that of a desertified area, but some factors (e.g. vegetation cover or irrigation), successfully mitigate the desertification process. On the other hand, sensitive land is a surface where the process leading to desertification is active, although the land is not yet unproductive.

The DPSIR (Driving force‐Pressure‐State‐Impact‐Response) framework has been adopted as a reference. Using the national soil information system and socio‐economic layers, an atlas of indicators of desertification risks was created, which was organized into different soil degradation systems. 51.8 per cent of Italy was considered to be at potential risk of desertification. Some 21.3 per cent of Italy (41.1 per cent of the area at potential risk) featured land degradation phenomena. Specifically, 4.3 per cent of Italy is already unproductive; 4.7 per cent is sensitive and 12.3 per cent is vulnerable. In the territory at potential risk of desertification, unproductive lands, plus areas vulnerable or sensitive to soil erosion, are at least the 19 per cent. Areas affected by aridity also sum up to 19 per cent. Salt‐affected soils in Italy are estimated to cover >1 million ha. Irrigation can mitigate soil aridity and salinization, nevertheless, only about 15 per cent of the sensitive and vulnerable lands of southern Italy are actually equipped with irrigation networks. Copyright © 2009 John Wiley & Sons, Ltd.
Is rural migration a threat to environmental sustainability in Southern Burkina Faso?
Authors: Ouedraogo I. , Savadogo P. , Tigabu M. , Cole R. , Odén P. C. , Ouadba J.‐M.
Published: March 2009

There is growing evidence that population pressure on the land has become the most intractable problem in the developing countries where demand for food exceeds the food production capacity of the land. Southern Burkina Faso has experienced rapid population growth, mostly driven by immigration of farmers. This study was carried out in Sissili Province and used satellite images acquired over 31‐year period, census and survey data to capture migration patterns and its impacts on land use change. Results showed that migrant population which accounted for only 3 per cent in the study area in 1976 shifted to 57 per cent in 2007. Migrant people were using improved technology to progressively convert forest land to cropland. Cropland increased at an annualized rate of 0·46 per cent to the detriment of the dense forest and woodland which decreased at 0·57 per cent per annum. Population growth was highly correlated with increasing area of cropland (r2 = 0·95, p = 0·014) and declining dense forest (r2 = 0·78) and woodland (r2 = 0·95) covers. It can be concluded that rural migration, driven by the relatively good soil and rainfall conditions in the recipient area, is accounted for deforestation in the study area. If rural migration is not checked, it will seriously degrade the environment. Copyright © 2009 John Wiley & Sons, Ltd.
How can we control erosion of roadslopes in semiarid mediterranean areas? Soil improvement and native plant establishment
Authors: Bochet E. , García‐Fayos P. , Tormo J.
Published: March 2009

Road building triggers vegetation and soil degradation which affects road safety. We present conclusive results in terms of roadslope protection against erosion from several studies performed on semiarid roadslopes since 2000 (in Eastern Spain). We aim to (1) improve our understanding about slope and vegetation factors which control soil erosion and plant colonisation on semiarid roadslopes; (2) assess the effectiveness of topsoiling, hydroseeding and species selection in the protection of soil against erosion and (3) set scientifically based priorities on ecosystem components that have to be taken into account in future roadslope restoration plans.

Erosion and vegetation cover estimations, vegetation surveys, drilling and hydroseeding experiments with commercial and native species were performed on roadslopes, in addition to seed germination and root penetration experiments.

Our results indicate that slope type and angle are the main factors controlling soil erosion and plant colonisation on semiarid roadslopes. Microsite availability is more limiting to plant establishment than seed availability. Restoration strategies based on the improvement of soil properties and the appropriate selection of native species, able to overcome harsh hydrological and structural soil conditions, are proposed and tested according to slope characteristics. Drilling proved to be a promising technique for roadcut restoration, whereas topsoiling followed by hydroseeding with a seed mixture of selected native species was the most efficient treatment, in terms of cost and benefit, to control erosion on roadfills.

This study clearly shows that ecological knowledge is needed to guide restoration efforts in Mediterranean ecosystems. Moreover, an efficient transfer of scientific knowledge from researchers to the institutions concerned (restorers, policymakers and practitioners) is also needed in the perspective of a more appropriate management of these ecosystems. Copyright © 2009 John Wiley & Sons, Ltd.
Macromol. Biosci. 3/2009
Authors: Rekas Agata , Lo Victor , Gadd Gerry E. , Cappai Roberto , Yun Seok I.
Published: March 2009

Back Cover: Dendrimer PAMAM interferes with amyloid pathway of α‐synuclein in two ways: it inhibits fibrillation in early stages and dissociates existing fibrils. The redirection of the protein by dendrimers from pathological forms to non‐toxic aggregates or preservation of native conformation, and especially their ability to dissociate existing fibrils offer therapeutic outlook for Parkinson's disease. Further details can be found in the article by A. Rekas, V. Lo, G. E. Gadd, R. Cappai, S. I. Yun on page 230.
The Influence of Counterion Type and Temperature on Flory‐Huggins Binary Interaction Parameter in Polyelectrolyte Hydrogels
Authors: Safronov Alexander P. , Blyakhman Felix A. , Shklyar Tatyana F. , Terziyan Tatyana V. , Kostareva Marina A. , Tchikunov Sergey A. , Pollack Gerald H.
Published: March 2009

The Flory‐Huggins binary interaction parameter and its enthalpy and entropy parts were experimentally determined for polyelectrolyte hydrogels based on poly(acrylic) acid (PAAc) and poly(methacrylic) acid (PMAc) with various mono‐ and divalent counterions. It was shown that water is a poor solvent for acrylic and methacrylic polyelectrolyte hydrogels, as the binary interaction parameter is around 0.8 for mono‐ and 0.6 for divalent counterions. The type of counterion affects the enthalpy‐interaction parameter and according to its increase in PAAc gels, counterions can be placed in the following order: Li+<Ca2+<Mg2+<TMA+<Na+ = K+. For most of the gels studied, the enthalpy interaction parameter was much lower than the entropy contribution.

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Formation of Crystallosolvates from Mixtures of Poly(L‐lactide) and Diphenyl Ether
Authors: Nakajima Hajime , Wataoka Isao , Ohara Hitomi , Kimura Yoshiharu
Published: March 2009

Poly(L‐lactide) (PLLA) was mixed homogeneously with diphenyl ether (DE) at high temperature in a range of PLLA/DE compositions from 100/0 to 100/75 in wt.‐%. Cooling of the mixtures yielded white solid products without migration of the liquid DE. Their melting temperature was lowered from 173 to 123 °C as the DE content increased. At an optimum PLLA/DE composition of 100/60, a unique crystallosolvate consisting of large spherulite of PLLA, as detected using polarized optical microscopy, was exclusively generated in powder form. Wide and small angle X‐ray scattering revealed that the PLLA chains form a lamellar structure with a highly ordered crystalline state (α‐form) and that the lamellar spacing is extraordinarily thick, reaching 34 nm. It was therefore suggested that DE partitions into the amorphous layers sandwiched between the crystalline layers and that the specific solvation interaction between DE and PLLA may stabilize the crystallosolvates.

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Copolymerization of Ethylene with 2,7‐Octadienyl Methyl Ether in the Presence of Metallocene and Nickel Diimine Catalysts
Authors: Fernandes Mércia , Kaminsky Walter
Published: March 2009

In this work, copolymers of ethylene with 2,7‐octadienyl methyl ether have been synthesized in the presence of three single‐site catalysts. The obtained copolymers not only have a polar ether function but also a double bond in the side chains that is useful for secondary reactions. The polymers were characterized by GPC, EA, DSC, NMR, and FT‐IR. The catalytic activity depends on the kind of catalysts, the concentration of the polar monomer, and the concentration of the protecting agent. Up to 7.3 wt.‐% of MODE could be incorporated by the metallocene catalyst. These are in average 120 functional side groups in a polymer molecule with a molecular mass of 230 000.

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Synthesis and Characterization of Oxetane‐Functionalized Phosphorescent Ir(III)‐Complexes
Authors: Ulbricht Christoph , Rehmann Nina , Holder Elisabeth , Hertel Dirk , Meerholz Klaus , Schubert Ulrich S.
Published: March 2009

In order to incorporate iridium(III) complexes covalently into an oxetane‐bearing hole‐transporting matrix, a new oxetane‐equipped acetoacetate derivative was introduced as an ancillary ligand. Model complexes with an analogical nonpolymerizable ligand were also prepared in order to perform comparative investigations.

Therefore, a series of bis‐cyclometalated Ir(III) complexes, showing orange (C⁁N‐ligand, coumarin 6) and green (C⁁N‐ligand, phenylpyridine) emission were synthesized and fully characterized. The emission maxima are 569 nm for the orange and 518 nm for the green‐emitting Ir(III) complexes. Entirely solution processed devices, based on crosslinkable hole‐conductors, partially doped with the described orange and green Ir(III) emitters, respectively, were fabricated and tested.

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Synthesis of Symmetrical Triblock Copolymers of Styrene and N‐isopropylacrylamide Using Bifunctional Bis(trithiocarbonate)s as RAFT Agents
Authors: Bivigou‐Koumba Achille M. , Kristen Juliane , Laschewsky Andre , Müller‐Buschbaum Peter , Papadakis Christine M.
Published: March 2009

Six new bifunctional bis(trithiocarbonate)s were explored as RAFT agents for synthesizing amphiphilic triblock copolymers ABA and BAB, with hydrophilic “A” blocks made from N‐isopropylacrylamide and hydrophobic “B” blocks made from styrene. Whereas the extension of poly(N‐isopropylacrylamide) by styrene was not effective, polystyrene macroRAFT agents provided the block copolymers efficiently. End group analysis by 1H NMR spectroscopy supported molar mass analysis and revealed an unexpected side reaction for certain bis(trithiocarbonate)s, namely a fragmentation to simple trithiocarbonates while extruding ethylenetrithiocarbonate. The amphiphilic block copolymers with short polystyrene blocks are directly soluble in water and self‐organize into thermoresponsive micellar aggregates.

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Defined Comonomer Re‐Feeding During the Metallocene‐Catalyzed Copolymerization of 10‐Undecene‐1‐olate with Propene through FTIR In‐Line Monitoring
Authors: Sahre Karin , Schulze Ulrich , Eichhorn Klaus‐J. , Voit Brigitte
Published: March 2009

The consumption of 10‐undecene‐1‐olate (UOA) during its continuous re‐feeding in the metallocene‐catalyzed copolymerization with propene was investigated by ATR‐FTIR spectroscopy in‐line monitoring through evaluation of the integral absorbances of the characteristic IR bands. For the quantitative determination of the comonomer concentration during the copolymerization reaction with and without continuous re‐feeding of UOA, multiple calibration functions based on the chemometric partial least squares method were applied. For the first time, a direct correlation between the consumption of an olefin and the addition of a polar comonomer during a metallocene‐catalyzed copolymerization was demonstrated. By means of this technique, a relatively constant molar stoichiometric ratio of the comonomer and propene over the whole polymerization time was achieved, which is very important in obtaining copolymers with defined random structure and, thus, from the point of view of reaction engineering, constant product quality.

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Synthesis of Folic Acid Functionalized PLLA‐b‐PPEGMA Nanoparticles for Cancer Cell Targeting
Authors: Hu Feixiong , Neoh Koon Gee , Kang En‐Tang
Published: March 2009

Poly(L‐lactic acid)‐block‐poly(poly(ethylene glycol) monomethacrylate) (PLLA‐b‐PPEGMA) has been prepared by the ring‐opening polymerization of lactide with a double‐headed initiator, 2‐hydroxyethyl 2′‐methyl‐2′‐bromopropionate (HMBP), followed by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA). PLLA‐b‐PPEGMA nanoparticles with encapsulated Fe3O4are prepared by a solvent evaporation/extraction technique, and then further functionalized with folic acid, a cancer targeting ligand. Our results show that such functionalized PLLA‐b‐PPEGMA nanoparticles have good potential as carriers for targeted drug delivery in cancer treatment.

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A twisted factorization method for symmetric SVD of a complex symmetric tridiagonal matrix
Authors: Xu Wei , Qiao Sanzheng
Published: March 2009

This paper presents an O(n2) method based on the twisted factorization for computing the Takagi vectors of an n‐by‐n complex symmetric tridiagonal matrix with known singular values. Since the singular values can be obtained in O(n2) flops, the total cost of symmetric singular value decomposition or the Takagi factorization is O(n2) flops. An analysis shows the accuracy and orthogonality of Takagi vectors. Also, techniques for a practical implementation of our method are proposed. Our preliminary numerical experiments have verified our analysis and demonstrated that the twisted factorization method is much more efficient than the implicit QR method, divide‐and‐conquer method and Matlab singular value decomposition subroutine with comparable accuracy. Copyright © 2009 John Wiley & Sons, Ltd.
Mechanical properties and thermal analysis of low‐density polyethylene + polypropylene blends with dialkyl peroxide
Authors: Şirin Kamil , Balcan Mehmet
Published: March 2009

Polypropylene + low density polyethylene (PP + LDPE) blends involving 0, 25, 50, 75 and 100 wt% of PP with dialkyl peroxide (DAP) were prepared by melt blending in a single‐screw extruder. The effects of adding dialkyl peroxide on mechanical and thermal properties of PP + LDPE blends have been studied. It was found that at lower concentrations of peroxide (e.g., 0–0.08 wt% of dialkyl peroxide) LDPE component is cross‐linked and Polypropylene (PP) is degraded in all compositions of PP + LDPE blends. Mechanical properties (Tensile strength at break, at yield and elongation at break), Melt flow index (MFI), hardness, Scanning Electron Microscope (SEM) and thermal analyses (DSC) of these blends were examined. Because of serious degradation or cross‐linking the mechanical properties and the crystallinty (%) of those products were decreased as a result of increasing peroxide content. Copyright © 2009 John Wiley & Sons, Ltd.
Fibrillin‐1 staining anomalies are associated with increased staining for TGF‐β and elastic fibre degradation; new clues to the pathogenesis of emphysema
Authors: Koenders Mieke MJF , Wismans Ronnie G , Starcher Barry , Hamel Ben CJ , Dekhuijzen Richard PN , van Kuppevelt Toin H
Published: March 2009

We recently demonstrated aberrant staining of fibrillin‐1 in lung tissue specimens with emphysematous lesions. In this study, we have extended this observation by an elaborate analysis of the elastic fibre. Using domain‐specific antibodies to fibrillin‐1, and to other elastin fibre‐associated molecules, lung tissue derived from patients without obvious clinical emphysema, but harbouring various degrees of microscopical emphysematous lesions, was analysed. In addition, the fibrillin‐regulated growth factor TGF‐β was studied. Electron microscopy and biochemical analysis of desmosine (a marker for elastin) were also performed. Results were compared with lung tissue derived from patients with clinical emphysema. Domain‐specific antibodies recognizing the C‐terminal, N‐terminal, and middle part of fibrillin‐1 showed aberrant staining patterns associated with increasing degrees of microscopical emphysema. Staining for elastin, emilin‐1, and fibulin‐2 was, however, not aberrant. TGF‐β staining was markedly increased. On the electron microscopic, but not light microscopical, level, initial elastic fibre degradation was noticed in specimens with microscopical emphysema. Lung specimens from patients with clinical emphysema also displayed fragmented fibrillin‐1 staining and, in addition, displayed extensive degradation of the elastic fibre. The results suggest that fibrillin‐1 anomalies and TGF‐β overexpression are associated with initial events occurring during the emphysematous process. Based on these and other data, a mechanism for emphysematogenesis is proposed. Copyright © 2009 Pathological Society of Great Britain and Ireland. Published by John Wiley & Sons, Ltd.
Gastrointestinal upset following improvement of HbA1con initiation of pump therapy
Authors: Partridge H , Kerr D
Published: March 2009

Continuous subcutaneous insulin infusion therapy is being increasingly used across the world in our armamentarium to improve blood glucose control in type 1 diabetes. Significant and rapid declines in HbA1c can be achieved because of the potential to reduce hypoglycaemic episodes and, whilst this is one of our goals in diabetes management, we must be conscious of the possible adverse effects of this. Here we report a case of transient gastroparesis with small bowel bacterial overgrowth following initiation of insulin pump therapy and a rapid drop in HbA1c. Copyright © 2009 John Wiley & Sons.
Pharmacovigilance in traditional chinese medicine safety surveillance
Authors: Wang Hainan , Ye Xiaofei , Gao Qingbin , Wu Cheng , Qian Yifeng , Luo Baozhang , Sun Yalin , He Jia
Published: March 2009

Purpose

To give an overview of the current status including problems and efforts about pharmacovigilance in Traditional Chinese Medicine (TCM) safety surveillance.

Methods

It is based on literature review and publicly available data in China.

Results

TCM led to several adverse drug reactions (ADRs) during the past few years and pharmacovigilance about TCM remained as a problem though great effort had been made to improve it.

Conclusions

Pharmacovigilance in TCM is still facing many challenges in playing critical roles in China. More attention should be paid to pharmacovigilance in TCM safety surveillance. Copyright © 2009 John Wiley & Sons, Ltd.
A comparison of mycophenolate use in Australia and Northern Europe, and the impact on the pharmaceutical benefits scheme
Authors: Staatz Christine E. , Smith Alesha J. , Tett Susan E.
Published: March 2009

Purpose

The aim of this study was to characterise utilisation of mycophenolate in Australian transplant recipients from 2001 to 2007; to identify specific patterns of mycophenolate mofetil and enteric‐coated mycophenolate sodium usage; to examine expenditure on mycophenolate prescription and to compare Australian usage with Danish, Finish and Netherlands populations.

Methods

Data on mycophenolate usage were obtained from Medicare Australia, Finish and Danish Medicines Agency and Netherlands Healthcare Insurance Board databases. Utilisation of mycophenolate was described as daily defined dose (DDD/per 1000 population/day).

Results

From 2001 to 2007, utilisation of mycophenolate in Australia increased approximately 30‐fold. In 2007, mycophenolate sodium accounted for 8.3% of mycophenolate total DDDs. In 2007, AUD$4 890 000 was spent on mycophenolate prescription. In 2006, utilisation of mycophenolate was five‐ to eight‐fold higher in Northern Europe compared to Australia. Renal transplant rates per 1000 population/year were similar across countries.

Conclusions

Differences in the rate of mycophenolate utilisation between Northern Europe and Australia exist and may be due to differences in approved indications between countries, prescribing habits, or because of a more mature market in Europe. If the Australian market increases to that of North Europe the cost of prescribing mycophenolate will eventually be in the vicinity of AUD$20–80 million. Copyright © 2009 John Wiley & Sons, Ltd.
Influence of reaction conditions on the formation of nanotubes/nanoparticles of polyaniline in the presence of 1‐amino‐2‐naphthol‐4‐sulfonic acid and applications as electrostatic charge dissipation material
Authors: Bhandari Hema , Bansal Vineet , Choudhary Veena , Dhawan Sundeep K
Published: March 2009

BACKGROUND: Poly(1‐amino‐2‐naphthol‐4‐sulfonic acid) and its copolymers with aniline are a new class of conducting polymers which can acquire intrinsic protonic doping ability, leading to the formation of highly soluble self‐doped homopolymers and copolymers. Free OH and NH2 groups in the polymer chain can combine with other functional groups that could be present in protective paints which can thus be successfully used as antistatic materials.

RESULTS: This paper reports the formation of nanotubes of polyaniline on carrying out oxidative polymerization of aniline in the presence of 1‐amino‐2‐naphthol‐4‐sulfonic acid (ANSA) in p‐toluenesulfonic acid (PTSA) as an external dopant. The presence of SO3H groups in the ANSA comonomer allows the copolymer to acquire intrinsic protonic doping ability. The polymerization mechanism was investigated by analysing the 1H NMR, 13C NMR, Fourier transform infrared and X‐ray photoelectron spectra of the copolymers and homopolymers, which revealed the involvement of OH/NH2 in the reaction mechanism. Scanning and transmission electron microscopy showed how the reaction route and the presence of a dopant can affect the morphology and size of the polymers. Static decay time measurements were also carried out on conducting copolymer films prepared by blending of 1 wt% of copolymers of ANSA and aniline with low‐density polyethylene (LDPE) which showed a static decay time of 0.1 to 0.31 s on dissipating a charge from 5000 to 500 V.

CONCLUSION: Copolymers of ANSA with aniline were synthesized in different reaction media, leading to the formation of nanotubes and nanoparticles of copolymer. Blends of 1 wt% of PTSA‐ and self‐doped copolymers of ANSA and aniline with LDPE can be formulated into films with effective antistatic properties. Copyright © 2009 Society of Chemical Industry
Cure reaction of multi‐walled carbon nanotubes/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites: effect of carboxylic functionalization of MWCNTs
Authors: Zhou Tianle , Wang Xin , Wang Tianchi
Published: March 2009

BACKGROUND: The aim of this work was to study, using differential scanning calorimetry, the effect of carboxylic functionalization of multi‐walled carbon nanotubes (MWCNTs) on the cure reaction of MWCNTs/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites. This is important for the practical design, analysis and optimization of novel materials processing.

RESULTS: Comparing the influence of non‐functionalized MWCNTs and carboxyl‐functionalized MWCNTs, it was found that, at the initial curing stage, both MWCNTs act as catalyst and COOH functionalization of MWCNTs has a catalytic effect on the curing process. Then, at the later curing stage, non‐functionalized MWCNTs prevent the occurrence of vitrification, whereas COOH functionalization of MWCNTs promotes vitrification. Non‐functionalized MWCNTs decrease the degree of curing, as evidenced by lower total heat of reaction and lower glass transition temperatures of nanocomposites compared to neat epoxy; however, COOH functionalization of MWCNTs increases the degree of curing.

CONCLUSION: For the development of composites, COOH functionalization of MWCNTs could bring a positive influence to the composite process. Its acceleration of cure could help shorten pre‐cure time or lower pre‐treatment temperature, and its effect of promoting vitrification could help shorten post‐cure time or lower post‐treatment temperature. Copyright © 2009 Society of Chemical Industry
Hidden chemistry in phenoxyl radical (C6H5O•) coupling reaction mechanism revealed
Authors: Das Tomi Nath
Published: March 2009

A novel hidden reaction of the phenoxyl radical (C6H5O•) with a specific daughter is found to significantly alter its hitherto accepted coupling reactions' scheme. Transient characterizations and mechanistic evaluations in highly acidic to strongly alkaline aqueous medium reveal this concurrent reaction competing favorably in nanosecond–microsecond time‐scale with the five distinct C6H5O• + C6H5O• reactions, which produce various phenolic end‐products as reported earlier (M. Ye and R. H. Schuler, J. Phys. Chem. 1989, 93, 1898). Presently, only the symmetric 4,4′‐dioxo transient precursor, OC6H5H5C6O that leads to the stable 4,4′‐biphenol product, gets partially oxidized by a fraction of remaining C6H5O•. The resulting secondary transient •C12H9O2 radical is generated at diffusion‐controlled rate, k > 5.0 × 109 M−1 s−1, and follows an independent chemistry. Consequently, when the previously reported five coupled end product distribution ratios were appropriately updated, the respective fractional values revealed a closer match for the symmetric 2,2′‐ and 4,4′‐biphenols with their suggested coupling reaction branching probabilities based on the atomic spin‐density distributions in the C6H5O• radical (P. Neta, R. W. Fessenden, J. Phys. Chem., 1974, 78, 523). Results also suggest that in the remaining fraction, differential solvation in aqueous medium of various orientation‐related encounter complexes (C6H5O…C6H5O) formed during coupling favors rearrangement only toward 2,4′‐biphenolic product, at the cost of 2‐ and 4‐phenoxyphenolic species. Copyright © 2009 John Wiley & Sons, Ltd.
Broad‐spectrum cross‐resistance in Spodoptera exigua from selection with a marginally toxic Cry protein
Authors: Hernández‐Martínez Patricia , Ferré Juan , Escriche Baltasar
Published: March 2009

BACKGROUND: Spodoptera exigua (Hübner) has developed resistance to a wide range of chemical insecticides. Products based on Bacillus thuringiensis Cry toxins are used in integrated pest management as an ecologically friendly alternative for pest control. Since there are few B. thuringiensis Cry proteins highly active against S. exigua, it is desirable to apply appropriate resistance management strategies to prevent the evolution of resistance to these proteins.

RESULTS: Spodoptera exigua larvae were selected with Cry1Ab, a protein with low activity against this pest. Selected larvae developed > 30‐fold resistance to Cry1Ab in 13 generations, relative to an unselected strain. The estimated realised heritability (h2) for the first five generations of selection was 0.15. Cross‐resistance was also observed to the more active proteins Cry1Ca, Cry1Da and Cry1Fa (>20, 26 and > 8 respectively). The activity of midgut proteases to degrade the ingested toxin was tested, although no differences in activity were found between selected and unselected larvae.

CONCLUSION: Spodoptera exigua is able to evolve cross‐resistance to highly active Cry proteins when exposed to a protein with marginal toxicity to this species. It is important to take this into account in areas where S. exigua is a secondary pest and B. thuringiensis Cry1A toxins are used to control other pests. Copyright © 2009 Society of Chemical Industry
Breeding approaches for crenate broomrape (Orobanche crenata Forsk.) management in pea (Pisum sativum L.)
Authors: Rubiales Diego , Fernández‐Aparicio Monica , Pérez‐de‐Luque Alejandro , Castillejo Mari A , Prats Elena , Sillero Josefina C , Rispail Nicolas , Fondevilla Sara
Published: March 2009

BACKGROUND: Pea cultivation is strongly hampered in Mediterranean and Middle East farming systems by the occurrence of Orobanche crenata Forsk. Strategies of control have been developed, but only marginal successes have been achieved. Most control methods are either unfeasible, uneconomical, hard to achieve or result in incomplete protection. The integration of several control measures is the most desirable strategy.

RESULTSL: Recent developments in control are presented and re‐evaluated in light of recent developments in crop breeding and molecular genetics. These developments are placed within a framework that is compatible with current agronomic practices.

CONCLUSION: The current focus in applied breeding is leveraging biotechnological tools to develop more and better markers to speed up the delivery of improved cultivars to the farmer. To date, however, progress in marker development and delivery of useful markers has been slow. The application of knowledge gained from basic genomic research and genetic engineering will contribute to more rapid pea improvement for resistance against O. crenata and/or the herbicide. Copyright © 2009 Society of Chemical Industry
An alternative and fast method for determination of glyphosate and aminomethylphosphonic acid (AMPA) residues in soybean using liquid chromatography coupled with tandem mass spectrometry
Authors: Martins‐Júnior Helio A. , Lebre Daniel T. , Wang Alexandre Y. , Pires Maria A. F. , Bustillos Oscar V.
Published: March 2009

A simple and specific method using reversed‐phase liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC/ESI‐MS/MS) was investigated, which allowed the determination of residues of glyphosate and its metabolite, aminomethylphosphonic acid (AMPA), in soybean samples. An aqueous extraction with liquid‐liquid partition followed by protein precipitation was performed before the LC/MS/MS determination. The quantitation of glyphosate and AMPA was performed in positive and negative ESI mode, respectively, using the multiple reaction monitoring (MRM) mode with three transitions for each analyte to enhance the specificity of the method and avoid false positives. The methodology reported in this work is capable of detecting residues of glyphosate and AMPA in soybean samples with limits of quantification of 0.30 and 0.34 mg kg−1, respectively. This alternative method has throughput advantages such as simpler sample preparation and faster chromatographic analysis. Copyright © 2009 John Wiley & Sons, Ltd.
Coast and year effect on H, O and C stable isotope ratios of Tyrrhenian and Adriatic italian olive oils
Authors: Bontempo L. , Camin F. , Larcher R. , Nicolini G. , Perini M. , Rossmann A.
Published: March 2009

The paper discusses the 2H/1H, 18O/16O and 13C/12C ratios of 196 authentic Italian extra‐virgin olive oils produced in 3 years on the Tyrrhenian and Adriatic coasts. The 2H/1H and 18O/16O ratios were linearly and positively correlated. The year of production influenced mainly 18O/16O in relation to the amount of rainfall and the atmospheric humidity in the period of oil accumulation in the olives. The 2H/1H ratio significantly distinguished the olive oils produced on the Adriatic coast from those on the Tyrrhenian coast in each year. This coast effect is a consequence of the different sources and isotopic compositions of the rainfall and the different climatic conditions on the two coasts. The paper contributes towards understanding the influence of climatic factors on isotopic variability and towards improving the traceability of the geographical origin of olive oils, using 2H/1H as a more innovative parameter. Copyright © 2009 John Wiley & Sons, Ltd.
Measuring leg length and offset with an imageless navigation system during total hip arthroplasty: is it really accurate?
Authors: Renkawitz Tobias , Schuster Tibor , Herold Thomas , Goessmann Holger , Sendtner Ernst , Grifka Joachim , Kalteis Thomas
Published: March 2009

Background

A novel imageless measurement algorithm to assess leg length (LL) and offset (OS) changes during total hip arthroplasty (THA) has been established, the purpose of this study was to describe the process and establish whether or not it is accurate.

Methods

THA was performed on 17 cadaver hip specimens. LL and OS changes were determined intra‐operatively, using an imageless navigation system. Pre‐ and postoperatively, all specimens had a computed tomography scan (CT) and the LL and OS changes were analysed by two blinded investigators.

Results

With mean differences of less than 1 mm (LL, 0.74; SD, 2.4 mm; OS, 0.89; SD, 1.8 mm) supported by substantial significant correlations [r = 0.83 (LL) and r = 0.92 (OS)] imageless navigation values demonstrated a high accuracy when compared to CT measurements.

Conclusions

Intra‐operative LL and OS measures are reliable and accurate when using an imageless calculation algorithm which stores the position of the femoral reference frame in relation to the pelvic coordinate system before and after reconstruction. Copyright © 2009 John Wiley & Sons, Ltd.